Introduction to Biomass Direct Liquefaction

BEEMS Module C3
Introduction to
Biomass Direct Liquefaction
Brian He, Shengjun Hu, and Yebo Li
Biological and Agricultural Engineering

BEEMS
University of Idaho
Contact: bhe@uidaho.edu, (208) 885-7435
Sponsored by: USDA Higher Education Challenger Program2009-38411-19761

Outline
A concept from coal liquefaction
Biomass liquefaction basics
Biomass liquefaction technologies
Examples of liquefaction processes
Polyols production from liquefaction of lignocellulosic
biomass
Introduction to Biomass Direct Liquefaction

- B. Brian He, PhD & PE
Technologies for biomass conversion
Thermochemical conversion is a chemical reforming process of organic polymers
in a heated enclosure, usually in an oxygen-free or very low oxygen environment

What is liquefaction?
Liquefied under-soils (in geology)
Liquefied natural gas (LNG)
Liquefied sugars via fermentation (for alcohols)
Liquefied biomass by chemical reagents (e.g.,Ethylene
carbonate + 97% sulfur acid )
Liquefied coal/biomass via gasification (indirect liquefaction)
Coal/biomass syngas F-T syntheses liquid hydrocarbons
Other uses of liquefaction ?
Introduction to Biomass Direct Liquefaction Richard P. Ray. Univ. of South California

Coal direct liquefaction
The main purposes are to
(1) get liquids and
(2) utilize low energy coal in a more efficient way
From: anonymous
Coal direct liquefaction
Coal direct liquefaction is the conversion of coal into liquids by
thermal decomposition and hydrogenation under pressures
Single- and two-stage processes are used
Catalysts are needed at
<500oC
Hydrocarbons,straight-chain
& cyclic, are used as solvent
Product contains more
aromatics suitable for as
high octane gasoline
components
Product contains sulfur,
nitrogen, minerals, etc, -
requiring extensive post-
treatment John Marano, April 2006, presentation to NETL

Biomass direct liquefaction
Process/ Definition
Direct liquefaction is a thermochemical conversion process of organic
matters directly into a liquid biocrude and co-products under moderate
temperatures (300-400oC) and pressures (10-20MPa), with the addition
of a reducing agent (typically hydrogen or CO).
If the biomass is wet (high water content) or processed in

aqueous slurry form, then the direct liquefaction is also
commonly referred in the literature as hydrothermal
Processing

Catalysts are needed, depending on processes
Acids,bases,alkali metals carbonates,e.g.,sodium/ potassium carbonate
Carrying medium/ solvent is a necessity

Organic solvents/ recycled oil,phenol,glycols,etc.
In the cases of water as the solvent,e.g.,processing of organic matters as water
slurries, the direct liquefaction is also commonly referred as hydrothermal
processing.
Requires a reducing agent,e.g.,H2,CO
Requires fine biomass particle size,< 0.5 mm
Needs to overcome the challenge of feeding high pressure
slurry
e.g., extruder,in continuous flow

Process
Capable of processing high water content feedstocks, up to90%
Advantageous in treating
MSW,food processing waste,animal manure,ag wastes
Serves roles of waste treatment and renewable energy production
Process parameters include
Solids content,T,P,pH,time,and application of catalysts
Chemical reactions - complicated

Hydrogenolysis
Solubilization
Hydrogenation
Depolymerization
re-condensation
Decarboxylation
Mechanism of hydrothermal liquefaction
formate formation from carbonate
Na2CO3 + H2O + CO 2HCO2Na + CO2
sodium carbonate sodium formate
dehydration of hydroxyl groups to carbonyl compounds via enols,and

Reduction of carbonyl group to an alcohol
HCO2Na + C6H10O5 C6H10O4 + NaHCO3
woody biomass oil bicarbonate
H2 + C6H10O5 C6H10O4 + H2O
Regeneration of formate
NaHCO3 + CO HCO2Na + CO2
Regeneration of hydrogen
HCO2Na +H2O NaHCO3 + H2

Products / biocrude
Dependent also on the reagent added (derivatization)
The major product from direct liquefaction is the liquid biocrude,a
dark tar- or asphalt-like, highly viscous organic mixture.
Converts up to 70 % carbon into biocrude
Co-products include gaseous (CO2, CH4 and light HC,etc.) and
water-soluble in the case of hydrothermal processing.
Possess similar carbon to hydrogen ratio as in feedstock
Complex mixture of aromatics,aromatic oligomers,etc.
Oxygen is reduced,10-20 %wt,less than pyrolysis oils
Heating value of 35-40 MJ/kg (dry basis), higher than pyrolysisoils

