Rekind A.1 Reva

TECH.
RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 1 dari 136
RANCANGAN KONSEPTUAL PROSES DAN PABRIK BIOETANOL KAJIAN PATEN DAN LISENSI TEKNOLOGI
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Issued for Comment
C.B. Rasrendra/ Stephanie Sutoko
Prepared By
M.T.A. Penia Kresnowati
Ronny Purwadi
Checked By
Approved By
Reviewed By
Approved By
REV
STATUS REVISI
Peneliti
Peneliti
Peneliti Utama
TRD Engineer
Sr. Mgr. TRD
APPROVAL KONSULTAN
APPROVAL REKIND
REVISION RECORD
Rev A Status Revisi Issue for Review Tanggal Terbit 13 Agustus 2012 Deskripsi Initial Release
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TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 2 dari 136
RIWAYAT PERUBAHAN DOKUMEN

Rev Tanggal Deskripsi Perubahan
DAFTAR ISI
EXECUTIVE SUMMARY ................................................... Error! Bookmark not defined. 1. PENDAHULUAN ....................................................................................................... 5 1.1. Latar Belakang ................................................................................................... 5 1.2. Tujuan ................................................................................................................ 5 1.3. Ruang Lingkup ................................................................................................... 5 2. STUDI PUSTAKA...................................................................................................... 7 2.1. Biomass Lignosellulosa ...................................................................................... 7 2.1.1. Selulosa ...................................................................................................... 7 2.1.2. Hemiselulosa............................................................................................... 8 2.1.3. Lignin .......................................................................................................... 9 2.1.4. Jenis dan Tipikal Komposisi Biomassa Lignoselulosa ............................... 10 2.2. Proses Produksi Bioetanol Lignoselulosa ......................................................... 11 2.3. Perbandingan Proses Produksi Bioetanol Lignoselulosa dengan Bioetanol Generasi Pertama ................................................................................................... 13
2.4. Produksi Bioetanol Lignoselulosa ..................................................................... 14

2.4.1. Perlakuan Awal (Pretreatment) ................................................................. 14 2.4.2. Sakarifikasi ................................................................................................ 19 2.4.3. Hidrolisis Asam ......................................................................................... 19 2.4.4. Hidrolisis Enzimatik ................................................................................... 20 2.4.5. Perbandingan Hidrolisis Asam dan Enzimatik ........................................... 20 2.5. Fermentasi ....................................................................................................... 21 2.5.1. Mikroorganisme untuk Fermentasi Biomassa Lignoselulosa Menjadi Etanol 21 2.5.2. Teknologi Fermentasi ................................................................................ 24 2.6. Pemisahan dan Pemurnian .............................................................................. 27 2.7. Pemanfaatan Produk Samping ......................................................................... 27 3. 4. METODOLOGI ........................................................................................................ 28 HASIL DAN PEMBAHASAN.................................................................................... 28 4.1. Teknologi Proses Produksi Bioetanol Lignoselulosa dan Status Pengembangannya ................................................................................................. 28 4.1.1. Status Pengembangan dan Komersialisasi ............................................... 28 4.1.2. Bahan Baku dan Perlakuan Awal .............................................................. 30 4.1.3. Metoda Sakarifikasi: Hidrolisis asam encer ............................................... 30 4.1.4. Hidrolisis Enzimatik ................................................................................... 31 4.1.5. Fermentasi ................................................................................................ 31 4.1.6. Proses Integrasi ........................................................................................ 32 4.2. Perbandingan Teknologi Produksi Bioetanol Lignoselulosa .............................. 32 5. KESIMPULAN DAN SARAN ................................................................................... 39 5.1. KESIMPULAN .................................................................................................. 39
5.2. SARAN............................................................................................................. 39
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6. DAFTAR PUSTAKA ................................................................................................ 40 7. LAMPIRAN.............................................................................................................. 41 LAMPIRAN 1 ............................................................................................................... 42 ABENGOA .............................................................................................................. 42 AE BIOFUELS (AEMETIS) ...................................................................................... 48 AMERICAN PROCESS ........................................................................................... 49 ARKENOL BLUE FIRE ETHANOL ....................................................................... 53 BBI BIO VENTURES LLC ....................................................................................... 58 BIOGASOL ............................................................................................................. 59 BLUE SUGARS (d.h KL ENERGY) ......................................................................... 64 BORREGAARD....................................................................................................... 67 CHEMTEX PROESA - MGM ................................................................................ 71 DEDINI .................................................................................................................... 73 DuPONT Danisco Cellulosic Ethanol (DDCE) ......................................................... 75 FUTUROL PROCETHOL ........................................................................................ 78 GREEN FIELD ETHANOL ...................................................................................... 81 INBICON ................................................................................................................. 84 IOGEN .................................................................................................................... 88 LIGNOL ................................................................................................................... 94 MASCOMA (SunOpta) ............................................................................................ 97 METSA BOARD (d.h. M-REAL-HALEIM AG) .......................................................... 98 PACIFIC ETHANOL .............................................................................................. 100 POET-DSM ........................................................................................................... 103 QTEROS ............................................................................................................... 110 SEKAB .................................................................................................................. 112 SUD CHEMIE (SUN LIQUIDS) .............................................................................. 115 VERENIUM ........................................................................................................... 118 WEYLAND AS ...................................................................................................... 120 ZEACHEM ............................................................................................................ 121 LAMPIRAN 2 ............................................................................................................. 124 INDONESIA .......................................................................................................... 124 CHINA ................................................................................................................... 125 JEPANG ............................................................................................................... 127 THAILAND ............................................................................................................ 128 MALAYSIA ............................................................................................................ 129 VIETNAM .............................................................................................................. 130
1. PENDAHULUAN
1.1. Latar Belakang
Bioetanol lignoselulosa, sering disebut sebagai bioetanol generasi kedua, diidentifikasi sebagai salah satu bahan bakar nabati yang atraktif dari sumber terbarukan. Hal ini didukung oleh keberadaan biomassa lignoselulosa yang melimpah dan tidak berkompetisi dengan bahan pangan. Pengembangan teknologi dan proses untuk komersialisasi bioetanol lignoselulosa menjadi perhatian kalangan ilmuwan, praktisi, dan pelaku industri bioetanol pada dasawarsa ini. Meskipun bioetanol generasi pertama yang berbahan baku tetes tebu (molase) dan pati telah berhasil diproduksi pada skala komersial dari pada dekade 1970, hingga saat ini (2012) skala komersial bioetanol lignoselulosa belum tersedia. Namun demikian, pengembangan proses produksi bioetanol lignoselulosa pada skala pilot dan demonstrasi telah tersedia. Beberapa pengembang teknologi telah mencanangkan dan berproses untuk membuat produksi bioetanol lignoselulosa skala komersial pertama di dunia pada periode 2013. Selaras dengan upaya untuk mengoversi bahan baku lignoselulosa lokal Indonesia menjadi bioetanol dengan teknologi milik sendiri, paparan pada laporan ini menyampaikan tahapan proses produksi bioetanol lignoselulsa, pilihan-pilihan teknologi yang tersedia termasuk perbandingan keunggulan dan kekurangannya, dan ulasan status dan teknologi proses bioetanol lignoselulosa yang telah dan akan dikembangkan untuk mencapai skala produksi komersial.
1.2. Tujuan
Laporan ini bertujuan untuk menyajikan perkembangan terkini (state of the art) teknologi bioetanol lignoselulosa secara terperinci. Hasil dari kajian ini akan digunakan sebagai basis pemilihan teknologi dan penyusunan ugeran-ugeran untuk studi rancangan konseptual dan perancangan pabrik bioetanol lignoselulosa.
1.3. Ruang Lingkup

Ruang lingkup laporan ini adalah: 1. Laporan kajian pustaka mengenai state of the art dan kajian komprehensif paten-paten teknologi produksi bioetanol berbasis lignoselulosa yang berpotensi untuk diterapkan dalam proyek pengembangan bioetanol perusahaan.
2. Telaah/review mengenai hasil kajian teknologi bioetanol lignoselulosa, mencakup kekurangan dan kelebihan dari masing-masing teknologi tersebut. 3. Identifikasi lisensi teknologi-teknologi produksi bioetanol dan menyusun daftar lisensor dari teknologi tersebut, termasuk perkembangan penerapan teknologi tersebut di industri bioetanol. 4. Analisis kelemahan dan kekuatan lisensor teknologi yang ada dan analisis peluang perbaikannya.
2. STUDI PUSTAKA
2.1. Biomass Lignosellulosa
Biomassa lignoselulosa pada dasarnya terdiri atas tiga biopolimer utama, yaitu selulosa (biopolimer rantai lurus dengan monomer glukosa), hemiselulosa (biopolimer gula yang tersusun dengan dominasi monomer pentosa), dan lignin (biopolimer kompleks dengan senyawa fenol sebagai monomernya). Ilustrasi biomassa lignoselulosa dan struktur biopolimer-biopolimernya disajikan pada Gambar A.1.1.
Gambar A.1.1 Komponen biomassa lignoselulosa
2.1.1. Selulosa
Selulosa merupakan biopolimer gula (polisakarida) yang keberadaanya paling melimpah di bumi. Selulosa tersusun atas rantai linear monomer glukosa yang saling terikat oleh ikatan (1-4) glikosida. Struktur polimer rantai lurus glukosa ini sering disebut juga dengan istilah glukan. Adanya interaksi antara atom oksigen dan gugus hidoksi (OH) melalui ikatan hidrogen membuat struktur selulosa mempunyai kekuatan tarik (tensile strength) yang tinggi dan membentuk struktur serat-serat mikro. Hal ini pulalah yang mengakibatkan selulosa mempunyai struktur kristalinitas yang kuat.
(a)
(b)
Gambar A.1.2. Struktur selulosa (a) monomer dan struktur ikatan (1-4) glikosidik antar monomer dalam selulosa, (b) ikatan hidrogen pada selulosa
Apabila digunakan sebagai bahan baku bioetanol melalui jalur fermentasi, glukosa dari selulosa merupakan komponen utama yang dikonversi menjadi etanol. Dibandingkan dengan biopolimer pati yang menjadi bahan baku bioetanol generasi pertama, proses memperoleh unit monomer glukosa dari selulosa lebih susah. Hal ini menjadi salah satu pembatas (barrier) komersialiasi bioetanol lignoselulosa. Perbandingan antara selulosa dan pati disajikan pada Tabel A.1.1
Tabel A.1.1 Perbandingan selulosa dan pati Selulosa terusun atas -glukosa yang terhubung dengan ikatan (1-4) glikosidik linear tinggi perlu T:300 C, 250 bar Tidak Pati terusun atas -glukosa yang terhubung dengan ikatan (1-4) glikosidik linear: amilosa bercabang: amilopektin rendah cukup pada T > 60 C Ya
strukur
Rantai Kristalinitas Berubah menjadi amorf di air Ketercernaan (digestibility)
2.1.2. Hemiselulosa
Hemiselulosa merupakan biopolimer gula komplek yang khas terdapat dalam biomassa lignoselulosa. Hemiselulosa tersusun atas beragam monomer gula yang saling terikat dan tidak memiliki pola (Gambar A.1.3). Komposisi dan struktur hemiselulosa ini sangat beragam tergantung pada jenis biomassa dan lingkungannya. Komposisi hemiselulosa umumnya didominasi oleh gula berkarbon lima (pentosa) seperti xilosa dan arabinosa. Meskipun demikian, gula berkarbon enam (heksosa) seperti glukosa, manosa, dan galaktosa juga terdapat dalam biopolimer ini.
Hemiselulosa kaya akan xilosa, seperti tongkol jagung atau tandan kosong sawit sering disebut sebagai xilan. Dibandingkan dengan selulosa, hemiselulosa lebih mudah dihidrolisis untuk mendapatkan monomer-monomer gula penyusunnya. Monomer-monomer gula penyusun hemiselulosa
merupakan bahan yang dapat dikonversi menjadi bioetanol. Mempertimbangkan kemampuan metabolisme mikroba yang digunakan dalam proses fermentasi bioteanol, sumber gula heksosa dapat difermentasi bersama glukosa yang dihasilkan dari selulosa, sedangkan gula pentosa perlu difermentasi menjadi bioetanol secara terpisah.
glukosa xilosa gugus asetil
arabinosa
asam ferulik
mannosa
Gambar A.1.3 Struktur hemiselulosa
galaktosa
2.1.3. Lignin
Lignin merupakan biopolimer komplek dan khas yang terdapat dalam biomassa lignoselulosa. Strukutur lignin tersusun atas jaringan aromatik (fenol) yang terikat secara silang (cross-linked) dan tidak berpola (Gambar A.1.4). Lignin beperan sebagai pengikat selulosa dan hemiselusosa dan penyokong (support) yang memberikan kekuatan struktur pada biomassa. Di dalam produksi bioetanol, keberadaan lignin ini merupakan salah satu pembatas yang perlu dibongkar agar gula-gula yang terdapat pada selulosa dan hemiselulosa dapat diakses dan dihidrolisis. Lignin merupakan produk samping atau limbah dalam produksi bioetanol. Kisaran komposis lignin sekitar 30% pada biomassa lignoselulosa memotivasi pemanfaatan produk samping ini untuk meningkatkan keekonomian bioetanol selulosa.
Gambar A.1.4 Struktur lignin
2.1.4. Jenis dan Tipikal Komposisi Biomassa Lignoselulosa

Jenis biomassa lignoselulosa dapat dikategorikan menjadi 4 jenis yaitu, (1) residu kayu, limbah/sisa dari industri kayu, termasuk industri kertas (2) residu pertanian, seperti tandan kosong sawit, jerami, tongkol jagung, bagas, kulit batang sagu, dan sekam padi, (3) tanaman energi (energy crops) seperti rumput gajah, miscanthus, dan (4) limbah padat (selulosa)
perumahanUntuk residu kayu atau sisa kayu industri, para pengembang teknologi konversi lignoselulosa sering menggunakan istilah yang biasa digunakan dalam perkayuan, yaitu hardwood dan softwood. Tabel A.1.2 menyajikan komposisi biopolimer beragam biomassa lignoselulosa. Komposisi tipikal biopolimer secara berturut-turut untuk selulosa, hemiselulosa dan lignin adalah 38-50%, 23-32%, dan 15-25%, variasi bergantung pada jenis biomassa lignoselulosa, usia dan tahap pertumbuhan, dan kondisi lainya (Kumar, dkk., 2009).
Tabel A.1.2 Tipikal komposisi biomassa lignoselulosa* (Kumar, dkk., 2009) Biomassa Lignoselulosa selulosa (%) hemiselullosa (%) lignin (%)
TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA
batang kayu keras (hardwood) batang kayu ringan (softwood) kulit biji (nut sheels) tongkol jagung rerumputan (grasses) wheat straw dedaunan limbah pabrik pulp switch grass tandang kosong sawit (Zainudin, 2012) jerami padi (Sarkar, 2012) bagas pabrik (Sarkar, 2012) 40-55 45-50 25-30 45 25-40 30 15-20 60-70 45 42.85-51.28
Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01

24-40 25-35 25-30 35 35-50 50 80-85 10-20 31.4 24.01-28.51
Revisi: A Hal 11 dari 136

18-25 25-35 30-40 15 10-30 15 0 5-10 12 11.70-15.17 5-24 18.4
32-47 19-27 65 (total karbohidrat)
*perhitungan komposisi yang disajikan menggunakan basis kering

Indonesia memilki sumber biomassa lignoselulosa yang beragam dan aktratif sebagai bahan baku bioetanol generasi kedua, seperti residu pertanian: tandan kosong kelapa sawit, jerami dan sekam padi, dan kulit batang sagu. Ketersediaan dan potensi biomassa lignoselulosa tersebut akan diulas secara mendalam dan detail pada Sub-Paket B.1. dan A.3., tentang evaluasi ketersediaan tandan kosong sawit sebagai bahan baku bioetanol generasi kedua dan 3 (tiga) bahan baku lignoselulosa lokal alternatif.
2.2. Proses Produksi Bioetanol Lignoselulosa

Bioetanol lignoselulosa pada umumnya dapat diperoleh melalui empat jalur proses yang dapat dikelompokkan menjadi dua kelompok proses konversi, yaitu proses konversi secara biologis (biochemical conversion) dan proses konversi termal (thermochemical conversion). Skema A.1.1 memberikan ilustrasi diagram proses dari jalur-jalur proses produksi bioetanoll lignoselulosa.
Proses konversi secara biologis (biochemical conversion)
Jalur proses 1: Hidrolisis enzimatik-fermentasi gula` Biomassa Lignoselulosa Perlakuan awal Hidrolisis Enzimatik Fermentasi Gula Pemurnian Etanol Bioetanol
Jalur proses 2: Hidrolisis asam-fermentasi gula Biomassa Lignoselulosa Perlakuan awal Hidrolisis Asam Fermentasi Gula Pemurnian Etanol Bioetanol
Proses konversi termal (thermochemical conversion)

Jalur proses 3: Gasifikasi-fermentasi Biomassa Lignoselulosa Gasifikasi Syngas Fermentasi Syngas Pemurnian Etanol Bioetanol
Jalur proses 4: Gasifikasi-sintesa katalitik Biomassa Lignoselulosa Gasifikasi Syngas Sintesa Katalitik Pemurnian Etanol Bioetanol
Skema A.1.1 Skema jalur-jalur proses konversi produksi bioetanol lignoselulosa
Inti dari proses produksi bioetanol secara biologis adalah proses fermentasi gula yang terkandung dalam biomassa lignoselulosa menjadi etanol. Ada dua cara memperoleh gula yang dapat difermentasi dari biomassa lignoselulosa, yaitu melalui hidrolisis enzimatik (jalur proses 1) dan hidrolisis asam (jalur proses 2). Berbeda dengan proses konversi secara biologis, proses konversi termal melibatkan reformasi biopolimer di dalam biomassa lignoselulosa menjadi gas sintesa (syngas) melalui proses gasifikasi (T>600 C). Selanjutnya, syngas yang terbentuk dikonversi menjadi etanol melalui jalur fermentasi (Jalur proses 3) atau sintesa katalitik (Jalur proses 4). Tabel A.1.3 menyajikan jalur proses konversi bioetanol lignoselulosa dan pengembang teknologi prosesnya. Selain keempat jalur utama konversi bioetanol terdapat beberapa pengembang teknologi yang menggunakan jalur gabungan (konversi termal dan fermentasi) untuk mengonversi gula menjadi etanol. Tabulasi pengembang teknologi tersebut mengindikasikan bahwa jalur produksi bioetanol melalui jalur fermentasi gula merupakan jalur produksi yang lebih popular dan lebih banyak dikembangkan daripada jalur poses konversi termal. Selaras dengan ruang lingkup dan fokus pekerjaan ini, kajian paten dan proses teknologi bioetanol lignoselulosa difokuskan pada teknologi bioetanol melalui jalur fermentasi gula (biochemical conversion). Selanjutnya, istilah teknologi bioetanol lignoselulosa yang dimaksd pada bagian laporan ini adalah teknologi bioetanol menggunakan jalur konversi secara biologis.
Tabel A.1.3 Tabel jalur proses konversi bioetanol lignoselulosa dan pengembang teknologinya.
No 1
Jalur Proses Jalur 1: Hidrolisis enzimatik-fermentasi gula
Pengembang Teknologi POET-DSM, IOGEN, Inbicon Biomass Refinery, Mossi & Ghisolfi - Chemtex Italia, Dupont Danisco Cellulosic Ethanol LLC, Lignol, KL Energy, AE Biofuels, Logos Technologies, Inc. Abengoa Bioenergy
Jalur 2: Hidrolisis Asam-fermentasi gula
Bluefire
ethanol,
SEKAB,
Archer
Daniels
Midland, Weyland AS 3 4 Jalur 3: Gasifikasi-fermentasi Jalur 4: Gasifikasi-sintesa katalitik Coskata, INEOS New Planet Bioenergy LLC Enerkem, Range Fuels (d.h. Kergy)
TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA 5 Jalur Proses Gabungan/Alternatif a) Fermentasi asetat) b) Fermentasi langsung biopolimer gula menjadi etanol Mascoma, Qteros (d.h. Sun Ethanol), American Process, Inc., Pacific Ethanol alternatif (jalur Zeachem Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 13 dari 136
2.3. Perbandingan Proses Produksi Bioetanol Lignoselulosa dengan Bioetanol Generasi Pertama
Produksi bioetanol pada dasarnya terdiri atas tiga (3) tahap utama, yaitu perolehan gula yang dapat difermentasi (fermentable sugar), fermentasi, dan pemisahan dan pemurnian produk. Skema A.1.2 menampilkan overview proses produksi bioetanol dari beragam sumber bahan baku, meliputi bioetanol generasi pertama (tetes gula/molase dan pati singkong) dan biomassa lignoselulosa. Tahap sebelum fermentasi, untuk memperoleh gula yang dapat difermentasi, merupakan pembeda utama tahapan proses produksi bioetanol dari gula sederhana (tetes gula/molase), pati, dan bahan lignoselulosa.Tetes tebu (molase) dapat langsung difermentasi menjadi etanol, sedangkan pati singkong perlu melalui tahapan likuifaksi dan sakarifikasi untuk memperoleh gula yang dapat difermentasi. Sementara itu, biomassa lignoselulosa membutuhkan tahapan perlakuan awal dan tahapan hidrolisis untuk menghasilkan gula yang dapat difermentasi. Selain glukosa, biomassa lignoselulosa juga menghasilkan gula pentosa yang juga dapat dikonversi menjadi bioetanol.
Produksi gula-dapat-difermentasi Fermentasi Pemisahanan & Pemurnian Pemurnian Etanol Pemurnian Etanol Bioetanol
Tetes gula (molase)
Fermentasi Heksosa Fermentasi Heksosa
Pati
Likuifaksi
Sakarifikasi
Bioetanol
Biomassa Lignoselulosa
Perlakuan awal
Hidrolisis
Fermentasi Heksosa Fermentasi Pentosa
Pemurnian Etanol
Bioetanol
Skema A.1.2 Perbandingan tahap produksi bioetanol lignoselulosa (generasi kedua) dengan bioetanol generasi pertama
Proses fermentasi dan pemurnian etanol dari dari ketiga jenis bahan baku tersebut relatif sama, kecuali untuk tahap tambahan fermentasi pentosa. Para pengembang teknologi bioetanol lignoselulosa menggunakan proses fermentasi dan pemurnian etanol yang sama dengan proses bioetanol generasi pertama yang telah mencapai tahap komersial.
2.4. Produksi Bioetanol Lignoselulosa

