CN102992980A - Method for preparing acrolein - Google Patents
Method for preparing acrolein Download PDFInfo
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- CN102992980A CN102992980A CN201110265436XA CN201110265436A CN102992980A CN 102992980 A CN102992980 A CN 102992980A CN 201110265436X A CN201110265436X A CN 201110265436XA CN 201110265436 A CN201110265436 A CN 201110265436A CN 102992980 A CN102992980 A CN 102992980A
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- Prior art keywords
- catalyst
- catalyzer
- propylene
- preparation
- propylene oxidation
- 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.)
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- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 162
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 238000002360 preparation method Methods 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 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 83
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 83
- 239000002002 slurry Substances 0.000 claims description 59
- 238000007254 oxidation reaction Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 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
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 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
- 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
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [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
- 239000011701 zinc Substances 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
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 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
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000004480 active ingredient Substances 0.000 description 35
- 230000000694 effects Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 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
- 238000012545 processing Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 239000002245 particle Substances 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
- 206010013786 Dry skin Diseases 0.000 description 4
- 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
- 238000011049 filling Methods 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
- 239000011777 magnesium Substances 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
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011068 loading method Methods 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
- 238000012856 packing Methods 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
- 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
- 230000002730 additional effect Effects 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
- 239000012467 final product 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
- 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
- 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
- 238000005406 washing Methods 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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 the method that corresponding unsaturated aldehyde is produced in a kind of propylene or selective isobutene oxidation, be particularly useful for Propylene Selectivity is oxidized to propenal.
Background technology
At present, industrially namely usually adopt fixed-bed reactor mainly with propylene two-step oxidation legal system vinylformic acid, the propylene initial oxidation becomes propenal, and propenal is reoxidised into vinylformic acid.It is strong exothermal reaction that the propylene gas phase catalytic oxidation reaction prepares propenal, moment is assembled a large amount of reaction heat in reactor, form hot localised points, if can not remove timely and effectively reaction heat, the heat that moment is gathered is constantly accumulated, will cause the catalyst activity component loss, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause aggravating the formation of by product because of over oxidation reaction, even cause and uncontrolled reaction make sintering of catalyst.
The appearance of " progress of oxidation acrylic acid synthesizing process and catalyzer " (petrochemical complex, the 7th phase of the 39th volume in 2010) social focus also can make the catalyst damage evil, shortens the work-ing life of catalyzer.Take 80,000 ton/years of acroleic acid devices as example, propylene oxidation prepares and needs more than 25000 tubulation in the acrolein reaction device, and acrolein oxidation prepares also needs more than 25000 tubulation in the vinylformic acid reactor, load altogether more than 100 ton of propenal, vinylformic acid catalyzer.More than 50,000 reaction tubes, the filling of catalyzer guarantee 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, carry out under cold condition as much as possible for propenal, acrylic acid production, because the reaction needed salt bath heating, its energy consumption of keeping production also is huge spending; Because the generation of focus is high temperature resistant to the requirement of reaction tubes tubing, for up to ten thousand reaction tubess, the tubing expense is exactly a very large cost.Therefore, if the generation of establishment 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 the focus, namely by preparing multiple catalyzer with different possessive volumes, and the mode from the unstripped gas inlet side to the minimizing of outlet one side catalyzer possessive volume, fill successively reaction tubes, but the possessive volume of catalyzer is subjected 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 with different activities in reaction tubes, according to active uprise arranged sequentially above-mentioned several catalyst-loaded from the entrance of unstripped gas to outlet.The method that other is also arranged, for example inert substance and catalyst mix, reduce the activity of catalyzer, be loaded into the reactor inlet place, Japan special permission disclose 10614/1972 to sneak into heat resistanceheat resistant point formation catalyzer in catalyzer is inert substance with catalyst dilution, and Japanese Patent Publication 36739/1987 is made catalyzer the method for tubulose.The catalyst loading that the unstripped gas ingress reduces with active ingredient is arranged again.CN01111960.8 uses fixed bed shell and tube reactor, in the presence of catalyzer, prepare propenal and acrylic acid by the propylene gas phase catalytic