Open access peer-reviewed chapter - ONLINE FIRST

Systematic Generation of Reactions Pathways for Manufacturing Bulk Industrial Chemicals from Biomass

Written By

Rakesh Govind, Shiva Charan and Jack Baltzersen

Submitted: February 7th, 2022 Reviewed: February 8th, 2022 Published: March 20th, 2022

DOI: 10.5772/intechopen.103123

Biomass Edited by Mohamed Samer

From the Edited Volume

Biomass [Working Title]

Prof. Mohamed Samer

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The objective of this work was to develop a systematic strategy for generating efficient, alternate reaction paths that could be used to manufacture the top 100 industrial chemicals, currently produced from crude oil, using renewable feedstocks. Manufacturing these chemicals from oil, coal, or natural gas results in increasing carbon dioxide levels in the atmosphere, responsible for global climate change. The methodology employed here uses the existing knowledge on the conversion of carbon-neutral feedstocks, such as biomass, wood, etc., to suitable precursor raw materials. Known industrial reaction paths, currently used for manufacturing the top 100 industrial organic chemicals, are then combined with the known conversion of carbon-neutral feedstocks to systematically develop and evaluate alternate carbon-efficient reaction paths. The fractional carbon economy was determined from a comprehensive listing of industrial reactions paths, which also gives the yields and efficiencies of these industrial reaction paths, currently being practiced in the chemical industry. Reaction pathways with maximum carbon economy for manufacturing the top 100 industrial chemicals from carbon-neutral feedstocks have been presented in this chapter.


  • reactions
  • carbon
  • economy
  • carbon-neutral
  • industrial chemicals

1. Introduction

Sustainable production of industrial chemicals requires the use of biomass as a raw material, which can be converted into intermediate chemicals, currently being used as raw materials derived from non-renewable feedstocks, such as coal, crude oil, natural gas, etc. This allows the chemical industry to preserve its current petrochemical plants, except changing its source of feedstock from nonrenewable sources to renewable materials, such as biomass. The challenges posed by shifting to renewable feedstocks involve new chemistries which convert a variety of biomass materials into the known feedstocks, and in some cases starting with completely different raw materials. In addition, biomass conversions by fermentation involve slow reactions, conducted in the liquid phase, with low conversions, resulting in dilute aqueous solutions.

Traditionally, the chemical industry has relied on gas phase, catalytic, high temperature, and often high-pressure reactions, which require short residence times in smaller reactors and produce a high concentration of product(s). In comparison, biomass conversions using fermentation are biological, liquid-phase reactions, conducted at near ambient temperature and usually atmospheric pressure. The reaction rates in fermentation chemistry are orders of magnitude lower than in gas-phase chemical conversions.

Notwithstanding these challenges, in this chapter, known reactions for converting a variety of biomass sources into known chemical feedstocks have been detailed. Conversion and yield information from the publications of these chemical reactions was used to generate and rank these reactions based on their carbon economy. Carbon economy is the ratio of the mass of carbon atoms in the feedstock produced to the mass of carbon atoms present in the biomass source. By maximizing the carbon economy, the mass of carbon atoms present in the waste product(s) is minimized.

In addition, chemical reaction pathways, currently used to manufacture the top 100 industrial chemicals from nonrenewable feedstocks, were derived from known sources [1, 2, 3, 4], and each reaction pathway was also evaluated by its carbon economy. A computer program was developed to link the biomass conversion reactions with the industrial chemical pathways, with the objective of maximizing the overall carbon economy starting with the biomass material and ending with the industrial chemical. This provided multiple reaction pathways, in order of decreasing the overall carbon economy, to convert a biomass feedstock to each of the top 100 industrial chemicals.


2. Biomass conversion reaction pathways

In our analysis, seventeen different biomass materials were considered and information on the conversion of these biomass materials to known feedstock chemicals was derived from publications cited in this section.

