Jurnal Integrasi Proses Vol. 10, No.

1 (Juni 2021) 21 - 26

JURNAL INTEGRASI PROSES

Website: http://jurnal.untirta.ac.id/index.php/jip

Submitted : 22 Februari 2021 Revised : 9 April 2021 Accepted : 16 Mei 2021

PENGARUH SUHU REAKSI DAN KONSENTRASI KATALISATOR ZEOLIT ALAM BAYAH

TERMODIFIKASI PADA REAKSI ESTERIFIKASI

Nuryoto1*, Wijoyono Setionegoro1, dan Muhammad Ridwan Mubarok1

1Jurusan Teknik Kimia, Fakultas Teknik, Universitas Sultan Ageng Tirtayasa

Banten, Indonesia
*Email: nuryoto@untirta.ac.id

Abstrak

Suhu reaksi dan konsentrasi katalisator merupakan faktor yang mempengaruhi kecepatan suatu laju reaksi kimia.
Peningkatan suhu reaksi akan berdampak pada peningkatan tumbukan pada molekul zat yang bereaksi,
sementara peningkatan konsentrasi katalisator padat akan meningkatan jumlah sisi aktif yang akan berinteraksi
dengan reaktan yang terlibat di dalam sistem bereaksi tersebut. Penelitian ini dilakukan dengan tujuan untuk
mengetahui sejauh mana dan seberapa efektif pengaruh suhu dan konsentrasi katalisor padat berupa zeolit alam
bayah termodifikasi pada reaksi esterifikasi etanol dan asam asetat. Observasi dilakukan dengan menggunakan
reaktor batch dengan waktu reaksi selama 60 menit. Hasil observasi menunjukan bahwa konversi reaktan
berbasis asam asetat tertinggi diperoleh sebesar 23,41 %, yang dicapai pada suhu reaksi 70°C dan konsentrasi
zeolit alam bayah 10 % massa asam asetat.

Kata kunci: Esterifikasi, Suhu, Reaktor, Asam Asetat, Zeolit

Abstract

The reaction temperature and catalyst are the factors affect the speed of a chemical reaction rate. Increasing the
reaction temperature will have an impact on increasing collisions on reacting molecules, while increasing the
concentration of solid catalysts will increase the number of active sites that will interact with the reactants
involved in the reacting system. The purpose of this research was knowing the extent and how effective the effect
of temperature and solid catalyst concentration in the form of modified bayah natural zeolite in the esterification
reaction of ethanol and acetic acid. Observations were made using a batch reactor for 60 minutes reaction times.
The results showed that the highest conversion of acetic acid-based reactants was 23.41 %, which was achieved
at reaction temperature of 70°C and bayah natural zeolite concentration of 10 % by mass of acetid acid.

Keywords: Esterification, Temperature, Reactor, Acetic Acid, Zeolite

1. PENDAHULUAN katalisator. Suhu reaksi akan mempengaruhi laju reaksi

Esterifikasi adalah reaksi antara asam karboksilat
dengan alkohol dengan produk utama berupa ester,
dan seringkali berjalan lambat. Sintesis etil asetat tanpa
kehadiran katalis pada pembuatan etil asetat hanya
menghasilkan konversi reaktan sebesar 12,15 %
selama 60 menit (Nuryoto dkk., 2020). Untuk
meningkatkan kecepatan reaksi esterifikasi diperlukan
kolaborasi antara faktor-faktor yang berpengaruh pada
reaksi kimia seperti suhu reaksi dan konsentrasi
esterifikasi yang terjadi, yang mana jika mengacu pada
persamaan Arrhenius, besarnya peningkatan laju
reaksi esterifikasi yang dihasilkan akan berbanding
secara eksponesial satu per satuan suhu reaksi.
Sementara itu, konsentrasi katalisator yang diberikan
pada sistem reaksi pada jumlah tertentu, akan
memaksimalkan interaksi antara reaktan-sisi aktif
katalisator, sehingga reaksi akan berjalan lebih cepat
serta hasil reaksi yang dihasilkan akan lebih maksimal.

