CN111744493A - Ammonia oxidation catalyst particles, and preparation method and application thereof - Google Patents
Ammonia oxidation catalyst particles, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111744493A CN111744493A CN201910247518.8A CN201910247518A CN111744493A CN 111744493 A CN111744493 A CN 111744493A CN 201910247518 A CN201910247518 A CN 201910247518A CN 111744493 A CN111744493 A CN 111744493A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- precursor
- content
- catalyst particles
- optional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 229
- 239000002245 particle Substances 0.000 title claims abstract description 102
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 58
- 229910021529 ammonia Inorganic materials 0.000 title claims description 28
- 230000003647 oxidation Effects 0.000 title claims description 27
- 238000007254 oxidation reaction Methods 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 81
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims description 110
- 238000006243 chemical reaction Methods 0.000 claims description 67
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 14
- 229910001882 dioxygen Inorganic materials 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052792 caesium Inorganic materials 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 229910052716 thallium Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000013618 particulate matter Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 238000011068 loading method Methods 0.000 description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 14
- -1 and particularly Chemical compound 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000859 sublimation Methods 0.000 description 13
- 230000008022 sublimation Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910003110 Mg K Inorganic materials 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8878—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/18—Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to ammoxidation catalyst particles, a preparation method thereof and application thereof in the field of preparing acrylonitrile by propylene ammoxidation. The composition of the ammoxidation catalyst particles contains at least a Mo element, a Bi element and a carrier, wherein the ratio of the surface Mo element content to the bulk Mo element content of the catalyst particles is 0.2-0.98: 1. The ammoxidation catalyst particles can maintain a high acrylonitrile single pass yield over a long period of time.
Description
Technical Field
The present invention relates to a catalyst particle, in particular an ammonia oxidation catalyst particle. The invention also relates to a preparation method of the ammoxidation catalyst particles and application of the ammoxidation catalyst particles in the field of preparing acrylonitrile by propylene ammoxidation.
Background
The catalyst for acrylonitrile synthesis has been successfully commercialized in acrylonitrile plants all over the world as a catalyst for synthesizing acrylonitrile from propylene by a fluidized bed ammoxidation process, but the research and improvement of the catalyst have never been interrupted as one of the core technologies of the process.
At present, Mo-Bi catalysts are widely used industrially as relatively mature ammoxidation catalysts. For example, CN102371156A discloses an ammoxidation catalyst having better selectivity for acrylonitrile and more stable single pass yield of acrylonitrile at a temperature of around 430 ℃.
However, with the increasing demand for acrylonitrile in the international market, higher demands are being made on the acrylonitrile production technology. Further improvements are also required with respect to the performance of the ammoxidation catalyst, particularly how to better maintain the stability of the ammoxidation catalyst in the case of long-term operation of the acrylonitrile production apparatus.
Disclosure of Invention
The inventors have found, through long-term studies, that in ammoxidation catalyst particles including at least a Mo element, a Bi element and a carrier, by controlling the ratio of the surface Mo element content to the bulk Mo element content of the particles within a certain range, the rate of migration of the Mo element in the catalyst from the catalyst bulk to the catalyst surface can be effectively controlled, thereby effectively suppressing sublimation of the Mo component in the catalyst during long-term operation, and further, the catalyst can maintain a high acrylonitrile single-pass yield, and have accomplished the present invention based thereon.
In particular, the present invention relates to the following aspects:
1. an ammoxidation catalyst particle having a composition containing at least a Mo element, a Bi element and a carrier (preferably at least one selected from refractory oxides, preferably at least one selected from silica, zirconia and titania, more preferably silica), wherein the ratio of the surface Mo element content to the bulk Mo element content of the catalyst particle is from 0.2 to 0.98: 1, preferably from 0.3 to 0.98: 1, more preferably from 0.4 to 0.9: 1, more preferably from 0.5 to 0.8: 1 or from 0.45 to 0.65: 1. 2. The ammonia oxidation catalyst particles of any of the preceding or subsequent aspects, wherein the Mo element (as MoO) is present in an amount of Mo based on the total weight of the catalyst particles3Based on) weight percentThe content of Bi element (as Bi) is 15-55 wt% (preferably 20-45 wt%)2O3In a dry basis or in the form of oxides) in an amount of from 0.5 to 3.5% by weight, preferably from 1.0 to 3.5% by weight, and in an amount of from 30 to 70% by weight, preferably from 40 to 60% by weight, of the support (dry basis or in the form of oxides).
3. The ammonia oxidation catalyst particles according to any one of the preceding or subsequent aspects, wherein the composition further contains an Fe element, an a element selected from at least one of Li, Na, K, Rb, Cs, Tl and Ag (preferably at least one selected from Na, K, Rb, Cs, Tl and Ag), a B element selected from at least one of Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P, V, Ba, Ti, Pt and Nb (preferably at least one selected from Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P and Nb), and a C element selected from at least one of rare earth elements (preferably at least one selected from La, Ce, Pr, Nd, Sm and Eu).
4. The ammonia oxidation catalyst particles of any of the preceding or subsequent aspects, wherein the Mo element (as MoO) is present in an amount of Mo based on the total weight of the catalyst particles3Calculated by Bi) is 15 to 55 weight percent, and the Bi element (calculated by Bi) is2O3Calculated by weight percent) of 0.5 to 3.5 percent, and the Fe element (calculated as Fe)2O3In terms of oxide) in an amount of 1.0 to 5.0 wt.%, the element a (in terms of oxide) in an amount of 0.03 to 10 wt.%, the element B (in terms of oxide) in an amount of 0.01 to 40 wt.%, the element C (in terms of oxide) in an amount of 0.05 to 20 wt.%, and the carrier (dry basis or in terms of oxide) in an amount of 30 to 70 wt.% (preferably 40 to 60 wt.%).
5. The ammonia oxidation catalyst particles according to any one of the preceding or subsequent aspects, having an average particle size of from 30 to 70 μm, preferably from 40 to 60 μm.
6. The ammonia oxidation catalyst particles of any one of the preceding aspects, wherein the composition is measured after calcination at 500 ℃ for 3 hours in an air atmosphere.
7. A method for producing ammonia oxidation catalyst particles, comprising the steps of:
(a-1) mixing a Mo element precursor, a Bi element precursor, an optional Fe element precursor, an optional A element precursor, an optional B element precursor, an optional C element precursor, and at least one selected from the group consisting of a carrier and a carrier precursor in the presence of a liquid (preferably at least one selected from the group consisting of an alcohol and water, more preferably water) at a stirring speed of more than 200rpm (preferably 250-,
or
(a-2) first mixing a Mo element precursor with at least one selected from the group consisting of a carrier and a carrier precursor in the presence of a liquid (preferably at least one selected from the group consisting of an alcohol and water, more preferably water), and then second mixing with a Bi element precursor, an optional Fe element precursor, an optional A element precursor, an optional B element precursor, an optional C element precursor, and an optional at least one selected from the group consisting of a carrier and a carrier precursor in the presence of a liquid (preferably at least one selected from the group consisting of an alcohol and water, more preferably water) at a stirring speed of more than 200rpm (preferably 250-,
wherein the element A is selected from at least one of Li, Na, K, Rb, Cs, Tl and Ag (preferably at least one selected from Na, K, Rb, Cs, Tl and Ag), the element B is selected from at least one of Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P, V, Ba, Ti, Pt and Nb (preferably at least one selected from Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P and Nb), the element C is selected from at least one of rare earth elements (preferably at least one selected from La, Ce, Pr, Nd, Sm and Eu), and the carrier is selected from at least one of refractory oxides (preferably at least one selected from silica, zirconia and titania, more preferably silica);
(b) spray drying the slurry to obtain particulate matter; and
(c) calcining the particulate matter.
