ZA200107560B - Catalyst for ester production and process for producing ester. - Google Patents
Catalyst for ester production and process for producing ester. Download PDFInfo
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- ZA200107560B ZA200107560B ZA200107560A ZA200107560A ZA200107560B ZA 200107560 B ZA200107560 B ZA 200107560B ZA 200107560 A ZA200107560 A ZA 200107560A ZA 200107560 A ZA200107560 A ZA 200107560A ZA 200107560 B ZA200107560 B ZA 200107560B
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- moles
- catalyst
- ester
- nitrate
- oxide
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- 150000002148 esters Chemical class 0.000 title claims description 79
- 239000003054 catalyst Substances 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 52
- 238000000034 method Methods 0.000 title claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 61
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- 235000019441 ethanol Nutrition 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 33
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 26
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 23
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 23
- 239000012018 catalyst precursor Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 16
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 14
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- 239000012808 vapor phase Substances 0.000 claims description 6
- 229910017767 Cu—Al Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000003754 zirconium Chemical class 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 239000002994 raw material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 4
- HCMKERMTTKZRCR-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O.CCOC(C)=O HCMKERMTTKZRCR-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000006423 Tishchenko reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ILCRHUJGVUEAKX-UHFFFAOYSA-N butan-1-ol;butyl acetate Chemical compound CCCCO.CCCCOC(C)=O ILCRHUJGVUEAKX-UHFFFAOYSA-N 0.000 description 1
- NDWFDLCIEWNKGN-UHFFFAOYSA-N butan-1-ol;butyl butanoate Chemical compound CCCCO.CCCCOC(=O)CCC NDWFDLCIEWNKGN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000006709 oxidative esterification reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
‘. ) i IN TN. . -1- 20017580 - FP1023-PCT
CATALYST FOR ESTER PRODUCTION AND
PROCESS FOR PRODUCING ESTER
This invention relates to a new catalyst for ester production and a process for producing a lower ester by this catalyst.
Lower esters represented by ethyl acetate have been used in large quantities as paint solvents, extracting solvents, intermediates for chemical products and medicines, or the like, and are important materials in the chemical industry.
Such lower esters have conventionally been produced by dehydrating esterification from carboxylic acids and alcohols or condensation of aldehydes which is called
Tishchenko reaction. In recent years, a process for the production of esters from carboxylic acids and olefins using a heteropolyacid catalyst has been reported (JP-A 5-65248, etc.) and noted as a new process for producing ethyl acetate.
In prior art processes for the production of ethyl acetate, however, plural raw materials such as acids and alcohols or acids and olefins have been used and thus the procurement of plural sources for the raw materials has been
“y -2- 20017560 required, or otherwise, raw materials such as acetaldehyde, which are not easy to procure in a non-industrial area and difficult to handle, have been used and thus procuring, stockpiling and handling the raw materials have not been easy.
For the manufacture of esters having different carbon chain lengths, dehydrating esterification from the corresponding acids and alcohols has been effective means.
However, there has been a problem of corrosion of an apparatus, etc., since acids are used as raw materials.
A process for producing ethyl acetate from ethyl alcohol by oxidative esterification using a palladium catalyst is reported in Kogyou Kagaku Zasshi, vol. 71, No. 9, pages 1517-1522, 1968. JP-A 9-29099 discloses a process for producing an ester from an alcohol and an aldehyde by a palladium-lead catalyst. In these reactions which consume oxygen, however, industrially useful hydrogen is not utilizable as by-product, although esters are produced.
An object of the invention is to solve the technical problems in the prior art as mentioned above, and to provide a new catalyst for ester production and a process for producing an ester from a lower alcohol, or a lower alcohol and a lower aldehyde.
We have zealously studied and found a process for producing an ester from an alcohol, or an ester from an alcohol and an aldehyde by dehydrogenation, using a catalyst prepared in a particular manner which contains copper and zirconium oxide as essential components, and further, at least one metal oxide selected from the group consisting of zinc oxide, chromium oxide, aluminum oxide and silicon oxide, thus leading to the completion of the present invention.