Produksi bioetanol lignoselulosa melalui jalur fermentasi terdiri atas 5 tahap, yaitu (1) tahap perlakuan awal (pretreatment), (2) tahap hidrolisis, (3) tahap fermentasi, (4) pemisahan dan pemurnian, dan (5) pemanfaatan produk samping. Sub-bab berikut mengulas secara
komprehensif tiap tahap produksi bioetanol beserta status perkembangannya.
2.4.1. Perlakuan Awal (Pretreatment)

Proses perlakukan awal bertujuan untuk memecah lignin dan merusak struktur kristalin dari selulosa seperti yang diilustrasikan pada Gambar A.1.5 sehingga struktur biomassa menjadi lebih mudah diakses oleh media penghidrolisis (Mosier, dkk., 2005). Perlakuan awal dilaksanakan sebagai proses pendahuluan bagi konversi bahan baku berlignoselulosa dengan
mempertimbangkan kompleksitas dari struktur lignoselulosa yang telah dijelaskan pada subbab 2.1.
lignin selulosa
bagian amorf
perlakukan awal
bagian kristalin
hemiselulosa Gambar A.1.5 Skema tujuan perlakukan awal biomassa lignoselulosa (diambil dari (Mosier, dkk., 2005))
Proses perlakuan awal yang efektif diharapkan dapat memenuhi beberapa target seperti berikut (Yang dan Wyman, 2008): kebutuhan bahan kimia dapat diminimalisasi,
menghindari proses reduksi ukuran partikel karena proses membutuhkan biaya dan energi yang besar,
perolehan gula tereduksi dari hemiselulosa (mendekati 100%) dan selulose (lebih besar dari 90%) yang tinggi,
konsentrasi gula pada proses pretreatment dan fermentasi lebih besar dari 10% agar efisiensi proses downstream dapat terjaga,
reaktor pretreament harus ekonomis (minimalisasi volume dan penggunaan material yang sesuai),
tidak menghasilkan residu yang mengganggu kontuinitas proses pretreatment maupun proses selanjutnya,
lignin dan konstituen lainnya dapat diambil kembali sebagai produk samping serta bertujuan untuk tidak mengganggu proses downstream, dan
kebutuhan panas dan energi rendah serta dapat diintegrasikan secara termal dalam proses.
Dengan demikian, pemilihan teknologi perlakuan awal harus dilakukan dengan seksama dengan mempertimbangkan konsentrasi padatan dan pola pelepasan gula sehingga sesuai dengan keseluruhan proses, bahan baku yang digunakan, media penghidrolisis, organisme yang digunakan, serta kondisi optimum tercapai. Pilihan-pilihan teknologi serta perbandingannya ditunjukkan pada Tabel A.1.4.
Tabel A.1.4. Perbandingan perlakuan awal (Kumar dan Murthy, 2011; Limayem dan Ricke, 2012; Mosier, dkk., 2005; Sun dan Cheng, 2002; Taherzadeh dan Karimi, 2007; Taherzadeh dan Karimi, 2007; Yang dan Wyman, 2008) Perlakuan Awal Fisik/Physical pretreatment (penggilingan, iradiasi, dan lainlain) Hidrolisis Asam encer (HCl/H2SO4, 0.5-5%) Perlakuan Air panas (Hot waterHydrothermal Treatment) Karakteristik Kunci Membutuhkan energi yang tinggi Tidak dapat menghilangkan lignin Tidak disarankan untuk aplikasi pada industri Tidak membutuhkan bahan kimia Teknik sederhana dan praktis. Tidak butuh energi termal tinggi Efektif untuk menghidrolisis hemiselulosa pada kondisi moderate Menghasilkan inhibitor bersifat toksik Membutuhkan tahap recovery dan netralisasi/detoksifikasi Sebagian besar hemiselulosa dapat dilarutkan Tidak menghasilkan bahan kimia ataupun inhibitor toksik Diapplikasikan pada beban padatan ratarata Tidak cocok untuk softwood Perolehan gula pentosa dan heksosa total yang tinggi Efektif untuk hardwood dan residu pertanian Temperatur dan tekanan operasi tinggi Masalah pada skala komersial Efektif untuk residu pertanian (bonggol Efek 1+, 2# Tipikal Bahan Baku Tipikal Kondisi Operasi Ref (Taherzadeh dan Karimi, 2008)
1+, 3+, 5+
Serpihan kayu, straw
Konsentrasi : 0.05-5% o T : 160-220 C t : 1-60 menit P : tekanan uap jenuh
(Limayem dan Ricke, 2012; Mosier, dkk., 2005)
1+, 3+, 5#
Fiber jagung, straw
pH : 4-7 T : 160-230 C t : 12-60 menit P : hingga 5 Mpa
(Limayen, 2012)(Mosier, 2005) (Hendrik, 2009) Kumar, 2011)
Hidrolisis Alkalin (Lime)
1+, 3#, 4+, 5+
Softwood dengan kandungan lignin < 26% dan jerami dengan kandungan lignin 1018% Bahan baku tidak
Konsentrasi : 0.5-3% o T : > 100 C t : beberapa menit jam P : tekanan uap jenuh
(Limayen, 2012)(Mosier, 2005)(Kumar, 2009)(Kumar, 2011) (Limayen, 2012)
Ammonia Fiber Expansion
1+,2+,3#,4+,
Konsentrasi : 1-2 kg
Perlakuan Awal (AFEX) -
Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 17 dari 136
Efek 5+ Tipikal Bahan Baku berlignin tinggi Tipikal Kondisi Operasi ammonia cair/kg biomassa kering o T : 90 C t : 30 menit Ref
Karakteristik Kunci jagung) tanpa pembentukan produk akhir yang bersifat toksik Tidak cocok untuk bahan baku berlignin tinggi Ammonia recovery Tidak menghasilkan air limbah Redistribusi lignin tinggi (85%) Daur ulang amoniak Mendekati perolehan teoritik Efektif untuk residu pertanian dan hardwood, namun tidak terlalu efekti untuk softwood Penghilangan fraksi hemiselulosa tinggi Tidak terlalu efektif untuk softwood Perolehan tinggi dicapai dengan kombinasi asam Efektif untuk softwood dan hardwood Konsentrasi gula dari hemiselulosa rendah Membentuk inhibitor toksik Kebutuhan daur ulang pelarut organik Modal kapital investasi tinggi Efektif untuk bahan baku berlignin tinggi, hardwood, dan softwood Efisiensi energi tertinggi Pembentukan inhibitor minimal Kompatibiltas bahan baku tinggi Kombinasi SPORL dan steam explosion
Ammonia Recycle Percolation (ARP)
1+, 2+, 3#, 4+, 5+
Ledakan Kukus Katalitik (steam explosion with catalyst)
3+, 5+
Limbah pertanian, moderate utk hardwood, softwood tidak sesuai Hardwood dan residu pertanian
Konsentrasi : 10-15% w/w o T : 150-170 C t : 14 menit T : 160-290 C T : beberapa detik - menit P : 0.69-4.83 Mpa
o
Pelarutan Lignin dengan senyawa Organik (Organosolv) Sulfite pretreatment top overcome recalcitrance (SPORL) -
3+, 4+
Serpihan kayu
Konsentrasi : 35-70% alkohol pH : 2.0-3.8 o T : 180-195 C t : 30-90 menit
1+, 2+, 3#, 4+, 5+
Serpihan kayu, kayu bahan baku kertas
Perlakuan Awal
Efek Tipikal Bahan Baku Tipikal Kondisi Operasi Ref
Karakteristik Kunci dengan kehadiran enzim sangat efektif untuk softwood Biaya efektif Penghilangan lignin efektif Kompatibiltas bahan baku luas Tidak menghasilkan inhibitor Mahal Kombinasi oksigen, air, temperatur tinggi, dan alkali mengurangi inhibitor toksik Delignifikasi dan pelarutan bahan baku yang tinggi Hidrolisis oligomer rendah Ramah lingkungan Penggunaan energi dan bahan kimia yang rendah Biokonversi lambat 4+
Penghilangan Lignin dengan Ozone Bioconversi lignin dengan fungal -
Jerami, bagas, sekam, hardwood
Oksidasi basah alkalin
1+, 5+
2+, 3+, 5+
Waste material
Keterangan notasi kolom Efek: Angka: (1) meningkatkan luas permukaan akses, (2) dekristalinasi selulosa, (3) menghilangkan hemiselulosa, (4) menghilangkan lignin, (5) merubah/merusak struktur lignin. Notasi setelah angka: positif(+): efek signifikan, tanda binang(#) efek tidak signifikan]
2.4.2. Sakarifikasi
Sakarifikasi adalah proses hidrolisis untuk memecah polisakarida menjadi monomer-monomer gula terlarut. Sakarifikasi biomassa lignoselulosa ditujukan untuk memecah biopolimer gula menjadi monomer gula yang dapat difermentasi dengan bantuan katalis melalui proses hidrolisis (Tahap ini sering juga disebut sebagai tahap hidrolisis). Ada dua metoda yang digunakan untuk menghidrolisis biomassa lignoselulolsa, yaitu hidrolisis asam dan enzimatik.
2.4.3. Hidrolisis Asam

Hidrolisis asam menggunakan bantuan asam (biasanya HCl atau H2SO4) sebagai katalis. Ion hidronium (H3O ) berperan memutus ikatan glikosidik yang menghubungkan monomer-monomer gula. Berdasarkan konsentrasi asam, proses hidrolisis asam dibagi menjadi hidrolisis asam encer (dilute acid) dan hidrolisis asam pekat (concentrated acid). Hidrolisis asam encer biasanya diselenggarakan pada rentang konsentrasi asam 2-5 wt% pada temperatur di atas 120 C. Hemiselulosa dapat dihidrolisis dengan metoda ini pada temperatur moderat (T: 120-150 C), tetapi dibutuhkan kondisi yang ekstrim untuk menghidrolisis selulosa (T>190 C). Pada proses hidrolisis ini, reaksi dilakukan pada kondisi temperatur dan tekanan yang tinggi dan karena perolehan glukosa yang rendah dari selulosa pada proses hidrolisis ini, maka perolehan etanol pun rendah. Hidrolisis asam pekat biasanya diselenggarakan pada konsentrasi asam 10-30 wt%, rentang temperatur operasi di bawah 50 C, dan tekanan atmosfir. Proses ini membutuhkan waktu tinggal yang lebih lama dan menghasilkan perolehan etanol yang lebih tinggi dibandingkan dengan hidrolisis asam terlarut. Meskipun hidrolisis asam memiliki kehandalan dalam hal menghidrolisis biopolimer selulosa dan hemiselulosa secara serempak, namun metoda ini memiliki kekurangan yaitu terjadinya reaksi lanjutan (konsekutif) dari gula yang terbentuk. Glukosa yang terbentuk akan membentuk hidroksimetilfurfural (HMF) dan xilosa dapat terkonversi menjadi furfural. Selain menurunkan perolehan gula yang terbentuk, komponen HMF dan furfural merupakan inhibitor mikroorganisme pada proses fermentasi. Strategi umum yang biasa dilakukan untuk hidrolisis biomassa ini adalah (1) menyelenggarakan hidrolisis pada kondisi yang tepat dan menghentikan reaksi saat gula terproduksi pada level optimum dan (2) melakukan detoksifikasi hidrolisat sebelum diumpankan untuk menghilangkan zat racun bagi microorganism. Detoksifikasi biasanya dilakukan dengan menambahkan basa seperti Ca(OH)2 atau amoniak (Taherzadeh dan Karimi, 2007).
+
2.4.4. Hidrolisis Enzimatik

Hidrolisis biopolimer secara enzimatik menggunakan enzim yang diproduksi oleh sejumlah mikroorganisme yang dapat memecah komponen lignoselulosa menjadi gula. Proses ini biasanya diselenggarakan pada temperatur rendah tetapi membutuhkan waktu reaksi yang lebih lama. Sesuai dengan sifat enzim yang bekerja spesifik, hidrolisis selulosa dan hemiselulosa memerlukan jenis enzim yang berbeda, yaitu enzim selulase dan enzim hemiselulase.
Hidrolisis Selulosa (Selulase) Proses hidrolisis selulosa secara enzimatik melibatkan peran selulase. Tahapan kinerja selulase melalui tahap-tahap berikut: adsorpsi selulase pada permukaan selulosa, biodegradasi selulosa menjadi gula tereduksi, dan desorpsi selulase. Selulase terdiri dari 3 kelas utama enzim yaitu endo-glukanase, ekso-glukanase, dan -glukosidase. Ketiga kelas enzim tersebut memiliki karakteristik kinerja enzim yang berbeda; endo-glukanase menyerang serat selulosa yang memiliki kristalitas rendah serta menghasilkan rantai bebas, ekso-glukanase mendegradasi rantai gula dengan menyingkirkan unit selobiosa pada rantai bebas, dan -glukosidase memotong selobiosa menjadi glukosa. Selulase dapat dihasilkan oleh mikroorganisme di antaranya Trichoderma spp., dan Aspergillus niger (Taherzadeh dan Karimi, 2007).
Hidrolisis Hemiselulosa (Hemiselulase) Hemiselulase berperan pada proses hidrolisis hemiselulosa. Sama halnya dengan selulase, hemiselulase juga terdiri dari beberapa kelas enzim seperti endo-1,4--D-xylanase, ekso-1,4--Dxylanase, endo-1,4--D-mannanase, -manosidase, asetil xylan esterase, -glukuronidase, -Larabinofuranosidase, dan -galaktosidase. Perbedaan karakteristik dari beberapa kelas enzim tersebut dapat dilihat pada pola penyerangan, daerah yang diserang, hasil konversi, dan lain-lain. Beberapa spesies bakteri dari kelas Clostridium, Cellumonas, Thermomonospora, Bacillus, Bacteriodes, Ruminococcus, Erwinia, Acetovibrio, Microbispora, dan Streptomyces serta fungi dari kelas Trichoderma, Penicillium, Fusarium, Phanerochaete, Humicola, dan Schizophillum dapat memproduksi hemiselulase (Taherzadeh dan Karimi, 2007).
2.4.5. Perbandingan Hidrolisis Asam dan Enzimatik

Tabel A.1.5 menyajikan perbandingan antara hidrolisis asam dan enzimatik. Karena hidrolisis enzimatik menghasilkan perolehan gula yang lebih tinggi dari lignoselulosa, teknologi enzimatik lebih banyak dipilih untuk produksi bioetanol lignoselulosa. Namun demikian, harga enzim selulase yang tinggi menjadi salah satu pembatas komersialisasi bioetanol lignoselulosa.
Tabel A.1.5 Perbandingan Hidrolisis Asam dan Enzimatik No Variabel Asam Encer 1 Kondisi hidrolisis ringan (mild) Temperatur rendah (T < 50 C) Tekanan atmosferik Perolehan gula tinggi Terjadi inhibisi produk selama hidrolisis Terbentuk produk inhibitor fermentasi Biaya katalis murah Waktu reaksi singkat Rekoveri katalis Tidak Tidak ( > 130 C) Tidak (>10 bar) Tidak Tidak Ya Ya Ya (Menit) Tidak Hidrolisis Asam Pekat Tidak Ya Ya Ya Tidak Tidak Ya Ya (1-6 jam) Ya Enzimatik Ya Ya Ya Ya Ya Tidak Tidak Tidak (xx jam) Tidak
2 3 4 5 6 7
2.5. Fermentasi
2.5.1. Mikroorganisme untuk Fermentasi Biomassa Lignoselulosa Menjadi Etanol
Sesuai dengan komposisi gula yang dapat difermentasi, produksi bioetanol lignoselulosa dapat dihasilkan dari fermentasi heksosa dan fermentasi pentosa. Mikroorganisme yang digunakan untuk fermentasi heksosa pada bioetanol lignoselulosa ini sama dengan mikroorganisme yang digunakan pada fermentasi heksosa pada proses produksi bioetanol generasi pertama. Sementara itu, umumnya fermentasi pentosa menjadi etanol harus diselenggarakan terpisah dengan mikroorganisme lain. Error! Reference source not found. menampilkan mikroorganisme untuk fermentasi biomass lignoselulosa menjadi bioetanol, meliputi karakteristik beserta keunggulan dan kerugiannya.
Tabel A.1.6 Mikroorganisme untuk Fermentasi Biomassa Lignoselulosa Menjadi Etanol Spesies Saccharomyces cerevisiae Karakteristik Ragi fakultatif anaerobik Keunggulan - Secara alami fermentasi etanol terjadi - Perolehan alkohol tinggi (90%) - Toleransi etanol (10% v/v) dan inhibitor tinggi - Cocok untuk modifikasi genetik - Fermentasi xilosa Kerugian - Tidak dapat memfermentasi xylosa dan arabinosa - Tidak tahan terhadap temperatur tinggi Refs
Candida shehatae
Ragi mikro-aerofilik
Zymomonasmobilis
Bakteri Gram negatif ethanologenic
Pichia stiplis
Ragi fakultatif anaerobik
- Perolehan etanol tinggi (perolehan teoritik 97%) - Toleransi etanol tinggi (14% v/v) - Produktivitas etanol tinggi - Cocok untuk modifikasi genetik - Tidak membutuhkan tambahan oksigen - Memberikan performansi terbaik pada fermentasi xilosa - Perolehan etanol 82% - Dapat memfermentasi sebagian besar gula tereduksi dari selulosa - Rekomendasi selulase pada proses SSF
Toleransi etanol rendah Perolehan etanol rendah Membutuhkan kondisi mikro-aerofilik Tidak melakukan fermentasi xylosa pada pH rendah - Tidak dapat melakukan fermentasi xylosa - Toleransi terhadap inhibitor rendah - Rentang pH netral
- Tidak tahan etanol pada konsentrasi > 40g/l - Tidak melakukan fermentasi pada pH rendah - Sensitif terhadap inhibitor kimiawi - Membutuhkan kondisi mikro-aerofilik - Reasimilasi etanol yang terbentuk
Pachysolen tannophilus
Fungi aerobik
- Fermentasi xilosa
- Perolehan etanol rendah - Membutuhkan kondisi mikro-aerofilik - Tidak melakukan fermentasi xilosa
Spesies Esherichia coli Karakteristik Bakteri Gram negatif mesofilik
Kerugian pada pH rendah Represi katabolime mengganggu cofermentasi Toleransi etanol terbatas Rentang pH dan temperatur pertumbuhan yang sempit Produksi asam organik Stabilitas genetik belum terbukti Toleransi rendah terhadap etanol dan inhibitor Gula berlebih mempengaruhi perolehan etanol Toleransi etanol rendah Fermentasi xylosa rendah Pembentukan xylitol Refs
Keunggulan - Mampu fermentasi gula pentosa dan heksosa - Cocok untuk modifikasi genetik -
Kluveromycesmarxianus
Ragi termofilik
Thermophilicbacteria: Thermoanaerobacterium saccharolyticum Thermoanaerobacter ethanolicus Clostridium thermocellum
Bakteri anaerobik ekstrim
Dapat tumbuh pada temperatur > 52 C Cocok untuk proses SSF/CBP Mengurangi biaya pendinginan Mengurangi kontaminasi Fermentasi rentang fula tereduksi yang lebar Cocok untuk modifikasi genetik o Tahan pada temperatur tinggi ekstrim 70 C Cocok untuk proses SSCF/ CBP Fermentasi variasi gula Menunjukkan aktivitas selulolitik Cocok untuk modifikasi genetik
- Toleransi etanol rendah
2.5.2. Teknologi Fermentasi

Untuk memperoleh hasil yang optimal fermentasi dapat diselenggarakan pada beberapa konfigurasi hidrolisis dan fermentasi yang sesuai. Berikut diulas strategi-strategi hidrolisis dan fermentasi bioetanol lignoselulosa. Strategi-strategi tersebut dilakukan dengan
mempertimbangkan keuntungan dan kerugian tersebut dengan aspek efisiensi sumber daya (enzim, mikroorganisme, utilitas) dan efektivitas proses (konsentrasi gula, konsentrasi etanol, keberlangsungan proses downstream) sehingga proses fermentasi ini menjadi optimal. Umumnya strategi-strategi berikut diaplikasikan pada hidrolisis enzimatik.
Separate Enzymatic Hydrolysis and Fermentation (SHF) Proses SHF meliputi proses hidrolisis menjadi glukosa dan fermentasi etanol secara berurutan dalam unit yang terpisah. Ilustrasi konfigurasi ini ditampilkan pada Gambar A.1.6. Proses fermentasi pentosa dan heksosa dilakukan secara terpisah dalam unit bioreaktor yang berbeda.
Hidrolisis Enzimatik
Fermentasi
Mikroorganisme fermentasi heksosa Nutrisi dan Antibusa CO2 (scrubber) Air pendingin
Biomassa setelah mendapat perlakuan awal
Ensim Selulase
Steam Bioetanol (distilasi) Mikroorganisme fermentasi pentosa Residu padat (terutama lignin) Hidrolisat kaya pentosa Air pendingin Nutrisi dan Antibusa CO2 (scrubber)
Sentrifugasi
Gambar A.1.6 Skema hidrolisis enzimatik dan fermentasi SHF
Simultaneous Saccharification and Fermentation (SSF) Proses hidrolisis enzimatik dan proses fermentasi dalam 1 unit diterapkan dalam konfigurasi SSF ini. Glukosa yang dihasilkan melalui hidrolisis enzimatik langsung dikonsumsi oleh mikroorganisme
dalam proses fermentasi dalam unit bioreaktor yang sama. Teknologi fermentasi ini diilustrasikan pada Gambar A.1.6. Fermentasi pentosa dilakukan dalam bioreaktor yang terpisah dengan fermentasi heksosa karena hidrolisat yang kaya akan pentosa telah dipisahkan terlebih dahulu selama proses perlakuan awal.
Hidrolisis & Fermentasi Serempak

