CN112642430A - Preparation method of microspherical catalyst for preparing butadiene through oxidative dehydrogenation of butene - Google Patents
Preparation method of microspherical catalyst for preparing butadiene through oxidative dehydrogenation of butene Download PDFInfo
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- CN112642430A CN112642430A CN201910963041.3A CN201910963041A CN112642430A CN 112642430 A CN112642430 A CN 112642430A CN 201910963041 A CN201910963041 A CN 201910963041A CN 112642430 A CN112642430 A CN 112642430A
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- Prior art keywords
- catalyst
- preparing
- nitrate
- calcium chloride
- anhydrous calcium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 21
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims description 9
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 110
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012065 filter cake Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000009718 spray deposition Methods 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 128
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 18
- 239000007921 spray Substances 0.000 claims description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 description 18
- 238000001914 filtration Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- -1 butylene Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/843—Arsenic, antimony or bismuth
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a microspherical catalyst for preparing butadiene by oxidative dehydrogenation of butylene, which comprises the steps of adding zinc nitrate, anhydrous calcium chloride and an auxiliary agent into an iron nitrate solution, wherein the molar ratio of the iron nitrate to the zinc nitrate is 500: 125-500: 375, adding an alkaline precipitator after dissolution, and carrying out parallel-flow precipitation to obtain a hydroxide precursor; then adding Fe thereto2O3Sol; then, aging and washing the colloidal solution, and keeping a filter cake; will filterGrinding the cakes, preparing slurry, adding a stabilizer, performing spray forming to obtain a microspherical catalyst, roasting at 200-400 ℃ for 1-4 hours, and roasting at 400-600 ℃ for 3-7 hours to obtain a catalyst finished product. The catalyst has higher catalytic activity and stability for butylene oxidative dehydrogenation reaction.
Description
Technical Field
The invention relates to a preparation method of a microspherical catalyst for preparing butadiene by oxidative dehydrogenation of butylene, in particular to a preparation method of a ferrite spinel catalyst for preparing butadiene by oxidative dehydrogenation of butylene.
Background
Butadiene is an important petrochemical basic raw material second only to ethylene and propylene, is mainly used for producing synthetic rubber, resin and some chemical products, and has wide application. The traditional butadiene production methods are mainly of two types: one is obtained from the dehydrogenation of refinery oil fractions; the other method is to extract and separate the byproduct C4 fraction of ethylene cracking, which is a main source of butadiene and has lower cost, but with the lightening of raw materials of an ethylene cracking device, the yield of butadiene is greatly reduced, and the demand of butadiene is more and more increased due to the rapid development of the rubber industry. In addition, since the surplus C4 is required to be used as a high value-added fuel after natural gas is used as a fuel instead of liquefied gas, technologies for producing butadiene by oxidative dehydrogenation of butene are receiving more and more attention.
The catalyst used for preparing butadiene by oxidative dehydrogenation of butylene mainly comprises bismuth molybdate series, ferrite spinel series and other catalysts, wherein the ferrite catalyst has the advantages of high activity, high selectivity, low generation rate of oxygen-containing compounds, no toxicity and the like, and has wide application prospect and more researches.
Patents US3450788 and US3450787 describe various spinel-type ferrochromate butene oxidative dehydrogenation catalysts, wherein the spinel-type ferrochromate catalysts have a good reaction performance for preparing butadiene by oxidative dehydrogenation of butene, the single-pass molar conversion of butene is 70%, and the molar selectivity of butadiene is up to 92%.
Patent CN105772001A discloses a ferrite catalyst, a preparation method and application thereof, wherein the catalyst has a general formula FeAaDbOcWherein A is Mg, Zn or a mixture thereof in any proportion; d is one or more of Ni, Co, Mn, Ca, Mo or V; a is 0.01 to 0.6; b is 0-0.30; c is a number satisfying a valence of an atom. The preparation method of the catalyst comprises the following steps: the ferrite catalyst is obtained by mixing metal oxide precursors according to a chemical ratio and ball milling, and the catalyst shows excellent activity and selectivity when used for preparing butadiene by oxidative dehydrogenation of butylene, and the catalyst has the advantages of simple and controllable preparation process, good repeatability and no generation of wastewater and waste gas in the preparation process.