oxidation reaction, the method is the generation of focus or the hot polymerization collection on focus in the 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 the specification sheets.The feature of the method is the multiple catalysts that preparation has above-mentioned composition, but (α) temperature of possessive volume, (β) calcining and/or (γ) kind and/or the quantity of alkali metal is different, and press the mode of catalyst activity from the 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 the Mo-Bi-Fe compound, produce propenal and acrylic acid by the vapor phase propylene oxide, described catalyzer is filled in the 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 each distinguishes the filling different catalysts in each tubular reactor that disposes vertically two or more reaction zones, the ratio of namely filling out Bi the catalyzer and/or Fe content and Mo content from the gas inlet end to gas outlet end reduces.CN1672790A provides a kind of catalyzing propone aldehyde gaseous oxidation system acrylic acid catalyzer, described catalyzer comprises molybdenum and vanadium, also comprise at least a 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, comprises and originally has in the highly active catalyzer by the volatility toxic component that makes specified quantitative, and catalytic activity descends momently, can reduce the temperature of hot spot.CN1165055A by catalytic active component is divided be loaded on the carrier after, calcine the generation that the catalyzer of load sharing suppresses focus, the median size of catalyzer is 4～16mm, the median size of carrier is 3～12mm, calcining temperature is 500～600 ℃.CN1314331A provides the catalyzer of a kind of Mo-W-Bi-Fe of containing, this catalyzer by changing possessive volume calcining temperature and/or alkali metal kind and/or quantity and according to catalyst activity from the inlet side of unstripped gas to the mode that outlet one side increases, fill successively reaction zone with described multiple types catalyzer.Catalyzer reaction tubes axially on be divided at least 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 the focus are by establishment.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 (such 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 described carrier deposition comprise any order at least one molybdenum-containing layer, at least one contains the vanadium layer, at least one contains the catalyst composition that tellurium layer and at least one contain the X layer and forms the load carrier, after roasting supported catalyst.Be oxidized to unsaturated carboxylic acid for paraffinic hydrocarbons and become unsaturated nitrile with ammoxidation of paraffins, enough transformation efficiencys and suitable selectivity are provided.
All there is a problem in the method that above-mentioned inhibition focus produces, the catalyzer that is filled in the reaction tubes all has been diluted with various forms from the inlet to the outlet, active decline also can not change thinning ratio after both having made the catalyst runs some cycles, catalyzer also can't provide higher activity again, not only loading, dismantle, separate, reclaim catalyzer makes 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, part active ingredient molybdenum loses because of distillation from catalyst surface in the catalyzer.Propylene, air and water vapour mixed airflow wash away the loss of active component that also can make in the catalyzer.For the loss that suppresses the molybdenum distillation causes active decay, CN1121504 can suppress dissipation effect and the over reduction of molybdenum composition by mixing copper component and zirconium and/or Titanium and/or Cerium with specified particle diameter and specific surface area; CN1445020 adds a small amount of tellurium and plays stable free molybdic oxide and the effect of molybdic acid copper crystal structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is take molybdenum, vanadium, copper, tungsten and/or niobium as main ingredient, and the composite oxides or its hopcalite that consist of with other element form the loss that catalyzer suppresses molybdenum.
Summary of the invention
The purpose of this invention is to provide the method that corresponding unsaturated aldehyde is produced in a kind of 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, there is gradient difference in this granules of catalyst to exterior active combination of components substrate concentration internally, 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 characteristics of good stability.
The method of Propylene Selectivity oxidation acrolein provided by the invention is as follows: adopt the fixed bed single tube reactor; Reaction raw materials propylene, water, air enter reactor after the preheating through preheater more than 120 ℃, salt bath heating, and reaction process condition is: 290～335 ℃ of salt temperatures, preferred 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 the reactor, and the chief component of this catalyzer is represented by following general formula (I)
Mo
aBi
bFe
cNi
dSi
fA
mB
nO
i (I)
Wherein: Mo is molybdenum, and Bi is bismuth, and Fe is iron, and Ni is nickel, and Si is silicon, and silicon is the carrier that adds in the catalyzer, and A is at least a element that is selected from cobalt, niobium, zinc, vanadium, lanthanum, the potassium; B is at least a element that is selected from the 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, preferred 2～6; C is a number of 1～8, preferred 1～5; D is a number of 1～10, preferred 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 the silicon carbide is different, the total content of one or more in outer silicon-dioxide, aluminum oxide or the 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, there is gradient difference in catalyzer to exterior active combination of components substrate concentration internally, mainly be achieved concentration difference by add the materials such as different amount silicon-dioxide, aluminum oxide, silicon carbide at ectonexine, that is to say, the total content of one or more in outer silicon-dioxide, aluminum oxide or the silicon carbide is higher than internal layer parent, in molar content, outer each constituent content is than this constituent content of internal layer low 0.5～30%, preferred 1～15%.Catalyst inner layer of the present invention also can not add silicon.