21
 Jurnal Integrasi Proses Vol. 10, No. 1 (Juni 2021) 21 - 26
Percobaan yang dilakukan oleh Khayoon & Hameed
(2013), Reddy dkk. (2011), dan Mallesham dkk. (2014)
menunjukan fenomena tersebut. Pada percobaan
Kayoon & Hameed (2013), yang dilakukan pada suhu
reaksi pada rentang suhu 25 sampai 65°C, mampu
menghasilkan konversi reaktan sebesar 100% yang
diperoleh pada rentang suhu 45 sampai 65°C.
Sementara itu pada percobaan uji konsentrasi
katalisator, peningkatan konsentrasi katalisator pada
kajian reaksi ketalisasi gliserol yang dilakukan dengan
katalisator zirconia pada konsentrasi katalisator 1
sampai 5 % massa gliserol (Reddy dkk., 2011) dan
konsentrasi katalisator 1 sampai 7 % massa gliserol
(Mallesham dkk., 2014), menunjukkan bahwa seiring
dengan meningkatnya konsentrasi katalisator yang
diberikan ke sistem reaksi diikuti dengan peningkatan
konversi gliserol yang dihasilkan.
Penelitian terkait reaksi esterifikasi antara asam
asetat dan etanol sebenarnya telah banyak dilakukan
observasi dengan capaian yang bervariasi, dengan
konversi reaktan berkisar antara 50 sampai 90 %-an
(Guzman Barrera dkk., 2018; Inui dkk., 2002).
Katalisator yang digunakan juga bermacam-macam ada
yang menggunakan katalis padat seperti berbasis
tembaga (Santacesria dkk., 2012; Inui dkk., 2002), dan
resin penukar ion (Guzman Barrera dkk., 2018;
Bhandare, 2018), sedangkan untuk katalis cair seperti
asam sulfat (Ahmed Zeki dkk., 2010) dan asam klorida
(Nst & Sutri (2015)). Penggunaan zeolit alam bayah
sebagai katalis pada reaksi antara asam asetat dan
etanol sebenarnya juga sudah pernah dilakukan oleh
Nuryoto dkk. (2016) dengan perbandingan pereaksi 8
mol asam asetat/mol etanol dan Nuryoto dkk. (2020)
dengan perbandingan pereaksi 3 mol etanol/mol asam
asetat. Perbedaan dengan penelitian ini dengan
sebelumnya yaitu pada Nuryoto dkk. (2016) terletak
pada perbandingan pereaksinya yaitu 3 mol
etanol/mol asam asetat, sedangkan pada Nuryoto dkk.
(2020) berbeda variasi pengamatan. Pada penelitian ini
berfokus pada pengamatan terhadap dampak suhu
reaksi dan konsentrasi katalisator, sementara pada
Nuryoto dkk. (2020) berfokus kepada ukuran katalis
Gambar 1. Mekanisme reaksi esterifikasi antara etanol dan asam asetat
dan kecepatan pengadukan. Dengan dilakukan kajian
lebih jauh terhadap faktor-faktor yang berpengaruh
pada reaksi kimia (ukuran katalis, kecepatan
pengadukan, suhu reaksi dan konsentrasi katalisator),
maka diharapkan akan mendapatkan informasi yang
lebih detail terkait layak atau tidaknya zeolit alam
bayah untuk dikembangkan lebih lanjut jika digunakan
sebagai katalisator pada reaksi esterifikasi antara asam
asetat dan etanol guna menggantikan katalisator
komersial yang sering digunakan, seperti resin
penukar ion. Zeolit alam bayah sendiri tergolong zeolit
jenis mordenit, walaupun tidak murni karena
didalamnya juga mengandung jenis klinotilolit
(Suminta & Las, 2006), dengan komposisi mordenit
59,26 % dan klinoptilolit 40,74 %. Zeolit alam pada
umumnya, termasuk zeolit alam bayah mempunyai
harga yang murah, tetapi perlu dilakukan aktivasi
sebelum digunakan (Nuryoto & Hartono, 2018), karena
banyak mengandung pengotor dan ukuran pori yang
relatif kecil, sehingga ketika langsung digunakan
sebagai katalisator tidak akan berdampak pada laju
reaksi pada sistem reaksi.
Secara teoritik mekanisme reaksi esterifikasi
antara asam asetat dan etanol dapat dilihat pada
Gambar 1. Berdasarkan Gambar 1, asam karboksilat
berupa asam asetat diprotonasi oleh katalis asam lalu
terbentuk karbonil, selanjutnya karbonil diserang oleh
alkohol berupa etanol, dan terbentuk ester berupa etil
asetat sebagai produk utama serta air sebagai produk
sampingnya. Etil asetat sendiri merupakan suatu
pelarut yang banyak digunakan dalam suatu reaksi
kimia (Vergaelen dkk., 2020) dan pelarut makanan,
obat-obatan dan lainnya (Newseed, 2015). Tujuan
penelitian ini dilakukan adalah untuk mengetahui
sejauh mana dan seberapa efektif pengaruh suhu dan
konsentrasi katalisor padat berupa zeolit alam bayah
pada reaksi esterifikasi etanol dan asam asetat. Pada
penelitian ini dilakukan uji validasi model matematika
menggunakan model Pseudohomogen orde 2 searah
yang telah digunakan sebelumnya oleh Nuryoto dkk.
(2020), dengan hasil curve fitting yang baik antara data
dan hitungan. Pengujian model tersebut bermaksud
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Jurnal Pangan dan Agroindustri Vol. 3 No 1 p.271-280, Januari 2015

PENGARUH PENAMBAHAN ANTIINVERSI DAN SUHU IMBIBISI

TERHADAP TINGKAT KESEGARAN NIRA TEBU

Effect of Concentration of Anti-inversion and Temperature of The Water

Imbibition to The Freshness of Sugarcane

Ellen Demi Winata1*, Wahono Hadi Susanto1

1) Jurusan Teknologi Hasil Pertanian, FTP Universitas Brawijaya Malang

Jl. Veteran, Malang 65145
*Penulis Korespondensi, email: ellendemi@yahoo.com

ABSTRAK

Kehilangan sukrosa selama proses pengolahan gula diakibatkan oleh reaksi inversi.
Penghambatan reaksi inversi diperlukan supaya laju hidrolisa sukrosa oleh enzim dapat
diturunkan. Hal ini dilakukan dengan memberikan suhu ekstrim dan penambahan antiinversi.
Tujuannya untuk mengetahui pengaruh konsentrasi antiinversidan suhuimbibisi terhadap
tingkat kesegaran nira tebu. Rancangan percobaan menggunakan RAK faktorial. Faktor I
adalah konsentrasi antiinversi yang dilarutkan dalam air imbibisi terdiri dari 3 level (400 ppm,
500 ppm, 600 ppm) dan faktor II adalahsuhu air imbibisi yang terdiri dari 3 level (700C, 800C,
900C). Analisa yang dilakukan yaitu sukrosa, gula invert, pH, TPC, rendemen, dankadar nira
tebu. Data dianalisa secara statistik dengan menggunakan analisa ragam (ANOVA),Hasil
penelitian menunjukkan bahwa adanya pengaruhnyata antara konsentrasi antiinversi dan
suhu imbibisi pada kadar sukrosa, kadar gula invert, pH, rendemen dan jumlah mikroba.
Suhu imbibisi memberikan pengaruh nyata tterhadap kadar nira tebu (KNT). Hasil
penghambatan efektifyang dicapai yaitu 500 ppm dan suhu 800C.