However, the traditional butylene oxidative dehydrogenation catalyst forming method is a roasting and press forming method, and the process has the problems of complex process, serious dust pollution, low catalyst yield, uneven catalyst particles, poor strength, high production cost and the like. The spray forming process can effectively solve the problems existing in the process, so the spray forming process is applied to the preparation of the microsphere iron-based catalyst for preparing butadiene through oxidative dehydrogenation of butylene.
Patent CN105536796A provides a wear-resistant microspherical Fe2O3/SiO2The preparation method of the catalyst comprises the steps of roasting the precipitation-method silicon dioxide powder or white carbon black at the temperature of 730-760 ℃, adding water for uniformly mixing, and grinding silicon dioxide microparticles to the temperature of 730-760 ℃ by using grinding dispersion equipmentAdding silica sol into the mixture with the average diameter of 2-5 mu m, uniformly mixing, performing spray granulation, roasting at 650-720 ℃ to prepare a microspherical silicon dioxide carrier, soaking in ferric nitrate solution, drying, and roasting to prepare wear-resistant microsphere Fe2O3/SiO2A catalyst. The prepared catalyst has high mechanical strength and wear resistance, high catalytic activity and suitability for fluidized bed catalytic reaction.
The patent CN102580749B discloses a production process of a catalyst for preparing butadiene by oxidative dehydrogenation of butylene, which comprises the steps of adding mixed slurry of calcium chloride, calcium hydroxide and zinc oxide into ferric nitrate solution, then using ammonia water as a precipitator to gelatinize the solution, and enabling the pH value of a precipitation end point to be 8.3-8.4; adding a binder and activated carbon into the precipitated colloid, aging at 70-80 ℃ for 10-60 min, cooling to room temperature, filtering and washing until the pH value of the filtrate is 7, and retaining a filter cake; preparing the filter cake into slurry with the water content of 60-75%, and performing spray forming, wherein the pressure of a high-pressure spray nozzle is 1.0-10.0 MPa, the temperature of a feed inlet of a spray tower is 300-500 ℃, and the temperature of a discharge outlet is 120-200 ℃, so as to obtain a finished microspherical catalyst product; the catalyst does not contain chromium element, has good wear resistance, and is mainly used for the reaction of preparing butadiene by catalyzing butylene oxidative dehydrogenation by a baffle fluidized bed. However, the catalyst has low butadiene yield and selectivity, and the operation stability of the catalyst is not investigated.
The patent CN105749930A discloses a catalyst for preparing butadiene by oxidative dehydrogenation of butene and a preparation method thereof, wherein a metal precursor A, B, C, D is respectively ground into microspheres of 40-100 meshes, a metal precursor A is divided into two parts which are respectively added into a mixed precursor B, C, D at intervals of 30-90 min, and a binder is added after reaction for 20-80 min to obtain slurry of a precursor precipitate; then adjusting the pH value of the slurry to 7.5-10.0 by using ammonia water, thermally modifying the slurry at 80-95 ℃ for 60-180 min, filtering and washing, and adjusting the solid content of the slurry to 5-40% and the pH value to 7.0-7.5; carrying out spray forming on the obtained slurry, and roasting for 6-12 h at 400-500 ℃ to obtain a catalyst finished product; the obtained catalyst has the general formula AaBbCcDd·FexOeWherein A is Cu,Zn or Cr; b is Co, Mn, Ni or Mo; c is Ca, Sr, Ba or Mg; d is W; a is 1-6, b is 0.01-0.3, c is 0.1-1.0, d is 0.01-0.1, x is 4-18, and e is any value meeting the valence requirement. The catalyst is used in the reaction of preparing butadiene by oxidative dehydrogenation of butylene, and the reaction temperature is 380 ℃, and the volume space velocity of the butylene is 800h-1The catalyst has good stability, and the preparation process shows that the catalyst is easy to have the problems of low particle uniformity, uneven distribution of active components and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a microspherical catalyst for preparing butadiene by oxidative dehydrogenation of butylene2O3The catalyst has high catalytic activity and stability for oxidative dehydrogenation reaction of butylene, and has the advantages of uniform particles, uniform distribution of active components, low roasting temperature, high specific surface area, good wear resistance and the like.
