CN111822041A - Composite catalyst, preparation method and application thereof - Google Patents
Composite catalyst, preparation method and application thereof Download PDFInfo
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- CN111822041A CN111822041A CN201910299011.7A CN201910299011A CN111822041A CN 111822041 A CN111822041 A CN 111822041A CN 201910299011 A CN201910299011 A CN 201910299011A CN 111822041 A CN111822041 A CN 111822041A
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- Prior art keywords
- catalyst
- molecular sieve
- gas
- mor molecular
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000002808 molecular sieve Substances 0.000 claims abstract description 67
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 67
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 43
- 230000006315 carbonylation Effects 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 32
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 69
- 150000007530 organic bases Chemical class 0.000 claims description 43
- 238000011282 treatment Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a composite catalyst, a preparation method thereof and a method for preparing methyl acetate and acetic acid by using the composite catalyst in methanol carbonylation. The composite catalyst is formed by compounding a water-vapor conversion catalyst and a modified H-MOR molecular sieve. The composite catalyst comprises a water-gas shift catalyst and a carbonylation catalyst; the carbonylation catalyst comprises a modified H-MOR molecular sieve; wherein the modified H-MOR molecular sieve is an H-MOR molecular sieve treated by organic alkali. The composite catalyst is used for methanol carbonylation, and the selectivity of methyl acetate is over 80 percent.
Description
Technical Field
The application relates to a composite catalyst for preparing methyl acetate by methanol carbonylation, a preparation method and application thereof.
Background
Methyl acetate is an important chemical, and downstream products of the methyl acetate can be produced mainly by ethanol, acetic acid, acetic anhydride, methyl acrylate, vinyl acetate, acetamide and the like, and the methyl acetate has wide application in the fields of energy and chemical industry. The traditional route for the production of methyl acetate is to produce acetic acid first by carbonylation of methanol and then to produce methyl acetate by esterification of acetic acid. At present, in the methanol carbonylation process, Rh-I or Ir-I is mainly used as a catalyst to produce methyl acetate, and the reaction system has the defects of high catalyst cost, strong corrosivity of the reaction system, iodine-containing reaction products and the like. The use of acidic molecular sieves as carbonylation catalysts can effectively solve the above problems. However, the methanol is dehydrated to generate dimethyl ether and water molecules on the acid catalyst, and the carbonylation efficiency of the methanol on the acidic molecular sieve is not high because the water molecules can inhibit the carbonylation reaction of the methanol, so that how to effectively avoid the influence of water in the reaction system and how to improve the carbonylation efficiency of the methanol on the acid catalyst have certain difficulty.
Disclosure of Invention
According to one aspect of the application, the composite catalyst is provided, and is applied to the preparation of methyl acetate by methanol carbonylation, wherein the selectivity of methyl acetate can reach 86%.
The composite catalyst is characterized in that the composite catalyst comprises a water-gas shift catalyst and a carbonylation catalyst;
the carbonylation catalyst comprises a modified H-MOR molecular sieve;
wherein the modified H-MOR molecular sieve is an H-MOR molecular sieve treated by organic alkali.
Alternatively, the carbonylation catalyst is a modified H-MOR molecular sieve.
The composite catalyst is formed by compounding a water-vapor conversion catalyst and a modified H-MOR molecular sieve.
Optionally, the compounding is: compounding is performed by particle mixing or mechanical ball milling.
Optionally, the modified H-MOR molecular sieve is a pre-adsorbed organic base treated H-MOR molecular sieve.
Optionally, the pre-adsorption organic base treatment comprises:
and (3) contacting the H-MOR molecular sieve with gas containing organic alkali to carry out pre-adsorption organic alkali treatment to obtain the modified H-MOR molecular sieve.
Optionally, the organic base treatment conditions are: the temperature is 150-350 ℃, and the time is 0.5-4 h.
Optionally, the organic base is selected from at least one of triethylamine, pyridine, pyridazine, pyrimidine and pyrazine.
Optionally, the water-gas shift catalyst is a catalyst in which water reacts with carbon monoxide.
Optionally, the water-gas shift catalyst is an oxide.
