CN102992980B - Method for preparing acrolein - Google Patents
Method for preparing acrolein Download PDFInfo
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- CN102992980B CN102992980B CN201110265436.XA CN201110265436A CN102992980B CN 102992980 B CN102992980 B CN 102992980B CN 201110265436 A CN201110265436 A CN 201110265436A CN 102992980 B CN102992980 B CN 102992980B
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- catalyzer
- propylene
- preparation
- propylene oxidation
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- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 161
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 238000002360 preparation method Methods 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 82
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 82
- 239000002002 slurry Substances 0.000 claims description 59
- 238000007254 oxidation reaction Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 230000003647 oxidation Effects 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 25
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052622 kaolinite Inorganic materials 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229960001866 silicon dioxide Drugs 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000004480 active ingredient Substances 0.000 description 35
- 230000000694 effects Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 239000012018 catalyst precursor Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 11
- 239000007921 spray Substances 0.000 description 9
- 238000007669 thermal treatment Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 7
- 229910010271 silicon carbide Inorganic materials 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical class [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- -1 nickelous nitrates Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ORSLXQZSKCIHDH-UHFFFAOYSA-N prop-2-enal;prop-2-enoic acid Chemical compound C=CC=O.OC(=O)C=C ORSLXQZSKCIHDH-UHFFFAOYSA-N 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000000576 supplementary effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of acrolein, which adopts a fixed bed sheet reactor; the reaction raw materials enter a reactor after being preheated, a Mo-Bi series composite multi-metal oxide catalyst is filled in the reactor, and the composition of the catalyst can be represented by the following general formula . MoaBibFecNidSifAmBnOi(I) The production method can effectively reduce the local heat accumulation of the single-tube reactor, inhibit the formation of hot spots, ensure that the catalyst is not easy to be crossed and meet the requirement of long-period stable operation of the device.
Description
Technical field
The present invention relates to a kind of method that corresponding unsaturated aldehyde is produced in propylene or selective isobutene oxidation, be particularly useful for Propylene Selectivity to be oxidized to propenal.
Background technology
At present, industrially mainly with propylene two-step oxidation legal system vinylformic acid, conventionally adopt fixed-bed reactor, propylene initial oxidation becomes propenal, and propenal is reoxidised into vinylformic acid.It is strong exothermal reaction that propylene gas phase catalytic oxidation reaction is prepared propenal, in reactor, moment is assembled a large amount of reaction heat, form hot localised points, if can not remove timely and effectively reaction heat, the heat that moment is gathered is constantly accumulated, by cause catalyst activity component loss, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause, because over oxidation reacts the formation that aggravates by product, even causing uncontrolled reaction, make sintering of catalyst.
The progress > > (petrochemical complex of < < oxidation acrylic acid synthesizing process and catalyzer, the 39th the 7th phase of volume in 2010) appearance of social focus also can make catalyst damage evil, shortens the work-ing life of catalyzer.The 80000 tons/year of acroleic acid devices of take are example, and propylene oxidation is prepared and in acrolein reaction device, needed more than 25000 tubulation, acrolein oxidation to prepare in vinylformic acid reactor also to need more than 25000 tubulation, load altogether more than 100 ton of propenal, vinylformic acid catalyzer.More than 50000 reaction tubes, the filling of catalyzer guarantees not fill empty certain difficulty that has, if because focus is crossed the very fast sintering of high catalyst, again change in a short time agent, it is huge can envisioning its financial loss again; In addition, for propenal, acrylic acid production, carry out as much as possible under cold condition, because reaction needed salt bath heating, its energy consumption that maintains production is also huge spending; Due to the generation of focus, high temperature resistant to the requirement of reaction tubes tubing, for up to ten thousand reaction tubess, tubing expense is exactly a very large cost.Therefore,, if effectively suppress the generation of beds focus, can bring huge economic benefit to large-scale commercial production.