Therefore, the invention provides a preparation method of a microspherical catalyst for preparing butadiene by oxidative dehydrogenation of butene, which specifically comprises the following steps:
(1) adding zinc nitrate, anhydrous calcium chloride and an auxiliary agent into a ferric nitrate solution in sequence to obtain a mixed aqueous solution, wherein the molar ratio of ferric nitrate to zinc nitrate in the ferric nitrate solution is 500: 125-500: 375;
(2) adding an alkaline precipitator into the mixed aqueous solution of the step (1), and obtaining Fe (OH) through cocurrent flow precipitation3、Zn(OH)2Uniformly mixing the hydroxide precursor aqueous solution;
(3) preparation of Fe (NO)3)3Precipitating the solution under the action of alkaline precipitant to obtain Fe2O3Sol of said Fe2O3Fe in sol2O3The mass fraction of (A) is 5-20%;
(4) mixing Fe2O3Adding the sol into the hydroxide precursor aqueous solution and fully stirring to obtain a colloidal solution, wherein the Fe is2O3The using amount of the sol is 0.3-3.0% of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride;
(5) aging, filtering and washing the colloidal solution obtained in the step (4), and keeping a filter cake;
(6) grinding the filter cake, preparing slurry, adding a stabilizer, and performing spray forming to obtain a microspherical catalyst;
(7) roasting the catalyst obtained in the step (6) at 200-400 ℃ for 1-4 h, and roasting at 400-600 ℃ for 3-7 h to obtain a catalyst finished product.
In some embodiments, in step (3), the Fe (NO)3)3Precipitating the solution with alkaline precipitant at 80 deg.C and pH of 5-8 to obtain Fe2O3And (3) sol.
In some embodiments, in steps (2) and (3), the alkaline precipitating agent is selected from NaOH, KOH, Na2CO3、K2CO3And ammonia water.
In some embodiments, in step (1), the additive is at least one selected from the group consisting of nitrates of Mg, Cu, Ni, Co, Bi, Sr and chlorides of Mg, Cu, Ni, Co, Bi, Sr.
In some embodiments, in the step (1), the amount of the auxiliary agent is 2.0-4.0% of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride.
In some embodiments, in step (1), the ratio of the amount of ferric nitrate to the amount of anhydrous calcium chloride material is 500:2 to 500: 15.
In some embodiments, in step (2), the pH during the co-current precipitation is 7.5 to 10.
In some embodiments, in step (4), the Fe is added2O3And adding the sol into a hydroxide precursor aqueous solution, and stirring for 3-12 h to fully react.
In some embodiments, in the step (5), the aging treatment is performed at 70-100 ℃ for 0.5-3 hours.
In some embodiments, in the step (6), the stabilizer is at least one (including two or more) selected from the group consisting of propylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether and polyethylene glycol, and the amount of the stabilizer is 1.0-3.0% of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride.
In some embodiments, in step (6), the filter cake is milled in a colloid mill to an average diameter of 30 to 80 μm.
In some embodiments, in step (6), the milled filter cake is configured into a slurry with a solid content of 5-30%.
In some embodiments, in the step (6), the spray forming is performed by using a centrifugal spray tower, wherein the temperature of a feed inlet of the centrifugal spray tower is 200-400 ℃, the temperature of a discharge outlet of the centrifugal spray tower is 100-150 ℃, and the rotating speed of a centrifugal nozzle is 5000-12000 r/min.
In some embodiments, in the step (7), the catalyst product is spherical particles with the particle size of 60-120 μm.