Optionally, the water vapor shift catalyst is selected from at least one of the compounds having the formula of formula (I):
(ZnO)aMb(Al2O3)1-a-bformula (I)
Wherein M is an oxide of at least one element of Zr, Cr and Ce; a is 0.1 to 0.9, and b is 0.05 to 0.8.
Alternatively, a and b are the molar ratio of the corresponding oxides in the whole components.
Alternatively, the upper range limit of said a in formula (I) is selected from 0.4, 0.5, 0.6, 0.8 or 0.9; the lower limit is selected from 0.1, 0.4, 0.5, 0.6 or 0.8.
Optionally, a is a value between 0.1 and 0.9.
Alternatively, the upper limit of b is selected from 0.1, 0.4, 0.5, 0.6 or 0.8; the lower limit is selected from 0.05, 0.1, 0.4, 0.5 or 0.6.
Optionally, b is a value between 0.05 and 0.8.
Optionally, the mass ratio of the water-vapor shift catalyst to the modified H-MOR molecular sieve in the composite catalyst is as follows:
a water-vapor shift catalyst: the ratio of the modified H-MOR molecular sieve to the modified H-MOR molecular sieve is 20-80: 20-80.
Optionally, the upper mass content limit of the steam shift catalyst is selected from 30 wt.%, 40 wt.%, 60 wt.%, 66.7 wt.%, 70 wt.% or 80 wt.%; the lower limit is selected from 20 wt.%, 30 wt.%, 40 wt.%, 60 wt.%, 66.7 wt.%, or 70 wt.%.
Optionally, the upper limit of the mass content of the modified H-MOR molecular sieve is selected from 30 wt.%, 40 wt.%, 60 wt.%, 66.7 wt.%, 70 wt.%, or 80 wt.%; the lower limit is selected from 20 wt.%, 30 wt.%, 40 wt.%, 60 wt.%, 66.7 wt.%, 70 wt.%, or 80 wt.%.
Optionally, the mass ratio of the water-vapor shift catalyst to the modified H-MOR molecular sieve in the composite catalyst is as follows:
a water-vapor shift catalyst: modified H-MOR molecular sieve 50: 50.
optionally, the H-MOR molecular sieve has a silicon-aluminum atomic ratio of 5-60.
Alternatively, the H-MOR molecular sieve has an upper limit on the atomic ratio of silicon to aluminum selected from 10, 30, 40, 50, or 60; the lower limit is selected from 5, 10, 30, 40 or 50.
According to another aspect of the present application, there is provided a method for preparing the composite catalyst, which comprises at least:
(1) obtaining a water-vapor shift catalyst;
(2) obtaining a modified H-MOR molecular sieve;
(3) and (3) molding a mixture containing the water-vapor shift catalyst in the step (1) and the modified H-MOR molecular sieve in the step (2) to obtain the composite catalyst.
Optionally, the water-gas shift catalyst in the step (1) is prepared by a coprecipitation method.
Optionally, step (1) comprises:
mixing a salt solution containing Zn element, M' element and Al element with a solution containing a precipitator in a parallel flow mode, controlling the pH value of the system to be 7-9, precipitating, aging and roasting to obtain the water-vapor conversion catalyst;
wherein, M' is selected from at least one of Zr, Cr and Ce.
Specifically, the preparation of the water-gas shift catalyst comprises the following steps: under the condition of stirring, mixing a salt solution containing Zn element, M' element and Al element with a solution containing a precipitator in a parallel flow mode, controlling the pH value of the system to be 7-9, and after precipitation is finished, aging, carrying out solid-liquid separation, washing, drying and roasting a solid phase to obtain the composite catalyst.
Optionally, the aging time is 2-4 h;
roasting for 1-6 h at 400-600 ℃;
the Zn element, the M' element and the Al element in the salt solution are at least one of nitrate, hydrochloride, acetate, acetylacetone salt and sulfate corresponding to each element.
Alternatively, the drying conditions are 100 ℃ for 6 hours.
Optionally, the agitation is vigorous agitation.
Optionally, the stirring speed is 250-5000 rpm/min.
Optionally, the precipitating agent is a lye.
Optionally, the alkali liquor is selected from at least one of ammonia water, ammonium carbonate, sodium carbonate, urea, NaOH, KOH.
