CN1285237A - Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation - Google Patents
Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation Download PDFInfo
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- CN1285237A CN1285237A CN99113988A CN99113988A CN1285237A CN 1285237 A CN1285237 A CN 1285237A CN 99113988 A CN99113988 A CN 99113988A CN 99113988 A CN99113988 A CN 99113988A CN 1285237 A CN1285237 A CN 1285237A
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- Prior art keywords
- catalyst
- span
- acrylonitrile
- fluidized bed
- ammonia oxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims description 13
- 238000007254 oxidation reaction Methods 0.000 title claims description 13
- GLAKNHGQBRSLIO-UHFFFAOYSA-N azane;prop-1-ene Chemical compound N.CC=C GLAKNHGQBRSLIO-UHFFFAOYSA-N 0.000 title claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 20
- 229910052716 thallium Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000011651 chromium Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- -1 antimony halides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 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
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 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
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [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
- 238000010276 construction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 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 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical class [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a fluidized-bed catalyst for preparing acrylonitrile by the arnmoxidation of propylene. Said catalyst contains silicon dioxide carrier and the composition whose chemical formula is Aa Bb Cc Ge dNa e Frf Big Mo12Ox. Where A is at least two selected from Li, K, Rb, Cs, Sm, In or Tl; B is at least one selected from P, Sb, Cr, W, Rr, Ce, As, B, Te, Cd or Vi and C is Ni and Co or their mixture. Said invented catalyst is specially used under the conditions of higher reaction pressure and high propylene load, and can keep high acrylonitrile single-pass yield, can be used in industrial production.
Description
The present invention relates to fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation.
Acrylonitrile is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to catalyst activity partly, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of acrylonitrile once through yield, and the raising of producing load.
Ammonia oxidation is produced acrylonitrile through 30 years of development, and the production capacity of factory and the market demand are near balance.The main development tendency of acrylonitrile process has been turned to the transformation of original factory, further to cut down the consumption of raw materials and to increase production capacity by the construction new equipment at present.By transformation to original factory, change the bottleneck in effective catalyst and the elimination production technology, the production capacity of acrylonitrile might improve 50～80%, and required investment only is 20～30% of a new device, economic benefit is very huge.
Can produce two problems during factory transforms: 1. the reaction pressure of fluidized-bed reactor will rise; 2. the useful load of catalyst can not be too many.The catalyst that for this reason requires to use instead should have higher propylene load and can bear higher reaction pressure.
The reaction pressure of fluidized-bed reactor is to be determined to the resistance drop that absorbs a series of heat exchangers, tower and pipe arrangement the cat head by reactor outlet.Because the increase of production capacity obviously increases the inventory of reactor outlet, above-mentioned resistance drop is increased.In addition, each heat exchanger heat transfer area also need increase heat transmission equipment inadequately, and resistance drop is further increased.Because environmental requirement, the reactor off-gas that absorbs cat head is forbidden directly to be discharged in the atmosphere, deliver to stove and burn.If like this without air-introduced machine, then must improve the absorption tower top pressure.For all the foregoing reasons, the operating pressure of reactor will increase by 0.5～1.0 times than design load at present, promptly reaches more than the 0.08MPa.
Above-mentioned second load that problem is a catalyst, i.e. WWH.Its definition is a catalyst per ton, per hour can handle what ton propylene.Because the increase of reactor feed amount, if the load of catalyst is constant, then the catalyst useful load is also wanted corresponding increase.But cooling water pipe insufficient height in the intrinsic fluidized-bed reactor, so the fluid height of catalyst reactor might surpass the height of cooling water pipe.In addition, because the increase of reactor feed amount, so operating linear velocity also significantly improves.The combined influence of these two variations might make reactor dilute phase temperature rise, and causes carbon dioxide production to increase, and the acrylonitrile selectivity descends.Therefore the WWH of catalyst is higher can prevent the problems referred to above.
The WWH that improves catalyst in theory should increase the adsorption capacity of catalyst to propylene, but at present still in the catalyst-free certain element can improve theory to the propylene adsorption capacity.The catalyst of following composition has been proposed in document CN1021638C:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hM
iMo
jO
x
Wherein A is potassium, rubidium, caesium, samarium, thallium; B is manganese, magnesium, strontium, calcium, barium, lanthanum, rare earth element; C is phosphorus, arsenic, boron, antimony, chromium; M is tungsten, vanadium.
