CN100368085C - Preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene - Google Patents
Preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene Download PDFInfo
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- CN100368085C CN100368085C CNB2004100678660A CN200410067866A CN100368085C CN 100368085 C CN100368085 C CN 100368085C CN B2004100678660 A CNB2004100678660 A CN B2004100678660A CN 200410067866 A CN200410067866 A CN 200410067866A CN 100368085 C CN100368085 C CN 100368085C
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- China
- Prior art keywords
- preparation
- cuprammonia
- gas phase
- fluidized bed
- phase hydrogenation
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- 238000007598 dipping method Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000011218 segmentation Effects 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 26
- 238000005303 weighing Methods 0.000 description 20
- 238000013019 agitation Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000011651 chromium Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000007664 blowing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical group [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- -1 copper complex ion Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- XABJJJZIQNZSIM-UHFFFAOYSA-N azane;phenol Chemical compound [NH4+].[O-]C1=CC=CC=C1 XABJJJZIQNZSIM-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method of a fluid bed catalyst for producing aniline through nitrobenzene gas-phase hydrogenation, which mainly solves the problems of few cuprammonia sources, complicated catalyst preparation, short disposable service life, etc. in the prior art. In the preparation method, copper is used as raw material, silicon dioxide is used as a carrier, and the cuprammonia with the chemical formula of Cu<a>(NH<3>)<b>X<c> is used as steeping liquor, wherein x is selected from at least one of OH<->, NO3<->, SO4<2->, CO3<2->, CH3COO<->, HCOO<-> or (CO2)2<2->; chrome, molybdenum, etc., and active components which are not enforcedly added are added simultaneously; with the technical scheme, the preparation method better solves the problems of the prior art and can be used in industrial production for preparing the aniline through nitrobenzene hydrogenation.
Description
Technical field
The present invention relates to a kind of preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene.
Technical background
Aniline (Aniline; Benzenamine; Aminobenzene), be commonly called as aniline oil, be a kind of important Organic Chemicals and fine-chemical intermediate, reach kind more than 300 by Aniline Production than staple product, it is the important source material of plastics, spices, clothes, medicine and rubber accelerator, age resistor, the stabilizing agent that also is used for explosive, the anti-knock agent in the gasoline etc., and can make solvent.Because the demand to products such as synthetic leather, polyurethane constantly increases, 80% of global aniline output is used for the production of methyl diphenylene diisocyanate (MDI).
Aniline in 1826 is made when indigo by chemist O.Unverdorben destructive distillation first, and Bechamp in 1854 has developed nitrobenzene is reduced into aniline in the presence of iron powder and acetic acid industrialized preparing process, and carries out industrial production in 1857 by Perkin.
The aniline industrial production mainly adopts nitrobenzene (NB) reduction and phenol ammonia to separate technology.At present, each Aniline Production factory of the world mostly uses the nitrobenzene reduction route.Reduction of nitrobenzene is divided into iron powder reducing and hydrogenating reduction again.Hydrogenating reduction is divided into gas phase hydrogenation method and liquid-phase hydrogenatin method again.Gas phase hydrogenation has fluidized-bed process and fixed-bed process again.
According to the document of having delivered, the catalyst system that is used for the nitrobenzene gas phase hydrogenation has copper system, nickel system and precious metal palladium etc.Catalyst carrier has silica gel, zeolite, activated alumina and diatom scholar etc.Copper catalyst has higher activity and selectivity; Raney nickel is often made the multielement composite catalyst, to keep the high selectivity and the activity of reaction, avoids benzene ring hydrogenation.In concrete the production, adopt fixed bed or fluidized-bed reactor usually.
The bibliographical information of having delivered claims that the preparation method of Cu-series catalyst has equi-volume impregnating and ion-exchange usually, and the latter is by ammoniacal copper complex ion Cu (NH
3)
4 2+After the hydroxyl H on microsphere silica gel surface exchange, form stable
Structure is evenly distributed on the silica gel surface, has good decentralization, thereby has very high activity and selectivity.