The present invention preferably adds the active ingredient lanthanum, and the composition of catalyzer is a number of 0.1～2 with general formula (II) expression, the middle m of general formula (II), and n is a number of 0.1～1.Lanthanum and nickel, cobalt etc. can both form stable crystal phase structure, lose because of distillation from catalyst surface thereby suppress part active ingredient molybdenum, and active ingredient molybdenum content is substantially constant before and after the catalyst reaction, 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 m is a number of 0.1～2 in the general formula (I), and n is a number of 0.1～2.
Two-layer compound multi-metal-oxide catalyst of the present invention adopts common preparation method to get final product, as adopting following step preparation.
At first, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, A among the Bi, the compound of Fe, Ni, Si and general formula (I)
mB
nEach the elementary composition compound dissolution that relates to and mix, carry out forming after the co-precipitation internal layer parent slurries, oven dry, moulding, roasting get the catalyst inner layer parent;
Secondly, method according to Kaolinite Preparation of Catalyst internal layer parent slurries prepares the outer layer catalyst slurries, add in silicon-dioxide, aluminum oxide or the silicon carbide one or more in the outer layer catalyst slurries preparation process, so that each concentration of element is lower than the concentration of this element of adjacent inner layer in the outer layer catalyst slurries;
At last, the outer layer catalyst for preparing is coated on the catalyst inner layer parent successively, after roasting, gets finished catalyst.
Catalyst inner layer parent of the present invention is after the moulding and outer all need to compare not the respectively catalyzer of roasting at 300～500 ℃ of lower roasting 3～10h after coating, and repeatedly roasting can improve the active and stable of catalyzer.Can be that open roasting also can be enclosed roasting, calcination atmosphere can be the rare gas elementes such as helium, nitrogen, argon gas.
Catalyst layer chaps during thick roasting very much easily, 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 the internal layer parent is 1.0～2.5mm, preferred 1.5～2mm.
The compound of each component of catalyzer of the present invention can use 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 that when roasting, produces, and be not easy moulding, production schedule is slow, but nitrate is easy to dissolving, and nitrate preferably uses with other forms of compound, be easy to moulding, faster production efficient.
After the catalyst inner layer parent slurries of the present invention oven dry, the preferred forming methods such as extrusion moulding, granulating and forming, compression molding that adopt are processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical usually.
Compound multi-metal-oxide catalyst of the present invention preferably uses binding agent when applying, and makes ectonexine catalyzer bonding more firm.Be under the rolling condition at the internal layer parent and spray binding agent and infiltrate the surface, the outer layer catalyst powder for preparing of spraying more also can be put into the internal layer parent outer layer catalyst slurries that the prepare coating of rolling.Binding agent is selected from one or more in water, alcohols or the ethers.Alcohols such as ethanol, propyl alcohol, butanols; Ethers such 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 the internal layer parent.
Intensity, the efflorescence degree of the present invention in order to improve catalyzer can add in glass fibre, graphite, pottery or the various whisker one or more in above-mentioned outer layer catalyst.
Catalyzer of the present invention can directly use, and also can be carried on the 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 that reaction unit feeds intake, catalyst activity is high, so be easy to produce focus or produce heat built-up at the tubular reactor bed, catalyzer is easy to sintering, and this loses concerning suitability for industrialized production propenal vinylformic acid is very serious.Pass into a certain amount of water vapour in the raw material, because specific heat of water is large, can take away a large amount of reaction heat, make active decline but the water vapour input greatly often makes catalyst member active ingredient solution-off.
The present invention has double-deck compound multi-metal-oxide catalyst by preparation, make granules of catalyst have gradient difference to exterior active combination of components substrate concentration internally, and the every outer active ingredient concentration of catalyzer is lower than its adjacent inner layer active ingredient concentration, like this, under the high-speed reaction conditions, because the active ingredient concentration of catalyzer outside surface is low, so corresponding activity is also low, therefore can emerging of establishment focus and gathering of heat, reduce the growing amount of by product (such as hydrocarbon), improve the selectivity of purpose product.This has double-deck catalyzer and has good water repelling property.And when catalyst runs after for some time, catalyzer has release effects, wash away lower in the mixed airflow long period, even the catalyst surface active component has part to run off, but because internal layer catalyst active ingredient concentration is higher, can play additional effect, so can keep the production lasting stability of propenal to carry out.