Comparison of biocrude, biooil, and petroleum fuel
Elliott et al., 2010. Presentation at the

Frontiers in Bioenergy Symposium. May 25, 2010

Example
[Hydrothermal Upgrading (HTU), TNO Organisation for Applied Research, 2005]
Cat. DeNOx Flue gas
air Furnace
LIGHT
BIOCRUDE
Gas
Feedstock
HTU PRODUCT BIOCRUDE

Pretreat- Pump Heating Separation
REACTOR SEPARATION PRODUCT
ment Section
Process
water HEAVY
BIOCRUDE
Anaerobic
Biogas
digestion
concentrated
demineral. minerals soln
Clean
water

An example Biomass liquefaction process, US 4,266,083 (1981)

An example Biomass liquefaction process, US 4,266,083 (1981)
Nomenclature (major device only)

4 blender (recycle oil) 33 vacuum still
9 pre-heater 41 vacuum distillate
10 reactor assembly 42 trap-out oil
11 mix of heavy oil slurry + CO2 + light HC 44 compressor
14 partial oxidation reactor (for H2) 45 hydro-treatment unit
15 dip-leg 46 hydrogen
16 liquefied product mix 47 flash gas
18 light-end stripper 48 hydrotreated oil
20 vapor / light HC 49 fractionation unit
21 cooler / separator 51 heavy oil slurry
22 decanter 57 light HC
24 water-insoluble reflux 59 condensables
23 Crude oil slurry 64 H2 (syngas)
66 CO2 recycle
Example Biomass liquefaction process, US 4,266,083 (1981)
This invention is directed to a process for the conversion of solid cellulosic

biomass materials or lignite to oil.A solids-oil slurry is contacted in a reactor with
carbon monoxide and water vapor in the presence of an alkali metal and alkaline
earth metal carbonate, bicarbonate or formate catalyst at a temperature of from
about 250 oC and to about 450 oC at a pressure of from about 2000 psig to about
5000 psig.The gases from the reactor and oil hydrocarbon fuel, preferably a
recycled heavy fraction of product oil containing spent catalyst, are burned at a
pressure above the reactor pressure with oxygen to provide a carbon monoxide-
water vapor gas having a temperature of from about 1100 oC to about 1600 oC.
Said gas is introduced under the surface of the oil slurry in the reactor to provide
heat, carbon monoxide, water vapor, and, desirably, regenerated catalyst to said
reactor.

Example
[K.Seri et al.2002.Lanthanum (III)-catalyzed degradation of cellulose at 250C.Biores.Technol.81:257-260]
Cellulose hydrothermal processing in pressurized water at 250 C, LaCl3 (lanthanum

chloride) as catalyst
MI = methanol insoluble (cellulose)

MS = methanol soluble
WS = water soluble
G = gas
Example an early research
(Appell et al. 1980, Converting Organic Wastes to Oil: A Replenishable Energy Source, Bureau of Mines, U.S. Department of the Interior)
250400 oC, and 20004100 psig (136281 atm)

Reactions were carried out in the presence of catalyst, sodium carbonate
CO and water were added as reactants/ solvent
Higher oil yield was achieved at lower temperature (250oC) a than that at higher
temperature (350oC)
the presence of CO heavily affected the oil yield and conversion rate
Example - 200psi initial CO, 6000 psi operating pressure, 20 min at 380C;the
conversion rate is 99% and the oil yield is 47%,
Constituents Composition of Manure, % Composition of

As used Dry, ash-free basis oil (%)
Carbon 20.5 52.2 79.6
Hydrogen 2.5 6.4 9.5
Nitrogen 1.3 3.3 4.2
Sulfur 0.5 1.2 0.37
Oxygen 14.5 36.9 7.3
Ash 15.1 - -
Water 45.5 - -