Cuprammonia is a kind of complicated alkaline solution that has the number of chemical balance, is made up of different kinds of ions and more free ammonia.According to the document introduction of having delivered, the corresponding acid of acid ion is non-oxidizing acid in cuprammonia, and promptly X is OH
-, CO
3 2-, CH
3COO
-, HCOO
-, (CO
2)
2 2-, copper can not directly be dissolved in this class acid, needs oxidants such as blowing air, hydrogen peroxide, could oxidized dissolving, simultaneously with contain the ammonia solution effect and form corresponding cuprammonia; When the corresponding acid of acid ion is acid with strong oxidizing property, promptly X is NO
3 -, SO
4 2-, copper can directly be dissolved in acid and become soluble copper salt, again with contain the ammonia solution complexing and become corresponding cuprammonia.
The Australia scholar is at document Applied Catalysis[1987 (31)] in report be that raw material makes cuprammonia (PH=8～10) with copper nitrate and ammoniacal liquor, be that raw material, employing ion-exchange make Cu/SiO with this solution
2Catalyst, and compare with the catalyst that equi-volume impregnating makes, the former has better reactivity.
The patent US of document American Cyanamid Company 2891094 reports are with Cu (NO
3)
2.3H
2O and concentrated ammonia liquor are initiation material, make cuprammonia, and the catalyst that makes with this solution is used for the aniline production by gas phase hydrogenation of nitrobenzene reaction, and the selectivity of aniline and the conversion ratio of nitrobenzene all are higher than 99.5% for a long time.
The patent US 2822397 of U.S. Unichem is with nickel/aluminium catalyst series, adopt the Fixed Bed Gas Phase hydrogenation method, the mol ratio of nitrobenzene and hydrogen is 1: 9, and load reaches per hour every liter of catalyst, the inlet amount of nitrobenzene is 300 grams, and its nitrobenzene air speed is about 0.5 hour
-1, reaction temperature is 300 ℃, the initial yield of aniline is 99.5%.
Patent US 4265834 is with Pd-V-Mo-Cr-Pb-Bi-Zn/ α-Al
2O
3Be catalyst, adopt tubular reactor, 260～270 ℃ of reaction temperatures, hydrogen is than 1: 6, the initial yield 99.85% of aniline.Shortcoming is that fixed bed is removed difficulty of heat, needs frequently to stop.
Patent GB 1385454 is a catalyst with Cu-Cr-Ba-Mg, fixed bed reactors, and 200～300 ℃ of reaction temperatures, pressure is 0.2～0.4MPa, adopts hydrogen, nitrogen mixture body, ratio is NB: H
2: N
2=1: 7～19: 1.8～2.9, catalyst reaches 1 year entire life after repeatedly regenerating.But this technology nitrobenzene conversion ratio is 85～90% to need recycled, and the hydrogen use amount is bigger.
Patent US 3504035 is a catalyst with Cu-Si or Cu-Al, and Cr, Ba, Zn etc. carry out modification, 200～400 microns of catalyst particle sizes.Adopt fluid bed gas phase hydrogenation method, 250～300 ℃ of reaction temperatures, reaction pressure 0.4～1.0Mpa, the mol ratio of nitrobenzene and hydrogen is 1: 3, the initial yield of aniline is greater than 99%.
Above document has only reported one, the preparation method of two kind of cuprammonia, though and the initial yield of the aniline that has higher, can reach 99.85%, but all less than disclosing its concrete lifetime data.Catalyst in the above-mentioned document is 5.0 hours through the inventor in the nitrobenzene air speed
-1, adopting hydrogen, nitrogen mixture body, mol ratio is NB: H
2: N
2=1: 9～18: under 1.4～2.0 conditions, reach 0.1% as test endpoint with the concentration that detects nitrobenzene NB in the product, accelerate degradation and measure a life-span discovery of catalyst, a life-span is all less than 50 hours, be that reaction unit needs catalyst is carried out frequent regeneration, could satisfy production requirement.