Above-mentioned catalyst can obtain higher single-pass yield of acrylonitrile, but the propylene of catalyst load is lower, and single-pass yield of acrylonitrile descends bigger under higher reaction pressure.Studies show that further the B component in the above-mentioned catalyst is relevant with performance under high pressure to the load of catalyst with M.Though some element in the B component has effect to improving single-pass yield of acrylonitrile, and the raising of catalyst loading and the performance of high-response pressure are had negative effect, be unfavorable for that catalyst adapts to elevated pressures, operates under the higher load condition.Once in stipulating in CN1021638C in addition that above-mentioned catalyst was formed, the summation of i and j is 12, promptly is a constant.Cancel this regulation in the present invention,, will influence single-pass yield of acrylonitrile because molybdenum component will reduce when increasing by this regulation M component.
Introduced a kind of germanic ammoxidation catalyst that obtains the high acrylonitrile yield among document US 5688739 and the US5770757.Adopt molybdenum, bismuth, germanium system in the document, alkali metal containing in the optional elements, but the unexposed example that contains sodium among the embodiment, only disclosing reaction pressure in addition in the document is the reaction condition of normal pressure, not the concrete investigation data under high pressure, high-load condition.
The objective of the invention is to overcome the catalyst that exists in the above-mentioned document and do not relate to the problem of adaptation, a kind of new fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation is provided than high-response pressure and operational load.This catalyst can adapt under higher reaction pressure and higher loading condiction to be operated, and keeps high acrylonitrile once through yield.
The objective of the invention is to realize by following technical scheme: a kind of fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation, contain with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cGe
dNa
eFe
fBi
gMo
12O
x
A is selected among Li, K, Rb, Cs, Sm, In or the Tl at least two kinds in the formula:
B is selected from least a among P, Sb, Cr, W, Pr, Ce, As, B, Te, Cd or the V;
C is selected from Ni, Co or its mixture;
The span of a is 0.01～1.5;
The span of b is 0.01～3.0;
The span of c is 0.1～12.0;
The span of d is 0.01～2.0;
The span of e is 0.01～0.7;
The span of f is 0.1～8;
The span of g is 0.01～6;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein catalyst carrier is selected from silica, aluminium oxide or its mixture, and its consumption is 30～70% by weight percentage.
The value preferable range of c is 2～10 in the technique scheme, and the value preferable range of d is 0.01～1.0, and the value preferable range of e is 0.05～0.5, and the value preferable range of f is 1.0～3.0, and the value preferable range of g is 0.1～2.0.The preferred silica of catalyst carrier, its consumption are 40～60% by weight percentage.
The manufacture method of catalyst of the present invention there is no specific (special) requirements, can be undertaken by well-established law.At first the catalyst each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyst is made in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyst of the present invention is:
The molybdenum component is with molybdenum oxide or ammonium molybdate in the catalyst.
The most handy corresponding acids of phosphorus, arsenic and boron or its ammonium salt in the catalyst; Tungsten can be with ammonium tungstate or its oxide; Vanadium can be used ammonium metavanadate; Its oxide of germanium; The most handy chromium trioxide of chromium, chromic nitrate or the mixture of the two; Antimony can generate the antimony halides or the antimony colloidal sol of antimony oxide with antimony trioxide, antimony pentaoxide, hydrolysis; Other component can maybe can be decomposed into the salt of oxide with its nitrate, oxide, but preferably uses water miscible nitrate.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silica.If use Ludox, its quality will meet the requirement of CN1005248C.
It is 47～55% back spray-dryings that the prepared slurry heating is concentrated to solid content.Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyst of making has good size distribution with centrifugal better.
The roasting of catalyst can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyst.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Sintering temperature is 500～800 ℃, is preferably 550～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be divided into two zones in a stove, also can finish simultaneously in the continous way rotary roasting furnace and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air, prevent that catalyst is by over reduction.
Adopt the specification of catalyst manufacturing acrylonitrile of the present invention required propylene, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Though the low molecule saturated hydrocarbon content in the raw material propylene to the reaction did not influence, considers that from economic point of view density of propylene is more preferably greater than 85% (mole).Ammonia can be used fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be used pure oxygen from technical standpoint, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propylene is 8～10.5, is preferably 9.0～9.8.If owing to some operational reason must with higher air than the time, can increase to 11, reaction is not had significant impact.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fluidized-bed reactor, reaction temperature was 420～470 ℃, was preferably 430～450 ℃.Therefore catalyst of the present invention is a kind of high pressure, high load capacity catalyst of being applicable to, reaction pressure can be more than 0.08MPa in process units, for example, and 0.08～0.15MPa.Also do not have any adverse effect if reaction pressure is lower than 0.08MPa, single-pass yield of acrylonitrile can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.06～0.15 hour
-1, be preferably 0.07～0.10 hour
-1Loading to hang down not only wastes catalyst, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.Loading does not too highly have practical significance, because the catalyst addition is very few, the heat transfer area that can make cooling water pipe in the catalyst layer causes reaction temperature uncontrollable less than removing the required area of reaction heat.
