Overview of The Catalytic Production of Isoprene From Different Raw Materials Prospects of Isoprene Production From Bio Ethanol
Overview of The Catalytic Production of Isoprene From Different Raw Materials Prospects of Isoprene Production From Bio Ethanol
Overview of The Catalytic Production of Isoprene From Different Raw Materials Prospects of Isoprene Production From Bio Ethanol
used practically in all spheres of industry and national economy with its Synthesis, Moscow, Russia Chemical Technology,
global production exceeding 1.3 million tons per year In this paper, various 86 Vernadsky avenue, Moscow, Russia
methods for its production and their shortfalls were studied; the prospect
for isoprene production from bio-ethanol was also highlighted.
Keywords
Isoprene • Synthetic rubber (SR) • Catalyst • Isopentane • Isopentene
* E-mail: [email protected]
Unauthenticated
100
Download Date | 8/21/15 2:47 PM
Overview of the Catalytic Production of Isoprene from different raw
materials; Prospects of Isoprene production from bio-ethanol.
corn feedstocks, while the second generation bioethanol from side reactions, trimethyl carbinol, methylal, dioxane alcohols,
lignocellulosic feedstock is under extensive development [9]. diols, ethers etc, are formed. The formation of isoprene in the
In this paper, the most common industrial methods of isoprene second step is also accompanied with the decomposition
production and their shortfalls were studied; the possibility of of dimethyldioxane to iso- butylenes and formaldehyde,
isoprene production from ethanol was also highlighted. dihydromethylpyran, hexadiene, piperylene, terpene
compounds, green oil etc.
2. Synthesis methods Isobutylene contained in C5 fraction of liquid hydrocarbon
pyrolysis is the raw material mainly used. However, the presence
2.1. Extraction of isoprene from C5 fraction of liquid of n- butane compounds and butadiene leads to the formation of
petroleum pyrolysis. isomeric dioxane compounds which decompose to a wide range
This is the simplest method of isoprene production which of by- products.
involves its extraction from C5 fraction of liquid petroleum The second step of isoprene synthesis from isobutylene
pyrolysis containing about 15 – 20% isoprene. This fraction is and formaldehyde is carried out in a section type reactor using
produced as a by – product in the production of ethylene and energy from steam heated to 973K. Acid phosphates of group
propylene. However, the transportation of raw materials from II metals are used as catalysts, calcium phosphate in particular.
different refineries for the industrial realization of this method The selectivity of phosphate catalyst is increased by its continous
creates some difficulties [1]. Environmental issues are also activation in the process, by the introduction of small amounts
there to be tackled especially with the recent tightening of of phosphoric acid vapour directly into the catalysis zone which
environmental laws. leads to the formation of acidic phosphates on the surface of the
calcium phosphate catalyst.
2.2. Two step isoprene production from isobutylene Ca3(PO4)2 + H3PO4 → 3CaHPO4
and formaldehyde During catalysis, coke is deposited on the surface of the
The reaction of unsaturated hydrocarbons with formaldehyde catalyst, this is the reason for which regeneration is done every
was first described by H. Prince in 1917, he studied the reaction 2 -3 hrs by burning off the coke in a stream of air mixed with
of styrene and formaldehyde in the presence of sulfuric acid steam at temperatures above 773K. The process flow diagram of
as the catalyst, which resulted to the formation of formals of isoprene production from the decomposition of dimethyl dioxane
dioxane -1, 3. Fitski and Friedrickson in 1932 discovered the is shown in the figure below.
possibility of using princes reaction for the synthesis of diene Dimethyldioxane vapour is mixed with steam and sent to
hydrocarbons. In 1946, soviet scientists M. I. Farberov and M. reactor (2) to which steam heated to 973K from the the steam
S. Nemtsov et. al discovered the possibility of developing highly heater (1) is supplied. The gas mixture enters the cascade of
efficient process for isoprene production using this method. The heat exchangers (3), in which the products are condensed.
method was actualized and implemented in 1964. The condensate consisting of two phases –the organic and
The synthesis of isoprene using this method is carried out aqueous, is allowed to settle in (4). The oily layer gets washed
in two steps. In the first step, isobutylene is condensed with out in (5) where the extraction of dissolved formaldehyde takes
formaldehyde in the presence of an acidic catalyst such as place. The washed stream is sent to rectification column (6),
diluted sulphuric acid to form 4, 4- dimethyldioxane -1,3 as where the lighter products, mainly isobutylene and isoprene are
depicted below. separated from the decomposed dimethyl dioxane and other
CH3 less volatile substances. The stream from (6) then enters the
CH3
rectification column (7), where highly concentrated isobutylene
CH3 C CH2 2CH2O CH3 C CH2 CH2 is collected and returned for synthesis of dimethyl dioxane.