Summary of the invention
Technical problem to be solved by this invention be the preparation catalyst that provides in the prior art the cuprammonia source less, preparation is complicated, the disposable life-span of catalyst is short, cause catalyst regeneration frequent, the problem that influence is produced provides a kind of preparation method of new fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene.The catalyst that uses this method to prepare is used for the manufacturing process of aniline through nitrobenzene hydrogenation process and has the initial yield height of aniline, long characteristics of disposable life-span of catalyst.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene may further comprise the steps:
(1) in the presence of air and ammonia source, reaction temperature is 40～65 ℃, and oxidized metal copper becomes cuprammonia, and cuprammonia is formed expression with mole and comprised following general formula: Cu
a(NH
3)
bX
c
Wherein, the span of a is 1～2;
The span of b is 1～5;
The span of c is 0.5～4;
X is selected from OH
-, NO
3 -, SO
4 2-, CO
3 2-, CH
3COO
-, HCOO
-Or (CO
2)
2 2-In at least a;
(2) carrier silica is selected from aqueous metal salt incipient impregnation at least a among Cr, Mo, Ba, Zn, Ce, Ni, V, Pb or the Pt with containing, oven dry, roasting;
(3) will obtain catalyst through the silica supports and the cuprammonia hybrid infusion of above-mentioned processing.
In the technique scheme, the value preferable range of a is 1 or 2; The preferred span of b is 2～4; The preferable range of c is 1～2; The preferable range of x is OH
-, CO
3 2-, CH
3COO
-Or (CO
2)
2 2-In at least a.In the cuprammonia, copper content preferable range is 1.70～2.20 mol; The pH value preferable range of cuprammonia is 9～11; The preferable range of cuprammonia proportion is 1.10～1.20.Described slaine is preferably nitrate or ammonium salt.By weight, the liquid-solid ratio of cuprammonia and treated carrier silica is 0.9～2.0, and dipping temperature is 45～95 ℃, and impregnation pressure is 2.66 * 10
-3～0.25MPa is preferably 2.66～3.99 * 10
-3The negative pressure of MPa or the malleation of 0.11～0.25MPa.The impregnation method of cuprammonia and carrier is preferably segmentation dipping or constant temperature dipping.Segmentation dipping optimum condition is 1～4 hour, 85～95 ℃ dippings of 2～5 hours, 60～80 ℃ dippings of 45～60 ℃ of dippings 3～8 hours.Constant temperature dipping optimum condition is 60～95 ℃ of dippings 5～12 hours.
Preparation method of the present invention is as follows:
A) metallic copper is put into reaction pot, impurity such as the oxide on first purifying a spot of other metal of removal and surface thereof, chloride, final copper content needs greater than 99.0% (weight).After adding water, add blowing air behind ammonia, corresponding acid or the ammonium salt-containing again, metallic copper is the oxidized cuprammonia that forms constantly;
B) at least a slaine wiring solution-forming that will contain among Cr, Mo, Ba, Zn, Ce, Ni, V, Pb or the Pt mixes drying, roasting with carrier silica;
C) will flood a few hours through the silica and the cuprammonia of above-mentioned processing, filter, washing, oven dry gets the catalyst finished product after the roasting.
The raw material of preparation manufacturing process of aniline through nitrobenzene hydrogenation fluid catalyst is:
Copper is cathode copper or copper powder;
Acid is sulfuric acid, glacial acetic acid (weight percent concentration is 36～100%), formic acid, oxalic acid, carbonic acid or carbon dioxide etc.;
Ammonia is ammonia or concentrated ammonia liquor (weight percent concentration is 25%);
Ammonium salt-containing is ammonium salt or hydrogen ammonium salt, and the anion of salt is the acid ion of above-mentioned acid;
The chromium source is chromic nitrate, potassium chromate, ammonium chromate, chromic anhydride or chromium+oxalic acid;
The molybdenum source is an ammonium molybdate;
The barium source is barium nitrate or barium hydroxide;
The zinc source is zinc nitrate, zinc acetate or zinc hydroxide;
The cerium source is cerous nitrate or cerium oxalate;
The nickel source is a nickel nitrate.