8. The production method of any one of the preceding or subsequent aspects, wherein in the step (a-1), the mixing conditions include: a mixing temperature of 10 to 50 ℃ (preferably 10 to 30 ℃) for 0.5 to 2.5 hours (preferably 0.5 to 2 hours), or in said step (a-2), said first mixing conditions comprise: the first mixing temperature is 20-70 ℃, and the second mixing conditions comprise: the second mixing temperature is 10-60 deg.C (preferably 10-30 deg.C, more preferably lower than the first mixing temperature, more preferably 5-50 deg.C or 10-30 deg.C lower than the first mixing temperature), and the second mixing time is 0.1-2h (preferably 0.5-1.5 h).
9. The production method of any one of the preceding or subsequent aspects, wherein in the step (b), the spray-drying conditions include: the drying heat source is air, the drying temperature is 250-350 ℃ (preferably 300-350 ℃), the drying time is 0.5-2h (preferably 0.5-1.5h), and the average diameter of the spray droplets is 40-200 μm (preferably 40-180 μm).
10. The production method of any one of the preceding or subsequent aspects, wherein in the step (c), the firing conditions include: the roasting temperature is 200 ℃ and 750 ℃ (preferably 300 ℃ and 700 ℃) in the oxygen-containing atmosphere, and the roasting time is 2-8h (preferably 4-6 h).
11. A process for producing acrylonitrile, which comprises subjecting propylene to an ammoxidation reaction in the presence of the ammoxidation catalyst particles according to any one of the above aspects or the ammoxidation catalyst particles produced by the production process according to any one of the above aspects to produce acrylonitrile.
12. The production process according to any one of the preceding aspects, wherein the reaction conditions for the ammoxidation reaction include: the mol ratio of the propylene to the ammonia gas to the air (calculated by molecular oxygen) is 1: 1.1-1.3: 1.8-2.0, the reaction temperature is 420--1。
Technical effects
The ammoxidation catalyst of the present invention can maintain a high single-pass yield of acrylonitrile over a long period of time.
According to the method for producing acrylonitrile, the reduction range of the yield of the acrylonitrile and the selectivity of the acrylonitrile along with the prolonging of the reaction time is obviously reduced, and the high single-pass yield and selectivity level of the acrylonitrile can be still maintained after the operation for a long time.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present invention, the "surface Mo element content" of the catalyst particles is determined using X-ray photoelectron spectroscopy (XPS). Here, the "surface" means a range of depth (generally < 10nm) of the surface of the catalyst which can be measured by XPS. Specifically, in the context of the present invention, the equipment used in the XPS measurements is an X-ray photoelectron spectrometer from AXIS UltraDLDKratos Analytical Ltd. In the sample preparation stage, the catalyst powder is directly fixed on a copper sheet by using a double-sided adhesive tape and then placed on a sample table. Ensuring sample analysis Chamber vacuum better than 1.0X10 before testing-8The specific test steps are that the CCTV is used for roughly adjusting the position of a sample, the test position is adjusted to the position which is most clear in imaging and is positioned at the central mark position of the imaging position, the Mg K α is used for exciting a light source, the current is 40mA, the full spectrum is prescanning, the content, the position and the strongest peak position of the sample element are determined, the height of the sample is adjusted to the strongest signal at the strongest peak position, the full spectrum and the acquisition parameters of each element spectrogram are set, the information of the sample spectrogram is collected and stored, after the XPS spectral line is obtained, the correction is carried out through the C1s spectral line of the polluted carbon, the mass percentage of the surface Mo element is calculated according to the peak area proportion and"surface Mo element (in MoO)3Meter) content ".
In the context of the present invention, the "bulk Mo element content" of the catalyst particles is determined by X-ray fluorescence analysis. Here, the "bulk phase" refers to the entire catalyst particle. Specifically, S4 Pioneer X-ray fluorescence spectrometer of Bruker, Germany is adopted to measure Mo element (MoO) in catalyst bulk3Meter) content was measured. And in the sample preparation stage, 3g of sample and 3g of boric acid are mixed, put into a ball mill for ball milling for 1.5min, and pressed into tablets. The mass of the Mo element in the sample is determined and the mass percentage is calculated as the 'bulk Mo element content' of the catalyst particles by measuring the intensity of the secondary X-rays generated by the sample with the X-rays as an excitation light source and then comparing the intensity with the intensity of the secondary X-rays generated by the standard sample. In the context of the present invention, the value obtained by dividing the "surface Mo element content" of the catalyst particles by the "bulk Mo element content" of the catalyst particles is defined as the "ratio of the surface Mo element content to the bulk Mo element content" of the catalyst particles.
In the context of the present invention, the method of measuring average particle size is measured using a malvern MS2000 laser particle sizer. Before the sample is tested, the circulating water of the device needs to be opened. Before sample measurement, the refractive index of the catalyst needs to be selected and measured by SiO2Is the refractive index of the catalyst sample, 1.45. The background needs to be measured before the sample is measured, the sample is added to 10% of the shading degree after the measurement, and the average value is selected after three measurements are carried out.
In the context of the present invention, the term "oxide" refers to the most stable oxide at ambient temperature and pressure, for example, Na oxide refers to Na2The oxide of O, Ni refers to NiO, and the oxide of Fe refers to Fe2O3。
In the context of the present invention, the composition of the catalyst (including the content) is measured after calcination in air at a temperature of 500 ℃ for 3 h.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
In the context of this specification, any two or more embodiments of the invention may be combined in any combination, and the resulting solution is part of the original disclosure of this specification, and is within the scope of the invention.
According to one embodiment of the present invention, there is provided an ammonia oxidation catalyst particle having a composition containing at least a Mo element, a Bi element and a carrier.
According to one embodiment of the present invention, the carrier is not particularly limited, and examples thereof include any carriers known to be used in the art for the ammoxidation catalyst particles, more specifically, refractory oxides, and more specifically, silica, zirconia, or titania, and particularly, silica. These carriers may be used singly or in combination in any ratio.
According to one embodiment of the present invention, the ammonia oxidation catalyst is a particulate material (i.e., a shaped material) rather than an amorphous material such as a powder. The shape of the particles may be various shapes conventionally known in the art as particles of an ammonia oxidation catalyst, and examples thereof include spherical, columnar, and plate-like shapes, and spherical or columnar shapes are preferable. Examples of the spherical shape include a spherical shape and an ellipsoidal shape. Examples of the columnar shape include a columnar shape, a square columnar shape, and a columnar shape having a non-uniform cross section (for example, clover).
According to one embodiment of the present invention, the average particle size of the ammonia oxidation catalyst particles is generally 30 to 70 μm, preferably 40 to 60 μm, but is not limited thereto in some cases.
According to one embodiment of the invention, the ratio of the surface Mo element content to the bulk Mo element content of the catalyst particles is 0.2-0.98: 1, preferably 0.3-0.98: 1, more preferably 0.4-0.9: 1, more preferably 0.5-0.8: 1 or 0.45-0.65: 1. When the ratio is controlled within the above range, the decrease of the acrylonitrile yield and the acrylonitrile selectivity with the increase of the reaction time is remarkably reduced, and the high acrylonitrile yield per pass and the acrylonitrile selectivity can be maintained after the operation for a long time.
According to an embodiment of the present invention, the composition optionally further includes Fe element, a element, B element, and C element, as the case may be. These elements, Mo element, Bi element, and the like may be supported on the carrier in the form of a simple substance, an oxide, or the like, and constitute the respective components of the ammonia oxidation catalyst particles.
According to an embodiment of the present invention, the a element is selected from at least one of Li, Na, K, Rb, Cs, Tl and Ag, preferably from at least one of Na, K, Rb, Cs, Tl and Ag. These elements may be used singly or in combination in any ratio.
According to an embodiment of the present invention, the B element is at least one selected from Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P, V, Ba, Ti, Pt and Nb, preferably at least one selected from Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P and Nb. These elements may be used singly or in combination in any ratio.
According to one embodiment of the invention, the C element is selected from at least one of the rare earth elements, preferably from at least one of La, Ce, Pr, Nd, Sm and Eu. These elements may be used singly or in combination in any ratio.