Seventeen biomass sources, considered in this paper, are as follows:

  • Beech wood

  • Pine sawdust

  • Municipal solid waste (pilot plant)

  • Sewage sludge

  • Sunflower residue

  • Rape residue

  • Switchgrass

  • Sunflower shells

  • Rice husk

  • Pine chip

  • Tropical lauan

  • Paddy straw

  • Corn cob

  • Yellow poplar sawdust

  • Alaskan spruce

  • Wheat straw

  • Rice hulls

The biomass conversion processes employed to convert these biomass sources to feedstock chemicals include pyrolysis, which is heating the biomass material, either in the presence of a catalyst, such as alumina, or noncatalytically. The flash pyrolysis process is conducted in an oxygen-free, inert gas atmosphere in the temperature range of 600–1000°C and 1 atmosphere pressure. Products of pyrolysis consist of gases, such as carbon monoxide, carbon dioxide, methane, etc., and liquids, such as heavier hydrocarbon oils and ammonia.

Another biomass conversion process used is hydrothermal liquefaction, where the biomass material, once shredded into small pieces, is heated in water under hydrothermal pressures and temperatures ranging from 500 to 700°C. This converts the biomass material into a liquid oil product, which is then processed as crude oil, using cracking and distillation.

Gasification of biomass under controlled oxidative conditions produces synthesis gas, which can be converted to chemicals using the well-known Fisher-Tropsch chemistry.

Hydrolysis, using acids, followed by fermentation converts biomass into chemicals, such as ethanol, acetic acid, etc. These chemicals become the feedstocks for a variety of industrial chemicals.

Table 1 lists the chemical composition of the various biomass sources and their carbon economy [5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20].

Biomass source% Carbon% Hydrogen% Oxygen% Carbon economyReference
Pine sawdust48.36.545.20.48[6]
Municipal solid waste52.36.538.30.52[7]
Sewage sludge49.57.335.60.50[8]
Sunflower residue43.65.849.30.44[9]
Rape residue44.75.848.10.45[9]
Switch grass46.[10]
Sunflower shells41.[11]
Rice husk38.34.435.40.38[12, 13]
Pine chips51.[14]
Tropical luan51.16.342.40.51[14]
Paddy straw35.65.343.10.36[15]
corn cob46.65.945.50.47[16]
Yellow poplar sawdust48.55.943.70.48[17]
Alaskan spruce50.[12]
Wheat straw43.[18]
Rice hulls66.[20]

Table 1.

Biomass sources, composition and carbon economy.


3. Reactions for manufacturing industrial chemicals

Production of industrial chemicals utilizes a variety of reactions to convert the raw materials to the desired products. The following is a list of the reactions involved in the manufacture of the top 100 industrial chemicals and their chemical classification.

  • Methane → acetylene: pyrolysis

  • Acetylene → ethylene: hydration

  • Ethanol → ethylene: dehydration

  • Propane → acetylene: pyrolysis

  • Isobutane → isobutylene: dehydrogenation

  • N-butane → N-butylene: dehydrogenation

  • Acetylene → butadiene: reaction of acetylene and formaldehyde

  • Ethanol → butadiene: dehydration/dehydrogenation

  • Ethylene → ethanol: hydration

  • Benzene → cyclohexane: hydrogenation

  • Benzene → ethyl benzene: reaction of benzene and ethylene

  • Ethylene → acetaldehyde: oxidation

  • Carbon monoxide → methanol: hydrogenation

  • Methanol → acetic acid: carbonylation

  • Acetic acid → acetic anhydride: reaction of acetic acid and ketone

  • Acetic acid → acetone: decarboxylation

  • Acetaldehyde → acrolein: reaction of acetaldehyde and formaldehyde

  • Acetic acid → acrylic acid: reaction of acetic acid and formaldehyde

  • Butadiene → adiponitrile: chlorination of butadiene with sodium cyanide

  • Propylene → allyl chloride: chlorination of propylene

  • Allyl chloride → allyl alcohol: hydrolysis

  • Acetylene → acetaldehyde: hydration

  • Acetaldehyde → crotonaldehyde: dimerization

  • Crotonaldehyde → N-butanol: hydrogenation

  • Ethanol → acetaldehyde: oxidation

  • Crotonaldehyde → N-butyraldehyde: hydrogenation

  • N-butyraldehyde → N-butanol: hydrogenation

  • N-butylene → S-butanol: sulfonation

  • Benzene → chlorobenzene: oxychlorination

  • Benzene → cumene: reaction of benzene and propylene

  • Cyclohexane → cyclohexanol: oxidation-boron assisted

  • Cyclohexanol → cyclohexanone: dehydrogenation

  • Methanol → formaldehyde: oxidation

  • Formaldehyde → ethylene glycol: carbonylation

  • Ethylene glycol → diethylene glycol: reaction of ethylene glycol and ethylene oxide