The distillate from (7) – raw isoprene is sent to columns 8, 9 for
O CH2 O further rectification in order to remove impurities with high boiling
points, mainly cyclopetadiene and carbonyl compounds, which
4, 4 dimethyldioxane- 1, 3 are washed out in colum (10). The distillate from column (11)
is sent to vacuum column (12) in which by-products with high
In the second step, 4 - 4- dimethyldioxane -1, 3 is boiling points, mainly isoprene oligomers or green oil from the
decomposed into isoprene on a solid phosphate catalyst such second stage of the synthesis are removed from the recycled
as calcium phosphate. dimethyldioxane. An extragent (made up of the mixture of iso-
CH3 CH3 propyl alcohol and dimethyldioxane) can be recovered for the
extraction of the byproducts of the first stage of the process from
CH3 C CH2 CH2 CH2 C CH CH2 CH2O H2O
the recycled dimethyldioxane, by rectification.
O CH2 O Isoprene The contact gas from the reactor goes for condensation,
while the condensate is sent to the settler where stratification
In each of these steps, the main reaction is accompanied into oily and aqueous layers is carried out. The oily layer
by numerous side reactions. In the first step, as a result of the undergoes rectification in a double column system, which gives
Unauthenticated
101
Download Date | 8/21/15 2:47 PM
G.O. Ezinkwo et al.
Figure 1. Flow diagram of isoprene production from dimethyl dioxane decomposition. [1]
1-Steam heater, 2- reactor, 3 – condenser, 4-settler, 5, 10 – columns for washing, 6 – crude isoprene distillation column, 7 – distillation column
for recycled iso – butylenes, 8, 9 – column for isoprene rectificate, 11- MDGP fraction column, 12 – recycled DMD column, 13 - absorber,
14 – desorber, 15 – distillation column for light organic compounds, 16 – recovery column for formaldehyde.
Streams
I steam, II- DMD Vapour, III – washing water, IV- recycled isobutylene, V- boiling impurities, VI- isoprene rectificate, VII- MDGP fraction; VIII –
recycled DMD; IX- recovered formaldehyde, X- waste water.
yields to iso- butylenes (which is returned to the first stage of 2.2.2. Disadvantages
the synthesis), fraction of raw dimethyl dioxane, and isoprene One of the major disadvantages of this process is the formation
distillate which contains traces of carbonyl compounds (mainly of numerous by products up to 0,5 ton/ton isoprene. In order
aldehydes). The raw isoprene is sent for rectification (distillation), to utilize some of the byproducts, trimethyl carbonyl fraction
in order to get isoprene distillate, which is further rinsed with undergoes decomposition which leads to the formation of
condensate in order to get rid of carbonyl compounds. Finally, isobutylene that is recycled into the process which significantly
polymerization inhibitors are added to prevent the polymerization reduces its consumption relative to 1 ton of isoprene. The
of isoprene in the distillation columns. decomposition of dihydromethylpyran fractions allows for the
production of additional 2% of isoprene.
2.2.1. Advantages of the method The need for the recovery of formaldehyde formed during
One of the major advantages of this method in comparison the decomposition or cracking of dimethyloxidane is another
with others is the production of a product with high purity and shortfall but it can be taken care of by using a process in which
with relatively simple methods of synthesis and purification intermediate products like methylbutanediol or isoamylene
employed. Below, in Table 1 is the composition of the isoprene alcohols are formed, which can easily be converted to isoprene
distillate in %wt. with high yields at relatively mild conditions (453 – 527 K) on
phosphate catalysts. However, the development of an industrial
process which inculcates the formation of these intermediate
Table 1. Composition of the isoprene distillate. [1] compounds is hampered by the absence of methods for their
selective production.
