CN102992996B - Preparation method of acrylic acid - Google Patents
Preparation method of acrylic acid Download PDFInfo
- Publication number
- CN102992996B CN102992996B CN201110265098.XA CN201110265098A CN102992996B CN 102992996 B CN102992996 B CN 102992996B CN 201110265098 A CN201110265098 A CN 201110265098A CN 102992996 B CN102992996 B CN 102992996B
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- CN
- China
- Prior art keywords
- catalyst
- catalyzer
- acrylic acid
- volume
- acrolein
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 51
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 162
- 239000003054 catalyst Substances 0.000 claims abstract description 150
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910001868 water Inorganic materials 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 229910052750 molybdenum Inorganic materials 0.000 claims description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 239000011733 molybdenum Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 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 19
- 229910052622 kaolinite Inorganic materials 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229960001866 silicon dioxide Drugs 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000004480 active ingredient Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000012018 catalyst precursor Substances 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- -1 nickelous nitrates Chemical class 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical class [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 150000002170 ethers Chemical class 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
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000012808 vapor phase Substances 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 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
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 125000000468 ketone group Chemical group 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
- 239000011133 lead Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000011112 process operation 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
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000576 supplementary effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A method for preparing acrylic acid by selective oxidation of acrolein adopts a fixed bed single-tube reactor, and is characterized in that reaction raw materials of acrolein, water and oxygen enter the reactor after being preheated by a preheater at a temperature of more than 180 ℃, salt bath heating is carried out, and the reaction process conditions are as follows: the salt bath temperature is 242-265 ℃, and the airspeed is 1200-2400 h-1The feed composition is as follows: 8-12% by volume of acrolein, 10-17% by volume of water vapor, 10-17% by volume of oxygen and 60-71% by volume of nitrogen; the reactor is filled with Mo-V series composite multi-metal oxide catalyst, and the main composition of the multi-metal oxide catalyst is represented by the following general formula aVbWcNidAeBfSigOx(I) The invention can effectively reduce the local heat accumulation of the fixed bed sheet reactor, inhibit the formation of hot spots, and has the characteristics of high reaction activity and selectivity and long service life.
Description
Technical field
The present invention relates to a kind of by acrolein oxidation acrylic acid.
Background technology
Current industrial main employing propylene two-step oxidation style prepares vinylformic acid, and first propylene catalytic gas phase oxidation generates propenal, and propenal is reoxidised into vinylformic acid.Acrolein oxidation reaction is strong exothermal reaction, focus can be produced in beds, the heat gathered instantaneously is constantly accumulated, to the loss of catalyst activity component be caused, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause the formation aggravating by product because of over oxidation reaction, even cause uncontrolled reaction, make sintering of catalyst.
The appearance of " progress of oxidative synthesis acrylic acid process and catalyzer " (petrochemical complex, the 39th volume the 7th phase in 2010) social focus also can make catalyst damage evil, shortens the work-ing life of catalyzer.For 80,000 tons/year of acroleic acid devices, propylene oxidation is prepared in acrolein reaction device needs more than 2.5 ten thousand tubulation, and acrolein oxidation is prepared in vinylformic acid reactor also needs more than 2.5 ten thousand tubulation, loads propenal, acrylic acid catalyst more than 100 ton altogether.More than 50000 reaction tubes, the filling of catalyzer ensures that not filling sky has certain difficulty, if because focus is crossed high catalyst and sintered very soon, again change agent more in a short time, it is huge for can envisioning its financial loss; In addition, carry out under cryogenic as much as possible for propenal, acrylic acid production, because reaction needed salt bath heating, it maintains the energy consumption of producing also is huge spending; Due to the generation of focus, require high temperature resistant to reaction tubes tubing, for up to ten thousand reaction tubess, tubing expense is exactly the very large cost of item.Therefore, if effectively suppress the generation of beds focus, huge economic benefit can be brought to large-scale commercial production.