According to one embodiment of the present invention, the Mo element (in MoO) is present in an amount of the total weight of the catalyst particles3In weight percent) is generally from 15 to 55 weight percent, preferably from 20 to 45 weight percent.
According to one embodiment of the present invention, the Bi element (in Bi) is present in a total amount of the catalyst particles2O3In weight percent) is generally from 0.5 to 3.5 weight percent, preferably from 1.0 to 3.5 weight percent.
According to one embodiment of the invention, the Fe element (as Fe) is based on the total weight of the catalyst particles2O3Based on) is generally 1.0 to 5.0 wt%.
According to one embodiment of the invention, the weight percentage of the a element (calculated as oxide) is generally in the range of 0.03 to 10 wt%, based on the total weight of the catalyst particles.
According to one embodiment of the invention, the weight percentage of the B element (calculated as oxide) is generally in the range of 0.01 to 40 wt%, based on the total weight of the catalyst particles.
According to one embodiment of the invention, the weight percentage of the C element (in terms of oxide) is generally between 0.05 and 20 wt%, based on the total weight of the catalyst particles.
According to one embodiment of the invention, the weight percentage of the support (dry basis or as oxide) is generally in the range of 30 to 70 wt%, preferably 40 to 60 wt%, based on the total weight of the catalyst particles.
According to one embodiment of the present invention, the ammonia oxidation catalyst particles can be produced by the following method, but the production of the ammonia oxidation catalyst particles is not limited to this method. Here, the manufacturing method includes at least the step (a-1) or (a-2), the step (b), and the step (c).
(a-1) mixing a Mo element precursor, a Bi element precursor, an optional Fe element precursor, an optional A element precursor, an optional B element precursor, an optional C element precursor, and at least one selected from a carrier and a carrier precursor in the presence of a liquid at a stirring speed of more than 200rpm to obtain a slurry.
According to an embodiment of the present invention, as specific embodiments of the step (a-1), there may be mentioned, for example: subjecting the Mo element precursor, the Bi element precursor, the optional Fe element precursor, the optional A element precursor, the optional B element precursor, the optional C element precursor, the at least one selected from the group consisting of a support and a support precursor, and the liquid to the mixing in any order or combination of orders at a stirring speed of greater than 200rpm, thereby obtaining the slurry.
According to an embodiment of the present invention, in the step (a-1), the temperature of the mixing is not particularly limited, but is generally 10 to 50 ℃, preferably 10 to 30 ℃.
According to an embodiment of the present invention, in the step (a-1), the mixing time is not particularly limited, but is generally 0.5 to 2.5 hours, preferably 0.5 to 2 hours.
According to one embodiment of the present invention, in the step (a-1), the Mo element precursor, the Bi element precursor, the optional Fe element precursor, the optional a element precursor, the optional B element precursor, the optional C element precursor, and the at least one selected from the support and the support precursor are not particularly limited in proportion to each other or in the respective amounts so long as the contents of the respective components in the finally produced ammonia oxidation catalyst particles satisfy any one of the aforementioned provisions of the present invention.
(a-2) first mixing a Mo element precursor with at least one selected from a support and a support precursor in the presence of a liquid, and then second mixing with a Bi element precursor, an optional Fe element precursor, an optional a element precursor, an optional B element precursor, an optional C element precursor, and an optional at least one selected from a support and a support precursor in the presence of a liquid at a stirring speed of more than 200rpm to obtain a slurry.
According to an embodiment of the present invention, as specific embodiments of the step (a-2), there may be mentioned, for example: the Mo element precursor, the liquid and the at least one selected from the group consisting of the support and the support precursor are mixed in an arbitrary order or combination of orders (optionally under stirring, the stirring speed at this time is not particularly limited by the present invention, but is generally 200-400rpm) to obtain a mixture, and then the Bi element precursor, the optional Fe element precursor, the optional A element precursor, the optional B element precursor, the optional C element precursor and the optional at least one selected from the group consisting of the support and the support precursor are added to the mixture in an arbitrary order or combination of orders under a stirring speed of more than 200rpm to perform the second mixing, thereby obtaining the slurry. Here, the "optional at least one selected from the group consisting of a carrier and a carrier precursor" means that a first amount of the at least one selected from the group consisting of a carrier and a carrier precursor is used when the first mixing is performed, and a second amount (which may be 0) of the at least one selected from the group consisting of a carrier and a carrier precursor is used when the second mixing is performed. The sum of the first amount and the second amount constitutes a total amount of the at least one selected from the group consisting of the carrier and the carrier precursor. The relative proportions of the first and second amounts are not particularly limited, and are typically, for example, 100: 0 to 50: 50 or 40: 60 to 60: 40, although the invention is not limited thereto. In addition, the first amount of at least one selected from the group consisting of a carrier and a carrier precursor and the second amount of at least one selected from the group consisting of a carrier and a carrier precursor may be the same or different, and each is independently selected from the ranges listed in the present specification for at least one selected from the group consisting of a carrier and a carrier precursor.
According to one embodiment of the present invention, in the step (a-2), the Mo element precursor, the Bi element precursor, the optional Fe element precursor, the optional a element precursor, the optional B element precursor, the optional C element precursor, and the at least one selected from the support and the support precursor are not particularly limited in proportion to each other or in the respective amounts so long as the contents of the respective components in the finally produced ammonia oxidation catalyst particles satisfy any one of the aforementioned provisions of the present invention.
According to an embodiment of the present invention, in the step (a-2), the temperature of the first mixing (referred to as a first mixing temperature) is not particularly limited, but is generally 20 to 70 ℃.
According to an embodiment of the present invention, in the step (a-2), the time of the first mixing is not particularly limited, and may be arbitrarily selected by those skilled in the art, but is generally 0.5h to 48 h.
According to an embodiment of the present invention, in the step (a-2), the temperature of the second mixing is not particularly limited, but is generally 10 to 60 ℃, preferably 10 to 30 ℃, more preferably lower than the first mixing temperature, more preferably 5 to 50 ℃ or 10 to 30 ℃ lower than the first mixing temperature.
According to an embodiment of the present invention, in the step (a-2), the time of the second mixing is not particularly limited, but is generally 0.1 to 2 hours, preferably 0.5 to 1.5 hours.
According to one embodiment of the present invention, in the step (a-1) or (a-2), the stirring speed is generally greater than 200rpm, preferably 250-800rpm, preferably 250-450rpm, and more preferably 250-350 rpm.
According to an embodiment of the present invention, in the step (a-1) or (a-2), the liquid may be any liquid that is used in the art for mixing raw materials (e.g., precursors) for producing the ammoxidation catalyst particles, and more specifically, the liquid may be an alcohol and water, particularly C1-6Monohydric alcohols (such as ethanol) and water, preferably water. These liquids may be used singly or in combination in any ratio. In addition, the amount of the liquid used in the present invention is not particularly limited as long as the dissolution of all the element precursors (including the Mo element precursor, the Bi element precursor, the optional Fe element precursor, the optional a element precursor, the optional B element precursor, and the optional C element precursor) can be achieved and the slurry stirring is easy, and can be selected conventionally by those skilled in the art. From the viewpoint of convenient handling, it is obvious to those skilled in the art that the liquid may be additionally introduced into the step (a-1) or (a-2), may be contained in the respective raw materials themselves (for example, the silica sol as a carrier precursor itself contains water), or a combination of both, and is not particularly limited. In addition, the solid content of the slurry at the end of the step (a-1) or (a-2) is generally 40 to 60% by weight, but the present invention is not limited thereto.
According to an embodiment of the present invention, in the step (a-1) or (a-2), the carrier is not particularly limited, and may be any carrier known to be used in the art for producing the ammoxidation catalyst particles, and more specifically, a refractory oxide, and more specifically, silica, zirconia, or titania, and particularly silica, may be mentioned. These carriers may be used singly or in combination in any ratio.