The catalysts for ester production according to the invention are defined in the following items (1) to (11). (1) A catalyst for ester production which comprises zirconium oxide, copper and at least one oxide selected from the group consisting of zinc oxide, chromium oxide, aluminum oxide and silicon oxide, and is obtainable by reducing with hydrogen a catalyst precursor prepared by the reaction of a salt containing at least one of metals constituting the oxides, a zirconium salt and a copper salt with an alkali hydroxide. (2) The catalyst for ester production as defined in item (1), which comprises not more than 5 moles of zinc oxide, not more than 5 moles of chromium oxide, not more than 5 moles of aluminum oxide, not more than 200 moles of silicon oxide and 0.05-5 moles of zirconium oxide, per mole of copper. (3) The catalyst for ester production as defined in item (1), which comprises not more than 2 moles of zinc
<y - 4 - oxide, not more than 5 moles of aluminum oxide and 0.05-5 moles of zirconium oxide, per mole of copper. (4) The catalyst for ester production as defined in item (1), which comprises not more than 5 moles of zinc oxide and 0.05-5 moles of zirconium oxide, per mole of copper. (5) The catalyst for ester production as defined in item (1), which comprises not more than 5 moles of aluminum oxide and 0.05-5 moles of zirconium oxide, per mole of copper. (6) A Cu-Zn0-Al,0;-Zr0, catalyst for ester production, which is obtainable by reducing with hydrogen a calcined form (a catalyst precursor) of a precipitate prepared from a mixed aqueous solution of copper nitrate, zinc nitrate,
aluminum nitrate and zirconyl nitrate, and an alkali hydroxide. (7) The catalyst for ester production as defined in item (6) wherein the mixed aqueous solution contains not more than 2 moles of zinc nitrate, not more than 10 moles of aluminum nitrate and 0.05-5 moles of zirconyl nitrate, per mole of copper nitrate. (8) A Cu-Zn0-Zr0,; catalyst for ester production which is obtainable by reducing with hydrogen a calcined form (a catalyst precursor) of a precipitate prepared from a mixed aqueous solution of copper nitrate, zinc nitrate and zirconyl nitrate, and an alkali hydroxide.
Cy - 5 2 (9) The catalyst for ester production as defined in item (8) wherein the mixed aqueous solution contains not more than 5 moles of zinc nitrate and 0.05-5 moles of zirconyl nitrate, per mole of copper nitrate. (10) A Cu-Al,03;-2r0; catalyst for ester production, which is obtainable by reducing with hydrogen a calcined form (a catalyst precursor) of a precipitate prepared from a mixed aqueous solution of copper nitrate, aluminum nitrate and zirconyl nitrate, and an alkali hydroxide. (11) The catalyst for ester production as defined in item (10) wherein the mixed aqueous solution contains not more than 10 moles of aluminum nitrate and 0.05-5 moles of zirconyl nitrate, per mole of copper nitrate.
The processes for the production of esters according to the present invention are defined in the following items (12)-(18). (12) A process for producing an ester, characterized by bringing an alcohol into contact with a catalyst as defined in any one of items (1)-(11) in vapor phase, and dehydrogenating the alcohol to form an ester. (13) The process for producing an ester as defined in item (12) wherein the alcohol is an alcohol having 1-4 carbon atoms. (14) The process for producing an ester as defined in item (12) wherein ethyl acetate is produced from ethyl alcohol.
Tw - 6 - (15) A process for producing an ester, characterized by bringing an alcohol and an aldehyde into contact with a catalyst as defined in any one of items (1)-(1l1l) in vapor phase to form an ester. (16) The process for producing an ester as defined in item (15) wherein the alcohol and the aldehyde are an alcohol and an aldehyde each having 1-4 carbon atoms. (17) The process for producing an ester as defined in item (15) wherein ethyl acetate is produced from ethyl alcohol and acetaldehyde. (18) The process for producing an ester as defined in item (15) wherein butyl acetate is produced from butyl alcohol and acetaldehyde.
The catalyst for ester production according to the present invention is characterized by comprising zirconium oxide, copper and at least one oxide selected from the group consisting of zinc oxide, chromium oxide, aluminum oxide and silicon oxide, and being obtainable by reducing with hydrogen a catalyst precursor prepared by the reaction of a salt containing at least one of metals constituting the oxides, a zirconium salt and a copper salt with an alkali hydroxide.