Compound %wt A more successful way of isoprene production through
methylbutanediol formation stage was developed by the Russian
Isobutylene 0,006 institute of organic chemistry in collaboration with All – unioin
Isopentane 0,002 scientific research and design institute of monomers in Tula,
Russia [1].
Isoprene 99,69
Unauthenticated
102
Download Date | 8/21/15 2:47 PM
Overview of the Catalytic Production of Isoprene from different raw
materials; Prospects of Isoprene production from bio-ethanol.
step methods. In the two step method, isopentane in the first - Isomerization with the migration of double bonds in pentene.
stage is dehydrogenated to isoamylene, which are further CH CH
dehydrogenated to isoprene in the second stage of the process
CH3 CH2 CH2 CH CH2 CH3 CH2 CH3
as shown below:
one- step method is different from the two step in the - Cracking of the feed substance, intermediate, and final
sense that the dehydrogenation of isopentane and isopentane- products.
isoamylene mixtures is carried out on the same catalyst without - Deeper dehydrogenation accompanied by cyclization,
intermediate separation of isopentane and isoamylenes. aromatization and formation of compounds with triple bonds;
An important advantage of the two-step process is the - Reaction of olefins, diene hydrocarbons and water vapour
possibility of the use of highly selective catalyst at each stage resulting to the formation of oxy- compounds;
and high energy consumption significantly undermines the - Coke formation.
competitiveness of the two-step method in comparison with
the one- step method. The dehydrogenation of isopentane to isopentene is also
The dehydrogenation of alkanes, isopentane in particular is a accompanied by the formation of light hydrocarbons of C1 – C4,
reversible endothermic reaction. heavier of C6 and above, CO, CO2 and coke. The production of
isoprene from isopentane in comparison with the production of
CnH2n + 2 CnH2n CnH2n - 2
butadiene is more complicated by the fact that a larger amount
of isomers are formed in this process than those formed during
Alongside the dehydrogenation of isopentane, the following the dehydrogenation of butane.
reactions also occur:
Shortfall of the method
CH3 CH2 CH CH3 CH3 CH2 C CH2 H2
Isopentane and isopentene which posses the hydrocarbon
CH3 skeleton of the final product are scarce due to their wide usage
CH3
as high quality gasoline additive instead of tetraethyl lead. This
2-methylbutene-1
limits their usage for isoprene production.
CH3 Catalyst
CH3
The process is carried out on Al-Cr-Li, Al-Cr-Pb catalyst system
2-methylbutene-2 promoted on K2O. Al- Cr-Li, Al-Cr-Pb, Al-Cr-Zn systems are
more active than Al-Cr system promoted on K2O. The process
In this case three isomers of isopentene; 2-methyl butene-1, flow diagram of isopentane dehydrogenation in fluidized
3-methylbutene-1 and 2 methyl butene are formed. However (boiling) pulverized catalyst developed and implemented in a
3 – methylbutene is about 65% of the products formed. In semi industrial scale at the research institute of monomers for
addition to the formation of isomers, a large number of other synthetic rubber, Yaroslav, Russia is as shown below.
side reactions occur but the most important ones are as follows:
- Skeletal isomerization of isopentane Dehydrogenation of isopentene to isoprene (stage-2)
iso C5H12 n C5H12 iso C5H10 iso C5H8 H2 H
- Isomerization with the migration of double bonds in
isopentene. This process is a reversible endothermic reaction. The industrial
2-methylbutene = 1 3-methylbutene-1 = 2-methybutene-2; dehydrogenation of iso-pentene is carried out on solid catalysts
Unauthenticated
103
Download Date | 8/21/15 2:47 PM
G.O. Ezinkwo et al.
Unauthenticated
104
Download Date | 8/21/15 2:47 PM
Overview of the Catalytic Production of Isoprene from different raw
materials; Prospects of Isoprene production from bio-ethanol.