According to one embodiment of the present invention, in the step (a-1) or (a-2), the carrier precursor is not particularly limited, and examples thereof include any material known in the art to be usable as a carrier precursor for an ammonia oxidation catalyst. Specifically, for example, a precursor of a porous refractory oxide, preferably a precursor of a porous inorganic refractory oxide, more specifically, a silica precursor, a zirconia precursor, or a titania precursor, particularly a silica precursor, can be mentioned. Examples of the silica precursor include, in particular, water-soluble silicon-containing compounds and silicon-containing compounds that can be hydrolyzed in an aqueous medium to form a silica gel or a sol, and more specifically, water glass, silica sol, silica gel, silicate ester, and the like. The zirconia precursor includes, in particular, a water-soluble zirconium-containing compound or a zirconium-containing compound that can be hydrolyzed in an aqueous medium to form a zirconium gel or sol, and more specifically, zirconium tetrachloride, zirconium oxychloride, zirconate, zirconium hydroxide, and the like. The titania precursor is particularly a water-soluble titanium-containing compound or a titanium-containing compound which can be hydrolyzed in an aqueous medium to form a titanium gel or sol, and more specifically, titanium tetrachloride, titanium oxychloride, titanate, titanium hydroxide, or the like. These precursors may be used alone or in combination in any ratio.
According to one embodiment of the invention, the support precursor is a silica sol. The silica sol generally has a solids content (calculated as silica) of from 20 to 50% by weight and an average particle size distribution of from 10 to 25 nm. Preferably, the silica sol has a particle size distribution conforming to a normal distribution curve.
According to an embodiment of the present invention, in the step (a-1) or (a-2), the Mo element precursor is not particularly limited, and may be an oxide of Mo or an oxide which can be generated after firingSpecific examples of the optional substance of (b) include oxides, hydroxides, inorganic acid salts, organic acid salts and ammonium salts of oxygen-containing acids of Mo (including hydrates of these compounds), among which water-soluble inorganic acid salts, water-soluble organic acid salts and ammonium salts of oxygen-containing acids of Mo are preferable, and ammonium salts of oxygen-containing acids of Mo such as (NH) are more preferable4)6Mo7O24Or a hydrate thereof.
According to one embodiment of the present invention, in the step (a-1) or (a-2), the Bi element precursor, the Fe element precursor, the a element precursor, the B element precursor, and the C element precursor are not particularly limited, and may be oxides of the respective elements or any substances that can produce the oxides after firing, and specifically, for example, oxides, hydroxides, inorganic acid salts, and organic acid salts (including hydrates of these compounds) of the respective elements, preferably water-soluble inorganic acid salts and water-soluble organic acid salts, more preferably halides, alkoxides, organic acid nitrates, and acetates, and particularly nitrates, may be cited. These precursors may be used alone or in combination in any ratio.
According to an embodiment of the present invention, in the step (a-1) or (a-2), a forming aid may also be used as the case may be. The molding aid is not particularly limited, and any molding aid known in the art to be used in the production of a catalyst may be used. Specifically, for example, water, extrusion aids, peptizers, pH adjusters, pore formers, lubricants and the like can be mentioned, and more specifically, water, potassium hydroxide, sesbania powder, citric acid, methyl cellulose, starch, polyvinyl alcohol and polyvinyl alcohol can be mentioned. These molding aids may be used singly or in combination in any ratio. The amount of these molding aids is not particularly limited, and may be determined by referring to information known in the art.
(b) Spray drying the slurry to obtain a particulate.
According to an embodiment of the present invention, in the step (b), conditions of the spray drying are not particularly limited, and a method of the spray drying is also not particularly limited, and may be conventionally selected by those skilled in the art. However, as a specific example, the drying heat source is generally air, the drying temperature is generally 250-350 ℃, preferably 300-350 ℃, the drying time is generally 0.5-2h, preferably 0.5-1.5h, and the average diameter of the spray droplets is generally 40-200 μm, preferably 40-180 μm.
(c) Calcining the particulate matter, thereby obtaining ammonia oxidation catalyst particles.
According to an embodiment of the present invention, in the step (c), the firing conditions are not particularly limited, and the firing method is not particularly limited, and may be conventionally selected by those skilled in the art. However, as a specific example, the calcination is generally carried out in an oxygen-containing atmosphere, the calcination temperature is generally 200-750 ℃, preferably 300-700 ℃, and the calcination time is generally 2-8h, preferably 4-6 h.
According to one embodiment of the present invention, the oxygen content in the oxygen-containing atmosphere is generally greater than 0% and less than 100%, preferably greater than 0% and less than 50%, by volume relative to the total volume of the oxygen-containing atmosphere.
The invention also relates to a method for manufacturing acrylonitrile according to an embodiment. The production process comprises a step of subjecting propylene to ammoxidation reaction in the presence of any one of the ammoxidation catalyst particles of the present invention to produce acrylonitrile.
According to an embodiment of the present invention, the process for producing acrylonitrile may be carried out in any manner and any method conventionally known in the art, and such information is known to those skilled in the art and will not be described herein. Nevertheless, as the operating conditions of the production process, specific examples thereof include a propylene/ammonia/air (in terms of molecular oxygen) molar ratio of generally 1: 1.1 to 1.3: 1.8 to 2.0, a reaction temperature of generally 420 ℃ to 440 ℃, a reaction pressure (gauge pressure) of generally 0.03 to 0.14MPa, and a weight hourly space velocity of generally 0.04 to 0.10h-1。
Examples
The present invention will be described in further detail below by way of examples and comparative examples, but the present invention is not limited to the following examples.
In the following examples and comparative examples, the catalysts directly obtained from the examples or comparative examples were referred to as fresh catalysts, and the ratio of the surface Mo element content to the bulk Mo element content of the fresh catalysts was measured and calculated.
The fresh catalyst was used for the production of acrylonitrile, and the propylene conversion, acrylonitrile selectivity and once-through yield were calculated as indices for evaluating the catalyst performance. Propylene conversion, acrylonitrile selectivity and acrylonitrile single pass yield are defined as follows:
after a certain reaction time, the catalyst was taken out, and the ratio of the surface Mo element content to the bulk Mo element content was measured and calculated again.
Comparative example 1
5.4 g KOH, 937 g (NH)4)6Mo7O24·4H2O was dissolved in water and 2750 g of 40% strength by weight silica sol was added at 60 ℃ to give solution I. 89.7 g of Bi (NO)3)3·5H2O, 775.7 g Ni (NO)3)2·6H2O, 301.7 g Fe (NO)3)3·9H2O, 203.1 g Mg (NO)3)2·6H2O, 21.3 g Cr2O34.1 g of KOH were dissolved in water to give solution II. And mixing the solution I and the solution II, and stirring at a stirring speed of 100rpm for 0.5h at the temperature of 80 ℃ to obtain slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 300 ℃ for 0.5h, wherein the average diameter of spray droplets is 100 microns, thus obtaining the particles. Finally, the obtained granulesThe pellets were calcined at 490 ℃ for 3 hours in an oxygen-containing atmosphere (oxygen volume fraction: 21%) to obtain ammoxidation catalyst particles.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％K0.15Fe1.4Ni5.0Mg1.5Cr0.4Bi0.35Mo10Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The fresh catalyst was determined to have a ratio of surface Mo element content to bulk Mo element content of 0.16.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0.
The catalyst after running for 3 hours was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the content of the surface Mo element in the catalyst was 6.8%, the content of the bulk Mo element was 25.6%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.26. The conversion of propylene was 93%, the propylene selectivity was 72%, and the once-through yield of acrylonitrile was 66.9%.
The reaction was continued, and 500 hours after the start of the reaction, analysis was again conducted, and the catalyst had a surface Mo element content of 50.6%, a bulk Mo element content of 22%, and a ratio of the surface Mo element content to the bulk Mo element content of 2.3. The conversion of propylene was 86.6%, the propylene selectivity was 71.3%, and the once-through yield of acrylonitrile was 61.7%.