Kata kunci: Antiinversi, Imbibisi,Inversi

ABSTRACT

The problem that often appears in the factory is the inversion process. Inhibition of
inversion reaction can be done by providing temperature and giving anti-inversion. This
study aims to determine the effect of concentration of anti-inversion and temperature of the
water imbibition to the freshness of sugarcane. The experimental design that used was a two
factorial RAK. The first factor is the concentration of the anti-inversion that dissolved in water
imbibition consists of 3 levels (400 ppm, 500 ppm, 600 ppm)and the second factor is the
temperature of the water imbibition which consists of 3 levels (700C, 800C, 900C). Analysis
of the observation consist of pH analysis, invert sugar, sucrose levels, TPC, sucrose content,
and the sap content of the cane. The data obtained were analyzed statistically using
ANOVA.The results showed that the real influence appears on concentration and
temperature of imbibition to level of sucrose, invert sugar, pH, yield and number of microbes.
Imbibition temperature levels give the real influence to sugar cane (KNT). The best results is
500 ppm and 800C.

Keywords: Anti-inversion, Imbibition, Inversion

PENDAHULUAN

Kondisi industri gula di Indonesia dewasa ini semakin memprihatinkan. Hal tersebut
dapat terlihat dari produksi gula nasional yang semakin menurun dari tahun ke tahun.
Sementara kebutuhan konsumsi gula dalam negeri semakin meningkat karena jumlah
penduduk Indonesia semakin bertambah.
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Kebutuhan gula nasional Indonesia sebesar 3.2 juta ton per tahunnya sementara
produksi dalam negeri sekitar 2 juta ton [1]. Hal ini merupakan suatu kemunduran bagi
bangsa Indonesia karena pada tahun 1975-1995, produksi gula nasional Indonesia bisa
mencapai sekitar 2.5 juta ton. Kondisi tersebut menunjukkan bahwa jumlah produksi gula
tebu harus ditingkatkan kembali dengan memperbaiki faktor-faktor yang terkait dalam
produksi gula tebu yaitu peningkatan produksi di bagian on farm dan off farm.
Salah satu permasalahan yang menyebabkan rendemen gula di Indonesia rendah
adalah reaksi inversi. Kehilangan gula (sukrosa) menjadi gula-gula sederhana (invert),
seperti glukosa dan fruktosa atau senyawa turunan lainnya dapat mengganggu proses
kristalisasi, sehingga dapat menurunkan rendemen gula sukrosa [2]. Permasalahan ini dapat
diatasi dengan pemilihan kondisi proses pengolahan yang tepat dan dapat juga
ditambahkan pengawet yang bersifat inhibitor enzim atau antimikrobial ke dalam nira tebu
[3]
Beberapa penelitian yang telah dilakukan, lebih banyak membahas mengenai
penghambatan degradasi sukrosa dengan menggunakan akar kawao (Milletia sericea) [2] ;
menggunakan tembaga sulfat (CuSO4) [4] ; serta penyemprotan buffer sucrose pada ujung
batang tebu [5]. Kekurangan dari penelitian terdahulu adalah tidak adanya pembahasan
mengenai penambahan antiinversi yang dilarutkan dalam air imbibisi untuk menghambat
hidrolisa sukrosa. Penelitian ini dilakukan penghambatan aktivitas invertase sehingga
hidrolisa sukrosa dapat dikontrol dengan memberikan kondisi suhu imbibisi ekstrim dan
penambahan inhibitor bagi reaksi hidrolisis oleh invertase. Bahan inhibitor yang aman untuk
nira tebu adalah antiinversi berupa karboksil benzena dan pottasium sorbat.

BAHAN DAN METODE

Bahan
Bahan yang digunakan dalam penelitian ini adalah tebu varietas BL berumur 12 bulan
yang diperoleh dari Kebun Glanggang Pakisaji Malang. Bahan-bahan untuk analisis kimia
meliputi Antiinversi (merk Bufferos) yang didapatkan dari Kantor Pusat Buferos Malang,
dinitrosalisilat, glukosa anhidrat, agar PCA, aquades, Pb-asetat, Alumunium Foil dan NaOH
0,1 N.

Alat
Alat yang digunakan dalam penelitian meliputi Juice Cane Extraction, timbangan,
termometer, spektrofotometer (panjang gelombang 330-1000 nm, 2D plus, merk Labomed,
Inc), timbangan analitik (ketelitian 0.10 mg), pHmeter (merk Hanna), laminer air flow, colony
counter, autoklaf, lemari pendingin, labu ukur (volume 25, 50, 100, dan 250 ml), erlenmeyer
(volume 50, 100, dan 250 ml), beaker glass 500 ml, gelas ukur 100 ml, botol semprot 500
ml, pipet ukur 1 ml, pipet ukur 10 ml, pipet tetes, mikropipet, mikrotip, spatula, tabung reaksi,
kompor, bunsen, rak tabung reaksi, dan cawan petri.

Tahapan Penelitian
Pelaksanaan penelitian ini dilakukan dua tahap yaitu penelitian pendahuluan dan
penelitian lanjutan. Penelitian pendahuluan dilakukan untuk menentukan variasi perlakuan
konsentrasi antiinversi. Penelitian lanjutan dilakukan untuk mengetahui pengaruh antara
suhu air imbibisi dengan konsentrasi antiinversi. Penelitian lanjutan dilakukan dengan
langkah sebagai berikut
1. Pengambilan sampel di lahan perkebunan tebu.
2. Pemilihan tebu secara acak setelah di tebang.
3. Penyiapan larutan antiinversi yang telah ditentukan tiap konsentrasinya.
4. Penyimpanan tebu dalam kondisi terbuka selama 12 jam
5. Lalu tebu diekstraksi berdasarkan perlakuan
6. Ditambahkan antiinversi yang dilarutkan dalam air imbibisi pada proses penggilingan
terakhir lalu diambil niranya dan dilakukan analisa untuk masing-masing perlakuan.

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berfungsi menginaktivasi enzim seperti invertase yang aktivitasnya terhenti dengan

pemanasan selama 2 menit pada suhu 90° C [7].