For instance, an aqueous solution of an alkali hydroxide is added to an aqueous solution of a nitrate of a metal contained in the catalyst to precipitate a catalyst precursor comprising a metal hydroxide. The catalyst precursor is washed with water, dried and baked, and then reduced with hydrogen at 120-500°C for 1-48 hours, thus reducing copper oxide to prepare an active metallic copper/zirconium oxide/oxide catalyst.
The catalyst for ester production according to the invention contains metallic copper and zirconium oxide as essential ingredients, and further contains one or more oxides selected from the group consisting of zinc oxide, chromium oxide, aluminum oxide and silicon oxide.
The contents of the oxides and zirconium oxide are not more than 5 moles of zinc oxide, not more than 5 moles of chromium oxide, not more than 5 moles of aluminum oxide, not more than 200 moles of silicon oxide and 0.05-5 moles of zirconium oxide, per mole of copper.
There is no limitation on reaction apparatuses used in the manufacture of the catalyst for ester production according to the invention particularly. Preferably, a predetermined amount of a catalyst precursor is charged in the reaction apparatus used in the manufacture of esters, and reduced with hydrogen and activated to form a catalyst.
The apparatus is then charged with an ester raw material.
For instance, a predetermined amount of a catalyst precursor is charged into a vapor-circulating reaction apparatus and reduced with hydrogen to form an active catalyst layer within the apparatus for ester manufacture.
a. - 8 -
In the preparation of the precipitate comprising metal hydroxides by reaction of metal nitrates with alkali hydroxides, methods such as coprecipitation and impregnation are suitably applied, but not limited thereto.
The contents of copper or metal oxides in the Cu-
Zn0-Al,0;-2r0, catalyst of the present invention are preferably not more than 2 moles of zinc oxide, not more than 5 moles of aluminum oxide and 0.05-5 moles of zirconium oxide, per mole of copper, and more preferably 0.05-1 mole of zinc oxide, 0.1-1 mole of aluminum oxide and 0.1-1 mole of zirconium oxide, per mole of copper. The content outside the preferred range results in the lower selectivity to the intended ester.
This catalyst is prepared by reducing with hydrogen a calcined form (a catalyst precursor) of the precipitate prepared from a mixed aqueous solution of copper nitrate, zinc nitrate, aluminum nitrate and zirconyl nitrate, and an alkali hydroxide. The mixed aqueous solution contains preferably not more than 2 moles of zinc nitrate, not more than 10 moles of aluminum nitrate and 0.05-5 moles of zirconyl nitrate, and more preferably 0.05-1 mole of zinc nitrate, 0.2-2 moles of aluminum nitrate and 0.1-1 mole of zirconyl nitrate, per mole of copper nitrate.
The contents of copper or metal oxides in the Cu-
Zn0-2r0, catalyst of the present invention are preferably not more than 5 moles of zinc oxide and 0.05-5 moles of zirconium oxide, per mole of copper, and more preferably
Te - 9 - 0.1-1 mole of zinc oxide and 0.1-1 mole of zirconium oxide, per mole of copper. The content outside the preferred range results in the lower selectivity to the intended ester.
This catalyst is prepared by reducing with hydrogen a calcined form (a catalyst precursor) of the precipitate obtained from a mixed aqueous solution of copper nitrate, zinc nitrate and zirconyl nitrate, and an alkali hydroxide. The mixed aqueous solution contains preferably not more than 5 moles of zinc nitrate and 0.05-5 moles of zirconyl nitrate, and more preferably 0.1-1 mole of zinc nitrate and 0.1-1 mole of zirconyl nitrate, per mole of copper nitrate.
The contents of copper or metal oxides in the Cu-
Al;0;-Zr0; catalyst of the present invention are preferably not more than 5 moles of aluminum oxide and 0.05-5 moles of zirconium oxide, per mole of copper, and more preferably 0.1-1 mole of aluminum oxide and 0.1-1 mole of zirconium oxide, per mole of copper. The content outside the preferred range results in the lower selectivity to the intended ester.