At present, there is several different methods can reduce or avoid gathering and peroxidation of focus, as: Japanese patent laid-open 04-217932 has proposed a kind of method that suppresses the appearance of focus or the hot polymerization collection on focus, by preparing the multiple catalyzer with different possessive volumes, and the mode reducing to outlet one side catalyzer possessive volume from unstripped gas inlet side, fill successively reaction tubes, but the possessive volume of catalyzer is subject to the restriction of reaction tube diameter, and it is also very difficult that multiple catalysts is filled into reaction tubes.CN1210511A prepares the multiple catalyst-loaded catalyst layer that arranges in reaction tubes with different activities, according to the entrance from unstripped gas, to the active order uprising of outlet, arranges above-mentioned several catalyst-loaded.Also the method that has other, for example, inert substance and catalyst mix, reduce the activity of catalyzer, be loaded into reactor inlet place, Japanese Unexamined Patent Publication 10614/1972 is sneaked into heat resistanceheat resistant point to form catalyzer is inert substance with by catalyst dilution in catalyzer, and Japanese Patent Publication 36739/1987 is made catalyzer the method for tubulose.There is again the catalyst loading that unstripped gas ingress reduces by active ingredient.CN01111960.8 is used fixed bed shell and tube reactor, under catalyzer exists, by propylene gas phase catalytic oxidation reaction, prepare propenal and acrylic acid, the method is the generation of focus or the hot polymerization collection on focus in inhibited reaction district effectively, this catalyzer consist of Mo
aw
bbi
cfe
da
eb
fc
gd
he
io
x, wherein the implication of Mo, W, Bi, Fe, A, B, C, D, E and O and a, b, c, d, e, f, g, h, i and x is as described in specification sheets.The feature of the method is the multiple catalysts that preparation has above-mentioned composition, but kind and/or the quantity of the temperature that (α) possessive volume, (β) calcine and/or (γ) alkali metal are different, and press the mode of catalyst activity from unstripped gas entrance to Increasing exports, catalyzer is filled into reaction zone successively.CN00122609.6 provides under the condition that has the oxide catalyst that contains Mo-Bi-Fe compound, by vapor phase propylene oxide, produce propenal and acrylic acid, described catalyzer is filled in multitubular reactor of fixed bed, and the method can generate propenal and vinylformic acid with high stable yield in long-time.The method is characterized in that in each tubular reactor that configures vertically two or more reaction zones that each district's filling different catalysts is filled out catalyzer Bi and/or Fe content and reduced with the ratio of Mo content from gas inlet end to gas outlet end.CN1672790A provides a kind of catalyzing propone aldehyde gaseous oxidation system acrylic acid catalyzer, described catalyzer comprises molybdenum and vanadium, also comprise at least one volatile catalyst toxic component, its amount is 10 to 100ppb quality through ion chromatography measurement, this catalyzer can reduce the temperature of hot spot, and suppresses the reduction of the reaction efficiency of thermal destruction.Specific practice is that, by the volatility toxic component of specified quantitative being comprised and originally having in highly active catalyzer, catalytic activity declines momently, can reduce the temperature of hot spot.CN1165055A is by after dividing catalytic active component and being loaded on carrier, calcines the generation that the catalyzer of load sharing suppresses focus, and the median size of catalyzer is 4～16mm, and the median size of carrier is 3～12mm, and calcining temperature is 500～600 ℃.CN1314331A provides the catalyzer of a kind of Mo-W-Bi-Fe of containing, this catalyzer, by the mode that changes the kind of possessive volume calcining temperature and/or alkali metal and/or quantity and increase to outlet one side from the inlet side of unstripped gas according to catalyst activity, is filled reaction zone successively with described multiple types catalyzer.Catalyzer reaction tubes axially on be at least divided into two-layerly, this catalyzer is the multiple types catalyzer with different activities level, can be by changing calcining temperature and/or wherein kind and/or the quantity of alkali metal obtain.The appearance of focus or the hot polymerization collection on focus are effectively suppressed.CN1472008A provides a kind of supported catalyst, and this support of the catalyst has multidimensional structure, with the self supporting type multidimensional carrier structure of premolding (as foam, one-piece construction, fabric or other) or comprise Nb
2o
5, trichroite, partially stabilized zirconium white, ceramic fiber or its mixture carrier, in succession on described carrier deposition comprise any order at least one molybdenum-containing layer, at least one containing vanadium layer, at least one forms load carrier containing tellurium layer and at least one containing the catalyst composition of X layer, after roasting supported catalyst.For paraffinic hydrocarbons, be oxidized to unsaturated carboxylic acid and become unsaturated nitrile with ammoxidation of paraffins, enough transformation efficiencys and applicable selectivity are provided.
All there is a problem in the method that above-mentioned inhibition focus produces, the catalyzer being filled in reaction tubes has all been diluted with various forms from the inlet to the outlet, both after having made catalyst runs some cycles, active decline also can not change thinning ratio, catalyzer also cannot provide higher activity again, not only load, dismantle, separated, reclaim catalyzer and make troubles, and can reduce the reactive behavior of catalyzer, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.