Mikroorganisme fermentasi heksosa Biomassa setelah mendapat perlakuan awal Air pendingin Nutrisi dan Antibusa Ensim Selulase CO2 (scrubber) Sentrifugasi Bioetanol (distilasi)
Residu padat (terutama lignin) Mikroorganisme fermentasi pentosa Hidrolisat kaya pentosa Air pendingin Nutrisi dan Antibusa CO2 (scrubber)
Gambar A.1.7 Skema hidrolisis SSF
Simultaneous Saccharifiaction and Cofermentation (SSCF) Konfigurasi SSCF melibatkan proses sakarifikasi dan proses ko-fermentasi secara simultan dalam 1 unit biorekaktor. Istilah ko-fermentasi memiliki pengertian fermentasi baik pentosa dan heksosa menjadi etanol oleh 1 mikroorganisme. Dengan demikian, hanya dibutuhkan 1 tahap untuk memproses hidrolisat dan fraksi padat dari lignoselulosa yang telah diberi perlakuan awal. Proses diagram teknologi SSCF ditampilkan pada Gambar A.1.8.
Mikroorganisme fermentasi heksosa dan pentosa Biomassa setelah mendapat perlakuan awal & Hidrolisat hemiselulosa Air pendingin
Nutrisi dan Antibusa Ensim Selulase CO2 (scrubber) Sentrifugasi Bioetanol (distilasi)
Residu padat (terutama lignin)

Gambar A.1.8 Strategi Hidrolisis dan Fermentasi SSCF
Consolidated Bioprocessing (CBP) Untuk menghilangkan unit operasi produksi enzim secara terpisah, teknologi CBP dikembangkan dan memberikan kontribusi terhadap produksi enzim serta etanol dalam 1 bioreaktor dari populasi mikroorganisme tunggal. Aplikasi teknologi CBP membutuhkan pengembangan strain
mikroorganisme lebih lanjut untuk menghasilkan strain yang dapat menghasilkan baik etanol dan selulase yang efektif. Diagram alir proses teknologi CBP diilustrasikan padaGambar A.1.9.
Mikroorganisme fermentasi heksosa dan pentosa serta penghasil cellulase Biomassa setelah mendapat perlakuan awal & Hidrolisat hemiselulosa Air pendingin
Nutrisi dan Antibusa Ensim Selulase CO2 (scrubber) Sentrifugasi Bioetanol (distilasi)
Residu padat (terutama lignin)

Gambar A.1.9 Strategi Hidrolisis dan Fermentasi CBP
Tabel A.1.7 Perbandingan Keuntungan dan Keterbatasan Strategi Hidrolisis dan Fermentasi (Sarkar, dkk., 2012; Taherzadeh dan Karimi, 2007) Strategi Fermentasi dan Hidrolisis Separate Enzymatic Hydrolysis and Fermentation (SHF) Fitur dan keuntungan Setiap tahap dapat diproses pada kondisi operasi optimum Meminimasi interaksi antara tahap Biaya rendah Perolehan etanol lebih tinggi karena penghilangan inhibisi Mengurangi jumlah reaktor yang diperlukan Penggunaan 1 bioreaktor Perolehan etanol tinggi (91,992,8% terhadap perolehan teoritik) Tidak ada biaya operasi dan modal investasi untuk pembelian serta produksi enzim Konversi substrat tinggi Keterbatasan Inhibisi produk akhir meminimasi perolehan etanol Resiko kontaminasi karena durasi proses yang lama Perbedaan kondisi optimum enzim untuk hidrolisis dan fermentasi Kebutuhan enzim besar
Simultaneous Saccharification and Fermentation (SSF)
Simultaneous Saccharifiaction and Cofermentation (SSCF)
Consolidated Bioprocessing (CBP)
Membutuhkan mikrooganisme rekayasa yang termofilik, tidak menghasilkan asam organik, dan tahan pada konsentrasi etanol tinggi
2.6. Pemisahan dan Pemurnian

Bioetanol yang diperoleh dari proses fermentasi membutuhkan proses pemisahan dan pemurnian. Pada umumnya, proses hilir (downstream) ini didominasi oleh proses distilasi yang dilakukan secara terfraksionasi. Prinsip dasar dari proses distilasi ini adalah perbedaan titik didih komponen air dan etanol. Konsentrasi etanol yang diperoleh setelah proses distilasi adalah sekitar 95%. Untuk mencapai konsentrasi etanol yang lebih tinggi lagi (mendekati 100%), dibutuhkan distilasi azeotrop karena batasan sifat azeotropis dari campuran etanol dan air dengan konsentrasi etanol 98%. Aplikasi pada industri menitikberatkan pada kontinuitas proses distilasi.[ref]
2.7. Pemanfaatan Produk Samping

Komponen lignin yang terdapat dalam biomassa lignoselulosa biasanya menjadi produk samping utama dalam proses produksi bioetanol. Pada umumnya, lignin digunakan sebagai bahan bakar boiler. Beberapa pengembang teknologi mengupayakan pemanfaatan lignin menjadi bahan kimia yang lebih bermanfaat untuk meningkatkan keekonomian (misalnya sumber fenol digunakan sebagai bahan baku adesif kayu). Beberapa pengembang mengonversi lignin menjadi sumber energi lain dengan mengubah menjadi sumber metana (biogas) atau hidrogen (gasifikas).
3. METODOLOGI
Kajian pustaka diawali dengan ulasan ringkas tentang biomassa lignoselulosa dan komponenkomponen utamanya. Kajian produksi bioetanol lignoselulosa meliputi deskripsi struktur-struktur serta fungsi-fungsi yang diperlukan disajikan secara komprehensif. Kajian pustaka tersebut dikumpulkan dari beragam pustaka ilmiah terkini. Sementara itu perkembangan teknologi produksi bioetanol lignoselulosa dikumpulkan dari pustaka ilmiah, laporan-laporan berbagai gugus kerja di dunia untuk pengembang bioetanol lignoselulosa, berita-berita komersial, dan penelusuran informasi dari website dan presentasi dari pihak pengembang teknologi, serta paten-paten yang didaftarkan atau dimiliki pengembang teknologi bioetanol. Telaah perkembangan teknologi bioetanol diulas secara komprehensif meliputi pilihan bahan baku, teknologi perlakuan awal, strategi fermentasi termasuk fitur-fitur unit/khas yang dimiliki dari pengembang teknologi.
4. HASIL DAN PEMBAHASAN

4.1. Teknologi Proses Produksi Bioetanol Lignoselulosa dan Status Pengembangannya
Tabel A.1.10 menyajikan rekapitulasi pengembang teknologi bioetanol lignoselulosa beserta dengan teknologi yang digunakan dan status pengembangannya. Detail uraian meliputi deskripsi singkat, diagram blok proses, dan paten-paten para pengembangang teknologi bioetanol lignoselulosa disajikan pada Lampiran 1. Perkembangan teknologi dan bioetanol lignoselulosa selanjutnya diuraikan berdasarkan arah perkembangan dan karakter-karakter kunci untuk mengidentifikasi status perkembangan teknologi dan arah pengembangannya.
4.1.1. Status Pengembangan dan Komersialisasi

Pengembangan teknologi dan komersialisasi bioetanol lignoselulosa berkembang pesat pada era tahun 2005 setelah beragam program insentif dari berbagai negara untuk memproduksi bahan bakar dari sumber terbarukan, terlebih dari bahan baku non-pangan. Keberadaan selulosa sebagai biopolimer yang paling melimpah menjadi target yang atraktif untuk dikonversi menjadi bioetanol. Beberapa pengembang teknologi mencanangkan proses pengembangan, dari skala pilot, demonstrasi, dan mayoritas merencanakan untuk komersialisasi bioetanol lignoselulosa pada tahun 2012-2013 (Tabel A.1.8). Meskipun hingga saat ini belum ada pabrik bioetanol lignoselulosa skala komersial, beberapa pengembang yang masih aktif dan sesuai target untuk membangun skala komersial bioetanol selulosa adalah: ABENGOA, POET-DSM , ZEACHEM, CHEMTEX M&G (Thane, 2012). Namun demikian, meskipun telah mencapai skala demonstrasi
untuk memproduksi bioetanol dari switch grass, Royal Shell Dutch (mitra kerja IOGEN) memutuskan kerjasama dan pendanan untuk IOGEN ENERGY pada bulan Juni 2012 ini. Hal ini mengakibatkan IOGEN mengatur ulang strategi komersialisasi bioetanol selulosa dengan fokus integrasi bioetanol selulosa dengan pengolahan gula (sugar cane) di Brazil dan bisnis teknologi enzim mereka.
Tabel A.1.8 Tahap Pengembangan Bioetanol Lignoselulosa (hingga tahap demonstrasi dan rencana komersialisasi) Pengembang ABENGOA Skala Pilot Nebraka, AS Operasi: 2008 Etanol: 75 kL/tahun Ottawa, Kanada Operasi 1984 Produk gula Kayu: 1 ton/hari Ballerup, Denmark Operasi: 2011 Skala Demonstrasi Salamanca, Spanyol Operasi: 2009 Etanol:5000 kL/tahun Ottawa, Kanada Operasi 2004 Etanol:2000 kL/tahun l (1600 ton/tahun jerami) Bornholm, Denmark Sedang dibangun, operasi 2016 Etanol 5200 kL/tahun Kalundborg, Denmark Operasi: 2010 Etanol: 5700 kL/hari Jerami 100 ton/hari Emmetsburg, Iowa, AS Rencana: 2013 Etanol:95 000 kL/tahun Crescention, Italia Rencana: 2012 Etanol: Nevada Rencana: 2012 Etanol: 105 000 kL/tahun rnskldsvik, Swedia Operasi: 2012 Etanol: 15000 kL/hari (tunda) Boardman, Oregon, AS Operasi: 2012 Etanol: 95 000 kL/tahun Skala Komersial Hugoton, US Rencana 2012-2013 Etanol:95 000 kL/tahun l Ottawa, Kanada Direncanakan 2012 Etanol:90 000 kL/tahun (750 ton/hari jerami) Status: batal
IOGEN
BIOGASOL
INBICON (DONG ENERGI)
Fredericia, Denmark Operasi: 2003 Jerami 0,1 ton/tahun South Dakota, S Operasi: 2008 Etanol: 75 kL/tahun Tortona, Piedmont, Italia Operasi: 2009 Jerami: 50 ton/tahun
POET-DSM
TM
CHEMTEX (PROESA )
DuPont Danisco
SEKAB (Swedia)
rnskldsvik, Swedia Operasi: 2004 Etanol: 0,3 kL/tahun
ZeaChem
Vonore, Tennessee, AS Operasi: 2011 Etanol: 1000 kL/tahun rnskldsvik, Swedia Operasi: 2011 Etanol: 6000 kL/tahun Operasi dihentikan (biaya operasi) Boardman, Oregon, AS Operasi: 2008 Etanol: 1000 kL/tahun
Bioetanol generasi pertama
Masa Transisi dan Pengembangan

Pengembangan teknologi dan pematangan 1. perlakuan awal 2. metoda sakarifikasi efisien dan pengembangan enzim 3. fermentasi efisien gula pentosa 4. proses integrasi 5. reduksi harga produksi
Bioetanol Lignoselulosa (generasi kedua)
Skala Komersial Pertama 2012-2013
Skala
2000
2012
Gambar A.1.10 Garis waktu pengembangan dan komersialisasi bioetanol lignoselulosa
Sebagian besar para pengembangan teknologi melanjutkan rute pengembangan bioetanol berbasis fermentasi generasi pertama. Oleh karena itu, pada masa transisi dan pengembangan tersebut, fokus para pengembang diarahkan pada (1) perlakuan awal, (2) metoda hidrolisis dan pengembangan enzim, (3) fermentasi pentosa, (4) proses integrasi, dan (5) reduksi harga produksi (Gambar A.1.10).
4.1.2. Bahan Baku dan Perlakuan Awal

Jenis perlakuan awal yang ditujukan untuk meningkatkan aksebilitas terhadap biopolimer gula (selulosa dan hemiselulosa) bergantung pada karakteristik bahan baku yang digunakan para pengembang. Pada umumnya untuk bahan baku residu pertanian dan jerami, para pengembang teknologi menggunakan metode perlakuan awal steam explositon (ABENGOA ), modified steam explosition (IOGEN), hydrothermal pretratment (INBICON). Sementara itu, untuk limbah kayu, para pengembang menggunakan hidrolisis asam encer (SEKAB) dan hidrolisis asam pekat (ARKINOV, BORREGAARD).
4.1.3. Metoda Sakarifikasi: Hidrolisis asam encer

Strategi hidrolisis biopolimer selulosa dan hemiselulosa untuk menghasilkan gula yang dapat fermentasi dapat ditempuh dengan cara hidrolisis asam atau hidrolisis encer. Hidrolisis asam encer biasanya digabungkan perlakuan awal untuk mengoptimalkan perolehan gula pentosa dari hemiselulosa dan gula heksosa dari selulose. Strategi ini dikenal sebagai hidrolisis asam encer
dua tahap. Hidrolisis pertama diselenggarakan pada temperatur moderat (150 C, 15 menit) denga katalias asam sulfat (1-3 %wt) untuk menghidrolisis hemiselulosa menjadi gula dapat fermentasi. Hidrolisat kaya gula pentosan ini dinetralkan lalu diumpankan ke fermentasi heksosa untuk mengubah gula pentose menjadi Etanol. Sementara itu, sisa padatan dihidrolisis pada
temperature lebih tinggi (200 C, 2-3 menit) untuk menghasilkan gula heksosa dari selulosa. Selanjutnya, hidrolisat kaya heksosa difermentasi menjadi bioetanol. SEKAB menggunakan teknik ini untuk memperoleh gula yang dapat difermentasi dari residu kayu. Proses ini mempunyai keunggulan tidak melibatkan enzim yang menjadi salah satu kendala (harga tinggi) pada proses hidrolisis enzimatik, meskipun proses ini menghasilkan produk samping yang dapat menjadi inhibitor proses fermentasi.
4.1.4. Hidrolisis Enzimatik

Seiring dengan perkembangan teknologi enzim, mayoritas pengembangan menggunakan metoda enzimatik untuk memperoleh gula dapat difermentasi dari selulosa dan hemiselulosa. Untuk menekan biaya proses, para pengembang teknologi bioetanol lignoselulosa menambah unit produksi enzim dalam prosesnya (IOGEN, POET-DSM, DUPONT). Sementara itu, beberapa pihak mengandalkan enzim yang diproduksi oleh pihak produsen enzim. Untuk keperluan pembangunan skala demonstrasi dan komersial, para pengembang ini bekerjasama dan mengandalkan fasilitas produksi produsen enzim. Chemtex dengan proses PROESA menggunakan enzim yang produksi oleh Novozyme. Kolaborasi dan kontrak penyediaan enzim menjadi titik kunci jaminan ketersediaan enzim, termasuk pabrik penyedia enzim yang dekat dengan pabrik bioetanol lignoselulosa.
4.1.5. Fermentasi
Pilihan teknologi fermentasi sangat bergantung pada jenis bahan baku dan konsentrasi gula yang dapat fermentasi terbentuk. Umumnya para pengembang teknologi menggunakan proses hidrolisis dan fermentasi terpisah (SHF) atau hidrolisis dan fermentasi serempak (SSF). Dua proses ini akan melibatkan dua mikroorganisme yang berbeda untuk memfermentasi gula heksosa dan gula pentosa. Strategi pengembangan diambil Sud Chemie dengan proses Sun Liquids teknik fermentasi gula heksosa dan pentosa secara serempak
TM
nya menggunakan
(SSCF). Kemampuan
pengembangan mikroorganisme yang dapat mengonversi serentak gula heksosa dan pentose menjadi salah satu kunci proses sun liquids. Sementara itu, pengembang Mascoma menggunakan teknologi konversi biopolimer secara serempak menjadi etanol. Teknologi ini dikenal sebagai
Consolidate Bioprocessing (CBP). Pada proses ini, penggunaan enzim sakarolitik (enzim untuk mengonversi) dan mikroorganisme untuk memfermentasi tidak diperlukan.
Gambar A.1.11 Pilihan teknologi fermentasi
4.1.6. Proses Integrasi

Untuk meningkatkan keekonomian bioetanal selulosa, strategi proses integrasi menjadi salah satu titik penting untuk diperhatikan. Proses terintegrasi dengan industri yang sudah ada diambil oleh para pengembang untuk mengembangkan bioetanol lignoselulosa. POET-DSM mengintegrasikan proses dan pabrik skala komersial mereka dengan fasilitas pabrik bioetanol generasi pertama dari pati jagung (corn starch ethanol). Dedini mengintegrasikan rencana pembangunan pabrik bioetanol generasi pertama mereka dengan pabrik bioetanol generasi pertama dari tebu. Bagas yang merupakan limbah dari pabrik bioetanol generasi pertama menjadi bahan baku proses mereka. American Process Inc menggunakan strategi serupa dengan memanfaatkan bagas dari pabrik gula/bioetanol gula.
4.2. Perbandingan Teknologi Produksi Bioetanol Lignoselulosa

Tabel A.1.9 menyajikan perbandingan pengembang utama bioetanol lignoselulosa yang telah mencapai tahap demonstrasi. Keunggulan dan karakteristik kunci terletak dari teknologi yang dipilih pada perlakuan awal, hidrolisis, dan fermentasi. Sementara itu, keterbatasan pengembang adalah fleksibilitas penggunana bahan baku, terutama untuk mengolah bahan baku berkategori
kayu (hardwood maupun softwood). Proses dengan jalur teknologi asam, baik asam encer mapun pekat, telah teruji untuk memproduksi bioetanol dari bahan baku berbasis kayu (SEKAB, BORREGAARD).
Tabel A.1.9 Perbandingan Teknologi Utama Bioetanal Lignoselulosa Proses/Lisensor CHEMTEX Nama Dagang Proses TM PROESA Karakteristik Kunci dan Keunggulan Perlakukan awal tidak membutuhkan katalis atau bahan kimia Fermentasi gula pentose dan heksosa terpisah Keterbatasan Enzim bergantung pada penyediaan novozym
BIOGASOL
Carbofrac TM Pentofrac
TM
ABENGOA
Perlaukan awal tidak membutuhkan katalis atau bahan kimia Unit produksi enzim terpadu Perlaukan awal tidak membutuhkan katalis atau bahan kimia Fermentasi melalui jalur acetic acid (carbon efisiensi tinggi) Fraksionasi hemiselulosa dan selulosa, tanpa menggunakan bahan kimia Enzim DSM dapat dioperasikan pada temperatur relatif tinggi Unit produksi enzim terpadu Perlakuan awal tidak membutuhkan zat kimia, fermentasi gula heksosa dan pentose serempak Tidak membutuhkan enzim Membutuhkan proses netralisasi
IOGEN INBICON
Belum teruji untuk proses hardwood Enzim bergantung pada penyediaan novozym Belum teruji untuk proses hardwood Enzim bergantung pada penyediaan novozym Belum teruji untuk proses hardwood Belum teruji untuk proses hardwood
ZEACHEM AMERICAN PROCESS INC POET-DSM

TM
GreenPower
TM
Intensifikasi energi tinggi (gasifikas dan esterifikasi) Belum teruji untuk proses hardwood Belum teruji untuk proses hardwood Belum teruji untuk proses hardwood
SUD CHEMIE
Sun Liquids
SEKAB
Proses sedikit korosif Menghasilkan limbah yang bersifat korosif
Tabel A.1.10 Pengembang Teknologi Bioetanol dan Teknologi yang Digunakan No Lisensor/ Pengembang Teknologi Abengoa (EU/Spanyol, AS) Bahan baku Kapasitas produksi Perlakuan awal Corn stover, wheat straw, dan switchgrass 16 Mgal/tahun dan 75 MW Renewable Power Biomass Handling, acid impregnation, steam explosion, neutralization Teknologi Fermentasi Sakarifikasi, yeast propagation dan fermentasi Permisahan Distiasli (ethanol recovery dan stillage processing)
American Energy Enterprise (AS)
Plant biomass dan wood waste
Bluefire Ethanol (AS)
Cellulosic waste diverted dari landfill
ICM (AS)
Sorgum, switchgrass, dan bonggol jagung
Mascoma (AS)
Bervariasi termasuk hardwood
POET-DSM (Project Liberty) (US) Raven Biofuels, Pure Energy, Eco-
Corn cobs dan stover
30-38 ML/tahun (perkembangan 300-380 ML/tahun) 15 ML/tahun (Lancester) dan 72 ML/tahun (Fulton) 10 ML/tahun (demosntrasi) dan 190 ML/tahun (komersial) 0,8-1,9 ML/tahun untuk komersial 151 ML/tahun (Kinross, Michigan) 25Mgal/tahun
AEE Distilasi (beban kerja 24-50 Mgal/tahun) -
Hidrolisis asam
Fermentasi ragi konvensional
Biochemical pretreatment
Fermentasi C5/C6 (Suplai Novozymes)
Wood waste
79,5 ML/tahun
Hidrolisis asam (asam sulfat
Fermentasi C6
Distilasi
No Lisensor/ Pengembang Teknologi Energy dan Price Biostock Verenium dan British Petroleum (AS/UK) Bahan baku

Kapasitas produksi Perlakuan awal lemah) 2 tahap

Teknologi Fermentasi Permisahan
Iogen, Otawa (Kanada)
Agricultural residu (BB wheat 40 tpd)
10 11
Lignol (Kanada) Dedini, Sao Paulo (Brasil) SEKAB, Ornskoldsvik dan Etek Etanolteknik AB (EU/Swedia) INBICON Biomass Refinery (Kalundborg) (EU/Denmark) BioGasol (EU/Denmark)
Switchgrass, corn stover, dan wheat straw Residu tebu
5,5 ML/tahun (BB 2tpd) dan 136 ML/tahun (Highlands Florida) 2,5 ML/tahun (BB 30 tpd) dan 70 ML/tahun (Prince Albert, Sask) [340 L etanol/ton BB] 0,1 ML/tahun (BB 1 tpd) 1,81 ML/tahun
Hidrolisis asam lemah
Fermentas hemiselulosa dan sakarifikasi serta fermentasi
Distilasi
Modified steam explosion
Sakarifikasi /hidrolisis enzimatik(selulase) dan Fermentasi C5/C6
Distilasi
12
Pine wood chips, bagas, wheat, corn stover, recycled waste, dan energy grasses Wheat straw, corn cobs dan stover
13
0,14 ML/tahun, 6 ML/tahun (demonstrasi), dan 120 ML/tahun (komersial) 20 Mgal/tahun (BB 460000 tpy)
Solvent based pretreatment Diluted acid hydrolysis dan lignin solvent Acid and steam pretreatment o (200 C) dan hidrolisis enzimatik Hydrothermal pretreatment
Sakarifikasi dan fermentasi Sakarifikasi (Novozymes) dan fermentasi Fermentasi C5 dan C6 (Taurus Energy, Modified strain yeast); SSF atau SHF Hidrolisis enzimatik (supplier Danisco Genencor & Novozymes) dan fermentasi Hidrolisis enzimatik dan fermentasi glukosa (yeast). Fermentasi
Distilasi Distilasi
Distilasi
14
Agricultural residu
5 ML/tahun
wet explosion (Kombinasi steam explosion dan wet
Distilasi
No Lisensor/ Pengembang Teknologi Bahan baku