This catalyst is prepared by reducing with hydrogen a calcined form (a catalyst precursor) of the precipitate obtained from a mixed aqueous solution of copper nitrate, aluminum nitrate and zirconyl nitrate, and an alkali hydroxide. The mixed aqueous solution contains preferably not more than 10 moles of aluminum nitrate and 0.05-5 moles of zirconyl nitrate, and more preferably 0.1-1
© -10 - mole of aluminum nitrate and 0.1-1 mole of zirconyl nitrate, per mole of copper nitrate.
The process for the production of esters according to the present invention is characterized by bringing either an alcohol or an alcohol and an aldehyde into contact with the catalyst of the present invention in vapor phase and subjecting to dehydrogenation to prepare an ester.
According to the present invention, preferable catalysts for ester production used in the processes for the production of esters are metallic copper/zirconium oxide/metal oxides, which are specifically Cu-Zn0O-Al,03;-Zr0O;-
Si0;, Cu-zZnO-Al,03;-Zr0;, Cu-Zn0-Zr0,, Cu-Zr0,, Cu-Cr,0;-Zr0; or the like.
For the manufacture of ethyl acetate from alcohol, the manufacture of ethyl acetate from alcohol and acetaldehyde, or the like, preferable are Cu-ZnO-Al,0;-ZrO,- $i0,, Cu-Zn0-Al,0;-Zr0,, Cu-Zn0O-2r0,, Cu-2r0,, Cu~-Cr,0;-Zr0, or the like.
Alcohols for a raw material are preferably methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol or the like. Aldehydes are preferably acetaldehyde, propionaldehyde, isobutylaldehyde, butylaldehyde or the like.
Esters produced from these raw materials include methyl formate, ethyl acetate, propyl propionate, butyl butyrate, n-butyl acetate and n-propyl acetate.
In particular, the present process for the production of esters is used preferably for the manufacture of ethyl acetate from ethyl alcohol and the manufacture of ethyl acetate from ethyl alcohol and acetaldehyde.
The reaction temperature in the process for the production of esters is suitably in the range of from 150 to 400°C. That is, it is the temperature at which an alcohol and an aldehyde exist in vapor phase. The reaction may insufficiently progress at lower than 150°C, while the selectivity to the product may lower at higher than 400°C.
The water content in alcohols and aldehydes as the raw materials is allowable in the range of 0-30% by weight, and it is preferably in the range of 0-15% by weight.
The effect of the present invention is concretely illustrated by the following Examples and Comparative
Examples, to which the invention is not limited.
A normal-pressure vapor-circulating fixed-bed reaction apparatus used in the Examples and Comparative
Examples is a reactor having a inner diameter of 17 mm and a total length of 600 mm (the upper part 400 mm in length is a vaporization layer packed with ceramic rings and the lower part is a catalyst layer 100 mm in length), equipped with a carrier gas introducing inlet and a raw material flowing inlet at the top end, and at the bottom end a vessel
- -12 = (cooled) for collecting a crude reaction solution which has a gas vent.
The crude reaction solution collected in the collecting vessel was determined by gas chromatography.
After calibration correction and water content correction, the yield of ethyl acetate, etc. and the residual amount of raw materials such as ethyl alcohol were determined. From these values, conversion (% by weight), selectivity (% by weight) and yield (% by weight) were calculated. (Example 1) (Preparation of catalyst)
In a flask, 97 g of copper nitrate, 40 g of zinc nitrate, 504 g of aluminum nitrate and 36 g of zirconyl nitrate were dissolved in 5 liters of water. To this solution was added an aqueous solution of 227 g of sodium hydroxide dissolved in 1 liter of water to prepare a precipitate. The precipitate (prepared by a so-called coprecipitation method) was washed with water, dried and baked to form a catalyst precursor.
In the normal-pressure vapor-circulating fixed-bed reaction apparatus, 15 g of the catalyst precursor were charged in the catalyst layer (17 mm in inner diameter, about 100 mm in length) and then reduced with a nitrogen- diluted hydrogen as a reducing agent at 200°C or lower for 4 hours, and a Cu-Zn0O-Al,0;-Zr0, catalyst layer for ester production was provided within this reaction apparatus. (Production of ester)
A nitrogen gas was flowed as a carrier gas at a constant rate of 20 ml/min from the top of the reaction apparatus provided with the Cu-zZn0-Al,0;-Z2r0O, catalyst layer.