In the above invention, the zinc nitrate may be added in the form of a solid or in the form of an aqueous solution as long as it satisfies the molar ratio with respect to the iron nitrate and can be completely dissolved.
The active phase of the butylene oxidation dehydrogenation iron-based catalyst is ferrite spinel crystal phase and Fe2O3The catalytic activity is best in the coexistence of the crystal phase. The preparation method of the catalyst adopts the proper proportion of ferric nitrate and zinc nitrate, and accurately controls Fe through parallel-flow precipitation2(NO3)3、ZnNO3Rate of precipitation such that Fe (OH) is present in the precipitate3And Zn (OH)2Distributed more uniformly and decomposed at a lower roasting temperature to form spinel-type ZnFe2O4The distribution of the oxides of Fe and Zn is more uniform, thereby achieving the effect of controlling the crystal structure.
In addition, by introducing Fe in the preparation of the catalyst2O3The sol serves as a binder on the one hand and supplements Fe on the surface of the catalyst during the roasting process on the other hand2O3A crystalline phase. Thereby precipitating and Fe by co-current flow2O3Synergistic effect of sol to make Fe2O3Higher temperatures are not required for the crystal phase to escape from the ferrite spinel. And the reduction of the roasting temperature increases the specific surface area of the catalyst and has higher catalytic activity.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
All ranges disclosed herein are inclusive of the endpoints and independently combinable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values.
The raw materials in the preparation process of the catalyst are analytically pure (AR): iron nitrate, zinc nitrate, magnesium nitrate, copper nitrate and cobalt chloride were purchased from basf chemical limited, Tianjin; cobalt nitrate, strontium nitrate, propylene glycol monomethyl ether and propylene glycol dimethyl ether were purchased from the national pharmaceutical group chemical agents, ltd; magnesium chloride, copper chloride, sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate were purchased from chemical reagents ltd, miuiou, department of tianjin; anhydrous calcium chloride was purchased from bodi chemical industries, ltd; ammonia was purchased from cigarette tai iii and chemical agents limited; propylene glycol and polyethylene glycol were purchased from metropolis chemical reagent plants.
Example 1
To 10L of an aqueous solution containing 1.9kg of ferric nitrate were added zinc nitrate, anhydrous calcium chloride, and MgCl in an amount of 2.5% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride2Mixing an aqueous solution, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:200, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:8, and stirring to uniformly disperse the aqueous solution; adding appropriate amount of NaOH as precipitant, and controlling pH to 8.5 by parallel-flow precipitation method to obtain Fe (OH))3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Adding NaOH into the solution at 80 ℃ for gel precipitation to obtain Fe with the mass fraction of 8%2O3Dissolving sol, adding Fe accounting for 1.5 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 5h, standing and aging the formed colloidal solution at a constant temperature of 75 ℃ for 2h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30-80 μm to prepare slurry with a solid content of 10%, adding propylene glycol accounting for 1.8% of the total mass of ferric nitrate, zinc nitrate and anhydrous calcium chloride, and spray-forming. The temperature of a feed inlet of the spray tower is 260 ℃, the temperature of a discharge outlet is 120 ℃, the rotating speed of a centrifugal nozzle is 8000r/min, the microsphere catalyst is obtained, the microsphere catalyst is roasted for 1h at 400 ℃, and then the microsphere catalyst is roasted for 4h at 500 ℃, and the finished catalyst product is obtained.
Example 2
To 10L of an aqueous solution containing 1.2kg of ferric nitrate were added zinc nitrate, anhydrous calcium chloride, and Cu (NO) in an amount of 4.0% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride3)2Mixing an aqueous solution, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:150, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:10, and stirring to uniformly disperse the aqueous solution; adding a proper amount of Na2CO3As a precipitant, by cocurrent precipitation, pH was controlled to 9.0 to obtain Fe (OH)3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Dissolving in Na at 80 deg.C2CO3Precipitating to obtain Fe with the mass fraction of 6%2O3Dissolving sol, adding Fe accounting for 1.0 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 8h, standing and aging the formed colloidal solution at a constant temperature of 95 ℃ for 1h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30 to80 mu m, preparing slurry with the solid content of 30 percent, adding propylene glycol monomethyl ether accounting for 1.5 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride, and spraying and forming. The temperature of a feed inlet of the spray tower is 400 ℃, the temperature of a discharge outlet is 140 ℃, the rotating speed of a centrifugal nozzle is 7000r/min, the microspherical catalyst is obtained, the microspherical catalyst is roasted for 3 hours at the temperature of 240 ℃, and then the microspherical catalyst is roasted for 6 hours at the temperature of 550 ℃, and the finished catalyst is obtained.