Propylene Selectivity oxidation provided by the invention prepares the method for propenal, can effectively reduce fixed bed single tube reactor localized heat and gather, suppress focus emerge and the active ingredient molybdenum runs off because of distillation, catalyzer is easy-sintering not.This catalyzer has the characteristics of activity and selectivity height, good stability under high-speed spare.
Embodiment
The below illustrates the method for Propylene Selectivity oxidation with specific embodiment, but scope of the present invention is not limited to these embodiment.The propylene that following examples adopt is the high density propylene of propylene content 〉=99.6% (volume fraction).
The mole number of propylene * 100% in the total mole number/raw material of propylene conversion (%)=propylene reaction
Propenal selectivity (%)=propylene is converted into the total mole number of propenal mole number/propylene reaction * 100%
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 gram ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 142.5 the gram nickelous nitrates, 7 the gram saltpetre, 113 the gram iron nitrates be dissolved in (water temperature is more than 65 ℃) in the 1000ml pure water, fully mix, obtain slurries (2).Get again 237.7 gram 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 the slurries (4), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
In active ingredient slurries (a), add 16 gram silicon-dioxide, 80 ℃ of strong stirrings carried out coprecipitation reaction post-heating drying in 2 hours, in nitrogen with 160 ℃ of thermal treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion molding, 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 the embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 32 gram silica powders are carried out 40 minutes post-heating dryings of coprecipitation reaction, and with 150 ℃ of thermal treatments 3 hours, then 500 ℃ of roastings were 4 hours in nitrogen, processed to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 1
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic soln to catalyst Precursors, under the condition of abundant 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 namely got catalyzer 1 in 4 hours by 500 ℃ of roastings.
The propylene oxidation method
Fixed bed single tube reactor internal diameter 20mm, in establish thermopair, the reactor feedstocks gas inlet side above-mentioned catalyzer 1 of 30ml of packing into, reaction raw materials propylene, water, air enter reactor after the preheating through preheater more than 120 ℃, salt bath heating, the 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 Examples 1:
Take the internal layer parent of catalyzer 1 as comparative catalyst 1, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion molding then, the 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 Examples 2:
Take the skin of catalyzer 1 as comparative catalyst 2, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion molding then, the 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 gram ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 81.4 the gram nickelous nitrates, 12.9 the gram magnesium nitrates, 183.8 the gram iron nitrates be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Get again 169.8 gram 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 the slurries (4), obtain active ingredient slurries (a).
(2) preparation of catalyst Precursors
In slurries (a), add 18 gram silicon-dioxide, 80 ℃ of strong stirrings carried out coprecipitation reaction post-heating drying in 2 hours, in nitrogen with 160 ℃ of thermal treatments 3 hours, then be a granulated into the ball shape that diameter is 2mm through banded extruder extruding, rolling, 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 the embodiment 2 catalyst inner layer parents is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 35 gram silica powders are carried out answering 50 minutes post-heating dryings after the co-precipitation, and with 160 ℃ of thermal treatments 3 hours, then 500 ℃ of roastings were 4 hours in nitrogen, processed to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 2
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic soln to catalyst Precursors, abundant 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 putting into the round bottom container that catalyst outer layer is housed continues to apply, until coat-thickness stops to apply when 1.0～2.0mm, 95 ℃ of oven dry of gained catalyzer namely got catalyzer 2 in 3 hours by 550 ℃ of roastings.
The propylene oxidation method
Fixed bed single tube reactor internal diameter 20mm, in establish thermopair, the reactor feedstocks gas inlet side above-mentioned catalyzer 2 of 35ml of packing into, reaction raw materials propylene, water, air enter reactor after the preheating through preheater more than 120 ℃, salt bath heating, the 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 Examples 3:
Take the internal layer parent of catalyzer 2 as comparative catalyst 3, make the ball that diameter is 4mm, the propylene oxidation method is with catalyzer 2.369 ℃ of hot(test)-spot temperatures, propylene conversion 98.4%, propenal selectivity 83.4%.
Comparative Examples 4:
Take the skin of catalyzer 2 as comparative catalyst 4, make the ball that diameter is 4mm, the 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)
With preparation method and raw materials used identical (following examples are identical) of embodiment 1 catalyst activity component slurries (a), just add 40.7 gram Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 6.5 gram magnesium nitrates.
