10/1/2012

Biomass Liquefaction (Liquid Fuel Production)

Sergio Capareda Biological and Agricultural Engineering Department Texas A&M University

Liquid Fuel Production from Thermal Conversion of Biomass

Biomass liquefaction convert biomass directly into liquid fuels Two Types

Indirect Liquefaction (synthesis gas as feedstock)

Traditionally based from conversion of coal natural gas into liquid products Formation of slurry from biomass through acid hydrolysis and proceed with thermal conversion

Direct Liquefaction

Liquid Fuel Production Using Syngas as Feedstock

Methanol Production from Synthesis Gas (Indirect)

1. Methanol Production from Synthesis Gas CO + 2H2 CH3OH (methanol)
Catalyst (CuO, ZnO)

Indirect Liquefaction

Methanol production from synthesis gas Mobil Process Fischer Tropsch Process China Lake Process Laurence Berkeley Lab (LBL) Process Pittsburg Energy Research Center (PERC) Process

Steps:

1. Steam reforming: CH4 + H2O CO + 3H2 2. Water shift reaction: CO + H2O CO2 + H2 Synthesis: 2H2 + CO CH3OH

Direct Liquefaction

Used extensively in petrochemical industry for methanol production High pressure (100 atm) at 300oC Methanol yield from wood = 360 kg/dry tonne Conversion efficiency = 30-40% (i.e. energy in methanol divided by total energy input) Energy content methanol = 19.8 GJ/tonne Gasoline energy content = 43.7 GJ/tonne Methanol, a versatile fuel can be burnt in diesel and gas engines

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Schematic Diagram of Producing Methanol from Syngas (Adapted from Trifiro, 2009)

Indirect Liquefaction (Mobil Process)

2. Mobil Process: Conversion of methanol to high octane gasoline To avoid the need for engine modification Based on the use of shape selective zeolite catalysts (ZSM-5) Pilot-plant studies gives conversion efficiencies in the order of 90% Sometimes begin with methanol derived from natural gas This is a two stage catalytic process. In the first stage methanol is produced. The methanol is then used as feedstock to generate hydrocarbons of varying chain length. In the conversion, a number of reactions take place in the gas phase. The conversion is initiated by the removal of water to produce dimethyl ether: 2CH3OH(g) -> CH3OCH3(g) + H2O(g)

This is then further dehydrated over a zeolute catalyst (ZSM-5) to give gasoline with 80% by weight of C5 + other hydrocarbon products

Indirect Liquefaction (Mobil Process)

Various other reactions occur in which further molecules of water are removed resulting in gradual increase in chain length. Chemical reactions: 2CH3OCH3(g) + 2CH3OH(g) -> C6H12(g) + 4H2O(g) 3CH3OCH3(g) -> C6H12(g) + 3H2O(g) As a result of other dehydration reactions occurring in parallel a mixture of hydrocarbons is produced of which about 80% is suitable for petrol production. The mixture contains (w/w) around 50% highly branched alkanes, 12% highly branched alkenes, 7% cycloalkanes and 30% aromatics. This process has been commercialized by Methanex in New Zealand using methanol produced from natural gas.

MethanolfromWoodConversionEfficiency
Determinetheefficiencyofconvertingatonne ofwoodwaste withahigh heatingvalueof20MJ/kgintopuremethanolhavingayieldof360kgfor everytonne.Theenergycontentofpuremethanolis19.8MJ/kg.Convertall unitsinEnglishsystem.
Solution a. This is the energy of methanol divided by total energy input from wood as follows:
Input Energy ( MJ ) 1tonne wood
Ouput Energy ( MJ ) Efficiency

1000kg 20MJ 20,000MJ 1tonne kg

360 kg MeOH 19.8MJ 7,128MJ kg output 7,128MJ 100% 100% 35.64% input 20,000MJ

b. The English system of units is shown below:

Btu 1x106 J 18.96MMBtu 1055J 1MJ 7,128MJ Btu 1x106 J Output Energy ( MMBtu) 6.76MMBtu 1055 J 1MJ Input Energy ( MMBtu) 20,000MJ
Efficiency output 6.76 MMBtu 100% 100% 35.64% input 18.96 MMBtu

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Indirect Liquefaction (China Lake Process)

3. China Lake Process (US Naval Weapons Center, China Lake, CA) Employs an advanced fast pyrolysis step Produces gaseous product containing large amounts of olefins than standard pyrolysis methods Subsequent polymerization under pressure to form a mixture of higher MW hydrocarbons Refined to yield useful fuels Overall conversion efficiencies = 22% The China Lake trash-to-gasoline process involves a series of noncatalytic petrochemical processes to convert organic wastes to a synthetic hydrocarbon crude oil containing about 90% high-octane gasoline and 10% fuel and lubricating oils. By-product char and gases would be consumed for process energy. Key features of the process: the relative confidence of commercial scale up and the projected economics based on an independent thirdparty evaluation.