Example 3
To 25L of an aqueous solution containing 4.8kg of ferric nitrate, zinc nitrate, anhydrous calcium chloride, and Co (NO) in an amount of 3.0% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride were added3)2Mixing an aqueous solution, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:250, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:6, and stirring to uniformly disperse the aqueous solution; adding appropriate amount of ammonia water as precipitant, and controlling pH to 8.5 by cocurrent flow precipitation method to obtain Fe (OH)3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Adding ammonia water into the solution at the temperature of 80 ℃ for gel precipitation to obtain Fe with the mass fraction of 10%2O3Dissolving sol, adding Fe accounting for 2.5 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 12h, standing and aging the formed colloidal solution at a constant temperature of 85 ℃ for 2.5h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30-80 μm to prepare slurry with a solid content of 25%, adding propylene glycol monomethyl ether accounting for 2.0% of the total mass of ferric nitrate, zinc nitrate and anhydrous calcium chloride, and spray-forming. The temperature of a feed inlet of the spray tower is 350 ℃, the temperature of a discharge outlet is 135 ℃, the rotating speed of a centrifugal nozzle is 11000r/min, the microsphere catalyst is obtained, the microsphere catalyst is roasted for 2 hours at 320 ℃, and then the microsphere catalyst is roasted for 4 hours at 550 ℃, and the finished catalyst product is obtained.
Example 4
To 15L of an aqueous solution containing 2.9kg of ferric nitrate, zinc nitrate, anhydrous calcium chloride, and Ni (NO) 2.2% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride were added3)2Mixing water solutionThe liquid is prepared by stirring, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:300, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:12, so that the ferric nitrate and the anhydrous calcium chloride are uniformly dispersed; adding appropriate amount of ammonia water as precipitant, and controlling pH to 9.5 by cocurrent flow precipitation method to obtain Fe (OH)3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Adding ammonia water into the solution at the temperature of 80 ℃ for gel precipitation to obtain Fe with the mass fraction of 15%2O3Dissolving sol, adding Fe accounting for 0.5 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 10h, standing and aging the formed colloidal solution at a constant temperature of 90 ℃ for 0.5h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30-80 μm to prepare slurry with a solid content of 8%, adding propylene glycol accounting for 3.0% of the total mass of ferric nitrate, zinc nitrate and anhydrous calcium chloride, and spray-forming. The temperature of a feed inlet of the spray tower is 230 ℃, the temperature of a discharge outlet is 110 ℃, the rotating speed of a centrifugal nozzle is 5000r/min, the microsphere catalyst is obtained, the microsphere catalyst is roasted for 3 hours at 380 ℃, and then the microsphere catalyst is roasted for 5 hours at 450 ℃, and the finished catalyst product is obtained.