CH3 CH CH CH2 CH3 CH2 C CH2 formation of 1 mole of isoprene requires 2 moles of iodine, which
invariably makes the realization of this process economically
Unauthenticated
105
Download Date | 8/21/15 2:47 PM
G.O. Ezinkwo et al.
by the thermal cracking of the dimer. The yield of isoprene was The raw material used is propane – propylene fraction, which is
however low but interests in this process was revived in the pre-dried and purified. The reactor unit consists of two units. At
1960’s. the exit of reactor (1), the feed mixture is throttled to a pressure
Isoprene synthesis by the dimerization of propylene gained level close to atmospheric, condensed in the cooling units and
practical attention after the discovery of selective oligomerization then fed to the separation units. Conversion of propylene in the
of lower olefins in the presence of organoalumininum catalysts described conditions is 70 – 85% at 97% yield of dimmers based
by K. Ziegler. Dimerization of propylene in the presence of on the reacted olefin. The condensed feed enters the evaporation
solid acid catalysts takes place by the mechanism of cationic column (2), where the catalyst is separated from higher oligomers
oligomerization of olefins. In this case, a mixture of isomeric of propylene which accumulate in the system as a result of
dimmers are formed from which isoprene is obtained by the continuous operation. A small portion of the catalyst (tripropyl-
pyrolysis of 2-methylpentene -2. This process includes the aluminum) is removed from the reactor and replaced with freshly
following steps; prepared catalyst and sent for regeneration due to poisoning and
1. Dimerization of propylene to form 2-methylpentene-1 thermal decomposition. 2-methylpentene-1, along with other light
2CH3 CH CH2 CH2 C CH2 CH2 CH3 hydrocarbons and unreacted propylene is distilled from the top
of the evaporation column (2) and enters the rectification column
CH3 (3), where the separation of low boiling hydrocarbons takes place.
2-methyl pentene goes through a system of rectification columns
2 Isomerization of 2-methylpentene-1 to 2-methylpentene -2 and then into the reactor (4) for isomerization.
CH2 C CH2 CH2 CH3 CH3 C CH CH2 CH3 Isomerization of 2-methylpentene-1 into 2-methylpentene
is conducted in the gaseous phase at a temp range of 423
CH3 CH3 – 573K and a flow rate of 0,15 – 0,5 L/L(kat)/h over a fixed
bed of solid catalyst at atmospheric pressure. The reaction
3 Demethanation (cracking) of 2-methylpentene-2 with the mixture enters the pyrolysis furnance (6) to which over
formation of isoprene. heated steam is also fed. Furthermore, the separation of the
CH3 C CH CH2 CH3 CH2 C CH CH2 CH4 hydrocarbon and aqueous phases take place with hydrogen
bromide dissolved in the later. Aqueous solution of hydrogen
CH3 CH3
bromide is mixed again with fresh feed. Methane and light
Figure 3 below shows the basic process flow diagram for hydrocarbons are released from the hydrocarbon fraction while
isoprene from propylene production implemented by Goodyear the target fraction is sent for purification and subsequently the
scientific design method separation of isoprene.
1.Dimerization reactor, 2- evaporation column, 3-rectification
column, 4- isomerization reactor; 5-separation column; 6- Disadvantage
reactor for initiated cracking The disadvantage of this method is the low efficiency of the
Streams process of pyrolysis: Isoprene yield does not exceed 50 – 60%,
I propylene; II- catalyst solution, III- residual oil; IV – 2 – methyl and therefore the overall yield of isoprene is 45 – 50 %. In the
pentene – 1; V- 2-methylpentene-2; V- isoprene. industry, this method is used on a limited scale.
rocess flow diagram for isoprene from propylene production implemented by Goodyear scientific design method. [1]
Figure 3. P
Unauthenticated
106
Download Date | 8/21/15 2:47 PM
Overview of the Catalytic Production of Isoprene from different raw
materials; Prospects of Isoprene production from bio-ethanol.
2.5.1. Isoprene synthesis from ethylene and propylene In the presence of excess acetylene, mono or disodium acetylene
The possibility of obtaining isopentene and subsequently isoprene is formed.
from ethylene and propylene was proved by Ziegler et al. The NaNH2 + HC≡CH → HC≡CNa + NH3,
process was carried out in two stages. In the first stage, reaction 2NaNH2 + HC≡CH → NaC≡CNa + 2NH3.
between alkyl-aluminum and propylene takes place with the In liquid ammonia, sodium acetylide reacts with acetone to form
formation of diethyl-isopentyl-aluminum at approximately 473K and an alcoholate of dimethylacetynylcarbinol.