2. Kadar Sukrosa
Kadar sukrosa merupakan parameter yang berkaitan langsung pada pengujian
kerusakan dalam nira tebu. Sukrosa merupakan faktor penentu jumlah rendemen akhir
dalam proses pengolahan gula kristal [8]. Hasil pengukuran kadar sukrosa pada penelitian
ini bervariasi antara 19 % - 21 %. Selama 24 jam, penambahan antiinversi dan suhu imbibisi
memberikan pengaruh nyata terhadap kadar sukrosa. Gambar 2 menunjukkan pengaruh
penambahan konsentrasi antiinversi dan suhu imbibisi terhadap kadar sukrosa selama 24
jam.

Gambar 2. Kadar Sukrosa Selama 24 Jam

Penurunan terendah diperoleh pada nira kontrol. Semakin lama maka penurunan
sukrosa semakin cepat. Sedangkan perlakuan konsentrasi antiinversi 400 ppm; 700C kadar
sukrosa cenderung menurun lebih landai. Berbeda dengan konsentrasi 500 ppm dan 600
ppm, keduanya belum memberikan dampak penghambatan inversi yang maksimal. Hasil
penelitian menunjukkan bahwa keduanya mampu menghambat terjadinya inversi yang
ditandai dengan sedikitnya penurunan kadar sukrosa selama 24 jam. Berdasarkan analisa
keragaman penambahan konsentrasi antiinversi 500 ppm dan 600 ppm tidak berbeda nyata.
Suhu imbibisi 800C dan 900C juga tidak berbeda nyata. Sehingga dapat dikatakan
konsentrasi 500 ppm dan suhu 800C sudah efektif dalam penghambat inversi.
Penurunan sukrosa disebabkan oleh terjadinya inversi yaitu adanya enzim invertase
yang memecah sukrossa menjadi gula-gula invert. Antiinversi mampu menginaktifkan enzim
yang sudah terbentuk dengan cara mengikat gugus -SH pada enzim invertase dan membuat
enzim menjadi inaktif. Sehingga sukrosa tidak dapat dipecah karena keterbatasan enzim
sehingga metabolisme mikroba akan terhambat karena nutrisi yang dibutuhkan untuk
metabolismenya tidak terpenuhi [9].

3. Kadar Gula Invert

Gula invert mempunyai gugus aldehid atau keton bebas yang dalam suasana basa
dapat mereduksi logam-logam [10]. Selain itu gula invert juga bisa mengalami oksidasi
menjadi asam-asam (asam aldonat, asam uronat, dan asam ketonat). Keberadaan gula
invert tersebut menandakan adanya hidrolisa sukrosa yang tidak dikehendaki dalam nira
tebu. Reaksi inversi merupakan reaksi hidrolisis irreversible yang dapat dipercepat oleh
suhu tinggi dan optimal pada suhu 550C. Reaksinya adalah indotermik dengan energi
aktivasi 25.90 kilokalori per mol pada 20°C. Reaksi ini dapat juga melalui katalisis biokimia
dengan beberapa enzim, khususnya invertase [11][12]. Rerata produksi gula invert dalam
penelitian ini berkisar 0.3% - 0.7%. Sedangkan kadar gula invert nira tebu berkisar 0.3% –
3% [13]. Hal ini berarti jumlah gula invert cukup rendah karena adanya perlakuan
penghambatan dengan menggunakan antiinversi. Pengolahan nira tebu menjadi gula tidak

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Jurnal Pangan dan Agroindustri Vol. 3 No 1 p.271-280, Januari 2015

menghendaki adanya gula invert karena merupakan indikasi hidrolisa sukrosa yang dapat
mengganggu proses kristalisasi sukrosa.
Kadar gula invert di awal inkubasi dalam nira kontrol adalah 0,38 %. Jam ke 24 kadar
gula invert mencapai jumlah yang maksimal pada masing-masing perlakuan yaitu 0.74 %
pada nira kontrol. Sedangkan pada sampel yang lain menunjukkan adanya penghambatan
terbentuknya gula invert. Peningkatan terbentuknya gula invert yang paling landai terdapat
pada sampel 600 ppm; 900C. Sedangkan peningkatan terbentuknya gula invert yang paling
curam terdapat pada sampel kontrol.

Gambar 3. Grafik Peningkatan Kadar Gula Invert Selama 24 jam

Gambar 3 menunjukkan peningkatan kadar gula invert secara terus menerus. Selang
waktu antara jam ke 0 – 10 terjadi peningkatan kadar gula invert yang lebih landai daripada
peningkatan kadar gula invert antara jam ke 10 – 24 [3]. Peningkatan kadar gula invert yang
landai pada jam ke 0 hingga jam ke 10 menggambarkan bahwa reaksi inversi masih berjalan
lambat. Namun tanpa penambahan antiinversi, nira tebu kurang dapat dipertahankan
kualitasnya karena tidak ada penghambatan terhadap reaksi inversi sehingga kadar gula
invert yang terbentuk terus meningkat.
Peningkatan kadar gula invert yang sedikit lebih curam antara jam ke 12 hingga jam
ke 24 menunjukkan bahwa antiinversi mulai berkurang jumlahnya sehingga penghambatan
reaksi inversi berikutnya mulai kurang maksimal. Seiring dengan peningkatan jumlah
mikroba yang mampu bertahan hidup maka pembentukan sel yang baru semakin sedikit dan
kemampuan memecah substrat menjadi sumber karbon akan semakin tinggi. Ketersediaan
sumber karbon yang terbatas akan menghambat perkembangbiakan mikroba. Hal tersebut
sesuai dengan pernyataan [14] yang menyebutkan bahwa potassium sorbet pada antiinversi
dapat menurunkan tingkat penggunaan karbon dari beberapa substrat termasuk glukosa.