  • Toluene → dinitrotoluene: nitration

  • Acrolein → epichlorohydrin: chlorination

  • Ethylene → ethylene dichloride: chlorination

  • Ethylene → ethylene oxide: chlorohydration

  • Propylene → isopropanol: hydration

  • Acetic acid → ketene: pyrolysis

  • Methane → methyl chloride: chlorination

  • Methanol → methyl chloride: hydrochlorination

  • Benzene → nitrobenzene: nitration

  • Acetaldehyde → peracetic acid: oxidation

  • Benzene → phenol: sulfonation

  • Carbon monoxide → phosgene: reaction of carbon monoxide and chlorine

  • Naphthalene → phthalic anhydride: oxidation

  • Propylene → propylene dichloride: chlorination

  • Propylene → propylene oxide: chlorohydration

  • Toluene → terephthalic acid: reaction of toluene and carbon monoxide

  • Dinitrotoluene → toluene diamine: hydrogenation

  • Acetylene → trichloroethylene: chlorination

  • Ethylene dichloride → trichloroethylene: chlorination

  • Acetylene → vinyl chloride: hydrochlorination

  • Ethylene dichloride → vinyl chloride: dehydrochlorination

  • Acetylene → acrylonitrile: cyanation

  • Acetaldehyde → acrylonitrile: cyanation/dehydration

  • Benzene → aniline: reaction of benzene and ammonia

  • Toluene → benzoic acid: oxidation

  • Phenol → bisphenol-A: reaction of phenol and acetone

  • Cyclohexane → caprolactam: nitration

  • Methane → chloroform: chlorination

  • Methyl chloride → chloroform: chlorination

  • Acetylene → chloroprene: dimerization

  • Butadiene → chloroprene: chlorination

  • Phenol → cresylic acid: methylation

  • Methane → carbon tetrachloride: chlorination

  • Carbon tetrachloride → dichlorofluoromethane: reaction with hydrogen fluoride

  • Methyl chloride → carbon tetrachloride: chlorination

  • Terephthalic acid → dimethyl terephthalate: esterification

  • Acetic acid → ethyl acetate: esterification

  • Acrylic acid → ethyl acrylate: esterification

  • Ethylene → ethyl chloride: hydrochlorination

  • Ethylene → ethyl dibromide: bromination

  • N-butyraldehyde → 2-ethylhexanol: dimerization

  • Epichlorohydrin → glycerin: hydrolysis

  • Adiponitrile → hexamethylenediamine: hydrogenation

  • Acetone → isoprene: reaction of acetylene and acetone

  • Benzene → maleic anhydride: oxidation

  • Ethylene dichloride → methyl chloroform: chlorination

  • Methane → methylene dichloride: chlorination

  • Methyl chloride → methyl dichloride: chlorination

  • N-butylene → methyl ethyl ketone: oxidation

  • Acetone → methyl isobutyl ketone: dimerization

  • Acetone → methyl methacrylate: cyanation

  • Carbon tetrachloride → perchloroethylene: pyrolysis

  • Propylene oxide → propylene glycol: hydration

  • Butadiene → styrene: cyclohydrogenation

  • Toluene diamine → toluene diisocyanate: phosgenation

  • Carbon tetrachloride → trichlorofluoromethane: reaction of carbon tetrachloride and hydrogen fluoride

  • Ethylene oxide → ethylene glycol: hydration (in book)

  • Diethylene glycol → triethylene glycol: reaction of diethylene glycol and ethylene oxide

  • Carbon monoxide → urea: reaction of ammonia and carbon monoxide

  • Acetic acid → vinyl acetate: reaction of acetylene and acetic acid

  • Carbon monoxide → formic acid: hydrolysis

  • Cyclohexanol → adipic acid: oxidation

  • Methane → hydrogen cyanide: ammoxidation

  • Propane → hydrogen cyanide: reaction of propane and ammonia

  • Carbon monoxide → isobutanol: reaction of carbon monoxide and hydrogen

Table 2 lists the chemical reactions, yield, and the calculated atom economy, used in the analysis, based on the reported reaction yields [4]. The following equation was used to calculate the carbon economy from the reported data and a balanced reaction pathway:

Industrial reactionYield (product/reactant)Atom economy
Methane → acetylene0.45450.5
Acetylene → ethylene0.91741.0
Ethanol → ethylene0.58481.0
Propane → acetylene0.34480.50
Isobutane → isobutylene0.66671.0
n-Butane → N-butylene0.66671.0
Acetylene → butadiene1.49251.0
Ethanol → butadiene0.33331.0
Ethylene → ethanol1.51521.0
Benzene → cyclohexane1.07531.0
Benzene → ethyl benzene1.31581.0
Ethylene → acetaldehyde1.49251.0
Carbon monoxide → methanol1.01.0
Methanol → acetic acid1.85191.0
Acetic acid → acetic anhydride1.61291.0
Acetic acid → acetone0.45870.75
Acetaldehyde → acrolein0.95241.0
Acetic acid → acrylic acid1.201.0
Butadiene → adiponitrile1.21951.0
Propylene → allyl chloride1.42861.0
Allyl chloride → allyl alcohol0.66671.0
Acetylene → acetaldehyde1.61291.0
Acetaldehyde → crotonaldehyde0.74071.0
Crotonaldehyde → n-butanol1.01.0
Ethanol → acetaldehyde0.86961.0
Crotonaldehyde → n-butyraldehyde1.01.0
n-Butyraldehyde → n-butanol0.97091.0
n-Butylene → butanol1.11111.0
Benzene → chlorobenzene1.21951.0
Benzene → cumene1.26581.0
Cyclohexane → cyclohexanol0.97091.0
Cyclohexanol → cyclohexanone0.95241.0
Methanol → formaldehyde0.86961.0
Formaldehyde → ethylene glycol1.53851.0
Ethylene glycol → diethylene glycol1.42861.0
Toluene → dinitro toluene1.85191.0
Acrolein → epichlorohydrin1.28471.0
Ethylene → ethylene dichloride3.33331.0
Ethylene → ethylene oxide1.251.0
Propylene → isopropanol1.38891.0
Acetic acid → ketene0.62891.0
Methane → methyl chloride2.4391.0
Methanol → methyl chloride1.42861.0
Benzene → nitro benzene1.53851.0
Acetaldehyde → peracetic acid1.56250.5
Benzene → phenol0.90091.0
Carbon monoxide → phosgene0.90091.0
Naphthalene → phthalic anhydride0.95240.8
Propylene → propylene dichloride2.4391.0
Propylene → propylene oxide1.06381.0
Toluene → terephthalic acid1.80431.0
Dinitro toluene → toluene diamine0.63691.0
Acetylene → trichloroethylene4.76191.0
Ethylene dichloride → trichloroethylene1.26581.0
Acetylene → vinyl chloride2.27271.0
Ethylene dichloride → vinyl chloride0.59881.0
Acetylene → acrylonitrile1.66671.0
Acetaldehyde → acrylonitrile1.20451.0
Benzene → aniline1.19231.0
Toluene → benzoic acid1.19051.0
Phenol → bisphenol a1.13641.0
Cyclohexane → caprolactam0.76921.0
Methane → chloroform7.14291.0
Methyl chloride → chloroform2.27271.0
Acetylene → chloroprene1.33331.0
Butadiene → chloroprene1.33331.0
Butadiene → chloroprene1.251.0
Phenol → cresylic acid1.14940.5
Methane → carbon tetrachloride9.09091.0
Carbon tetrachloride → dichlorofluoromethane9.09091.0
Methyl chloride → carbon tetrachloride2.77781.0
Terephthalic acid → dimethyl terephthalate1.14941.0
Acetic acid → ethyl acetate1.44931.0
Acrylic acid → ethyl acetate1.29871.0
Ethylene → ethyl chloride2.0001.0
Ethylene → ethyl dibromide6.25001.0
N-butyraldehyde → 2-ethyl hexanol0.81301.0
Epichlorohydrin → glycerine0.95241.0
Adiponitrile → hexamethylenediamine1.07531.0
Acetone → isoprene1.05261.0
Benzene → maleic anhydride0.76920.66
Ethylene dichloride → methyl chloroform1.21951.0
Methane → methylene dichloride5.00001.0
Methyl chloride → methyl dichloride1.61291.0
n-Butylene → methyl ethyl ketone1.11111.0
Acetone → methyl isobutyl ketone0.80001.0
Acetone → methyl methacrylate1.38891.0
Carbon tetrachloride0.50001.0
Propylene oxide → propylene glycol1.17651.0
Butadiene → styrene0.96961.0
Toluene diamine → toluene diisocynate1.20481.0
Carbon tetrachloride → trichlorofluoromethane0.71431.0
Ethylene oxide → ethylene glycol1.13641.0
Diethylene glycol → triethylene glycol2.8571.10
Carbon monoxide → urea1.31581.0
Acetic acid → vinyl acetate1.38891.0
Carbon monoxide → formic acid1.64281.0
Cyclohexanol → adipic acid1.36991.0
Methane → hydrogen cyanide1.2195
Propane → hydrogen cyanide1.56251.0
Carbon monoxide → isobutanol0.14990.8