2,0 MPa. In the second stage, diethyl-isopentyl-aluminum reacts
with the remaining ethylene at room temperature and average
CH3 CH3
pressure. Light hydrocarbons separated from the reaction mixture by
rectification which is composed of 80 – 85 % of 2-methylbutene-1, CNa
CH3 C O HC CH3 C C CH
undergoes dehydrogenation with the formation of isoprene.
ONa
Disadvantage
The main set back of this process is the large number of The alcoholate is then reduced in excess acetylene:
circulating organoaluminum compounds which makes the CH3 CH3
process presently infeasible for industrial application. HC CH CH3 C C CH HC CNa
CH3 C C CH
ONa OH
2.6. Isoprene from acetylene and acetone
The first attempt to synthesize isoprene from acetylene and acetone In the second step of the process, dehydrogenation of
was made by Merling in 1914. He conducted the condensation dimethylacetynylcarbinol ( methylbutynol) to dimethylvinylcarbinol
of acetylene with acetone through dimethylethylcarbinol ( methylbutenol):
and subsequently obtained isoprene. However, due to the CH3 CH3
stagnation in the development of the method at that time, it was
not implemented in the industry. Interests in this method was CH3 C C CH H2 CH3 C CH CH2
revived in the 1930’s when A. E. Favorskyi et al again conducted
the condensation of acetone with acetylene and proposed an OH OH
industrial method for isoprene production. However, this method
had a number of shortcomings that inhibited its implementation in Colloidal palladium on a carrier is used as the catalyst source.
the industry especially the low selectivity of the second stage of The hydrogenation of methylbutynol is conducted in a liquid
the process and the use of explosive solvents such as ethers at phase at a temperature range of 303 – 353K and 0. 5 – 1 MPa.
the condensation stage of acetylene and acetone. Subsequently, The selectivity of 99 – 99,5 % is achieved in the presence of an
the Italian company SNAM improved this method. inhibitor which allows for complete conversion of methylbutynol
The synthesis of isoprene using Favorskyi’s method is made to methylbutenol.
up of 3 stages. In the first stage, condensation of acetylene In the third step of isoprene synthesis by Favorskyi’s method,
with acetone (ethylization) takes place with the formation of catalytic dehydration of methylbutenol is carried out as shown below:
dimethylacetynyl carbinol. Firstly, potassium acetylide is formed CH3
CH3
alongside the formation of a monohydrate of KOH as a result
of water molecules bonding with the unreacted KOH as shown CH3 C CH CH2 CH2 C CH CH2
H2O
below:
HC≡CH + KOH → HC≡CK + H2O , OH
KOH + H2O → KOH ∙ H2O.
Then potassium acetylide reacts with acetone to form The dehydration process of dimethylvinylcarbinol proceeds
dimethylacetynylcarbinol: with complete conversion (~97%) and selectivity of 99,8%.
CH3 The produced isoprene is about 98,5% pure and does not
CH3
require further purification, since it does not contain harmful
CH3 C O HC CK CH3 C C CH contaminants and can be sent for stereospecific polymerization.
Methylbutynol can also be converted into isoprene through iso-
OK propenyl acetylene formation stage. The reaction takes place at
553K on aluminum phosphate catalyst
Hydroxides of other metals in these conditions do not react with
CH3 CH3
acetone and cannot catalyze ethylization reaction.
A method was developed using liquid ammonium solvent. In CH3 C CH CH CH2 C CH CH
this case, the catalyst is sodium amide, which is formed by the H2O
Unauthenticated
107
Download Date | 8/21/15 2:47 PM
G.O. Ezinkwo et al.
As a result of the hydrogenation of the triple bond of iso-propenyl 2. Reaction of hydroperoxide with 2-methylbutene-2, which is
acetylene, Isoprene is produced. and intermediate product of the process, and then the production
of 2-methylbutene-2 oxide.