4. Nilai pH
Penurunan nilai pH berarti menunjukkan peningkatan ion H+ yang dihasilkan dari
peningkatan kadar asam dalam larutan nira. Peningkatan kadar asam dalam larutan
menunjukan adanya aktivitas degradasi lanjut sukrosa baik yang disebabkan oleh aktivitas
mikroorganisme maupun enzim [3]. Antiinversi mengandung komponen kimia yang bersifat
sebagai antimikroba, yaitu karboksil benzena yang bekerja dengan cara merusak dinding
sel. Sehingga dinding sel tidak dapat menyaring zat-zat yang keluar masuk. Efek
antimikrobial karboksil benzena dalam medianya disebabkan karena bentuk asam benzoat
yang tidak terdisosiasi terdifusi secara bebas melalui membran sel. Lalu terionisasi dalam
sel menghasilkan ion hidrogen yang akan menambah keasaman protoplasma sehingga
menyebabkan terjadinya denaturasi protein enzim. Sehingga dapat mengakibatkan
terganggunya proses metabolisme mikroba dan mikroba akan mati [15]. Berikut grafik
penurunan pH nira tebu selama 24 jam yang bisa dilihat pada Gambar 4.
Gambar 4 menunjukkan bahwa semakin lama penyimpanan, nilai pH semakin turun.
Hal ini disebabkan karena adanya mikroorganisme yang mampu menghasilkan asam-asam
organik. Penurunan pH dalam nira yang lebih curam menunjukan bahwa aktivitas
mikroorganisme yang mengkontaminasi nira tersebut lebih tinggi daripada yang
mengkontaminasi nira tebu dengan penambahan antiinversi. Hal ini disebabkan karena
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 Chemical Engineering Journal 156 (2010) 395–403

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Dilute acid hydrolysis of lignocellulosic biomass

P. Lenihan, A. Orozco, E. O’Neill, M.N.M. Ahmad, D.W. Rooney, G.M. Walker ∗
School of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast BT9 5AG, Northern Ireland, UK

a r t i c l e i n f o a b s t r a c t

Article history: The overall aim of this work was to establish the optimum conditions for acid hydrolysis of hemicellulosic
Received 26 February 2009 biomass in the form of potato peel. The hydrolysis reaction was undertaken in a 1l high pressure pilot
Received in revised form 22 October 2009 batch reactor using dilute phosphoric acid. Analysis of the decomposition rate of hemicellulosic biomass
Accepted 30 October 2009
(namely Cellulose, Hemicellulose and lignin) was undertaken using HPLC of the reaction products namely,
5 and 6 carbon sugars. Process parameters investigated included, reactor temperature (from 135 ◦ C to
Keywords:
200 ◦ C) and acid concentration (from 2.5% (w/w) to 10% (w/w)). Analysis of the reactor products indicated
Acid hydrolysis
that high conversion of cellulose to glucose was apparent although arabinose conversion was quite low
Cellulosic biomass
Saccharification
due to thermally un-stability. However, an overall sugar yield is 82.5% was achieved under optimum con-
Phosphoric acid ditions. This optimum yield was obtained at 135 ◦ C and 10% (w/w) acid concentration. 55.2 g sugar/100 g
dry potato peel is produced after a time of 8 min. The work indicates that the use of potato peel may be a
feasible option as a feed material for the production of sugars for biofuel synthesis, due its low cost and
high sugar yields.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
1.1. Dilute acid hydrolysis
Dilute or concentrated acids break down the cellulose and hemi-
cellulose polymers in lignocellulosic biomass to form individual
sugar molecules which can be fermented into ethanol [1]. It is
important to note that hemicellulose is more easily hydrolysed than
cellulose [2].
The advantages of acid hydrolysis are that the acid can penetrate
lignin without pretreatment, the rate of acid hydrolysis is faster
than enzyme hydrolysis, but glucose also degrades rapidly under
acidic conditions [3]. The acid hydrolysis process employs usually
sulphuric acid and hydrochloric acid at concentrations of 1–10%
using a moderate temperature (in the range of 100–150 ◦ C) [4].
But in these relatively moderate operational conditions, it proves
less effective in the formation of hexoses [5]. This is mainly due
to the decomposition of the monosaccharides into less desirable
compounds during hydrolysis. These compounds include furfural,
a product of dehydration of pentoses and hydroxymethylfurfural-
HMF, a product of the dehydration of hexoses. These compounds
along with acetic acid which forms during initial decomposition of
the hemicelluloses, as a result of hydrolysis of acetyl groups linked
to the sugar, inhibit the later fermentation, leading to reduced
ethanol yields [6]. The production of these inhibitors increases
∗ Corresponding author. Tel.: +44 0 2890 974253; fax: +44 0 2890 974627.
E-mail address: g.walker@qub.ac.uk (G.M. Walker).
when hydrolysis takes place at higher temperatures and higher acid
concentrations [7].
Sulphuric and hydrochloric acids are the most commonly used
catalysts for hydrolysis of lignocellulosic residues. In contrast to
these acids, phosphoric acid can be more advantageous for hydrol-
ysis. Phosphoric acid is less aggressive than other acids which
give solutions with higher concentrations of growth inhibitors of
microorganisms such as furfural or acetic acid [6].
Dilute phosphoric acid, on hydrolysates from sugarcane bagasse,
has shown fermentable sugars with 21.4 g of sugar L−1 with less
than 4 g L−1 of inhibitors at operating conditions of 6% acid con-
centration at 100 ◦ C for 300 min [8]. Similarly on hydrolysates
from olive tree pruning, have shown hemicelluloses conversion
rates of 77% with glucose and reducing sugar concentrations being
observed as 89% of the hemicellulosic sugars contained in the raw
material at conditions of 8% acid concentration at 90 ◦ C for 240 min
[6].
These hydrolysates obtained after the acid hydrolysis need to
be processed if they are going to be used as fermentation media.
In general the following operations are needed (in this sequence):
concentration, detoxification, neutralisation and supplementation
with nutrients. This process is illustrated in Fig. 1. The concentra-
tion of hydrolysates by evaporation is usual to increase the sugar
concentration. In this operation, besides water, small amounts of
growth inhibitors such as acetic acid, furfural and HMF are removed
[8]. A detoxification operation by adsorption on active carbon in
the form of charcoal can remove the growth inhibitors cited. In this
operation, phenolic compounds proceeding from lignin can also be
removed [8]. In the operation of neutralisation, it is usual to add