At present, there is multiple method can reduce or avoid gathering and peroxidation of focus, can from the viewpoint of the improvement two of the improvement of reaction unit and catalyzer.In catalyzer, as: Japanese Patent Laid-Open 04-217932 propose a kind of suppress focus appearance or focus on the method for hot polymerization collection, namely by the multiple catalyzer with different possessive volume of preparation, and from the mode that unstripped gas inlet side reduces to outlet side catalyzer possessive volume, fill reaction tubes successively, but the possessive volume of catalyzer is by the restriction of reaction tube diameter, and it is also very difficult multiple catalysts to be filled into reaction tubes.Japanese Unexamined Patent Publication 10614/1972, US200421442A are mixed into heat resistanceheat resistant point in the catalyst and form catalyzer and inert substance with by catalyst dilution, and the method for tubulose made by catalyzer by Japanese Patent Publication 36739/1987.Further, the catalyst loading that unstripped gas ingress reduces by active ingredient.CN200510007929.8 provides the acrylic acid catalyzer of a kind of catalyzing propone aldehyde gaseous oxidation system, 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 the reduction of the reaction efficiency of suppression thermal destruction.Specific practice is, comprise by making the volatility toxic component of specified quantitative and originally had in highly active catalyzer, catalytic activity declines momently, can reduce the temperature of hot spot.CN97104224.1 is loaded in after on carrier by catalytic active component being divided, and calcine the catalyzer of load sharing to suppress the generation of focus, the median size of catalyzer is 4 ~ 16mm, and the median size of carrier is 3 ~ 12mm, and calcining temperature is 500 ~ 600 DEG C.CN01111960.8 provides a kind of catalyzer containing Mo-W-Bi-Fe, this catalyzer, by the mode changing the kind of possessive volume calcining temperature and/or alkali metal and/or quantity and increase to outlet side from the inlet side of unstripped gas according to catalyst activity, fills reaction zone successively with described multiple types catalyzer.Catalyzer is at least divided into two-layer in the axial direction of the reaction tube, and this catalyzer is the multiple types catalyzer with different activities level, can by changing calcining temperature and/or the wherein kind of alkali metal and/or quantity and obtain.Hot polymerization collection on the appearance of focus or focus is effectively suppressed.CN00122609.6 provides a kind of PROPENE IN GAS PHASE OXIDATION to produce propenal and acrylic acid, use the oxide catalyst containing Mo-Bi-Fe compound, described packed catalyst is 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 and configure in each tubular reactor of two or more reaction zone vertically, each district's filling different catalysts, namely fill out Bi and/or Fe content catalyzer from gas inlet end to gas outlet end and reduce with the ratio of Mo content.US2009415167A discloses a kind of method of producing unsaturated aldehyde and unsaturated acid, two or more catalyst layer is loaded in reactor, each catalyst layer by different holes density and or aperture size the shaping packed catalyst of catalytic active component, particular table area from reactor inlet to outlet catalytic active component increase gradually with control punch density and or aperture size, and then inhibited reaction focus.Even if under CN200410007263.1 provides a kind of condition forming focus, activity, selectivity, life-span are all excellent, demonstrate the catalyzer of stability for a long time, and use the method for producing acrylic acid of this catalyzer.Said catalyzer is following general formula (1) Mo
av
bw
ccu
da
eb
fc
go
xrepresent.A is at least one selected from cobalt, nickel, iron, lead, bismuth, B is at least one selected from antimony, niobium, tin, C is at least one selected from silicon, aluminium, titanium, zirconium, a, b, c, d, e, f, g, x represent the atomic ratio of Mo, V, W, Cu, A, B, C, O respectively, during a=12,2≤b≤15,0 < c≤10,0 < d≤6,0 < e≤30,0≤f≤6,0≤g≤60, x is the numerical value determined by the state of oxidation of each element.This catalyzer can not effectively suppress being emerged of beds focus, and under higher hot-spot conditions, reaction unit requires to have superpower resistance to elevated temperatures, and reaction later separation, to absorb process operations expense also very high.CN200410048021.7 discloses a kind of O composite metallic oxide catalyst for carrying out selective oxidation reaction in the gas phase containing the gas of unsaturated aldehyde and a kind of gas of molecule-containing keto, particularly relates to the O composite metallic oxide catalyst that a kind of propenal or Methylacrylaldehyde vapor phase catalytic oxidation produce corresponding acrylic or methacrylic acid.Catalyzer is by 1. molybdenum, vanadium, copper main active component and 2. requisite at least by stable component and the 3. composite oxides that form of nickel, iron, silicon, aluminium, basic metal, alkaline-earth metal of antimony and titanium.2. and be 3. wherein can composite oxides that within the scope of 120 DEG C to 900 DEG C prepared by roasting.This catalyzer shows the permanent stability under high reactivity and good selectivity.CN 03121882.2 discloses a kind of composite multi-metal oxide catalyst and preparation method, and be specially adapted to propenal vapor phase catalytic oxidation vinylformic acid, its catalyzer consists of Mo
av
bcu
cte
dx
1 ex
2 fx
3 gx
4 hx
5 io
x, X
1a kind of element being at least selected from tungsten and niobium, X
2a kind of element being at least selected from magnesium, calcium, strontium and barium, X
3a kind of element of at least chosen from Fe, cobalt and nickel, X
4a kind of element being at least selected from silicon, aluminium and titanium, X
5it is a kind of element being at least selected from antimony, tin and bismuth, catalyzer is at least containing molybdenum, vanadium and copper, add necessary tellurium again and make catalyzer main active component molybdenum oxide and copper molybdate crystalchecked, have lasting high reactivity and highly selective when carrying out catalyzed reaction, delaying catalyzer because of molybdenum runs off the inactivation caused.CN03148701.7 provides a kind of supported catalyst, and this support of the catalyst has multidimensional structure, with premolding (as foam, one-piece construction, fabric or other) self supporting type multidimensional carrier structure or comprise Nb
2o
5, trichroite, partially stabilized zirconium white, ceramic fiber or its mixture carrier, in succession on the carrier deposition comprise any order at least one molybdenum-containing layer, at least one containing vanadium layers, at least one containing tellurium layer and at least one containing X layer catalyst composition formed 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 applicable selectivity are provided.
