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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.
*Address all correspondence to: govindr@ucmail.uc.edu
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.
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].
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
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 reaction
Yield (product/reactant)
Atom economy
Methane → acetylene
0.4545
0.5
Acetylene → ethylene
0.9174
1.0
Ethanol → ethylene
0.5848
1.0
Propane → acetylene
0.3448
0.50
Isobutane → isobutylene
0.6667
1.0
n-Butane → N-butylene
0.6667
1.0
Acetylene → butadiene
1.4925
1.0
Ethanol → butadiene
0.3333
1.0
Ethylene → ethanol
1.5152
1.0
Benzene → cyclohexane
1.0753
1.0
Benzene → ethyl benzene
1.3158
1.0
Ethylene → acetaldehyde
1.4925
1.0
Carbon monoxide → methanol
1.0
1.0
Methanol → acetic acid
1.8519
1.0
Acetic acid → acetic anhydride
1.6129
1.0
Acetic acid → acetone
0.4587
0.75
Acetaldehyde → acrolein
0.9524
1.0
Acetic acid → acrylic acid
1.20
1.0
Butadiene → adiponitrile
1.2195
1.0
Propylene → allyl chloride
1.4286
1.0
Allyl chloride → allyl alcohol
0.6667
1.0
Acetylene → acetaldehyde
1.6129
1.0
Acetaldehyde → crotonaldehyde
0.7407
1.0
Crotonaldehyde → n-butanol
1.0
1.0
Ethanol → acetaldehyde
0.8696
1.0
Crotonaldehyde → n-butyraldehyde
1.0
1.0
n-Butyraldehyde → n-butanol
0.9709
1.0
n-Butylene → butanol
1.1111
1.0
Benzene → chlorobenzene
1.2195
1.0
Benzene → cumene
1.2658
1.0
Cyclohexane → cyclohexanol
0.9709
1.0
Cyclohexanol → cyclohexanone
0.9524
1.0
Methanol → formaldehyde
0.8696
1.0
Formaldehyde → ethylene glycol
1.5385
1.0
Ethylene glycol → diethylene glycol
1.4286
1.0
Toluene → dinitro toluene
1.8519
1.0
Acrolein → epichlorohydrin
1.2847
1.0
Ethylene → ethylene dichloride
3.3333
1.0
Ethylene → ethylene oxide
1.25
1.0
Propylene → isopropanol
1.3889
1.0
Acetic acid → ketene
0.6289
1.0
Methane → methyl chloride
2.439
1.0
Methanol → methyl chloride
1.4286
1.0
Benzene → nitro benzene
1.5385
1.0
Acetaldehyde → peracetic acid
1.5625
0.5
Benzene → phenol
0.9009
1.0
Carbon monoxide → phosgene
0.9009
1.0
Naphthalene → phthalic anhydride
0.9524
0.8
Propylene → propylene dichloride
2.439
1.0
Propylene → propylene oxide
1.0638
1.0
Toluene → terephthalic acid
1.8043
1.0
Dinitro toluene → toluene diamine
0.6369
1.0
Acetylene → trichloroethylene
4.7619
1.0
Ethylene dichloride → trichloroethylene
1.2658
1.0
Acetylene → vinyl chloride
2.2727
1.0
Ethylene dichloride → vinyl chloride
0.5988
1.0
Acetylene → acrylonitrile
1.6667
1.0
Acetaldehyde → acrylonitrile
1.2045
1.0
Benzene → aniline
1.1923
1.0
Toluene → benzoic acid
1.1905
1.0
Phenol → bisphenol a
1.1364
1.0
Cyclohexane → caprolactam
0.7692
1.0
Methane → chloroform
7.1429
1.0
Methyl chloride → chloroform
2.2727
1.0
Acetylene → chloroprene
1.3333
1.0
Butadiene → chloroprene
1.3333
1.0
Butadiene → chloroprene
1.25
1.0
Phenol → cresylic acid
1.1494
0.5
Methane → carbon tetrachloride
9.0909
1.0
Carbon tetrachloride → dichlorofluoromethane
9.0909
1.0
Methyl chloride → carbon tetrachloride
2.7778
1.0
Terephthalic acid → dimethyl terephthalate
1.1494
1.0
Acetic acid → ethyl acetate
1.4493
1.0
Acrylic acid → ethyl acetate
1.2987
1.0
Ethylene → ethyl chloride
2.000
1.0
Ethylene → ethyl dibromide
6.2500
1.0
N-butyraldehyde → 2-ethyl hexanol
0.8130
1.0
Epichlorohydrin → glycerine
0.9524
1.0
Adiponitrile → hexamethylenediamine
1.0753
1.0
Acetone → isoprene
1.0526
1.0
Benzene → maleic anhydride
0.7692
0.66
Ethylene dichloride → methyl chloroform
1.2195
1.0
Methane → methylene dichloride
5.0000
1.0
Methyl chloride → methyl dichloride
1.6129
1.0
n-Butylene → methyl ethyl ketone
1.1111
1.0
Acetone → methyl isobutyl ketone
0.8000
1.0
Acetone → methyl methacrylate
1.3889
1.0
Carbon tetrachloride
0.5000
1.0
Propylene oxide → propylene glycol
1.1765
1.0
Butadiene → styrene
0.9696
1.0
Toluene diamine → toluene diisocynate
1.2048
1.0
Carbon tetrachloride → trichlorofluoromethane
0.7143
1.0
Ethylene oxide → ethylene glycol
1.1364
1.0
Diethylene glycol → triethylene glycol
2.8571
.10
Carbon monoxide → urea
1.3158
1.0
Acetic acid → vinyl acetate
1.3889
1.0
Carbon monoxide → formic acid
1.6428
1.0
Cyclohexanol → adipic acid
1.3699
1.0
Methane → hydrogen cyanide
1.2195
Propane → hydrogen cyanide
1.5625
1.0
Carbon monoxide → isobutanol
0.1499
0.8
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 chemical
Reaction path with the highest carbon economy
Overall carbon economy
Butadiene
Beech wood → methane → acetylene → butadiene
0.4173
Di ethylene glycol
Pine saw dust → carbon monoxide → methanol → formaldehyde → ethylene glycol → di ethylene glycol
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:
Gasification of beech wood: conducted at 700°C and atmospheric pressure produces methane with an atom economy of 83.5% [7].
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.
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.
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.
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Written By
Rakesh Govind, Shiva Charan and Jack Baltzersen
Submitted: 07 February 2022Reviewed: 08 February 2022Published: 20 March 2022
Open access peer-reviewed chapter