After the catalyst runs for 500 hours, the content of the Mo element in the bulk phase is reduced to 22% from 25.6% of the fresh agent, which shows that the Mo component in the catalyst is obviously sublimated.
Example 1
958.8 g (NH)4)6Mo7O24·4H2The O is dissolved in the water, and the water,and 2750 g of 40% strength by weight silica sol was added at 20 ℃ to obtain solution I. 125.3 g of Bi (NO)3)3·5H2O, 583.6 g Ni (NO)3)2·6H2O, 227.0 g Fe (NO)3)3·9H2O, 152.8 g Mg (NO)3)2·6H2O, 11.6 g Co (NO)3)2·6H2O, 17.1 g Pr (NO)3)3·6H2O, 23.7 g La (NO)3)3·6H2O, 34.5 g Nd (NO)3)3·6H2O, 8.1 g KOH, 24.1 g Cr3O2Dissolved in water to give solution II. Solution I was mixed with solution II at 10 ℃ and stirred at 200rpm for 0.5h to give slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 350 ℃ for 0.5h, wherein the average diameter of spray droplets is 90 mu m, so as to obtain particles. Finally, the obtained particles were calcined at 590 ℃ for 3 hours in an oxygen-containing atmosphere (oxygen volume fraction: 21%) to obtain ammoxidation catalyst particles having an average catalyst particle size of 40 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％K0.30Co0.1Fe1.4Ni5.0Mg2.0Cr0.6La0.15Nd0.20Pr0.10Bi0.65Mo13.6Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The fresh catalyst was determined to have a ratio of surface Mo element content to bulk Mo element content of 0.55.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0.
The catalyst after running for 3 hours was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the content of the surface Mo element in the catalyst was 15%, the content of the bulk Mo element was 25%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.6. The conversion of propylene was 98.5%, the selectivity of acrylonitrile was 83.3%, and the once-through yield of acrylonitrile was 82.1%.
After running for 500h, the content of Mo element on the surface of the catalyst is 22%, the content of Mo element in bulk phase is 24%, and the ratio of the content of Mo element on the surface to the content of Mo element in bulk phase is 0.92. The conversion of propylene was 98.3%, the selectivity of acrylonitrile was 82.5%, and the once-through yield of acrylonitrile was 81.1%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 25 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 2
960.1 g (NH)4)6Mo7O24·4H2O, 2750 g of silica sol with weight concentration of 40 percent and 125.3 g of Bi (NO)3)3·5H2O, 583.7 g Ni (NO)3)2·6H2O, 227 g Fe (NO)3)3·9H2O, 152.8 g Mg (NO)3)2·6H2O, 5.8 g Co (NO)3)2·6H2O, 8.1 g KOH, 39.5 g La (NO)3)3·6H2O, 34.6 g Nd (NO)3)3·6H2O, 24.1 g Cr3O2Dissolved in water and stirred at a stirring speed of 250rpm for 0.5h at 50 ℃ to obtain a slurry. And (3) carrying out spray drying on the slurry, wherein the drying temperature is 300 ℃, the drying time is 0.5h, and the average diameter of spray droplets is 100 mu m to obtain the particles. Finally, the obtained particles were calcined at 600 ℃ for 3 hours in an oxygen-containing atmosphere (oxygen volume fraction: 21%) to obtain an ammoxidation catalyst having an average particle size of 45 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％K0.30Co0.05Fe1.4Ni5.0Mg1.5Cr0.6La0.25Nd0.20Bi0.65Mo13.6Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The fresh catalyst was determined to have a ratio of surface Mo element content to bulk Mo element content of 0.57.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0.
The catalyst after 3 hours of operation was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the catalyst contained 14.5% of the surface Mo element, 25% of the bulk Mo element, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.58. The conversion of propylene was 98.2%, the selectivity of acrylonitrile was 83.1%, and the once-through yield of acrylonitrile was 81.6%.
After running for 500h, the content of the surface Mo element in the catalyst is 25%, the content of the bulk Mo element in the catalyst is 24%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element is 1.04. The conversion rate of propylene is 98.3%, the selectivity of acrylonitrile is 82.3%, and the once-through yield of acrylonitrile is 80.9%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 25 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 3
958.7 g (NH)4)6Mo7O24·4H2O was dissolved in water and 2750 g of 40% strength by weight silica sol was added at 30 ℃ to give solution I. 125.3 g of Bi (NO)3)3·5H2O, 583.6 g Ni (NO)3)2·6H2O, 227 g Fe (NO)3)3·9H2O, 152.8 g Mg (NO)3)2·6H2O, 11.6 g Co (NO)3)2·6H2O, 42.8 g Pr (NO)3)3·6H2O, 34.5 g Nd (NO)3)3·6H2O, 8.1 g KOH, 24.1 g Cr3O2Dissolved in water to give solution II. And mixing the solution I and the solution II at 15 ℃, and stirring at a stirring speed of 250rpm for 0.5h to obtain slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 350 ℃ for 1.0h, wherein the average diameter of spray droplets is 100 microns, so as to obtain particles. Finally, the obtained particles were calcined at 610 ℃ for 3 hours in an oxygen-containing atmosphere (oxygen volume fraction: 21%) to obtain an ammoxidation catalyst having an average particle size of 51 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％K0.30Co0.10Fe1.4Ni5.0Mg1.5Cr0.6Nd0.20Pr0.25Bi0.65Mo13.6Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The ratio of the surface Mo element content to the bulk Mo element content of the fresh catalyst was determined to be 0.50.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0.
The catalyst after 3 hours of operation was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the catalyst contained 12.4% of the surface Mo element, 24.8% of the bulk Mo element, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.5. The conversion of propylene was 98.0%, the selectivity of acrylonitrile was 82.8%, and the once-through yield of acrylonitrile was 81.1%.
After running for 500h, the content of the surface Mo element in the catalyst is 30.2%, the content of the bulk Mo element in the catalyst is 24%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element is 1.26. The conversion of propylene was 97.5%, the selectivity of acrylonitrile was 82.5%, and the once-through yield of acrylonitrile was 80.4%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 24.8 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 4
1038.8 g (NH)4)6Mo7O24·4H2O was dissolved in water and 2750 g of 40% strength by weight silica sol was added at 40 ℃ to obtain solution I. 124.2 g of Bi (NO)3)3·5H2O, 578.8 g Ni (NO)3)2·6H2O, 225.1 g Fe (NO)3)3·9H2O, 7.0 g Mn (NO)3)222.9 g CsNO3151.5 g Mg (NO)3)2·6H2O, 31.3 g La (NO)3)3·6H2O, 42.4 g Pr (NO)3)3·6H2O, 23.9 g Cr3O2Dissolved in water to give solution II. Solution I was mixed with solution II at 30 ℃ and stirred at 450rpm for 2h to give slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 250 ℃ for 1.5h, wherein the average diameter of spray droplets is 100 microns, so as to obtain particles. Finally, the obtained particles are roasted for 6 hours at 590 ℃ under the condition of oxygen-containing atmosphere (oxygen volume fraction is 40 percent), so as to obtain the ammoxidation catalyst, and the average particle size of the catalyst is 50 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％Cs0.30Mn0.05Fe1.4Ni5.0Mg1.5Cr0.6La0.20Pr0.25Bi0.65Mo13.6Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The fresh catalyst was determined to have a ratio of surface Mo element content to bulk Mo element content of 0.52.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0.
The catalyst after 3 hours of operation was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the catalyst contained 13.6% of the surface Mo element, 24.8% of the bulk Mo element, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.55. The conversion rate of propylene is 97.3%, the selectivity of acrylonitrile is 82.3%, and the once-through yield of acrylonitrile is 80.1%.