Using the specific surface area of catalyst of the inventive method preparation is 200～500 meters
2/ gram, pore volume is 0.2～1.5 centimetre
3/ gram, average pore size is greater than 5 nanometers, and average grain diameter is 40～200 microns.
Examination device of the present invention is 38 * 1800 millimeters stainless steel fluidized-bed reactors of , in adorn 250 milliliters of catalyst.
The examination process conditions are: 180～300 ℃ of reaction temperatures, and 220～270 ℃ of reasonable scopes, the mol ratio of nitrobenzene and hydrogen are 1: 4～12, reasonable scope 1: 6～9, reaction pressure is generally normal pressure, also can operate at pressurized conditions.
Reacted air-flow cools off through condenser, carries out gas-liquid separation, and product is collected in the receiver.Be sampled as one hour, the conversion ratio of gas chromatographic analysis nitrobenzene and the yield of aniline at every turn.
Computing formula:
The present invention is because employing new copper ammoniacal liquor is that maceration extract prepares copper-based catalysts, added the active constituent of chromium, molybdenum etc. and non-imposed adding simultaneously, the inventor is surprised to find that, catalyst not only can keep the higher initial yield of aniline, and the disposable life-span can reach 176 hours, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
After placing 5～10% sodium hydroxide solutions to boil 3 hours the electrolysis copper billet that reclaims, lixiviating liquid soaked 8 hours with 3% rare nitric acid or dilute sulfuric acid again, and disacidify liquid is washed to neutrality, the purifying copper that obtains, and content is greater than 99.5% (weight), and is standby.
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds entry 418 grams, glacial acetic acid 113 grams, stir down logical ammonia to PH greater than 7.0, add above-mentioned copper billet 63.6 grams, blowing air and ammonia maintain the temperature at below 70 ℃, add above-mentioned copper billet 21.8 grams after about 4 hours again, continuation blowing air, ammonia to copper powder react completely, and need 7 hours approximately, cooling, cross a small amount of residue of elimination, obtain cuprammonia (1).By analysis, total copper content (molar concentration) is 2.14 mol, and proportion 1.15, pH value are 10.9.
Take by weighing 1.8 gram (NH
4)
2CrO
4, 1.1 the gram (NH
4)
6Mo
7O
244H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (A).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 530 gram and mix stirring with carrier (A), prior to 50～60 ℃ the dipping 2 hours, be warming up to 70～80 ℃ the dipping 4 hours, rise to again 85～90 ℃ the dipping 4 hours, cooling, filter, with 500 milliliters of washed twice of 2.5% weak aqua ammonia, blue with the deionized water washing again to not having, in 100 ℃ of oven dry 12 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 2]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.2 gram Ba (NO
3)
2With 2.7 gram Zn (NO
3)
26H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (B).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 450 gram and mix stirring with carrier (B), prior to 50～60 ℃ the dipping 2 hours, be warming up to 70～80 ℃ the dipping 2 hours, rise to again 85～90 ℃ the dipping 8 hours, cooling, filter, with 500 milliliters of washed twice of 2.5% weak aqua ammonia, blue with the deionized water washing again to not having, in 100 ℃ of oven dry 12 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 3]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.1 gram (NH
4)
6Mo
7O
244H
2O, 1.2 gram Ba (NO
3)
2With 2.7 gram Zn (NO
3)
26H
2O and 3.0 gram Ni (NO
3)
26H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (C).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 485 gram and mix stirring with carrier (C), prior to 50～60 ℃ the dipping 2 hours, be warming up to 70～80 ℃ the dipping 3 hours, rise to again 85～90 ℃ the dipping 5 hours, cooling, filter, with 500 milliliters of washed twice of 2.5% weak aqua ammonia, blue with the deionized water washing again to not having, in 100 ℃ of oven dry 12 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 4]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 3.1 gram Ce (NO
3)
36H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (D).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 530 gram and mix stirring with carrier (D), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 5]
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, add entry 364 gram, glacial acetic acid 77.3 grams, stir down logical ammonia to PH greater than 7.5, disposable adding copper powder (weight 99.7%, 100 orders) 68.2 grams (1.07 moles), blowing air and ammonia maintain the temperature at below 70 ℃, need 4～5 hours fully approximately to copper powder dissolving, the a small amount of residue of elimination is crossed in cooling, obtains cuprammonia (2).By analysis, total copper content (molar concentration) is 2.07 mol, and proportion 1.17, pH value are 10.5.
