CN112624940A - Method for preparing isophthalonitrile - Google Patents
Method for preparing isophthalonitrile Download PDFInfo
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- CN112624940A CN112624940A CN201910906242.XA CN201910906242A CN112624940A CN 112624940 A CN112624940 A CN 112624940A CN 201910906242 A CN201910906242 A CN 201910906242A CN 112624940 A CN112624940 A CN 112624940A
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- Prior art keywords
- catalyst
- oxygen
- xylene
- carrier
- mixed solution
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- 238000000034 method Methods 0.000 title claims abstract description 27
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 23
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229920006391 phthalonitrile polymer Polymers 0.000 abstract description 10
- 238000010998 test method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- -1 aromatic nitrile Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 2
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RJAAXVMENUVEAN-UHFFFAOYSA-N antimony vanadium Chemical compound [V].[Sb] RJAAXVMENUVEAN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- XIFXXKFWUBNGAP-UHFFFAOYSA-N [P].[V].[Cr] Chemical compound [P].[V].[Cr] XIFXXKFWUBNGAP-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing m-phthalonitrile, which comprises the steps of reacting m-xylene, ammonia and oxygen or oxygen-containing gas in the presence of a catalyst; the catalyst has an attrition rate of less than 1.5% as measured by a test method conforming to ASTM D5757-00. The reaction temperature is 300-500 ℃, and the reaction pressure is 0.1-3 bar. Solves the technical problems that the existing method for producing the m-phthalonitrile uses a catalyst which has poor environmental protection performance, has poor performance of replacing the catalyst and is not suitable for a fluidized bed reaction process.
Description
Technical Field
The invention relates to a method for preparing isophthalonitrile, in particular to a method for preparing isophthalonitrile by using a vanadium-phosphorus-loaded catalyst.
Background
The arylnitrile is an important fine chemical, can be used for synthesizing various synthetic intermediates so as to produce medicines, pesticides, dyes, special materials and the like, and has wide application. The m-phthalonitrile is the variety with the largest yield and use amount in the aromatic nitrile product, the efficient and low-toxicity fungicide tetrachloro-isophthalonitrile can be prepared through chlorination reaction, and the m-xylylenediamine prepared through hydrogenation reaction can be used for producing a temperature-resistant epoxy resin curing agent and synthesizing special nylon and polyurethane, and has higher economic value.
The production of the m-phthalonitrile is similar to other aromatic nitrile products, and has methods such as chemical synthesis, gas phase ammoxidation and the like, wherein aromatic hydrocarbon, ammonia and air are subjected to gas phase ammoxidation to synthesize the aromatic nitrile in one step, the process is short, the pollution is less, and the method is a main method for producing the aromatic nitrile at present. The reaction is characterized in that the main and side reactions are strong exothermic reaction processes. The gas phase ammoxidation process of aromatic hydrocarbon mainly comprises fixed bed and fluidized bed processes, wherein the fluid in the fixed bed is in approximate plug flow motion, and the catalyst has higher catalytic efficiency, but the heat transfer performance is poorer, the amplification effect is obvious, and the device is difficult to enlarge; the fluidized bed has the advantages of high heat and mass transfer efficiency, easy large-scale production and the like, but has higher requirements on the physical and chemical properties of the catalyst and the fluidization quality control in the reactor.
Among the existing fluidized bed catalysts, the vanadium catalyst is the most effective catalyst system proved by a large number of researches, and generally, the main catalyst is a composite oxide formed by vanadium and another element, and is matched with a cocatalyst and a carrier to prepare spherical particles with different particle sizes to be applied in a fluidized bed reactor. For isophthalonitrile fluidized bed catalyst, a plurality of research patents are published, for example, CN99113575.X relates to a granular fluidized bed catalyst for preparing isophthalonitrile by the ammoxidation of metaxylene, and a vanadium-chromium system is taken as the main part; US6429330 discloses an aromatic ammoxidation catalyst, mainly based on a vanadium-chromium-antimony-iron system; CN106208890 introduces an aromatic ammoxidation catalyst, mainly comprising a vanadium-chromium-phosphorus system, and introduces a molecular sieve as a carrier component, thereby improving the strength and performance of the catalyst.