In addition, under hot conditions, in catalyzer, part active ingredient molybdenum loses because of distillation from catalyst surface.Washing away also of propylene, air and water vapour mixed airflow can make the loss of active component in catalyzer.For suppressing the loss of molybdenum distillation, cause active decay, CN1121504, by mixing copper component and zirconium and/or Titanium and/or the Cerium with specified particle diameter and specific surface area, can suppress dissipation effect and the over reduction of molybdenum composition; The effect that CN1445020 adds a small amount of tellurium to play to stablize free molybdic oxide and molybdic acid copper crystal structure, sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 be take molybdenum, vanadium, copper, tungsten and/or niobium as main ingredient, and the composite oxides or its hopcalite that form with other element form the loss that catalyzer suppresses molybdenum.
Summary of the invention
The object of this invention is to provide a kind of method that corresponding unsaturated aldehyde is produced in propylene or selective isobutene oxidation.Different from the method for above-mentioned reduction focus, the present invention uses a kind of double-deck compound multi-metal-oxide catalyst that has, from inside to exterior active combination of components substrate concentration, there is gradient difference in this granules of catalyst, can effectively reduce fixed bed single tube reactor localized heat and gather, suppress emerging of focus.This catalyzer has reactive behavior and selectivity is high, the feature of good stability.
The method of Propylene Selectivity oxidation acrolein provided by the invention is as follows: adopt fixed bed single tube reactor; Reaction raw materials propylene, water, air more than 120 ℃ enter reactor after preheating through preheater, salt bath heating, and reaction process condition is: 290～335 ℃ of salt temperatures, preferably 300～330 ℃; Air speed 800～1400h
-1, preferred 800～1200h
-1, feed composition: propylene 8～13 volume %, air 69～75 volume %, water vapour 15～18%; It is compound multi-metal-oxide catalyst that Mo-Bi is housed in reactor, and the chief component of this catalyzer is by general formula (I) expression below
Mo
aBi
bFe
cNi
dSi
fA
mB
nO
i (I)
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Ni is nickel, and Si is silicon, and silicon is the carrier adding in catalyzer, and A is at least one element being selected from cobalt, niobium, zinc, vanadium, lanthanum, potassium; B is at least one element being selected from alkaline-earth metal; O is oxygen; A, b, c, d, f, m and n represent respectively each element atomic ratio, and wherein a is a number of 12～14, and b is a number of 2～10, preferably 2～6; C is a number of 1～8, preferably 1～5; D is a number of 1～10, preferably 3～8; F is a number of 0.5～50, m is a number of 0.5～5, n is a number of 0～3, i is the numerical value by the oxygen decision of each oxide compound, described compound multi-metal-oxide catalyst has interior outer double-layer structure, every layer of catalyzer chief component is identical, but the total content of one or more in silicon-dioxide, aluminum oxide or silicon carbide is different, the total content of one or more in outer silicon-dioxide, aluminum oxide or silicon carbide is than the height of internal layer parent, in molar content, each component concentration concentration ratio internal layer parent of catalyst outer layer is low.
Catalyzer of the present invention is bilayer structure, from inside to exterior active combination of components substrate concentration, there is gradient difference in catalyzer, mainly by add the materials such as different amount silicon-dioxide, aluminum oxide, silicon carbide to be achieved concentration difference at ectonexine, that is to say, the total content of one or more in outer silicon-dioxide, aluminum oxide or silicon carbide is higher than internal layer parent, in molar content, outer each constituent content is lower by 0.5～30% than this constituent content of internal layer, and preferably 1～15%.Catalyst inner layer of the present invention also can not add silicon.
The present invention preferably adds active ingredient lanthanum, general formula for composition (II) expression of catalyzer, and in general formula (II), m is a number of 0.1～2, n is a number of 0.1～1.Lanthanum and nickel, cobalt etc. can form stable crystal phase structure, thereby suppress part active ingredient molybdenum, from catalyst surface, lose because of distillation, and before and after catalyst reaction, active ingredient molybdenum content is substantially constant, delays active deterioration rate, catalyst activity and good stability.
Mo
aBi
bFe
cNi
dSi
fLa
mB
nO
i (II)
The present invention also can add a small amount of alkaline-earth metal, and in general formula (I), m is a number of 0.1～2, and n is a number of 0.1～2.
Two-layer compound multi-metal-oxide catalyst of the present invention adopts common preparation method, as adopted following step preparation.
First, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, Bi, A in the compound of Fe, Ni, Si and general formula (I)
mb
neach elementary composition compound dissolution relating to and mix, carry out forming internal layer parent slurries after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, method according to Kaolinite Preparation of Catalyst internal layer parent slurries is prepared outer layer catalyst slurries, in outer layer catalyst slurries preparation process, add one or more in silicon-dioxide, aluminum oxide or silicon carbide, make in outer layer catalyst slurries each concentration of element lower than the concentration of this element of adjacent inner layer;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
Catalyst inner layer parent of the present invention after moulding and outer all need to be at 300～500 ℃ after coating roasting 3～10h, compare not the catalyzer of roasting respectively, repeatedly roasting can improve activity and the stability of catalyzer.Can be that open roasting can be also enclosed roasting, calcination atmosphere can be the rare gas elementes such as helium, nitrogen, argon gas.