(2) preparation of catalyst inner layer parent
In slurries (a), add 15 gram silicon-dioxide, 80 ℃ of strong stirrings carried out coprecipitation reaction post-heating drying in 2 hours, in nitrogen with 160 ℃ of thermal treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion molding, 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 the embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 62 gram silica powders are carried out answering 50 minutes post-heating dryings after the co-precipitation, and with 160 ℃ of thermal treatments 3 hours, then 500 ℃ of roastings were 4 hours in nitrogen, processed to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 3
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray diethyl ether solution to catalyst Precursors, under the condition of abundant 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 namely got catalyzer 3 in 3 hours by 550 ℃ of roastings.
The propylene oxidation method
The above-mentioned catalyzer 3 of the 30ml that packs in the fixed bed single tube reactor, reaction raw materials propylene, water, air enter reactor after 160 ℃ of preheatings of preheater, salt bath heating, the 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 Examples 5:
Take the internal layer parent of catalyzer 3 as comparative catalyst 5, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion molding then, the 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 gram zinc nitrates, 16.4 gram cesium nitrates, adds 5.2 gram 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 gram silicon oxide and 15 gram aluminum oxide.
Step 3: Kaolinite Preparation of Catalyst 4
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic soln to catalyzer, under the condition of abundant 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 got catalyzer 4 in 5 hours by 450 ℃ of roastings.
The propylene oxidation method
The above-mentioned catalyzer 4 of the 30ml that packs in the fixed bed single tube reactor, reaction raw materials propylene, water, air enter reactor after the preheating through preheater more than 120 ℃, salt bath heating, the 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 Examples 6:
Take the outer layer catalyst of catalyzer 4 as comparative catalyst 6, make the ball that diameter is 4mm, the 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 gram saltpetre, 9.1 gram lanthanum nitrates, 10.2 gram 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 gram silicon oxide and 10.6 gram silicon carbide.
Step 3: Kaolinite Preparation of Catalyst 5
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray distilled water to catalyst Precursors, under the condition of abundant 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 got catalyzer 5 in 6 hours by 500 ℃ of roastings.
The propylene oxidation method
The above-mentioned catalyzer 5 of the 35ml that packs in the fixed bed single tube reactor, reaction raw materials propylene, water, air enter reactor after 150 ℃ of preheatings of preheater, salt bath heating, the 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%.Catalyzer establishment focus, the difficult losses such as catalyst reaction front and back active ingredient molybdenum, catalyst catalytic performance is stable.After running in 500 hours, active, selectivity can reach the live catalyst level substantially, and catalyst stability is good.
Comparative Examples 7:
Take the internal layer catalyst of catalyzer 5 as comparative catalyst 7, but do not contain lanthanum, catalyzer consists of Mo
12Bi
9Fe
3Ni
8K
1, make the ball that diameter is 4mm, the 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%.
Prepare propenal and compare with comparative catalyst 7 with catalyzer 5: through 500 hours oxidizing reaction, the generation of catalyzer 5 establishment focuses, the difficult losses such as active ingredient molybdenum, catalyst activity is stable, satisfies the oxidizing reaction long period and carries out.Comparative Examples 7 catalyzer can not the establishment focus, and poor selectivity reacts behind 500 hours rear catalysts that activity obviously descends under the washing away of the mixed airflows such as water vapour.
Embodiment 6:
With the preparation method of embodiment 5 catalyzer and raw materials used identical, internal layer adds 8 gram silicon oxide, the outer 19.7 gram silicon oxide that add, and the catalyst inner layer parent consists of: Mo
12Bi
5Fe
3.5Ni
3Mg
0.5La
1.1
The propylene oxidation method
The above-mentioned catalyzer 6 of the 35ml that packs in the fixed bed single tube reactor, reaction raw materials propylene, water, air enter reactor after 180 ℃ of preheatings of preheater, salt bath heating, the 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 gram ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 93.6 the gram nickelous nitrates, 99 the gram iron nitrates be dissolved in (water temperature is more than 65 ℃) in the 1000ml pure water, fully mix, obtain slurries (2).Get again 203.7 gram 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 the slurries (4), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
In active ingredient slurries (a), add 7 gram silicon-dioxide, 80 ℃ of strong stirrings carried out coprecipitation reaction post-heating drying in 2 hours, in nitrogen with 160 ℃ of thermal treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion molding, 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 the embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 12 gram silica powders and 4 gram Graphite Powder 99s are carried out 40 minutes post-heating dryings of coprecipitation reaction, in nitrogen with 150 ℃ of thermal treatments 3 hours, then 480 ℃ of roastings are 4 hours, process to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 7
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic soln to catalyst Precursors, under the condition of abundant 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 namely got catalyzer 7 in 4 hours by 450 ℃ of roastings.