Take by weighing 7.2 gram (NH
4)
2CrO
4, 4.4 the gram (NH
4)
6Mo
7O
244H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (E).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (2) 485 grams and mix stirring with carrier (E), all the other operations are with [embodiment 3].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 6]
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds entry 350 grams, carbonic hydroammonium 122 grams (1.55 moles), logical ammonia is molten entirely to salt under stirring, add copper powder 65.6 gram (1.03 moles) (weight 99.7%, 100 orders), blowing air and ammonia, maintain the temperature at below 65 ℃, complete to the copper powder dissolving, need 5～6 hours approximately, cooling, cross a small amount of residue of elimination, obtain cuprammonia (3).By analysis, total copper content (molar concentration) is 1.87 mol, and proportion 1.13, pH value are 10.5.
Carrier (A) preparation is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (3) 520 grams and mix stirring with carrier (A), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 7]
The preliminary treatment of copper is with [embodiment 1].
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds 435 gram water, glacial acetic acid (weight 36%) 70.5 gram (0.38 mole), oxalic acid C
2H
2O.H
2O 49.0 gram (0.38 mole), stir down logical ammonia to PH greater than 7.5, add above-mentioned copper billet 54.5 grams (0.86 mole), blowing air and ammonia, maintain the temperature at below 60 ℃, react completely to copper powder, need 8～10 hours approximately, the a small amount of residue of elimination is crossed in cooling, obtains cuprammonia (4).By analysis, total copper content (molar concentration) is 1.79 mol, and proportion 1.18, pH value are 11.0.
Carrier (A) preparation is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (4) 540 grams and mix stirring with carrier (A), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 8]
The preliminary treatment of copper is with [embodiment 1].
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds entry 435 grams, oxalic acid 49.0 grams (0.38 mole), and ammonium carbonate 37.3 grams (0.38 mole), all the other are operated with embodiment 7, obtain cuprammonia (5).By analysis, total copper content (molar concentration) is 1.85 mol, and proportion 1.12, pH value are 10.5.
Carrier (A) preparation is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (5) 523 grams and mix stirring with carrier (A), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 9]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.2 gram Ba (NO
3)
2With 2.7 gram Zn (NO
3)
26H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (B).
Take by weighing cuprammonia (1) 450 gram and go into 1 liter of withstand voltage reaction bulb (joining Pressure gauge) and mixes stirrings with carrier (B), flooded 2 hours prior to 50～60 ℃, be warming up to 70～80 ℃ and flooded 2 hours, rise to 85～90 ℃ again and flooded 8 hours, impregnation pressure is 0.2MPa.All the other operations are with [embodiment 2].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 10]
The preparation method of cuprammonia (1) is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 450 gram and mix stirring, at system pressure 3 * 10 with 160 gram silica
-3The MPa dipping, all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 11]
The preparation method of cuprammonia (1) is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 530 gram and mixes stirrings with 160 gram silica, flooded 10 hours in 80～85 ℃, all the other operate [embodiment 1] together.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 1]
With 139 gram Cu (NO
3)
23H
2O adds water 400 grams and is dissolved into blue liquid, adds 160 in 50～60 ℃ and restrains the silica incipient impregnations, stirs after 30 minutes, dries 10 hours for 110 ℃, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 2]
With 139 gram Cu (NO
3)
23H
2O, 1.8 gram (NH
4)
2CrO
4, 1.1 the gram (NH
4)
6Mo
7O
244H
2O adds hot water 400 gram dissolvings, adds 160 gram silica incipient impregnations while hot, stirs after 30 minutes, in 110 ℃ of oven dry 8 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 3]
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.1 gram (NH
4)
6Mo
7O
244H
2O, 1.2 gram Ba (NO
3)
2, 2.7 gram Zn (NO
3)
26H
2O, 3.0 gram Ni (NO
3)
26H
2O and 139 gram Cu (NO
3)
23H
2O is dissolved in the 400 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, dries 8 hours for 110 ℃, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 4]
The cuprammonia preparation is with [embodiment 5].