The product of making acrylonitrile with catalyst of the present invention reclaims process for refining, and available existing production technology need not done any transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, with water at low temperature whole organic products is absorbed again.Absorption liquid is through extractive distillation, dehydrogenation cyanic acid and dewater high-purity propylene nitrile product.
The present invention is by adding component germanium in molybdenum, bismuth, iron and sodium catalyst system and catalyzing, find that this catalyst system and catalyzing has than high-response pressure (0.14MPa), and (WWH is 0.09 hour to higher load
-1) operational capacity under the condition, suitably add other effective active components in addition, this catalyst is operated under elevated pressures, higher load condition, its acrylonitrile once through yield reaches as high as 82.3%, has obtained effect preferably.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 550g, 440 ℃ of reaction temperatures, reaction pressure 0.14MPa, raw material proportioning (mole) is a propylene: ammonia: air=1: 1.2: 9.8, the propylene load (WWH) of catalyst is 0.090 hour
-1
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.[embodiment 1]
With 1.8 gram cesium nitrates, 4.64 gram sodium nitrate and 1.87 gram potassium nitrate mixing, add water 30 grams, the dissolving of heating back gets material (A); 9.34 gram chromium trioxides are dissolved in the 8.4 gram water, get material (B); 395.2 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 325 grams, get material (C); 90.45 gram bismuth nitrates, 135.6 are restrained cobalt nitrates, 14.7 gram praseodymium nitrates, 0.97 gram germanium oxide, 298.38 gram nickel nitrates and 150.8 gram ferric nitrates mixing, add water 70 grams, the dissolving of heating back gets material (D).
With material (A) and 1250 gram weight concentration is that 40% Ludox mixes, under agitation add material (B) and (C) and (D), fully stir slurry, by well-established law the slurry of making is shaped to framboid in spray dryer, it is 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (89 * 1700 millimeters of φ) in 610 ℃ of roastings 1 hour, the catalyst of making consists of: 50%Mo
12Bi
1.0Fe
2.0Co
2.5Ni
5.5K
0.1Cs
0.05Cr
0.5Pr
0.3Ge
0.05Na
0.29O
x+ 50%SiO
2[embodiment 2～9 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst of forming in the following table, and, the results are shown in Table 1 with carrying out the reaction that ammoxidation of propylene generates acrylonitrile under the prepared catalyst reaction condition below.
The reaction condition of the foregoing description and comparative example is:
38 millimeters fluidized-bed reactors of φ
440 ℃ of reaction temperatures
Reaction pressure 0.14MPa
Loaded catalyst 550g
Catalyst propylene load (WWH) 0.090 hour
-1
Raw material proportioning (mole) C
3 -/ NH
3/ air=1/1.2/9.8
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % | Acrylonitrile selectivity % | Propylene conversion % |
| Embodiment 1 | Mo 12Bi 1.0Fe 2.0Co 2.5Ni 5.5K 0.1Cs 0.05Cr 0.5Pr 0.3Ge 0.05Na 0.29O x | ????80.6 | ????81.7 | ????98.7 |
| Embodiment 2 | Mo 12Bi 1.0Fe 2.0Co 2.5Ni 5.5K 0.07Cs 0.08Cr 0.8Ge 0.5Na 0.29Sb 0.5O x | ????81.4 | ????82.1 | ????99.2 |
| Embodiment 3 | Mo 12Bi 1.0Fe 2.5Co 1.5Ni 6.0K 0.15Cs 0.05Ge 0.5Na 0.29W 1.0P 0.25O x | ????80.0 | ????81.2 | ????98.5 |
| Embodiment 4 | Mo 12Bi 1.0Fe 1.5Ni 7.0Cs 0.1Pr 0.3Ge 0.2Na 0.29W 0.8Sb 0.5O x | ????79.8 | ????81.5 | ????97.9 |
| Embodiment 5 | Mo 12Bi 1.0Fe 2.0Co 5.0Ni 2.5K 0.05Cs 0.2Cr 0.5Ge 0.5Na 0.29V 0.5P 0.5O x | ????81.1 | ????82.2 | ????98.7 |
| Embodiment 6 | Mo 12Bi 1.0Fe 2.5Co 2.5Ni 6.0K 0.05Cs 0.2Tl 0.05Pr 0.3Ge 0.3Na 0.29Sb 0.5O x | ????80.9 | ????81.8 | ????98.9 |
| Embodiment 7 | Mo 12Bi 1.0Fe 1.5Co 2.5Ni 6.0Cs 0.2Tl 0.25Cr 0.45Pr 0.3Ge 0.03Na 0.29P 0.5O x | ????79.5 | ????81.0 | ????98.1 |
| Embodiment 8 | Mo 12Bi 1.0Fe 2.0Co 2.0Ni 7.0K 0.09Cs 0.05Tl 0.25Ge 0.03Na 0.29W 0.1V 0.3Sb 0.5O x | ????82.3 | ????82.9 | ????99.3 |
| Embodiment 9 | Mo 12Bi 1.0Fe 2.5Co 2.5Ni 6.5K 0.13Cs 0.08Cr 0.5Pr 0.3Ge 0.5Na 0.29W 0.5Sb 0.5O x | ????80.7 | ????81.5 | ????99.0 |
| Comparative example 1 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.17Cs 0.05O x | ????76.8 | ||
| Comparative example 2 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.21O x | ????76.2 | ||
| Comparative example 3 | Mo 12Bi 0.9Fe 1.8Ni 2.4Co 4.3Na 0.15W 0.45Cr 0.45K 0.15Cs 0.07O x | ????77.1 | ||