The propylene oxidation method
The above-mentioned catalyzer 7 of the 35ml that packs in the fixed bed single tube reactor, reaction raw materials propylene, water, air enter reactor after 180 ℃ of preheatings of preheater, salt bath heating, the 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 (12)
1. the method for a propylene oxidation acrolein adopts the fixed bed single tube reactor, it is characterized in that; Reaction raw materials propylene, water, air enter reactor after the preheating through preheater more than 120 ℃, 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%; It is compound multi-metal-oxide catalyst that Mo-Bi is housed in the reactor, and the chief component of this catalyzer is by following general formula (I) expression Mo
aBi
bFe
cNi
dSi
fA
mB
nO
i(I)
Wherein: Mo is molybdenum, and Bi is bismuth, and Fe is iron, and Ni is nickel, and Si is silicon, and silicon is the carrier that adds in the catalyzer, and A is at least a element that is selected from cobalt, niobium, zinc, vanadium, lanthanum, the potassium; B is at least a element that is selected from the 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, outer silicon-dioxide by the numerical value of the oxygen decision of each oxide compound, the total content of one or more in aluminum oxide or the 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.
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 catalyst system therefor is bilayer structure, and in molar content, outer each constituent content is successively than this constituent content of adjacent inner layer low 0.5～30%.
5. the method for propylene oxidation acrolein according to claim 4 is characterized in that outer each constituent content of catalyst system therefor is successively than this constituent content of adjacent inner layer low 1～15%.
6. the method for propylene oxidation acrolein according to claim 1 is characterized in that the middle b of catalyst system therefor general formula (I) 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 A is selected from lanthanum in the catalyst system therefor general formula (I), and catalyzer forms shown in general formula (II): Mo
aBi
bFe
cNi
dSi
fLa
mB
nO
i(II), wherein m is a number of 0.1～2, and n is a number of 0.1～1.
8. the method for propylene oxidation acrolein according to claim 1 is characterized in that A is at least a element that is selected from cobalt, niobium, zinc, vanadium, lanthanum, the potassium in the catalyst system therefor general formula (I); B is at least a element that is selected from the alkaline-earth metal, and m is a number of 0.1～2, and n is a number of 0.1～2.
9. the method for each described propylene oxidation acrolein is characterized in that the preparation method of catalyst system therefor comprises the steps: according to claim 1～8
At first, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, A among the Bi, the compound of Fe, Ni, Si and general formula (I)
mB
nEach the elementary composition compound dissolution that relates to and mix, carry out forming after the co-precipitation internal layer parent slurry, oven dry, moulding, roasting get the catalyst inner layer parent;
Secondly, prepare the outer layer catalyst slurry according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, add in silicon oxide, aluminum oxide or the silicon carbide one or more in the outer layer catalyst slurry preparation process;
At last, the outer layer catalyst for preparing is coated on the catalyst inner layer parent successively, after roasting, gets finished catalyst.
10. the method for propylene oxidation acrolein according to claim 9, it is characterized in that catalyst system therefor internal layer parent after the moulding and outer after coating at 300～580 ℃ of lower roasting 3～10h, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
11. the method for propylene oxidation acrolein according to claim 9 is characterized in that using binding agent when catalyst system therefor applies, binding agent is selected from one or more in water, silicon sol or the aluminium colloidal sol.
12. the method for propylene oxidation acrolein according to claim 9 is characterized in that using binding agent when catalyst system therefor applies, binding agent is selected from one or more in alcohols or the ethers.
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| CN104646011A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Low-carbon olefin oxidation catalyst and preparation method thereof |
| CN104646012A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Propylene selective oxidation catalyst and preparation method thereof |
| CN111116335A (en) * | 2019-11-25 | 2020-05-08 | 中国寰球工程有限公司 | Method and device for preparing acrolein or methacrolein |
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| CN111116335B (en) * | 2019-11-25 | 2023-05-23 | 中国寰球工程有限公司 | Process for preparing acrolein or methacrolein |
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