After running for 500h, the content of the surface Mo element in the catalyst is 40.1%, the content of the bulk Mo element in the catalyst is 24%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element is 1.67. The conversion of propylene was 97.1%, the selectivity of acrylonitrile was 82.2%, and the once-through yield of acrylonitrile was 79.8%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 24.8 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 5
949.8 g (NH)4)6Mo7O24·4H2O was dissolved in water and 2750 g of 40% strength by weight silica sol was added at 50 ℃ to give solution I. 124.3 g of Bi (NO)3)3·5H2O, 578.9 g Ni (NO)3)2·6H2O, 225.2 g Fe (NO)3)3·9H2O, 22.9 g CsNO313.9 g Mn (NO)3)223.9 g of Cr2O370.3 g La (NO)3)3·6H2O, 151.6 g Mg (NO)3)2·6H2O was dissolved in water to give solution II. Mixing the solution I and the solution II at 30 ℃ and stirring at a stirring speed of 350rpm for 0.5h to obtainTo slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 350 ℃ for 2h, wherein the average diameter of spray droplets is 200 mu m, so as to obtain particles. Finally, the obtained particles are roasted for 3 hours at 250 ℃ under the condition of oxygen-containing atmosphere (oxygen volume fraction is 50%), so that the ammoxidation catalyst is obtained, and the average particle size of the catalyst is 50 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％Cs0.30Mn0.10Fe1.4Ni5.0Mg1.5Cr0.6La0.45Bi0.65Mo13.6Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The ratio of the surface Mo element content to the bulk Mo element content of the fresh catalyst was determined to be 0.60.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0.
The catalyst after 3 hours of operation was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the catalyst contained 17.5% of the surface Mo element, 25% of the bulk Mo element, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.7. The conversion of propylene was 97.5%, the selectivity of acrylonitrile was 82.6%, and the once-through yield of acrylonitrile was 80.5%.
After running for 500h, the content of the surface Mo element in the catalyst is 31.4%, the content of the bulk Mo element in the catalyst is 24%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element is 1.31. The conversion rate of propylene is 97.3%, the selectivity of acrylonitrile is 82.5%, and the once-through yield of acrylonitrile is 80.3%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 25 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 6
959.4 g (NH)4)6Mo7O24·4H2O was dissolved in water and 2750 g of 40% strength by weight silica sol was added at 70 ℃ to give solution I. 125.4 g of Bi (NO)3)3·5H2O, 584.0 g Ni (NO)3)2·6H2O, 227.2 g Fe (NO)3)3·9H2O, 152.9 g Mg (NO)3)2·6H2O, 8.1 g KOH, 77.1 g Pr (NO)3)3·6H2O, 24.1 g Cr2O3Dissolved in water to give solution II. Mixing solution I and solution II at 50 deg.C, and adding 2.5 g ZrO2And stirred at a stirring speed of 350rpm for 0.5h to obtain slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 300 ℃ for 0.5h, wherein the average diameter of spray droplets is 100 microns to obtain particles. Finally, the obtained particles are roasted for 2 hours at 590 ℃ under the condition of oxygen-containing atmosphere (oxygen volume fraction is 21 percent), so as to obtain the ammoxidation catalyst, wherein the average particle size of the catalyst is 50 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％K0.30Zr0.05Fe1.4Ni5.0Mg1.5Cr0.6Pr0.45Bi0.65Mo13.6Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The fresh catalyst was determined to have a ratio of surface Mo element content to bulk Mo element content of 0.61.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0. For 3 hours of operationThe measurement of the surface Mo element content and the bulk Mo element content of the catalyst showed that the catalyst contained 16% of the surface Mo element, 24.6% of the bulk Mo element, and a ratio of the surface Mo element content to the bulk Mo element content was 0.65. The conversion of propylene was 98.0%, the selectivity of acrylonitrile was 83.0%, and the once-through yield of acrylonitrile was 81.3%.
After running for 500h, the content of the surface Mo element in the catalyst is 34.3%, the content of the bulk Mo element in the catalyst is 24%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element is 1.43. The conversion of propylene was 98.0%, the selectivity of acrylonitrile was 82.5%, and the once-through yield of acrylonitrile was 80.9%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 24.6 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 7
956.7 g (NH)4)6Mo7O24·4H2O was dissolved in water and 2750 g of 40% strength by weight silica sol was added at 60 ℃ to give solution I. 125.0 g of Bi (NO)3)3·5H2O, 582.4 g Ni (NO)3)2·6H2O, 226.5 g Fe (NO)3)3·9H2O, 152.5 g Mg (NO)3)2·6H2O, 8.1 g KOH, 77.5 g Nd (NO)3)3·6H2O, 24.0 g Cr2O3Dissolved in water to give solution II. Mixing solution I and solution II at 40 deg.C, adding 4.9 g ZrO2And stirred at a stirring speed of 350rpm for 0.5h to obtain slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 300 ℃ for 0.5h, wherein the average diameter of spray droplets is 100 microns, thus obtaining the particles. Finally, the obtained particles are roasted for 4 hours at 590 ℃ under the condition of oxygen-containing atmosphere (oxygen volume fraction is 21 percent), so as to obtain the ammoxidation catalyst, and the average particle size of the catalyst is 50 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％K0.30Zr0.10Fe1.4Ni5.0Mg1.5Cr0.6Nd0.45Bi0.65Mo13.6Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The fresh catalyst was determined to have a ratio of surface Mo element content to bulk Mo element content of 0.65.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0. The catalyst after 3 hours of operation was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the catalyst contained 16.8% of the surface Mo element, 24.9% of the bulk Mo element, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.67. The conversion of propylene was 98.8%, the selectivity of acrylonitrile was 83.5%, and the once-through yield of acrylonitrile was 82.5%.
After running for 500h, the content of the surface Mo element in the catalyst is 29.3%, the content of the bulk Mo element in the catalyst is 24%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element is 1.22. The conversion of propylene was 98.3%, the selectivity of acrylonitrile was 83.5%, and the once-through yield of acrylonitrile was 82.1%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 24.9 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 8
996.9 g (NH)4)6Mo7O24·4H2O was dissolved in water and 2750 g of 40% strength by weight silica sol was added at 60 ℃ to give solution I. Mixing 110.7 g Bi (NO)3)3·5H2O, 515.8 g Ni (NO)3)2·6H2O, 200.6 g Fe (NO)3)3·9H2O, 135 g Mg (NO)3)2·6H2O, 21.3 g Cr2O310.2 g CsNO32.4 g KOH, 68.6 g Nd (NO)3)3·6H2O, 2.6 g RbNO3Dissolved in water to give solution II. Mixing solution I and solution II at 50 deg.C, adding 4.9 g ZrO2And stirred at a stirring speed of 350rpm for 0.5h to obtain slurry III. And (3) carrying out spray drying on the slurry III at the drying temperature of 300 ℃ for 0.5h, wherein the average diameter of spray droplets is 100 microns to obtain particles. Finally, the obtained particles were calcined at 590 ℃ for 3 hours in an oxygen-containing atmosphere (oxygen volume fraction: 21%) to obtain an ammoxidation catalyst having an average particle size of 50 μm.
The composition of the catalyst obtained according to the above procedure is represented by the following formula:
50％Rb0.05Cs0.15K0.10Zr0.10Fe1.4Ni5.0Mg1.5Cr0.6Nd0.45Bi0.65Mo16Ox+50％SiO2
wherein x is the number of oxygen atoms necessary to satisfy the valences of the other elements.
The fresh catalyst was determined to have a ratio of surface Mo element content to bulk Mo element content of 0.35.
The reaction conditions of the catalyst for propylene ammoxidation to produce acrylonitrile are as follows: phi 38 mm fluidized bed reactor, reaction temperature: 430 ℃; reaction pressure: 0.085 MPa; catalyst loading: 300 g; catalyst propylene loading (WWH): 0.06 hour-1(ii) a The raw material proportion (mol): c3 ＝/NH3Air (in terms of molecular oxygen) is 1/1.25/2.0. The catalyst after 3 hours of operation was measured for the content of the surface Mo element and the content of the bulk Mo element, and the results showed that the catalyst contained 12.5% of the surface Mo element, 25% of the bulk Mo element, and the ratio of the content of the surface Mo element to the content of the bulk Mo element was 0.5. The conversion of propylene was 98.5%, the selectivity for acrylonitrile was 84.3%, and the once-through yield of acrylonitrile was 83.0%.