Table 2.

Industrial chemical reactions, commercial yield and atom economy.

%Carbon economy=Unit weight of product/Unit weight ofrawmaterials×Molecular Weight ofrawmaterials/Molecular Weight of product×Moles of carbon in product/Moles of carbon inrawmaterials×100.E1

4. Reaction pathways from biomass to industrial chemicals

The reaction pathways for the top industrial chemicals, as listed in the previous section, were combined with the biomass conversion reactions to maximize the overall carbon economy. This yielded biomass conversion reaction pathways to the major industrial chemicals, and these conversion paths with the maximum carbon economy are listed in Table 3.

Industrial chemicalReaction path with the highest carbon economyOverall carbon economy
ButadieneBeech wood → methane → acetylene → butadiene0.4173
Di ethylene glycolPine saw dust → carbon monoxide → methanol → formaldehyde → ethylene glycol → di ethylene glycol0.5940
Carbon monoxidePine saw dust → carbon monoxide0.5940
Carbon dioxideBeech wood → carbon dioxide0.2923
MethaneBeech wood → methane0.8346
EthyleneBeech wood → methane → acetylene → ethylene0.4173
EthaneAlaskan spruce → ethane0.0713
AcetyleneBeech wood → methane → acetylene0.4173
PropyleneBeech wood → propylene0.0236
PropaneTropical luan → propane0.1700
IsobutaneSunflower residue → isobutane0.0100
n-ButaneSunflower residue → n-butane0.0400
n-ButyleneSunflower residue → methylene dichloride → n-butylene
n-PentaneCannot be produced from biomass
Iso-PentaneRape residue → iso-pentane0.0300
EthanolBeech wood → methanol → acetylene → ethylene → ethanol0.4173
CyclohexaneSewage sludge → benzene → cyclohexane0.0852
BenzeneSewage sludge → benzene0.0852
Ethyl benzeneSewage sludge → benzene → ethyl benzene0.0852
NaphthaleneAlaskan spruce → naphthalene0.0203
TolueneRice husk → toluene0.0388
0-Xylene, m-XyleneCannot be produced from biomass
p-XyleneAlaskan spruce → p-xylene0.0096
AcetaldehydeBeech wood → methane → acetylene → ethylene → acetaldehyde0.4173
Acetic acidPine saw dust → carbon monoxide → methanol → acetic acid0.5940
Acetic anhydridePine saw dust → carbon monoxide → methanol → acetic acid → acetic anhydride0.5940
AcetonePine saw dust → carbon monoxide → methanol → acetic acid → acetone0.4455
AcroleinBeech wood → methane → acetylene → ethylene → acetaldehyde → acrolein0.4173
Acrylic acidPine saw dust → carbon monoxide → methanol → acetic acid → acrylic acid0.5940
AdiponitrileBeech wood → methane → acetylene → butadiene → adiponitrile0.4173
Allyl alcoholBeech wood → propylene → allyl chloride → allyl alcohol0.0236
Allyl chloridebeech wood ⇒ propylene → allyl chloride0.0236
n-Butanolbeech wood → methane → acetylene → acetaldehyde → crotonaldehyde → n-butanol0.3091
Iso-Butanolsunflower residue → methylene dichloride → methyl iso butyl ketone → iso-butanol0.0004
n-ButyraldehydeBeech wood → methane → acetylene → acetaldehyde → crotonaldehyde → n-butyraldehyde0.3091
ChlorobenzeneSewage sludge → benzene → chlorobenzene0.0852
CrotonaldehydeBeech wood → methane → acetylene → ethylene → acetaldehyde → crotonaldehyde0.3091
CumeneSewage sludge → benzene → cumene0.0852
CyclohexanolSewage sludge → benzene → cyclohexane → cyclohexanol0.0852
CyclohexanoneSewage sludge → benzene → cyclohexane → cyclohexanol → cyclohexanone0.0852
Dinitro tolueneRice husk → toluene → dinitro toluene0.0388
EpichlorohydrinBeech wood → methane → acetylene → acetaldehyde → acrolein → epichlorohydrin0.4173
Ethylene dichlorideBeech wood → methane → acetylene → ethylene → ethylene dichloride0.4173
Ethylene oxideBeech wood → methane → acetylene → ethylene → ethylene oxide0.4173
Ethylene glycolPine saw dust → carbon monoxide → methanol → formaldehyde → ethylene glycol0.5940
