CN106423200B - 一种流化床加氢催化剂及其制备方法 - Google Patents
一种流化床加氢催化剂及其制备方法 Download PDFInfo
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- CN106423200B CN106423200B CN201610820669.4A CN201610820669A CN106423200B CN 106423200 B CN106423200 B CN 106423200B CN 201610820669 A CN201610820669 A CN 201610820669A CN 106423200 B CN106423200 B CN 106423200B
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- powder
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- metal
- earth metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000000843 powder Substances 0.000 claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 35
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003292 glue Substances 0.000 claims abstract description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 239000003595 mist Substances 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 9
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 44
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 19
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- 238000007598 dipping method Methods 0.000 claims description 16
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000002803 maceration Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910052789 astatine Inorganic materials 0.000 claims 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract description 19
- 150000004056 anthraquinones Chemical class 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 32
- 229960002163 hydrogen peroxide Drugs 0.000 description 16
- 239000012224 working solution Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- WUKWGUZTPMOXOW-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)CC)=CC=C3C(=O)C2=C1 WUKWGUZTPMOXOW-UHFFFAOYSA-N 0.000 description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 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 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 2
- 238000003969 polarography Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- RGHILYZRVFRRNK-UHFFFAOYSA-N anthracene-1,2-dione Chemical compound C1=CC=C2C=C(C(C(=O)C=C3)=O)C3=CC2=C1 RGHILYZRVFRRNK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XASUTLWDRZFPII-UHFFFAOYSA-N hydrogen peroxide;prop-1-ene Chemical group OO.CC=C XASUTLWDRZFPII-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000008207 working material Substances 0.000 description 1
- 239000011701 zinc 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
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Abstract
本发明提供了一种流化床加氢催化剂及其制备方法,其中所述制备方法,包括以下步骤:(1)将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为70‑90:30‑10混合制胶,并将得到的溶胶与一定量的过渡金属或稀土金属盐均匀混合,固含量为20‑50wt%的浆液;(2)利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在600‑1100℃的条件下对该粉末进行煅烧处理,煅烧时间4‑10h,最终得到含有过渡金属或稀土金属氧化物的多孔氧化铝微球载体,氧化铝与过渡金属或稀土金属的质量比为100:0.25‑10。本发明所述的一种流化床加氢催化剂的制备方法,原料来源广泛,操作简单,成本低廉,可获得催化活性高,选择性好的微球粉末状催化剂,使其可广泛适用于流化床蒽醌加氢反应。
Description
技术领域
本发明属于催化剂生产领域,尤其是涉及一种流化床加氢催化剂及其制备方法。
背景技术
双氧水是过氧化氢的水溶液,由于其在使用过程中无污染的特点,故被称为最清洁的氧化剂。目前双氧水主要被用来制备漂白剂、消毒剂、脱氧剂、聚合物引发剂和交联剂等产品,广泛应用于造纸、纺织、医药、化工、环保等行业。近年来,我国的双氧水事业得到快速发展,其产能以每年15%速度增长,目前全国产能已经超过500万吨/年(以浓度27.5%计算)。另外,随着过氧化氢在各种绿色化工合成领域中的迅速推广,尤其是在过氧化氢丙烯环氧化制备环氧丙烷(HPPO)以及绿色己内酰胺合成等技术中的应用,使我国双氧水产业迎来了新的发展契机。
目前,双氧水工业生产的主流方法是蒽醌法,蒽醌法的生产原理可以概括如下:用有机溶剂溶解工作载体(烷基蒽醌)配置成工作液,在催化剂和氢气的作用下,蒽醌加氢还原生成氢蒽醌,然后经过空气或氧气氧化氢蒽醌变回蒽醌,同时得到过氧化氢。利用纯水对含有过氧化氢的工作液进行萃取得到双氧水,同时萃余液即工作液经过过滤、再生后返回氢化工序继续进行加氢反应。
在蒽醌法中,蒽醌氢化的效率直接决定了过氧化氢的产量和浓度,对整个双氧水生产过程有着重要意义。根据加氢反应器形式的不同可以将加氢工艺分为固定床蒽醌加氢工艺和流化床(或淤浆床)蒽醌加氢工艺。目前国内双氧水生产厂主要使用固定床即滴流床蒽醌加氢工艺,该工艺主要不足是催化剂利用率低、床层温度分布不均匀、容易产生偏流或沟流,工作液降解严重等,固定床加氢工艺的氢化效率较低,一般在6-7g/L。而流化床或淤浆床蒽醌加氢工艺则具有反应效率高、物料混合均匀、不易产生局部热点、生产能力大等优点,采用流化床蒽醌加氢工艺可以使氢化效率达到12g/L以上,国外大型双氧水生产装置主要采用流化床加氢工艺。所以研究新型流化床蒽醌加氢工艺及相应流化床加氢催化剂,对进一步促进我国双氧水工业的发展有重要意义。
专利CN1261347C提供了一种淤浆床加氢催化剂,该催化剂由球形载体和选自铂或钯的贵金属活性组分组成,其中球形载体由氧化铝和磁性颗粒组成,其中磁性颗粒由二氧化硅包覆层和含铁物质内核组成。该催化剂具有容易从反应产物中分离的特点。专利CN104549236A提供的流化床加氢催化剂是由硼修饰的二氧化硅和氧化铝组成的复合氧化物载体,活性组成为金属钯,另外添加了镁、钙、铁等助活性组分,该催化剂具有较好的抗磨损性能。
发明内容