After running for 500h, the content of the surface Mo element in the catalyst is 22%, the content of the bulk Mo element in the catalyst is 24%, and the ratio of the content of the surface Mo element to the content of the bulk Mo element is 1.35. The conversion of propylene was 98.3%, the selectivity of acrylonitrile was 83.5%, and the once-through yield of acrylonitrile was 82.1%.
After the catalyst is operated for 500 hours, the content of the Mo element in the bulk phase is reduced from 25 percent after the catalyst is operated for 3 hours to 24 percent, and compared with the comparative example, the sublimation of the Mo component in the catalyst is effectively inhibited.
Example 9
The catalyst prepared in example 8 was used in a fluidized bed reactor having a diameter of 7.5 m to conduct the ammoxidation of propylene to produce acrylonitrile. Catalyst loading 130 tons, at a reaction temperature of 435 ℃, air (in molecular oxygen): the mol ratio of the propylene is 1.8: 1, the reaction pressure is 0.040Mpa, and the reaction load is 0.07 h-1The single-pass yield of the acrylonitrile is respectively about 81 percent and 80.5 percent after the operation for 1 year and after the operation for 3 years, and better effect is obtained.
After running for 1 year and 3 years, the content of surface Mo element in the catalyst is 35% and 40%, the content of bulk Mo element is 24% and 24%, and the ratio of the content of surface Mo element to the content of bulk Mo element is 1.45 and 1.67 respectively.
After the catalyst is operated for 3 years, the content of the Mo element in the bulk phase is the same as that after the catalyst is operated for 1 year and is 24 percent, which shows that the measure can effectively inhibit the sublimation of the Mo component.
Example 10
The catalyst prepared in example 1 was used in a fluidized bed reactor having a diameter of 9.5 m to conduct the ammoxidation of propylene to produce acrylonitrile. The loading of the catalyst was 240 tons, the reaction temperature was 430 ℃, the molar ratio of air (calculated as molecular oxygen) to propylene was 1.8: 1, the reaction pressure was 0.040MPa, and the reaction load was 0.07 hours-1The single-pass yield of the acrylonitrile is respectively about 81.6 percent and 81.2 percent after 1 year of operation and 3 years of operation, and better effects are obtained.
After running for 1 year and 3 years, the content of surface Mo element in the catalyst is 33% and 37%, the content of bulk Mo element is 24% and 24%, and the ratio of the content of surface Mo element to the content of bulk Mo element is 1.38 and 1.54 respectively.
After the catalyst is operated for 3 years, the content of the Mo element in the bulk phase is the same as that after the catalyst is operated for 1 year and is 24 percent, which shows that the measure can effectively inhibit the sublimation of the Mo component.
From the results of examples 1 to 10 and comparative example 1, it is understood that by controlling the ratio of the surface Mo element content to the bulk Mo element content of the ammoxidation catalyst particles within the range specified in the present invention, the migration rate of the Mo component in the catalyst, i.e., the rate of Mo element migration from the catalyst bulk to the catalyst surface, can be effectively controlled during long-term operation of the catalyst, so that the sublimation rate of the Mo component can be controlled under the reaction conditions for propylene ammoxidation, the problem of decrease in the single-pass yield of acrylonitrile due to sublimation of Mo can be suppressed, and the catalyst can exhibit a high single-pass yield level of acrylonitrile during long-term reaction.
Claims (12)
1. An ammoxidation catalyst particle having a composition containing at least a Mo element, a Bi element and a carrier (preferably at least one selected from refractory oxides, preferably at least one selected from silica, zirconia and titania, more preferably silica), wherein the ratio of the surface Mo element content to the bulk Mo element content of the catalyst particle is from 0.2 to 0.98: 1, preferably from 0.3 to 0.98: 1, more preferably from 0.4 to 0.9: 1, more preferably from 0.5 to 0.8: 1 or from 0.45 to 0.65: 1.
2. The ammonia oxidation catalyst particles of claim 1, wherein the Mo element (in MoO) is present in an amount of about the total weight of the catalyst particles3Calculated as Bi) in a weight percentage of 15-55 wt% (preferably 20-45 wt%), and the Bi element (calculated as Bi)2O3In a dry basis or in the form of oxides) in an amount of from 0.5 to 3.5% by weight, preferably from 1.0 to 3.5% by weight, and in an amount of from 30 to 70% by weight, preferably from 40 to 60% by weight, of the support (dry basis or in the form of oxides).
3. The ammonia oxidation catalyst particles of claim 1, wherein the composition further comprises an Fe element selected from at least one of Li, Na, K, Rb, Cs, Tl and Ag (preferably at least one selected from Na, K, Rb, Cs, Tl and Ag), an B element selected from at least one of Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P, V, Ba, Ti, Pt and Nb (preferably at least one selected from Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P and Nb), and a C element selected from at least one of rare earth elements (preferably at least one selected from La, Ce, Pr, Nd, Sm and Eu).
4. The ammonia oxidation catalyst particles of claim 3, wherein the Mo element (as MoO) is present in the catalyst particles in a total amount based on the total weight of the catalyst particles3Calculated by Bi) is 15 to 55 weight percent, and the Bi element (calculated by Bi) is2O3Calculated by weight percent) of 0.5 to 3.5 percent, and the Fe element (calculated as Fe)2O3In terms of oxide) in an amount of 1.0 to 5.0 wt.%, the element a (in terms of oxide) in an amount of 0.03 to 10 wt.%, the element B (in terms of oxide) in an amount of 0.01 to 40 wt.%, the element C (in terms of oxide) in an amount of 0.05 to 20 wt.%, and the carrier (dry basis or in terms of oxide) in an amount of 30 to 70 wt.% (preferably 40 to 60 wt.%).
5. The ammonia oxidation catalyst particles of claim 1 having an average particle size of from 30 to 70 μm, preferably from 40 to 60 μm.
6. The ammonia oxidation catalyst particles of claim 1 wherein the composition is measured after calcination at 500 ℃ for 3 hours in an air atmosphere.
7. A method for producing ammonia oxidation catalyst particles, comprising the steps of:
(a-1) mixing a Mo element precursor, a Bi element precursor, an optional Fe element precursor, an optional A element precursor, an optional B element precursor, an optional C element precursor, and at least one selected from the group consisting of a carrier and a carrier precursor in the presence of a liquid (preferably at least one selected from the group consisting of an alcohol and water, more preferably water) at a stirring speed of more than 200rpm (preferably 250-,
or
(a-2) first mixing a Mo element precursor with at least one selected from the group consisting of a carrier and a carrier precursor in the presence of a liquid (preferably at least one selected from the group consisting of an alcohol and water, more preferably water), and then second mixing with a Bi element precursor, an optional Fe element precursor, an optional A element precursor, an optional B element precursor, an optional C element precursor, and an optional at least one selected from the group consisting of a carrier and a carrier precursor in the presence of a liquid (preferably at least one selected from the group consisting of an alcohol and water, more preferably water) at a stirring speed of more than 200rpm (preferably 250-,
wherein the element A is selected from at least one of Li, Na, K, Rb, Cs, Tl and Ag (preferably at least one selected from Na, K, Rb, Cs, Tl and Ag), the element B is selected from at least one of Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P, V, Ba, Ti, Pt and Nb (preferably at least one selected from Ca, Mn, Co, Ni, Mg, Cr, W, Zr, P and Nb), the element C is selected from at least one of rare earth elements (preferably at least one selected from La, Ce, Pr, Nd, Sm and Eu), and the carrier is selected from at least one of refractory oxides (preferably at least one selected from silica, zirconia and titania, more preferably silica);
(b) spray drying the slurry to obtain particulate matter; and
(c) calcining the particulate matter to obtain the ammonia oxidation catalyst particles.
