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Reagent Byproducts
Substitution
Feedstock Product
reaction
Byproducts
Reagent
Elimination
Feedstock Product
reaction
12.3. BIOLOGICAL FEEDSTOCKS
Organisms have provided a huge share of the materials used by
humans throughout their existence.
Biomass: Plant material generated by photosynthesis
• Leading candidate to replace petroleum as a feedstock for the
organic chemicals industry
• Partially oxidized biomass material avoids expensive, sometimes
difficult oxidation steps in oxidizing petroleum
Major Categories of Biomass That Can Be Used for Feedstock
1. Carbohydrate, general formula of approximately CH2O
• Glucose sugar from photosynthesis • In cellulose
2. Lignin, a complex biological polymer in wood having few uses
3. Lipid oils extracted from seeds, including soybeans, sunflowers,
and corn.
4. Hydrocarbon terpenes produced by rubber trees, pine trees, and
some other kinds of plants.
5. Proteins, produced in relatively small quantities, but potentially
valuable as nutrients and other uses.
Obtaining Feedstocks from Biomass
Pathways by which feedstocks can be obtained from biomass
• Simple physical separation of biological materials, such as tapping
latex from rubber trees
• Extraction of oils by organic solvents
• Physical and chemical processes such as separation of cellulose
bound together by lignin “glue” in making paper
Carbohydrate Feedstocks
Carbohydrates as feedstocks for chemical processes
Carbohydrates in several forms
• Sucrose sugar, C12H22O11, squeezed from sugar cane as sap and
extracted from sugar beets and sugar cane with water
• Starch, a polymer of glucose readily isolated from grains, such as
corn, or from potatoes and readily broken down adding water to
give glucose
• Huge amounts of cellulose, which occurs in woody parts of plants
and broken down to glucose with cellulase enzymes
Lipid Oils and Terpenes
Lipid oils are extracted from the seeds of some plants
• Volatile solvent n-hexane, C6H14, is used to extract oils
• Solvents are distilled off from the extract and recirculated through
the process.
Hydrocarbon terpenes can be tapped from rubber trees as a latex
suspension in tree sap
Steam treatment and distillation to extract terpenes from sources
such as pine or citrus tree biomass
Proteins
Grain seeds as sources of protein
• Generally used for food
• Potentially useful as chemical feedstocks for specialty applications
• Transgenic plants to make specialty proteins, such as medicinal
agents
12.4. FERMENTATION AND PLANT SOURCES OF
CHEMICALS
Two main biological sources of materials to provide specialty and
commodity chemicals and feedstocks
• Plants • Microorganisms, especially bacteria and yeasts
Fermentation refers to the action of microorganisms on nutrients
under controlled conditions to produce desired products
• Anaerobic (anoxic, absence of air)
• Aerobic (oxic, presence of air)
Fermentation used for thousands of years to produce alcoholic
beverages, sauerkraut, vinegar, pickles, cheese, yogurt, other foods
and ethanol
Lactic acid from fermentation
O H H
HO C C C H
HO H Lactic acid
More recently production by fermentation of organic acids,
antibiotics, enzymes, and vitamins
Penicillin Starting in the 1940s, Later, Other Antibiotics from
Fermentation
O C H C H
H H
3-Dehydros hikimic acid
C C
HO OH
12.6. CELLULOSE
Segment of the cellulose molecule CH2OH
in which from 1500 to several H H
C O
thousand anhydroglucose units C OH H C
(glucose molecules less H2O) are CH2OH
C C
H
bonded together: C
H H
O O
H OH
Cellulose is the most abundant C OH H C
natural material produced by C C
H
(C6H11O5)1500-6000
organisms H OH
• Annual world production around Bond to remainder of polymer
H O H H H H
5-Cyanovaleramide (12.10.4)
N C C C C C C N
H H H H H
• Isolation of the 5-cyanovaleramide product entails dissolving the
hot reaction mixture in toluene solvent, which is then cooled to
precipitate the product
• For each kilogram of 5-cyanovaleramide product isolated,
approximately 1.25 kg of waste MnO2 requires disposal
Biosynthesis of 5-Cyanovaleramide (Cont.)
Biochemical synthesis of 5-cyanovaleramide with microoorganisms
that had nitrile hydratase enzymes to convert the CN functional
group to the amide group using Pseudomonas chloroaphis B23
• Run at 5˚C over cells immobilized in beads of calcium alginate, the
salt of alginic acid isolated from the cell walls of kelp with 97%
conversion
• Water-based reaction mixture simply separated mechanically from
the calcium alginate beads containing the microorganisms, which
are then recycled for the next batch of reactant
• Water then distilled off of the product to leave an oil, from which
the 5-cyanovaleramide product was dissolved in methanol, leaving
adipamide and other byproducts behind with only 0.006 kg of
water-based catalyst waste residue produced per kg of product