The research on the catalyst basically takes a vanadium-chromium catalyst as the main stream, but the use of a large amount of chromium is not environment-friendly enough for the catalyst material per se, and simultaneously, the cost is raised. Therefore, the research on more environmentally friendly meta-xylene ammoxidation catalysts is one of the development directions. WO2007125052 proposes a novel supported catalyst containing no chromium, using a vanadium antimony catalyst, and common oxides of silicon, aluminum, zirconium, etc. as a carrier.
Besides vanadium-antimony catalysts, vanadium-phosphorus-oxygen (VPO) catalysts have enjoyed great success in catalyzing the reaction of selective oxidation of gas-phase hydrocarbons, particularly the reaction of preparing maleic anhydride by the oxidation of n-butane. The redox characteristics are also suitable for the ammoxidation of aromatic hydrocarbons. Meanwhile, compared with chromium and antimony, phosphorus is cheaper and more easily obtained. However, a vanadium phosphorus oxide catalyst consisting of only a single vanadium phosphorus oxygen element tends to be unsatisfactory in terms of activity selectivity, particularly selectivity. In addition, an important problem of VPO catalysts is their poor strength, and how to increase the attrition resistance of VPO catalysts in a fluidized bed reaction environment is also an important factor in the suitability of VPO catalysts for this reaction.
Disclosure of Invention
The invention aims to solve the technical problems that the existing isophthalonitrile production method is insufficient in environmental protection property due to the use of a catalyst, insufficient in performance of a substitute catalyst and not suitable for a fluidized bed reaction process, and aims to provide an improved isophthalonitrile production method.
The present invention provides a method for preparing isophthalonitrile, which does not solve the above technical problems, comprising reacting m-xylene, ammonia and oxygen or an oxygen-containing gas in the presence of a catalyst; the catalyst has an attrition rate of less than 1.5% as measured by a test method conforming to ASTM D5757-00.
According to a preferred embodiment of the present invention, the reaction temperature is 300-500 ℃, preferably 350-450 ℃; the reaction pressure is from 0.1 to 3bar, preferably from 0.1 to 1.5 bar.
According to a preferred embodiment of the invention, the process comprises reacting meta-xylene, ammonia and an oxygen-containing gas, preferably air, in the presence of a catalyst.
The mol ratio of the m-xylene, the ammonia and the oxygen is 1: (4-20): (15-50), preferably 1: (5-15): (20-40). For the reaction for preparing the isophthalonitrile, ammonia and oxygen are consumed in the reaction process, the reaction activity is reduced due to the excessively high ammonia ratio, and a large amount of ammonia is consumed; and if the air ratio is too high, the oxidation activity is too strong, so that a large amount of deep oxidation reaction occurs, and therefore, the ammonia ratio and the air ratio are controlled to be in proper ranges.
According to a preferred embodiment of the invention, the catalyst is a supported vanadium phosphorus catalyst; the catalyst comprises a carrier and an active component; the weight of the carrier in the catalyst accounts for 30-70% of the total weight of the catalyst.
According to a preferred embodiment of the present invention, the support comprises at least one of silica, alumina and zirconia.
According to a preferred embodiment of the present invention, the active component may be represented as vpxayddzem in addition to oxygen; in the formula (I), the compound is shown in the specification,
a is selected from at least one of B, W, Zr;
d is selected from at least one of Ti, Zn, Mn, Mo, Co, Nb, La, Ce, Fe, Sb and Bi;
e is selected from at least one of alkali metal and alkaline earth metal;
the value range of x is 1-1.6;
the value range of y is 0.01-0.5;
the value range of z is 0.01-0.3;
the value range of m is 0.005-0.1.