All there is a problem in the method that above-mentioned suppression focus produces, the catalyzer be filled in reaction tubes is diluted from the inlet to the outlet all in a variety of manners, both after having made catalyst runs some cycles, activity decrease also can not change thinning ratio, catalyzer also cannot reoffer higher activity, not only load, dismantle, be separated, reclaim catalyzer and make troubles, and the reactive behavior of catalyzer can be reduced, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.Therefore, need to develop a kind of high activated catalyst that effectively can suppress focus, to meet industrial propylene high-speed, highly selective oxidation acrolein, acrylic acid needs.In addition, under the high temperature conditions, in catalyzer, part active ingredient molybdenum loses from catalyst surface because of distillation.In addition, under the high temperature conditions, in catalyzer, part active ingredient molybdenum loses from catalyst surface because of distillation.The mixed airflows such as propenal, air (oxygen), nitrogen and water vapour wash away the loss of active component that also can make in catalyzer.For suppressing the loss of molybdenum distillation to cause active decay, CN1121504, by mixing copper component and zirconium and/or Titanium and/or Cerium with specified particle diameter and specific surface area, can suppress dissipation effect and the over reduction of molybdenum composition; CN1445020 adds the effect that a small amount of tellurium plays stable free molybdic oxide and copper molybdate crystalline structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is with molybdenum, vanadium, copper, tungsten and/or niobium for main ingredient, and the composite oxides formed with other element or its hopcalite form the loss that catalyzer suppresses molybdenum.
Summary of the invention
The invention provides a kind of for acrolein selectivity oxidation vinylformic acid method processed, in acrolein oxidation process, can react under low temperature, high-load condition.
The invention provides a kind of method that propenal or Methylacrylaldehyde selective oxidation produce corresponding unsaturated acid.Different from the method for above-mentioned reduction focus, there is gradient difference from inside to exterior active combination of components substrate concentration in used catalyst particle of the present invention, effectively can reduce reactor localized heat and gather, and suppresses being emerged of focus.
Acrolein selectivity oxidation provided by the invention acrylic acid processed is as follows: adopt fixed bed single tube reactor; Reaction raw materials propenal, water, oxygen enter reactor, salt bath heating after preheater more than 180 DEG C preheatings, and reaction process condition is: salt temperature 242 ~ 265 DEG C, preferably 247 ~ 260 DEG C; Air speed 1200 ~ 2400h
-1, preferably 1300 ~ 2000h
-1, feed composition: propenal 8 ~ 12 volume %, water vapour 10 ~ 17%, oxygen 10 ~ 17 volume %, nitrogen 60 ~ 71 volume %; Reactor is built with Mo-V system composite multi-metal oxide catalyst, and the main composition of this multi-metal-oxide catalyst is by general formula (I) expression below.
Mo
aV
bW
cNi
dA
eB
fSi
gO
x(I)
Wherein: Mo is molybdenum, V is vanadium, and W is tungsten, and Ni is nickel, and A is at least one element be selected from copper, cobalt, manganese; B is at least one element in selected among zirconium, strontium, lanthanum, magnesium and titanium; Si is silicon, and silicon is the carrier added, and O is oxygen; A, b, c, d, e, f, g represent each Elements Atom ratio respectively, and wherein when a=12 is benchmark, b is a number of 3 ~ 10, preferably 3 ~ 7; C is a number of 0.5 ~ 5, preferably 1 ~ 3; D is a number of 1 ~ 5, preferably 1.5 ~ 3; E is a number of 0 ~ 3, f is a number of 0 ~ 3, g is a number of 0.5 ~ 30, x is the numerical value determined by the oxygen of each oxide compound, described composite multi-metal oxide catalyst has multilayer structure, namely outer double-layer structure in, every layer of catalyzer mainly forms identical, but one or more the total content in silicon-dioxide, aluminum oxide or silicon carbide is different, one or more total content in outer silicon-dioxide, aluminum oxide or silicon carbide is than the height of internal layer parent, in molar content, catalyst outer layer each constituent content concentration ratio internal layer parent is low.
Catalyzer of the present invention is multilayer structure, concentration difference is achieved mainly through adding the materials such as different amount silicon-dioxide, aluminum oxide, silicon carbide at ectonexine, that is, one or more total content 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 0.5 ~ 10%.Catalyst inner layer of the present invention also can not add silicon.
Acrolein selectivity oxidation vinylformic acid processed is because temperature of reaction is more than 270 DEG C, and long period is under such pyroreaction condition, and the active ingredient molybdenum in catalyzer is easy to run off because of distillation.A in catalyzer of the present invention preferably copper, B is strontium and/or lanthanum, and strontium can regulate catalyst surface acid, and the composition of catalyzer represents with general formula (II), and wherein e is a number of 0.5 ~ 3, and f is a number of 0.05 ~ 3.Lanthanum and molybdenum, nickel, copper etc. can form stable crystal phase structure and be conducive to suppressing part active ingredient molybdenum to lose because of distillation from catalyst surface, and before and after catalyst reaction, active ingredient molybdenum content is substantially constant, delays active deterioration rate, and catalyst stability is good.