Iso-ButyraldehydeCannot be manufactured from biomass
IsopropanolBeech wood → isoprene → isopropanol0.0236
KeteneOne saw dust → ethyl acrylate → methanol → acetic acid → ketene0.5940
MethanolPine saw dust → carbon monoxide → methanol0.5940
Methyl chlorideBeech wood → methane → methyl chloride0.8346
Nitro benzeneSewage sludge → benzene → nitrobenzene0.0852
Peracetic acidBeech wood → methane → acetylene → acetaldehyde → peracetic acid0.2087
PhenolSewage sludge → benzene → phenol0.0852
PhosgenePine saw dust → ethyl acrylate → phosgene0.5940
AcrylonitrileBeech wood → ethylene dibromide → hexamethylene diamine → acrylonitrile0.4173
AnilineSewage sludge → benzene → aniline0.0852
Benzoic acidRice husk → toluene → benzoic acid0.0388
Bisphenol ASewage sludge → benzene → phenol → bisphenol A0.0852
CaprolactamSewage sludge → benzene → cyclohexane → caprolactam0.0852
ChloroformBeech wood → methane → chloroform0.8346
ChloropreneBeech wood → methane → acetylene → chloroprene0.4173
Cresylic acidSewage sludge → benzene → phenol → cresylic acid0.0426
Dichloro difluoro methaneBeech wood → methane → carbon tetrachloride → dichloro difluoro methane0.8346
Dimethyl terephtalateRice husk → toluene → terepthalic acid dimethyl terephtalate0.0388
Ethyl acetatePine saw dust → carbon monoxide → methanol → acetic acid → ethyl acetate0.5940
Ethyl acrylatePine saw dust → carbon monoxide → methanol → acetic acid → acrylic acid → ethyl acrylate0.5940
Ethyl chlorideBeech wood → methane → acetylene → ethylene → ethyl chloride0.4173
Ethylene dibromideBeech wood → methane → acetylene → ethylene → ethylene dibromide0.4173
2-Ethyl hexanolPaddy straw → ethanol → acetaldehyde → crotonaldehyde → n-butyraldehyde → 2-ethyl hexanol0.2934
GlycerinePaddy straw → ethanol → acetaldehyde → cumene → epichlorohydrin → glycerine0.3961
Hexamethylene diamineBeech wood → methane → acetylene → methyl methacrylate → adiponitrile → hexamethylene diamine0.4173
IsoprenePine saw dust → carbon monoxide → methanol → acetic acid → acetone → isoprene0.4455
Maleic anhydrideSewage sludge → benzene → maleic anhydride0.0852
Methyl chloroformBeech wood → methane → acetylene → ethylene → ethylene dichloride → methyl chloroform0.4173
Methylene dichlorideBeech wood → methane → methylene dichloride0.8346
Methyl ethyl ketoneSunflower residue → methylene dichloride → methyl iso butyl ketone → methyl ethyl ketone0.0400
Methyl iso butyl ketonePine saw dust → carbon monoxide → methanol → acetic acid → acetone → methyl iso butyl ketone0.4455
Methyl methacrylatePine saw dust → carbon monoxide → methanol → acetic acid → acetone → methyl methacrylate0.4455
PerchloroethyleneBeech wood → propylene → carbon tetrachloride → perchloroethylene0.8346
Propylene glycolBeech wood → propylene → propylene oxide → propylene glycol0.0236
StyreneBeech wood → methane → acetylene → methyl methacrylate → styrene0.4173
Toluene di isocyanateRice husk → toluene → dinitro toluene → toluene diamine → toluene di iso cyanate0.0388
Trichloro fluoro methaneBeech wood → methane → carbon tetrachloride → trichloro fluoro methane0.8346
Triethylene glycolBeech wood → ethylene → ethylene oxide → ethylene glycol → diethylene glycol → triethylene glycol0.0843
UreaPine saw dust → carbon monoxide → urea0.5940
Vinyl acetatePine saw dust → carbon monoxide → methanol → acetic acid → vinyl acetate0.5940
HexaneRape residue → hexane0.0800
Formic acidPine saw dust → carbon monoxide → formic acid0.5940
Adipic acidSewage sludge → benzene → cyclohexane → cyclo hexanol → adipic acid0.0852
Carbon tetrachlorideBeech wood → methane → carbon tetrachloride0.8346
Hydrogen cyanideBeech wood → hydrogen cyanide0.8346
IsobutanolPine saw dust → carbon monoxide → iso-butanol0.4752