Together with this nitrogen gas, 99.5% by weight of ethyl alcohol were supplied, and ethyl alcohol was vaporized in the vaporization layer and fed to the catalyst layer to carry out the reaction. The temperatures in the vaporization and catalyst layers were 260°C.
Conversion of ethanol, selectivity to ethyl acetate and yield of ethyl acetate at respective LHSV's (Liquid Hourly Space Velocity) of ethanol are shown in the following table. [Table 1] (h™) ethanol ethyl acetate ethyl acetate (%) (%) (%)
Cos | ee | ew | ws (Example 2) (Preparation of catalyst)
In 5 liters of water were dissolved 97 g of copper nitrate, 40 g of zinc nitrate and 36 g of zirconyl nitrate.
To this solution was added an aqueous solution of 64 g of sodium hydroxide dissolved in 1 liter of water to prepare a precipitate. The precipitate (prepared by a so-called coprecipitation method) was washed with water, dried and baked to form a catalyst precursor.
In accordance with the procedure of Example 1, a
Cu-Zn0-Zr0, catalyst layer for ester production was provided in the normal-pressure vapor-circulating fixed-bed reaction apparatus. (Production of ester)
Ethyl acetate was produced by performing the reaction in accordance with the procedure of Example 1, except for using the fixed-bed reaction apparatus provided with the Cu-Zn0O-Zr0O, catalyst layer and 99% ethyl alcohol.
The result of the reaction is shown in the following table. [Table 2] (h™!) ethanol ethyl acetate ethyl acetate (%) (%) (%) (Example 3)
The reaction was performed under the same condition as in Example 2, except for using 95% ethanol as a reaction material. The result is shown in the following table. [Table 3] (h™!) ethanol ethyl acetate ethyl acetate (%) (%) (%)
(Example 4)
The reaction was performed under the same condition as in Example 2, except that the reaction temperature was 300°C. The result is shown in the following table. [Table 4] (h™!) ethanol ethyl acetate ethyl acetate (%) (%) (%) (Example 5)
The reaction was performed under the same condition as in Example 2, except for using n-butanol and acetaldehyde (mole ratio of n-butanol : acetaldehyde = 80 : 20) as a raw material. The result is shown in the following table. [Table 5] (h™!) n-butanol n-butyl acetate | n-butyl acetate (%) (%) (%) (Example 6)
The reaction was performed under the same condition as in Example 2, except for using n-butanol as a raw material. The result is shown in the following table.
[Table 6] (h™1) n-butanol butyl butyrate | butyl butyrate (%) (%) (%)
Cea | ee [wer [aa (Example 7) (Preparation of catalyst)
In a flask, 156 g of copper nitrate, 162 g of aluminum nitrate and 58 g of zirconyl nitrate were dissolved in 5 liters of water. To this solution was added an aqueous solution of 191 g of sodium hydroxide dissolved in 1 liter of water. The resulting precipitate was washed with water, dried and baked to form a catalyst precursor.
In the normal-pressure vapor-circulating fixed-bed reaction apparatus, 15 g of the catalyst precursor were charged in the catalyst layer (17 mm in inner diameter, about 100 mm in length) and then reduced with a nitrogen- diluted hydrogen as a reducing agent at 200°C or lower for 4 hours, and a Cu-Al,0;-Zr0O, catalyst layer for ester production was provided within the reaction apparatus. (Production of ester)
Ethyl alcohol (99.5%) as a raw material and nitrogen as a carrier gas were supplied from the top of the fixed-bed reaction apparatus provided with the Cu-Al;0;-Zr0, catalyst layer, thereby initiating a reaction. Ethyl alcohol was vaporized in the vaporization layer and fed to the catalyst layer. The amount of nitrogen supplied as a
Claims (18)
1. A catalyst for ester production which comprises zirconium oxide, copper and at least one oxide selected from the group consisting of zinc oxide, chromium oxide, aluminum oxide and silicon oxide, and is obtainable by reducing with hydrogen a catalyst precursor prepared by the reaction of a salt containing at least one of metals constituting the oxides, a zirconium salt and a copper salt with an alkali hydroxide.