Mo
aV
bW
cNi
dCu
eB
fSi
gO
x(II)
In catalyzer of the present invention, active ingredient comprises Mo, V, W, Ni, also can add in cobalt, manganese, zirconium, strontium, magnesium and titanium one or more, be conducive to improving the dispersiveness of active ingredient on the carriers such as silicon-dioxide and tack, and then improve selectivity of catalyst.In catalyzer composition general formula (I), e is a number of 0.1 ~ 2, and f is a number of 0.05 ~ 2.The granules of catalyst that the present invention has multilayer structure reduces successively from inside to exterior active combination of components substrate concentration, effective reduction single tube reactor localized heat gathers, and suppress being emerged of focus, catalyzer is easy-sintering not, reactive behavior is stablized, and can bear long period steady running.
Composite multi-metal oxide catalyst of the present invention adopts common preparation method, prepares as adopted following step.
First, Kaolinite Preparation of Catalyst internal layer parent:
By A in the compound containing Mo, V, W, Ni and general formula (I)
eb
fthe each elementary composition compound dissolution related to and mix, form internal layer parent slurries after carrying out co-precipitation, dry, shaping, roasting obtains catalyst inner layer parent;
Secondly, outer layer catalyst slurries are prepared according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, add one or more of the materials such as silicon-dioxide, aluminum oxide, silicon carbide in outer layer catalyst slurry production process, make each concentration of element in outer layer catalyst slurries lower than the concentration of this element of internal layer;
Finally, the outer layer catalyst of preparation is coated on successively on catalyst inner layer parent, after roasting, obtains finished catalyst.
Catalyst inner layer parent of the present invention after shaping and skin all need roasting 3 ~ 10h at 300 ~ 480 DEG C after application, compare not the catalyzer of respectively roasting, repeatedly roasting can improve activity and the stability of catalyzer.Can be open roasting also can be enclosed roasting, calcination atmosphere can be the rare gas elementes such as helium, nitrogen, argon gas.Catalyst layer too thick roasting time easily chap, in order to avoid be full of cracks preferably 55 ~ 125 DEG C of oven dry after application, and then roasting.The outer layer catalyst thickness being coated on internal layer parent is 0.5 ~ 2.5mm, preferably 1.0 ~ 2mm.
The compound of each component of catalyzer of the present invention can use the nitrate, ammonium salt, vitriol, oxide compound, oxyhydroxide, muriate, acetate etc. of each element.
After catalyst inner layer parent slurries of the present invention are dried, the forming methods such as extrusion moulding, granulating and forming, compression molding are usually preferably adopted to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Catalyzer of the present invention preferably uses binding agent when applying, and ectonexine catalyzer is bondd more firm.Under internal layer parent is in rolling condition, sprays binding agent infiltrates surface, then spray the outer layer catalyst powder prepared, also internal layer parent can be put into the outer layer catalyst slurries prepared and carry out rolling coating.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 layer surface preferably uneven, surface irregularity of catalyzer of the present invention, is conducive to coating, bonds more firm between ectonexine.
The present invention, in order to improve intensity, the efflorescence degree of catalyzer, can to add in glass fibre, graphite, pottery or various whisker one or more in above-mentioned outer layer catalyst.
The present invention has bilayer structure, and internal layer also can be called internal layer parent.
Due to the initial stage of feeding intake, catalyzer initial reaction activity is very high, so be easy to produce focus or produce heat built-up on single tube reactor bed, catalyzer is easy to sintering, and this is very serious concerning loss suitability for industrialized production propenal vinylformic acid.Pass into a certain amount of water vapour in raw material, because specific heat of water is large, a large amount of reaction heat can be taken away, but water vapour input greatly often makes catalyst member active ingredient solution-off and makes activity decrease.The present invention has the composite multi-metal oxide catalyst of multilayer structure by preparation, granules of catalyst is made to there is gradient difference from inside to exterior active combination of components substrate concentration, and the every outer active component concentration of catalyzer is lower than its adjacent inner layer active component concentration, like this, under high-speed reaction conditions, because the active component concentration of catalyst external surface is low, so corresponding activity is also low, therefore being emerged of focus and gathering of heat can effectively be suppressed, reduce the growing amount of by product (as hydrocarbon), improve the selectivity of object product.Double-deck catalyzer has good water repelling property.And when after catalyst runs for some time, catalyzer has release effects, under mixed airflow washes away, even if catalyst surface active component has part to run off, but because internal layer catalyst active component concentration is higher, supplementary effect can be played, so catalyst activity lasting stability can be kept.