1385-8947/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2009.10.061
396 P. Lenihan et al. / Chemical Engineering Journal 156 (2010) 395–403

Fig. 1. General operations required after hydrolysis prior to fermentation.

chemicals that neutralise the acids of the hydrolysates, forming where K1 is the rate of conversion of glucan to glucose and K2 is the
salts [9]. rate of decomposition of glucose. Both have units of the reciprocal of
These salts have low solubility and are normally removed by time (min−1 ). Both reactions were considered to be first order and
filtration. For example, hydrolysates containing sulphuric acid are irreversible. Saeman’s model could also be applied to the hydrolysis
neutralised with calcium carbonate, forming calcium sulphate [5]. of hemicellulosic fraction. Therefore this reaction was generalised
Finally, the processed hydrolysates are supplemented with several to:
nutrients to be a favorable fermentation medium. These nutrients K1 K2
contribute the nitrogen and micronutrients needed for the growth Polymer−→Monomer−→decomposition products (2)
of the microorganisms [10].
where the polymer can be glucose, xylose or araban.
The interest in the use of H3 PO4 is that after neutralisation of
From this reaction model and solving differential equations,
hydrolysates with NaOH, the salt formed is sodium phosphate. This
monomer concentration (M) as a function of time (t) can be rep-
salt can remain in the hydrolysates because it is used as nutri-
resented by [15]:
ent by microorganisms. Therefore, an operation of filtration is not
needed with the consequent advantage: improve the economics of  k P 
(e−k1 t − e−k2 t ) + M0 e−k2 t
1 0
the process (avoid the filtration to remove the salts and decrease M= (3)
k2 − k1
the amount of nutrient needed for fermentation) and is friendly
with the environment (the salt formed is not a waste) [5]. where M is the monomer concentration, g L−1 ; P the polymer con-
centration, g L−1 ; M0 is the initial monomer concentration, g L−1 .
Assuming that the initial monomer concentration to be approx-
imately equal to 0, then Eq. (1) can be simplified to [15]:
1.2. Kinetics of acid hydrolysis of cellulose
 k P 
(e−k1 t − e−k2 t )
1 0
The hydrolysis reactions using dilute acid are very complex, M= (4)
k2 − k1
mainly because the substrate is in a solid phase and the catalyst in a
liquid phase. The reaction rate of hydrolysis depends on a number of An alternative model called the two fraction model is often used
variables, such as: temperature, acid concentration, time, substrate to describe the reaction kinetics and is tested against the Saeman’s
concentration and substrate composition. The practical objective of model to provide accuracy. This model considers that only a fraction
studying the kinetic model is, on a first level, to optimise the process of the polymer reacts. This is called the fast fraction, and the fraction
and, on a second level, to obtain equations useful for economi- that does not react or reacts slowly is called the slow fraction. The
cal estimations [8]. The models usually associated with dilute acid ratio between them is the parameter ˛. In the case that the slow
hydrolysis were first proposed by Saeman [11], for the hydrolysis of fraction does not react, the following equation is used [8]:
Douglas fir wood using sulphuric acid. The models proposed in the  k P 
(e−k1 t − e−k2 t )
1 0
literature use irreversible pseudo-homogeneous first-order reac- M=˛ (5)
k2 − k1
tions [12–14]. They proposed that hydrolysis of cellulose involves
the polymer glucan of cellulose being degraded to monomer glu- When determining kinetic parameters it is more thorough to apply
cose which is subsequently converted to decomposition products. both models to see if there is deviation of results. If both results
This is represented below: returned do not match then it can be concluded that the two frac-
tion model is more accurate. If on the other hand the kinetics reveal
K1 K2 similar results, it can be concluded that the reaction is 100% fast
glucan(s)−→glucose−→decomposition products (1) fraction with ˛ = 1 g g−1 .
 P. Lenihan et al. / Chemical Engineering Journal 156 (2010) 395–403
Fig. 3. The effect of Acid concentration on total sugar yield at 135 ◦ C. The “total
sugar” is the sum of the individual sugars determined by HPLC.
3.2. The effect of acid concentration on total sugar yield
It is evident from observing Fig. 3 that increasing acid concen-
tration will dramatically increase the reaction rate at a temperature
of 135 ◦ C. At 2.5% (w/w) phosphoric acid concentration the rate of
sugar production is low, and over the course of the reaction only
increases slightly. The maximum yield obtained is a modest 8.01 g
per 100 g of dry potato peel. However, it must be taken into account
that, by the end of the reaction time the sugar yield is still steadily
rising which indicates that the total possible total yield at these
conditions will be at a higher level. One advantage of using less
aggressive conditions is the negligible rate of sugar decomposition
which can be seen.
As the acid concentration starts to rise the reactions rates begin
to increase rapidly. A noticeable shift in the sugar production rate is
evident when the acid concentration is increased from 2.5 to 5.0%
(w/w). The reaction takes place at a moderate rate at first increasing
to its maximum yield of 26.32 g sugar/100 g dry potato peel at a
reaction time of 30 min. The reaction rate begins to decrease slowly
however over 75% of the maximum sugar yield is retained by the
end of the reaction.
Further increases in the reaction rate occur as the acid con-
centration is increased to a level of 7.5% (w/w). The rate of sugar
production increases rapidly initially before reaching a maximum
level of 38.78 g sugar/100 g of dry potato peel 15 min after the reac-
tion starts. This level is diminished by the degradation of sugars as
only 44% of this sugar remains at the end of the reaction or 17.41 g
sugar/100 g of dry potato peel.
The optimum yield obtained at 135 ◦ C is seen at 10% (w/w) acid
concentration. 55.2 g sugar/100 g dry potato peel is produced after
a time of 8 min. It must also be noted that due to the timing of sam-
pling that between 4 and 8 min this level may have been higher than
that level. This yield is also found to be the maximum experimen-
tal yield obtained across all the variable conditions of temperature
and acid concentration carried out as part of this research into
acid hydrolysis of biomass. As the reaction continues a high rate of
sugar decomposition ensues resulting in a greatly diminished final
yield of sugars by the end of the reaction period with only 17.27 g
sugar/100 g dry potato peel remaining. The proportion of glucose
which contributes to the total sugar yield for acid concentration vs.
time at 135 ◦ C is between 84.2 and 100% of the total yield.
From Fig. 3 it can be concluded that the acid concentration has
an important relationship with the rate of reaction for both sugar
production and decomposition. As the acid concentration increases
the rate for both becomes more rapid however it is noticeable that
the decomposition rate is only excessive once the acid concentra-
tion is increased to 10% (w/w). If this is compared to the effect
of temperature on the reaction rate then it can be concluded that
temperature has a stronger relationship with the net rate of sugar
399
Fig. 4. The effect of acid concentration and temperature on glucose yield.
production compared to the acid concentration. Therefore it can be
concluded that increasing the acid concentration is a more effective
means of maximising sugar yields than increasing the operating
temperature.
3.3. Effects of temperature and acid concentration on sugar yields
3.3.1. Glucose production
As mentioned previously the majority of the potato peel’s com-
position is made up of hexosans, in the form of cellulose, therefore it
not surprising that the majority of the sugar yield which is derived
from acid hydrolysis is comprised of glucose. Over the range of
temperatures and acid concentration, for which this experiment
was carried out, it was found that the percentage of glucose in the
total sugar yield varied from between 84.1% to 100%. As this is the
primary product of the reaction it must be noted that the results
for total sugars and glucose produced are strikingly similar. The
yield obtained for glucose was 53.8 g sugar/100 g dry potato peel
at the optimum operating condition of 135 ◦ C and 10% (w/w) acid
concentration after 4 min reacting. This constitutes 98.02% of the
maximum total yield of sugar for the reaction thus emphasising its
importance as the primary product.
Fig. 4 illustrates the overall effect acid concentration and
temperature has on the glucose yields obtained. At a moderate tem-
perature of 150 ◦ C it can be seen that glucose production peaks at
46.02 g sugar/100 g potato peel at 10% (w/w) after 8 min. By com-
paring the effect of acid concentration with that of the temperature
it can clearly be seen that increasing the temperature will have a
detrimental effect on the net rate of sugar production.
In Fig. 4(a) it is observed that at a low temperature of 135 ◦ C
at 7.5% (w/w) acid concentration a maximum yield of 36.8 g
glucose/100 g dry potato peal is obtained after 15 min. As the tem-
802 C he m i ca l K i net i cs I