| Comparative example 4 | Mo 12Bi 0.9Fe 1.8Ni 5.0Mg 2.0Na 0.15W 0.45Cr 0.45Cs 0.09O x | ????77.4 |
Claims (7)
1, a kind of fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation, contain with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cGe
dNa
eFe
fBi
gMo
12O
x
A is selected among Li, K, Rb, Cs, Sm, In or the Tl at least two kinds in the formula;
B is selected from least a among P, Sb, Cr, W, Pr, Ce, As, B, Te, Cd or the V;
C is selected from Ni, Co or its mixture;
The span of a is 0.01～1.5;
The span of b is 0.01～3.0;
The span of c is 0.1～12.0;
The span of d is 0.01～2.0;
The span of e is 0.01～0.7;
The span of f is 0.1～8;
The span of g is 0.01～6;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein catalyst carrier is selected from silica, aluminium oxide or its mixture, and its consumption is 30～70% by weight percentage.
2, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that d is 0.01～1.0.
3, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that c is 2～10.
4, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that e is 0.05～0.5.
5, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that f is 1.0～3.0.
6, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that g is 0.1～2.0.
7, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, it is characterized in that catalyst carrier is a silica, its consumption is 40～60% by weight percentage.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113988A CN1101264C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation |
| JP2001518186A JP4095302B2 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for the ammoxidation of propylene to acrylonitrile. |
| BRPI0013338-8A BR0013338B1 (en) | 1999-08-19 | 2000-06-21 | fluidized bed catalyst for propylene amoxidation to acrylonitrile. |
| DE10084931.8T DE10084931B3 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for the ammoxidation of propylene to acrylonitrile |
| ROA200200166A RO120244B1 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for ammoxidation of propylene into acrylonitrile |
| PCT/CN2000/000167 WO2001014057A1 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| AU53871/00A AU5387100A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| MXPA02001574A MXPA02001574A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile. |
| US09/642,289 US6420307B1 (en) | 1999-08-19 | 2000-08-18 | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113988A CN1101264C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1285237A true CN1285237A (en) | 2001-02-28 |
| CN1101264C CN1101264C (en) | 2003-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113988A Expired - Lifetime CN1101264C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384533C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Propylene Ammoxidation Catalyst |
| CN100408172C (en) * | 2005-01-26 | 2008-08-06 | 中国石油化工股份有限公司 | Fluid bed catalyst for acrylonitrile |
| CN101279264B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | High load fluidized bed catalyst for preparing acrylonitrile |
| WO2020177140A1 (en) * | 2019-03-07 | 2020-09-10 | 营口市向阳催化剂有限责任公司 | Acrylonitrile catalyst, preparation method therefor, and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3058961B2 (en) * | 1991-11-22 | 2000-07-04 | 積水化学工業株式会社 | Exterior wall with eaves attachment means |
| JP3058962B2 (en) * | 1991-11-28 | 2000-07-04 | サンデン株式会社 | Compressor |
| US5834394A (en) * | 1996-08-06 | 1998-11-10 | China-Petro-Chemical Corporation | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
| CN1063101C (en) * | 1996-08-06 | 2001-03-14 | 中国石油化工总公司 | Fluidized bed catalyst for preparing acrylonitrile |
| CN1055285C (en) * | 1997-12-11 | 2000-08-09 | 中国石油化工总公司 | Catalyst for propylene and isobutylene ammoxidation fluidized bed |
-
1999
- 1999-08-19 CN CN99113988A patent/CN1101264C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408172C (en) * | 2005-01-26 | 2008-08-06 | 中国石油化工股份有限公司 | Fluid bed catalyst for acrylonitrile |
| CN100384533C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Propylene Ammoxidation Catalyst |
| CN101279264B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | High load fluidized bed catalyst for preparing acrylonitrile |
| WO2020177140A1 (en) * | 2019-03-07 | 2020-09-10 | 营口市向阳催化剂有限责任公司 | Acrylonitrile catalyst, preparation method therefor, and application thereof |
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