Acrylic acid is prepared in acrolein selectivity provided by the invention oxidation, effectively can reduce fixed bed single tube reactor localized heat and gather, and suppresses being emerged and the loss of active ingredient molybdenum of focus.Catalyzer is easy-sintering not, and under high-speed part, this catalyzer has that activity and selectivity is high, the feature of good stability.
Embodiment
Illustrate that acrylic acid is prepared in acrolein selectivity oxidation with specific embodiment below, but scope of the present invention is not limited to these embodiments.
Mole number × 100% of propenal in the total mole number/raw material of acrolein conversion rate (%)=acrolein reaction
Acrylic acid selectivity (%)=propenal is converted into total mole number × 100% of acrylic acid mole number/acrolein 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, get 148 grams of ammonium molybdates, ammonium meta-vanadate 24.6 grams, be dissolved in (water temperature more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 64 grams of ammonium paratungstates, 5.5 grams of strontium nitrates, 17.9 grams of cupric nitrates, 10.2 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
4.2 grams of silicon-dioxide are added in active ingredient slurries (a), 80 DEG C of strong stirrings carry out the drying of coprecipitation reaction post-heating for 3 hours, with 160 DEG C of thermal treatments 3 hours in nitrogen, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion molding, dry rear 450 DEG C of roastings 5 hours for 70 DEG C, obtained catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
3w
35ni
4cu
11co
0.5sr
03si
1
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Identical with the preparation of active ingredient slurries (a) in embodiment 1 catalyst inner layer parent.
(2) preparation of catalyst outer layer
Active ingredient slurries (a) and 45 grams of silicon dioxide powders and 3 grams of graphite are carried out coprecipitation reaction post-heating drying in 2.5 hours, with 150 DEG C of thermal treatments 3 hours in nitrogen, then 500 DEG C of roastings 4 hours, process to obtain catalyst outer layer powder through pulverizing, grinding, sieve.
Step 3: Kaolinite Preparation of Catalyst 1
Catalyst inner layer parent step 1 prepared is placed in round bottom container, ethanolic soln is sprayed to catalyst Precursors under container rotation condition, stop operating under the condition of fully wetting catalyst inner layer parent, put it into rapidly another rotate be placed with in the round bottom container of outer layer catalyst powder of step 2 gained, apply, coat-thickness is at 1.0 ~ 2.0mm, and namely gained catalyzer 85 DEG C obtains catalyzer 1 in 4.5 hours through 450 DEG C of roastings after drying.
Acrolein oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, and the gas mixture of reaction raw materials propenal, water, oxygen, nitrogen enters reactor after preheater more than 180 DEG C preheatings, and reactor loads the above-mentioned catalyzer 1 of 40ml, salt bath heating.From above-mentioned reaction tubes ingress with air speed 1300h
-1import the mixed gas of propenal 8 volume %, oxygen 11 volume %, water vapour 10 volume %, nitrogen 71 volume %, salt temperature 245 DEG C.Hot(test)-spot temperature 278 DEG C, acrolein conversion rate 98.4%, acrylic acid selectivity 88.3%.
Comparative example 1:
With the internal layer parent of catalyzer 1 for comparative catalyst 1, banded extruder extrusion molding is the hollow columnar particle of φ 5 × 5mm, acrolein oxidation method and processing condition with embodiment 1, hot(test)-spot temperature 284 DEG C, acrolein conversion rate 98.7%, acrylic acid selectivity 86.1%.
Comparative example 2:
With the skin of catalyzer 1 for comparative catalyst 2, banded extruder extrusion molding is the hollow columnar particle of φ 5 × 5mm, acrolein oxidation method and processing condition with embodiment 1, hot(test)-spot temperature 277 DEG C, acrolein conversion rate 97.4%, acrylic acid selectivity 87.0%.
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, get 148 grams of ammonium molybdates, ammonium meta-vanadate 40.9 grams, be dissolved in (water temperature more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 54.8 grams of ammonium paratungstates, 61 grams of nickelous nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active ingredient slurries (a).
(2) preparation of catalyst Precursors
5 grams of silicon-dioxide are added in slurries (a), 80 DEG C of strong stirrings carry out the drying of coprecipitation reaction post-heating for 2 hours, with 160 DEG C of thermal treatments 3 hours in nitrogen, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion molding, dry rear 450 DEG C of roastings 4 hours for 90 DEG C, obtained catalyst Precursors, this catalyst Precursors consists of: Mo
12v
5w
3ni
3
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Identical with the preparation of active ingredient slurries (a) in embodiment 2 catalyst inner layer parent.
(2) preparation of catalyst outer layer
Answer post-heating drying in 50 minutes after active ingredient slurries (a) and 14 grams of silicon dioxide powders are carried out co-precipitation, with 160 DEG C of thermal treatments 3 hours in nitrogen, then 500 DEG C of roastings 4 hours, process to obtain catalyst outer layer powder through pulverizing, grinding, sieve.