有鉴于此,本发明旨在提出一种流化床加氢催化剂,以解决现有技术中流化床蒽醌加氢催化剂活性、选择性有待提高,活性组分易脱,制备方法复杂且成本较高的问题。
为达到上述目的,本发明的技术方案是这样实现的:
一种流化床加氢催化剂,该催化剂为负载型催化剂;催化剂载体为含有碱金属或碱土金属,及过渡金属或稀土金属氧化物的多孔氧化铝微球粉末,所述氧化铝晶型为γ、δ、θ、α中的一种或两种的混合晶型;所述催化剂载体中的碱金属为Na或K,碱土金属为Mg或Ca,过渡金属为Zn、Cu、Fe、Co、Ni、Mn、Zr、Nb、Mo中至少一种,稀土金属为La、Ce、Pr、Nd、Sm中至少一种;且所述氧化铝与碱金属或碱土金属的质量比为100:0.15-4.85,氧化铝与过渡金属或稀土金属的质量比为100:0.25-10;所述氧化铝微球粉末的粒径分布为1-100μm,比表面积为100-300m2/g。
优选的,所述催化剂载体所用的氧化铝为δ型和θ型混合相氧化铝;所述氧化铝微球粉末中90wt%的氧化铝粒径为10-90μm,体积平均粒径为30-50μm;所述氧化铝微球粉末的比表面积为130-250m2/g,孔容0.1-1ml/g,孔径分布为0-200nm。
优选的,所述催化剂载体上担载有活性金属;所述活性金属为钯或铂,所述活性金属的担载量为1-10wt%。
本发明的另一目的在于提出一种制备如上所述的流化床加氢催化剂的方法,以制备上述流化床加氢催化剂。
为达到上述目的,本发明的技术方案是这样实现的:
一种流化床加氢催化剂的制备方法,包括以下步骤:
(1)将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为70-90:30-10混合制胶,并将得到的溶胶与一定量的过渡金属或稀土金属盐均匀混合,固含量为20-50wt%的浆液;
(2)利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在600-1100℃的条件下对该粉末进行煅烧处理,煅烧时间4-10h,最终得到含有过渡金属或稀土金属氧化物的多孔氧化铝微球载体,氧化铝与过渡金属或稀土金属的质量比为100:0.25-10;
(3)将步骤(2)制得的氧化铝载体,放入碱金属或碱土金属的硝酸盐或硫酸盐或碳酸盐或碳酸氢盐的水溶液中,进行等体积浸渍,浸渍温度50-100℃,浸渍时间30-60min,然后在200-500℃的空气中煅烧2-10h,最终得到负载有碱金属或碱土金属的氧化铝载体,其中碱金属为Na或K,碱土金属为Mg或Ca,载体氧化铝与碱金属或碱土金属的质量比为100:0.15-4.85;
(4)将步骤(3)得到的氧化铝载体进行水化处理,水化处理温度100-150℃,处理时间为2-5h,处理完毕后再100-300℃下干燥2-5h;
(5)将氯化钯或氯化铂溶解于稀盐酸中制得氯钯酸或氯铂酸溶液,或将金属钯或铂溶解于王水,再经赶硝制成氯钯酸或氯铂酸溶液,然后调节溶液pH至2-6,得到浸渍液;
(6)将步骤(4)得到的载体放入氯钯酸或氯铂酸浸渍液中进行等体积浸渍,浸渍温度50-100℃,浸渍时间60-120min;然后用脱盐水对浸渍好的载体进行洗涤,至洗涤水的电导率为1-10μS/cm,再将洗涤干净的载体在100-150℃下干燥3-6h,400-600℃煅烧2-10h,得催化剂原粉;再将催化剂原粉在含氢气体中还原即得负载有活性金属钯或铂的流化床加氢催化剂。
优选的,所述步骤(1)中偏铝酸钠和硫酸铝的中和反应中,偏铝酸钠和硫酸铝的物质的量的比为6-6.5:1,中和反应温度为60-80℃。
优选的,所述步骤(1)中,硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为75-88:25-8混合制胶。
优选的,所述步骤(3)中煅烧温度为250-480℃,煅烧时间为3-9h。
优选的,所述步骤(4)中干燥温度为120-270℃,干燥时间为2.5-4.5h。
本发明所述流化床加氢催化剂评价装置采用高压反应釜,具体方法为:所用的工作液由2-叔戊基蒽醌溶于偏三甲苯和磷酸三辛酯的混合溶液中,溶剂比为75:25,蒽醌总浓度为150g/L;反应釜容积为0.5L。工作液加氢条件为:工作液使用量为150ml,催化剂添加量为5g,反应温度60℃,反应压力0.3Mpa,搅拌速度500rpm,反应条件30min。氢化反应后,从反应器取样口取出5ml氢化液置于分液漏斗中并用纯氧气充分氧化,经萃取后由高锰酸钾标准溶液滴定生成的过氧化氢,由此计算催化剂的氢化效率。用极谱法测定催化剂的选择性,规定氢化液氧化后工作液中的有效蒽醌(2-戊基蒽醌+四氢2-戊基蒽醌)浓度与氢化前总蒽醌浓度的比值为催化剂的选择性。
相对于现有技术,本发明所述的一种流化床加氢催化剂具有以下优势:
本发明所述的一种流化床加氢催化剂,在载体制备及活性组分金属负载过程中引入少量碱金属、碱土金属、过渡金属或稀土金属等助剂,使催化剂的稳定性得到改善,催化剂活性及选择性得到提高。
本发明所述的一种流化床加氢催化剂的制备方法,原料来源广泛,操作简单,成本低廉,可获得催化活性高,选择性好的微球粉末状催化剂,使其可广泛适用于流化床蒽醌加氢反应。
具体实施方式
除非另外说明,本文中所用的术语均具有本领域技术人员常规理解的含义,为了便于理解本发明,将本文中使用的一些术语进行了下述定义。
所有的数字标识,例如pH、温度、时间、浓度,包括范围,都是近似值。要了解,虽然不总是明确的叙述所有的数字标识之前都加上术语“约”。同时也要了解,虽然不总是明确的叙述,本文中描述的试剂仅仅是示例,其等价物是本领域已知的。
下面结合实施例来详细说明本发明。
实施例1
将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为80:20混合制胶,并将得到的溶胶与一定量的硝酸铜和硝酸镧均匀混合,得到固含量为40wt%的浆液。利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在700℃的条件下对该粉末进行煅烧处理,煅烧时间4小时,得到含有氧化铜和氧化镧的多孔氧化铝微球粉末,载体中氧化铝与元素铜和镧的质量比均为100:0.5。将获得的氧化铝载体放入碳酸钾溶液中进行等体积浸渍,浸渍温度60℃、浸渍时间30min,然后在300℃的温度下煅烧2h,煅烧后氧化铝与钾的质量比为100:0.2。然后将载体在110℃下水热处理2小时,再在150℃下干燥2h。将一定量的氯化钯溶解于稀盐酸中,并调节pH为3.0,再将上述处理好的氧化铝粉末载体放入氯钯酸溶液中进行等体积浸渍,浸渍温度60℃,浸渍时间120min;将浸渍好的载体用脱盐水进行洗涤,至洗涤水的电导率为7.5μS/cm。将洗涤干净的载体在110℃下干燥3小时,于500℃煅烧10小时,煅烧后的催化剂在含氢气体中,于100℃还原2小时,即得负载有活性金属钯的流化床加氢催化剂,其中金属钯的担载量为1.5wt%。最终催化剂的氧化铝载体的粒径分布为1-100μm,其中90wt%的氧化铝粒径为10-90μm,体积平均粒径为35μm;比表面积170m2/g,孔容0.6ml/g,孔径分布2-50nm。
实施例2
将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为80:20混合制胶,并将得到的溶胶与一定量的硝酸钕均匀混合,得到固含量为45wt%的浆液。利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在450℃的条件下对该粉末进行煅烧处理,煅烧时间6小时,得到含有氧化钕的多孔氧化铝微球粉末,载体中氧化铝与元素钕的质量比均为100:1.3。将获得的氧化铝载体放入硝酸钾溶液中进行等体积浸渍,浸渍温度70℃、浸渍时间60min,然后在450℃的温度下煅烧6h,煅烧后氧化铝与钾的质量比为100:0.8。然后将载体在150℃下水热处理4小时,再在150℃下干燥2h。将一定量的金属钯粉用王水溶解,赶硝制成氯钯酸溶液,调节pH为2.5。再将上述处理好的氧化铝粉末载体放入氯钯酸溶液中进行等体积浸渍,浸渍温度80℃,浸渍时间120min。将浸渍好的载体用脱盐水进行洗涤,至洗涤水的电导率为10μS/cm。将洗涤干净的载体在120℃下干燥5小时,450℃煅烧10小时,煅烧后的催化剂在含氢气体中,100℃还原2小时,即得负载有活性金属钯的流化床加氢催化剂,其中金属钯的担载量为1wt%。最终催化剂的氧化铝载体的粒径分布为1-100μm,其中90wt%的氧化铝粒径为10-90μm,体积平均粒径为50μm;比表面积180m2/g,孔容0.54ml/g,孔径分布2-50nm。
实施例3
将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为85:10混合制胶,并将得到的溶胶与一定量硝酸锰和硝酸铁均匀混合,得到固含量为50wt%的浆液。利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在1000℃的条件下对该粉末进行煅烧处理,煅烧时间6小时,得到含有氧化锰和氧化铁的多孔氧化铝微球粉末,载体中氧化铝与金属锰和铁的质量比均为100:2.0。将获得的氧化铝载体放入硫酸镁溶液中进行等体积浸渍,浸渍温度80℃、浸渍时间40min,然后在400℃的温度下煅烧6h,煅烧后氧化铝与镁的质量比为100:1.5。