In Eq. (32.7c) we chose to write the volume in cubic metres and the concentration in
moljm 3 • In these equations we could equally well choose to use litres for the volume unit
and moljL for the concentration unit. All that is required is that the two be in conformable
units ; that is, the product of concentration times volume must equal the amount of sub­
stance. For the remainder of this chapter we will use concentrations in moljL, which is the
customary unit.

• EXAMPLE 32 . 1 The rate of decomposition of acetaldehyde can be studied by

measuring the pressure in a system at constant volume and temperature. Express the

-
rate of reaction in terms of the rate of change of the pressure. The overall reaction is
CH 3 CHO(g) CH 4 (g) + CO(g)
with mole numbers

Then

The initial pressure, p O = n OR T/V ; then p = p o + (R T/V)� ; and we obtain

1 1
dp R T d� d� dp
or
dt V dt V dt R T dt.·
Alternatively, we can use Eq. (32.7a). We see that : op/o n i = R T/V for all i ; then Eq.

_-
(32.7a) becomes
dp
dt
_- (Vi RT
V +
V2 V
RT
+
) -_
R T d�
V 3 V dt
fl.vR T
V
_- ( - 1 + 1 + 1) R T d�
V dt
R T d�
V dt '

32.3 RATE LAWS

The rate of reaction will be a function of temperature, pressure, and the concentrations of
the various species in the reaction, Ci ' and may depend on the concentrations, cx , of
species such as catalysts or inhibitors that may not appear in the overall reaction. Further­
more, if the reaction occurs homogeneously (that is, exclusively within a single phase), the
rate is proportional to the volume of the phase, V. If the reaction occurs on an active sur­
face the rate is proportional to the area of the active surface, A. Thus, in a very general way
we can write the rate of reaction as the sum of the rates of the homogeneous and surface
reaction :
(32.8)

wheref(T, p, Ci ' cJ and F(T, p, C j , cJ are functions to be determined from the experimental
data. Equation (32.8) is the rate law for the reaction.
Reactions are classified kinetically as homogeneous or heterogeneous. A homo­
geneous reaction occurs entirely in one phase ; a heterogeneous reaction occurs, at least in
part, in more than one phase. A common type of heterogeneous reaction has a rate which
 R ate laws 803

depends on the area of a surface that is exposed to the reaction mixture. This surface may
be the interior wall of the reaction vessel or it may be the surface of a solid catalyst. At some
stage in any kinetic study it is necessary to find out if the reaction is influenced by the walls
of the vessel. If the vessel is made of glass, it is usually packed with glass wool or beads or
many fine glass tubes so as to increase the exposed area. Any effect on the rate of the reac­
tion is noted. If the reaction is strictly homogeneous, the rate will not be affected by packing
the vessel in this way. In this chapter the discussion will be restricted almost entirely to
homogeneous reactions.
For homogeneous reactions, the second term on the right-hand side of Eq. (32.8) is
negligible and we have
d�
= Vf(T, p, Ci , cx) · (32.9a)
dt
In this situation it is convenient to deal with the rate of the reaction per unit volume,
(1/V) (d�/dt). In view of Eq. (32.8), the rate per unit volume becomes
d(�/V)
-----;[t = f(T, p, Ci , cx), (32.9b)

which is the rate law for a homogeneous reaction.

Dividing Eq. (32.5) by the volume, we obtain
1 d� 1 dn i
V dt v; V dt '
- -

If the volume does not change with time, this equation takes the form
d(�/V) dCi
1
(32. 10)
dt V i dt '

in which Ci is the conc'::ntration of the ith species ; Ci = n/V.