8. The manufacturing method as set forth in claim 7, wherein in the step (a-1), the conditions of the mixing include: a mixing temperature of 10 to 50 ℃ (preferably 10 to 30 ℃) for 0.5 to 2.5 hours (preferably 0.5 to 2 hours), or in said step (a-2), said first mixing conditions comprise: the first mixing temperature is 20-70 ℃, and the second mixing conditions comprise: the second mixing temperature is 10-60 deg.C (preferably 10-30 deg.C, more preferably lower than the first mixing temperature, more preferably 5-50 deg.C or 10-30 deg.C lower than the first mixing temperature), and the second mixing time is 0.1-2h (preferably 0.5-1.5 h).
9. The manufacturing method of claim 7, wherein in the step (b), the conditions of the spray drying include: the drying heat source is air, the drying temperature is 250-350 ℃ (preferably 300-350 ℃), the drying time is 0.5-2h (preferably 0.5-1.5h), and the average diameter of the spray droplets is 40-200 μm (preferably 40-180 μm).
10. The manufacturing method of claim 7, wherein in the step (c), the firing conditions include: the roasting temperature is 200 ℃ and 750 ℃ (preferably 300 ℃ and 700 ℃) in the oxygen-containing atmosphere, and the roasting time is 2-8h (preferably 4-6 h).
11. A process for producing acrylonitrile, which comprises subjecting propylene to ammoxidation in the presence of the ammoxidation catalyst particles according to claim 1 or the ammoxidation catalyst particles produced by the production process according to claim 7 to produce acrylonitrile.
12. The production process according to claim 11, wherein the reaction conditions for the ammoxidation reaction include: the mol ratio of the propylene to the ammonia gas to the air (calculated by molecular oxygen) is 1: 1.1-1.3: 1.8-2.0, the reaction temperature is 420--1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910247518.8A CN111744493A (en) | 2019-03-28 | 2019-03-28 | Ammonia oxidation catalyst particles, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910247518.8A CN111744493A (en) | 2019-03-28 | 2019-03-28 | Ammonia oxidation catalyst particles, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111744493A true CN111744493A (en) | 2020-10-09 |
Family
ID=72671244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910247518.8A Pending CN111744493A (en) | 2019-03-28 | 2019-03-28 | Ammonia oxidation catalyst particles, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111744493A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113648991A (en) * | 2021-09-03 | 2021-11-16 | 北京碧水源膜科技有限公司 | Deamination catalyst capable of stably producing nitrite nitrogen, preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061163A (en) * | 1990-11-05 | 1992-05-20 | 中国石油化工总公司 | The method of catalyst activity of acrylonitrile fluidized bed long-term stability |
| US5663113A (en) * | 1994-04-25 | 1997-09-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Ammoxidation catalyst composition |
| CN1361719A (en) * | 1999-07-21 | 2002-07-31 | 三菱丽阳株式会社 | Molybdenum-bismuth-iron containing metal oxide catalyst for fluidized layer, method for preparation thereof, and use thereof |
| JP2004105951A (en) * | 2002-08-27 | 2004-04-08 | Daiyanitorikkusu Kk | Catalyst for synthesizing acrylonitrile and production method for the same and production method for acrylonitrile |
| CN104923248A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | High-pressure high-load catalyst for olefin ammoxidation reaction |
| CN106423190A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Propylene ammoxidation catalyst for rich production of acetonitrile and hydrocyanic acid |
| CN106582696A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | High selectivity catalyst for production of acrylonitrile by propylene ammoxidation |
| JPWO2018043007A1 (en) * | 2016-08-31 | 2018-12-20 | 旭化成株式会社 | Method for producing catalyst and method for producing acrylonitrile |
-
2019
- 2019-03-28 CN CN201910247518.8A patent/CN111744493A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061163A (en) * | 1990-11-05 | 1992-05-20 | 中国石油化工总公司 | The method of catalyst activity of acrylonitrile fluidized bed long-term stability |
| US5663113A (en) * | 1994-04-25 | 1997-09-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Ammoxidation catalyst composition |
| CN1361719A (en) * | 1999-07-21 | 2002-07-31 | 三菱丽阳株式会社 | Molybdenum-bismuth-iron containing metal oxide catalyst for fluidized layer, method for preparation thereof, and use thereof |
| JP2004105951A (en) * | 2002-08-27 | 2004-04-08 | Daiyanitorikkusu Kk | Catalyst for synthesizing acrylonitrile and production method for the same and production method for acrylonitrile |
| CN104923248A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | High-pressure high-load catalyst for olefin ammoxidation reaction |
| CN106423190A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Propylene ammoxidation catalyst for rich production of acetonitrile and hydrocyanic acid |
| CN106582696A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | High selectivity catalyst for production of acrylonitrile by propylene ammoxidation |
| JPWO2018043007A1 (en) * | 2016-08-31 | 2018-12-20 | 旭化成株式会社 | Method for producing catalyst and method for producing acrylonitrile |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113648991A (en) * | 2021-09-03 | 2021-11-16 | 北京碧水源膜科技有限公司 | Deamination catalyst capable of stably producing nitrite nitrogen, preparation method and application thereof |
| CN113648991B (en) * | 2021-09-03 | 2023-11-03 | 北京碧水源膜科技有限公司 | Deamination catalyst capable of stably producing nitrous nitrogen, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR910010126B1 (en) | Process for producing cerium oxide particulates | |
| US10479760B2 (en) | Synthetic methods for the preparation of propylene ammoxidation catalysts | |
| JP5763711B2 (en) | Ceria-zirconia composite oxide, production method thereof, and exhaust gas purification catalyst using the ceria-zirconia composite oxide | |
| CN101679174B (en) | Method for production of acrolein | |
| US10479759B2 (en) | Synthetic methods for the preparation of propylene ammoxidation catalysts | |
| WO2008099961A9 (en) | Catalyst for alcohol production | |
| JP2020514217A (en) | Aging resistant mixed oxides for automotive catalytic converters made from cerium, zirconium, aluminum and lanthanum | |
| JP2004508190A (en) | Catalyst for oxidative dehydrogenation of hydrocarbons | |
| JP2603776B2 (en) | Catalyst composition for production of α, β-unsaturated aldehyde by oxidation of olefin | |
| JP5746716B2 (en) | Porous alumina material, method for producing the same, and catalyst | |
| JP5832785B2 (en) | Catalyst for ammoxidation, method for producing the same, and method for producing acrylonitrile or methacrylonitrile | |
| CN1374149A (en) | Catalyst based on cobalt and its application in Fi-Tuo action | |
| WO2014157040A1 (en) | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid | |
| JP2008289985A (en) | Method for manufacturing catalytic carrier for cleaning exhaust gas | |
| JP2019521937A (en) | Mixed oxides based on cerium and zirconium | |
| EP2990108A1 (en) | Catalyst for producing unsaturated aldehyde and/or unsaturated carboxylic acid, method for producing catalyst, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid using catalyst | |
| CN111744497B (en) | Ammonia oxidation catalyst particles, manufacturing method and application thereof | |
| JP5210834B2 (en) | Method for producing catalyst for acrylonitrile synthesis and method for producing acrylonitrile | |
| KR101735862B1 (en) | Process for production of composite oxide catalyst | |
| CN115501881B (en) | Catalyst particles for preparing acrylonitrile by ammoxidation of propylene, preparation method and application thereof | |
| JP5011178B2 (en) | Method for producing catalyst for acrylonitrile synthesis and method for producing acrylonitrile | |
| CN111744493A (en) | Ammonia oxidation catalyst particles, and preparation method and application thereof | |
| JP2023537205A (en) | Process and catalyst for oxidative esterification with mechanically strong and chemically resistant catalysts | |
| JP2014518757A (en) | Method for preparing cobalt-containing hydrocarbon synthesis catalyst precursor | |
| JP2010131576A (en) | Method of producing catalyst for synthesizing acrylonitrile, and method of producing acrylonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |