US2469701A - Preparation of acrylic acid - Google Patents

Preparation of acrylic acid Download PDF

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Publication number
US2469701A
US2469701A US647425A US64742546A US2469701A US 2469701 A US2469701 A US 2469701A US 647425 A US647425 A US 647425A US 64742546 A US64742546 A US 64742546A US 2469701 A US2469701 A US 2469701A
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acid
acrylic acid
hydracrylic
catalyst
pressure
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US647425A
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Bryan C Redmon
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Wyeth Holdings LLC
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American Cyanamid Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups

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  • Example 1 v Parts 85% phosphoric acid 68 Powdered copper metal 1 l-lfydracrylic acid 250 The phosphoric acid and copper powder are placed in a suitably equipped vessel and dehydrated by heating under a progressively decreased pressure until the temperature at 16 mm. pressure is 150 C.
  • the hydracrylic acid is allowed to flow gradually under the surface of the hot catalyst.
  • the catalyst mass begins to boil immediately and a clear water-white liquid distills off.
  • the distilling head temperature slowly rises from 3738 C. to 78 C. at 50 mm.
  • the pressure is gradually decreased to 26 mm. and the catalyst temperature increased to 170-180 C. Under these conditions, the distilling head temperature varies from 65-80 C.
  • the rate of addition of the hydracrylic acid is regulated so that the total volume of catalyst in the reaction vessel remains as nearly the same as possible.
  • the total time consumed in adding the feed is about 1 /2 hours at the rate of about 70-100 drops per minute.
  • the clear colorless liquid has a 72.2% acrylic acid content, therefore 163.9 parts of pure acrylic acid are produced. If it is assumed that the hydracrylic acid starting material is 100% pure, the yield of acrylic acid therefrom is 82%. It is more accurate, however, to calculate the yield of acrylic acid from the weight of the ethylene cyanohydrin which was used in the preparation of the hydracrylic acid according to the process of copending application Serial No. 462,050 filed October 14, 1942, now abandoned, and Patent No. 2,369,491 dated February 13, 1945. This is 77.4%.
  • Pure acrylic acid is separated from the 72.2% aqueous solution by fractional distillation at reduced pressures.
  • the following fractions comprise the pure acid:
  • Example 2 Parts phosphoric acid 49 Copper powder 2 Hydracrylic acid 568 mm. and the hydracrylic acid is allowed to drip slowly under the surface of the heated catalyst.
  • the distilling head temperature rises rapidly, remains at 8090 C. for the major part of the run, and then rises almost to C. at the end.
  • a pressure of 40 mm. is held for the major part of the run but it is decreased to 30 mm. toward the end.
  • the temperature of the catalyst is held at -190 C. throughout the run.
  • the total time consumed in adding the hydracrylic acid is about 4 hours at the rate of 70-120 drops per minute.
  • the product is collected at about the same rate.
  • the product is 510 parts of a clear, colorless liquid which corresponds to 89.6% of the weight of the hydracylic acid.
  • the liquid is 77% acrylic acid, representing a yield of 392.7 parts pure acid or 86.4% based on 100% pure hydracrylic acid. This figure corresponds to a yield of 76% based on the ethylene cyanohydrin from which the hydracrylic acid may be prepared.
  • Example 3 Parts 95% sulfuric acid 300 Powdered metallic copper 5 Hydracrylic acid 1581 The mixture of sulfuric acid and copper is placed in a suitably equipped vessel and heated to 141 C. The pressure is then reduced to 35 mm. and the hydracrylic acid is allowed to drip below the surface of the heated catalyst.
  • the pressure is decreased to 25 mm. and is held at 23-26 mm. throughout the run.
  • the temperature of the catalyst is held at 125135 C. during the first half of the run and raised to 140-150 C. during the last half.
  • a total of about hours is required for addition of all the hydracrylic acid at the rate of 400-500 cc. per hour for about 3 /2 hours and 200-300 cc. per hour for the remaining period of time.
  • hydracrylic acid used as starting material in the preceding examples was obtained from ethylene cyanohydrin according to the process disclosed and claimed in Patent No. 2,369,491 issued February 13, 1945, and copending application Serial No. 462,950 filed October 14-, 1942, but hydracrylic acid from any other source may be used in the process of the invention.
  • Dehydration catalysts other than phosphoric and sulfuric acids may be used.
  • boric acid, zinc chloride, benzene sulfonic acid, and p-toluene sulfonic acid are equally as effective.
  • the copper powder may be replaced by other polymerization inhibitors such as bronze powder, chromium, manganous salts, hydroquinone, catechol, ferric sulfate, etc., without departing from the spiirt of the invention.
  • the dehydration reaction is carried out below 40 atmospheric pressure to avoid polymer formation and thereby provide good yields of acrylic acid. Pressures below 100 mm. of Hg and especially around 20-60 mm. of Hg are preferred.
  • hydracrylic acid may be continuously dehydrated to produce good yields of acrylic acid.
  • water-white product obtained which contains no impurity other than about 20% water may be used for many purposes without further purification.
  • the process of preparing acrylic acid which comprises adding hydracrylic acid gradually to concentrated phosphoric acid maintained at a temperature of about 150-190 C. and a pressure of about 26-50 mm. of Hg in the presence of powdered metallic copper and separating the aqueous acrylic acid formed from the catalyst by distillation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Patented May 10, 1949 UNITED STATES ATENT OFFICE PREPARATION OF ACRYLIC ACID Bryan C. Redmon, Amherst, Mass., assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine N Drawing. Application February 13, 1946, Serial No. 647,425
4 Claims.
The following specific examples, in which the proportions of reactants are given in parts by weight unless otherwise indicated, are illustrated only and it is not intended that the scope of the invention should be restricted to the details therein set forth.
Example 1 v Parts 85% phosphoric acid 68 Powdered copper metal 1 l-lfydracrylic acid 250 The phosphoric acid and copper powder are placed in a suitably equipped vessel and dehydrated by heating under a progressively decreased pressure until the temperature at 16 mm. pressure is 150 C.
With the above-prepared catalyst at a temperature of 150 C. and a pressure of 50 mm., the hydracrylic acid is allowed to flow gradually under the surface of the hot catalyst. The catalyst mass begins to boil immediately and a clear water-white liquid distills off. The distilling head temperature slowly rises from 3738 C. to 78 C. at 50 mm. During the course of the run, the pressure is gradually decreased to 26 mm. and the catalyst temperature increased to 170-180 C. Under these conditions, the distilling head temperature varies from 65-80 C.
The rate of addition of the hydracrylic acid is regulated so that the total volume of catalyst in the reaction vessel remains as nearly the same as possible. The total time consumed in adding the feed is about 1 /2 hours at the rate of about 70-100 drops per minute.
227 parts, representing a 90.8% Weight recovery of the total hydracrylic acid feed, of a clear colorless liquid having a very strong, sharp odor are obtained. The weight loss as acrylic acid polymer and material retained in the catalyst is 23 parts or 9.2% of the weight of the feed.
The clear colorless liquid has a 72.2% acrylic acid content, therefore 163.9 parts of pure acrylic acid are produced. If it is assumed that the hydracrylic acid starting material is 100% pure, the yield of acrylic acid therefrom is 82%. It is more accurate, however, to calculate the yield of acrylic acid from the weight of the ethylene cyanohydrin which was used in the preparation of the hydracrylic acid according to the process of copending application Serial No. 462,050 filed October 14, 1942, now abandoned, and Patent No. 2,369,491 dated February 13, 1945. This is 77.4%.
Pure acrylic acid is separated from the 72.2% aqueous solution by fractional distillation at reduced pressures. The following fractions comprise the pure acid:
Pressure, mm. Eg. p i i t j O.
Example 2 Parts phosphoric acid 49 Copper powder 2 Hydracrylic acid 568 mm. and the hydracrylic acid is allowed to drip slowly under the surface of the heated catalyst. The distilling head temperature rises rapidly, remains at 8090 C. for the major part of the run, and then rises almost to C. at the end. A pressure of 40 mm. is held for the major part of the run but it is decreased to 30 mm. toward the end. The temperature of the catalyst is held at -190 C. throughout the run. The total time consumed in adding the hydracrylic acid is about 4 hours at the rate of 70-120 drops per minute. The product is collected at about the same rate.
The product is 510 parts of a clear, colorless liquid which corresponds to 89.6% of the weight of the hydracylic acid. The liquid is 77% acrylic acid, representing a yield of 392.7 parts pure acid or 86.4% based on 100% pure hydracrylic acid. This figure corresponds to a yield of 76% based on the ethylene cyanohydrin from which the hydracrylic acid may be prepared.
Example 3 Parts 95% sulfuric acid 300 Powdered metallic copper 5 Hydracrylic acid 1581 The mixture of sulfuric acid and copper is placed in a suitably equipped vessel and heated to 141 C. The pressure is then reduced to 35 mm. and the hydracrylic acid is allowed to drip below the surface of the heated catalyst.
Shortly after the beginning of the reaction, the pressure is decreased to 25 mm. and is held at 23-26 mm. throughout the run. The temperature of the catalyst is held at 125135 C. during the first half of the run and raised to 140-150 C. during the last half.
A total of about hours is required for addition of all the hydracrylic acid at the rate of 400-500 cc. per hour for about 3 /2 hours and 200-300 cc. per hour for the remaining period of time.
1264.5 parts of clear, colorless liquid product, equivalent to 80% of the total weight of the feed, is obtained. The product is 81.4% acrylic acid or 1029.3 parts of the pure acid, a yield from assumed 100% pure hydracrylic acid of 81.3% and from ethylene cyanohydrin 76.1%.
The hydracrylic acid used as starting material in the preceding examples Was obtained from ethylene cyanohydrin according to the process disclosed and claimed in Patent No. 2,369,491 issued February 13, 1945, and copending application Serial No. 462,950 filed October 14-, 1942, but hydracrylic acid from any other source may be used in the process of the invention.
Dehydration catalysts other than phosphoric and sulfuric acids may be used. For example, boric acid, zinc chloride, benzene sulfonic acid, and p-toluene sulfonic acid are equally as effective. Similarly, the copper powder may be replaced by other polymerization inhibitors such as bronze powder, chromium, manganous salts, hydroquinone, catechol, ferric sulfate, etc., without departing from the spiirt of the invention.
The dehydration reaction is carried out below 40 atmospheric pressure to avoid polymer formation and thereby provide good yields of acrylic acid. Pressures below 100 mm. of Hg and especially around 20-60 mm. of Hg are preferred.
The dehydration temperature giving best results will vary somewhat with the particular catalyst employed, but in general I have found it advantageous to carry out the reaction at temperatures of between about 130 C. and 190 C.
It is an advantage of the present invention that hydracrylic acid may be continuously dehydrated to produce good yields of acrylic acid. Moreover, the water-white product obtained which contains no impurity other than about 20% water may be used for many purposes without further purification.
I claim:
1. In the process of preparing acrylic acid by dehydration of hydracrylic acid, the steps which comprise adding the hydracrylic acid gradually to an acid dehydration catalyst maintained at dehydration temperatures of between about 130 to 190 C. under pressures below 100 mm. of Hg to form an aqueous solution of acrylic acid and distilling ofi the aqueous acrylic acid as formed, the .rate of addition of hydracrylic acid being so regulated that the total volume of catalyst remains nearly constant.
2. In the process of preparing acrylic acid by dehydration of hydracrylic acid, the steps which comprise adding the hydracrylic acid gradually to an acid dehydration catalyst maintained at dehydration temperatures of between about to 190 C. under pressures below 100 mm. of Hg to form an aqueous solution of acrylic acid, distilling off the aqueous acrylic acid as formed, the rate of addition of hydracrylic acid being so regulated that the total volume of catalyst remains nearly constant, and recovering pure acrylic acid from the aqueous solution thereof by fractional distillation at reduced pressures.
3. The process of preparing acrylic acid which comprises adding hydracrylic acid gradually to concentrated phosphoric acid maintained at a temperature of about 150-190 C. and a pressure of about 26-50 mm. of Hg in the presence of powdered metallic copper and separating the aqueous acrylic acid formed from the catalyst by distillation.
4- The process of preparing acrylic acid which comprises heating a mixture of concentrated sulfuric acid and powdered metallic copper to about C., reducing the pressure to about 35 mm. of Hg, gradually adding hydracrylic acid, controlling the temperature and pressure throughout the addition so the temperature remains between 125 C. and C. and the pressure between 23 mm. and 26 mm. of Hg, and separating the aqueous acrylic acid formed from the catalyst by distillation.
BRYAN C. REDMON.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,026,894 Hill Jan. 7, 1936 2,174,830 McAllister et al Oct. 3, 1939 2,305,663 Beer et a1. Dec. 22, 1942 2,341,663 Schulz Feb. 15, 1944 2,356,247 Kirk et al Aug. 22, 1944 2,361,036 Kung Oct. 24, 1944 2,374,051 Spence Apr. 17, 1945 FOREIGN PATENTS Number Country Date 427,810 Great Britain Oct. 4, 1934 455,087 Great Britain Oct. 13, 1936 OTHER REFERENCES Moldenhauer, Wislicenus, Beilstein (4th ed.), (1864).
Wislicenus, Liebigs Ann., vol. 166, pages 23-25 (1873).
Erlenmeyer, Liebigs Annalen, vol. 191, pp. 261- 284 (1878).
Moldenhau-re, Wislicenus, Beilstein (4th ed.), Vol.3, page 296 (.1921).
Van der Burg, Rec. Trav. Chim., vol. 41, pp. 22-23 (1922').
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Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568636A (en) * 1950-07-29 1951-09-18 Goodrich Co B F Process for preparing anhydrous alpha-beta unsaturated carboxylic acids
US2623067A (en) * 1950-01-10 1952-12-23 Goodrich Co B F Preparation of beta-substituted acrylic acids
US2790822A (en) * 1953-08-12 1957-04-30 Knapsack Ag Process for the preparation of aliphatic alpha-unsubstituted alpha-beta-unsatureated carboxylic acids and their derivatives
DE1151501B (en) * 1959-01-30 1963-07-18 Basf Ag Process for the production of acrylic acid by the continuous cleavage of acrylic acid derivatives
DE1153014B (en) * 1959-09-29 1963-08-22 Knapsack Ag Process for the preparation of ª ‡, ª ‰ -unsaturated carboxylic acid nitriles by elimination of water from hydroxycarboxylic acid nitriles
US3176042A (en) * 1959-10-20 1965-03-30 Celanese Corp Treating propiolactone with heated phosphoric acid to produce acrylic acid
DE1189986B (en) * 1962-03-22 1965-04-01 Basf Ag Process for the continuous cleavage of residues which occur in the catalytic production of acrylic acid or its esters from acetylene, carbon monoxide and water or. Alcohols are formed
US3666805A (en) * 1965-03-12 1972-05-30 Lonza Ag Preparation of methacrylic acid
US4435598A (en) 1977-10-28 1984-03-06 National Distillers And Chemical Corporation Process for the catalytic oxidation of propylene to acrylic acid
US20050222458A1 (en) * 2004-04-02 2005-10-06 Liliana Craciun Preparation of acrylic acid derivatives from alpha-or beta-hydroxy carboxylic acids
US20070219397A1 (en) * 2006-03-15 2007-09-20 Battelle Memorial Institute Method for conversion of beta-hydroxy carbonyl compounds
US20070219391A1 (en) * 2006-03-15 2007-09-20 Battelle Memorial Institute Method for conversion of beta-hydroxy carbonyl compounds
US20090023006A1 (en) * 2005-02-28 2009-01-22 Evonik Stockhausen Gmbh Water-absorbent polymer structures based on renewable resources and method for producing said structures
EP2036879A1 (en) 2007-09-17 2009-03-18 Rohm and Haas Company Process For Converting A Hydroxy Carboxylic Acid Or Salts Thereof, To An Unsaturated Carboxylic Acid And/Or Its Esters
JP2010006819A (en) * 2002-03-25 2010-01-14 Cargill Inc METHOD FOR PRODUCING DERIVATIVE OF beta-HYDROXYCARBOXYLIC ACID
US20100210017A1 (en) * 2007-01-12 2010-08-19 Gill Ryan T Compositions and methods for enhancing tolerance for the production of organic chemicals produced by microorganisms
JP2010180171A (en) * 2009-02-06 2010-08-19 Nippon Shokubai Co Ltd Method for producing acrylic acid
US20110125118A1 (en) * 2009-11-20 2011-05-26 Opx Biotechnologies, Inc. Production of an Organic Acid and/or Related Chemicals
JP2011225533A (en) * 2010-03-31 2011-11-10 Nippon Shokubai Co Ltd Method for producing acrylic acid and its polymer
WO2012081723A1 (en) 2010-12-17 2012-06-21 三菱化学株式会社 Synthetic pathway constructing equipment, synthetic pathway constructing method, synthetic pathway constructing program, and processes for manufacturing 3-hydroxypropionic acid, crotonyl alcohol and butadiene
WO2012129450A1 (en) 2011-03-22 2012-09-27 Opx Biotechnologies, Inc. Microbial production of chemical products and related compositions, methods and systems
US8652816B2 (en) 2007-12-04 2014-02-18 Opx Biotechnologies, Inc. Compositions and methods for 3-hydroxypropionate bio-production from biomass
US8809027B1 (en) 2009-09-27 2014-08-19 Opx Biotechnologies, Inc. Genetically modified organisms for increased microbial production of 3-hydroxypropionic acid involving an oxaloacetate alpha-decarboxylase
US8883464B2 (en) 2009-09-27 2014-11-11 Opx Biotechnologies, Inc. Methods for producing 3-hydroxypropionic acid and other products
US9012686B2 (en) 2010-09-23 2015-04-21 Olan S. Fruchey Acrylic acid from lactide and process
US9029596B2 (en) 2010-12-28 2015-05-12 Nippon Shokubai Co., Ltd. Methods for producing acrylic acid and/or ester thereof and polymer of the acrylic acid and/or ester thereof
US9181170B2 (en) 2012-12-07 2015-11-10 Samsung Electronics Co., Ltd. Method for preparing unsaturated carboxylic acid
EP2066611B1 (en) 2006-08-22 2016-06-22 Evonik Degussa GmbH Process for preparing acrylic acid purified by crystallization from hydroxypropionic acid and apparatus therefor
US9512057B2 (en) 2013-03-15 2016-12-06 Cargill, Incorporated 3-hydroxypropionic acid compositions
US9701610B2 (en) 2013-10-17 2017-07-11 Dow Global Technologies Llc Ammonium bisulfate catalyzed dehydration of beta-hydroxy acids
US10047383B2 (en) 2013-03-15 2018-08-14 Cargill, Incorporated Bioproduction of chemicals
US10239819B2 (en) 2014-10-17 2019-03-26 Cargill, Incorporated Methods for producing an ester of an alpha, beta-unsaturated carboxylic acid
US10337038B2 (en) 2013-07-19 2019-07-02 Cargill, Incorporated Microorganisms and methods for the production of fatty acids and fatty acid derived products
US10465213B2 (en) 2012-08-10 2019-11-05 Cargill, Incorporated Microorganisms and methods for the production of fatty acids and fatty acid derived products
US10494654B2 (en) 2014-09-02 2019-12-03 Cargill, Incorporated Production of fatty acids esters
WO2020128618A2 (en) 2018-12-18 2020-06-25 Braskem S.A. Co-production pathway for 3-hp and acetyl-coa derivatives from malonate semialdehyde
US10710955B2 (en) 2013-10-17 2020-07-14 Cargill, Incorporated Methods for producing alkyl hydroxyalkanoates
US11345938B2 (en) 2017-02-02 2022-05-31 Cargill, Incorporated Genetically modified cells that produce C6-C10 fatty acid derivatives
US11408013B2 (en) 2013-07-19 2022-08-09 Cargill, Incorporated Microorganisms and methods for the production of fatty acids and fatty acid derived products
US12091381B2 (en) 2017-10-26 2024-09-17 Noroo Ic Co., Ltd. Production and separation of 3-hydroxypropionic acid
US12123045B2 (en) 2022-05-02 2024-10-22 Cargill, Incorporated Genetically modified cells that produce C6-C10 fatty acid derivatives

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GB427810A (en) * 1933-10-31 1935-04-30 John William Croom Crawford Improvements in or relating to the production of esters of methacrylic acid
US2026894A (en) * 1933-04-13 1936-01-07 Ici Ltd Manufacture of acrylic acid
GB455087A (en) * 1935-03-13 1936-10-13 Triplex Safety Glass Co Improvements in or relating to the manufacture of polymerisable compounds
US2174830A (en) * 1937-08-06 1939-10-03 Shell Dev Process for producing unsaturated carbonylic compounds
US2305663A (en) * 1939-01-18 1942-12-22 Beer Ludwig Method for preparing methacrylic acid esters
US2341663A (en) * 1944-02-15 Process fob the production of un
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US2361036A (en) * 1941-07-31 1944-10-24 Goodrich Co B F Preparation of alpha-beta unsaturated carboxylic acids
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GB427810A (en) * 1933-10-31 1935-04-30 John William Croom Crawford Improvements in or relating to the production of esters of methacrylic acid
GB455087A (en) * 1935-03-13 1936-10-13 Triplex Safety Glass Co Improvements in or relating to the manufacture of polymerisable compounds
US2174830A (en) * 1937-08-06 1939-10-03 Shell Dev Process for producing unsaturated carbonylic compounds
US2305663A (en) * 1939-01-18 1942-12-22 Beer Ludwig Method for preparing methacrylic acid esters
US2356247A (en) * 1941-04-12 1944-08-22 American Cyanamid Co Process for producing unsaturated derivatives of alpha-hydroxyisobutyric acid esters
US2374051A (en) * 1941-05-17 1945-04-17 Rohm & Haas Manufacture of acrylonitrile from ethylene cyanohydrin
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Cited By (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2623067A (en) * 1950-01-10 1952-12-23 Goodrich Co B F Preparation of beta-substituted acrylic acids
US2568636A (en) * 1950-07-29 1951-09-18 Goodrich Co B F Process for preparing anhydrous alpha-beta unsaturated carboxylic acids
US2790822A (en) * 1953-08-12 1957-04-30 Knapsack Ag Process for the preparation of aliphatic alpha-unsubstituted alpha-beta-unsatureated carboxylic acids and their derivatives
DE1151501B (en) * 1959-01-30 1963-07-18 Basf Ag Process for the production of acrylic acid by the continuous cleavage of acrylic acid derivatives
DE1153014B (en) * 1959-09-29 1963-08-22 Knapsack Ag Process for the preparation of ª ‡, ª ‰ -unsaturated carboxylic acid nitriles by elimination of water from hydroxycarboxylic acid nitriles
US3176042A (en) * 1959-10-20 1965-03-30 Celanese Corp Treating propiolactone with heated phosphoric acid to produce acrylic acid
DE1277250B (en) * 1959-10-20 1968-09-12 Celanese Corp Process for the preparation of acrylic acid by treating ª ‰ -propiolactone with an acid
DE1189986B (en) * 1962-03-22 1965-04-01 Basf Ag Process for the continuous cleavage of residues which occur in the catalytic production of acrylic acid or its esters from acetylene, carbon monoxide and water or. Alcohols are formed
US3666805A (en) * 1965-03-12 1972-05-30 Lonza Ag Preparation of methacrylic acid
US4435598A (en) 1977-10-28 1984-03-06 National Distillers And Chemical Corporation Process for the catalytic oxidation of propylene to acrylic acid
JP2010006819A (en) * 2002-03-25 2010-01-14 Cargill Inc METHOD FOR PRODUCING DERIVATIVE OF beta-HYDROXYCARBOXYLIC ACID
US8846353B2 (en) 2002-03-25 2014-09-30 Cargill, Incorporated Methods of manufacturing acrylic acid
JP2015083568A (en) * 2002-03-25 2015-04-30 カーギル，インコーポレイティド METHOD FOR PRODUCING DERIVATIVE OF β-HYDROXY CARBOXYLIC ACID
US20050222458A1 (en) * 2004-04-02 2005-10-06 Liliana Craciun Preparation of acrylic acid derivatives from alpha-or beta-hydroxy carboxylic acids
US7538247B2 (en) 2004-04-02 2009-05-26 Ciba Specialty Chemicals Corporation Preparation of acrylic acid derivatives from α- or β-hydroxy carboxylic acids
US20100113822A1 (en) * 2004-04-02 2010-05-06 Liliana Craciun Preparation of acrylic acid derivatives from alpha- or beta-hydroxy carboxylic acids
US20090023006A1 (en) * 2005-02-28 2009-01-22 Evonik Stockhausen Gmbh Water-absorbent polymer structures based on renewable resources and method for producing said structures
US8703450B2 (en) * 2005-02-28 2014-04-22 Evonik Degussa Gmbh Water-absorbent polymer structures based on renewable resources and method for producing said structures
US20070219391A1 (en) * 2006-03-15 2007-09-20 Battelle Memorial Institute Method for conversion of beta-hydroxy carbonyl compounds
US7687661B2 (en) 2006-03-15 2010-03-30 Battelle Memorial Institute Method for conversion of β-hydroxy carbonyl compounds
US20070219397A1 (en) * 2006-03-15 2007-09-20 Battelle Memorial Institute Method for conversion of beta-hydroxy carbonyl compounds
EP2066611B1 (en) 2006-08-22 2016-06-22 Evonik Degussa GmbH Process for preparing acrylic acid purified by crystallization from hydroxypropionic acid and apparatus therefor
US20100210017A1 (en) * 2007-01-12 2010-08-19 Gill Ryan T Compositions and methods for enhancing tolerance for the production of organic chemicals produced by microorganisms
US7754916B2 (en) 2007-09-17 2010-07-13 Rohm And Haas Company Process for converting a hydroxycarboxylic acid, or salts thereof, to an unsaturated carboxylic acid and/or its esters
EP2036879A1 (en) 2007-09-17 2009-03-18 Rohm and Haas Company Process For Converting A Hydroxy Carboxylic Acid Or Salts Thereof, To An Unsaturated Carboxylic Acid And/Or Its Esters
US8652816B2 (en) 2007-12-04 2014-02-18 Opx Biotechnologies, Inc. Compositions and methods for 3-hydroxypropionate bio-production from biomass
JP2010180171A (en) * 2009-02-06 2010-08-19 Nippon Shokubai Co Ltd Method for producing acrylic acid
US9428778B2 (en) 2009-09-27 2016-08-30 Cargill, Incorporated Method for producing 3-hydroxypropionic acid and other products
US10100342B2 (en) 2009-09-27 2018-10-16 Cargill, Incorporated Method for producing 3-hydroxypropionic acid and other products
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