Step 3: Kaolinite Preparation of Catalyst 2
Catalyst inner layer parent step 1 prepared is placed in round bottom container, ethanolic soln is sprayed to catalyst Precursors under container rotation condition, fully wetting catalyst inner layer parent, put it into rapidly another rotate be placed with in the round bottom container of the catalyst outer layer of step 2 gained, apply, coat-thickness is when 0.8 ~ 1.0mm, taking-up internal layer parent is put into the rotation of another round bottom container and is sprayed ethanolic soln again after one to two minutes, then put into the round bottom container that catalyst outer layer is housed and continue coating, until coat-thickness stops coating when 1.0 ~ 2.0mm, namely gained catalyzer obtains catalyzer 2 in 3 hours through 500 DEG C of roastings after drying.
Acrolein oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, and the gas mixture of reaction raw materials propenal, water, oxygen, nitrogen enters reactor after preheater more than 180 DEG C preheatings, and reactor loads the above-mentioned catalyzer 2 of 45ml, salt bath heating.From above-mentioned reaction tubes ingress with air speed 1200h
-1import the mixed gas of propenal 8 volume %, oxygen 10 volume %, water vapour 11 volume %, nitrogen 71 volume %, salt temperature 252 DEG C.Hot(test)-spot temperature 278 DEG C, acrolein conversion rate 98.2%, acrylic acid selectivity 88.0%.
Embodiment 3:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation, get 148 grams of ammonium molybdates, 24.6 ammonium meta-vanadates gram, be dissolved in (water temperature more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 18.3 grams of ammonium paratungstates, 21.2 cupric nitrates, 40.7 grams of nickelous nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
8.4 grams of silicon-dioxide are added in slurries (a), 80 DEG C of strong stirrings carry out the drying of coprecipitation reaction post-heating for 3 hours, with 160 DEG C of thermal treatments 3 hours in nitrogen, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion molding, dry rear 350 DEG C of roastings 8 hours, obtained catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
3w
1ni
2cu
13
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
With preparation and raw materials used identical (following examples are identical) of active ingredient slurries (a) in embodiment 3 catalyst inner layer parent.
(2) preparation of catalyst outer layer
Post-heating drying in 50 minutes is answered after active ingredient slurries (a) and 7.8 grams of silicon dioxide powders and 5.7 grams of aluminum oxide are carried out co-precipitation, with 160 DEG C of thermal treatments 3 hours in nitrogen, then 400 DEG C of roastings 5 hours, process to obtain catalyst outer layer powder through pulverizing, grinding, sieve.
Step 3: Kaolinite Preparation of Catalyst 3
Catalyst inner layer parent step 1 prepared is placed in round bottom container, diethyl ether solution is sprayed to catalyst Precursors under container rotation condition, stop operating under the condition of fully wetting catalyst inner layer parent, put it into rapidly another rotate be placed with in the round bottom container of the catalyst outer layer of step 2 gained, apply, coat-thickness is at 1.5 ~ 2.0mm, and namely gained catalyzer 85 DEG C obtains catalyzer 3 in 4 hours through 450 DEG C of roastings after drying.
Acrolein oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, and the gas mixture of reaction raw materials propenal, water, oxygen, nitrogen enters reactor after preheater more than 180 DEG C preheatings, and reactor loads the above-mentioned catalyzer 3 of 45ml, salt bath heating.From above-mentioned reaction tubes ingress with air speed 1850h
-1import the mixed gas of propenal 11 volume %, oxygen 13 volume %, water vapour 12 volume %, nitrogen 64 volume %, salt temperature 253 DEG C.Hot(test)-spot temperature 288 DEG C, propylene conversion 98.5%, acrolein selectivity 88.9%.
Comparative example 3:
With the internal layer parent of catalyzer 3 for comparative catalyst 3, then be the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion molding, acrolein oxidation method and processing condition with embodiment 3, hot(test)-spot temperature 295 DEG C, acrolein conversion rate 99.3%, acrylic acid selectivity 86.6%.
Embodiment 4:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation, get 148 grams of ammonium molybdates, 57.3 ammonium meta-vanadates gram, be dissolved in (water temperature more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 36.6 grams of ammonium paratungstates, 14.6 strontium nitrates, 30.5 grams of nickelous nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, add 5.6 grams of titanium dioxide again, be fully uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
6.5 grams of silicon-dioxide are added in slurries (a), 80 DEG C of strong stirrings carry out the drying of coprecipitation reaction post-heating for 3 hours, with 160 DEG C of thermal treatments 3 hours in nitrogen, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion molding, dry rear 350 DEG C of roastings 8 hours for 90 DEG C, obtained catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
7w
2ni
15sr
08ti
10
Step 2: Kaolinite Preparation of Catalyst is outer
With preparation method and raw materials used identical (following examples are identical) of embodiment 4 catalyst outer layer, just add 6.3 grams of silicon-dioxide and 20 grams of silicon carbide.