然后将载体在120℃下水热处理4.5小时,再在150℃下干燥3h。将一定量的金属铂粉用王水溶解,赶硝制成氯铂酸溶液,调节pH为5。再将上述处理好的氧化铝粉末载体放入氯铂酸溶液中进行等体积浸渍,浸渍温度80℃,浸渍时间120min。将浸渍好的载体用脱盐水进行洗涤,至洗涤水的电导率为8μS/cm。将洗涤干净的载体在150℃下干燥2小时,550℃煅烧10小时,煅烧后的催化剂在含氢气体中,100℃还原2小时,即得负载有活性金属铂的流化床加氢催化剂,其中金属铂的担载量为4.6%。最终催化剂的氧化铝载体的粒径分布为1-100μm,其中90wt%的氧化铝粒径为15-88.3μm,体积平均粒径为50μm;比表面积175m2/g,孔容0.59ml/g,孔径分布2-50nm。
实施例4
将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为90:10混合制胶,并将得到的溶胶与一定量硝酸镨均匀混合,得到固含量为50wt%的浆液。利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在800℃的条件下对该粉末进行煅烧处理,煅烧时间10小时,得到含有氧化镨的多孔氧化铝微球粉末,载体中氧化铝与金属镨的质量比均为100:2.5。将获得的氧化铝载体放入碳酸钠溶液中进行等体积浸渍,浸渍温度50℃、浸渍时间30min,然后在450℃的温度下煅烧6h,煅烧后氧化铝与钠的质量比为100:1.0。然后将载体在100℃下水热处理4小时,再在150℃下干燥2.5h。将一定量的氯化铂溶于稀盐酸中制成氯铂酸溶液,调节pH为4。再将上述处理好的氧化铝粉末载体放入氯铂酸溶液中进行等体积浸渍,浸渍温度80℃,浸渍时间120min。将浸渍好的载体用脱盐水进行洗涤,至洗涤水的电导率为8μS/cm。将洗涤干净的载体在150℃下干燥2小时,550℃煅烧10小时,煅烧后的催化剂在含氢气体中,于100℃还原2小时,即得负载有活性金属铂的流化床加氢催化剂,其中金属铂的担载量为6.1%。最终催化剂的氧化铝载体的粒径分布为1-100μm,其中90wt%的氧化铝粒径为11-85μm,体积平均粒径为45μm;比表面积180m2/g,孔容0.63ml/g,孔径分布2-50nm。
实施例5
将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为88:10混合制胶,并将得到的溶胶与一定量硝酸钴和硝酸钐均匀混合,得到固含量为50wt%的浆液。利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在1000℃的条件下对该粉末进行煅烧处理,煅烧时间6小时,得到含有氧化钴和氧化钐的多孔氧化铝微球粉末,载体中氧化铝与金属钴和钐的质量比均为100:4。将获得的氧化铝载体放入碳酸氢钾溶液中进行等体积浸渍,浸渍温度80℃、浸渍时间40min,然后在400℃的温度下煅烧6h,煅烧后氧化铝与钾的质量比为100:4.5。然后将载体在120℃下水热处理3.5小时,再在150℃下干燥2h。将一定量的氯化钯溶于稀盐酸制成氯钯酸溶液,调节pH为3.5。再将上述处理好的氧化铝粉末载体放入氯铂酸溶液中进行等体积浸渍,浸渍温度80℃,浸渍时间120min。将浸渍好的载体用脱盐水进行洗涤,至洗涤水的电导率为8μS/cm。将洗涤干净的载体在150℃下干燥2小时,550℃煅烧10小时,煅烧后的催化剂在含氢气体中,100℃还原2小时,即得负载有活性金属铂的流化床加氢催化剂,其中金属铂的担载量为7.5%。最终催化剂的氧化铝载体的粒径分布为1-100μm,其中90wt%的氧化铝粒径为15-88.3μm,体积平均粒径为50μm;比表面积175m2/g,孔容0.59ml/g,孔径分布2-50nm。
催化剂评价:
对实施例1-5中所述流化床加氢催化剂采用高压反应釜进行评价,具体方法为:所用的工作液由2-叔戊基蒽醌溶于偏三甲苯和磷酸三辛酯的混合溶液中,溶剂比为75:25,蒽醌总浓度为150g/L;反应釜容积为0.5L。工作液加氢条件为:工作液使用量为150ml,催化剂添加量为5g,反应温度60℃,反应压力0.3Mpa,搅拌速度500rpm,反应条件30min。氢化反应后,从反应器取样口取出5ml氢化液置于分液漏斗中并用纯氧气充分氧化,经萃取后由高锰酸钾标准溶液滴定生成的过氧化氢,由此计算催化剂的氢化效率。用极谱法测定催化剂的选择性,规定氢化液氧化后工作液中的有效蒽醌(2-戊基蒽醌+四氢2-戊基蒽醌)浓度与氢化前总蒽醌浓度的比值为催化剂的选择性。实施例1-5所述流化床加氢催化剂的评价结果见表1:
表1实施例1-5所述流化床加氢催化剂的评价结果
催化剂 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
氢化效率,g H<sub>2</sub>O<sub>2</sub>/L | 12.4 | 12.6 | 12.4 | 13.2 | 13.4 |
选择性,% | 99.6 | 99.8 | 99.5 | 99.8 | 99.5 |
由表1可已看出,本发明所述流化床加氢催化剂的氢化效率在12gH2O2/L以上,选择性大于等于99.5%。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种流化床加氢催化剂,其特征在于:该催化剂为负载型催化剂;催化剂载体为含有碱金属或碱土金属,及过渡金属或稀土金属氧化物的多孔氧化铝微球粉末,所述氧化铝晶型为γ、δ、θ、α中的一种或两种的混合晶型;所述催化剂载体中的碱金属为Na或K,碱土金属为Mg或Ca,过渡金属为Zn、Cu、Fe、Co、Ni、Mn、Zr、Nb、Mo中至少一种,稀土金属为La、Ce、Pr、Nd、Sm中至少一种;且所述氧化铝与碱金属或碱土金属的质量比为100:0.15-4.85,氧化铝与过渡金属或稀土金属的质量比为100:0.25-10;所述氧化铝微球粉末的粒径分布为1-100μm,比表面积为100-300m2/g;所述催化剂载体上担载有活性金属;所述活性金属为钯或铂,所述活性金属的担载量为1.5-10wt%;所述氧化铝微球粉末中90wt%的氧化铝粒径为10-90μm,体积平均粒径为30-50μm;所述氧化铝微球粉末的比表面积为130-250m2/g,孔容0.1-1ml/g,孔径分布为0-200nm。
2.根据权利要求1所述的一种流化床加氢催化剂,其特征在于:所述催化剂载体所用的氧化铝为δ型和θ型混合相氧化铝。
3.权利要求1或2所述的一种流化床加氢催化剂的制备方法,其特征在于:包括以下步骤:
(1)将硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为70-90:30-10混合制胶,并将得到的溶胶与一定量的过渡金属或稀土金属盐均匀混合,固含量为20-50wt%的浆液;
(2)利用喷雾干燥技术对上述浆液进行喷雾造粒得到固体微球粉末,并在600-1100℃的条件下对该粉末进行煅烧处理,煅烧时间4-10h,最终得到含有过渡金属或稀土金属氧化物的多孔氧化铝微球载体,氧化铝与过渡金属或稀土金属的质量比为100:0.25-10;
(3)将步骤(2)制得的氧化铝载体,放入碱金属或碱土金属的硝酸盐或硫酸盐或碳酸盐或碳酸氢盐的水溶液中,进行等体积浸渍,浸渍温度50-100℃,浸渍时间30-60min,然后在200-500℃的空气中煅烧2-10h,最终得到负载有碱金属或碱土金属的氧化铝载体,其中碱金属为Na或K,碱土金属为Mg或Ca,载体氧化铝与碱金属或碱土金属的质量比为100:0.15-4.85;
(4)将步骤(3)得到的氧化铝载体进行水化处理,水化处理温度100-150℃,处理时间为2-5h,处理完毕后再100-300℃下干燥2-5h;
(5)将氯化钯或氯化铂溶解于稀盐酸中制得氯钯酸或氯铂酸溶液,或将金属钯或铂溶解于王水,再经赶硝制成氯钯酸或氯铂酸溶液,然后调节溶液pH至2-6,得到浸渍液;
(6)将步骤(4)得到的载体放入氯钯酸或氯铂酸浸渍液中进行等体积浸渍,浸渍温度50-100℃,浸渍时间60-120min;然后用脱盐水对浸渍好的载体进行洗涤,至洗涤水的电导率为1-10μS/cm,再将洗涤干净的载体在100-150℃下干燥3-6h,400-600℃煅烧2-10h,得催化剂原粉;再将催化剂原粉在含氢气体中还原即得负载有活性金属钯或铂的流化床加氢催化剂。
4.根据权利要求3所述的一种流化床加氢催化剂的制备方法,其特征在于:所述步骤(1)中偏铝酸钠和硫酸铝的中和反应中,偏铝酸钠和硫酸铝的物质的量的比为6-6.5:1,中和反应温度为60-80℃。
5.根据权利要求3或4所述的一种流化床加氢催化剂的制备方法,其特征在于:所述步骤(1)中,硫酸铝与偏铝酸钠中和制得的粉体与拟薄水铝石按质量为75-88:25-8混合制胶。
6.根据权利要求3所述的一种流化床加氢催化剂的制备方法,其特征在于:所述步骤(3)中煅烧温度为250-480℃,煅烧时间为3-9h。
7.根据权利要求3所述的一种流化床加氢催化剂的制备方法,其特征在于:所述步骤(4)中干燥温度为120-270℃,干燥时间为2.5-4.5h。
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