Schematic Diagram of the China Lake Process

Indirect Liquefaction (Fisher-Tropsch)

Indirect Liquefaction (Fisher-Tropsch)

The Fischer-Tropsch process is a catalyzed chemical reaction in which carbon monoxide and hydrogen are converted into liquid hydrocarbons of various forms. Generally the catalysts used, for the following reaction, are based on iron and cobalt. (2n+1)H2 + n(CO) -> CnH2n+2 + nH2O The FT process is an established technology and is already applied on a large scale from coal or natural gas. Developed in the 1920s in Germany, it was used by both Germany and Japan during World War II and later by South Africa and to a lesser extent in the United States. One problem is the high capital cost of the multistage process. This may be greater when biomass is used as feedstock, since the scale of operation may be limited by the distance over which biomass can be transported to the factory at an economic price.

The three basic steps in the production of liquid hydrocarbon fuels via the Fischer-Tropsch process is as follows:

synthesis gas preparation Fischer-Tropsch synthesis product upgrading low calorific value gas or LCV gas with heating values between 3.8-7.6 MJ/m3 medium calorific value gas or MCV gas with heating values between 10.5-16 MJ/m3 high calorific value gas (HCV) with heating values greater than 21 MJ/m3

Three classes of synthesis gas used as follows:

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Schematic Diagram of the FischerTropsch Process

Indirect Liquefaction (Fisher-Tropsch)

Problem: wide variety of products formed including olefins, alcohols and waxes Current research: finding catalyst which give cleaner product mix Advantage: Low sulfur of biomass reduces problem of catalyst poisoning compared with coal Running and maintenance costs are also comparatively high. High capital cost of equipment and complexity of process and requirement for very large facilities. The economy of scale is decreased compared to a large coal or gas-based operation.

Commercial F-T Plants in Operation

Direct Liquefaction
Direct Liquefaction: direct hydrogenation of biomass at high temperature and very high pressures using CO & H2 as reducing agent 1. Laurence Berkeley Lab (LBL) Process Performed on aqueous cellulose slurry derived from acid hydrolysis of wood chips 2. Pittsburg Energy Research Center (PERC) Process Wood to oil process Liquefaction occurs following the blending of dried wood powder with recycled product oil and sodium carbonate catalyst Oily liquid is produced which can be fractionated for use as fuel (ethylene is produced as intermediate product) Temperature of 370C and pressures of 4,000 psig used Oxygen content of the resulting complex liquid mixture is still high (6 to 10 wt%),

Sasol (Sasolburg and Secunda, South Africa) PetroSA/Mossgas (Mossel Bay, South Africa) Shell SMDS (Bintulu, Malaysia) Additional similar facilities being built

China, Nigeria, the US, Iran, Australia, and Indonesia using combinations of HTFT and LTFT.

HTFT = high temperature FT process LTFT = low temperature FT Process

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Schematic of the Bureau of Mines (BOM) or PERC Liquefaction Process (Adapted from Elliott, 2012)

Schematic of the Laurence Berkeley Laboratory (LBL) Process (Adapted from Elliott, 2012)

Schematic of the HydroThermal Liquefaction (HTL) Process (Adapted from Elliott, 2012)

Refined Fuels of Interest

General Criteria

High energy value Fuel must vaporize and ignite easily Relatively safe to handle Parrafin: CnH2n+2 Olefin: CnH2n Diolefin: CnH2n-2 Naphthaline: CnH2n Aromatics: CnH2n-6

Hydrocarbons (86% C and 14%H)

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Advantages of Direct Liquefaction Process

Disadvantages of Direct Liquefaction Process

Drying and grinding may not be necessary Catalysts may be mixed with the slurry Catalysts and the water may be recycled Recycled oil may be used to prepare the slurry Hydrolysis acid may be used to form the slurry The base catalyst may be used to make the pH of the slurry neutral

There is pumping issue with very high solids slurry. Complex co-products are produced. The product has high water content. The equipment costs are high. The engineering materials for conveying high-solids slurry are specialized and costly.

Advantages of the Indirect Liquefaction Process

Disadvantages: Indirect Liquefaction Process

Syngas may be produced from wide range of biomass resources. Other gases may be used, such as methane from biogas, or natural gas (i.e. pure methane). The H2/CO ratios may be easily adjusted during operation. The rate of syngas production is high, thereby improving production throughput. There are various fixed or moving bed thermal conversion systems possible in both the gasification and pyrolysis modes. gas purification is easy and thus will have less problem with catalyst coking

The basic syngas compounds may need to be oligomerized catalytically. The bio-oil produced is quite complex and may need to be upgraded. Condensing the oil or liquid product may be difficult in some designs. Catalysts are necessary for most indirect liquefaction processes. The biomass must be dried and ground. Syngas is not transportable; it must be used onsite or conveyed properly.

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Concluding Remarks on Biomass Liquefaction

Hydrocarbon fuels production is still the primary goal of biomass conversion due to large requirement for transport fuels As in many other conversion processes, this is also complex with various products and coproducts and would need further refining, fractionation and product enhancement Thermal conversion processes are quick and products may be produced within minutes of reaction