Step 3: Kaolinite Preparation of Catalyst 4
Catalyst inner layer parent step 1 prepared is placed in round bottom container, ethanolic soln is sprayed to catalyzer under container rotation condition, the outer layer catalyst powder of step 2 gained is sprayed under the condition of fully wetting catalyst inner layer parent, apply, coat-thickness is at 0.8 ~ 1.5mm, and gained catalyzer 80 DEG C obtains catalyzer 4 in 5 hours through 450 DEG C of roastings after drying.
Acrolein oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, and the mixture gas of reaction raw materials propenal, water, oxygen, nitrogen enters reactor after preheater more than 180 DEG C preheatings, and reactor loads the above-mentioned catalyzer 4 of 45ml, salt bath heating.From above-mentioned reaction tubes ingress with air speed 1500h
-1import the mixed gas of propenal 9 volume %, oxygen 11 volume %, water vapour 14 volume %, nitrogen 66 volume %, salt temperature 260 DEG C.Hot(test)-spot temperature 392 DEG C, acrolein conversion rate 99.1%, acrylic acid selectivity 89.0%.
Comparative example 4:
With the internal layer catalyst of catalyzer 4 for comparative catalyst 4,300 DEG C of roastings 2.5 hours, through the hollow columnar particle that banded extruder extrusion molding is φ 5 × 5mm, acrolein oxidation method and processing condition are with embodiment 4, hot(test)-spot temperature 397 DEG C, acrolein conversion rate 99.4%, acrylic acid selectivity 86.0%.
Embodiment 5:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation, get 148 grams of ammonium molybdates, 73.7 ammonium meta-vanadates gram, be dissolved in (water temperature more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 82.3 grams of ammonium paratungstates, 14.6 grams of strontium nitrates, 29.3 grams of cupric nitrates, 3.5 grams of saltpetre, 16.8 grams of magnesium nitrates, 20.4 grams of nickelous nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active ingredient slurries (a).
(2) preparation of catalyst inner layer parent
12.6 grams of silicon-dioxide are added in slurries (a), 80 DEG C of strong stirrings carry out the drying of coprecipitation reaction post-heating for 3 hours, with 160 DEG C of thermal treatments 3 hours in nitrogen, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion molding, dry rear 480 DEG C of roastings 4 hours for 120 DEG C, obtained catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
9w
45ni
1cu
1.8k
0.5mg
13
Step 2: Kaolinite Preparation of Catalyst is outer
Preparation with embodiment 5 catalyst outer layer is identical, just adds 9.7 grams of silicon-dioxide, 4 grams of graphite and 36 grams of aluminum oxide.
Step 3: Kaolinite Preparation of Catalyst 5
Catalyst inner layer parent step 1 prepared is placed in round bottom container, distilled water is sprayed to catalyst Precursors under container rotation condition, the outer layer catalyst powder of step 2 gained is sprayed under the condition of fully wetting catalyst inner layer parent, apply, coat-thickness is at 0.8 ~ 1.2mm, and gained catalyzer 125 DEG C obtains catalyzer 5 in 6 hours through 450 DEG C of roastings after drying.
Acrolein oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, and the gas mixture of reaction raw materials propenal, water, oxygen, nitrogen enters reactor after preheater more than 180 DEG C preheatings, and reactor loads the above-mentioned catalyzer 5 of 45ml, salt bath heating.From above-mentioned reaction tubes ingress with air speed 2000h
-1import the mixed gas of propenal 10 volume %, oxygen 14 volume %, water vapour 12 volume %, nitrogen 64 volume %, salt temperature 250 DEG C.Hot(test)-spot temperature 286 DEG C, propylene conversion 98.8%, acrolein selectivity 89.1%.
Comparative example 5:
With the internal layer catalyst of catalyzer 5 for comparative catalyst 5, then be the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion molding, acrolein oxidation method and processing condition with embodiment 5, hot(test)-spot temperature 291 DEG C, acrolein conversion rate 99.2%, acrylic acid selectivity 85.9%.
Embodiment 5 and comparative example 5 keep processing condition constant, and acrolein selectivity oxidizing reaction is after 500 hours, and hot(test)-spot temperature is respectively 286 DEG C and 288 DEG C, and acrolein conversion rate is respectively 98.7% and 98.4%, and acrolein selectivity is not 89.0% and 84%.After running in 500 hours, catalyzer 5 active ingredient not easily runs off, and catalyst activity is stablized.Comparative example 5 catalyzer effectively can not suppress focus, poor selectivity, and after reacting 500 hours rear catalysts, under the washing away of the mixed airflows such as water vapour, activity obviously declines.