Catalyst layer easily chaps during thick roasting very much, for fear of be full of cracks be preferably in apply after 55～125 ℃ of oven dry, and then roasting.The outer layer catalyst bed thickness that is coated on internal layer parent is 1.0～2.5mm, preferably 1.5～2mm.
The compound of each component of catalyzer of the present invention can be used nitrate, ammonium salt, vitriol, oxide compound, oxyhydroxide, muriate, acetate of each element etc.Active ingredient is not all used nitrate as far as possible, the oxide contaminant atmosphere producing when roasting, and be not easy moulding, production schedule is slow, but nitrate is easy to dissolve, and nitrate is preferably used together with other forms of compound, be easy to moulding, faster production efficiency.
After catalyst inner layer parent slurries of the present invention are dried, conventionally preferably adopt the forming methods such as extrusion moulding, granulating and forming, compression molding to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Compound multi-metal-oxide catalyst of the present invention is preferably used binding agent while applying, and makes ectonexine catalyzer bonding more firm.At internal layer parent, under rolling condition, spray binding agent and infiltrate surface, then the outer layer catalyst powder for preparing of spraying, also internal layer parent can be put into the outer layer catalyst slurries that the prepare coating of rolling.Binding agent is selected from one or more in water, alcohols or ethers.Alcohols is as ethanol, propyl alcohol, butanols; Ethers is as ether and butyl ether.
Each of catalyzer of the present invention layer surface be uneven, surface irregularity preferably, is conducive to apply, and bonding is more firm between layers.
The present invention has bilayer structure, and internal layer also can be called internal layer parent.
The present invention, in order to improve intensity, the efflorescence degree of catalyzer, can add one or more in glass fibre, graphite, pottery or various whisker in above-mentioned outer layer catalyst.
Catalyzer of the present invention can directly be used, and also can be carried on inert support and use.Related inert support can be one or more mixture of aluminum oxide, silicon-dioxide, silicon carbide, magnesium oxide etc.
At the initial stage feeding intake at reaction unit, catalyst activity is high, so be easy to produce focus or produce heat built-up on tubular reactor bed, catalyzer is easy to sintering, and this loses concerning suitability for industrialized production propenal vinylformic acid is very serious.In raw material, pass into a certain amount of water vapour, because specific heat of water is large, can take away a large amount of reaction heat, but water vapour input greatly often makes catalyst member active ingredient solution-off, make active decline.
The present invention has double-deck compound multi-metal-oxide catalyst by preparation, make granules of catalyst have gradient difference from inside to exterior active combination of components substrate concentration, and the every outer active ingredient concentration of catalyzer is lower than its adjacent inner layer active ingredient concentration, like this, under high-speed reaction conditions, because the active ingredient concentration of catalyzer outside surface is low, so corresponding activity is also low, therefore can effectively suppress emerging of focus and gathering of heat, reduce the growing amount of by product (as hydrocarbon), improve the selectivity of object product.This has double-deck catalyzer and has good water repelling property.And when catalyst runs is after for some time, catalyzer has release effects, under mixed airflow long period is washed away, even if catalyst surface active component has part to run off, but because internal layer catalyst active ingredient concentration is higher, can play supplementary effect, so can keep the production lasting stability of propenal to carry out.
The method of propenal is prepared in Propylene Selectivity provided by the invention oxidation, can effectively reduce fixed bed single tube reactor localized heat and gather, suppress focus emerge and active ingredient molybdenum runs off because of distillation, catalyzer is easy-sintering not.Under high-speed part, this catalyzer has that activity and selectivity is high, the feature of good stability.
Embodiment
The method of Propylene Selectivity oxidation is described with specific embodiment, but scope of the present invention is not limited to these embodiment below.The propylene that following examples adopt is the high density propylene of propylene content >=99.6% (volume fraction).