Take by weighing 10.8 gram (NH
4)
2CrO
4, 6.6 the gram (NH
4)
6Mo
7O
244H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (F).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (2) 485 grams and mix stirring with carrier (F), all the other operations are with [embodiment 3].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 5]
Operation is with [embodiment 1], and difference substitutes carrier (A) with silica.
[embodiment 12]
The catalyst of [embodiment 1～11] and [comparative example 1～5] preparation adopts fluid bed gas phase hydrogenation technology, and the nitrobenzene air speed is 5.0 hours
-1, adopting hydrogen, nitrogen mixture body, mol ratio is NB: H
2: N
2=1: 9～18: 1.4～2.0, reach 0.1% (GC analytic approach, area normalization method) as test endpoint with NB concentration in product, the rerum natura of catalyst and disposable life-span are as shown in table 1.
Table 1
| Sequence number | Catalyst is formed % (weight) | Specific surface rice 2/ gram | Pore volume centimetre 3/ gram | The average pore size nanometer | Disposable life-span hour | The initial yield % of aniline | ||||||
| Cu | Cr | Mo | Ni | Ba | Zn | Ce | ||||||
| Embodiment 1 | 19.0 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 435.28 | 0.71 | 6.81 | 148 | 99.92 |
| Embodiment 2 | 18.1 | 0.3 | 0 | 0 | 0.3 | 0.3 | 0 | 427.84 | 0.76 | 7.10 | 160 | 99.94 |
| Embodiment 3 | 17.5 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0 | 415.90 | 0.78 | 7.02 | 176 | 99.96 |
| Embodiment 4 | 18.3 | 0 | 0 | 0 | 0 | 0 | 0.5 | 418.37 | 0.74 | 7.05 | 140 | 99.94 |
| Embodiment 5 | 17.2 | 1.2 | 1.2 | 0 | 0 | 0 | 0 | 395.24 | 0.77 | 7.21 | 108 | 99.92 |
| Embodiment 6 | 19.9 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 450.74 | 0.71 | 6.50 | 124 | 99.94 |
| Embodiment 7 | 19.3 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 441.63 | 0.73 | 6.42 | 132 | 99.92 |
| Embodiment 8 | 19.6 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 440.82 | 0.72 | 6.34 | 116 | 99.90 |
| Embodiment 9 | 15.4 | 0.3 | 0 | 0 | 0.3 | 0.3 | 0 | 375.38 | 0.83 | 7.32 | 100 | 99.91 |
| Embodiment 10 | 18.8 | 0 | 0 | 0 | 0 | 0 | 0 | 451.32 | 0.69 | 8.21 | 92 | 99.90 |
| Embodiment 11 | 17.7 | 0 | 0 | 0 | 0 | 0 | 0 | 412.41 | 0.79 | 6.93 | 88 | 99.85 |
| Comparative example 1 | 18.5 | 0 | 0 | 0 | 0 | 0 | 0 | 60.34 | 0.45 | 5.38 | 26 | 99.51 |
| Comparative example 2 | 18.0 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 65.49 | 0.31 | 5.01 | 38 | 99.62 |
| Comparative example 3 | 18.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0 | 69.88 | 0.28 | 4.96 | 44 | 99.78 |
| Comparative example 4 | 17.4 | 1.8 | 1.8 | 0 | 0 | 0 | 0 | 405.13 | 0.74 | 7.21 | 82 | 99.88 |
| Comparative example 5 | 19.1 | 0 | 0 | 0 | 0 | 0 | 0 | 430.74 | 0.75 | 7.13 | 74 | 99.83 |
Claims (10)
1. the preparation method of a fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene may further comprise the steps:
(1) in the presence of air and ammonia source, reaction temperature is 40～65 ℃, and oxidized metal copper becomes cuprammonia, and cuprammonia is formed expression with mole and comprised following general formula: Cu
a(NH
3)
bX
c
Wherein, the span of a is 1～2;
The span of b is 1～5;
The span of c is 0.5～4;
X is selected from OH
-, NO
3 -, SO
4 2-, CO
3 2-, CH
3COO
-, HCOO
-Or (CO
2)
2 2-In at least a;