Example 5
To 20L of an aqueous solution containing 4.3kg of ferric nitrate, zinc nitrate, anhydrous calcium chloride, and Bi (NO) in an amount of 2.6% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride were added3)3Mixing an aqueous solution, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:260, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:15, and stirring to uniformly disperse the aqueous solution; adding a proper amount of K2CO3As a precipitant, by cocurrent precipitation, pH was controlled to 8.8 to obtain Fe (OH)3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Solution, adding K at 80 deg.C2CO3Precipitating to obtain 14% Fe2O3Dissolving sol, adding Fe accounting for 2.0 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 6h, then standing and aging the formed colloidal solution at constant temperature of 100 ℃ for 1.5h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30-80 μm to prepare slurry with a solid content of 15%, adding propylene glycol dimethyl ether accounting for 2.2% of the total mass of ferric nitrate, zinc nitrate and anhydrous calcium chloride, and spray-forming. The temperature of a feed inlet of the spray tower is 300 ℃, the temperature of a discharge outlet is 130 ℃, the rotating speed of a centrifugal nozzle is 9500r/min, the microspherical catalyst is obtained, the microspherical catalyst is roasted for 4 hours at the temperature of 300 ℃, and then the microspherical catalyst is roasted for 4 hours at the temperature of 580 ℃, and the finished catalyst is obtained.
Example 6
To 30L of an aqueous solution containing 5.8kg of ferric nitrate, zinc nitrate, anhydrous calcium chloride, and CoCl in an amount of 3.2% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride were added2Mixing an aqueous solution, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:240, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:8, and stirring to uniformly disperse the aqueous solution; adding a proper amount of Na2CO3As a precipitant, by cocurrent precipitation, pH was controlled to 8.2 to obtain Fe (OH)3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Dissolving in Na at 80 deg.C2CO3Precipitating to obtain 12% Fe2O3Dissolving sol, adding Fe accounting for 2.8 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 7h, standing and aging the formed colloidal solution at a constant temperature of 85 ℃ for 2h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30-80 μm to prepare slurry with a solid content of 20%, adding polyethylene glycol accounting for 2.5% of the total mass of ferric nitrate, zinc nitrate and anhydrous calcium chloride, and spray-forming. The temperature of a feed inlet of the spray tower is 350 ℃, the temperature of a discharge outlet is 130 ℃, the rotating speed of a centrifugal nozzle is 10000r/min, the microsphere catalyst is obtained, the microsphere catalyst is roasted for 2h at 330 ℃, and then the microsphere catalyst is roasted for 3h at 600 ℃, and the finished catalyst product is obtained.
Example 7
To 5L of an aqueous solution containing 0.48kg of ferric nitrate, zinc nitrate, anhydrous calcium chloride, and Sr (NO) in an amount of 2.0% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride were added3)2Mixing an aqueous solution, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:340, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:2, and stirring to uniformly disperse the aqueous solution; adding a proper amount of KOH as a precipitator, and controlling the pH to be 7.5 by a cocurrent flow precipitation method to obtain Fe (OH)3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Adding KOH into the solution at the temperature of 80 ℃ for gel precipitation to obtain 10 mass percent of Fe2O3Dissolving sol, adding Fe accounting for 0.3 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 4h, standing and aging the formed colloidal solution at a constant temperature of 70 ℃ for 3h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30-80 μm to prepare slurry with a solid content of 5%, adding propylene glycol monomethyl ether accounting for 1.0% of the total mass of ferric nitrate, zinc nitrate and anhydrous calcium chloride, and spray-forming. The temperature of a feed inlet of the spray tower is 200 ℃, the temperature of a discharge outlet is 100 ℃, the rotating speed of a centrifugal nozzle is 5000r/min to obtain the microspherical catalyst, the microspherical catalyst is roasted for 4 hours at the temperature of 200 ℃, and then the microspherical catalyst is roasted for 7 hours at the temperature of 400 ℃ to obtain the finished catalyst.