CH3 CH3
H2, Fe
CH3 CH3
CH2 C CH CH CH2 C CH CH2
CH3 C CH2 CH3 CH3 C CH CH3
Advantage O OH
The advantage of this process is the possibility of conducting it
under mild conditions. CH3 CH3
2.7. Isoprene production via Liquid phase oxidation of 3. Isomerization of 2-methylbutene-2-oxide to 2-methyl-1-ol-3
hydrocarbons. CH3 OH
CH3
Isoprene production via liquid phase oxidation of isopentene
is based on its epoxidation using organic hydroperoxide. The CH3 C CH CH3 CH2 C CH CH3
process in the early 1960’s was developed by an American firm
“Halcon”. It consists of 4 stages: O
1. Isopentane oxidation by atmospheric oxygen to tert- pentyl
hydroperoxide: 4. Dehydration of the alcohol to isoprene:
CH3 CH3 CH3 OH CH3
CH3 CH CH2 CH3 O2 CH3 C CH2 CH3 CH2 C CH CH2
CH2 C CH CH3 H 2O
isopentane O OH
tert - Pentylhydroperoxide The flow chart for the process is shown in the Figure 4.
unreacted alcohol
Isomerization of oxides
and dehydration
2-methylbutene - 2 oxide
Isopentane
2 - Methylbutene - 2
tret-Pentylhydro separation
Isopentane - peroxide and By Products
oxidation epoxidation extraction
O2
tret - pentyl alcohol
Dehydration of
alcohols
low chart for the process of isoprene production via Liquid phase oxidation of hydrocarbons.
Figure 4. F
Unauthenticated
108
Download Date | 8/21/15 2:47 PM
Overview of the Catalytic Production of Isoprene from different raw
materials; Prospects of Isoprene production from bio-ethanol.
3. Prospects of isoprene production from About 5% of the ethanol produced in the world in 2003 was
ethanol actually a petroleum product [10]. It is made by the catalytic
hydration of ethylene with sulfuric acid as the catalyst. It can
The depletion of oil reserves due to over dependence on fossil also be obtained from calcium carbide, coal, oil gas, and
fuels, issues related to the environment and climate changes other sources. Two million tons of petroleum-derived ethanol
have necessitated the exploration of other alternative and is produced annually. The principal suppliers are plants in the
sustainable resources. Ethanol is a renewable and potential United States, Europe, and South Africa [11]. Petroleum derived
source of bio-carbon today which can be used to produce wide ethanol (synthetic ethanol) is chemically identical to bio-ethanol
range of chemicals and bulk petrochemicals. and can be differentiated only by radiocarbon dating [12].
Bio-ethanol is usually obtained from the conversion of carbon
3.1. Bio-ethanol the potential feedstock for Isoprene based feedstock. Agricultural feedstocks are considered
production. renewable because they get energy from the sun using
Production of bio-ethanol is a prospective way to reduce photosynthesis, provided that all minerals required for growth
both the consumption of hydrocarbons of fossil sources (such as nitrogen and phosphorus) are returned to the land.
and environmental pollution [9]. The desire to produce bulk Ethanol can be produced from a variety of feed stocks such as
chemicals in a sustainable way and the availability of low-cost sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain,
bio-ethanol in large volumes has, however, resulted in a wave switch grass, barley, hemp, kenaf, potatoes, sweet potatoes,
of petrochemical production from this commodity. Ethanol is a cassava, sunflower, fruit, molasses, corn, stover, grain, wheat,
renewable energy source because the energy is generated by straw, cotton, other biomass as well as many types of cellulose
using a resource, sunlight, which cannot be depleted. Creation waste and harvestings The production of bio-ethanol from
of ethanol starts with photosynthesis causing a feedstock, such lignocellulosic biomass materials is shown in Figure 6.
as sugar cane or a grain such as maize (corn), to grow. These An alternative process to produce bio-ethanol from algae is
feedstocks are processed into ethanol. being developed by the company Algenol. Rather than grow
Unauthenticated
109
Download Date | 8/21/15 2:47 PM
G.O. Ezinkwo et al.
Biomass
Hemi cellulose
Separation
Cellulose hydrolysis
Xylose fermentation
low chart for the production of bio-ethanol from lignocellulosic biomass materials [9].