Kapasitas produksi Perlakuan awal oxidation)

Teknologi Fermentasi xylosa (immobilized reaktor) Fermentasi Permisahan
15
HCL Technologies, Israel
Woody biomass
16 17
TMO Renewables BioEthanol Japan (Celunol Proess from SunOpta Inc.) Marubeni,saraburi, Thailand China Resources Alcohol corporation (CRAC) Mission New Energy Ethtec, Australia
Cassava stalk Wodd construction waste
70-80gal/ ton BB 1,4 ML/tahun (berkembang menjadi 4ML/tahun) 3 ML/tahun
Hidrolisis hydrocloric acid (recycle full HCl in gas form) -
Fermentasi termofilik baketri Fermentasi C5 & C6 (modified E. coli)
Distilasi
18
Bagas tebu
Hidrolisis asam lemah Steam explosion (SunOpta Inc.) Chemical pretreatment, Feedstock impregnation dan hidrolisis asam Milling dan pretreatment ethanol TM Formicodeli (pelarutan dengan biosolvent) fraksionasi
19
Bonggol jagung
20 21
Agricultural waste Wood residu dan bagas (BB 2tpd) Wood crop salix, a variety of willow (BB 250 tpd) Agricultural residu
6 ML/tahun dan 1250 ML/tahun (komersial) 10000 gal/tahun -
Fermentas hemiselulosa dan sakarifikasi serta fermentasi -
Distilasi
Hydrolisis dan fermentasi Fermentasi simultan C5 & C6 Hidrolisis enzimatik (selulase) dan fermentasi Hidrolisis enzimatik dan fermentasi
Induksi pemisahan fasa dengan potasium karbonat Distilasi
22
Pure Power, Singapura Chempolis
23
Distilasi diintegrasi dengan TM formicopure (byproduct asetat dan
No Lisensor/ Pengembang Teknologi Sud-Chemie AG (EU/Jerman Barat) Statoil dan Innovation Norway (EU/Nowergia) Dupont Danisco Cellulosic Ethanol (AS) Qteros (Amerika Serikat) Bahan baku

Kapasitas produksi Perlakuan awal

Teknologi Fermentasi Hidrolisis enzimatik dan fermentasi C5 & C6 (modified yeast) Permisahan furfural) Reactification tower
24
Cereal straw
2000 metric ton/tahun 200000 L/tahun
25
26
27,5ML/tahun
Mechanical dan thermal pretreatment Hidrolisis asam (Weyland Process) Biological Pretreatment -
Hidrolisis enzimatik dan fermentasi C5 &C6 Consolidated Bioprocessing (Clostridium phytofermentans) SSF (Enzyme;ovozymes, Fermentis, Yeast) SSF (Enzyme;ovozymes, Fermentis, Yeast) Fermentasi (asam asetat), ester production (etil asetat) TM PROESA
28
Distilasi
29
IMECAL (AteneaProject) IMECAL (PERSEO Project) Zeachem (Amerika Serikat) Mossi & Ghisolfi Group (M&G) Italia (Chemtex) Biogasol dan Danish Energy Aganecy Biogasol dan Pacific Ethanol Inc.
Citric waste
30 31
Organic matter MWS (BB 500 tpd) Hardwood, softwood, switch grass, corn stover Non-foodchain crops, agricultural waste BB 27000 ton/tahun
16000L/day -
Biological Pretreatment (Fungi) Thermochemical treatment Chemical fractionation
Distilasi dan dehidrasi
Distilasi dan dehidrasi Hydrogenasi (etanol)
32
13Mgal/tahun
33
7 ML/tahun
Biogasol proses
34
Straw. Hybrid poplar, dan cornstover (BB 5,8
10 ML/tahun
Biogasol Proses
No Lisensor/ Pengembang Teknologi GreenField Ethanol American Process TM (AVAP process) Bahan baku

Kapasitas produksi Perlakuan awal

Teknologi Fermentasi Hydrolysis and fermentation continuously Hidrolisis asam hemiselulosa, hidrolisis enzimatik selulosa, dan fermentasi Permisahan Membran -
35 36
ton/hari) corn cobs, corn residue, wood pulp wood
Fractionation (Digester)
5. KESIMPULAN DAN SARAN

5.1. KESIMPULAN
1. Teknologi konversi produksi bioetanol lignoselulosa telah mencapai tahap matang (matur). Para pengembang teknologi telah mencapai pengembangan produksi skala pilot dan demonstrasi, dan tengah berproses untuk membangun skala komersial pertama bioetanol lignoselulosa pada tahun 2012-2013. 2. Pengembangan bioetanol lignoseluosa jalur biokonversi umumnya berbasis proses
fermentasi heksosa dan pemurnian etanol seperti pada proses komersial yang telah dioperasikan secara komersial. fokus para pengembang diarahkan pada (1) perlakuan awal, (2) pengembangan enzim, (3) fermentasi pentose, (4) proses integrasi, dan (5) reduksi harga produksi. 3. Karakteristik bahan bakau menentukkan piliah perlakuan awal yang tepat. Perlakuan awal yang optimal (hemat biaya dan energi) dan menghasilkan gula seoptimum merupakan salah satu kunci komersialisasi bioetanol selulosa. 4. Hidrolisis polisakarida menjadi gula yang dapat difermentasi secara efisien menjadi tantangan pengembangan metoda hidrolisis asam dan enzimatik. 5. Teknik fermentasi harus disesuaikan dengan karakteristik mikroorganisme dan tipe bahan baku (konsentrasi gula yang dihasilkan) 6. Pemanfaatan produk samping perlu dilakukan secara cermat. Di samping untuk mengurangi limbah, langkah ini dapat meningkatkan perolehan gula. 7. Teknologi pengembangan yang hampir mendekati skala komersial dan diuji pada skala pilot dan demonstrasi adalah IOGEN, Chemtex (PROESA ), SEKAB, Sud-Chemie (Sun liquids
TM TM
) dan
5.2. SARAN
1. Karakteristik bahan baku menentukan pilihan teknologi proses perlakuan awal dan sakarifikasi untuk produksi bioetanol lignoselulosa. Oleh karena itu, karakterisasi bahan baku dan pengujian perlakuan awal harus dilakukan secara memadai untuk menentukan pilihan teknologi biomassa. 2. Proses integrasi dalam pengembangan bioetanol lingnoselulosa dengan industri yang sudah ada penting untuk menunutun dan meningkatkan potensi ekonomi bioetanol
lignoselulosa. Sebagai contoh, instalasi pemroses bagas menjadi bioetanol di industri gula atau instalasi pemroses tandan kosong sawit di pabrik pengolahan kelapa sawit. Konsep ini merupakan proses pemanfaatan optimum seluruh komponen bahan baku menjadi beragam produk yang berguna, dan dikenal sebagai biorefineri.
6. DAFTAR PUSTAKA
Kumar, D., Murthy, G.S., Impact of pretreatmnt and downstream processing technologies on economics and energy in cellulosic ethanol production, Biotechnology for Biofuels, 4 (2011) 1-19. Kumar, S., Singh, S.P., Mishra, I.M., Adhikari, D.K., Recent advances in production of bioethanol from lignocellulosic biomass, Chemical Engineering and Technology, 32 (2009) 517-526. Limayem, A., Ricke, S.C., Lignocellulosic biomass for bioethanol production: Current perspectives, potential issues and future prospects, Progress in Energy and Combustion Science, 38 (2012) 449-467. Mosier, N., Wyman, C., Dale, B., Elander, R., Lee, Y.Y., Holtzapple, M., Ladisch, M., Features of promising technologies for pretreatment of lignocellulosic biomass, Bioresource Technology, 96 (2005) 673-686. Sarkar, N., Ghosh, S.K., Bannerjee, S., Aikat, K., Bioethanol production from agricultural wastes: An overview, Renewable Energy, 37 (2012) 19-27. Sun, Y., Cheng, J., Hydrolysis of lignocellulosic materials for ethanol production: A review, Bioresource Technology, 83 (2002) 1-11. Taherzadeh, M.J., Karimi, K., Acid-based hydrolysis processes for ethanol from lignocellulosic materials: A review, BioResources, 2 (2007) 472-499. Taherzadeh, M.J., Karimi, K., Enzyme-based hydrolysis processes for ethanol from lignocellulosic materials: A review, BioResources, 2 (2007) 707-738. Taherzadeh, M.J., Karimi, K., Pretreatment of lignocellulosic wastes to improve ethanol and biogas production: A review, International Journal of Molecular Sciences, 9 (2008) 1621-1651. Thane, P., Cellulosic ethanol becoming reality, in: Biofuels International, 2012, pp. 36-40. Yang, B., Wyman, C.E., Pretreatment: The key to unlocking low-cost cellulosic ethanol, Biofuels, Bioproducts and Biorefining, 2 (2008) 26-40.
7. LAMPIRAN
LAMPIRAN 1 Deskripsi Singkat Proses Teknologi Produksi Bioetanol Lignoselulosa dan Status Pengembangannya (Jalur Biokonversi) LAMPIRAN 2 Tenggara Daftar Pengembangan Bioetanol Lignoselulosa di Asia, khususnya Asia
LAMPIRAN 1
Deskripsi Singkat Proses, Diagram Blok Proses, Status dan Rencana Pengembangan, dan Daftar Paten Pengembang Teknologi Produksi
Bioetanol Lignoselulosa (Jalur Biokonversi)
ABENGOA
1. Deskripsi Singkat
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Abengoa Bioenergy New Tecnologies York, Nebraska, Amerika Serikat Lignoselulosa 330 ton/tahun; 520.000 ton/tahun Etanol Pilot: 75 ton/tahun; 0,02 juta galon/tahun (2007) Demo: Komersial: 56 juta galon/tahun; 210 ML/tahun Skala pilot beroperasi pada tahun 2007. Fasilitas pilot yang sangat fleksibel dengan pengujian konfigurasi proses yang sangat bervariasi (steam explosion batch vs kontinu, fraksionasi biomassa yang berbeda tingkat dan teknik, fermentasi C5/C6 terpisah atau ko-fermentasi). Fasilitas komersial dicapai dengan pemanasan batch kontinu dan proses fermentasi http://www.abengoabioenergy.com
Status dan Rencana Pengembangan Deskripsi proses ringkas
Website
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan
Status dan Rencana Pengembangan Deskripsi proses ringkas Website
Abengoa Bioenergy , Biocarburantes Castilla y Leon, Ebro Puleva Babilafuente, Salamanca, Spanyol Lignoselulosa; steam explosion, gandung/jerami gandum, residu jagung 25.000 ton/tahun Etanol Pilot: Demo: 4.000 ton/tahun; 1,32 juta galon/tahun (5000 kL) Komersial: Konstruksi skala demo selesai pada Desember 2008 dan mulai beroperasi sejak September 2009. Skala komersial direncakan untuk beberapa tahun ke depan. Teknologi hidrolisis enzimatik. Etanol yang diproduksi didistilasi hingga konsentrasi 42%, dipekatkan, dan kemudian didehidrasi. http://www.abengoabioenergy.com
Abengoa Bioenergy Biomass of Kansas, LLC Hugoton, Kansas, Amerika Serikat Lignoselulosa 1.000 ton/hari Etanol, listrik ko-generasi Pilot: -
Website
Demo:Komersial: 25 juta galon/tahun; 100 ML/tahun Skala komersial mulai dibangun pada Juli 2011 dan direncanakan akan beroperasi pada Juni 2013. Steam explosion digabungkan dengan fraksionasi biomassa, fermentasi C5/C6, distilasi untuk etanol recovery. Panas dan energi disediakan melalui gasifikasi biomassa. http://www.abengoabioenergy.com
2. Diagram Blok Proses
Gambar A.1.L1.1 Skema diagram blok bioetanol generasi kedua ABENGOA
3. Status dan Rencana Pengembangan
Gambar A.1.L1.2 Rencana pengembangan dan implementasi bioetanol generasi kedua ABENGOA
4. Daftar Paten Teknologi Bioetanol Lignoselulosa Milik ABENGOA

No Paten Tanggal Pendaftaran (Filling Date) Judul
Ringkasan
WO/2009/079183A1 US20110008489
2008-11-26 2008-11-26
Improved quality and value of co-products of the ethanol production industry
US20110262984 WO/2011/028554A1
2010-08-24 2010-08-24
Method for producing ethanol and co-products from cellulosic biomass
US20120045545 WO/2011/056991A1
2010-11-04 2010-11-04
High efficiency ethanol process and high protein feed co-product
A process for improving the nutritional quality of a feed co-product, resulting from the fermentation of a grain, sugar beets, or sugar cane to produce ethanol. The process comprises combining water, a source of nitrogen, a source of phosphorus, a feed coproduct comprising a cellulose and/or a hemi-cellulose, and a microbe to form a fluid fermentation mixture suitable for submerged fermentation, wherein the feed co-product is derived from the fermentation of a grain, sugar beet, or sugar cane to produce ethanol and wherein the microbe is a microbe capable of breaking down the cellulose and/or the hemi-cellulose to one or more sugars and then utilizing the sugars to proliferate; fermenting the fluid fermentation mixture such that the microbe converts at least a portion of the cellulose and/or the hemicellulose into at least one sugar and uses the sugar to proliferate thereby increasing the concentration of microbes in the fermentation mixture. The present invention generally relates to processes for production of ethanol from cellulosic biomass. The present invention also relates to production of various co-products of preparation of ethanol from cellulosic biomass. The present invention further relates to improvements in one or more aspects of preparation of ethanol from cellulosic biomass including, for example, improved methods for cleaning biomass feedstocks, improved acid impregnation, and improved steam treatment, or steam explosion. A process is disclosed for producing a feed co-product by ethanol fermentation of plant matter comprising starch and another polysaccharide selected from the group consisting of hemicellulose and cellulose. The process comprises: (i) carrying out a primary fermentation process, distilling the primary fermentation mixture to form a primary feed co-product derived from the fermentation of the primary fermentation mixture and a primary distillate product comprising ethanol
Ringkasan
US20120111321
2011-01-26
Method and apparatus for treating a cellulosic feedstock
US20110271875 WO/2011/140222A1
2011-05-04 2011-05-04
Process for recovery of values from a fermentation mass obtained in producing ethanol and products thereof
US20120006320
2011-09-19
Method for producing ethanol and co-products from cellulosic biomass
and (ii) carrying out a secondary fermentation process and distilling the secondary fermentation mixture to form the modified feed co-product and a secondary distillate product comprising ethanol. Methods and apparatus for treating, pre-treating, preparing and conveying a cellulosic feedstock, such as for ethanol production, are disclosed. More specifically, the invention relates to methods and apparatus for treating a cellulosic feedstock by mixing and heating the cellulosic feedstock and/or by moistening and heating the cellulosic feedstock. The invention also relates to a holding tank, and a method of utilizing the holding tank whereby bridging may be reduced or eliminated and may result in a product stream from autohydrolysis or hydrolysis having an improved yield. The invention further relates to methods and apparatus for obtaining and conveying a cellulosic feedstock, which may be used for the subsequent production of a fermentable sugar stream from the cellulose and hemicellulose in the cellulosic feedstock wherein the fermentable sugar stream may be used for subsequent ethanol production. The invention also relates to a method and apparatus for withdrawing one or more feedstock stream from a holding tank. The present invention generally relates to processes for recovery of values from a fermentation mass obtained in producing ethanol. Further, the present invention relates to processes for the recovery of values from an inorganic- and lignin-containing mass. The present invention generally relates to processes for production of ethanol from cellulosic biomass. The present invention also relates to production of various co-products of preparation of ethanol from cellulosic biomass. The present invention further relates to improvements in one or more aspects of preparation of ethanol from cellulosic biomass including, for example, improved methods for cleaning biomass feedstocks, improved acid impregnation, and
Ringkasan
WO/2012/103220A1
2012-01-25
Method and apparatus for treating a cellulosic feedstock
improved steam treatment, or steam explosion. Methods and apparatus for treating, pre-treating, preparing and conveying a cellulosic feedstock, such as for ethanol production, are disclosed. More specifically, the invention relates to methods and apparatus for treating a cellulosic feedstock by mixing and heating the cellulosic feedstock and/or by moistening and heating the cellulosic feedstock. The invention also relates to a holding tank, and a method of utilizing the holding tank whereby bridging may be reduced or eliminated and may result in a product stream from autohydrolysis or hydrolysis having an improved yield. The invention further relates to methods and apparatus for obtaining and conveying a cellulosic feedstock, which may be used for the subsequent production of a fermentable sugar stream from the cellulose and hemicellulose in the cellulosic feedstock wherein the fermentable sugar stream may be used for subsequent ethanol production. The invention also relates to a method and apparatus for withdrawing one or more feedstock stream from a holding tank.
AE BIOFUELS (AEMETIS)
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan AE Biofuels Butte, Montana, Amerika Serikat Lignoselulosa; switchgrass, bibit rumput, jerami rumput, dan tangkai jagung Etanol Pilot: 500 ton/tahun; 0,16 juta galon/tahun (2008) Demo: Komersial: 55 juta galon/tahun Skala pilot beroperasi pada tahun 2008. Hidrolisis pati selulosa pada temperatur ambien. Skala komersial menggunakan enzim ATSCH dan proses produksi enzim substrat padat. Proses ini menggunakan teknologi consolidated bioprocessing (CBP) untuk mengurangi tahap pemanasan dan pemakaian air. http://www.aebiofuels.com
Website
AMERICAN PROCESS
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan American Process Inc Amerika Serikat Wood, Baggas tebu 52.000 ton/tahun Etanol Pilot: Demo: Komersial: 13.000 ton/tahun; 4,5 juta galon/tahun Plant ini dibangun pada akhir tahun 2008 dan dilanjutkan dengan coba start-up pada pertengahan tahun 2009. Plant selanjutnya dirancang untuk kapasitas 5-15 juta galon/tahun. Tidak dilakukan fermentasi C5, menghindari produksi gipsum dan pembakaran lignin. http://www.bbibioventures.com
4. Daftar Paten Terkait Teknologi Bioetanol Lignoselulosa

No Paten Tanggal Pendaftaran (Filling Date) 1980-04-09 Judul Abstrak
4318748
Continuous process for saccharification of whole starchy materials Conversion of alcohols to aldehydes and hydrogen peroxide by substrate and product tolerant methanol oxidases
4920055
1986-02-04
WO/1987/00 4725A1
1987-02-04
Conversion of alcohols to aldehydes and hydrogen peroxide by substrate and product tolerant methanol oxidases
A continuous process is provided for effecting the acid hydrolysis of whole grains, e.g., corn, at high solids and in an economically desirable manner. The process produces glucose which is readily fermentable to produce ethanol. Disclosed is a process for converting alcohols to aldehydes and hydrogen peroxide through the use of a methanol oxidase enzyme. The process involves introducing a lower alkyl or lower alkylene alcohol, such as methanol, ethanol, or allyl alcohol, as an aqueous solution into a reaction zone. Methanol oxidase enzyme that is stable in methanol concentrations of at least 0.5% and formaldehyde concentrations of at least 1.0% is also introduced into the reaction zone, which is maintained at an elevated pressure in contact with an oxygen-containing gas. The preferred methanol oxidase enzyme has the properties of the methanol oxidase enzyme produced by Hansenula polymorpha ATCC 34438. Both batchwise and continuous processes are disclosed. Also disclosed is a process in which a catalase is present in the reaction zone to decompose hydrogen peroxide as it is formed, so that the net reaction is the conversion of alcohol to aldehyde. In one aspect of that process, the aldehyde may be removed as a gas and subsequently condensed to an essentially pure liquid. A process for converting alcohols to aldehydes and hydrogen peroxide through the use of a methanol oxidase enzyme. The process involves introducing a lower alkyl or lower alkylene alcohol, such as methanol, ethanol, or allyl alcohol, as an aqueous solution into a reaction zone. Methanol oxidase enzyme that is stable in methanol concentrations of at
WO/1999/03 1315A1
1998-12-10
Separation and determination of cellulosic components from plant material
US20070141 689
2005-03-18
Liquefaction process
least 0.5% and formaldehyde concentrations of at least 1.0% is also introduced into the reaction zone, which is maintained at an elevated pressure in contact with an oxygen-containing gas. The preferred methanol oxidase enzyme has the properties of the methanol oxidase enzyme produced by Hansenula polymorpha ATCC 34438. Both batchwise and continuous processes are disclosed. In one embodiment, a catalase is present in the reaction zone to decompose hydrogen peroxide as it is formed, so that the net reaction is the conversion of alcohol to aldehyde. In another aspect of the process, the aldehyde may be removed as a gas and subsequently condensed to an essentially pure liquid. A method for separating cellulosic components from, and determining cellulosic component content of, plant material. Plant material and an electromagnetic active solvent, e.g. ethanol, are heated by means of electromagnetic radiation (e.g. microwave radiation), whilst the material and solvent are in contact each with the other and are located in a closed chamber. The temperature of the solvent and the vapour pressure in the chamber are increased thus to effect solution in the solvent of non-cellulosic components of the plant material. The cellulosic components of the plant material are isolated from the solvent and the solute therein. A gravimetric determination may then be made of the cellulosic component content of the plant material. The present invention relates to method of liquefying starch-containing material, wherein the method comprises the steps of (a) treating the starchcontaining material with a bacterial alpha-amylase at a temperature around 70-90 C. for 15-90 minutes, and (b) treating the material obtained in step (a) with an alpha-amylase at a temperature between 60-80 C. for 30-90 minutes. The invention also relates to a process of producing a fermentation product, preferably ethanol, comprising a liquefaction step carried out according to the liquefaction method of the invention.
ARKENOL BLUE FIRE ETHANOL

Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Arkenol Orange, CA, Amerika Serikat Lignoselulosa; limbah 1 ton/hari; 190ton/hari (skala demo) Etanol, lignin Pilot : Demo : 3,9 juta galon/tahun Komersial : Skala pilot telah dibangun dan beroperasi sejak tahun 1994 hingga 2000. Uji skala pilot dilakukan oleh Arkenol kerja sama dengan JGS Jepang di Izumi, Jepang. Skala demo mulai dibangun pada tahun 2008 di Lancester, California. Proses ARKENOL dilanjutkan oleh BLUE FIRE Renewables. P Hidrolisis asam pekat, ko-fermentasi C5 dan C6 http://www.arkenol.com http://bfreinc.com
Status dan Rencana Pengembangan
Deskripsi proses ringkas Website
Gambar A.1.L1.3 Blok Proses Diagram Bioetanol Lignoselulosa Arkenol
Pegembangan selanjutnya dilakukan oleh BlueFire Renewables

Gambar A.1.L1.4 Rencana pengembangan dan implementasi bioetanol generasi kedua ARKENOL
4. Daftar Paten Terkait Bioetanol Lignoselulosa Milik ARKENOL

No Paten Tanggal Pendaftaran (Filling) 1993-03-26 Judul Abstrak
US5562777
Method of producing sugars using strong acid hydrolysis of cellulosic and hemicellulosic materials
US5620877
1995-06-06
Method of fermenting sugars resulting from strong acid hydrolysis
A economically viable method for producing sugars using concentrated acid hydrolysis of biomass containing cellulose and hemicellulose is disclosed. The cellulose and hemicellulose in the biomass is first decrystallized and then hydrolyzed to produce a hydrolysate containing both sugars and acid. Silica present in the biomass can then be removed for further processing. The remaining solids are then subjected to a second decrystallization and hydrolyzation to optimize the sugar yields. An improved method for separating the sugars from the acid in the hydrolysate is also disclosed. The resulting sugar stream can then be fermented, using an improved method which allows both hexose and pentose sugars to be fermented simultaneously. An economically viable method of fermenting a mixture of sugars resulting from the acid hydrolysis of material containing cellulose and hemicellulose
US5580389
1995-06-06
Method of separating acids and sugars resulting from strong acid hydrolysis
US5782982
1995-06-07
Method of removing silica or silicates from solids resulting from the strong acid hydrolysis of cellulosic and hemicellulosic materials Strong acid hydrolysis of cellulosic and hemicellulosic materials
US5597714
1995-06-07
US5820687
1996-06-13
Method of separating acids and sugars using ion resin separation
US5726046
1996-07-02
Method of producing sugars using strong acid hydrolysis
allows for the simultaneous fermentation of both pentose and hexose sugars. The sugar solution is mixed with a microbial organism known to produce a useful fermentation product, and the fermentation process is allowed to proceed for 3-5 days, during and after which the fermentation products are removed and purified. A economically viable method for producing sugars using concentrated acid hydrolysis of biomass containing cellulose and hemicellulose is disclosed. The cellulose and hemicellulose in the biomass is first decrystallized and then hydrolyzed to produce a hydrolysate containing both sugars and acid. Silica present in the biomass can then be removed for further processing. The remaining solids are then subjected to a second decrystallization and hydrolyzation to optimize the sugar yields. An improved method for separating the sugars from the acid in the hydrolysate is also disclosed. The resulting sugar stream can then be fermented, using an improved method which allows both hexose and pentose sugars to be fermented simultaneously. A method of removing silica or silicates from solids results from the acid hydrolysis of materials containing cellulose and hemicellulose is disclosed. The method includes the steps of treating the solids with a metal hydroxide solution to produce an extract, reducing the pH of the extract to produce silicic acid, and removing the silicic acid from the extract. A economically viable method for producing sugars using concentrated acid hydrolysis of biomass containing cellulose and hemicellulose is disclosed. The cellulose and hemicellulose in the biomass is first decrystallized and then hydrolyzed to produce a hydrolysate containing both sugars and acid. Silica and silicates present in the biomass can then be removed for further processing. The remaining solids are then subjected to a second decrystallization if necessary and a second hydrolyzation to optimize the sugar yields. A economically viable method for producing sugars using concentrated acid hydrolysis of biomass containing cellulose and hemicellulose is disclosed. The cellulose and hemicellulose in the biomass is first decrystallized and then hydrolyzed to produce a hydrolysate containing both sugars and acid. Silica present in the biomass can then be removed for further processing. The remaining solids are then subjected to a second decrystallization and hydrolyzation to optimize the sugar yields. An improved method for separating the sugars from the acid in the hydrolysate is also disclosed. The resulting sugar stream can then be fermented, using an improved method which allows both hexose and pentose sugars to be fermented simultaneously. A economically viable method for producing sugars using concentrated acid hydrolysis of biomass containing cellulose and hemicellulose is disclosed. The cellulose and hemicellulose in the biomass is first decrystallized and then hydrolyzed to produce a hydrolysate containing both sugars and acid. Silica and silicates present in the biomass can then be removed for further processing. The remaining solids are then subjected to a second decrystallization if necessary and a second hydrolyzation to optimize the sugar yields.
US5892107 1996-11-08
Method for the production of levulinic acid
US6054611
1998-05-13
Method for the production of levulinic acid and its derivatives
US6743610
2001-03-30
Method to produce succinic acid from raw hydrolysates
US20030017559
2001-03-30
Method to produce succinic acid from raw hydrolysates
US20070148750
2005-02-08
Method for producing monosaccharides from biomass and monosaccharide production device
US20080026101
2007-06-14
Food products
US20110065159
2010-06-24
BIOMASS HYDROLYSIS
A method of producing dehydration products from one or more 5-carbon or 6-carbon sugars includes reacting said one or more sugars at 40-240 C. for 1 to 96 hours in the presence of 10-90% sulfuric acid, separating the reaction products, and recovering levulinic acid. The sugars can be generated from strong acid hydrolysis of biomass, such as rice straw, paper, cotton and other cellulosic materials. A method of producing dehydration products from one more 5-carbon or 6-carbon sugars includes reacting said one or more sugars at 40-240 C. for 1 to 96 hours in the presence of 5-90% sulfuric acid, separating the reaction products, and recovering levulinic acid. The sugars are can be generated from strong acid hydrolysis of biomass, such as rice straw, paper, cotton and other cellulosic materials. A method for producing succinic acid from industrialgrade hydrolysates is provided, comprising supplying an organism that contains mutations for the genes ptsG, pflB, and ldhA, allowing said organism to accumulate biomass, and allowing said organism to metabolize the hydrolysate. Also provided is a bacteria mutant characterized in that it produces succinic acid from substrate contained in industrial-grade hydrolysate in a ratio of between 0.6:1 and 1.3:1 succinic acid to substrate. A method for producing succinic acid from industrialgrade hydrolysates is provided, comprising supplying an organism that contains mutations for the genes ptsG, pflB, and ldhA, allowing said organism to accumulate biomass, and allowing said organism to metabolize the hydrolysate. Also provided is a bacteria mutant characterized in that it produces succinic acid from substrate contained in industrial-grade hydrolysate in a ratio of between 0.6:1 and 1.3:1 succinic acid to substrate. This monosaccharide production method is a method for producing monosaccharides from biomass having a first step 3 in which a raw material biomass is pretreated in 65 to 85 (w/w) % sulfuric acid at a temperature of 30 to 70 C., and a second step 4 in which the first step treatment product pretreated in the first step is subjected to saccharification treatment in 20 to 60 (w/w)% sulfuric acid at a temperature of 40 to 100 C. Methods of producing a food product for mammals from the soluble by-product fraction of ethanol production are provided. One method comprises the step of incubating the treated soluble by-product fraction with an enzyme mixture capable of digesting complex polysaccharides to yield a food product having a fermentable sugar content of at least about 10% of the total carbohydrate content of the food product. Another method comprises the steps of incubating the unconcentrated soluble by-product fraction with an enzyme mixture capable of digesting complex carbohydrates followed by removal of at least a portion of the fatty acids from the digested material to render a food product having a fatty acid content of less than about 10% dry weight. High-yielding method for chemical hydrolysis of lignocellulose into monosaccharides. The process of the invention can additionally be applied to cellulose, xylan and related biomass polysaccharides, such as galactan, mannan, or arabinan. The method is employed for hydrolysis of a biomass polysaccharide
US20120167876
2011-12-29
US20120167875
2011-12-29
ORGANO-CATALYTIC BIOMASS DECONSTRUCTION SOLVOLYSIS OF BIOMASS USING SOLVENT FROM A BIOREFORMING PROCESS
substrate. The process is carried out in an ionic liquid in which cellulose is soluble in the presence of catalytic acid at a temperature sufficiently high to initiate hydrolysis. Water is added to the reaction mixture after initiation of hydrolysis at a rate controlled to avoid precipitation yet avoid undesired sugar dehydration products such ad HMF. Hydrolysis product is useful as feedstock for fermentations including fermentation processes for ethanol, butanol and other fuels. The present invention provides processes for catalytic deconstruction of biomass using a solvent produced in a bioreforming reaction. The present invention provides processes for deconstructing biomass using a solvent produced in a bioreforming reaction.
BBI BIO VENTURES LLC

Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan BBI BioVentures LLC Denver, Colorado, Amerika Serikat Lignoselulosa;pre-collected bahan baku yang tidak membutuhkan atau sedikit perlakukan awal 52.000 ton/tahun Etanol Pilot: Demo: Komersial: 13.000 ton/tahun; 4,5 juta galon/tahun Plant ini dibangun pada akhir tahun 2008 dan dilanjutkan dengan coba start-up pada pertengahan tahun 2009. Plant selanjutnya dirancang untuk kapasitas 5-15 juta galon/tahun. Tidak dilakukan fermentasi C5, menghindari produksi gipsum dan pembakaran lignin. http://www.bbibioventures.com
BIOGASOL
Lisensor
Lokasi Bahan Baku Input Produk Tahap Pengembangan BioGasol / AAU Ballerup, Denmark Lignoselulosa; fleksibel 0,5 ton/tahun Etanol, biogas, selulosa, hemiselulosa, lignin Pilot: 10 ton/tahun, 40L/hari Demo: Komersial: Konsep teknologi diimplementasikan pada tahun 2006 di Denmarks Technical Univeristy. Skala pilot beroperasi pada awal tahun 2011 dengan pembangunan selama 2 tahun (2008-2010). Uji coba teknologi perlakuan awal dan fermentasi C5 pada skala pilot serta fleksibiltas bahan baku. http://www.biogasol.com BioGasol Aakirkeby, Bornholm, Denmark Lignoselulosa;macam-macam rumput, limbah kebun, jerami 3,4 ton/tahun Etanol, biogas, lignin, hidrogen Pilot: Demo: 4.000 ton/tahun; 5,2 ML/tahun Komersial: Skala demo dalam perencanaan dan akan beroperasi pada tahun 2016. Uji skala pilot terletak pada Ballerup, Denmark. Perlakuaan awal wet explosion (kombinasi steam explosion dan oksidasi basah), hidrolisis dan fermentasi C6 secara simultan, fermentasi C5 dalam immobilized reaktor. Daur ulang pemakaian air proses. http://www.biogasol.com
Status dan Rencana Pengembangan Deskripsi proses ringkas Website Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan
Website
Bisnis penjualan/lisensi proses teknologi bioetanol lignoselulosa (proprietary core technologies) Perlakuan awal CarbofracTM Fermentasi pentose PentcrobeTM Konsep proses (integrasi)
Gambar A.1.L1.5 Skema digram blok bioetanol generasi kedua BIOGASOL
Gambar A.1.L1.6 Rencana pengembangan dan implementasi bioetanol generasi kedua BIOGASOL
4. Daftar Paten
No Paten Tanggal Pendaftaran (Filling) Judul Abstrak
US20100143 988 WO/2007/13 4607A1
2007-05-22 2007-05-22
Thermoanaerobacter mathranii strain bg1
US20090258 404 WO/2008/00 0809A1
2007-06-28 2007-06-28
Production of fermentation products in biofilm reactors using microorganisms immobilised on sterilised granular sludge
Strict anaerobic thermophilic bacterium belonging to the group of Thermoanaerobacter mathranii and mutants and derivatives thereof. The bacterium is particularly suitable for the production of fermentation products such as ethanol, lactic acid, acetic acid and hydrogen from lignocellulosic biomass. Production of fermentation products, such as ethanol and lactic acid in biofilm reactors by microorganisms immobilised on sterilised granular sludge.
No Paten Tanggal Pendaftaran (Filling) Judul
Abstrak
8236547 US20110287 501 WO/2010/01 0116A1
2009-07-22 2009-07-22 2009-07-22
Increased ethanol production in recombinant bacteria
US20120100 045 WO/2010/08 1477A1
2010-01-12 2010-01-12
Apparatus for rapid mixing of media and method
WO/2010/08 1476A1
2010-01-12
Method and apparatus for in-feeding of matter to a process reactor
WO/2011/07 6797A1
2010-12-21
Thermophilic thermoanaerobacter italicussubsp. marato having high alcohol productivity
The invention pertains to a recombinant bacterium with enhanced ethanol production characteristics when cultivated in a growth medium comprising glycerol. The recombinant bacterium comprises an inserted heterologous gene encoding glycerol dehydrogenase, and/or an up-regulated native gene encoding glycerol dehydrogenase. Particularly there is provided the recombinant bacterium BG1G1 of the Thermoanaerobacter mathranii species with an inserted heterologous gene encoding the E.C. 1.1.1.6 type, a NAD dependent glycerol dehydrogenase obtained from Thermotoga maritima. The present invention relates to an apparatus, which can be part of a pre-treatment system in a plant for the production of fuels, e. g. bioethanol, derived from plant biomass, e. g. first generation crops, such as grain, sugarcane and corn or second generation crops such as lignocellulosic biomass. The invention relates to an apparatus for processing, such as fluffing and mixing, at least two media, such as a solid, e. g. biomass, and a fluid, e. g. steam, so as to rendering the first medium susceptible to efficient receiving of energy and/or mass which is provided by localized release of the second medium. Although the description of the present invention focuses on biomass, it is envisaged that the invention is generally applicable to control the mixing of at least two media by crossing their stream of while dispersing at least one of them. The present invention relates to an apparatus, which can be part of a pretreatment (101) system in a plant for the production of fuels derived from plant biomass, e. g. first generation crops, such as grain, sugarcane and corn or second generation crops such as lignocellulosic biomass. The apparatus has the function of in-feeding and dewatering biomass so as to control water content in biomass before the dewatered biomass is introduced into a process reactor (215) in a plant for the production of, for example, bio-ethanol. The infeeding and dewatering processes are carried out at a pressure higher than or equal to the pressure inside the process reactor (215) providing the advantage of a fluid tight sealing of the process reactor and facilitating its continuous feeding. Strict anaerobic thermophilic bacterium belonging to the group of Thermoanaerobacter italicus subsp. marato subsp. nov. and mutants and derivatives thereof. The bacterium is particularly suitable for the production of fermentation products such as ethanol, lactic
Abstrak
acid, acetic acid and hydrogen from lignocellulosic biomass.
BLUE SUGARS (d.h KL ENERGY)

Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan KL Energy Corporation / Blue Sugars Upton, Wyoming, Amerika Serikat Lignoselulosa; limbah kayu termasuk papan dan kertas 33.500 ton/tahun Etanol Pilot: Demo: 4.500 ton/tahun; 1,5 juta galon/tahun Komersial: 10-15 kali lipat Skala demo beroperasi pada tahun 2009 Teknologi perlakuan awal dengan enzim tanpa menggunakan asam. http://bluesugars.com http://www.klenergycorp.com

(a)
(b)
Gambar A.1.L1.7

No Paten Tanggal Pendaftaran (Filling Date) Judul Ringkasan
WO/2011/044292
2009-12-16
PROCESS FOR THERMAL-MECHANICAL PRETREATMENT OF BIOMAS
Disclosed is a process for the thermalmechanical pretreatment of biomass. The process includes subjecting a biomass feedstock including fibers containing cellulose, hemicellulose and lignin, to thermal reaction under conditions exceeding atmospheric pressure, at a temperature exceeding ambient temperature, at a predetermined moisture content and for a predetermined amount of time. Subsequently, the pressure of said thermal reaction is reduced under conditions resulting in explosive decompression of said biomass. The decompressed biomass is then subjected to axial shear forces to mechanically reduce the size of the fibers of the biomass to obtain treated biomass. The resultant treated biomass has a high level of enzymatic digestability and a low concentration of degradation products.
BORREGAARD
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Borregaard Industries LTD Sarpsborg, Norwegia Lignoselulosa; sulfite spent liquor (SSL, 33% kadar kering) dari pulping kayu cemara 500.000 ton/tahun Etanol Pilot: Demo: Komersial: 15.800 ton/tahun; 20 ML/tahun Skala komersial beroperasi pada tahun 1930 Proses integrasi dan pengembangan produk dari industry kayu Pulp dari penggilingan kertas diproduksi dengan pemanasan potongan spruce dengan larutan panas asam kalsium bisulfit. Hemiselulosa dihidrolisis menjadi bermacam-macam gula selama proses pemanasan. Setelah SSL terkonsentratkan, gula diferentasi dan etanol didistilasi dalam beberapa tahap. Etanol 96% didehidrasi untuk mendapatkan etanol absolut http://www.borregaard.com
Website
Gambar A.1.L1.8 Skema produksi terpadu bioetanol BORREGARD
Gambar A.1.L1.9 Skema perlakuan awal BORREGARD

No Paten Tanggal Pendaftaran (Filling Date) Judul Ringkasan
WO/2010/078930 USP 20110250638
2009-12-16
LIGNOCELLULOSIC BIOMASS CONVERSION BY SULFITE PRETREATMENT
The present invention relates to a process for the production of second generation biofuels and/or sugar based chemicals - for example ethanol, butanol etc - and/or materials - for example plastics, single cell proteins etc. - together with sulfonated lignin from lignocellulosic biomass, in particular from lignocellulosic biomass comprising, among others, annual plants, agricultural waste, or wood. In particular, the present invention relates to a process for the production of sugar based chemicals, biofuels or materials together with sulfonated lignin from lignocellulosic biomass comprising the pretreatment of a lignocellulosic biomass in a sulfite cooking step.
CHEMTEX PROESA - MGM

Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Mossi & Ghisolfi Chemtex Italia Tortona, Piedmont, Italia Lignoselulosa; residu jagung, jerami, sekam, biomassa berkayu 200 ton/tahun Etanol Pilot: 50 ton/tahun (2009) Demo: Komersial: Skala pilot beroperasi pada tahun 2009 Konversi enzimatik untuk biomassa tertentu. Perlakuan awal, penanganan material yang telah diberi perlakukan awal dan hidrolisis dilakukan dalam peralatan yang didesain secara khusus http://www.gruppomg.com
Website

Paten berkait dengan detail PROESA belum ditemukan.
DEDINI
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan DEDINI Brasil Bagas tebu dan Jerami Etanol Pilot: (2007) Demo: Komersial:
Proses terintegrasi dengan Bioetanol generasi pertama dari Sugar Cane, Hidrolisis enzimatik, dari Novozym http://www.dedini.com.br/

WO/2010/08 5862A1
Process of fermentation for production of bioethanol
US20110232 343 WO/2009/15 5675A2 WO/2009/15 5675A3
2009-06-24 2009-06-24 2009-06-24
Process for the recovery of water and energy from the processing of sugar cane in sugar and ethanol production mills
'Process of fermentation for production of bioethanol', it refers to a process of alcoholic fermentation that uses strains of flocculant yeasts, in bioreactor of fixed tower kind, expanded bed or fluidized, with an unit of regeneration of biocatalytic coupled, using vegetable products that contain saccharose, glucose and fructose as raw material; the developed process is applied in the unit of fermentation of sugary materials containing saccharose, glucose and fructose, coming from vegetable sources of direct way or after hydrolysis, in the industries of production of alcoholic drunk, fuel alcohol, industrial alcohol and anhydrous alcohol; such process comprehends the following stages: 1) Preparation of the must, 2) Alimentation of the bioreactor, 3) Process of conversion, 4) Degassing of the fermented material, 5) Recovery of the biocatalytic, 6) Treatment of the biocatalytic, 7) Return of the biocatalytic to fermenter, and 8) Recovery of ethanol. A process is proposed for recovery of water in the sugar cane processing in production mills of sugar and alcohol or only alcohol (ethanol). In the process, the thermal energy available in the exhausted steam from the electric energy generation turbines is transferred to the different mixed juice processing phases, with the reuse of the exhausted steam condensates in the boilers and of the other condensates, after using thermal energy, for imbibition, in the juice extraction phase, for cooling in the process, after passing through cooling towers, for other industrial uses and for possible treatment or use in the irrigation out of the productive system in the mill
DuPONT Danisco Cellulosic Ethanol (DDCE)

Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan DDCE DuPont Danisco Cellulosic Ethanol Vonore, Tennessee, Amerika Serikat Lignoselulosa; residu jagung; bonggol dan serat; switchgrass Etanol Pilot: 750 ton/tahun; 0,25 juta galon/tahun Demo: Komersial: 27,5 juta galon/tahun (2012) Skala pilot dibangun pada tahun 2008 dan beroperasi pada tahun 2011. Lahan untuk plant skala komersial telah dibeli pada tahun 2012 di Nevada, Iowa Hidrolisis enzimatik http://www.ddce.com
Gambar A.1.L1.10 Blok Diagram Proses Produksi Bioetanol DuPONT Danisco (DDCE)
FUTUROL PROCETHOL
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan PROCETHOL 2G POMACLE, Perancis Lignoselulosa Etanol Pilot: 0,18 ML/tahun Demo: 2.700 ton/tahun; 3,5 ML/tahun Komersial: 180 juta liter/tahun Skala pilot dikonstruksi pada tahun 2008 dan beroperasi pada Oktober 2011. Skala demo dibangun di Tereos dan dikonstruksi sejak tahun 2011. Teknologi skala pilot yang telah matang diaplikasikan pada skala demo pada tahun 2015. Skala komersial diharapakan dapat diap pada tahun 2016. Pengembangan enzim dan fermentasi bermacam-macam bahan baku secara efektif. http://www.chemicals-technology.com/projects/futurol-project/
Deskripsi proses ringkas Website
GREEN FIELD ETHANOL