Table 3.

Chemical pathways for converting biomass to industrial chemicals with the overall carbon economy.

Although several biomass sources were used in the analysis, only beechwood, pine sawdust, sunflower residue, rape residue, sewage sludge, alaskan spruce, tropical luan, and rice husk were selected to maximize the overall carbon economy, with beechwood and pine sawdust being mostly used to generate the chemical intermediate. Sewage sludge was used to generate benzene as an intermediate chemical, which could then be converted to other aromatic compounds. The carbon economy for sewage sludge conversion to aromatics was less than 10%, which may render these chemical paths uneconomical.

The following examples from Table 3 illustrate the biomass conversion reactions which had the highest atom economy for two industrial chemicals.

Butadiene can be produced from biomass using the following steps:

  1. Gasification of beech wood: conducted at 700°C and atmospheric pressure produces methane with an atom economy of 83.5% [7].

  2. Conversion of methane to acetylene gas: using the arc process [3], methane is converted to acetylene gas with an atom economy of 50%; byproducts produced are ethylene and hydrogen gases.

  3. Reaction of acetylene with formaldehyde [3]: product is butadiene and steam.

Figure 1 shows a schematic of the reaction pathway to convert beech wood to butadiene.

Figure 1.

Reaction path for manufacturing butadiene from beech wood.

Another example of a reaction pathway is the conversion of pine sawdust to diethylene glycol, and this reaction pathway with their respective atom economies is shown in Figure 2. This pathway has the highest carbon economy for manufacturing diethylene glycol from a biomass source.

Figure 2.

Reaction path for manufacturing Di ethylene glycol from pine sawdust.


5. Conclusions

Sustainable industrial chemistry requires “optimum” reaction pathways, as defined by the highest carbon economy, starting with various biomass materials. Biomass is a sustainable feedstock, while currently used starting materials, such as crude oil, coal, and natural gas, are unsustainable. Furthermore, when industrial chemicals are made from unsustainable feedstocks, they eventually add additional carbon to the environment, typically in the form of carbon dioxide, an earth warming gas. Manufacturing industrial chemicals from biomass is an important step toward mitigating climate change.

The chemical industry has to recognize that continuing the use of nonsustainable feedstocks to manufacture industrial chemicals is not a viable option, especially with the growing concerns about climate change. Utilizing the existing chemical industry and simply using feedstocks derived from biomass is the most economical and expedient way to accomplish two major goals: make the chemical industry more sustainable and slow the increase in the atmospheric carbon dioxide concentration. Eventually, it will be a strategy to avoid carbon taxes on the top 100 industrial chemicals.

In this paper, a systematic method of generating the reaction pathways from various biomass sources to the top 100 industrial chemicals, which maximize the overall carbon economy, was presented. It provides a listing of multiple ways of manufacturing the industrial chemicals in the order of deceasing-carbon economy.