In many cases, the rate law has the simple form

�t
d( V)
= kc'A C� C t . . · , (32. 1 1)

in which CA , CB , CC , . . . , denote the concentrations of the participating species, and k, rx, j3 ,

and l' are constants. The constant k is the rate constant of the reaction, or the specific rate
of the reaction, since k is the rate if all the concentrations are unity. In general the rate
constant depends on temperature and pressure. The constant rx is the reaction order with
respect to A, j3 is the reaction order with respect to B, and l' is the reaction order with
respect to C. The overall reaction order is the sum : rx + j3 + 1'.
The order of the reaction governs the mathematical form of the rate law and therefore
the variation in concentration of all the species with time. The order of the reaction with
respect to the various species must be discovered from experiment. The experimental
determination of the order of the reaction with respect to the various substances taking
part is one of the first objectives of a kinetic investigation. It cannot be emphasized too
strongly that the order of the reaction with respect to a given substance has no relation
whatsoever to the stoichiometric coefficient of that substance in the chemical equation. For
example, in the chemical equation above, the coefficient ofN z O 5 is 2. We cannot infer from
this that the reaction is second order with respect to N z0 5 . (Elementary reactions­
reactions that take place in a single act -are excepted from this statement.)
804 C hemical K i n et i cs I

32.4 F I R ST- O R D E R R EACTI O N S

Consider a simple decomposition reaction of the type
A --------> Products.
Since substance A is the only reactant, we choose to balance the equation with the coef­
ficient of A equal to unity. Suppose that the reaction is first-order with respect to A and
that the rate does not depend on the concentrations of any products ; then the rate law,
Eq. (32. 1 1), becomes
d(�/V) =
dt kc (32. 12)

where c is the concentration of A.

To integrate this equation we must either express c as a function of �/V or �/V as a
function of c. In either case, we obtain the relation by dividing Eq. (32.2) by V,

c = Co - � ' (32. 1 3)
V
and then differentiate with respect to time :
dc d(�/V)
dt .
(32. 14)
dt
Using this value for d(�/V)ldt in Eq. (32.12), we find that
dc
- dt = kc. (32. 1 5)

By rearranging we can separate the variables,

dc =
k dt,
c -
-

and integrate from t = 0 when c= Co to t; then

Ic
Co
dc =
c - 0
- k dt,It
or
c
In - = - kt, (32. 16)
Co
which can also be written
(32. 1 7)
Thus for a first-order decomposition, the concentration of A decreases exponentially
with time. After measuring c as a function of time we can test whether the reaction is first
order in A by plotting In (clco) versus t. According to Eq. (32.16) this plot should be a
straight line if the reaction is first order in A. If we find that our experimental points lie on
a straight line we conclude that the reaction is first order in A. The slope of this line is

equal to - k.
The half-life, T, of the reaction is the time required for the concentration of A to reach
one-half of its initial value. Therefore, when t = T, C = !co . Putting these values into
 R a d i oactive D ecay 805

Eq. (32. 1 6), we obtain In t = - h , so that

1n 2 0.693
1: = T = -k-· (32. 1 8)

One way to evaluate the rate constant of a reaction is to determine the half-life for various
initial concentrations of the reactant A. If the half-life is independent of the initial con­
centration, then the reaction is first order, and the rate constant is calculated using Eq.
(32. 1 8). It is only for first-order reactions that the half-life is independent of the initial
concentration.
The decomposition of N 2 0 5 is an example of a first-order reaction. The stoichiometry
is represented by

and the rate law is

dCN20S = k
- --a;- CN20S ·

At 25 °C the rate constant is 3.38 x 10- 5 S - 1 . Note the absence of any relation between
the order of the reaction and the stoichiometric coefficient of N 2 0 5 in the chemical equa­
tion .
• EXAMPLE 32.2 Calculate the half-life for N 2 0 5 at 25 °C and the fraction
decomposed after 8 hours ; k= 3.38 X 10 - 5 S - 1 .
0.693 0.693
1: = -k- = 3.38 10 5 = 20 500 s. x S 1

Mter 8 hours the fraction remaining is given by Eq. (32. 1 7) ; since

8 hr = 8 hr (60 min/hr) (60 s/min) = 28 800 s, we have
-=- e - kt e � 3 . 3 8 x 1 0 - S s - 1 ( 2 8 8 0 0 s)
= = 0.378. e 3
Co
= = - O.97

Therefore the fraction decomposed is 1 .000 - 0.378 = 0.622

32.4.1 R a d i oact i ve D ecay

The radioactive decay of an unstable nucleus is an important example of a process that
follows a first-order rate law. Choosing CU 6 4 as an example, we have the transformation

1: = 12.8 hr.
The emission of a p-particle occurs with the formation of a stable isotope of zinc. The
pro bability of this occurrence in the time interval dt is simply proportional to dt . Therefore
dN = A dt (32. 19)
--N '
where - dN is the number of copper nuclei that disintegrate in the interval dt. Equation
(32. 1 9) is a first-order law, and can be integrated to the form
(32.20)
No being the number of CU 6 4 nuclei present at t = 0, N the number at any time t. The
 Suhu Akuades Suhu Konstan Akuades
33,6 33,6
33,5 33,4
33,4
33,2
Temperature (°C)

Temperature (°C)
33,3
33,2 33
33,1 32,8
33 32,6
32,9 32,4
32,8
32,2
32,7
32,6 32
32,5 31,8
0 1 2 3 4 5 6 7 8 9 0 5 10 15 20 25
Waktu (per 30 detik) Waktu (per 2menit)

Suhu Etanol Suhu Konstan

26,45 Akuades+Etanol
26,4 32,2
26,35 32
Temperature (°C)

Temperature (°C)
26,3 31,8
31,6
26,25
31,4
26,2
31,2
26,15 31
26,1 30,8
26,05 30,6
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 0 5 10 15 20
Waktu (per 30 detik) Waktu (per 2menit)