No Paten
7935514 US2009023 9276 US2011022 9949 US2010006 5128
Tanggal Pendafta ran (Filling Date) 2008-1114 2008-1114 2011-0323 2009-0916
Judul
Abstrak
Genetically modified yeast strain
A polyploid transformed yeast cell comprising a deleted or disrupted GDH1 gene encoding an NADPH-dependent glutamate dehydrogenase. The polyploid yeast cell shows increased production of ethanol and reduced production of glycerol when compared with a control polyploid yeast cell. A process for the production of ethanol from biomass is disclosed. The process relates to the pretreatment of corncob biomass and includes the steps of exposing corncob to steam in a reaction vessel at an elevated temperature and reaction pressure for a preselected exposure time. Volatile compounds are continuously vented during pretreatment. The reaction pressure is released for explosive decomposition of the corncob biomass into fibrous solids and condensate. The exposure is preferably carried out at a temperature of 190-210 C. and a pressure of 190 psig to 275 psig and an exposure time of 3 to 10 minutes. A process for the production of ethanol wherein a hydrolyzed lignocellulosic biomass is fermented in the presence of a stillage residue. The fermentation of cellulosic hydrolysates is improved by adding prior to and/or during fermentation a stillage residue side stream from a corn starch-to-ethanol process as a nutrient source for the yeast organisms used in the fermentation. Stillage residues from the grain dry mill ethanol producing process, including the whole stillage, wet cake, thin stillage, and/or syrup are added to assist as a nitrogen and nutrient source for the fermentive processes. The stillage residue is produced by any grain-to-ethanol process.
Cellulose pretreatment process
US2010015 9552
2009-1222
Process for alcoholic fermentation of lignocellulosic biomass
TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA WO/2010/0 71987A1 2009-1222 Use of stillage residue as a nutrient source for fermentation of hydrolyzed lignocellulosic biomass to ethanol Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 82 dari 136
US2010018 1034 WO/2010/0 81227A1
2010-0115 2010-0115
Removal of inhibitory compounds during pretreatment of lignocellulosic biomass
US2010026 3814 WO/2010/1 21348A1
2010-0407 2010-0407
Pretreatment of lignocellulosic biomass through removal of inhibitory compounds
US2010031 3882 WO/2010/1 21367A1 WO/2010/1 21367A8
2010-0423 2010-0423 2010-0423
Fractionation of biomass for cellulosic ethanol and chemical production
US2010026
2010-04-
Separation of reactive
A process for the production of ethanol wherein a hydrolyzed lignocellulosic biomass is fermented in the presence of a stillage residue. The fermentation of cellulosic hydrolysates is improved by adding prior to and/or during fermentation a stillage residue side stream from a corn starch-to-ethanol process as a nutrient source for the yeast organisms used in the fermentation. Stillage residues from the grain dry mill ethanol producing process, including the whole stillage, wet cake, thin stillage, and/or syrup are added to assist as a nitrogen and nutrient source for the fermentive processes. The stillage residue is produced by any grain-to- ethanol process. A process for the pretreatment of lignocellulosic biomass, in particular during the production of ethanol from biomass. The process including a cooking step where the biomass is exposed to steam at elevated temperatures and pressures for a preselected period of time in a treatment vessel. During the process, volatile and liquid compounds are purged from the treatment vessel. A process for the pretreatment of lignocellulosic biomass is disclosed. The process is intended for use in connection with biomass to ethanol processes and is directed in particular to an economical removal of inhibitory compounds generated in biomass pretreatment, which are inhibitory to downstream hydrolysis and fermentation steps. The process includes the steps of heating the lignocellulosic biomass with steam to a preselected temperature, at a preselected pressure and for a preselected time to hydrolyze and solubilize hemicelluloses in the biomass; explosively decomposing the biomass into fibers; and extracting from the resulting reaction mixture a liquefied portion of the lignocellulosic biomass before or after explosive decomposition. The liquefied portion is extracted to remove compounds from the lignocellulosic biomass which are inhibitory to enzymatic cellulose hydrolysis and sugar fermentation to ethanol. For improved efficiency and economy, the inhibitory compounds are not completely removed. Furthermore, xylose has been found to be a good indicator compound for the general level of inhibitory compounds in the reaction mixture and the extraction step is therefore controlled on the basis of the xylose content in the reaction mixture. In particular, the extracting step is discontinued once a dry matter (dm) content of xylose, as monomer or oligomer, in the reaction mixture of 4% to 8% (w/w dm) is achieved. This most economically balances the practical need for inhibitory compound removal with the economical need to control and preferably minimize the costs of the overall ethanol production process. A process is defined for the continuous steam pretreatment and fractionation of corn cobs and low lignin lignocellulosic biomass to produce a concentrated cellulose solid stream that is sensitive to enzymatic hydrolysis. Valuable chemicals are recovered by fractionating the liquid and vapor stream composed of hydrolysis and degradation products of the hemicellulose. Cellulosic derived glucose is produced for fermentation to biofuels. A hemicellulose concentrate is recovered that can be converted to value added products including ethanol. A process for separating the components of
TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA 9990 WO/2010/1 21366A1 23 2010-0423 cellulose from lignocellulosic biomass with high lignin content Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 83 dari 136
WO/2012/0 34230A1
2011-0913
De icing formulation utilizing co-products from lignocellulose to bio fuel process
US2012011 1514 WO/2012/0 58776A1
2011-1104 2011-1104
Bagasse fractionation for cellulosic ethanol and chemical production
US2012011 5200 WO/2012/0 61939A1 WO/2012/0 61939A8
2011-1108 2011-1108 2011-1108
Continuous process for the production of ethanol from lignocellulosic biomass
lignocellulosic biomass for the purpose of producing a pure reactive cellulose is disclosed. The process has two stages. In the first stage, the lignocellulosic biomass is pretreated with steam, with or without an acid catalyst, and then pressed, with or without the presence of an eluent, to remove hemicellulose and other impurities. In the second stage, the pretreated biomass is extracted with a solvent such as ethanol with or without acid catalysts in order to remove lignin and release a purified cellulose stream. The extracted cellulose is then rapidly decompressed to rupture the fibrous structure. The process provides a purified cellulose stream that is relatively easy to hydrolyze with enzymes and ferment to biofuels and other chemicals such as ethanol. The use of a side stream and residue from the lignocellulose to ethanol process for use in preventing the formation of ice and in melting ice and snow on roadways. The future lignocellulose to ethanol industry will provide a significant proportion of these streams that provide an organic solution that when added to chloride salts of calcium, magnesium and sodium provides an improved environmentally friendly road deicing product with reduced corrosiveness and increased friction. A deicer composition of calcium chloride aqueous solution containing 25-38% by weight calcium chloride mixed up to 50% by volume of hemicellulose hydrolysis side stream can reduce the corrosivity of calcium chloride to 70% less that of a sodium chloride solution. A process is defined for the continuous steam pretreatment and fractionation of bagasse to produce a concentrated cellulose solid stream that is sensitive to enzymatic hydrolysis. Valuable chemicals are recovered by fractionating the liquid and vapor stream composed of hydrolysis and degradation products of the hemicellulose. Cellulosic derived glucose is produced for fermentation to biofuels. A hemicellulose concentrate is recovered that can be converted to value added products including ethanol. A continuous process for the recovery of ethanol from hemicellulose and cellulose from lignocellulosic biomass. Yield of fermentable sugars can be maximized by continuous operation of the pretreatment system and careful selection of pretreatment conditions including the addition of only small amounts of dilute mineral acid and low pressure. With this approach, the xylose component that is mainly present in its unfermentable oligomeric form in known pre-hydrolysis Kraft processes can be recovered more efficiently and as a monomer that can be fermented by xylose fermenting yeasts and bacteria. Due to the use of only dilute acids, there is a very low loss of glucose and xylose hence very low production of toxic chemicals (e.g. HMF, furfural) in the pretreatment step. The resulting overall fermentation efficiency of both hexose and pentose sugars is 90% of the theoretical maximum.
INBICON
Lisensor
Lokasi Bahan Baku Input Produk Tahap Pengembangan
Inbicon (DONG Energy)

Fredericia, Denmark Lignoselulosa; jerami 0,1 ton/tahun Etanol, molase C5; biofuel padat Pilot: Demo: Komersial: Skala pilot beroperasi pada tahun 2003 Perlakuan awal hidrotermal, hidrolisis gravitasi tinggi, dan fermentasi ragi http://www.inbicon.com Inbicon (DONG Energy) Fredericia, Denmark Lignoselulosa 1 ton/tahun Etanol, molase C5; biofuel padat Pilot: Demo: Komersial: Skala pilot beroperasi pada tahun 2005 Perlakuan awal hidrotermal, hidrolisis gravitasi tinggi, dan fermentasi ragi http://www.inbicon.com Inbicon (DONG Energy) Kalundborg, Denmark Lignoselulosa; jerami gandum 30.000 ton/tahun Etanol, molase C5; biofuel padat Pilot: Demo: 4.300 ton/tahun; 1,5 juta galon/tahun Komersial: Skala demo dikonstruksi pada tahun 2007 dan beroperasi pada tahun 2009 Integrasi energi dengan stasiun daya http://www.inbicon.com
Gambar A.1.L1.11 Proses Produksi Bioetanol Lignoselulosa INBICON (1: Penyimpanan biomassa, 2) Perlakuan Mekanik (grinding), 3) Perlakuan Awal Hydrothermal, 4) Hidrolisis Enzimatik, 5) Fermentasi, 6) Penangkapan CO2, 7) Distilasi, 8) Pemisahan Padat/Cairan, 9) Penyimpanan Tetes Gula (Molase), 10) Evaporasi, 11) Penyimpanan Etanol, 12) Pengeringan, 13)Kogenerasi
4. Daftar Paten Terkait Teknologi Bioetanol Lignoselulosa INBICON

No Paten Tanggal Pendaftaran (Filling) 2005-11-07 2005-11-07 Judul Abstrak
US7842490 EP2154236A1
Enzymatic hydrolysis of biomasses having a high dry matter (DM) content
The present invention relates to a process for liquefaction and saccharification of polysaccharide containing biomasses, having a relatively high dry matter content. The present invention combines enzymatic hydrolysis with a type of mixing relying on
Abstrak
EP2172568A1 US8123864 US2012013824 6
2006-07-19 2006-07-19 2012-01-31
Method and apparatus for conversion of cellulosic material to ethanol
8187849 WO/2009/0904 80A2 WO/2009/0904 80A3 WO/2009/0904 80A4 US2012012217 4
2008-12-18 2008-12-18 2008-12-18 2008-12-18 2012-01-24
Non-sterile fermentation of bioethanol
the principle of gravity ensuring that the biomasses are subjected to mechanical forces, primarily shear and tear forces. Furthermore, the present invention relates to the further utilization of such processed biomasses, e.g. for subsequent fermentation into bioethanol, bio-gas, specialty carbohydrates for food and fees as well as carbon feedstock for processing into plastics and chemicals. The present invention provides an apparatus and a method for conversion of cellulosic material, such as chopped straw and corn stover, and household waste, to ethanol and other products. The cellulosic material is subjected to continuous hydrothermal pretreatment without addition of chemicals, and a liquid and a fibre fraction are produced. The fibre fraction is subjected to enzymatic liquefaction and saccharification. The method of the present invention comprises: - performing the hydrothermal pre-treatment by subjecting the cellulosic material to at least one soaking operation, and conveying the cellulosic material through at least one pressurised reactor, and subjecting the cellulosic material to at least one pressing operation, creating a fibre fraction and a liquid fraction; - selecting the temperature and residence time for the hydrothermal pretreatment, so that the fibrous structure of the feedstock is maintained and at least 80% of the lignin is maintained in the fibre fraction. A range of concentrations exists in which fermentation inhibitors derived from pretreatment of lignocellulosic feed stocks inhibit growth of lactic acid bacteria without affecting fermentive yeast. By optimizing levels of fermentation inhibitors to fall within this range, yeast fermentations of lignocellulosic biomass can be conducted under nonsterile conditions with ethanol yields comparable to those achieved under sterile conditions. Optimised inhibitor levels can be achieved by controlling the water/biomass ratio of a lignocellulosic biomass during and after pretreatment, for example by washing the fiber fraction of a previously pretreated lignocellulosic biomass with a pre-defined amount of fresh water or recycled process solutions. Crude extracts of liquid fraction or process solutions from pretreatment of lignocellulosic biomass can also provide an effective anti-bacterial treatment for first generation starch fermentations.
IOGEN
Lisensor
Iogen Corporation
Ottawa, Ontario, Kanada Lignoselulosa; jerami gandum, barley, dan oat 30 ton/hari Etanol Pilot: Demo: 1.600 ton/tahun; 2 ML/tahun (2004) Komersial: Skala demo beroperasi pada tahun 2004 Perlakuan awal steam explosion, hidrolisis enzimatik yang terpisah dengan fermentasi menggunakan proses hidrolisis multitahap, kofermentasi, dan distilasi konvensional. Skala besar didesain dengan intrgrasi panas, daur ulang air, dan produksi produk samping. http://www.iogen.com Iogen Corporation Birch Hills, Saskatchewan, Kanada Lignoselulosa; jerami gandum,dan lain-lain 750 ton/hari Etanol 90.000 kL /tahun Pilot: Demo: Komersial: 70.000 ton/tahun; 90 ML/tahun Perencanaan skala komersial dimulai sejak awal tahun 2008 dan beroperasi pada tahun 2011 Perlakuan awal steam explosion, hidrolisis enzimatik yang terpisah dengan fermentasi menggunakan proses hidrolisis multitahap, kofermentasi, dan distilasi konvensional. Skala besar didesain dengan intrgrasi panas, daur ulang air, dan produksi produk samping. http://www.iogen.com
Website Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan
Website
Gambar A.1.L1.12 Diagram Alir Produksi Bioetanol Lignoselulosa IOGEN

No Paten Tanggal Pendaftaran (Filling) 1997-06-09 Judul Abstrak
5916780
Pretreatment process for conversion of cellulose to fuel ethanol
6015703
1998-03-10
Genetic constructs and
An improved pretreatment of cellulosic feedstocks, to enable economical ethanol production by enzyme treatment. The improved pretreatment comprises choosing either a feedstock with a ratio of arabinoxylan to total nonstarch polysaccharides (AX/NSP) of greater than about 0.39, or a selectively bred feedstock on the basis of an increased ratio of AX/NSP over a starting feedstock material, and reacting at conditions that disrupt the fiber structure and hydrolyze a portion of the cellulose and hemicellulose. This pretreatment produces a superior substrate for enzymatic hydrolysis, by enabling the production of more glucose with less cellulase enzyme than any known procedures. This pretreatment is uniquely suited to ethanol production. Preferred feedstocks with an AX/NSP level greater than about 0.39 include varieties of oat hulls and corn cobs. This invention relates to the genetic modification of a
No Paten Tanggal Pendaftaran (Filling) 1999-03-09 Judul
Abstrak
WO/1999/04 6362A1
genetically modified microbes for enhanced production of betaglucosidase
EP0884391A 1 EP0884391B 1 US6090595
1998-06-04 1998-06-04
Improved pretreatment process for conversion of cellulose to fuel ethanol
1998-12-08
EP1320588A 2 EP1320588B 1 7419809 WO/2002/02 4882A2
2001-09-25 2001-09-25 2001-09-25 2001-09-25
Method for glucose production with a cellulase mixture comprising a modified cellulase
7901511 EP1364072A 2 EP1364072B 1 EP1767658A 1 EP2261381A 2 EP2261381A 3 WO/2002/07 0753A2 7993463 US20070148 751
2002-02-27 2002-02-27 2002-02-27 2002-02-27 2002-02-27 2002-02-27 2002-02-27 2007-01-31 2007-01-31
Method of processing lignocellulosic feedstock for enhanced xylose and ethanol production
microbe to enhance its production of an enzyme, beta-glucosidase, that is important in the cellulose conversion process. The inventors have discovered genetic constructs that, when expressed in recombinant microbes, dramatically increase the amount of beta-glucosidase produced relative to untransformed microbes. The genetic constructs comprise a promoter, a xylanase secretion signal, and a mature beta-glucosidase coding region. The increased level of beta-glucosidase significantly increases the efficiency of hydrolysis of cellulose to glucose by cellulase enzymes, thereby enhancing the production of fuel ethanol from cellulose. An improved pretreatment of cellulosic feedstocks, to enable economical ethanol production by enzyme treatment. The improved pretreatment comprises choosing either a feedstock with a ratio of arabinoxylan to total nonstarch polysaccharides (AX/NSP) of greater than about 0.39, or a selectively bred feedstock on the basis of an increased ratio of AX/NSP over a starting feedstock material, and reacting at conditions that disrupt the fiber structure and hydrolyze a portion of the cellulose and hemicellulose. This pretreatment produces a superior substrate for enzymatic hydrolysis, by enabling the production of more glucose with less cellulase enzyme than any known procedures. This pretreatment is uniquely suited to ethanol production. Preferred feedstocks with an AX/NSP level greater than about 0.39 include varieties of oat hulls and corn cobs. The present invention pertains to a method of converting cellulose to glucose by treating a pretreated lignocellulosic substrate with an enzyme mixture comprising cellulase enzyme and a modified CBHI, wherein the modified CBHI is present in the enzyme mixture at an amount relative to all CBHI-type enzymes from about 15% to about 100% (w/w), dpending upon the modified CBH1 used. The pretreated lignocellulosic substrate is selected from the group consisting of agricultural residues, residues after starch or sugar removal, dedicated ethanol crops, forestry products, and pulp and paper products, or combinations thereof. The present invention provides a method of producing xylose from lignocellulosic feedstock. The method comprises disrupting lignocellulosic feedstock; leaching the lignocellulosic feedstock by contacting the feedstock with at least one aqueous solution for a period greater than about 2 minutes to produce a leached feedstock and a leachate; removing the leachate from the leached feedstock; acidifying the leached feedstock to a pH between about 0.5 and about 3 to produce an acidified feedstock, and; reacting the acidified feedstock under conditions which disrupt fiber structure and hydrolyze a portion of hemicellulose and cellulose of the acidified feedstock, to produce a composition comprising xylose and a pretreated feedstock. The xylose may be purified from the pretreated feedstock or it may be converted to ethanol with the pretreated feedstock.
No Paten Tanggal Pendaftaran (Filling) 2003-03-05 2003-03-05 Judul
Abstrak
8012721 WO/2003/07 8644A2
Method for glucose production using endoglucanase core protein for improved recovery and reuse of enzyme
8057635
2007-06-28
Method and system for the large scale collection, preparation, handling and refining of lignocellulosic biomass
WO/2009/01 5481A1
2008-07-31
Cellulase enzyme based method for the production of alcohol and glucose from pretreated lignocellulosic feedstock
US20100190 226
2010-03-12
Process for producing a pretreated feestock
The present invention pertains to a method of converting cellulose to glucose by treating a pretreated lignocellulosic substrate with an enzyme mixture comprising cellulase enzyme and endoglucanase core proteins, wherein the endoglucanase core proteins are present in the enzyme mixture at an amount relative to all endoglucanases from about 35 wt. % to about 100 wt. % and wherein the endoglucanase cellulase enzymes are present in the enzyme mixture at an amount relative to the amount of CBH and EG enzymes from about 2 wt. % to about 50 wt. %. The pretreated lignocellulosic substrate is selected from the group consisting of agricultural residues, residues after starch or sugar removal, dedicated ethanol crops, forestry products, and pulp and paper products, or combinations thereof. A system for collecting ligno-cellulosic biomass over a large area to enable the commercial refining of biomass from 2,500 to in excess of 50,000 tons of biomass per day to produce ethanol or other products. The biomass is collected at a series of collection points and then transported through a network of conduit loops interconnecting each of the collection points and the central refining plant. The water used to transport the biomass, as a slurry, is recovered and sequentially recycled in the same pipeline system to push the biomass slurry around the system in a loop. A process for the production of glucose and ethanol from a pretreated lignocellulosic feedstock is provided. The method comprises enzymatically hydrolyzing the pretreated lignocellulosic feedstock with cellulase enzymes to produce a hydrolyzate slurry comprising glucose and unhydrolyzed cellulose and fermenting the hydrolyzate slurry in a fermentation reaction to produce a fermentation broth comprising alcohol. A process stream is obtained comprising unhydrolyzed cellulose, which is then subjected to a denaturing step, preferably comprising exposing the unhydrolyzedcellulose to elevated temperatures, thereby producing a heattreated streamcomprising the unhydrolyzed cellulose. The heat-treated stream comprising unhydrolyzed cellulose is then further hydrolyzed with cellulase enzymes to hydrolyze the cellulose to glucose. A process for producing ethanol from a pretreated feedstock is provided. The feedstock is selected from grasses, cereal straws, stover, and combinations thereof, and least about 80% of the feedstock has a particle length of between about 2 cm and about 40 cm. This process comprises wetting the feedstock in liquid, pressing the wet feedstock through one roll press or a series of roll presses to remove at least a portion of water and soluble substances from the wetted feedstock and to shear the feedstock to produce feedstock particles of a size suitable for pumping at a solids concentration of about 8% to about 20% when slurried. At least one roll press, or at least one roll press in the series of roll presses
Abstrak
US20110159 560
2010-12-30
Modified yeast strains exhibiting enhanced fermentation of lignocellulosic hydrolysates
8157955 US20110188 949
2011-02-04 2011-02-04
Method and system for the large scale collection of ligno-cellulosic biomass
US20120023 814
2011-10-04
Method and system for the large scale collection, preparation, handling and refining of lignocellulosic biomass
comprises rolls with circumferential v-shaped grooves. The pressed feedstock particles are slurried to produce a slurried feedstock having a consistency of between about 8% and about 20%, and the slurried feedstock pumped into a pretreatment reactor. Dilute acid pretreatment of the slurried feedstock is carried out at a temperature of 160 C. to 280 C. The present invention relates to novel xylosefermenting yeast strains (for example, yeast of the genus Saccharomyces, e.g., S. cerevisiae) with an enhanced ability to ferment the xylose (and/or another pentose sugar) present in a lignocellulosic hydrolysate to a fermentation product(s) (for example, an alcohol (e.g., ethanol) or a sugar alcohol (e.g., xylitol)). A system for collecting ligno-cellulosic biomass over a large area to enable the commercial refining of biomass from 2,500 to in excess of 50,000 tons of biomass per day to produce ethanol or other products. The biomass is collected at a series of collection points and then transported through a network of conduit loops interconnecting each of the collection points and the central refining plant. The water used to transport the biomass, as a slurry, is recovered and sequentially recycled in the same pipeline system to push the biomass slurry around the system in a loop. The outgoing and return legs of each loop optionally are located adjacent each other. A system for collecting ligno-cellulosic biomass over a large area to enable the commercial refining of biomass from 2,500 to in excess of 50,000 tons of biomass per day to produce ethanol or other products. The biomass is collected at a series of collection points and then transported through a network of conduit loops interconnecting each of the collection points and the central refining plant. The water used to transport the biomass, as a slurry, is recovered and sequentially recycled in the same pipeline system to push the biomass slurry around the system in a loop.
LIGNOL
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Lignol Energy Corporation Burnaby, British Columbia, Kanada Lignoselulosa; residu hardwood dan softwood 1 ton/hari Etanol, lignin Pilot: 80 ton/tahun; 0,1 ML/tahun Demo: Komersial: Skala pilot mulai dibangun pada tahun 2008 dan beroperasi pada tahun 2010 Proses delignifikasi untuk menghasilkan etnaol dan organosolv lignin untuk digunakan sebagai bahan bakar turbin gas. http://www.lignol.ca
Gambar A.1.L1.13
No Paten Tanggal Pendaftaran (Filling Date) 2007-08-15 2008-01-18 2008-01-30 2008-01-30 2008-04-25 2008-11-10 2008-11-10 Judul