2. The catalyst for ester production as claimed in claim 1, which comprises not more than 5 moles of zinc oxide, not more than 5 moles of chromium oxide, not more than 5 moles of aluminum oxide, not more than 200 moles of silicon oxide and 0.05-5 moles of zirconium oxide, per mole of copper.
3. The catalyst for ester production as claimed in claim 1, which comprises not more than 2 moles of zinc oxide, not more than 5 moles of aluminum oxide and 0.05-5 moles of zirconium oxide, per mole of copper.
4. The catalyst for ester production as claimed in claim 1, which comprises not more than 5 moles of zinc oxide and 0.05-5 moles of zirconium oxide, per mole of copper.
5. The catalyst for ester production as claimed in claim 1, which comprises not more than 5 moles of aluminum oxide and 0.05-5 moles of zirconium oxide, per mole of copper.
«
6. A Cu-Zn0O-Al,03;-Z2r0;, catalyst for ester production which is obtainable by reducing with hydrogen a calcined form (a catalyst precursor) of a precipitate prepared from a mixed aqueous solution of copper nitrate, zinc nitrate, aluminum nitrate and zirconyl nitrate, and an alkali hydroxide.
7. The catalyst for ester production as claimed in claim 6, wherein the mixed aqueous solution contains not more than 2 moles of zinc nitrate, not more than 10 moles of aluminum nitrate and 0.05-5 moles of zirconyl nitrate, per mole of copper nitrate.
8. A Cu-ZnO-Zr0O, catalyst for ester production which is obtainable by reducing with hydrogen a calcined form (a catalyst precursor) of a precipitate prepared from a mixed aqueous solution of copper nitrate, zinc nitrate and zirconyl nitrate, and an alkali hydroxide.
9. The catalyst for ester production as claimed in claim 8, wherein the mixed aqueous solution contains not more than 5 moles of zinc nitrate and 0.05-5 moles of zirconyl nitrate, per mole of copper nitrate.
10. A Cu-Al,;0;-Zr0; catalyst for ester production which is obtainable by reducing with hydrogen a calcined form (a catalyst precursor) of a precipitate prepared from a mixed aqueous solution of copper nitrate, aluminum nitrate and zirconyl nitrate, and an alkali hydroxide.
11. The catalyst for ester production as claimed in claim 10, wherein the mixed aqueous solution contains not
-- - 26 ~ more than 10 moles of aluminum nitrate and 0.05-5 moles of zirconyl nitrate, per mole of copper nitrate.
12. A process for producing an ester, characterized by bringing an alcohol into contact with a catalyst as claimed in any one of claims 1-11 in vapor phase, and dehydrogenating the alcohol to form an ester.
13. The process for producing an ester as claimed in claim 12, wherein the alcohol is an alcohol having 1-4 carbon atoms.
14. The process for producing an ester as claimed in claim 12, wherein ethyl acetate is produced from ethyl alcohol.
15. A process for producing an ester, characterized by bringing an alcohol and an aldehyde into contact with a catalyst as claimed in any one of claims 1-11 in vapor phase to form an ester.
16. The process for producing an ester as claimed in claim 15, wherein the alcohol and the aldehyde are an alcohol and an aldehyde each having 1-4 carbon atoms.
17. The process for producing an ester as claimed in claim 15, wherein ethyl acetate is produced from ethyl alcohol and acetaldehyde.
18. The process for producing an ester as claimed in claim 15, wherein butyl acetate is produced from butyl alcohol and acetaldehyde.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6013699 | 1999-03-08 |
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| Publication Number | Publication Date |
|---|---|
| ZA200107560B true ZA200107560B (en) | 2002-09-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200107560A ZA200107560B (en) | 1999-03-08 | 2001-09-13 | Catalyst for ester production and process for producing ester. |
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| Country | Link |
|---|---|
| ZA (1) | ZA200107560B (en) |
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2001
- 2001-09-13 ZA ZA200107560A patent/ZA200107560B/en unknown
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