Optionally, step (2) comprises:
and (3) contacting the H-MOR molecular sieve with gas containing organic alkali to carry out pre-adsorption organic alkali treatment to obtain the modified H-MOR molecular sieve.
Optionally, the organic base treatment conditions are: the temperature is 150-350 ℃, and the time is 0.5-4 h.
Optionally, the upper temperature limit of the organic base treatment is selected from 160 ℃, 200 ℃, 250 ℃, 300 ℃ or 350 ℃; the lower limit is selected from 150 deg.C, 200 deg.C, 250 deg.C, 300 deg.C or 340 deg.C.
Alternatively, the upper limit of time for the organic base treatment is selected from 0.6h, 1h, 2h, 3h or 4 h; the lower limit is selected from 0.5h, 1h, 2h, 3h or 3.9 h.
Optionally, the mass space velocity of the gas containing the organic base is 300-6000 mL-g-1·h-1。
Optionally, the upper limit of the mass space velocity of the gas containing the organic base is selected from 400 mL-g-1·h-1、500mL·g-1·h-1、1000mL·g-1·h-1、2000mL·g-1·h-1、3000mL·g-1·h-1、4000mL·g-1·h-1、5000mL·g-1·h-1Or 6000 mL. g-1·h-1(ii) a The lower limit is selected from 300mL g-1·h-1、500mL·g-1·h-1、1000mL·g-1·h-1、2000mL·g-1·h-1、3000mL·g-1·h-1、4000mL·g-1·h-1、4900mL·g-1·h-1Or 5000mL g-1·h-1。
Optionally, the gas containing an organic base comprises a carrier gas and an organic base;
the carrier gas is at least one of nitrogen, helium and argon;
the organic base is at least one of triethylamine, pyridine, pyridazine, pyrimidine and pyrazine;
the volume fraction of the organic base in the gas containing the organic base is 0.1-10%.
Optionally, the volume fraction upper limit of the organic base in the organic base-containing gas is selected from 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.9%, or 10%; the lower limit is selected from 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 9.9%.
Optionally, the H-MOR molecular sieve is activated in an inert atmosphere prior to contacting with a gas containing an organic base;
the activation temperature is 300-500 ℃, and the activation time is 3-5 h.
Optionally, the upper temperature limit of the activation is selected from 320 ℃, 350 ℃, 400 ℃, 450 ℃, 480 ℃ or 500 ℃; the lower limit is selected from 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 480 deg.C or 500 deg.C.
Optionally, the upper time limit for activation is selected from 3.2h, 3.5h, 4h, 4.5h, or 5 h; the lower limit is selected from 3h, 3.5h, 4h, 4.5h or 4.8 h.
Optionally, the modified H-MOR molecular sieve is a pre-adsorbed organic base treated H-MOR molecular sieve.
Optionally, the pre-adsorption organic base treatment step comprises at least: activating the H-MOR molecular sieve in an inactive atmosphere; and then adjusting the temperature to the pre-adsorption organic base treatment temperature, contacting with gas containing organic base to carry out pre-adsorption organic base treatment, purging, and cooling to room temperature to obtain the modified H-MOR molecular sieve.
Optionally, the purging is performed with at least one of nitrogen, helium, and argon.
Optionally, the purge gas is the same as the carrier gas.
Optionally, the pre-adsorption organic base treatment step comprises at least: activating the acid-treated H-MOR molecular sieve in an inactive gas atmosphere, then adjusting the temperature to the pre-adsorption organic base treatment temperature, contacting with gas containing organic base to perform pre-adsorption organic base treatment, purging after adsorption saturation, and cooling to room temperature to obtain the modified acidic molecular sieve.
As a specific embodiment, the step of subjecting the H-MOR to a pre-adsorption organic base treatment comprises at least: the H-MOR molecular sieve is required to be treated for a certain time by carrying organic base with carrier gas at a certain airspeed and temperature to pre-adsorb the organic base; wherein the volume fraction of the organic base in the mixed gas is 0.1-10%, the carrier gas can be any one or a mixture of any more of nitrogen, helium and argon, and the mass space velocity of the pretreatment gas is 300-5000 mL-g-1·h-1(ii) a The organic alkali is any one or a mixture of more of pyridine, pyridazine, pyrimidine and pyrazine; the pretreatment temperature range of the organic alkali is 150-350 ℃, and the pretreatment time is 0.5-4 h.