Figure 6. F
algae and then harvest and ferment it, the algae grow in sunlight and starch into sugars. Saccharification of cellulose is called
and produce ethanol directly which is removed without killing the cellulolysis. Enzymes are used to convert starch into sugar
algae. It is claimed the process can produce 6,000 US gallons [14-16].
per acre (56,000 litres per ha) per year compared with 400 US According to Bomgardner in [17] microbial fermentation holds
gallons per acre (3,750 l/ha) for corn production [13]. promise for making renewable rubber intermediates: isoprene,
Currently, the first generation processes for the production of iso- butane and butadiene. The compounds cover a wide swath
ethanol from corn use only a small part of the corn plant: the corn of ground for the rubber-making industry. Five-carbon isoprene
kernels are taken from the corn plant and only the starch, which is used to make synthetic latex similar to that of rubber tree.
represents about 50% of the dry kernel mass, is transformed Two leading tire makers – Goodyear and Michelin along with
into ethanol. Two types of second generation processes are Synthetic rubber manufacturer Lanxess have entered into
under development. parternership with industrial biotech firms to advance the
The first type uses enzymes and yeast fermentation to convert the commercial production of these rubber intermediates from
plant cellulose into ethanol while the second type uses pyrolysis sugar. They are motivated by tightening supplies of both natural
to convert the whole plant to either a liquid bio-oil or a syngas. and synthetic rubber, driven in recent years by strong global
Second generation processes can also be used with plants such demand, especially from emerging economies.
as grasses, wood or agricultural waste material such as straw. In Russia, Research work is ongoing in this direction at the A. V.
The basic steps for large scale production of ethanol are: Tropchieva Institute of Petrochemical Synthesis in collaboration
microbial (yeast) fermentation of sugars, distillation, dehydration with the Moscow State University of Fine Chemical Technology
and denaturing. Prior to fermentation, some crops require named after M. V. Lomonosov and is expected to continue in the
saccharification or hydrolysis of carbohydrates such as cellulose next few years.
References
[1] N.A. Plate, E.V. Slivinskii, Fundamentals of Chemistry and [2] R. R. Daminev, I. Kh. Bikbulatov, D. Sh. Yunusov, O. Kh.
Technology of Monomers Nauka/Interperiodika Publishing, Karimov, Bashkirskii Khimicheskii Zhurnal 16 /3 (2009) 133
2002, pp. 131 – 162. – 137.
Unauthenticated
110
Download Date | 8/21/15 2:47 PM
Overview of the Catalytic Production of Isoprene from different raw
materials; Prospects of Isoprene production from bio-ethanol.
[3] M. McCoy, Chem. Eng. News, 86 / 36 (2008) 15. [10] C. Berg, F. O. Licht, World Fuel Ethanol Analysis and Outlook
[4] S. K. Ogorodnikov, E.C Edlis, Proisvodstvo Isoprena : prepared for METI (2007).
Leningrad Khimia, (1973) 296 – 299. [11] J. M. Urbanchuk, M. A. George Barker, D. Phil. William
[5] A. L. Averko-Antonovich et al, Khimia & Teknologia Wells, Economics of a Queensland Ethanol Industry
synthetichekovo Kauchuka: Khimia Kolos (2008) 357 – prepared for the Queensland Dept. of State Development
360. and Innovation (2011).
[6] K. A. Juravleva, A. A. Nazarov, S. I. Ponikarov, Vestnik [12] www.ethanolproducer.com
Kazanskogo Universiteta 15/23 (2012) 36 – 38. [13] news.cnet.com/8301-11128_3-9966867-54.html, June 12,
[7] O. V. Litvin, Osnovi Teknologii syntheza kauchukov: Khimia, 2008 by M. LaMonica
(1972), 528 [14] www.greencarcongress.com/2005/06/new_enzyme_for_html
[8] M.D. Jones, C.G. Keir, C.D. Iulio, R.A.M. Robertson, C.V. [15] www.epiphergy.com/uploads/brazil_Hydrous_ethanol.pdf
Williams, D.C. Apperley, Catal. Sci. Technol. 1 (2011) 267 - [16] P.W. Madson, D. A. Monceaux, Katzen international inc.,
272. Cincinnati, Ohio, USA (2003).
[9] E.V. Makshina, W. Janssens, B.F. Sels, P.A. Jacobs, Catal. [17] M. M. Bomgardner, Chem. Eng. News, 89 / 50 (2011) 18 –
Today 198 (2012) 338 – 344. 19.
Unauthenticated
111
Download Date | 8/21/15 2:47 PM