Example 8
To 15L of an aqueous solution containing 2.4kg of ferric nitrate, zinc nitrate, anhydrous calcium chloride, and CuCl in an amount of 2.8% by mass based on the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride were added2Mixing an aqueous solution, wherein the mass ratio of ferric nitrate to zinc nitrate is 500:130, and the mass ratio of ferric nitrate to anhydrous calcium chloride is 500:5, and stirring to uniformly disperse the aqueous solution; adding a proper amount of Na2CO3As a precipitant, by cocurrent precipitation, pH was controlled to 8.0 to obtain Fe (OH)3、Zn(OH)2Uniformly mixing the hydroxide precursor; preparing Fe (NO) with lower concentration3)3Dissolving in Na at 80 deg.C2CO3Precipitating to obtain 18% Fe2O3Dissolving sol, adding Fe accounting for 1.8 percent of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride into the hydroxide precursor2O3And (3) dissolving the sol, stirring for 3h, standing and aging the formed colloidal solution at a constant temperature of 85 ℃ for 2.5h, cooling, filtering and washing until the pH value of the filtrate is 7.0, stopping washing, and keeping a filter cake. Grinding the filter cake in a colloid mill to an average diameter of 30-80 μm to prepare slurry with a solid content of 18%, adding polyethylene glycol accounting for 2.0% of the total mass of ferric nitrate, zinc nitrate and anhydrous calcium chloride, and spray-forming. The temperature of a feed inlet of the spray tower is 320 ℃, the temperature of a discharge outlet is 150 ℃, and the rotating speed of a centrifugal nozzle is 9000r/min to obtain the microspherical catalyst, the microspherical catalyst is roasted for 2 hours at 280 ℃, and then the microspherical catalyst is roasted for 4 hours at 550 ℃ to obtain the finished catalyst.
Comparative example 1
The catalyst was prepared according to the procedure of example 1, but using the coprecipitation method, the other preparation conditions were not changed.
Comparative example 2
The catalyst was prepared according to the procedure of example 1, but no auxiliary was added and the other preparation conditions were unchanged.
Comparative example 3
The catalyst was prepared according to the procedure of example 1, but no stabilizer was added and the other preparation conditions were unchanged.
Comparative example 4
The catalyst was prepared according to the procedure of example 1, but without addition of Fe2O3The colloid, instead of sesbania powder, is roasted at 350 ℃ for 3h and then at 900 ℃ for 8h, and other preparation conditions are unchanged.
Catalyst evaluation test method
The microspherical catalysts prepared in examples and comparative examples were loaded in a fluidized bed reactor, and the butadiene yield (%) and butadiene selectivity (%) of each catalyst and the attrition index (%) of the catalyst after the continuous operation of the catalyst for 500 hours were found in table 1.
TABLE 1
As can be seen from Table 1, after the catalyst prepared in examples 1 to 8 is reacted for 500 hours, the performance of the microspherical catalyst is relatively stable, the yield of butadiene is 80 to 85%, and the selectivity of butadiene is 94 to 97%. Compared with example 1, the catalyst prepared in comparative example 1 has a somewhat poorer reactivity, mainly because the calcination temperature of the catalyst prepared by the coprecipitation method is higher to achieve the same catalytic activity; the microsphere catalyst prepared in the comparative example 2 has low initial activity of reaction, which shows that the auxiliary has obvious influence on the activity and selectivity of the catalyst; the activity of the microspherical catalyst prepared in the comparative example 3 is obviously reduced after 500 hours of reaction, which shows that the addition of the stabilizer contributes to the uniform distribution of active components of the catalyst; finally, the microspherical catalyst prepared in comparative example 4 can achieve an activity close to that of the catalyst in example 1 at a calcination temperature higher than that of the present invention.