Abstrak
US20080299628 US20080295980 7465791 US20080299629 WO/2008/144878 A1 8227004 US20090117226
Continuous counter-current organosolv processing of lignocellulosic feedstocks
US20090011484 WO/2009/003292 A1
2008-07-03 2008-07-04
Concurrent saccharification and fermentation of fibrous biomass
WO/2010/081231 A1
2010-01-15
Organosolv biorefining of whole sugar cane
A modular process for organosolv fractionation of lignocellulosic feedstocks into component parts and further processing of said component parts into at least fuel-grade ethanol and four classes of lignin derivatives. The modular process comprises a first processing module configured for physico-chemically digesting lignocellulosic feedstocks with an organic solvent thereby producing a cellulosic solids fraction and a liquid fraction, a second processing module configured for producing at least a fuel-grade ethanol and a first class of novel lignin derivatives from the cellulosic solids fraction, a third processing module configured for separating a second class and a third class of lignin derivatives from the liquid fraction and further processing the liquid fraction to produce a distillate and a stillage, a fourth processing module configured for separating a fourth class of lignin derivatives from the stillage and further processing the stillage to produce a sugar syrup. A process for simultaneous saccharification and fermentation of a cellulosic solids fraction extracted from a lignocellulosic feedstock. The viscosity of the cellulosic solids fraction is reduced by intermixing with a liquid carbohydrate stream. A suitable liquid carbohydrate stream is a de-lignified liquids fraction that was previously separated from the solids fraction during processing of the lignocellulosic feedstock. Alternatively, the viscosity of the solids fraction may be reduced by commingling with a liquid carbohydrate stream comprising one or more monosaccharides. The reduced-viscosity cellulosic solids fraction is then commingled with a fermentative microbial inoculant and a cellulosic biomass-degrading enzyme composition. The commingled mixture is maintained in a pressurized reaction vessel under elevated temperatures to enable simultaneous enzymatic hydrolysis of the cellulosic solids to monosaccharides and fermentation of the monosaccharides to produce an ethanolic beer. The ethanolic beer is distillable for recovery of fuel-grade ethanol and a stillage that may be further processed. An apparatus for processing sugar cane to concurrently produce sugar from cane juice, and ethanol and other co-products from bagasse. The apparatus comprises equipment for separating a cane juice stream and a fibrous bagasse from a sugar cane feedstock, equipment for refining the cane juice, equipment for processing the fibrous bagasse for recovery therefrom of a cellulosic pulp and a liquor stream, equipment for saccharifcation and fermentation of the cellulosic pulp to produce a fermentation beer therefrom, and equipment for recovery of an ethanol stream from the fermentation beer. Legacy sugar mills may be retrofitted with a bagasse biorefining apparatus to concurrently produce ethanol and co-products, with existing cane juice extraction and processing operations.
MASCOMA (SunOpta)
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Mascoma Corporation Rome, New York, Amerika Serikat Lignoselulosa; potongan kayu; switchgrass, dan bahan baku lainnya 5 ton/hari Etanol, lignin Pilot: Demo: 500 ton/tahun; 0,125 juta galon/tahun Komersial: Skala demo beroperasi pada tahun 2003 Pengembangan ragi dan bakteri yang dimodifikasi sehinga menghasilka enzim dengan kuantitas yang besar. Consolidated Bioprocessing (CBP) mengkombinasikan 2 tahap yaitu sakarifikasi enzimatik dan fermentasi yang mengurangi jumlah enzim yang dibutuhkan http://www.mascoma.com
Website
Website
Frontier Renewable Resources Dibeli oleh Mascoma Kincheloe, Michigan, Amerika Serikat Lignoselulosa; potongan kayu 700 ton/hari Etanol, lignin Pilot: Demo: Komersial: 60.000 ton/tahunl 20 juta galon/tahun Pembangunan skala pilot dimulai pada akhir tahun 2011 atau awal tahun 2012. Consolidated Bioprocessing (CBP) mengkombinasikan 2 tahap yaitu sakarifikasi enzimatik dan fermentasi yang mengurangi jumlah enzim yang dibutuhkan http://www.frontier-renewable.com/
METSA BOARD (d.h. M-REAL-HALEIM AG)

Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan M-real Hallein AG Hallein, Austria Lignoselulosa; sulfite spent liqour (SSL) dari pulping kayu cemara 600.000 SSL (33% kadar kering) ton/tahun Etanol Pilot: Demo: 12.000 ton/tahun; 15 ML/tahun Komersial: Skala demo sedang direncanakan dan akan beroperasi pada tahun 2016 Pulp dari penggilingan kertas diproduksi dari pemanasan potongan cemara dengan larutan panas asam magnesium bisulfit. Setelah SSL terkonsentrasi dalam evaporator, SSL dibakar dalan boiler untuk menghasilkan steam dan listrik sedangkan magnesium oksida dan sulfur dioksida akan didaur ulang. Etanol hasil fermentasi didistilasi hingga konsentrasi 96% dan kemudian didehidrasi dengan molecular sieve untuk mendapatkan etanol absolut. http://www.m-real.com
Website
Gambar A.1.L1.14 Skema produksi bioetanol M-real Hallein AG
PACIFIC ETHANOL
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Pacific Ethanol Boardman, Oregon, Amerika Serikat Lignoselulosa; jerami gandum, residu jagung, residu poplar 5,8 ton/tahun Etanol, biogas, lignin Pilot: Demo: 8.000 ton/tahun; 2,7 juta galon/tahun (2008) Komersial: Skala demo dibanung sejak tahun 2008 dan beroperasi pada tahun 2010. Skala demo ini akan dikembangkan menjadi skala komersial pada tahun 2012. Teknologi proses BioGasol dan teknologi enzim didiukung oleh Joint BioEnergy Institute. http://www.pacificethanol.net
Gambar A.1.L1.15

No Paten Tanggal Pendaftar an (Filling Date) 2004-0723 2004-0723 Judul

Abstrak
7611716 WO/2005/01 4657A1
Method of processing seaweed
WO/2006/09 9593A2 WO/2006/09 9593A3
2006-0315 2006-0315
Carbon based electrocatalysts for fuel cells
WO/2007/14 9643A1
2007-0504
Formaldehyde free binder
A method of processing seaweed, preferably a brown seaweed, comprises the following steps: (I) treating seaweed with an alcohol having one to six carbon atoms, preferably ethanol, to form an alcoholic fraction and an insoluble first seaweed residue; (II) separating the alcoholic fraction; (III) removing the alcohol from the alcoholic fraction to form a concentrate comprising biologically active low molecular weight compounds; (iv) extracting the first seaweed residue with an aqueous solution at a pH of less than 6 to form an aqueous first extract and an insoluble second seaweed residue; (v) optionally concentrating the first extract; and (vi) adjusting the pH of the resulting concentrated extract to a value in the range of 5 to 8 to obtain a first polysaccharide, fraction comprising a mixture of laminaran and fucoidan. Novel proton exchange membrane fuel cells and direct methanol fuel cells with nanostructured components are configured with higher precious metal utilization rate at the electrodes, higher power density, and lower cost. To form a catalyst, platinum (735) or platinum-ruthenium nanoparticles are deposited onto carbon-based materials, for example, single-walled, dual-walled, multi-walled and cup-stacked carbon nanotubes (710). The deposition process includes an ethylene glycol reduction method (720). Aligned arrays of these carbon nanomaterials are prepared by filtering (740) the nanomaterials with ethanol. A membrane electrode assembly is formed by sandwiching the catalyst between a proton exchange membrane (770) and a diffusion layer (796) that form a first electrode. The second electrode may be formed using a conventional catalyst. The several layers of the MEA (790) are hot pressed (780) to form an integrated unit. Proton exchange membrane fuel cells and direct methanol fuel cells are developed by stacking the membrane electrode assemblies in a conventional manner. The present invention relates to a new formaldehydefree binder composition, to the related method of its use for making fibrous products (including glass fiber products and especially fiberglass insulation), and to the fiber products themselves. The present invention specifically relates to an aqueous binder composition containing a mofified copolymer of maleic anhydride and a vinyl aromatic compound such as styrene. The copolymer is modified by reaction with a primary alkanolamine (preferably mono ethanol amine (MEA) ). The modified copolymer is self-curing and cures as a consequence of cross-linking, esterification reactions between pendant carboxyls and hydroxyl groups on the solubilized (hydrolyzed) modified
7718832
2007-1228
Combination catalytic process for producing ethanol from synthesis gas
copolymer chains. Additional polyol (s), including diethanolamine and/or triethanolamine, can be added to the binder to increase either, or both the pH of the aqueous binder composition and the crosslink density of the cured binder. A catalytic process selectively produces ethanol by contacting synthesis gas (syngas), composed primarily of hydrogen and carbon monoxide, with three catalysts within a reactor. The first catalyst is a hydrogenation promoter comprising CuZn, Mo or Fe with an optional alkali metal additive and an optional support of aluminum oxide, silica, zeolite or clay. The second catalyst is a homologation promoter comprising one or more of the Group VIII metals in free or combined form with a co-catalyst metals consisting of Y or lanthanide or actinide series metals with optional additives and support. The third catalyst is a hydrogenation promoter. This series of catalysts improves the selectivity and yield for ethanol from syngas.
POET-DSM
Lisensor
POET - DSM
Scotland, South Dakota, Amerika Serikat Lignoselulosa; serat jagung, bonggol dan tangkai Etanol Pilot: 60 ton/tahun; 0,02 juta galon/tahun Demo: Komersial: Skala pilot beroperasi pada tahun 2008 Hidrolisis enzimatik http://www.poet.com POET Emmetsburg, Iowa, Amerika Serikat Lignoselulosa; bonggol jagung, residu pertanian 280.000 ton kering/tahun Etanol Pilot: Demo: Komersial: 75.000 ton/tahun; 25 juta galon/tahun Perancangan skala komersial telah dilakukan sejak tahun 2006 dan akan beroperasi pada tahun 2013 Hidrolisis enzimatik. Didukung oleh DSM untuk teknologi konversi (ragi dan enzim) serta ko-fermentasi [gula C6 dan C5 (xylosa dan arabinosa)]. http://www.projectliberty.com
TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA (a) Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 104 dari 136
(b)
Gambar A.1.L1.16

No Paten Tanggal Judul Pendaftaran (Filling Date) 2005-03-10 High protein distiller's dried grain and production thereof Abstrak
EP2281898A 1
7919291
2009-03-16
Method for producing ethanol using raw starch
WO/2010/07 5541A2 WO/2010/07
2009-12-23 2009-12-23
System for production of ethanol and co-products
The present invention relates to methods for producing high levels of alcohol during fermentation of plant material, and to the high alcohol beer produced. The method can include fractionating the plant material. The present invention also relates to methods for producing high protein distiller's dried grain from fermentation of plant material, and to the high protein distiller's dried grain produced. The method can include drying a co-product by ring drying, flash drying, or fluid bed drying. The present invention further relates to reduced stack emissions from drying distillation products from the production of ethanol. The present invention relates to methods for producing high levels of alcohol during fermentation of plant material, and to the high alcohol beer produced. The present invention also relates to methods for producing high protein distiller's dried grain from fermentation of plant material, and to the high protein distiller's dried grain produced. The present invention further relates to reduced stack emissions from drying distillation products from the production of ethanol. A system for the production of ethanol and coproducts is provided. The system facilitates an overall reduction in the use of energy, for example, by reducing the mass of wet solids supplied to a
5541A3
US20100178 675
2009-12-31
System for extracting protein from a fermentation product
WO/2010/07 8528A1
2009-12-31
Zein composition
WO/2010/10 2060A3
2010-03-03
Pre-treatment of biomass for the production of ethanol
WO/2010/10 2063A2
2010-03-03
System fro fermentation of biomass for the production of ethanol
distillation system. The system also reduces the amount of energy used to dry the wet solids component of a fermentation product, for example, by increasing the ethanol concentration of the wet solids. The system also facilitates the recovery of coproducts including bioproducts and other biochemicals extracted from components of the fermentation product. The solids component of the fermentation product may be dried and constituted into a meal that may be used for animal feed, among other uses. A method of producing bioproducts from a feedstock in a system configured to produce ethanol and distillers grains from a fermentation product is disclosed. A system configured to process feedstock into a fermentation product and bioproducts including ethanol and meal is disclosed. A bioproduct produced from a fermentation product produced from a feedstock in a biorefining system is disclosed. A method of producing bioproducts from a feedstock in a system configured to produce ethanol and distillers grains from a fermentation product is disclosed. A system configured to process feedstock into a fermentation product and bioproducts including ethanol and meal is disclosed. A bioproduct produced from a fermentation product produced from a feedstock in a biorefining system is disclosed. A system for the pre-treatment of biomass for use in a biorefinery to produce ethanol and other bioproducts is disclosed. The system comprises a method to pretreat biomass to be used in a biorefinery to produce a fermentation product. The method comprises the steps of preparing the biomass into prepared biomass; and pre-treating the prepared biomass into pre-treated biomass by application of a dilute acid having a concentration of about 0.8 to 1.1 percent by weight at a temperature of about 130 to about 170 degrees Celsius for a period of time in a range of about 8 to 12 minutes. A system for fermentation of biomass is disclosed. The system comprises a method for producing a fermentation product in a fermentation system from biomass that has been pre-treated and separated into a first component and a second component. The method comprises the steps of supplying the first component to the fermentation system; providing an ethanologen to the fermentation system; maintaining the first component and ethanologen in the fermentation system; and recovering the fermentation product from the fermentation system. A fermentation system configured to produce a fermentation product from biomass that has been pre-treated and separated into a first component and a second component is disclosed. The system comprises a first vessel configured to receive the first component and an ethanologen and a second vessel configured to propagate the ethanologen for supply to the first vessel. A biorefinery for producing a fermentation product from biomass is also disclosed. The biorefinery comprises a preparation system to prepare the biomass into prepared biomass; a pretreatment system to pre-treat the prepared biomass with a dilute acid for separation into a first component from which pentose can accessed for fermentation and a second component from which hexose can be made available for fermentation; a first treatment system to treat the first component into a treated first
WO/2010/10 2060A2
2010-03-03
System for pre-treatment of biomass for the production of ethanol
US20100261 243 WO/2010/11 8369A1 WO/2010/11
2010-04-09 2010-04-09 2010-04-09
System for recycling water to facilitate the production of ethanol
component by removing removed components from the first component; a first fermentation system to produce a first fermentation product from the pentose; a distillation system to recover ethanol from the first fermentation product; and a treatment system to process removed components. The biomass comprises lignocellulosic material; the lignocellulosic material comprises at least one of corn cobs, corn plant husks, corn plant leaves and corn plant stalks. The first component comprises pentose; the pentose comprises xylose. The ethanologen is capable of fermenting xylose into ethanol. A system for the pre-treatment of biomass for use in a biorefinery to produce ethanol and other bioproducts is disclosed. The system comprises a method to pretreat biomass to be used in a biorefinery to produce a fermentation product. The method comprises the steps of preparing the biomass into prepared biomass; and pre-treating the prepared biomass into pre-treated biomass by application of a dilute acid having a concentration of about 0.8 to 1.1 percent by weight at a temperature of about 130 to about 170 degrees Celsius for a period of time in a range of about 8 to 12 minutes. The system may also comprise a method to pre-treat biomass to be used in a biorefinery to produce a fermentation product. The method comprises the preparing the biomass into prepared biomass; and pre-treating the prepared biomass into pre-treated biomass by application of a dilute acid having a concentration of about 0.8 to 1.1 percent by weight at a temperature of about 130 to about 170 degrees Celsius for a period of time in a range of about 5 to 15 minutes. The fermentation product can be obtained by separating the pre-treated biomass into a liquid component comprising xylose and a solids component from which glucose can be made available and accessing xylose for fermentation into the fermentation product. A system for pretreating biomass to be used in a biorefinery to produce a fermentation product may comprise an apparatus to preparing the biomass into prepared biomass; an apparatus for pre-treating the prepared biomass into pre-treated biomass by application of a dilute acid having a concentration of about 0.8 to 1.1 percent by weight at a temperature of about 130 to about 170 degrees Celsius for a period of time in a range of about 5 to 15 minutes; an apparatus for separating the pre-treated biomass into a liquid component comprising pentose available to be fermented and a solids component comprising cellulose from which hexose can be made available for fermentation and lignin; a fermentation system configured to produce the fermentation product; and a distillation system configured to recover ethanol from the fermentation product. The fermentation product comprises ethanol produced by fermentation of pentose and ethanol produced from the fermentation of hexose. The biomass comprises lignocellulosic material. The lignocellulosic material comprises corn cobs, corn plant husks, corn plant leaves and corn plant stalks. A system for the production of ethanol is disclosed. The system comprises a system for recycling water in an ethanol production process. The system may comprise: a water supply that supplies water to the ethanol production process, a cooling tower system that supplies water to the ethanol production process,
8369A4
WO/2010/13 5366A1 US20120129 234
2010-05-18 2011-11-18
System for treatment of biomass to facilitate the production of ethanol
US20110079 219 WO/2011/04 3935A1
2010-09-23 2010-09-24
Biomass pretreatment
US20110111 085
2010-11-11
Methods and systems for producing ethanol using raw starch and fractionation
WO/2011/11 6317A1
2011-03-18
System for the treatment of biomass
WO/2011/15 9915A1
2011-06-16
Fermentation of biomass
and a treatment system that supplies water to the ethanol production process. The treatment system may be a reverse osmosis system that supplies a retentate stream to the ethanol production process. A method for treating fermented lignocellulosic biomass to be supplied to a distillation system for production of ethanol is provided. The method includes pre- treating lignocellulosic biomass into pretreated biomass and separating the pre-treated biomass into a liquid component comprising sugars and a solids component comprising cellulose and lignin. The method also includes hydrolysing the solids component of the pre-treated biomass into a hydrolysed biomass comprising sugars and lignin and fermenting the hydrolysed solids component of the pre-treated biomass into a fermentation product comprising ethanol and lignin. The method also includes treating the fermentation product and distilling the treated fermentation product to recover the ethanol. The lignocellulosic biomass comprises cellulose, hemi-cellulose and lignin. A system for pre-treating biomass for the production of ethanol is provided. The system comprises a method for pre-treating biomass. The method comprises supplying biomass to a steaming bin, wherein the biomass is mixed with water, and inputting the steamed biomass to a first pretreatment reactor, wherein the steamed biomass comprises liquids and solids. The method also comprises removing a bulk of liquids from the solids and feeding the solids into a second pretreatment reactor. The method further comprises applying a pressure drop to the solids in the second pretreatment reactor, wherein the pressure drop opens up a structure of the solids, and sending the solids to a fermentation process for ethanol processing. The present invention relates to methods for producing high levels of alcohol during fermentation of plant material, and to the high alcohol beer produced. The method can include fractionating the plant material. The present invention also relates to methods for producing high protein distiller's dried grain from fermentation of plant material, and to the high protein distiller's dried grain produced. The method can include drying a co-product by ring drying, flash drying, or fluid bed drying. The present invention further relates to reduced stack emissions from drying distillation products from the production of ethanol. A system for treating biomass for the production of ethanol is disclosed. A biorefinery for producing a fermentation product from biomass is disclosed. The biorefinery comprises a system for preparing the biomass into prepared biomass and a system for pretreating the biomass into pre-treated biomass. The biorefinery comprises a separator, a first treatment system, a second treatment system, and a fermentation system. A method for producing a fermentation product from biomass is disclosed. A method for producing a fermentation product in a fermentation system from biomass that has been pretreated and separated into a first component and a second component is provided. The method comprises preparing a slurry comprising: supplying the first component to the fermentation system; and providing an ethanologen to the fermentation system. The method also comprises adjusting the pH of the
WO/2012/07 8882A1
2011-12-08
System and methods for collecting biomass
WO/2012/07 8885A2
2011-12-08
System and methods for feedstock quality assessment
slurry to a range of about 4.5 to about 6.5, maintaining the first component and ethanologen in the fermentation system at a temperature of between about 25 and about 37 degrees Celsius, and recovering fermentation product from the fermentation system. The ethanologen is supplied to the fermentation system in a concentration of less than 2 grams of ethanologen on a dry basis per liter of slurry. The biomass comprises lignocellulosic material. The first component comprises pentose, which can comprise xylose. The ethanologen is capable of fermenting xylose into ethanol. A system for collecting biomass for the production of ethanol is disclosed. Also disclosed is a method for collecting biomass. The method comprising: harvesting biomass with a combine, wherein a first portion of the biomass is substantially forced against the ground and a second portion of the biomass passes through the combine and forming bales comprising the second portion of the biomass. According to an aspect, the bales comprise a majority of the second portion of the biomass and a small part of the first portion of the biomass. Assessing quality of feedstock is provided and may be useful for determining quality of feed (such as corn kernels). The assessment determines endogenous enzyme activity within the feedstock, which correlates with total ethanol yields in raw starch hydrolysis (noncooked) systems. In some embodiments, a sample containing flour (ground feedstock) is provided. In some cases, flour is diluted in water and buffered with a phosphate buffered solution. The buffered flour solution is contacted with a molecule, or fluorescent dye, such as fluorescein diacetate and/or difluorofluorescein that is altered by enzymatic (esterase) activity in a detectable fashion. Enzyme activity may be facilitated using an incubator. The detectible alteration may be measured using a fluorometer. In some embodiments, two incubations and fluorescence measurements can be performed. By subtracting the difference between the measured fluorescence, a fluorescence index may be found, which correlates with the endogenous enzyme activity in the feedstock sample.
QTEROS