As a specific embodiment, the co-precipitation method comprises the steps of: preparing an aqueous solution from at least one of compounds containing M' element and Zn and Al salt, and recording the aqueous solution as a solution A; preparing one or more of ammonia water, ammonium carbonate, sodium carbonate, urea, NaOH or KOH into an aqueous solution B; under the condition of intense stirring, mixing the solution A and the solution B in a parallel flow mode, adjusting the flow rate of the solution A and the flow rate of the solution B, and controlling the pH range of the mixed liquid to be 7-9; after precipitation is finished, aging for 2-4 h, filtering, washing and drying; then roasting for 1-6 h at the temperature of 400-600 ℃.
Optionally, the step (3) includes at least: and (3) fully mixing the components containing the water vapor catalyst in the step (1) and the modified H-MOR molecular sieve in the step (2) through ball milling, and tabletting to obtain the composite catalyst.
As a specific embodiment, the preparation method of the composite catalyst at least comprises the following steps:
(1) a water vapor catalyst;
(2) performing ammonium exchange on the molecular sieve to prepare a hydrogen type molecular sieve, performing acid treatment on H-MOR, and performing pre-adsorption organic base treatment;
(3) and (3) performing ball milling and mixing on the products in the steps (1) and (2), and tabletting to prepare the methanol carbonylation catalyst.
According to a further aspect of the present application there is provided a use of the composite catalyst and/or the composite catalyst prepared according to the method in the carbonylation of methanol to produce methyl acetate.
According to yet another aspect of the present application, there is provided a process for the carbonylation of methanol to produce methyl acetate and acetic acid comprising at least the steps of:
allowing raw material gas containing methanol and CO to pass through a reactor filled with a catalyst, and reacting to obtain methyl acetate and acetic acid;
wherein the catalyst is selected from at least one of the composite catalyst and the composite catalyst prepared by the method;
wherein the feed gas composition molar ratio satisfies the following requirements: CO: 5-50% of methanol: 1.
optionally, the reaction temperature is 200-300 ℃, the pressure is 1.0-8.0 MPa, and the mass space velocity of the raw material gas is 300-10000 mL-g-1·h-1。
Optionally, the upper temperature limit of the reaction is selected from 220 ℃, 280 ℃, 300 ℃, 320 ℃ or 350 ℃; the lower limit is selected from 200 deg.C, 220 deg.C, 280 deg.C, 300 deg.C or 320 deg.C.
Optionally, the upper reaction pressure limit is selected from 2.0MPa, 2.5MPa, 3.0MPa, 5.0MPa, 6.0MPa, or 8.0 MPa; the lower limit is selected from 1.0MPa, 2.0MPa, 2.5MPa, 3.0MPa, 5.0MPa or 6.0 MPa.
Optionally, the upper limit of the volume space velocity of the raw material gas is selected from 400 mL-g-1·h-1、500mL·g-1·h-1、1000mL·g-1·h-1、2300mL·g-1·h-1、4000mL·g-1·h-1、8000mL·g-1·h-1Or 10000mL g-1·h-1(ii) a The lower limit is selected from 300mL g-1·h-1、400mL·g-1·h-1、500mL·g-1·h-1、1000mL·g-1·h-1、2300mL·g-1·h-1、4000mL·g-1·h-1Or 8000mL g-1·h-1。
Optionally, the raw gas further comprises an inert gas;
the inactive gas is selected from at least one of nitrogen and methane;
the volume content of the inactive gas in the feed gas is less than or equal to 10 percent.
Optionally, the upper limit of the volume content of the inactive gas in the feed gas is selected from 1%, 3%, 5%, 8% or 10%; the lower limit is selected from 0%, 1%, 3%, 5% or 8%.
Optionally, the molar composition ratio of CO to methanol in the feed gas is selected from 5/1, 10/1, 50/1.
Optionally, the upper limit of the molar ratio of CO to methanol is selected from 15/1, 20/1, or 50/1; the lower limit is selected from 5/1, 10/1, or 45/1.
Optionally, the reactor is selected from at least one of a fixed bed reactor or a moving bed reactor.
As a specific embodiment, the method for preparing methyl acetate by methanol carbonylation of the composite catalyst at least comprises the following steps: the raw material gas containing methanol and CO passes through a reactor filled with a composite catalyst to prepare methyl acetate under certain reaction conditions; the raw material gas is methanol, CO and other gases; the reaction temperature is preferably 200-300 ℃; the other gas is selected from one of inert gases such as nitrogen, argon, helium and methaneOne or more, the volume content of the one or more in the raw material gas is less than 10%; the reaction pressure is preferably 1.0 to 8.0MPa, and the gas velocity is preferably 300 to 10000mL/g-1·h-1。
The preparation method of the methyl acetate is used for selectively preparing the methyl acetate by methanol carbonylation, and the selectivity of the methyl acetate reaches 86 percent.
As used herein, "H-MOR molecular sieve" refers to the hydrogen form of mordenite molecular sieve, which may be prepared by hydrogenation of the molecular sieve by preparation methods conventional in the art.
In the present application, all conditions relating to a numerical range may be independently selected from any intermediate range within said numerical range.
In this application, all conditions relating to numerical ranges are inclusive of the endpoints unless specifically stated otherwise.
The beneficial effects that this application can produce include:
1) the composite catalyst provided by the application compounds a water vapor shift catalyst and a carbonylation catalyst, and has the characteristics of high methanol conversion rate, high methyl acetate selectivity and the like.
2) The composite catalyst provided by the application has the advantages of simple preparation process and easiness in obtaining.
3) The composite catalyst provided by the application is applied to the process of preparing methyl acetate by carbonylation and hydrogenation of methanol, has the advantages of mild reaction conditions, simple process and the like, and has the potential of large-scale industrialization.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, all raw materials in the present application are commercially available and used as they are without treatment.
In the examples, the XRF of the elemental analysis of the samples was carried out by means of an X-fluorescence analyzer of the type Magix (PHILIPS)+The fluorescence intensity of the standard sample is corresponding to the standard composition without standard quantitative analysis program, and the influence of interference spectral lines is deducted.
The conversion and selectivity in the examples were calculated as follows:
conversion rate of methanol: x (meoh) ═ 1- (F)MeOHoutlet+2*FDMEoutlet)/(FMeOHintlet) 100 wherein FMeOHoutletAnd FDMEoutletFlow of MeOH or DME at the reactor outlet, viewing dimethyl ether as unconverted feedstock, FMeOHinletIs the reactor inlet MeOH flow.
The method for calculating the distribution of organic products in the products comprises the following steps: s (C)nHmOL)＝n*CnHmOL/Σ(n*CnHmOL)*100，CnHmOLIs the concentration of organic species at the reactor outlet, n is the number of C atoms in the product, m is the number of H atoms, and L is the number of O atoms.
Examples H-MOR molecular sieves were purchased from Nankai catalyst plants.
In the examples, "Si/Al" is the atomic ratio of silicon to aluminum.
Example 1
21.46g Zr (NO) were weighed out3)4·5H2O，11.90g Zn(NO3)2·6H2O and 7.5g Al (NO)3)3·9H2O in a beaker, 150mL of deionized water was added and stirred to obtain a salt solution A. 23.55g of ammonium carbonate was weighed into a beaker, and 150mL of deionized water was added and stirred well to obtain precipitant base solution B. Under the condition of intense stirring (the stirring speed is 450rpm/min), mixing the salt solution A and the precipitant alkali solution B in a parallel flow mode, and adjusting the relative flow rate of the solution A and the solution B to ensure that the pH value of the precipitation mixed solution is kept between 7 and 8. And after the coprecipitation is finished, aging for 2 hours. And then drying the catalyst in a 100 ℃ oven for 6h, and then roasting the catalyst in a 500 ℃ muffle furnace for 4h to obtain the water-vapor transformation catalyst. XRF elemental analysis shows that the water-gas shift catalyst composition is (ZnO)0.4(ZrO2)0.5(Al2O3)0.1。
Filling an H-MOR (Si/Al ═ 10) molecular sieve into a reactor, heating to 300 ℃ in a nitrogen atmosphere, activating for 4 hours, and then cooling to 250 ℃. Pyridine is carried by nitrogen (the volume fraction of pyridine in the mixed gas is 0.2 percent, and the mass space velocity of the mixed gas is 600 percent0mL·g-1·h-1) The pre-adsorption pyridine treatment is carried out. Adsorbing pyridine for 2H, then purging with nitrogen for 4H, and then cooling to room temperature to obtain the modified H-MOR molecular sieve.
The water-gas shift catalyst (15.0g) obtained above and a modified H-MOR molecular sieve (15.0g) were thoroughly ground and mixed by means of a ball mill. And (4) sheeting and forming to obtain the composite catalyst, wherein the catalyst is marked as No. 1. The mass content of the water-steam shift catalyst in the 1# composite catalyst is 50.0 wt.%, and the mass of the modified H-MOR molecular sieve is 50.0 wt.%,
3.0g of No. 1 catalyst is filled in a reactor, and the reaction of preparing ethyl acetate and acetic acid by methanol carbonylation is carried out under the following conditions: the reaction temperature is 280 ℃, the reaction pressure is 2.0MPa, the CO/methanol molar ratio is 10/1, and the volume space velocity (GHSV) of the raw material gas is 3300mL g-1·h-1. The reaction product was analyzed on-line by gas chromatograph, and the analysis results are shown in table 1. Table 1 shows that the composite catalyst has better carbonylation activity and methyl acetate selectivity.
Table 1 example 1 catalyst reaction results
Example 2
A vapor shift catalyst was obtained by the same preparation method and preparation conditions as in example 1. The specific conditions for the preparation of the modified H-MOR molecular sieve are shown in Table 2 below, and the rest of the procedure is the same as in example 1. The method and conditions for preparing the composite catalyst by using the water vapor catalyst and the modified H-MOR molecular sieve are the same as those in the example 1.
TABLE 2
Catalyst # 2: the difference from example 1 is that the carrier gas in the process of pre-adsorbing pyridine by H-MOR molecular sieve is helium.
Catalyst # 3: the difference from example 1 is that the carrier gas in the process of pre-adsorbing pyridine by H-MOR molecular sieve is helium.
The catalysts # 2 and # 3 were evaluated under the same reaction conditions as in example 1, and the results of the evaluation are shown in Table 3.
Table 3 example 2 catalyst reaction results
Table 3 shows that organic base treatment of MOR with organic base results in too high an amount of organic base to favor carbonylation.
Example 3
The coprecipitation method is adopted to prepare the water-gas shift catalyst with different metal compositions and different contents, wherein the composition of the water-gas shift catalyst is different from that of the water-gas shift catalyst in the embodiment 1 and the embodiment 3, the rest operation and conditions of the coprecipitation method are the same as the embodiment 1, and the rest operation and conditions of the impregnation method are the same as the embodiment 3. The obtained catalysts are respectively marked as 5# to 9#, and the specific composition of each catalyst is shown in Table 4. The catalysts No. 5# to No. 9 were evaluated under the same reaction conditions as in example 1, and the reaction products were analyzed on line by a gas chromatograph, and the analysis results are shown in Table 4.
Table 4 example 3 catalyst reaction results
The vapor shift catalyst sample composition was measured by XRF.
Table 4 shows that the composition and preparation conditions of the hybrid catalyst affect the water gas shift capability and thus the carbonylation capability.
Example 4
And (3) inspecting the types of the molecular sieve Si/Al and the pre-adsorbed organic alkali and the influence on the reaction for preparing the methyl acetate and/or the acetic acid by the carbonylation of the methanol. The composition and preparation of the vapor shift catalyst were the same as in example 1, and the conditions for preparing and evaluating the composite catalyst were the same as in example 1. The reaction products were analyzed on-line by gas chromatography, and the results are shown in Table 5.
Table 5 example 4 catalyst evaluation results
Table 5 shows that organic base species and molecular sieve silica-alumina ratio have a significant effect on carbonylation activity.
Example 5
The influence of the content of the water-vapor shift catalyst and the modified H-MOR molecular sieve in the composite catalyst on the reaction of preparing the methyl acetate and the acetic acid by the carbonylation of the methanol is examined. Except for changing the mass content of the vapor shift catalyst, other conditions including the composition of the vapor shift catalyst, the preparation process and the evaluation conditions of the composite catalyst were the same as in example 1, and the reaction product was analyzed on line by a gas chromatograph, and the results are shown in table 6.
Table 6 example 5 evaluation results of different catalyst reactions
Table 6 shows that there is a suitable range of water vapor shift catalyst and carbonylation catalyst levels, where too much or too little of one is detrimental to the carbonylation process.
Example 6
The catalytic performance of the 1# composite catalyst was examined at reaction temperatures of 200 deg.C, 280 deg.C, and 350 deg.C, and the evaluation conditions except for the reaction temperature were the same as those in example 1. The reaction product was analyzed on-line by gas chromatography, and the results are shown in Table 7.
TABLE 71 # catalysts evaluation results at different temperatures
Table 7 shows that increasing the temperature promotes carbonylation and increases acetic acid selectivity.
Example 7
The evaluation conditions were the same as in example 1 except that the molar ratio of the gases was changed by examining the influence of the molar composition of the raw materials on the reaction of producing methyl acetate and acetic acid by carbonylating methanol. The results of the evaluation of the feed gas molar ratio of CO/methanol ═ X 'and Y' values and their respective conditions (e.g., volume fraction of inert gas in the feed gas) are shown in table 8.
TABLE 8 results of methyl acetate preparation by carbonylation of methanol under different raw material gas conditions
Table 8 shows that the inert component dilutes the reactant concentration, reducing the carbonylation activity, but does not significantly affect the selectivity.
Example 8
The influence of the reaction pressure on the reaction of preparing methyl acetate and acetic acid by carbonylating methanol was examined under different total reaction pressures of 1.0, 3.0, 6.0 and 8.0MPa, the catalyst was a # 1 catalyst, the conditions other than the reaction pressure were the same as those in example 1, the reaction product was analyzed on line by gas chromatography, and the results are shown in table 9.
TABLE 9 results of the carbonylation of methanol to methyl acetate at different reaction pressures
Table 9 shows that increasing the pressure promotes the carbonylation.
Example 9
Respectively at 300, 4000, 8000 and 10000mL/gcatH (mass space velocity) under different reaction gas space velocities, the influence of the gas space velocity on the reaction of preparing methyl acetate and acetic acid by methanol carbonylation was examined, the catalyst was # 1, the other conditions except the gas space velocity were the same as those in example 1, the reaction product was analyzed on line by gas chromatograph, and the results are shown in table 10.
TABLE 10 results of the reaction of methyl acetate and acetic acid by carbonylation of methanol at different space velocities
Table 10 shows that increasing the volumetric space velocity, decreasing the contact time of the reactants, does not favor the carbonylation.
Example 10
The catalyst is sample No. 1, the reactor is a moving bed reactor, and other conditions are the same as example 1. The reaction products were analyzed on-line by gas chromatography, and the results are shown in Table 11.
TABLE 111 reaction results in different reactors for composite catalyst # s
Table 11 shows that the carbonylation activity in a moving bed reactor is consistent with that of a fixed bed.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A composite catalyst, wherein the composite catalyst comprises a water-gas shift catalyst and a carbonylation catalyst;
the carbonylation catalyst comprises a modified H-MOR molecular sieve;
wherein the modified H-MOR molecular sieve is an H-MOR molecular sieve treated by organic alkali.
2. The composite catalyst according to claim 1, wherein the organic base is at least one selected from triethylamine, pyridine, pyridazine, pyrimidine, pyrazine;
preferably, the water-gas shift catalyst is selected from at least one of the compounds having the formula set forth in formula (I):
(ZnO)aMb(Al2O3)1-a-bformula (I)
Wherein M is an oxide of at least one element of Zr, Cr and Ce; a is 0.1 to 0.9, b is 0.05 to 0.8;
preferably, the mass ratio of the water-steam shift catalyst to the modified H-MOR molecular sieve in the composite catalyst is as follows:
a water-vapor shift catalyst: the ratio of the modified H-MOR molecular sieve to the modified H-MOR molecular sieve is 20-80: 20-80;
preferably, the mass ratio of the water-steam shift catalyst to the modified H-MOR molecular sieve in the composite catalyst is as follows:
a water-vapor shift catalyst: modified H-MOR molecular sieve 50: 50;
preferably, the atomic ratio of silicon to aluminum of the H-MOR molecular sieve is 5-60.
3. The method for preparing the composite catalyst according to claim 1 or 2, characterized by comprising at least:
(1) obtaining a water-vapor shift catalyst;
(2) obtaining a modified H-MOR molecular sieve;
(3) and (3) molding a mixture containing the water-vapor shift catalyst in the step (1) and the modified H-MOR molecular sieve in the step (2) to obtain the composite catalyst.
4. The method of claim 3, wherein step (1) comprises:
mixing a salt solution containing Zn element, M' element and Al element with a solution containing a precipitator in a parallel flow mode, controlling the pH value of the system to be 7-9, precipitating, aging and roasting to obtain the water-vapor conversion catalyst;
wherein M' is selected from at least one of Zr, Cr and Ce;
preferably, the aging time is 2-4 h;
roasting for 1-6 h at 400-600 ℃;
zn element, M' element and Al element in the salt solution are at least one of nitrate, hydrochloride, acetate, acetylacetone salt and sulfate corresponding to each element;
the precipitant is alkali liquor;
preferably, the alkali liquor is selected from at least one of ammonia water, ammonium carbonate, sodium carbonate, urea, NaOH and KOH;
preferably, step (2) comprises:
contacting the H-MOR molecular sieve with gas containing organic alkali to carry out pre-adsorption organic alkali treatment to obtain the modified H-MOR molecular sieve;
preferably, the organic base treatment conditions are: the temperature is 150-350 ℃, and the time is 0.5-4 h;
preferably, the mass space velocity of the gas containing the organic base is 300-6000 mL-g-1·h-1；
Preferably, the gas containing an organic base comprises a carrier gas and an organic base;
the carrier gas is at least one of nitrogen, helium and argon;
the volume fraction of the organic base in the gas containing the organic base is 0.1-10%.
5. The process of claim 4, wherein said H-MOR molecular sieve is activated in an inert atmosphere prior to contacting with a gas comprising an organic base;
the activation temperature is 300-500 ℃, and the activation time is 3-5 h.
6. A process for the carbonylation of methanol to produce methyl acetate and acetic acid comprising at least the steps of:
allowing raw material gas containing methanol and CO to pass through a reactor filled with a catalyst, and reacting to obtain methyl acetate and acetic acid;
wherein the catalyst is selected from at least one of the composite catalyst of claim 1 or 2, and the composite catalyst prepared by the method of any one of claims 3 to 5.
7. The method according to claim 6, and characterized in that the molar ratio of methanol and CO in the feed gas is such that: CO: 5-50% of methanol: 1.
8. the method according to claim 6, wherein the temperature of the reaction is 200-300 ℃, the pressure is 1.0-8.0 MPa, and the mass space velocity of the raw material gas is 300-10000 mL-g-1·h-1。
9. The method of claim 6, wherein the feed gas further comprises an inert gas;
the inactive gas is selected from at least one of nitrogen and methane;
the volume content of the inactive gas in the feed gas is less than or equal to 10 percent.
10. The method of claim 6, wherein the reactor is selected from at least one of a fixed bed reactor or a moving bed reactor.
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| LIU JUNLONG: "Stability Enhancement of H-Mordenite in Dimethyl Ether Carbonylation to Methyl Acetate by Pre-adsorption of Pyridine", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114308115A (en) * | 2021-12-29 | 2022-04-12 | 延长中科（大连）能源科技股份有限公司 | Modification method of mordenite molecular sieve |
| CN114308115B (en) * | 2021-12-29 | 2023-11-21 | 延长中科（大连）能源科技股份有限公司 | Modification method of mordenite molecular sieve |
| CN114797963A (en) * | 2022-04-14 | 2022-07-29 | 厦门大学 | Catalyst for preparing acetic acid by synthesis gas one-step method and preparation method and application thereof |
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