Mole number * 100% of propylene in the total mole number/raw material of propylene conversion (%)=propylene reaction
Propenal selectivity (%)=propylene is converted into total mole number * 100% of propenal mole number/propylene reaction
Embodiment 1:
The preparation of catalyzer 1
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation condition, get 160 grams of ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in 500ml pure water, obtain slurries (1), then get 142.5 grams of nickelous nitrates, 7 grams of saltpetre, 113 grams of iron nitrates and be dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, fully be uniformly mixed, obtain slurries (2).Get again 237.7 grams of Bismuth trinitrates, under agitation condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in slurries (4), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
In active ingredient slurries (a), add 16 grams of silicon-dioxide, 80 ℃ of strong stirrings carry out coprecipitation reaction post-heating for 2 hours and are dried, in nitrogen with 160 ℃ of thermal treatments 3 hours, then through banded extruder extrusion molding, be the hollow columnar particle of φ 4.5 * 5mm, dry rear 450 ℃ of roastings 4 hours for 75 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13bi
7fe
4ni
7k
1si
3.8
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Preparation with active ingredient slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 32 grams of silica powders are carried out to 40 minutes post-heating of coprecipitation reaction dry, in nitrogen, with 150 ℃ of thermal treatments 3 hours, then 500 ℃ of roastings were 4 hours, through pulverizing, grind, sieving, processed to obtain catalyst outer layer powder.
Step 3: Kaolinite Preparation of Catalyst 1
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray ethanolic soln, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coat-thickness is at 1.5～2.0mm, and 50 ℃ of oven dry of gained catalyzer obtain catalyzer 1 for 4 hours by 500 ℃ of roastings.
Propylene oxidation method
Fixed bed single tube reactor internal diameter 20mm, inside establish thermopair, reactor feedstocks gas inlet side packs the above-mentioned catalyzer 1 of 30ml into, and reaction raw materials propylene, water, air more than 120 ℃ enter reactor after preheating through preheater, salt bath heating, oxidizing reaction processing condition are: 310 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1000h
-1import the mixed gas of propylene 9.3 volume %, air 72.2 volume %, water vapour 18.5 volume %.361 ℃ of hot(test)-spot temperatures, propylene conversion 98.0%, propenal selectivity 85.3%.
Comparative example 1:
The internal layer parent of catalyzer 1 of take is comparative catalyst 1, through banded extruder extrusion molding, is then the hollow columnar particle of φ 5 * 5mm, and propylene oxidation method is with catalyzer 1.Propylene conversion 98.1%, propenal selectivity 83.7%.369 ℃ of hot(test)-spot temperatures, propylene conversion 98.6%, propenal selectivity 83.2%.
Comparative example 2:
The skin of catalyzer 1 of take is comparative catalyst 2, through banded extruder extrusion molding, is then the hollow columnar particle of φ 5 * 5mm, and propylene oxidation method is with catalyzer 1.358 ℃ of hot(test)-spot temperatures, propylene conversion 97.2%, propenal selectivity 84.0%.
Embodiment 2:
The preparation of catalyzer 2
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation condition, get 173 grams of ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in 500ml pure water, obtain slurries (1), then get 81.4 grams of nickelous nitrates, 12.9 grams of magnesium nitrates, 183.8 grams of iron nitrates and be dissolved in (water temperature is more than 65 ℃) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Get again 169.8 grams of Bismuth trinitrates, under agitation condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in slurries (4), obtain active ingredient slurries (a).
(2) preparation of catalyst Precursors
In slurries (a), add 18 grams of silicon-dioxide, 80 ℃ of strong stirrings carry out coprecipitation reaction post-heating for 2 hours and are dried, in nitrogen with 160 ℃ of thermal treatments 3 hours, then through banded extruder extruding, rolling, be a granulated into the ball shape that diameter is 2mm, dry rear 450 ℃ of roastings 4 hours for 125 ℃, make catalyst Precursors, this catalyst Precursors consists of: Mo
14bi
5fe
6.5ni
4mg
1
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Preparation with active ingredient slurries (a) in embodiment 2 catalyst inner layer parents is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 35 grams of silica powders are carried out answering 50 minutes post-heating dry after co-precipitation, and in nitrogen, with 160 ℃ of thermal treatments 3 hours, then 500 ℃ of roastings were 4 hours, through pulverizing, grind, sieving, processed to obtain catalyst outer layer powder.
Step 3: Kaolinite Preparation of Catalyst 2
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray ethanolic soln, fully wetting catalyst inner layer parent, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coat-thickness is when 0.8～1.0mm, taking-up internal layer parent is put into another round bottom container rotation and is sprayed ethanolic soln after one to two minute again, then put into the round bottom container continuation coating that catalyst outer layer is housed, until coat-thickness stops applying when 1.0～2.0mm, 95 ℃ of oven dry of gained catalyzer obtain catalyzer 2 for 3 hours by 550 ℃ of roastings.