(2) carrier silica is selected from aqueous metal salt incipient impregnation at least a among Cr, Mo, Ba, Zn, Ce, Ni, V, Pb or the Pt with containing, oven dry, roasting;
(3) will obtain catalyst through the silica supports and the cuprammonia hybrid infusion of above-mentioned processing.
2. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1, the span that it is characterized in that a is 1 or 2; The span of b is 2～4; The span of c is 1～2; X is selected from OH
-, CO
3 2-, CH
3COO
-, or (CO
2)
2 2-In at least a.
3. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1 is characterized in that in the cuprammonia, and the molar concentration of copper is 1.70～2.20 mol; The pH value of cuprammonia is 9～11; The proportion of cuprammonia is 1.10～1.20.
4. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1 is characterized in that described slaine is nitrate or ammonium salt.
5. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1, it is characterized in that by weight, the liquid-solid ratio of cuprammonia and treated silica supports is 0.9～2.0, and dipping temperature is 45～95 ℃, and impregnation pressure is 2.66 * 10
-3～0.25MPa.
6. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 5 is characterized in that impregnation pressure is 2.66～3.99 * 10
-3The negative pressure of MPa.
7. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 5 is characterized in that impregnation pressure is the malleation of 0.11～0.25MPa.
8. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1, the impregnation method that it is characterized in that cuprammonia and carrier is segmentation dipping or constant temperature dipping.
9. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 8 is characterized in that the segmentation dipping is 1～4 hour, 85～95 ℃ dippings of 2～5 hours, 60～80 ℃ dippings of 45～60 ℃ of dippings 3～8 hours.
10. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 8 is characterized in that the constant temperature dipping is 60～95 ℃ of dippings 5～12 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100678660A CN100368085C (en) | 2004-11-05 | 2004-11-05 | Preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene |
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| CN102000612B (en) * | 2009-09-02 | 2013-03-06 | 中国石油化工集团公司 | Carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and preparation method of catalyst |
| CN106565504B (en) * | 2015-10-12 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of method of nitrobenzene liquid-phase hydrogenatin aniline |
| CN115532300B (en) * | 2021-06-29 | 2023-11-28 | 中石化南京化工研究院有限公司 | Catalyst for preparing aniline by nitrobenzene hydrogenation, preparation method and application |
| CN115999548A (en) * | 2021-10-21 | 2023-04-25 | 中石化南京化工研究院有限公司 | Catalyst for preparing aniline by nitrobenzene hydrogenation and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2891094A (en) * | 1955-02-17 | 1959-06-16 | American Cyanamid Co | New catalyst for reducing nitrobenzene and the process of reducing nitrobenzene thereover |
-
2004
- 2004-11-05 CN CNB2004100678660A patent/CN100368085C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2891094A (en) * | 1955-02-17 | 1959-06-16 | American Cyanamid Co | New catalyst for reducing nitrobenzene and the process of reducing nitrobenzene thereover |
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