Chinese J . Chem. Eng., 14(4) 4 1 F 4 2 7 (2006)
REVIEWS
Advances in the Research and Development of Acrylic Acid Production from Biomass*
XU
Xiaobo(?f& jk),
LIN Jianping(#&F) and CEN Peilin($$%)**
Institute of Bioengineering, Zhejiang University, Hangzhou 310027, China
Abstract The shortage of petroleum has resulted in worldwide efforts to produce chemicals from renewable re- sources. Among these attempts, the possibility of producing acrylic acid from biomass has caught the eye of many researchers. Converting the carbohydrates f i s t to lactic acid by fermentation and then dehydrating lactic acid to acrylic acid is hitherto the most effective way for producing acrylic acid from biomass. While the lactic acid fer- mentation has been commercialized since longer times, the dehydration process of lactic acid is still under devel- opment because of its low yield. Further efforts should be made before this process became economically feasible.
Because of the existence of acrylic acid pathways in some microorganisms, strain improvement and metabolic en- gineering provides also a possibility to produce acrylic acid directly from biomass by fermentation.
Keywords renewable resource, acrylic acid, biomass, lactic acid
1 INTRODUCTION
Energy resources are divided into two categories:
renewable and non-renewable. The fossil energy re- sources, such as petroleum, coal, natural gas and nu- clear energy, are non-renewable, whereas solar energy, hydraulic energy, wind power as well as biomass, etc., are renewable. Nowadays, worldwide efforts to reduce atmospheric COz emissions and to overcome the shortage and sharp price rise of fossil energy resources, especially petroleum, simultaneously trigger research on biomass-based technologies. Renewable resources have begun to become a popular phrase.
The renewable resources are inexhaustible and clean, among which, biomass is of particular impor- tance. Biomass is the product of photosynthesis of plants and microorganisms that is produced in huge quantities every year. The majority of biomass is hy- drocarbons, such as starch, semi-cellulose and cellu- lose, which can be hydrolyzed into fermentable sugars, mainly glucose and xylose. From fermentable sugars, various products can be produced by microbial proc- esses, such as ethanol, organic acids, amino acids, enzymes, antibiotics, etc. Among them, ethanol and lactic acid are of special importance. Ethanol has been used as gasoline additive for many years in various countries"] and has become the raw material for eth- ylene production. Traditionally, lactic acid is used in food industry, but the successful synthesis of biode-
gradable plylactic acid opens new oppoaUnity for lactic acid Compared with ethanol fermentation, lactic acid fermentation has the distin- guished advantage of high productivity. When glucose is used as substrate, the theoretical and practical etha- nol yields in ethanol fermentation are only 0.51 and 0.44--0.47g-g-' (ethanol glucose), whereas 1.0 and 0.90-0.94g.g-' (lactic acid glucose) can be obtained in lactic acid fermentation, respectively. Therefore, lactic acid fermentation is an atomic-saving process.
Acrylic acid and its ester derivatives are principal raw materials in the manufacture of polymeric prod- ucts. The polymers made of acrylic acid and its de- rivatives are characterized by colorless transparency, easy adhesion, elasticity, and stability to light, moder- ate heat as well as weathering, And they are widely applied in surface coatings, textiles, adhesives, paper treatment, polishes, leather, fibers, detergents, and super-absorbent materials, e t ~ . ' ~ ' ~ ] . Currently, all acrylic acid is produced from petrochemical industry by two-step gas-phase oxidation of propylene and the total worldwide productivity is more than 3 million tons per yearr6]. High price of crude oil promotes the research and development of acrylic acid production from new raw materials with new technology, in which, the dehydration of lactic acid for acrylic acid production is a competitive process and has attracted many scientists and engineers to develop new proc-
Received 2005-07-19, accepted 2006-03-3 1.
* Supported by the Special Funds for Major State Basic Research Program of China (973 Program, No.2004CCA05500).
**
To whom correspondence should be addressed. E-mail: [email protected]esses.
In this article, the recent advances in the research and development of lactic acid fermentation are re- viewed. Then, the dehydration methods of lactic acid for acrylic acid production are introduced. Finally, the prospect of acrylic acid production from biomass is discussed.
2 LACTIC ACID FERMENTATION AND SEPARATION
2.1 Lactic acid fermentation
The commercial production of lactic acid by fermentation was started at the end of the 19th cen- turyI7], so it is considered as one of the first biotech- nological processes operated under controlled condi- tions. It is possible to distinguish the lactic acid fer- mentation as homo- and hetero-lactic acid types. The existing commercial production processes use homo- lactic organisms, such as Lactobacillus delbriickii, L.
bulgaricus, L. leichmannii, except Rhizopus ~ r y z a e ' ~ ' ~ ' for L-lactic acid production via hetero-lactic acid pathway.
Lactic acid is one of the smallest chiral molecules with D-, L-isomers and racemic DL-lactic acid. The chemically synthesized lactic acid is racemic, whereas with different strains, the fermentation product can be D-, L- or DL-lactic acid. Microorganisms for lactic acid production and their properties are listed in Table 1.