  1. 1. Wittcoff HA. Reuben BG. Plotkin JS. Industrial Organic Chemicals. 2nd ed. New York: Wiley-Interscience; 2004. p. 93. DOI: 10.1002/0471651540
  2. 2. Industrial Organic Chemistry / Weissermel K. Arpe HJ. Transl. by Lindley CR. 4 ed. Weinheim: VCH; 1997. DOI: 10.1002/9783527619191
  3. 3. Stadtherr MA, Rudd DF. Systems study of the petrochemical industry. Chemical Engineering Science. 1976;31:101-1028
  4. 4. Blackford JL, Kashiwase D, Zalk SA. Chemical Conversion Factors and Yields: Commercial and Theoretical. Stanford Research Institute: Chemical Industries Division; 1984
  5. 5. Corte P, Lacoste C, Traverse JP. Gasification and catalytic conversion of biomass by flash pyrolysis. Journal of Analytical and Applied Pyrolysis. 1985;7:323-335
  6. 6. Garcia L, Salvador ML, Arauzo J, Bilbao R. Catalytic pyrolysis of biomass: Influence of the catalyst pretreatment on gas yields. Journal of Analytical and Applied Pyrolysis. 2001;58–59:491-501
  7. 7. Sanchez ME, Cuetos MJ, Martınez O, Moran A. Pilot scale thermolysis of municipal solid waste combustibility of the products of the process and gas cleaning treatment of the combustion gases. Journal of Analytical and Applied Pyrolysis. 2007;78:125-132
  8. 8. Kaminsky W, Kummer AB. Fluidized bed pyrolysis of digested sewage sludge. Journal of Analytical and Applied Pyrolysis. 1989;16:27-35
  9. 9. Sanchez ME, Lindao E, Margaleff D, Martinez O, Moran A. Pyrolysis of agricultural residues from rape and sunflowers: Production and characterization of bio-fuels and biochar soil management. Journal of Analytical and Applied Pyrolysis. 2009;85:142-144
  10. 10. Boateng AA, Hicks KB, Vogel KP. Pyrolysis of switch grass (Panicum virgatum) harvested at several stages of maturity. Journal of Analytical and Applied Pyrolysis. 2006;75:55-64
  11. 11. Guo S, Libin W, Wang C, Li J, Yang Z. Direct conversion of sunflower shells to alkanes and aromatic compound. Energy & Fuels. 2008;22:3517-3522
  12. 12. Maiti S, Banerjee P, Purakayastha S, Ghosh B. Silicon doped carbon semiconductor from rice husk char. Materials Chemistry and Physics. 2008;109:169-173
  13. 13. Ji-lu Z. Bio-oil from fast pyrolysis of rice husk: Yields and related properties and improvement of the pyrolysis system. Journal of Analytical and Applied Pyrolysis. 2007;80:30-35
  14. 14. Chang W, Qinglan H, Dingqiang L, Qingzhu J, Guiju L, Bo X. Production of light aromatic hydrocarbons from biomass by catalytic pyrolysis. Chinese Journal of Catalysis. 2008;29(9):907-912
  15. 15. Sudha Rani K, Swamy MV, Seenayya G. Production of ethanol from various pure and natural cellulosic biomass by clostridium thermocellum strains SS21 and SS22. Process Biochemistry. 1998;33(4):435-440
  16. 16. Cao NJ, Krishnan MS, Du JX, Gong CS, Ho NWY, Chen ZD, et al. Ethanol production from corn cob pretreated by the ammonia steeping process using genetically engineered yeast. Biotechnology Letters. 1996;18:1013-1018
  17. 17. Torget R, Hatzis C, Hayward TK, Hsd T-A, Philippidis GP. Optimization of reverse-flow, two-temperature, dilute-acid pre treatment to enhance biomass conversion to ethanol. Applied Biochemistry and Biotechnology. 1996;57/58:85
  18. 18. Spindler DD, Wyman CE, Grohmann K. All MohagheGHI, SIMULTANEOUS SACCHARIfication and fermentation of Pretreated wheat straw to ethanol with selected yeast strains and glycosidase supplementation. Applied Biochemistry and Biotechnology. 1989;20/2:I
  19. 19. Li H, Kim N-J, Jiang M, Kang JW, Chang HN. Simultaneous saccharification and fermentation of lingo cellulosic residues pretreated with phosphoric acid–acetone for bio ethanol production. Bioresource Technology. 2009;100:3245-3251
  20. 20. Saha BC, Cotta MA. Enzymatic saccharification and fermentation of alkaline peroxide pretreated rice hulls to ethanol. Enzyme and Microbial Technology. 2007;41:528-532

Written By

Rakesh Govind, Shiva Charan and Jack Baltzersen

Submitted: February 7th, 2022 Reviewed: February 8th, 2022 Published: March 20th, 2022