Propylene oxidation method
Fixed bed single tube reactor internal diameter 20mm, inside establish thermopair, reactor feedstocks gas inlet side packs the above-mentioned catalyzer 2 of 35ml into, and reaction raw materials propylene, water, air more than 120 ℃ enter reactor after preheating through preheater, salt bath heating, oxidizing reaction processing condition are: 315 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 850h
-1import the mixed gas of propylene 8 volume %, air 68 volume %, water vapour 24 volume %.363 ℃ of hot(test)-spot temperatures, propylene conversion 98.2%, propenal selectivity 85.9%.
Comparative example 3:
The internal layer parent of catalyzer 2 of take is comparative catalyst 3, makes the ball that diameter is 4mm, and propylene oxidation method is with catalyzer 2.369 ℃ of hot(test)-spot temperatures, propylene conversion 98.4%, propenal selectivity 83.4%.
Comparative example 4:
The skin of catalyzer 2 of take is comparative catalyst 4, makes the ball that diameter is 4mm, and propylene oxidation method is with catalyzer 2.362 ℃ of hot(test)-spot temperatures, propylene conversion 97.6%, propenal selectivity 84.2%.
Embodiment 3:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Preparation method and raw materials used identical (following examples are identical) with embodiment 1 catalyst activity component slurries (a), just add 40.7 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 6.5 grams of magnesium nitrates.
(2) preparation of catalyst inner layer parent
In slurries (a), add 15 grams of silicon-dioxide, 80 ℃ of strong stirrings carry out coprecipitation reaction post-heating for 2 hours and are dried, in nitrogen with 160 ℃ of thermal treatments 3 hours, then through banded extruder extrusion molding, be the hollow columnar particle of φ 4.5 * 5mm, dry rear 450 ℃ of roastings 4 hours for 105 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13bi
3fe
4ni
6co
2mg
0.5
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Preparation with active ingredient slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 62 grams of silica powders are carried out answering 50 minutes post-heating dry after co-precipitation, and in nitrogen, with 160 ℃ of thermal treatments 3 hours, then 500 ℃ of roastings were 4 hours, through pulverizing, grind, sieving, processed to obtain catalyst outer layer powder.
Step 3: Kaolinite Preparation of Catalyst 3
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray diethyl ether solution, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coat-thickness is at 1.5～2.0mm, and 80 ℃ of oven dry of gained catalyzer obtain catalyzer 3 for 3 hours by 550 ℃ of roastings.
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 3 of 30ml into, reaction raw materials propylene, water, air enter reactor after 160 ℃ of preheatings of preheater, salt bath heating, and oxidizing reaction processing condition are: 305 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1100h
-1import the mixed gas of propylene 10 volume %, air 72 volume %, water vapour 18 volume %.361 ℃ of hot(test)-spot temperatures, propylene conversion 98.3%, propenal selectivity 85.1%.
Comparative example 5:
The internal layer parent of catalyzer 3 of take is comparative catalyst 5, through banded extruder extrusion molding, is then the hollow columnar particle of φ 5 * 5mm, and propylene oxidation method is with catalyzer 3.368 ℃ of hot(test)-spot temperatures, propylene conversion 98.5%, propenal selectivity 84.4%.
Embodiment 4:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
Preparation method with embodiment 2 catalyst inner layer parents is identical, just adds 16.7 grams of zinc nitrates, 16.4 grams of cesium nitrates, adds 5.2 grams of silicon oxide, and this catalyst inner layer parent consists of: Mo
12bi
8fe
1.5ni
9zn
0.8cs
1.2
Step 2: Kaolinite Preparation of Catalyst is outer
With the preparation method of embodiment 2 catalyst outer layer and raw materials used identical, just add 22.4 grams of silicon oxide and 15 grams of aluminum oxide.
Step 3: Kaolinite Preparation of Catalyst 4
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyzer, spray ethanolic soln, under the condition of fully wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coat-thickness is at 0.8～1.5mm, and 120 ℃ of oven dry of gained catalyzer obtain catalyzer 4 for 5 hours by 450 ℃ of roastings.
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 4 of 30ml into, reaction raw materials propylene, water, air more than 120 ℃ enter reactor after preheating through preheater, salt bath heating, and oxidizing reaction processing condition are: 310 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1200h
-1import the mixed gas of propylene 12 volume %, air 71 volume %, water vapour 17 volume %.358 ℃ of hot(test)-spot temperatures, propylene conversion 98.4%, propenal selectivity 85.6%.
Comparative example 6:
The outer layer catalyst of catalyzer 4 of take is comparative catalyst 6, makes the ball that diameter is 4mm, and propylene oxidation method is with catalyzer 4.357 ℃ of hot(test)-spot temperatures, propylene conversion 97.1%, propenal selectivity 84.0%.