Embodiment 6
With the preparation process of embodiment 5 catalyzer 5 and raw material identical, just add 13.6 grams of lanthanum nitrates and, 5.5 grams of strontium nitrates, internal layer adds 7.3 grams of silicon-dioxide; Skin adds 10.4 grams of silicon-dioxide.Catalyzer 6 internal layer parent consists of: Mo
12v
5w
07ni
2.8cu
08sr
03la
06
Acrolein oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, and the gas mixture of reaction raw materials propenal, water, oxygen, nitrogen enters reactor after preheater more than 180 DEG C preheatings, and reactor loads the above-mentioned catalyzer 6 of 45ml, salt bath heating.From above-mentioned reaction tubes ingress with air speed 2300h
-1import the mixed gas of propenal 11 volume %, oxygen 15 volume %, water vapour 14 volume %, nitrogen 60 volume %, salt temperature 255 DEG C.Hot(test)-spot temperature 289 DEG C, acrolein conversion rate 99.4%, acrylic acid selectivity 89.6%.Catalyzer effectively suppresses focus, and active ingredient molybdenum etc. not easily runs off, and catalyst catalytic performance is stablized.Keep processing condition constant, acrolein selectivity oxidizing reaction is after 500 hours, hot(test)-spot temperature 287 DEG C, acrolein conversion rate 99.1%, acrolein selectivity 89.5%.After running in 500 hours, catalyst activity, selectivity can reach live catalyst level substantially, and catalyst stability is good.
Claims (8)
1. an acrolein selectivity oxidation acrylic acid processed, adopt fixed bed single tube reactor, it is characterized in that reaction raw materials propenal, water, oxygen enter reactor after preheater more than 180 DEG C preheatings, salt bath heating, reaction process condition is: salt temperature 242 ~ 265 DEG C, air speed 1200 ~ 2400h
-1, feed composition: propenal 8 ~ 12 volume %, water vapour 10 ~ 17 volume %, oxygen 10 ~ 17 volume %, nitrogen 60 ~ 71 volume %; Reactor is built with Mo-V system composite multi-metal oxide catalyst, and the main composition of this multi-metal-oxide catalyst represents Mo by leading to formula I below
av
bw
cni
da
eb
fsi
go
x(I)
Wherein: Mo is molybdenum, V is vanadium, and W is tungsten, and Ni is nickel, and A is at least one element be selected from copper, cobalt, manganese, B is at least one element in selected among zirconium, strontium, lanthanum, magnesium and titanium, Si is silicon, and silicon is the carrier added, and O is oxygen, a, b, c, d, e, f, g represents each Elements Atom ratio respectively, wherein when a=12 is benchmark, b is a number of 3 ~ 10, c is a number of 0.5 ~ 5, d is a number of 1 ~ 5, e is a number of 0 ~ 3, f is a number of 0 ~ 3, g is a number of 0.5 ~ 30, x is the numerical value determined by the oxygen of each oxide compound, described composite multi-metal oxide catalyst has interior outer double-layer structure, outer total silica content is than the height of internal layer parent, in molar content, catalyst outer layer Mo, V, W, Ni, A, each constituent content concentration ratio internal layer parent that B relates to is low, the preparation of used catalyst comprises the steps:
First, Kaolinite Preparation of Catalyst internal layer parent: by A in the compound containing Mo, V, W, Ni and logical formula I
eb
fthe each elementary composition compound dissolution related to and mix, form internal layer parent slurries after carrying out co-precipitation, dry, shaping, roasting obtains catalyst inner layer parent; Secondly, prepare outer layer catalyst slurries according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, in outer layer catalyst slurry production process, add silicon-dioxide; Finally, the outer layer catalyst of preparation is coated on successively on catalyst inner layer parent, after roasting, obtains finished catalyst.
2. acrolein selectivity is oxidized acrylic acid processed according to claim 1, it is characterized in that salt temperature 247 ~ 260 DEG C.
3. acrolein selectivity is oxidized acrylic acid processed according to claim 1, it is characterized in that sky
Speed 1300 ~ 2000h
-1.
4. acrolein selectivity is oxidized acrylic acid processed according to claim 1, it is characterized in that
It is copper that used catalyst leads to A in formula I, and the composition of catalyzer is represented by (II)
Mo
av
bw
cni
dcu
eb
fsi
go
x(II) wherein e is a number of 0.1 ~ 2.
5. acrolein selectivity oxidation according to claim 4 acrylic acid processed, is characterized in that
It is strontium and/or lanthanum that used catalyst leads to B in formula II, and wherein f is a number of 0.05 ~ 2.
6. acrolein selectivity oxidation according to claim 1 acrylic acid processed, it is characterized in that used catalyst is multilayer structure, in molar content, each constituent content that outer Mo, V, W, Ni, A, B relate to is lower by 0.5 ~ 30% than this constituent content of internal layer.
7. acrolein selectivity oxidation according to claim 1 acrylic acid processed, is characterized in that each constituent content that used catalyst outer Mo, V, W, Ni, A, B relate to is lower by 0.5 ~ 10% than this constituent content of adjacent inner layer.
8. acrolein selectivity oxidation according to claim 1 acrylic acid processed, it is characterized in that used catalyst leads to A in formula I is at least one element be selected from copper, cobalt, manganese; B is at least one element in selected among zirconium, strontium, magnesium and titanium; In the logical formula I of catalyzer composition, e is a number of 0.1 ~ 2, and f is a number of 0.05 ~ 2.
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