The fermentation technology can produce a de- sired stereoisomer of lactic acid or the racemate when a specific strain is used. A wide variety of carbohy- drate sources, such as molasses, starch hydrolytes,
whey, dextrose, cane or beet sugarr7', or even hydro- lytes of lignocellulosic materials"01, can be used as feedstocks. Most of lactic acid-producing strains can be cultivated anaerobically, except Rhizopus olyzue, which must be cultured aerobically. The advantages of anaerobic fermentation include low investment and low energy consumption. Generally, the theoretical yield of lactic acid, when glucose is used as carbon source, is loo%, whereas the practice yield of lactic acid is approximately 90% (by mass) in an anaerobic fermentation process. The lactate mass concentration in the fermentation broth can reach 10%-13%.
In classic industrial bioprocesses, alkali such as NaOH, CaC03 and NH3 must be added to the broth to maintain a low free-lactic acid concentration in order to prevent the inhibition of bacteria. However, their addition makes the purification process difficult and this has great environmental impact.
Apart from treatment with alkali, various tech- niques combining fermentation process with simulta- neous product separation have been proposed to con- tinuously remove the lactic acid as it is formed. A means to overcome the product inhibition is in situ product removal (TSPR)"ll such as extractive fermen-
tation[12- 161 , adsorption fermentation , mem- brane fermentation121-251.
Reactive extraction with specified extractant giving a higher distribution coefficient has been pro- posed as a promising technique for the recovery of lactic acid. Reactive liquid-liquid extraction has the advantage of easy removal of lactic acid from the fermentation broth, thereby preventing the lowering of
[17-201
Table 1 Microorganisms for lactic acid production and their properties"]
Name of strain Favorable carbon source Temperature, 'C Major products Isomer
L. delbriickii glucose, galactose 5 e 5 3 lactic acid DL-
L.bulgaricus glucose 45-55 lactic acid DL-
L. therrnophilus glucose 5-0 lactic acid DL-
L.leichmunnii glucose 28-32 LA/AA=l: 1 D-
L.casei Lxermenti
lactose glucose, lactose S.thcrmophilus glucose, lactose
S.lactis glucose, lactose
Sxaecalis glucose, maltose
28-32 lactic acid L-
35-40 LA/AA/CO2=I : 1 1 DL-
45-55 28-32 28-32
lactic acid DL-
lactic acid I,-
lactic acid L-
Pediococcus glucose, maltose 25--32 lactic acid DL-, L
Leucono.r toc glucose, sucrose 21-25 lactic acid D-
Rifidohacterium glucose 35-45 LAlAA=2 : 3 L-
Rhizopus olyzae glucose 25-35 lactic acid L-
Note: LA-lactic acid: AA-acetic acid.
Advances in the Research and Development of Acrylic Acid Production from Biomass 421
lactic acid fermentation broth
pH[13*141. The extraction process does not affect the thermal stability of bioproducts, and the energy de- mand is substantially low. In this method, the amine in the solvent phase reacts with the lactic acid in the aqueous phase, resulting in the extraction of acid into the organic phase"51. The applicability of different types of organic carriers and diluents has extensively been investigated[l6I. Secondary and tertiary long-chain alkylamines have been found to promote the extraction efficiency and selectivity, and alcohols are among the best dil~ents'~~."]. But the solvents used in ISPR are toxic as they rupture the cell membrane causing the metabolite to leak out. Long-chain alco- hols such as 1-octanol and 1-decanol are found to be less toxic than other diluents.
Adsorption fermentation process has been stud- ied wherein pH value is regulated by the adsorption of lactic acid. As an efficient absorbent, ion exchange resin is widely used in bioseparation and several dif- ferent ion exchar~gers"~-~~~ have been used for lactate separation in the last few years. This technique is competitive because of its high selectivity, high ex- change capacity and simple operation.
Membrane bioreactor combines the fermentation process with the simultaneous product separation. The lactic acid is continuously removed from the membrane as it is formed, so high cell density is obtained, which results in higher productivity. Different membranes, such as e l e c t r o d i a l y s i ~ [ ~ ~ ~ ~ ~ , hollow fiber ultrafiltration membrane"', reverse osmosis ~ n e m b r a n e ' ~ ~ ' ~ ~ ] are used in the cell-recycle. Vishal Shah et a1.[251 have achieved a maximum cell density of 145gdmP3 and a maximum productivity of 34g-dnP3-hP' in cell-recycle fermenta- tion. In this method, lactic acid fermentation is inves- tigated in a cell-recycle membrane bioreactor with a substrate concentration as high as 1 20g-dm-3.
Fed-batch process is also used in lactic acid fer- mentation to avoid substrate inhibitionr281. According to the work reported by Bai et aL., up to 21Og-L-' L-lactic acid was obtained and the average L-lactic
85% lactic acid
acid productivity was 2.2g-LP1K' in a fed-batch fer- mentation of Lactobacillus Z a c t i ~ ~ ~ ~ ~ . 2.2 Separation and purification of lactic acid
The economics of the fermentation process de- pend on the development of an effective recovery method for lactic acid from broth, because the separa- tion and purification steps account for up to 50% of the production costs'301. Although the difference in boiling point between lactic acid and water is quite large, it is almost impossible to obtain pure lactic acid crystal. The reasons are that lactic acid has highly af- finity to water and lactate dimmer will be formed when the concentration of lactic acid is high enough.
The commercial product of lactic acid is generally an aqueous solution with 85% lactic acid.
The separation and purification processes of lac- tic acid from fermentation broth are shown in Fig.1.
The calcium lactate solution is crystallized and con- verted into lactic acid by adding sulphuric acid. In this bioprocesses, extraction is carried out through pre- cipitation stages which produce large quantities of gypsum (calcium sulfate ) that have to be treated as wasteL3 'I.
Over the past few decades, lots of improvements have been made to reduce the high product recovery cost and the environmental impact. Many studies concerning lactic acid separation have been conducted using different separation techniques, such as reactive extraction, membrane separation, ion exchange, elec- trodialysis, chemical reaction distillation"*', and re- verse osmosis. Each of these exhibits some advan- tages and disadvantages that are also described with fermentation processes earlier in this review.
An alternative process is to form lactic es-
ter[32-351 , such as methyl lactate, then purify lactate ester by distillation. The lactate ester must be hydro- lyzed to obtain free lactic acid and methanol. Metha- nol and little amount of water can be removed by dis- tillation. Ma et ~ 1 . ' ~ ~ ~ ~ ~ ' have set up a whole process to
vacuum evaporation or
esterification
and distillation distillation
,--A:^ - hydrolyxation
-..- ......ianol Figure 1 Separation and purification processes of lactic acid from fermentation broth
422
purify lactic acid by esterification coupling catalytic distillation. This novel technology has considerable prospects because of its low energy consumption and low investment.
A completed recovery and purification process involving electromembrane operations has been re- ported'381. It includes broth clarification by cross-flow f i l t r a t i ~ n ' ~ ~ ' ~ ] , treatment by chelating resins, concen- tration of lactate salts into free acid by bipolar rnem- brane electrodialysis and ion exchange treatment.
3 DEHYDRATION OF LACTIC ACID TO PRODUCE ACRYLATES VIA CHEMICAL REACTION
There is a hydroxyl and a carboxyl group in lac- tic acid molecule; therefore, it is convenient to convert
lactic acid into various value-added p r o d u ~ t s ' ~ ~ , ~ ~ ] , such as a~etaldehyde'~~], acrylic acid, propylene gly-
C O ~ ' ~ ' , 2,3-pentanedi0ne'~~I, and polylactic acid[451.
Fig.2 shows some examples.
Because of their important applications in the production of biodegradable polymers and other compounds, lactic acid is regarded as one of the commodity or platform chemicals, in addition to its traditional application in food industry. Among these compounds, the production of acrylic acid or their ester is of special significance.
Acrylic acid can be produced by the catalytic dehydration of lactic acid. Holmen'*' filed a patent in
which the vapor-phase conversion of lactic acid to acrylic acid over several kinds of salt catalysts was performed for the first time. And the most effective catalyst was the mixture of CaS04 and Na2SO4 with the molar ratio of 25 1. It could give acrylic acid yield of 54% when the lactic acid solution (10%) passed the pyrolysis tube at 10-15ml.h-' and at 400°C. S a ~ i c k i ' ~ ~ ] reported a 58% acrylic acid yield at 350'C using Na2HP04 on silicdalumina as catalyst with NaHCO3as a pH adjuster. At the same time, Pa- p a r i ~ o s ' ~ ~ ' achieved 43% acrylic acid yield at 34072, the catalyst was AlP04, treated with N H 3 . In these processes, low-concentration lactic acid solution was used as raw material, which means that after acidifica- tion, lactic acid in fermentation broth can be directly converted into acrylic acid without further processing.
It is promising to dehydrate lactic acid for acrylic acid production in supercritical or near-critical water.
Mok et a1.[491 conducted the experiments at 385"Cand 34.5 MPa, with an initial lactic acid concentration of 0. Imol-L-' and a residence time of approximately 30s.
The result indicated that decarbonylation of acetalde- hyde predominated with the addition of H2SO4. In contrast, more acrylic acid, carbon dioxide and hy- drogen could be produced if NaOH was added.
In 1993, Perry and Carl'501 reported that the addi- tion of small amount (<O.Olrnol.L-') of N ~ ~ H P O ~ to the 0.4 mol-L-' reactant solution was able to raise the pH value and increase the acrylic acid yield from 35%
r w decarbonylation
8,
acetaldehyde decarboxylationdehydration
reduction 0
lactic acid
condensation
I
self-esterificationT O H acrylic acid
o \
7
OH propanoic acid 02.3-pentanedione 0
0
4'
dilactideO? 0
Figure 2 Important chemicals produced from lactic acid[411
Advances in the Research and Development of Acrylic Acid Production from Biomass acid 0
$oH+K
OH OH=q
AcO OH OH+ a
OHlactic acid acetic acid acrylic acid acetic acid
423
acid catalyst 0
OCH,
succinic
+mH, + O = = f Y
-
$OCH3-
methylmethyl lactate anhydride succinic
"oQ
acrylate anhydrideOH
0
Figure 3 Novel approaches for "acetoxylation"
to higher than 58% molar yield on the basis of con- version (BOC) of lactic acid. Their study showed that Na2HP0, provided moderate enhancement of the rate constant for acrylic acid production while dramatically suppressing of the rate constants for the competing decarbonylation, decarboxylation, and secondary re- actions.
The formation of esters or salts of lactic acid be- fore conversion can ease the dehydration process. For example, Papari~os[~*] got 61% yield of acrylic acid from ammonium lactate, whereas the yield from lactic acid was just about 43%. An integrated process was developed for producing lactate ester following fer- mentation, and then directly converting ester to acry- late[431. The pH value was adjusted by adding ammo- nia during fermentation, and then the esterification was carried out in a single step directly from ammo- nium lactate. Finally, dehydration of methyl lactate to acrylate was realized over CaS04 catalyst in a fixed bed reactor. The highest yield was 53%. The direct conversion of lactate ester or salt is favorable because the fermentation product is lactate salt and lactate es- ter is an intermediate during lactic acid purification.
Although there is a ready supply of purified lac- tic acid and its methyl ester, an effective and attractive process for conversion of lactic acid to acrylates by direct catalytic dehydration has not been realized commercially until now. The problem is the recalci- trant nature of the dehydration step although it is somewhat rectified by use of catalysts or formation of lactate. The principal competing reaction is formation of self-reaction products, such as lactide, which are subsequently more readily decomposed into fragments such as carbon monoxide, acetaldehyde, and water[431.
The preliminary replacement of the a-hydroxyl hydrogen by some other radical could avoid the lac- tide formation and decomposition. So, some ap-
proaches, such as acetoxylation, could be used to im- prove the leaving group capability of the a-hydroxyl late by this process[511. Reacting methyl lactate with acetic anhydride at 40-60"c gave methyl a-acetoxyl propionate with 93.5% yield. The ester was then thermally decomposed at 500-550"C to form methyl acrylate and acetic acid. The use of inert reactor packings and lesser contact times led to methyl acry- late yields of over 90% at 550°C[52-541
.
A problem with this approach was the use of expensive reagents such as acetic anhydride.In recent years, some novel method^['^-^^] for activating the a-hydroxyl group to dehydration have been performed to overcome the cost factor. Fig.3 shows the examples.
In one approach, inexpensive acetic acid serves as a replacement for acetic anhydride"']. Using acetic acid as the azeotropic solvent, acetoxylation can be achieved with greater than 90% yield at 73°C and 20kPa. Another approach considers easily formed an- hydrides, such as fermentation-derived succinic anhy- dride (SA), as an activating agent. The esterification of lactic acid at the a-hydroxyl group with SA has been accomplished with 98% yield at 70°Cr561. Re- cently, Michael et a1.[571 have published their findings illustrating the whole pathways commencing from formation of 2-acetoxy propionic acid or ester by ace- toxylation to production of corresponding acrylic acid or acrylate ester by pyrolysis. But unfortunately, these patents do not provide more information about the acrylic acid or acrylate ester product yield.
g r o ~ p ' ~ ~ - ' ~ ]
.
BWII s et al. first produced methyl acry-4 FO!%IBILl"Y OF PRODUCTION OF ACRYLIC FORMATION
ACID FROM LACTIC ACID BY BIOTRANS- According to the literature mentioned above,
acrylic acid can be produced from lactic acid by made much p r o g r e ~ s [ ~ ~ - ~ ~ ] .
chemical catalytic dehydration. The disadvantages of There are a few microorganisms that produce the chemical processes are the requirement of high acrylic acid as an intermediate in their metabolic temperature and low acrylic acid productivity. pathways. Gartner et aZ.'621 found the anaerobic forma- So far, acrylic acid has been produced by bacteria tion of acrylic acid in the direct reduction pathway of from a ~ r y l o n i t r i l e ~ ~ ~ ~ ~ ' and acrylarnider60'611. The lactic acid in Clostridium propionicum. The related highest yield of acrylic acid was observed from acry- metabolic pathway in C. propionicum is shown in lonitrile (39Og-L-'). However, both acrylonitrile and Fig.4. Lactyl-CoA is formed from lactic acid catalyzed acrylamide must be first produced from other raw by CoA-transferase, and it is then dehydrated to pro- materials. The high price of acrylonitrile or acryla- duce acrylyl-CoA catalyzed by lactyl-CoA dehydra- mide prohibits the commercial production of acrylic tase, whereas the accumulation of acrylic acid is pos- acid by these biotransformation procedures. sible only when propionyl-CoA dehydrogenase is
Although there is no clear information regarding blocked.
the method to obtain a high yield of acrylic acid from It is found that 3-butynoic acid (HC-C- renewable materials such as sugars, the research has CH,-COOH), a structural analog of acrylic acid, can
Chinese J. Ch. E. pol.
0 HC
I1
lactatedehydro- H3C\ / C - S-COA HC
L-alanine
genase
I
OH I actyl-CoA [2e-+2Hi]
0
[6-OH-FAD-ETF]
ferredoxin rubedoxin
WAD-H] 0
0
II
acetyl-CoA
FAD-ETF]
acrylic acid
H3C\ /c - S-CoA CH,
propionyl-CoA
/I
decarboxylase- acetatkinase
ATP COA-SH
H,C 0-
\c/
II
H3C\ /C - 0- C",
0 I1
acetate propionate
Figure 4 Direct reduction pathway in Clostridium propionicum'621
Advances in the Research and Development of Acrylic Acid Production from Biomass 425 inhibit the activity of propionyl-CoA dehydrogenase.
Akedo et ~ 2 . ‘ ~ ~ ’ and Sanseverino et aZ.[@] studied the effect of adding 3-butynoic acid on the accumulation of acrylic acid. In both works, acrylic acid concentra- tion never exceeded 1% of initial substrate concentra- tion. Such low acrylic acid yield was due to the exis- tence of the reduction equivalents (e.g., ferredoxin, rubedoxin, flavodoxin). These reduction equivalents inhibited the further growth of microorganisms. The regeneration of reduction equivalents could be real- ized if an electron acceptor was provided’621.
O’Brien et ~ 1 . ‘ ~ ~ ’ proposed another approach to produce acrylic acid. They co-cultured Lactobacilli and Propionibacterium s h e m n i i to convert carbon sources into propionic acid, and then, CZostridiurn propionicum was used to further convert propionate into acrylate in the presence of an electron acceptor such as the methylene blue. The conversion ratio of propionate into acrylate was about 18.5%.
Except for the conversion routes mentioned above, some other pathways for converting sugars into acrylate have also been hypothesized. Several meth- o d ~ [ ~ * ’ have been patented to convert sugars into 3-hydroxypropanoate (3-HP) which could be a pre- cursor for acrylate. Dalal et aZ.[631 found that C.
propionicum could accumulate 0.2mmol-L-’ of acry- late transiently when grown on /Manine. Recently, Ishii et aZ. have discovered that acrylyl-CoA was also an intermediate in the 3-HP cycle, a pathway for auto- trophic C 0 2 fixation. 3-HP-CoA was obtained from 3-HP and dehydrated to acrylyl-CoA in this path- Fairly recently, in order to identify the main hur- dles for the development of an industrial process for production of acrylic acid from sugars, the researchers designed the fermentation process including acrylic acid recovery conceptually and evaluated the process ec~nomically”~~. They discussed the toxicity of acrylic acid to potential host organisms, the stoichiometry and thermodynamics of different hypo- thetical metabolic pathways towards acrylate, and the export of acrylic acid. And their final conclusion is inspiring, which gives information regarding the fea- sibility of the degigned fermentation process.
5 PROSPECT OF ACRYLIC ACID PRODUC- TION FROM LACTIC ACID
Acrylic acid and its esters are among the most important bulk-chemicals. However, the rocketing
price rise of petroleum has pushed the production cost of acrylic acid even higher.
Lactic acid can be produced by fermentation process from renewable resources with high produc- tivity. The technology is already mature. From an economic point of view, acrylic acid production from lactic acid via chemical process is already feasible, but the study on the dehydration of lactic acid is far from mature. It is necessary to enhance the research and development of the dehydration of lactic acid for acrylic acid production.
Biological conversion of lactic acid to produce acrylic acid is a hopeful process. After strain im- provement, it is possible to increase acrylic acid pro- ductivity greatly. The understanding in the metabolic pathway and the identification of enzymes as well as corresponding genes will facilitate the construction of genetic engineering cells to perform the biological dehydration of lactic acid.
In our laboratory, the research works on the chemical dehydration of lactic acid to produce acrylic acid are making progress. With CaS04 as main cata- lyst and reaction at 40O0C, in a continuous fixed-bed reactor the yield of methyl acrylate by direct conver- sion of methyl lactate reached about 55%. A new zeo- lite catalyst for lactic acid dehydration is prepared and the effectiveness is under evaluation.
REFERENCES
Wheals, A.E., Basso, L.C., Alves, D.M.G., Amonm, H.V., “Fuel ethanol after 25 years”, Trends Biotechnol., 17(12), 482-487(1999).
Wang, C.Y., Zhao, Y.M., “Synthesis of biodegradable material polylactic acid”, Chem. Znd. Eng. Progr., 22(7), 678+80(2003). (in Chinese)
Jin, L.G., Ni, R.Q., “Study on polylactic acid fibers”, Synth. Fiber, 32(2), 25-27(2003). (in Chinese)
Hong, Z.L., The Machining of the Organic Chemical Material, Chemical Industry Press, Beijing, 363- 400(1997). (in Chinese)
Yan, R.X., Water-Soluble Macromolecule, Chemical lndustry Press, Beijing, 196-222( 1998). (in Chinese) Falbe, J., Rebitz, M., Rompp, H., Rompp Chemie Lexikon, Thieme, Stuttgart (1995).
Buchta, K., “Lactic acid”, In: Biotechnology, Dellweg, H., ed., Verlag Chemie, Weinheim, Federal Republic of Germany, 3,409-417(1983).
Du, J.X., Cao, N.J., “Production of L-lactic acid by Rhizopus oryzae in a bubble column fermenter”, Appl.
Biochem. Biotechnol., 70-72,323-329( 1998).
Li, X.M., Lin, J.P., Liu, M.E., Cen, P.L., “Repeated-batch and continuous production of L-lactic acid by Rhizopus
426
10
I 1
12
13
14
15
16
17
18
19
20
21
22
23
24
oryzae immobilized in calcium alginate beads: Perform- ance and kinetic model”, Chin. J. Chem. Eng., 6(4), 33C+339( 1998).
Luo, J., Xia, L.M., Lin, J.P., Cen, P.L., “Kinetics of si- multaneous saccharification and lactic acid fermentation processes”, Biotechnol. Pmgr., 13(6), 762-767( 1997).
Chauhan, R.P., Woodley, J.M., “Increasing the produc- tivity of bioconversion processes”, Chemtech., 27, 26- 39( 1997).
Lu, Y.H., Lin, J.P., Li, S.Z., Li, X.M., Yao, S., Cen P.L.,
“Extractive L-lactic acid fermentation with immobilized Rhizopus oryzae in a three-phase fluidized bed”, Chin. J.
Biotechml., 13(3), 169-176( 1997).
Kailas, L.W., Bert, M.H., Geert, F.V., Vishwas, GP., “Re- active extraction of lactic acid using alamine 336 MIBK:
Equilibria and kinetics”, J. Biotechnol., 97(1), 59- 68(2002).
Jarvinen, M., Myllykoski, L., Keiski, R., Sohlo, J.,
“Separation of lactic acid from fermented broth by reac- tive extraction”, Bioseparation, 9(3), 163--166(2OOO).
Kahya, E., Bayraktar, E., Mehmetoau, u., “Optimization of process parameter for reactive lactic acid extraction”, Turk. J. Chem., 25,223-230(2001).
Tik, N., Bayraktar, E., Mehmetoglue, U., “In-situ reac- tive extraction of lactic acid from fermentation media”, J.
Chem. Tech. Biotech., 76,764-768(2001).
Lin, J.P., Chen, B., Wu, J.P., Cen, P.L., “L-lactic acid fermentation in a rotating disc contactor with simultane- ous product separation by ion exchange”, Chin. J. Chem.
Eng., 5( I), 4+55( 1997).
Chol, J.I., Hong, W.H., “Recovery of lactic acid by batch distillation with chemical reactions using ion exchange resin”, J. Chem. Eng. Jpn., 32, 184-189(1999).
Cao, X.J., Yun, H.S., Koo, Y.M., “Recovery of L(+)-lactic acid by anion exchange resin Amberlite I R A - W , Biochem. Eng. J., 11, 189-196(2002).
Tong, W.Y., Fu, X.Y., Lee, S.M., Yu, J., Liu, J.W., Wei, D.Z., Koo, Y.M., “Purification of L(+)-lactic acid from fermentation broth with paper sludge as a cellulosic feedstock using weak anion exchanger Amberlite IRA-92”, Biochm. Eng. J., 18, 89-96(2004).
Li, X.M., Lin, J.P., Liu, M.E., “L-lactic acid production using immobilized Rhizopus o v z a e in a three-phase flu- idized-bed with simultaneous product separation by electrodialysis”, Bioproc. Eng., 20,23 1-237( 1999).
Timmer, J.K.M., Kromkamp, J., Robbertsen, T., “Lactic acid separation from fermentation broth by reverse os- mosis and nanofiltration”, J. Membr. Sci., 92, 185- 197(1994).
Madzingaidzo, L., Danner, H., Braun, R., “Process de- velopment and optimization of lactic acid purification using electrodialysis”, J. Biotechnol., 96, 223 - 239( 2002).
Tejayadi, S., Cheryan, M., “Lactic acid from cheese whey permeate. Productivity and economics of a con- tinuous membrane bioreactor”, Appl. Microbiol. Bio- technol., 43 (2), 242-248(1995).
25
26
27
28
29
30
31 32
33
34
35
36
37
38
39
40
Vishal, S., Nikki, G, Datta, M., “Lactic acid fermentation in cell-recycle membrane bioreactor”, Appl. Biochem.
Biotechnol., 128(2), 17 1-184(2006).
Siebold, M., Frieling, P., Joppien, R., Rindfleisch, D., Schiigerl, K., Roper, H., ‘Comparison of the production of lactic acid by three different lactobacilli and its recov- ery by extraction and electrodialysis”, Proc. Biochem., 30(1), 81-95(1995).
Hano, T., Matsumoto, M., Uenoyama, S., Ohtake, T., Kawano, Y., Miura, S., “Separation of lactic acid from fermented broth by solvent extraction”, Bioseparation, 3, 321-326( 1993).
Roukas, T., Kotzekidou, P., “Lactic acid production from deproteinized whey by mixed cultures of free and coim- mobilized Lactobacillus casei and Lactococcus lactis cells using fedbatch culture”, Enzyme Microb. Technol., 22, 199-204(1998).
Bai,D.M., Wei,Q.,Yan,Z.H.,Zhao, X.M.,Li,X.G,Xu, S.M., “Fed-batch fermentation of Lactobacillus lactis for hyper-production of L-lactic a c i d , Biotechnol. Lpt., 25, 1833-1835(2003).
Wasewar, K.L., Heesink, A.B.M., Versteeg, GF., Pan- garkar, V.G, “Equilibria and kinetics for reactive extrac- tion of lactic acid using Alamine 336 in decanol”, J.
Chem. Tech. Biotechnol., 77, 168(2002).
Kascak, S., Kominek, J., Roehr, M., “Lactic a c i d , Bio- technol. Bioeng., 28,26+282( 1986).
Sanz, M.T., Murga, R., Beltran, S., Cabezas, J.L., “Ki- netic study for the reactive system of lactic acid esterifi- cation with methanol: Methyl lactate hydrolysis reac- tion”, J. Ind. Eng. Chem., 43 (9), 2049-2053(2004).
Wei, T.Y., Tong, Z.F., “Water separation of esterification by azeotropic rectification with partial condensation”, Chin. J. Proc. Eng., 4(4), 300-304(2004).
Ohara, H., Ito, M., Sawa, S., “Process for producing lac- tide and process for producing polylactic acid from fer- mented lactic acid employed as starting material”, U. S.
Pat., 6569989 (2003).
Wang, Q.H., Sun, X.H., Ma,R., “Study on synthesis of polylactide from kitchen garbage”, J. Chin. Sci. Bull., 50( 13), 1315-13 19(2005).
Ma, L., Zhang, Y., Yang, J.C., “Purification of lactic acid by heterogeneous catalytic distillation using ion-exchange resins”, Chin. J. Chem. Eng., 13( I), 24-3 l(2005).
Zhang, M., Ma, L., Yang, J.C., Xu, Y.M., “Non-equilibrium stage static simulation of lactic acid purification reactive distillation process”, J. Chem. Znd. Eng. (China), 56(6), 1031--1034(2005). (in Chinese)
Roux-de Balmann, H., Bailly, M., Lutin, F., Aimar, P.,
“Modelling of the conversation of weak organic acids by bipolar membrane electrodialysis”, Desalination, 149, 399-404(2002).
C a d r e , H., Blaszkow, F., “Comparison of operating modes for clarifying lactic acid fermentation broths by batch cross-flow microfiltration”, Proc. Biochem., 36, 751-756(2001).
C a d r e , H., Blaszkow, F., Balmann, H.R., “Modelling of
Advances in the Research and Development of Acrylic Acid Production from Biomass 427
41
42
43
44
45
46
47 48
49
50
51
52
53 54
55
56
the clarification of lactic acid fermentation broths by cross-flow microfiltration”, J. Membr. Sci., 186, 21+
230(2001).
Wadley, D.C., Man, S.T., Dennis, J.M., “Lactic acid con- version to 2,3-pentanedione and acrylic acid over sil- ica-supported sodium nitrate: Reaction optimization and identification of sodium lactate as the active catalyst”, J.
Cutul., 165, 162-171(1997).
Gunter, GC., Jackson, J.E., Miller, D.J., “Formation of 2,3-pentanedione from lactic acid over supported phos- phate catalysts”, J. Cutul., 148,252-260( 1994).
Walkup, P.C., Rohrmann, C.A., Hallen, R.T., Eakin, D.E.,
“Production of esters of lactic acid, esters of acrylic acid, lactic acid, and acrylic acid”, U. S . Pat., 5252473 (1993).
Adkins, H., Billica, H.R., “The hydrogenation of esters to alcohols at 25-l5O0C”, J. Am. Chem. Soc., 70, 3121 (1948).
Lunt, J., “Large-scale production, properties, and com- mercial applications of polylactic acid polymers”, Polym.
Degrud. Stub., 59, 145-152(1998).