Example an early research
(Appell et al.1980,Converting OrganicWastes to Oil:A Replenishable Energy Source,Bureau of Mines,U.S.Dept.of the Interior)
Water is involved in many ways in this reaction. First, most substrates contain large
amounts of moisture. Second, since most organic wastes are highly oxygenated, water is
formed merely by heating them to reaction temperature; so it is a reaction product.Third,
water, as formed in the substrate during the reaction, or simply added to the reaction mixture,
is a mechanical vehicle for facilitating mixing of reactants and preventing condensations to
chars by diluting the reaction intermediates.
Water is also a solvent of sorts. It is true that most substrates are not soluble in water
under normal conditions, but solvation can occur between the hydroxyl groups of the substrate
and water. It is an excellent medium for intermediate hydrolysis of cellulose and other high-
molecular-weight carbohydrates to water-soluble sugars. The primary reactions in the
conversion to oil likely involve formation of low-molecular-weight, water soluble compounds
such as glucose or pyruvic acid. In addition, alkaline catalysts are water soluble, thus
facilitating their dispersion throughout the reaction vessel in readily available form.
Finally, but important, water is a reactant.The hydrogen added to the substrate comes from
water, which consumes carbon monoxide by reacting with it to form carbon dioxide and
hydrogen.
Whats polyols
Polyols: chemical compounds that contains 2 hydroxyl groups:
Monomeric polyols:glycerin,ethyelene glycol,etc
Polymeric polyols: higher molecular weight (typically
hundreds to thousands Dalton)
Typical polymeric polyols: polyether and polyester polyols.

Application of polyols
Polymeric polyols are mainly used for producing polyurethane
(PU) products,including PU foams,coatings,adhesives,sealant,
etc
O
A-OH + O=C=N-B A-O-C-NH-B
Polyol Isocyanate Polyurethane (PU)
PU foams are the predominant form of PU products:

Flexible foams:car seats,memory foams,cushion,etc;
Rigid foams: thermal insulation in fridges and construction
Polyol production by biomass liquefaction
Operational conditions: Liquefaction
Biomass
solvent
Temperature: 150-180
Liquefaction time: 60-90 min
Catalysts: 98 % H2SO4 (3-4% wt.
Reactor
of solvent)
Pressure: atmospheric
Typical liquefaction solvent:
Polyols
polyhydric alcohols such as EG,
DEG, PEG 400 and glycerol mixture
(Wt. 4:1)
Solvent to biomass ratio: ranging Refining
from 2:1 to 5: 1.
Refining: filtration to remove Refined
biomass residue; neutralization to Polyols
lower acid number, etc.

Biomass degradation
process
Complex and interactive:
Solvolysis
Oxidation
Esterification
Others
Reference: Yamada et al. 2007. J. Wood. Sci. 53: 487-493.

Polyol properties
Biomass conversion: 85-98 %

Hydroxyl number: Milligrams of KOH equivalent to the hydroxyl
content in one gram of polyol (200-500 mg KOH/g)
Suitable for rigid or semi-rigid PU foam production
Acid number: Milligrams of KOH needed for the neutralization of
acidic constituents in one gram of polyol (5-30 mg KOH/g )
Needs neutralization to <1 before reacting with isocyanates
Viscosity: 500 to 5000 mPa.s
Major challenges
Large solvent to biomass ratio used: typically 3:1 to 5:1
for high biomass conversion
The large quantity use of petrochemical solvents is
neither renewably nor economically favorable
Possible solutions: explore renewable and inexpensive
liquefaction solvents
An example: using crude glycerol as
an alternative liquefaction solvent
A recent study by Hu et al. (2012) investigated the use of crude glycerol as
an alternative liquefaction solvent. Under optimum conditions (240 C,
>180 min, 3% sulfuric acid), the produced polyols showed biomass
conversion around 70 %, hydroxyl numbers from 440 to 490 mg KOH/g,
acid numbers below 5 mg KOH/g, and viscosities from 16,000 to 45,000
mPas.
Compared to petroleum solvent based liquefaction
process:
Advantages: Disadvantages:
Low biomass conversion
Low cost solvent
High reaction temperature
Comparable hydroxyl number
Long reaction time
Low acid numbers High polyol viscosity
Reference: Hu et al. 2012. Bioresource technology, 103: 227-233

Summary of liquefaction for
biopolyols
Fast biomass conversion at 1500-180 and under

atmospheric pressure
Biomass liquefaction by polyhydric alcohols via complex

reactions
Polyols exhibit material properties suitable for semi-rigid or

rigid PU foam applications
The use of large amount of expensive petrochemical solvents

is the major economical challenge

Introduction to Biomass Direct Liquefaction

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Introduction to Biomass Direct Liquefaction

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BEEMS Module C3

Brian He, Shengjun Hu, and Yebo Li

Biological and Agricultural Engineering

Contact: bhe@uidaho.edu, (208) 885-7435

Sponsored by: USDA Higher Education Challenger Program2009-38411-19761