Embodiment 5:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
Preparation method with embodiment 2 catalyst inner layer parents is identical, adds 7 grams of saltpetre, 9.1 grams of lanthanum nitrates, 10.2 grams of silicon oxide, and this catalyst inner layer parent consists of: Mo
12bi
9fe
3ni
8k
1la
0.4
Step 2: Kaolinite Preparation of Catalyst is outer
Preparation with embodiment 2 catalyst outer layer is identical, just adds 38.1 grams of silicon oxide and 10.6 grams of silicon carbide.
Step 3: Kaolinite Preparation of Catalyst 5
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray distilled water, under the condition of fully wetting catalyst inner layer parent, spray the inferior outer layer catalyst powder of step 2 gained, apply, coat-thickness is at 0.8～1.2mm, and 45 ℃ of oven dry of gained catalyzer obtain catalyzer 5 for 6 hours by 500 ℃ of roastings.
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 5 of 35ml into, reaction raw materials propylene, water, air enter reactor after 150 ℃ of preheatings of preheater, salt bath heating, and oxidizing reaction processing condition are: 320 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1400h
-1import the mixed gas of propylene 11 volume %, air 71 volume %, water vapour 18 volume %.368 ℃ of hot(test)-spot temperatures, propylene conversion 98.5%, propenal selectivity 86.3%.Keep processing condition constant, Propylene Selectivity oxidizing reaction 500 hours, 367 ℃ of hot(test)-spot temperatures, propylene conversion 98.1%, propenal selectivity 86.1%.The difficult losses such as catalyzer effectively suppresses focus, catalyst reaction front and back active ingredient molybdenum, catalyst catalytic performance is stable.After running in 500 hours, active, selectivity can reach live catalyst level substantially, and catalyst stability is good.
Comparative example 7:
The internal layer catalyst of catalyzer 5 of take is comparative catalyst 7, but not containing lanthanum, catalyzer consists of Mo
12bi
9fe
3ni
8k
1, make the ball that diameter is 4mm, propylene oxidation method is with catalyzer 5.378 ℃ of hot(test)-spot temperatures, propylene conversion 98.5%, propenal selectivity 84.3%.Keep processing condition constant, Propylene Selectivity oxidizing reaction 500 hours, 376 ℃ of hot(test)-spot temperatures, propylene conversion 98.0%, propenal selectivity 82.0%.
With catalyzer 5, prepare propenal and compare with comparative catalyst 7: through the oxidizing reaction of 500 hours, catalyzer 5 effectively suppressed the generation of focus, the difficult losses such as active ingredient molybdenum, catalyst activity is stable, meets oxidizing reaction long period and carries out.Comparative example 7 catalyzer can not effectively suppress focus, and poor selectivity is reacted after 500 hours rear catalysts activity under the washing away of the mixed airflows such as water vapour and obviously declined.
Embodiment 6:
With the preparation method of embodiment 5 catalyzer and raw materials used identical, internal layer adds 8 grams of silicon oxide, and skin adds 19.7 grams of silicon oxide, and catalyst inner layer parent consists of: Mo
12bi
5fe
3.5ni
3mg
0.5la
1.1
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 6 of 35ml into, reaction raw materials propylene, water, air enter reactor after 180 ℃ of preheatings of preheater, salt bath heating, and oxidizing reaction processing condition are: 330 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1300h
-1import the mixed gas of propylene 11 volume %, air 72 volume %, water vapour 17 volume %.370 ℃ of hot(test)-spot temperatures, propylene conversion 98.4%, propenal selectivity 86.8%.
Embodiment 7:
The preparation of catalyzer 7
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation condition, get 160 grams of ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in 500ml pure water, obtain slurries (1), then get 93.6 grams of nickelous nitrates, 99 grams of iron nitrates are dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, fully be uniformly mixed, obtain slurries (2).Get again 203.7 grams of Bismuth trinitrates, under agitation condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in slurries (4), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
In active ingredient slurries (a), add 7 grams of silicon-dioxide, 80 ℃ of strong stirrings carry out coprecipitation reaction post-heating for 2 hours and are dried, in nitrogen with 160 ℃ of thermal treatments 3 hours, then through banded extruder extrusion molding, be the hollow columnar particle of φ 4.5 * 5mm, dry rear 450 ℃ of roastings 4 hours for 50 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13bi
6fe
3.5ni
4.6
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Preparation with active ingredient slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) are carried out to 40 minutes post-heating of coprecipitation reaction with 12 grams of silica powders and 4 grams of Graphite Powder 99s to be dried, in nitrogen with 150 ℃ of thermal treatments 3 hours, then 480 ℃ of roastings are 4 hours, through pulverizing, grind, sieving, process to obtain catalyst outer layer powder.