According to a preferred embodiment of the present invention, the preparation method of the catalyst comprises the steps of:
s1, preparing catalyst precursor powder containing active components;
s2, preparing a mixed solution containing precursor powder and a carrier I, and carrying out spray drying treatment to obtain supported catalyst precursor powder;
s3, preparing a mixed solution containing the supported catalyst precursor powder obtained in the step S2, a surface active dispersant and a carrier II, and performing spray drying treatment to obtain a supported catalyst precursor;
and S4, roasting the supported catalyst precursor to obtain the catalyst.
According to a preferred embodiment of the present invention, the step S1 includes:
mixing a vanadium source, an active component compound and an organic solvent, and heating and refluxing;
adding phosphoric acid into the mixed solution obtained in the step 1A, and continuously heating and refluxing;
and 1C, filtering the mixed solution obtained in the step 1B, and washing and drying the solid to obtain the catalyst precursor powder.
According to some embodiments of the invention, the heating reflux time in step 1A is 1 to 6 hours and the heating reflux time in step 1B is 2 to 24 hours.
According to a preferred embodiment of the present invention, the vanadium source is at least one of ammonium metavanadate, vanadium pentoxide and vanadyl oxalate; and/or the organic solvent is at least one of isobutanol, benzyl alcohol, oxalic acid, n-butanol and sec-butanol; and/or, the phosphoric acid concentration is H3PO4Calculated by 90 wt percent to 110 wt percent.
According to a preferred embodiment of the present invention, the carrier I is at least one of silica sol, polysiloxane compound, silicon-containing molecular sieve, aluminum sol and zirconia, and preferably silica sol.
According to some embodiments of the invention, the step S2 includes: mixing the precursor powder with a carrier I and water, and shearing to obtain a suspension; optionally, the mixed solution is concentrated, the solid content of the concentrated solution is 20 wt% -60 wt%, and then spray drying is carried out, so that the supported catalyst precursor powder is obtained.
According to a preferred embodiment of the present invention, the temperature of the spray drying in the step S2 is 150-.
According to a preferred embodiment of the invention, the carrier II is a polysilicic acid and/or a polysilicate, preferably a polysilicic acid.
According to a preferred embodiment of the invention, the weight ratio of carrier I to carrier II is (2-9): (1-8), preferably (2-5): (1-4).
According to some embodiments of the present invention, the polysilicic acid is generally prepared before use, for example, by mixing and stirring a metered amount of sodium silicate solution with a dilute sulfuric acid solution and adjusting the pH of the control solution. Polysilicic acid, SiO thereof, used in the present invention2The weight percentage concentration is 1-10%, and the pH value range is 2-5.
According to some embodiments of the invention, the step S3 includes: mixing the supported catalyst precursor powder, the surface active dispersant and the carrier II with water, and shearing to obtain a suspension; optionally, the mixed solution is concentrated, the solid content of the concentrated solution is 20 wt% -60 wt%, and then spray drying is carried out, so as to obtain the supported catalyst precursor.
According to a preferred embodiment of the present invention, the temperature of the spray drying in the step S3 is 200-450 ℃, preferably 250-400 ℃.
According to a preferred embodiment of the present invention, the surface active dispersant is at least one of polyvinyl alcohol, polyethylene glycol, and carboxymethyl cellulose.
According to the preferred embodiment of the present invention, the temperature of the calcination treatment in the step S4 is 300-600 ℃, and the time is 2-20 h.
According to a preferred embodiment of the invention, the catalyst particles have an average particle size of 30 to 80 μm. The average particle size can be determined by a laser particle sizer.
The catalyst prepared by the method has high wear resistance, the wear rate of the vanadium-phosphorus catalyst prepared by the technical scheme can be lower than 1.5%, and the vanadium-phosphorus catalyst has applicability in a fluidized bed reactor. The abrasion rate was measured using a test method in accordance with ASTM D5757-00 (relative abrasion characteristics of powder catalysts are judged by air jet abrasion) and is reported in weight percent per hour.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
[ example 1 ]
182g of vanadium pentoxide was added to a mixed solution of 1500ml of isobutanol and 300ml of benzyl alcohol, and the mixed solution was heated under stirring to reflux. After refluxing for 2h, adding 99 wt% phosphoric acid (the molar ratio of phosphorus to vanadium is about 1.1) dropwise into the mixed solution, heating the mixed solution, continuously refluxing for 20h, stopping heating, filtering the mixed solution, washing with isobutanol, and drying the obtained filter cake at 110 ℃ for 20h to obtain vanadium-phosphorus oxide powder.
Adding vanadium phosphorus oxide powder into deionized water, then adding zirconium nitrate, ammonium molybdate, cerium nitrate and potassium nitrate, heating and stirring, adding silica sol, evaporating and concentrating until the solid content of slurry is 35%, and performing spray drying to obtain a primary spray product. The product powder was added again to water and after stirring polyethylene glycol (6000) at about 6% by weight of the product powder and a polysilicic acid solution having a PH of 3 and a SiO2 content of 5% were added, the weight ratio of silica in the polysilicic acid to silica in the silica sol being 1: 6. The solution is stirred evenly and heated to be concentrated until the solid content is 35 percent. The obtained slurry was dried again by spray drying to obtain supported catalyst particles having an average particle size of 70 μm.
The active component of the obtained catalyst comprises VP besides oxygen1.1Mo0.2Ce0.05Zr0.03. The total weight of the carrier accounts for 50 percent. The catalyst was tested using a test method that met the ASTM D5757-00 (relative attrition characteristics of powder catalysts as judged by air jet attrition) standard, resulting in an attrition rate of 1.44%.
After the catalyst is activated, the evaluation is carried out in a stainless steel fluidized bed reactor with the diameter of 38 mm multiplied by 1800 mm, the adding amount of the catalyst is 550 g, the raw material is m-xylene, the reaction temperature is 425 ℃, the reaction pressure is 0.05MPa, the reaction space velocity is 0.05h < -1 > (WWH), and the raw material proportion is 1 (m-xylene): 9 (ammonia gas): 30 (air). As a result, the conversion rate of m-xylene was 98.6%, and the molar yield of m-phthalonitrile was 83.6%.
[ example 2 ]
The same preparation method as that of example 1 is adopted, the composition of the active component is changed, and the active component of the obtained catalyst except oxygen element has the composition of VP1.1Mo0.2Bi0.1W0.03. The total weight of the carrier accounts for 50 percent. The catalyst was tested using a test method that met the ASTM D5757-00 (relative attrition characteristics of powder catalysts as judged by air jet attrition) standard, resulting in an attrition rate of 1.49%.
After the catalyst is activated, the evaluation is carried out in a stainless steel fluidized bed reactor with the diameter of 38 mm multiplied by 1800 mm, the adding amount of the catalyst is 550 g, the raw material is m-xylene, the reaction temperature is 425 ℃, the reaction pressure is 0.05MPa, the reaction space velocity is 0.05h < -1 > (WWH), and the raw material proportion is 1 (m-xylene): 9 (ammonia gas): 30 (air). As a result, the conversion rate of m-xylene was 98.2%, and the molar yield of m-phthalonitrile was 84.1%.
[ example 3 ]
The same preparation method as in example 2 was adopted, but the composition of the carrier was changed, and the active component of the obtained catalyst except for oxygen had the composition of VP1.1Mo0.2Bi0.1W0.03. The total weight of the carrier accounts for 60 percent, and the ratio of the silica sol to the polysilicic acid is 5: 4. the catalyst was tested using a test method that met the ASTM D5757-00 (relative attrition characteristics of powder catalysts as judged by air jet attrition) standard, resulting in an attrition rate of 1.36%.
After the catalyst is activated, the evaluation is carried out in a stainless steel fluidized bed reactor with the diameter of 38 mm multiplied by 1800 mm, the adding amount of the catalyst is 550 g, the raw material is m-xylene, the reaction temperature is 425 ℃, the reaction pressure is 0.05MPa, the reaction space velocity is 0.05h < -1 > (WWH), and the raw material proportion is 1 (m-xylene): 9 (ammonia gas): 30 (air). As a result, the conversion of m-xylene was 97.8%, and the molar yield of m-phthalonitrile was 82.1%.
[ example 4 ]
The same preparation method as that of example 2 was adopted, and the active component of the obtained catalyst except for oxygen element had the composition of VP1.1Mo0.2Bi0.1W0.03. The total weight of the carrier accounts for 50 percent, and the ratio of the silica sol to the polysilicic acid is 6 based on the content of the silica. The catalyst was tested using a test method that met the ASTM D5757-00 (relative attrition characteristics of powder catalysts as judged by air jet attrition) standard, resulting in an attrition rate of 1.49%.
After the catalyst is activated, the evaluation is carried out in a stainless steel fluidized bed reactor with the diameter of 38 mm multiplied by 1800 mm, the adding amount of the catalyst is 550 g, the raw material is m-xylene, the reaction temperature is 435 ℃, the reaction pressure is 0.03MPa, the reaction space velocity is 0.05h < -1 > (WWH), and the raw material proportion is 1 (m-xylene): 8 (ammonia gas): 28 (air). As a result, the conversion rate of m-xylene was 98.0% and the molar yield of m-phthalonitrile was 83.6%.
Comparative example 1
The same preparation method as in example 1 was used, but the carrier was introduced by a non-secondary method, i.e. the silica sol and the polysilicic acid were added one after the other and dried simultaneously. The active component of the obtained catalyst comprises VP besides oxygen1.1Mo0.2Ce0.05Zr0.03. The total weight of the carrier accounts for 50 percent. The catalyst was tested using a test method that met the ASTM D5757-00 (relative attrition characteristics of powder catalysts as judged by air jet attrition) standard, resulting in an attrition rate of 1.78%.
After the catalyst is activated, the evaluation is carried out in a stainless steel fluidized bed reactor with the diameter of 38 mm multiplied by 1800 mm, the adding amount of the catalyst is 550 g, the raw material is m-xylene, the reaction temperature is 420 ℃, the reaction pressure is 0.06MPa, the reaction space velocity is 0.05h < -1 > (WWH), and the raw material proportion is 1 (m-xylene): 9 (ammonia gas): 30 (air). As a result, the conversion of m-xylene was 97.3%, and the molar yield of m-phthalonitrile was 80.9%.
Comparative example 2
The same preparation as in example 1 was carried out, but only with a single support, i.e. with the addition of silica sol, and the catalyst precursor was obtained directly by drying. The active component of the obtained catalyst comprises VP besides oxygen1.1Mo0.2Ce0.05Zr0.03. The total weight of the carrier accounts for 50 percent. Catalyst use was in accordance with ASTM D5757-00 (with air jet mill)Method of abrasion to determine the relative attrition characteristics of the powdered catalyst) the standard test method was used to determine the attrition rate of 2.21%.
After the catalyst is activated, the evaluation is carried out in a stainless steel fluidized bed reactor with the diameter of 38 mm multiplied by 1800 mm, the adding amount of the catalyst is 550 g, the raw material is m-xylene, the reaction temperature is 420 ℃, the reaction pressure is 0.06MPa, the reaction space velocity is 0.05h < -1 > (WWH), and the raw material proportion is 1 (m-xylene): 9 (ammonia gas): 30 (air). As a result, the conversion of m-xylene was 98.6%, and the molar yield of m-phthalonitrile was 81.9%.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A process for producing isophthalonitrile comprising reacting m-xylene, ammonia and oxygen or an oxygen-containing gas in the presence of a catalyst; the catalyst has an attrition rate of 1.5% or less.
2. The method as claimed in claim 1, wherein the reaction temperature is 300-500 ℃ and the reaction pressure is 0.1-3 bar.
3. The process according to claim 1 or 2, characterized in that the molar ratio of meta-xylene, ammonia and oxygen is 1: (4-20): (15-50).
4. A process according to any one of claims 1 to 3, wherein the catalyst comprises a support and an active component; the weight of the carrier in the catalyst accounts for 30-70% of the total weight of the catalyst.
5. The method of any one of claims 1-4, wherein the support comprises at least one of silica, alumina, and zirconia.
6. The method according to any of claims 1 to 5, characterized in that the active component, other than oxygen, can be represented by VPxAyDzEm; in the formula (I), the compound is shown in the specification,
a is selected from at least one of B, W, Zr;
d is selected from at least one of Ti, Zn, Mn, Mo, Co, Nb, La, Ce, Fe, Sb and Bi;
e is selected from at least one of alkali metal and alkaline earth metal;
the value range of x is 1-1.6;
the value range of y is 0.01-0.5;
the value range of z is 0.01-0.3;
the value range of m is 0.005-0.1.
7. The method according to any one of claims 1 to 6, wherein the preparation method of the catalyst comprises the following steps:
s1, preparing catalyst precursor powder containing active components;
s2, preparing a mixed solution containing precursor powder and a carrier I, and carrying out spray drying treatment to obtain supported catalyst precursor powder;
s3, preparing a mixed solution containing the supported catalyst precursor powder obtained in the step S2, a surface active dispersant and a carrier II, and performing spray drying treatment to obtain a supported catalyst precursor;
and S4, roasting the supported catalyst precursor to obtain the catalyst.
8. The method according to claim 7, wherein the step S1 includes:
mixing a vanadium source, an active component compound and an organic solvent, and heating and refluxing;
adding phosphoric acid into the mixed solution obtained in the step 1A, and continuously heating and refluxing;
and 1C, filtering the mixed solution obtained in the step 1B, and washing and drying the solid to obtain the catalyst precursor powder.
9. The method according to claim 7 or 8, wherein the vanadium source is at least one of ammonium metavanadate, vanadium pentoxide, vanadyl oxalate; and/or the organic solvent is at least one of isobutanol, benzyl alcohol, oxalic acid, n-butanol and sec-butanol; and/or, the phosphoric acid concentration is H3PO4Calculated by 90 wt percent to 110 wt percent.
10. A process according to any one of claims 1 to 9, characterised in that the catalyst particles have an average particle size of 30 to 80 μm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090118531A1 (en) * | 2006-04-28 | 2009-05-07 | Basf Aktiengesellschaft | Novel supported catalyst for ammoxidation |
| CN102219711A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing isophthalodinitrile |
| CN103896807A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Preparation method of terephthalonitrile through ammonium oxidation |
| CN106268890A (en) * | 2016-08-05 | 2017-01-04 | 中国石油化工股份有限公司 | Ammoxidation of aromatic hydrocarbon fluid catalyst, preparation method and purposes |
| CN106362760A (en) * | 2016-08-05 | 2017-02-01 | 中国石油化工股份有限公司 | Catalyst for ammoxidation of aromatic hydrocarbons, and preparation method and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090118531A1 (en) * | 2006-04-28 | 2009-05-07 | Basf Aktiengesellschaft | Novel supported catalyst for ammoxidation |
| CN102219711A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing isophthalodinitrile |
| CN103896807A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Preparation method of terephthalonitrile through ammonium oxidation |
| CN106268890A (en) * | 2016-08-05 | 2017-01-04 | 中国石油化工股份有限公司 | Ammoxidation of aromatic hydrocarbon fluid catalyst, preparation method and purposes |
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