No Paten Tanggal Pendaftaran (Filling Date) Judul Abstrak
7943363 WO/2010/0146 32A2 WO/2010/0146 32A3 US2012019633 8 WO/2010/1048 96A1 WO/2010/1048 96A9 US2010029861 1
2009-07-28 2009-07-28 2009-07-28 2011-04-14 2010-03-09 2010-03-09 2010-03-09
Methods and compositions for improving the production of products in microorganisms Production of fermentive end products from clostridium sp.
Methods and compositions are provided for improving the production of products, such as fuel products like ethanol, in microorganisms. In particular, methods and compositions are described for improving ethanol production utilizing genes identified in Clostridium phytofermentans.
US2011023068 2 WO/2011/1163 58A2 WO/2011/1163 58A3 WO/2011/0884 22A2 WO/2011/0884 22A3 WO/2012/0832 44A2
2010-03-22 2011-03-18 2011-03-18 2011-01-14 2011-01-14 2011-12-16
Microorganisms with inactivated lactate dehydrogenase gene (LDH) for chemical production Biofuel production using biofilm in fermentation
In one aspect, methods to enhance the production of ethanol and other fermentive end products from a wide variety of feedstocks by Clostridium microorganisms, such as Clostridium phytofermentans are disclosed. A method of improving fermentation performance of Clostridium microorganisms, such as Clostridium phytofermentans through the use of a fed-batch strategy is described, as well as methods of producing fermentive end products, such as alcohols and/or chemicals by fermenting Clostridium microorganisms, such as Clostridium phytofermentans in the presence of fatty acidcontaining compounds and/or at reduced pH. This invention provides systems and methods for the increased production of ethanol and other chemical compounds by recombinant Clostridium species whereby the recombinant species are geneticallyengineered to disrupt lactate dehydrogenase activity and to hydrolyze and ferment carbonaceous biomass and synthesize compounds of commercial value without production of lactic acid. Compositions and methods for improving the efficiency of bio fuels and chemicals, e.g., ethanol, production is described. Increased yield was obtained by facilitating biofilm formation in a bioreactor coupled with a particular microbial species. Compositions and methods for increased processing of solid biomass in a bioreactor are also described.
TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA WO/2011/1339 52A2 WO/2011/1339 52A3 WO/2011/1339 84A2 WO/2011/1339 84A3 WO/2011/1499 56A2 WO/2011/1499 56A3 2011-04-22 2011-04-22 2011-04-25 2011-04-25 New bacterium for production of chemicals and recombinants thereof Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01 Revisi: A Hal 111 dari 136
2011-05-24 2011-05-24
Methods for producing chemical products from fermentation byproducts
Provided is an isolated novel Gram-positive Clostridium bacterium, wherein the bacterium is an anaerobic, cellulolytic and xylanolytic mesophile that produces colonies that are beige pigmented, wherein the bacterium can use carbonaceous biomass as a carbon source and can ferment sugars into ethanol, biofuels, and other chemicals. Also provided are recombinant strains of several Clostridium species wherein sporulation is disrupted. Further provided are methods of using the bacterium and strains to degrade organic material and for use in industrial processes. Disclosed herein are processes in which carbonaceous byproducts from corn-ethanol production or grain processing plants are utilized as feed streams to a novel consolidated bioprocessing (CBP) process. CBP processes described herein are additional processes to initial fermentation step of dry milling process. In CBP processes, microorganisms disclosed herein produce either sugars or ethanol or other chemicals directly from various feed streams that are fed into the CBP process. By employing CBP processes, thus, the total amount of product production is increased. In addition, CBP processes described herein have other benefits: decrease waste; lower production cost; and increase value of animal feeds or other valuable chemical products.
SEKAB
Lisensor Lokasi Bahan Baku EtanolPiloten i Sveringe AB rnskldsvik, Swedia Lignoselulosa; umumnya potongan kayu dan bagas tebu, tetapi bahan mentah lainnya akan diujikan seperti gandum, residu jagung, rumputrumputan, limbah daur ulang, dan lainnya Etanol Pilot: 80 ton/tahun; 300 L/hari (2004) Demo I: 4.500 ton/tahun; 6 ML/tahun (2011_ Demo II : 50.000 ton/tahun; 60 ML/tahun (2011) Komersial: 120.000 ton/tahun; 150 ML/tahun (rencana 2012) Skala pilot beroperasi pada tahun 2004. Skala demo I telah beroperasi sejak 2011. Skala demo II sedang direncanakan dan akan beroperasi pada tahun 2014. Skala komersial sedang direncanakan dan akan beroperasi pada tahun 2016. Perlakuan awal dengan steam dan asam. Dua tahap hidrolisis asam encer dan enzimatik. Fermentasi dilakukan melalui SSF atau SHF tergantung dengan bahan baku dan produk samping yang akan digunakan http://www.sekab.com
Input Produk Tahap Pengembangan
Deskripsi proses ringkas
Website
Gambar A.1.L1.17 Proses Produksi Bioetanol Lignoselulosa SEKAB (1:perlakuan awal, 2: transportasi, 3:steaming, 4:prehidrolisis, 5: hidrolisis ensimatik, 6: fermentasi, 7: netralisasi, 8:detoksifikasi, 9: distilasi, 10:bioraktor )

EP2204433A1
Ethanol-based fuel for compression engines
WO/2009/1022 56A2 WO/2009/1022 56A3 WO/2009/1022 56A9
2009-02-10 2009-02-10 2009-02-10
Method of production of ethanol from two different starting materials
The present invention provides a fuel for a compression engine comprising a major amount of an ethanol liquid and minor amounts of an ignition improver and a viscosity increasing agent, wherein the viscosity of the fuel is 1.6 - 4.5 cSt at 40 C and the ignition improver and the viscosity increasing agent are the same or different. Further, there is provided a use of the fuel, a use of a chemical compound as a viscosity increasing agent and a method a producing an ethanol-based fuel. The present invention provides a method of improving the ethanol yield in production of an ethanolcontaining product from a lignocellulosic biomass and a sugar product containing fermentable sugars derived from a sugar-rich material. The method comprises treatment, involving hydrolysis, of said lignocellulosic biomass in one or more steps to obtain lignocellulose-derived treatment products including fermentable sugars; and fermentation, using a fermenting agent, of a mixture comprising at least part of said lignocellulose-derived treatment products and said fermentable sugars derived from said sugar-rich material to obtain the ethanol-containing product, wherein an amount of said sugar product is mixed with an amount of at least one of the following: (i) lignocellulose-derived material in the treatment; (ii)
EP2270190A1
2009-07-03
Pretreatment of nonwood lignocellulosic material
WO/2010/0715 95A1
2009-12-21
Denaturantcontaining, ethanolbased liquid
WO/2011/0007 12A1
2010-06-17
Pretreatment of nonwood lignocellulosic material
lignocellulose-derived treatment products from the treatment; and (iii) lignocellulose-derived treatment products in the fermentation, such that said fermentable sugars derived from said sugar-rich material and said at least part of said lignocellulosederived treatment products are present in the mixture, and said amounts are controlled such that the fermenting agent is subjected to stress by lignocellulose-derived treatment products to the extent that the ethanol yield is improved. Further, a corresponding method using a starch-rich starting material is provided as well as a corresponding use, composition and system. The present disclosure provides a method for pretreating non-wood lignocellulosic material containing less than 5 % (w/w) starch or sugar in a process for production of ethanol from lignocellulose, comprising the steps of: adding organic acid or organic acidproducing bacteria to the lignocellulosic material; storing the lignocellulosic material in the presence of the organic acid for a period of at least two weeks in an atmosphere of less than 5 % oxygen to obtain organic acid-impregnated material; and heating the organic acid-impregnated material at a temperature of at least 190 C for a period of at least 5 minutes to obtain pre-treated lignocellulosic material, wherein no, or substantially no, inorganic acid or base, including SO2, is added in the method The present invention relates to a method for explicit denaturation of, and/or addition of denaturing capacity to other denaturants in, ethanol-based liquids, i.e. liquids that consist predominantly of ethanol, by addition of an organic chemical, characterized in that the added chemical has the formula (I) Wherein is a single or double bond, is a single or double bond, y is a single or double bond if both and are single bonds, v is a single bond if or is a double bond, and R1 and R2 are independently selected from the group consisting of hydrogen, methyl, ethyl, methoxy and ethoxy. The present disclosure provides a method for pretreating non-wood lignocellulosic material containing less than 5 % (w/w) starch or sugar in a process for production of ethanol from lignocellulose, comprising the steps of: adding organic acid or organic acidproducing bacteria to the lignocellulosic material; storing the lignocellulosic material in the presence of the organic acid for a period of at least two weeks in an atmosphere of less than 5 % oxygen to obtain organic acid-impregnated material; and heating the organic acid-impregnated material at a temperature of at least 160 C to obtain pre-treated lignocellulosic material, wherein no, or substantially no, inorganic acid or base, including SO2, is added in the method.
SUD CHEMIE (SUN LIQUIDS)

Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Sud Chemie (Sun Liquids Process) Munich Lignoselulosa; residu jagung, jerami Etanol Pilot: 2009 Demo: 2012 Komersial: Skala pilot beroperasi pada tahun 2009 di Munich, Skala Demo dibangun di Straubing, diharapkan beroperasi pada tahun 2012 Inovasi: Produksi enzim terintegrasi; Co-fermentasi heksosa dan pentosa http://www.sudchemie.com/scmcms/web/content.jsp?nodeId=7760&lang=en
VERENIUM
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Verenium Jennings, Los Angeles, Amerika Serikat Lignoselulosa; bagas tebu, energy cane, produk kayu, dan switchgrass Etanol selulosa Pilot: 150 ton/tahun; 0,05 juta galon/tahun Demo: 4.200 ton/tahun; 1,4 juta galon/tahun Komersial: 30-60 juta galon/tahun Skala pilot dioperasikan pada tahun 2007. Skala demo dioperasikan pada tahun 2008. Skala komersial dapat diabngun pada lokasi yang sama ataupun di Texas, Lousiana dan Florida. Hidrolisis menggunakan steam dalam kondisi asam lemah, sakarifikasi enzimatik, fermentasi C5 dan C6 secara terpisah, dan distilasi. Residu distilasi dikumpulkan, didehidrasi, dan dibakar dalam boiler untuk integrasi energi dan steam. http://www.verenium.com
Website
Gambar A.1.L1.18 Proses Produksi Bioetanol Lignoselulosa Verenium
WEYLAND AS
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Weyland AS Blomsterdalen, Norwegia Lignoselulosa; asam pekat; coniferous wood sawdust 75 kg/jam Etanol Pilot: 158 ton/tahun; 53.000 galon/tahun (2009) Demo: Komersial: 6-8 juta galon/tahun Skala pilot dibangun pada tahun 2008 dan dioperasikan sejak tahun 2010. Proses asam pekat dan recovery asam pekat http://www.weyland.no
ZEACHEM
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan ZeaChem Boardman, Oregon, Amerika Serikat Lignoselulosa; pohon poplar, gula, potongan kayu Etanol, campuran alkohol, bermacam-macam bahan kimia Pilot: 250.000 galon/tahun (2008) Demo: Komersial: 25-50 juta galon/tahun (Direncanakan 2012) Skala pilot mulai direncanakan pada thaun 2008 serta dikonstruksikan pada tahun 2010. Skala pilot telah selesai dibangun pada awal tahun 2012. Skala komersial direncanakan akan dikonstruksi pada tahun 2012. Proses hybrid. Fraksionasi biomassa, fermentasi asetogenik, asam asetat dikonversi menjadi ester dan dikonversi menjadi etanol dengan direaksikan dengan hidrogen. Residu lignin didapatkan dari fraksionasi dan digasifikasi. http://www.zeachem.com
Website
Gambar A.1.L1.19. Proses Produksi Bioetanol Lignoselulosa ZEACHEM

No Paten Tanggal Pendaftaran (Filling Date) Judul Abstrak
EP1165820 A4 EP2011879 A2 EP2011879 A3
2000-03-10 2000-03-10 2000-03-10
Process for producing ethanol
A process for producing ethanol including a combination of biochemical and synthetic conversions results in high yield ethanol production with concurrent production of high value coproducts. An acetic acid intermediate is produced from carbohydrates, such as corn, using enzymatic milling and fermentation steps, followed by conversion of the
TECH. RESEARCH & DEVELOPMENT DEPARTMENT PROYEK STUDI KELAYAKAN DAN PERENCANAAN ROADMAP DAN STRATEGI PENELITIAN DAN PENGEMBANGAN BIOETANOL BERBAHAN BAKU LIGNOSELULOSA 6509180 US20030077 771 7351559 7682812 US20090023 192 7964379 US20100273 229 US8236534 US20110275 127 EP1813590 A1 2000-12-29 2002-12-04 2005-06-29 2008-03-19 2008-03-19 2010-01-26 2010-01-26 2011-05-05 2011-05-05 2000-03-10 Process for recovering an ester
A process for producing ethanol including a combination of biochemical and synthetic conversions results in high yield ethanol production with concurrent production of high value coproducts. An acetic acid intermediate is produced from carbohydrates, such as com, using enzymatic milling and fermentation steps, followed by conversion of the acetic acid into ethanol using esterification and hydrogenation reactions. Coproducts can include corn oil, and high protein animal feed containing the biomass produced in the fermentation. A process for producing ethanol by the conversion of carbohydrates from a corn dry milling process in which the bottoms fraction from distillation of ethanol in a conventional yeast fermentation is used in a process including a combination of biochemical and synthetic conversions. The process results in high yield ethanol production with concurrent production of high value coproducts. An acetic acid intermediate is produced from bottoms fraction, followed by conversion of the acetic acid into ethanol using esterification and hydrogenation reactions. Coproducts of the process include a high protein content solids fraction produced in the fermentation.
acetic acid into ethanol using esterification and hydrogenation reactions. Coproducts can include corn oil, and high protein animal feed containing the biomass produced in the fermentation.
7074603 7507562 US20060127 999 US7888082
2002-10-09 2006-01-24 2006-01-24 2008-11-26
Process for producing ethanol from corn dry milling
LAMPIRAN 2
Daftar Pengembangan Bioetanol Lignoselulosa di Asia, khususnya Asia Tenggara
INDONESIA
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan LIPI Puspitek Serpong Bekerjasama dengan KOICA Korea Selatan Puspitek Serpong Tandan Kosong Sawit Etanol Pilot: Demo: Komersial: Skala pilot sedang dibangung di puspitek serpon, ker
CHINA
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan China Resources Alcohol Corporation (CRAC) Zhaodong City, Heilongjiang, Cina Lignoselulosa; tangkai dan daun jagung Etanol Pilot: 5.000 ton/tahun; 1,7 juta galon/tahun Demo: Komersial: 1 juta ton/tahun; 330 juta galon/tahun CRAC dibantu oleh SunOpta sejak September 2006 dan mulai beroperasi sejak akhir Oktober 2006. Skala komersial akan dilakukan pada tahun 2012 ini. Perlakuan awal steam explosion didukung oleh paten SunOpta. Enzim yang digunakan dipasok oleh Novozymes. Shengquan Group Jinan City, Shandong, Cina Lignoselulosa; bonggol jagung, selulosa produk samping proses produksi furfural Etanol Pilot: 20.000 ton/tahun Demo: Komersial: 20 juta galon/tahun Fasilitas skala pilot sedang dalam proses konstruksi dan diharapkan telah siap pada Juli 2012. Skala komersial dalam tahap perencanaan dan pengembangan. Pasokan enzim diperoleh dari Novozymes. Shengquan Group menanamkan modal untuk pembuatan enzim khusus ini. Shandong Longlive Biotechnology Company Yucheng, Shandong, Cina Lignoselulosa; bonggol jagung Etanol; CO2 cair Pilot: 10.000 ton/tahun Demo: Komersial: Skala pilot sedang dalam pembangunan. Produksi cellulase on-site, proses sakarifikasi dan fermentasi secara simultan. Pengembangan teknologi bekerja sama dengan Shandong University. Henan Tianguan Fuel Ethanol Co., Ltd. Nanyang City, Henan, Cina Lignoselulosa; jerami 1juta ton/tahun Etanol Pilot: 120.000 ton/tahun (12 plant @ 10.000 ton/tahun) Demo: Komersial:
Website Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan
Konstruksi skala pilot dimulai sejaka akhir tahun 2011 dan direncanakan akan siap pada tahun 2014. Produksi cellulase, direncanakan untuk menggunakan lignin produk samping dari produksi etanol selulosa -
JEPANG
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan JGC Corporation Izumi, Kagoshima, Jepang Lignoselulosa; limbah kayu dan pertanian Etanol Pilot: Demo: Komersial: 8 juta galon/tahun; 3 ML/tahun Skala pilot telah diujikan oleh Arkenol dan bertempat di Orange, CA, Amerika Serikat. Skala komersial mulai direncanakan dan dikonstruksi pada awal tahun 2007. Start-up komersial dioperasikan pada awal tahun 2009. Teknologi hidrolisis asam pekat yang diadaptasi dari Arkenol. Marubeni and Tsukishima Kikai Co., Ltd. Osaka, Jepang Lignoselulosa Etanol Pilot: 1,3 juta galon/tahun Demo: 4 ML/tahun Komersial: Skala pilot mulai beroperasi sejak Agustus 2007. Skala demo dioperasikan sejak tahun 2008. Teknologi produksi diadaptasi dari teknologi Verenium. -
Deskripsi proses ringkas Website Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan
THAILAND
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Marubeni and Tsukishima Kikai Co., Ltd. Saraburi, Thailand Lignoselulosa; bagas tebu, sekam padi Etanol Pilot: Demo: 3 ML/tahun Komersial: Skala pilot telah diujikan melalui plant di Osaka. Pembangunan skala demo di Thailand dimulai pada tahun 2008. Teknologi produksi diadaptasi dari teknologi Verenium. -
MALAYSIA
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Sime Darby Selangor, Malaysia Lignoselulosa; empty fruit bunches (EFB) kelapa sawit. 1,25 metrik ton EFB/hari Etanol Pilot: 35.000-50.000 galon/tahun Demo: Komersial: Skala pilot mulai direncanakan sejak akhir 2009 dan beroperasi sejak tahun 2011. Teknologi produksi diadaptasi dari teknologi Inbicon (perlakuan awal hidrotermal dan hidrolisis enzimatik). Enzim yang digunakan dipasok oleh Novozymes. -
Website
VIETNAM
Lisensor Lokasi Bahan Baku Input Produk Tahap Pengembangan Phuc Yen Company Ho Chi Minh, City, Vietnam Lignoselulosa; limbah padat kota Etanol Pilot: Demo: 1 juta galon/tahun Komersial: Skala demo mulai direncanakan sejak akhir tahun 2008. Perlakuan awal kombinasi asam dan basa lemah. Teknologi diadaptasi oleh Agresti Biofuels. PetroVietnam Central Biofuels Dung Quat, Vietnam Lignoselulosa; bagas tebu Etanol Pilot: 50.000 ton/tahun Demo: Komersial: Skala pilot direncanakan sejak tahun 2011. Teknologi diadaptasi dari teknologi Chempolis -

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M.T.A. Penia Kresnowati

Sr. Mgr. TRD

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RIWAYAT PERUBAHAN DOKUMEN

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2.4. Produksi Bioetanol Lignoselulosa ..................................................................... 14

1.3. Ruang Lingkup

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Gambar A.1.1 Komponen biomassa lignoselulosa

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Rantai Kristalinitas Berubah menjadi amorf di air Ketercernaan (digestibility)

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glukosa xilosa gugus asetil

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Gambar A.1.4 Struktur lignin

2.1.4. Jenis dan Tipikal Komposisi Biomassa Lignoselulosa

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Kajian Paten dan Lisensi Doc. No: 1101-PR-001-A11-01

Revisi: A Hal 11 dari 136

32-47 19-27 65 (total karbohidrat)

*perhitungan komposisi yang disajikan menggunakan basis kering

2.2. Proses Produksi Bioetanol Lignoselulosa

Proses konversi termal (thermochemical conversion)

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Skema A.1.1 Skema jalur-jalur proses konversi produksi bioetanol lignoselulosa

Jalur Proses Jalur 1: Hidrolisis enzimatik-fermentasi gula

Jalur 2: Hidrolisis Asam-fermentasi gula

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Tetes gula (molase)

Fermentasi Heksosa Fermentasi Heksosa

Fermentasi Heksosa Fermentasi Pentosa

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2.4. Produksi Bioetanol Lignoselulosa

komprehensif tiap tahap produksi bioetanol beserta status perkembangannya.

2.4.1. Perlakuan Awal (Pretreatment)

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Serpihan kayu, straw

Konsentrasi : 0.05-5% o T : 160-220 C t : 1-60 menit P : tekanan uap jenuh

(Limayem dan Ricke, 2012; Mosier, dkk., 2005)

Fiber jagung, straw

pH : 4-7 T : 160-230 C t : 12-60 menit P : hingga 5 Mpa

(Limayen, 2012)(Mosier, 2005) (Hendrik, 2009) Kumar, 2011)

Hidrolisis Alkalin (Lime)

1+, 3#, 4+, 5+

(Limayen, 2012)(Mosier, 2005)(Kumar, 2009)(Kumar, 2011) (Limayen, 2012)