Step 3: Kaolinite Preparation of Catalyst 7
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray ethanolic soln, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coat-thickness is at 1.0～2.0mm, and 80 ℃ of oven dry of gained catalyzer obtain catalyzer 7 for 4 hours by 450 ℃ of roastings.
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 7 of 35ml into, reaction raw materials propylene, water, air enter reactor after 180 ℃ of preheatings of preheater, salt bath heating, and oxidizing reaction processing condition are: 320 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 850h
-1import the mixed gas of propylene 8.5 volume %, air 67.5 volume %, water vapour 24 volume %.359 ℃ of hot(test)-spot temperatures, propylene conversion 98.0%, propenal selectivity 85.2%.
Claims (11)
1. a method for propylene oxidation acrolein, adopts fixed bed single tube reactor, it is characterized in that; Reaction raw materials propylene, water, air more than 120 ℃ enter reactor after preheating through preheater, salt bath heating, and reaction process condition is: 290～335 ℃ of salt temperatures, air speed 800～1400h
-1, feed composition: propylene 8～13 volume %, air 69～75 volume %, water vapour 15～18 volume %; It is compound multi-metal-oxide catalyst that Mo-Bi is housed in reactor, and the chief component of this catalyzer represents Mo by leading to formula I below
abi
bfe
cni
dsi
fa
mb
no
i(I)
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Ni is nickel, and Si is silicon, and silicon is the carrier adding in catalyzer, and A is at least one element being selected from cobalt, niobium, zinc, vanadium, lanthanum, potassium; B is at least one element being selected from alkaline-earth metal; O is oxygen; A, b, c, d, f, m and n represent respectively each element atomic ratio, wherein a is a number of 12～14, b is a number of 2～10, c is a number of 1～8, d is a number of 1～10, f is a number of 0.5～50, m is a number of 0.5～5, n is a number of 0～3, i is that described O composite metallic oxide catalyst has interior outer double-layer structure by the numerical value of the oxygen decision of each oxide compound, and the total content of outer silicon-dioxide is than the height of internal layer parent, in molar content, each component concentration concentration ratio internal layer parent of catalyst outer layer is low.
2. the method for propylene oxidation acrolein according to claim 1, is characterized in that 300～330 ℃ of salt temperatures.
3. the method for propylene oxidation acrolein according to claim 1, is characterized in that air speed 800～1200h
-1.
4. the method for propylene oxidation acrolein according to claim 1, is characterized in that used catalyst is bilayer structure, and in molar content, outer each constituent content is lower by 0.5～30% than this constituent content of adjacent inner layer successively.
5. the method for propylene oxidation acrolein according to claim 4, is characterized in that outer each constituent content of used catalyst is lower by 1～15% than this constituent content of adjacent inner layer successively.
6. the method for propylene oxidation acrolein according to claim 1, is characterized in that b in the logical formula I of used catalyst is a number of 2～6, and c is a number of 1～5, and d is a number of 4～8.
7. the method for propylene oxidation acrolein according to claim 1, is characterized in that in the logical formula I of used catalyst, A is selected from lanthanum, and catalyzer forms as shown in logical formula II: Mo
abi
bfe
cni
dsi
fla
mb
no
i(II), wherein m is a number of 0.1～2, n is a number of 0.1～1.
8. the method for propylene oxidation acrolein according to claim 1, is characterized in that in the logical formula I of used catalyst, A is at least one element being selected from cobalt, niobium, zinc, vanadium, lanthanum, potassium; B is at least one element being selected from alkaline-earth metal, and m is a number of 0.1～2, and n is a number of 0.1～2.
9. according to the method for the propylene oxidation acrolein described in claim 1～8 any one, it is characterized in that the preparation method of used catalyst comprises the steps:
First, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, Bi, A in the compound of Fe, Ni, Si and logical formula I
mb
neach elementary composition compound dissolution relating to and mix, carry out forming internal layer parent slurry after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, prepare outer layer catalyst slurry, in outer layer catalyst slurry preparation process, add silicon oxide;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
10. the method for propylene oxidation acrolein according to claim 9, it is characterized in that used catalyst internal layer parent after moulding and outer after coating at 300～580 ℃ roasting 3～10h, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
The method of 11. propylene oxidation acroleins according to claim 9, is characterized in that using binding agent, binding agent to be selected from one or more in alcohols or ethers when used catalyst applies.
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| CN104646011B (en) * | 2013-11-19 | 2017-06-06 | 中国石油天然气股份有限公司 | Low-carbon olefin oxidation catalyst and preparation method thereof |
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