ZA200109928B - Catalyst for use in producing lower fatty acid ester, process for producing the catalyst, and process for producing lower fatty acid ester using the catalyst. - Google Patents
Catalyst for use in producing lower fatty acid ester, process for producing the catalyst, and process for producing lower fatty acid ester using the catalyst. Download PDFInfo
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- ZA200109928B ZA200109928B ZA200109928A ZA200109928A ZA200109928B ZA 200109928 B ZA200109928 B ZA 200109928B ZA 200109928 A ZA200109928 A ZA 200109928A ZA 200109928 A ZA200109928 A ZA 200109928A ZA 200109928 B ZA200109928 B ZA 200109928B
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- South Africa
- Prior art keywords
- catalyst
- acid
- producing
- fatty acid
- lower fatty
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 52
- -1 fatty acid ester Chemical class 0.000 title claims description 25
- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 23
- 239000000194 fatty acid Substances 0.000 title claims description 23
- 229930195729 fatty acid Natural products 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 21
- 150000003839 salts Chemical class 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- 239000011964 heteropoly acid Substances 0.000 claims description 12
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 8
- 238000004438 BET method Methods 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- 239000000725 suspension Substances 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
CATALYST FOR USE IN PRODUCING LOWER FATTY ACID ESTER,
PROCESS FOR PRODUCING THE CATALYST, AND PROCESS FOR
PRODUCING LOWER FATTY ACID ESTER USING THE CATALYST
This application is an application filed under 35
U.S.C. § 111(a) claiming benefit pursuant to 35 U.S5.C. § 119(e)(1l) of the filing date of the Provisional
Application 60/141,249 filed June 30, 1999, pursuant to 35 U.S.C. § 111(b).
The present invention relates to a catalyst for producing lower fatty acid esters, through a reaction between a lower aliphatic carboxylic acid and a lower olefin; a process for producing the catalyst; and a process for producing lower fatty acid esters by using the catalyst.
A reaction between a lower olefin and a lower aliphatic carboxylic acid in the presence of an acidic catalyst is known to yield the corresponding lower fatty acid ester. In addition, a heteropoly acid and a salt thereof are known to serve as an effective catalyst for the reaction. For example, Japanese Unexamined Patent
Publications (Kokai) No. 4-139148, No. 4-139149, No. 5- 65248, No. 5-163200, No. 5-170699, No. 5-255185, No. 5- 294894, No. 6-72951, and No. 9-118647 disclose conventional technigues in relation to the above process and catalyst.
In these techniques, catalyst components and reaction conditions are elaborated from various aspects, and lower fatty acid esters can be produced with a comparatively high yield. However, nowadays, there is a demand for a catalyst having higher performance and a higher activity per unit time.
Among these publications, Japanese Unexamined Patent
Publications (Kokai) No. 5-294894 and No. 9-11B647 disclose a so-called supported catalyst in which a heteropoly acid and/or a salt thereof serving as an active component are held on a carrier formed of a porous substance such as silica gel.
In general, the catalytic properties of a produced supported catalyst depend on the type and properties of the carrier for supporting the catalyst component. In addition, the catalyst performance, such as catalytic activity or selectivity of a target product during reaction, varies depending on the properties of the produced supported catalyst.
The aforementioned Japanese Unexamined Patent
Publications (Kokai) No. 5-294894 and No. 9-118647 fail to provide detailed discussion of a carrier, and furthermore, do not disclose the catalytic performance of a prepared supported catalyst, particularly performance attributed to the properties of the carrier.
In view of the foregoing, an object of the present invention is to provide a catalyst having higher catalytic activity in a process for producing a lower fatty acid ester through esterification of a lower olefin with a lower aliphatic carboxylic acid in the presence of a catalyst wherein at least one compound selected from heteropoly acids and salts thereof is caused to be held on a carrier. Another object of the invention is to provide a process for producing the catalyst. Still another object of the invention is to provide a process for producing a lower fatty acid ester by using the catalyst.
The present inventors have conducted intensive studies to obtain a catalyst which has high performance and is useful for producing lower fatty acid esters through reaction of a lower olefin and a lower aliphatic carboxylic acid.
- 3 =
Thus, the present inventors have found that the catalytic activity of a supported catalyst used in the above reaction containing a heteropoly acid and/or a salt thereof can be improved remarkably when the specific surface area of the catalyst, as measured by a BET method, falls within a specific range. The present invention has been accomplished on the basis of this finding.
Accordingly, the present invention (I) provides a catalyst for producing a lower fatty acid ester which catalyst contains at least one compound selected from heteropoly acids and salts thereof, which compound is caused to be held on a carrier and which catalyst is used in a process for producing a lower fatty acid ester through esterification of a lower aliphatic carboxylic acid with a lower olefin, wherein the specific surface area of the catalyst, as measured by a BET method, is 65 m?/g-350 m?/g.
The present invention (II) provides a catalyst according to the present invention (I) used for producing a lower fatty acid ester, which catalyst has a specific surface area of the carrier as measured by BET method of 100 m*/g-500 m?/g.
The present invention (III) provides a process for producing the catalyst as recited in the present invention (I) or (II) useful for producing a lower fatty acid ester.
The present invention (IV) provides a process for producing a lower fatty acid ester through esterification of a lower aliphatic carboxylic acid with a lower olefin in the presence of the catalyst as recited in the present invention (I) or (II).
Best Mode for Carrying Out the Invention
The present invention will now be described in detail.
The catalyst for producing a lower fatty acid ester
- 4 = according to the invention (I) will be described. The invention (I) encompasses a catalyst for producing a lower fatty acid ester, which catalyst contains at least one compound selected from heteropoly acids and salts thereof, which compound is caused to be held on a carrier and which catalyst is used in a process for producing a lower fatty acid ester through esterification of a lower aliphatic carboxylic acid with a lower olefin, wherein the specific surface area of the catalyst, as measured by a BET method, is 65 m?/g-350 m?/g.
The heteropoly acids used in the invention (I) comprise a hetero element and poly elements bonded to oxygen. The hetero element is typically silicon or phosphorus, but is not limited thereto, and can be optionally selected from elements belonging to Groups 1l- 17 in the periodic table (Nomenclature of Inorganic
Chemistry by International Union of Pure and Applied
Chemistry, revised edition (1989); the same applies hereinafter).
The hetero element is not particularly limited, and examples thereof include a cupric ion; a divalent ion of beryllium, zinc, cobalt, or nickel; a trivalent ion of boron, aluminum, gallium, iron, cerium, arsenic, antimony, phosphorus, bismuth, chromium, or rhodium; a tetravalent ion of silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese, nickel, platinum, thorium, hafnium, cerium, or other rare earth metals; a pentavalent ion of phosphorus, arsenic, vanadium, or antimony; a hexavalent tellurium ion; and a heptavalent iodine ion.
The poly element is not particularly limited, and examples thereof include tungsten, molybdenum, vanadium, niobium, and tantalum.
Such a heteropoly acid is well known as "a polyoxo anion," "a polyoxo metal salt," or "an oxidized metal cluster." Some structures of the well-known anions are named after researchers in this field, such as the Keggin
- 5 = structure, the Dawson structure, and the Anderson-Evans-
Pearov structure. A heteropoly acid typically has a high molecular weight, e.g., a molecular weight of 700-8500, and also encompasses a dimer complex thereof.
No particular limitation is imposed on the heteropoly-acid salt, and a metal salt or an onium salt may be used so long as a portion of or all hydrogen atoms of the hetercpoly-acid are substituted. Non-limitative examples include metal salts of lithium, sodium, potassium, cesium, magnesium, barium, copper, gold, and gallium; and onium salts such as ammonium salts.
A heteropoly acid compound, particularly when in the form of a free acid or a salt, has comparatively high solubility to a polar solvent such as water or a oxygen- containing compound solvent, and the solubility thereof can be controlled by the selection of a suitable counter ion of the salt.
Examples of heteropoly acids which can be used in the present invention include the following compounds: silicotungstic acid Hy [SiW;12040] - XH20; phosphotungstic acid Hi [PW12040]} « XH20; phosphomolybdic acid H3[PMo12040] . XH20; silicomolybdic acid He[SiM0;2040].%H20; and phosphovanadomolybdic acid H3:n [PVNMO12-n040] « XH20.
Examples of particularly preferred heteropoly acid salts include lithium salts, sodium salts, potassium salts, cesium salts, magnesium salts, barium salts, copper salts, gold salts, gallium salts, and ammonium salts of the above-described particularly preferred heteropoly acids.
The amount of a heteropoly acid or a salt thereof caused to be held on a carrier is preferably 10 wt%-200 wt%, more preferably 50 wt%-150 wt% based on the weight of the carrier.
When the amount of a heteropoly acid or a salt thereof is less than 10 wt%, the amount of an active
Claims (11)
1. A catalyst for producing a lower fatty acid ester which catalyst contains at least one compound selected from heteropoly acids and salts thereof, which compound is caused to be held on a carrier and which catalyst is used in a process for producing a lower fatty acid ester through esterification of a lower aliphatic carboxylic acid with a lower olefin, wherein the specific surface area of the catalyst as measured by BET method is 65 m?/g-350 m?/g.
2, A catalyst according to claim 1, wherein the heteropoly acids are selected from the group consisting of silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid and phosphovanadomolybdic acid.
3. A catalyst according to claim 1 or 2, wherein the heteropoly acid salts are selected from the group consisting of lithium, sodium, potassium, cesium, magnesium, barium, copper, gold, gallium and ammonium salts of an acid selected from silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid and phosphovanadomolybdic acid.
4. A catalyst according to any one of claims 1 through 3, wherein the specific surface area of the carrier as measured by BET method is 100 m?/g to 500 ’ n’/qg.
5. A process for producing a catalyst as described in any one of claims 1 through 4, comprising the following first and second steps: First step: A step of obtaining a solution or a suspension of the heteropoly-acid and/or salt thereof. Second step: A step of causing the solution or suspension obtained in the first step to be held on a carrier, to thereby obtain a catalyst for producing a lower fatty scid ester. PCT/JP00/03570
6. A process for producing a lower fatty acid ester, comprising esterifying a lower aliphatic carboxylic acid with a lower olefin in the presence of a catalyst as described in any one of claims 1 through 4.
7. A prccess according to claim 6, wherein the lower aliphatic carboxylic acid is esterified with a lower olefin in the presence of water.
8. A process eccording to claim 6 or 7, wherein the lower aliphatic carboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, acrylic zcid and methacrylic acid.
: 9. A prccess according to any one of claims 6 through 8, wherain the lower olefin is selected from the group consisting ci ethylene, propylene, n-butene and isobutene.
10. A process for producing a catalyst as described in any one of the catalyst preparation examples 1 to 10.
11. A process for producing a lower fatty acid ester as described in any one of the examples 1 to 10. AMENDED SHEET
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15606099A JP4329163B2 (en) | 1999-06-03 | 1999-06-03 | Catalyst for producing lower aliphatic ester, method for producing the catalyst, and method for producing lower fatty acid ester using the catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200109928B true ZA200109928B (en) | 2002-08-27 |
Family
ID=15619440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200109928A ZA200109928B (en) | 1999-06-03 | 2001-12-03 | Catalyst for use in producing lower fatty acid ester, process for producing the catalyst, and process for producing lower fatty acid ester using the catalyst. |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4329163B2 (en) |
| KR (1) | KR100451431B1 (en) |
| TW (1) | TWI267403B (en) |
| ZA (1) | ZA200109928B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002079088A (en) * | 2000-09-07 | 2002-03-19 | Showa Denko Kk | Catalyst for manufacturing lower aliphatic carboxylic acid ester, method for manufacturing the same and method for manufacturing lower aliphatic carboxylic acid ester by the catalyst |
| JP6986908B2 (en) | 2017-09-05 | 2021-12-22 | 昭和電工株式会社 | Method for producing aliphatic carboxylic acid ester |
| JP6910252B2 (en) | 2017-09-05 | 2021-07-28 | 昭和電工株式会社 | Method for manufacturing silica carrier |
| WO2022070674A1 (en) * | 2020-09-29 | 2022-04-07 | 昭和電工株式会社 | Method for producing ethyl acetate production catalyst |
-
1999
- 1999-06-03 JP JP15606099A patent/JP4329163B2/en not_active Expired - Lifetime
-
2000
- 2000-06-01 KR KR10-2001-7015507A patent/KR100451431B1/en not_active IP Right Cessation
- 2000-06-01 TW TW089110716A patent/TWI267403B/en not_active IP Right Cessation
-
2001
- 2001-12-03 ZA ZA200109928A patent/ZA200109928B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR100451431B1 (en) | 2004-10-06 |
| JP2000342980A (en) | 2000-12-12 |
| TWI267403B (en) | 2006-12-01 |
| JP4329163B2 (en) | 2009-09-09 |
| KR20020040671A (en) | 2002-05-30 |
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