Through comparative analysis, it can be seen that the adoption of the cocurrent flow precipitation method effectively improves the uniformity of the distribution of the active components of the catalyst, and the utilization of Fe2O3The colloid is used as both the adhesive and the active component, and through the synergistic effect of the adhesive and the active component, the prepared catalyst has lower roasting temperature, larger specific surface area and higher catalytic activity. In addition, the nitrate or chloride of the auxiliary agents of Mg, Cu, Ni, Co, Bi and Sr and the like are added in the preparation process of the catalyst, so that the activity and the operation stability of the catalyst can be effectively improved. In the preparation process of the microsphere catalyst, the stabilizer is added into the slurry formed by spraying, so that the system can be uniformly distributed, the suspension performance is increased, the solid content of the catalyst slurry can be effectively improved, the uniform nucleation of each active component in the preparation process of the catalyst is facilitated, and the stability and the abrasion resistance of the microsphere catalyst are further improvedEnergy is saved; after 500h of reaction, the butadiene yield in the examples decreased by less than 2 percentage points.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (13)
1. A preparation method of a microspherical catalyst for preparing butadiene by oxidative dehydrogenation of butene is characterized by comprising the following steps:
(1) adding zinc nitrate, anhydrous calcium chloride and an auxiliary agent into a ferric nitrate solution to obtain a mixed aqueous solution, wherein the molar ratio of ferric nitrate to zinc nitrate in the ferric nitrate solution is 500: 125-500: 375;
(2) adding an alkaline precipitator into the mixed aqueous solution obtained in the step (1), and performing parallel-flow precipitation to obtain a hydroxide precursor aqueous solution;
(3) preparation of Fe (NO)3)3Precipitating the solution under the action of alkaline precipitant to obtain Fe2O3Sol of said Fe2O3Fe in sol2O3The mass fraction of (A) is 5-20%;
(4) mixing Fe2O3Adding the sol into the hydroxide precursor aqueous solution and fully stirring to obtain a colloidal solution, wherein the Fe is2O3The using amount of the sol is 0.3-3.0% of the total mass of the ferric nitrate, the zinc nitrate and the anhydrous calcium chloride;
(5) aging and washing the colloidal solution obtained in the step (4), and reserving a filter cake;
(6) grinding the filter cake, preparing slurry, adding a stabilizer, and performing spray forming to obtain a microspherical catalyst;
(7) roasting the catalyst obtained in the step (6) at 200-400 ℃ for 1-4 h, and roasting at 400-600 ℃ for 3-7 h to obtain a catalyst finished product.
2. The process for preparing the catalyst according to claim 1, whereinIn the step (3), the Fe (NO)3)3Precipitating the solution with alkaline precipitant at 80 deg.C and pH of 5-8 to obtain Fe2O3And (3) sol.
3. The method of claim 1 or 2, wherein the alkaline precipitant is selected from the group consisting of NaOH, KOH, Na2CO3、K2CO3And ammonia water.
4. The method of preparing a catalyst according to claim 1, wherein the auxiliary is at least one selected from the group consisting of nitrates of Mg, Cu, Ni, Co, Bi, Sr and chlorides of Mg, Cu, Ni, Co, Bi, Sr.
5. The method for preparing the catalyst according to claim 1, wherein the amount of the auxiliary is 2.0 to 4.0% by mass of the total mass of the iron nitrate, the zinc nitrate and the anhydrous calcium chloride.
6. The method of preparing the catalyst according to claim 1, wherein in the step (1), the ratio of the amount of the ferric nitrate to the amount of the anhydrous calcium chloride is 500:2 to 500: 15.
7. The method of claim 1, wherein in step (2), the pH during the co-current precipitation is 7.5 to 10.
8. The method of claim 1, wherein the aging treatment is performed at 70 to 100 ℃ for 0.5 to 3 hours in the step (5).
9. The method of preparing the catalyst according to claim 1, wherein the stabilizer is at least one selected from the group consisting of propylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether and polyethylene glycol, and the amount of the stabilizer is 1.0 to 3.0% of the total mass of the iron nitrate, the zinc nitrate and the anhydrous calcium chloride.
10. The method for preparing the catalyst according to claim 1, wherein in the step (6), the filter cake is milled in a colloid mill to an average diameter of 30 to 80 μm.
11. The method for preparing the catalyst according to claim 1, wherein in the step (6), the filter cake is ground to prepare slurry with the solid content of 5-30%.
12. The method for preparing the catalyst according to claim 1, wherein in the step (7), the catalyst product is spherical particles with a particle size of 60-120 μm.
13. The preparation method of the catalyst according to claim 1, wherein in the step (6), the spray forming is performed by using a centrifugal spray tower, the temperature of a feed inlet of the centrifugal spray tower is 200-400 ℃, the temperature of a discharge outlet of the centrifugal spray tower is 100-150 ℃, and the rotating speed of a centrifugal nozzle is 5000-12000 r/min.
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