Holmen, R.E., “Acrylates by catalytic dehyddration of lactic acid and acrylates”, U. S. Pat., 2859240 (1958).
Sawicki, R.A., “Catalyst for dehydration of lactic acid to acrylic acid”, U. S. Pat., 4729978 (1988).
Paparizos, C., Dolhyj, S., Shaw, W.G, “Catalytic conver- sion of lactic acid and ammonium lactate to acrylic acid”, U. S . Pat., 4786756 (1988).
Mok, W., Antal, M.J., “Formation of acrylic acid from lactic acid in supercritical water”, J. Org. Chem., 54, 4596-4602 (1989).
Perry, J.M., Carl, T.L., “Conversion of lactic acid to acrylic acid in supercritical water”, I d . Eng. Chem. Res., 32.2608-2613(1993).
Burns, R, Jones, D.T., Ritchie P.D., “Studies in pyrolysis part I. The pyrolysis of derivatives of al- pha-acetoxypropionic acid and related substances”, J.
Chem. Soc., 400-406(1935).
Smith, L.T., Fisher, C.H., Ratchford, W.P. , “Pyrolysis of lactic acid derivatives”, I d . Eng. Chem., 34, 473- 479( 1942).
Fisher, C.H., Ratchford, W.P., “Methyl acrylate produc- tion”, Ind. Eng. Chem., 36,229-334(1944).
Ratchford, W.P., Fisher, C.H., “Methyl acrylate by pyro- lysis of methyl acetoxypropionate”, I d . Eng. Chem.. 37, 382-387( 1945).
Lilga, M.A., Werpy, T.A., Holladay, J.E., “Methods of forming alpha, beta-unsaturated acids and esters”, U. S.
Pat. Appl., 0110974 (2004).
Werpy, T.A., Lilga, M.A., “Ester compounds and their use in forming acrylates”, U. S. Pat., 6545175 (2003).
57
58
59
60
61
62
63
64
65
66
67
68
69
70
Michael, A.L., Todd, A.W., Johnathan, E.H., “Methods of forming alpha, beta-unsaturated acids and esters”, U.
S. Pat., 6992209 (2006).
Nagasawa, T., Nakamura, T., Yamada, H., “Production of acrylic acid and methacrylic acid using Rhodococcus rhodochrous J1 nitrilase”, Appl. Microbiol. Biotechnol., 34,322-324( 1990).
Narayanasamy, K., Shukla, S., Parekh, L.J., “Utilization of acrylonitrile by bacteria isolated from petrochemical waste waters”, Indian J. Exp. Biol., 28,968--971(1990).
Nawaz, M.S., Franklin, W., Cemiglia, C.E., “Degrada- tion of acrylamide by immobilized cells of a Pseudomo- m sp. and Xunt homonus mltophilia”, Can. J. Micro- biol., 39,207-212(1993).
Nawaz, M.S., Franklin, W., Cemiglia, C.E., “Degrada- tion of aliphatic amide mixture by immobilized and nonimmobilized cells of Pseudomom sp.”, Environ. Sci.
Technol., 28, 11061109(1994).
Gartner, D.H., Braun, R., “Biotechnological production of acrylic acid from biomass”. Appl. Biochem. Biotech- nol. Progr., 70(2), 887-894(1998).
Dalal, R.K., Akdo, M., Cooney, C.L., Sinskey, A.J., “ A microbial route to acrylic acid production”, Biosources Dig., 2 (2), 8!2-97(1980).
Sanseverino, J., Montenecourt, B.S., Sands, J.A., “De- tection of acrylic aicd formation in Megusphuera els- denii in the presence of 3-butynoic acid”, Appl. Micro- biol. Biotechnol., 30,23+242( 1989).
O’Brien, D.J., Panzer, C.C., Eisele, W.P., “Biological production of acrylic acid from cheese whey by resting cells of Clostridium propionicum”, Biotechnol. Progr., 6, 237-242( 1990).
Cameron, D.C., Suthers, P.F., “Production of 3-hydroxypropanoic acid in recombinant organisms”, World Pat. WO, 0116346 (2001).
Buckel, W., Selmer, T., Selofonova, O.V., Gokam, RR., a r t , S.J., Jessen, H., “3-Hydroxypropanoic acid and other organic compounds”, World Pat. WO, 0242418 (2002).
Gokam, R.R., Gort, S.J., Liao, H.H., Jessen. H.J., Selo- fonova, O.V., “Alanine-2,3-aminomutase”, World Pat.
WO, 03062173 (2003).
Ishii, M., Chuakrut, S., Arai, H., Igarashi, Y., “Occur- rence, biochemistry and possible biotechnological appli- cation of the 3-hydroxypropionate cycle”, Appl. Micro- biol. Biotechnol., 64,605-610(2004).
Straathof, A.J.J., Sie, S., Franco, T.T., Wielen, L.A.M.,
“Feasibility of acrylic acid production by fermentation”, Appl. Microbiol. Biotechnol., 67,727-734(2005).
