CN100509152C - 高钴含量、高钴表面积的催化剂及其制备和用途 - Google Patents
高钴含量、高钴表面积的催化剂及其制备和用途 Download PDFInfo
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- CN100509152C CN100509152C CNB2005800337194A CN200580033719A CN100509152C CN 100509152 C CN100509152 C CN 100509152C CN B2005800337194 A CNB2005800337194 A CN B2005800337194A CN 200580033719 A CN200580033719 A CN 200580033719A CN 100509152 C CN100509152 C CN 100509152C
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- Prior art keywords
- catalyst
- cobalt
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- aluminium
- hydrogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 70
- 239000010941 cobalt Substances 0.000 title claims abstract description 70
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001556 precipitation Methods 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 17
- 239000004411 aluminium Substances 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- -1 aluminium ions Chemical class 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 150000001869 cobalt compounds Chemical class 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 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 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 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
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010802 sludge Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 229940077746 antacid containing aluminium compound Drugs 0.000 abstract description 2
- 239000011872 intimate mixture Substances 0.000 abstract 1
- 230000009467 reduction Effects 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000000243 solution Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 16
- 238000001694 spray drying Methods 0.000 description 15
- 239000000725 suspension Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 239000000428 dust Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- UMWXOUAFWWUNGR-UHFFFAOYSA-N aluminum cobalt(2+) oxygen(2-) Chemical compound [Co+2].[O-2].[Al+3] UMWXOUAFWWUNGR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910020639 Co-Al Inorganic materials 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 229910020675 Co—Al Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 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
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001845 vibrational spectrum Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
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Abstract
一种粒状催化剂,该粒状催化剂包括钴与铝的原子比范围为10∶1-2∶1(Co∶Al)的钴和铝化合物的紧密混合物,当在425℃下被还原时,该粒状催化剂具有至少30m2/g催化剂的钴表面积,这通过在150℃下的氢气化学吸附来测量。在碱沉淀剂存在下,通过按序沉淀钴与铝离子,制备催化剂。该催化剂可用于不饱和化合物的氢化或者烃的费托合成。
Description
本申请涉及钴-氧化铝催化剂及其制备和用途。
其中钴为其元素或者还原态的被承载的钴催化剂是众所周知的,且用于其中涉及氢气的许多反应,例如氢化反应和烃的费托合成。认为该催化剂的活性直接与还原的催化剂中钴的表面积成正比,但为了实现高钴表面积,钴应当充分分散在载体上。此外,为了最小化反应器体积,催化剂应当优选具有尽可能高的钴含量。高的钴含量还提供催化剂循环和再生的改进效率。然而,当催化剂中钴含量增加到高于20wt%(基于还原的催化剂)时,钴变得更加难以分散,从而导致较低的钴表面积。钴是相对昂贵的金属,因此希望改进钴的分散(用每克催化剂钴的表面积来表达)。
迄今为止,典型地通过将钴化合物浸渍到“预成型”的氧化铝材料内,或者在氧化铝粉末或挤出物存在下,通过从溶液中沉淀钴化合物,通常接着进行加热步骤,然后在使用之前,使用氢气,还原所得钴化合物成元素形式,从而制备钴-氧化铝催化剂。
或者,可通过添加碱,同时共沉淀钴(Co)和铝(Al)化合物,从而制备钴-氧化铝催化剂。Khassin等人公开了以1:1、1:1.3和1:2的比例共沉淀Co2+和Al3+,得到含有水滑石的材料。一旦在470-480℃下焙烧和在氢气下还原,这些催化剂在烃的费托合成中活性低(参见Journal of Molecular Catalysis A:Chemical,168,2001,193-207)。
我们已令人惊奇地发现,可通过从溶液中按序沉淀钴和铝酸盐离子,从而获得适合于不饱和化合物的氢化或者烃的费托合成的新的高钴含量、高钴表面积的催化剂。
本发明提供粒状催化剂,该粒状催化剂包括钴与铝的原子比范围为10:1-2:1(Co:Al)的钴和铝化合物的紧密混合物,当在425℃下被还原时,该粒状催化剂具有至少30m2/g催化剂的钴表面积,这通过在150℃下的氢气化学吸附来测量。
优选地,催化剂的钴与铝的原子比范围为5:1-2.5:1,更优选4:1-3:1。尽管与以前公知的经浸渍或同时共沉淀的催化剂相比钴含量高,但催化剂在还原下仍保持高的钴表面积。例如,可制备钴含量≥60wt%,尤其≥75wt%的稳定的催化剂(还原的催化剂)。认为为了获得在这些钴含量下观察到的非常高的钴表面积,还原的钴的含量为未还原的催化剂内存在的钴的≥60%,优选≥70%。这样的高钴含量的优点是,一旦催化剂被废弃,为了获得钴而回收和循环催化剂在经济上是可行的。这还导致进一步的优势,即降低的废弃废物负担。
催化剂组合物(在还原之前,它也可被称为催化剂前体)包括紧密混合的钴和铝化合物,其中钴化合物可承载在钴-铝化合物上。一旦还原,钴化合物容易被还原,而钴-铝化合物更难以还原。所得结构难以通过浸渍或同时共沉淀技术获得,且提供改进的催化剂性能。认为在活化之前,在本发明催化剂内的至少大部分铝可以是一种或更多种钴-铝化合物形式。大部分是指>50%的铝原子。优选>75%,更优选基本上所有的铝已经反应以形成钴-铝化合物。这与现有技术中承载的催化剂相反,其中现有技术中认为小部分的铝为钴-铝化合物形式和大部分是氧化铝。可使用振动光谱,例如拉曼或红外光谱,测定钴-铝化合物的存在。或者,可使用程序升温反应(TPR),测定钴-铝化合物的紧密混合物的存在,其中用氢气在150-1000℃下进行还原,且所记录的TCD信号表明例如在400-800℃范围内的Co-Al水滑石结构的特征峰。
用表面重均直径D[3,2]表达的催化剂的粒度优选在5-100微米(μm)范围内。更优选粒度范围为5-30微米,特别是10-20微米。可通过附聚制备较大的颗粒。M.Alderliesten在论文“ANomenclature for Mean Particle Diameters”;Anal.Proc.,vol.21,1984年5月,第167-172页中定义了术语表面重均直径D[3,2],在其它情况下被称为Sauter平均直径,并通过粒度分析来计算它,所述粒度分析可方便地通过激光衍射,例如使用Malvern Mastersizer来进行。
本发明的催化剂具有孔径优选50-500埃或更大的多孔结构,这取决于Co:Al之比。例如,在Co:Al原子比为5:1时,在还原之前,催化剂的孔径可以是约200-250埃。在还原之前,催化剂的孔体积优选>0.3cm3/g,更优选>0.4cm3/g的催化剂。
在还原之前催化剂的BET表面积优选为50-250m2/g催化剂,更优选>90m2/g。合适地使用本领域技术人员公知的方法,使用氮气解吸,进行BET表面积和孔体积的测量。可根据(4×孔体积)/BET表面积计算平均孔径。
除了钴和铝化合物以外,催化剂还可包括一种或更多种可用于氢化反应和/或费托催化的合适的添加剂和促进剂。例如,催化剂可包括改变物理性能的一种或更多种添加剂和/或影响催化剂的可还原性或活性或选择性的促进剂。合适的添加剂选自钼(Mo)、镍(Ni)、铜(Cu)、铁(Fe)、锰(Mn)、钛(Ti)、锆(Zr)、镧(La)、铈(Ce)、铬(Cr)、镁(Mg)或锌(Zn)的化合物。合适的促进剂包括铑(Rh)、铱(Ir)、钌(Ru)、铼(Re)、铂(Pt)和钯(Pd)。可通过添加合适的化合物,例如金属盐,例如金属硝酸盐或金属乙酸盐,或者合适的金属-有机化合物,例如金属醇盐或金属乙酰丙酮酸盐到反应混合物中,将添加剂和/或促进剂掺入到催化剂内。
本发明进一步提供制备粒状催化剂的方法,该粒状催化剂包括钴与铝的原子比范围为10:1-2:1(Co∶Al)的钴和铝化合物的紧密混合物,当在425℃下被还原时,该粒状催化剂具有至少30m2/g催化剂的钴表面积,这通过在150℃下的氢气化学吸附来测量,该方法包括下述步骤:
(i)使用过量的碱沉淀剂,由钴盐的水溶液沉淀不可溶的钴化合物,
(ii)添加可溶的铝化合物,
(iii)老化所得的悬浮形式的沉淀物,和
(iv)回收并干燥该催化剂组合物,
因此,使用过量的碱沉淀剂,由钴盐的水溶液沉淀一种或更多种不可溶的钴化合物,随后使所述沉淀物以悬浮形式老化,然后收集,其中在钴离子沉淀之后,添加可溶的铝化合物。可溶的铝化合物可以以溶液形式添加,但也可以以未溶解的晶体形式添加。在钴离子基本上沉淀之后添加的可溶的铝化合物例如是硝酸铝、铝酸钠或至少部分溶解在过量碱内的氧化铝。优选地,可溶的铝化合物是硝酸铝或铝酸钠,尤其铝酸钠。
通过此处所述的按序沉淀方法就地形成铝“载体”,而不是使用氧化铝粉末、粒料、挤出物或类似物,本发明对所得催化剂的物理性能提供以前不可能的控制度。特别地,单独掌控沉淀和老化步骤提供以前没有提供过的控制度。例如,通过增加或降低老化步骤期间的温度,可控制催化剂的孔径。此外,通过老化混合物的搅拌程度,可控制催化剂的粒度。
在根据本发明的沉淀和老化之后,例如通过离心或者过滤从液体中回收沉淀物,通常洗涤并干燥该沉淀物。随后,使用本领域技术人员已知的方法,典型地在升高的温度下,通过用含氢气体还原钴化合物,从而进行催化剂的活化。这一制备方法的优点是不要求焙烧催化剂组合物,因此还原干燥的沉淀物直接导致高表面积的催化剂。然而,在一些情况下,可能希望在范围为200-800℃,优选200-600℃,更优选200-400℃的温度下,焙烧干燥的催化剂前体组合物。在活化之前,可在惰性气体例如氮气或氩气下或者可在空气中进行焙烧,以进行钴和/或铝化合物的氧化。
可用作催化剂起始材料的钴化合物是水溶性钴化合物,例如硝酸盐、硫酸盐、乙酸盐、氯化物和甲酸盐。引入到沉淀反应器内的溶液优选含有10-100,更优选10-80g钴/升,特别优选含有25-60g钴/升的溶液。
视需要,在沉淀之前,添加剂和/或促进剂的合适化合物可加入到钴化合物的溶液中。
碱沉淀剂可以是碱金属氢氧化物、碱金属碳酸盐、碱金属碳酸氢盐、相应的铵化合物,和以上提及的化合物的混合物。也可使用碳酸铵。加入到沉淀反应器内的碱溶液的浓度优选为20-300g碱材料(以无水材料形式计算)/升(在溶解度允许的范围内),更优选50-250g/l。
优选地,沉淀剂溶液包括碱金属碳酸盐,尤其Na2CO3,更优选沉淀剂包括NaOH和Na2CO3的摩尔比为≤1:1的NaOH和Na2CO3。在碱金属氢氧化物和碱金属或铵的碳酸盐的混合物用作沉淀剂的情况下,认为钴最初以前水滑石状(pre-hydrotalcite-like)结构沉淀,所述结构容易接受来自溶液的铝阳离子,从而在老化步骤期间形成稳定的钴-铝水滑石状结构。
方便的是使用几乎相同浓度(用当量表达)的(钴化合物和碱化合物)二者的溶液,以便可反应大致相同的体积。
含钴的溶液和碱溶液单位时间的添加量使得在沉淀步骤期间存在过量的碱化合物,以便pH优选在7-11,更优选7-10范围内。
相对于被泵送的液体量,沉淀反应器的尺寸优选可获得短的平均停留时间。典型地,可在沉淀反应器内使用0.1秒-10分钟,优选0.2秒-4.5分钟的平均停留时间。
在其中连续进行沉淀步骤(步骤1)的优选实施方案中,通过测量,任选地连续测量反应器流出物的当量浓度或pH,从而控制加入到沉淀反应器内的溶液量。
可通过调节加入到沉淀反应器内的液体的温度,来控制发生沉淀时的温度。优选地,温度维持在低于90℃,更优选低于50℃,最优选低于30℃。优选在机械能输入为5-2000瓦/kg溶液的情况下,进行在沉淀反应器内所需的液体的剧烈搅拌。更优选在机械能输入为100-2000瓦/kg溶液的情况下,进行搅拌。从沉淀反应器中获得的反应混合物之后立即进入显著较高容量的搅拌的后反应器(老化反应器)中,在此搅拌并老化该悬浮液。在这一阶段,添加可溶的铝化合物。所添加的铝化合物的用量为0.1-0.5mol铝离子/g悬浮液内的钴原子。
视需要,紧跟在钴的沉淀之后,可溶的硅酸盐化合物也可与铝源一起添加。合适的可溶的硅酸盐化合物例如是水玻璃,其中包括中性水玻璃和硅酸钾。所添加的硅酸盐的用量可以是0.05-1mol/g钴原子,优选0.1-0.5mol。
另外,在这一阶段中可添加添加剂和/或促进剂,或者作为替代,也可在沉淀之前将它们加入到钴溶液中。合适用量的添加剂和/或促进剂以未还原的催化剂中的钴的重量计算,为0.5-10wt%。
优选地,在老化步骤期间老化反应器内的液体保持在10-100℃,优选40℃-100℃的温度。在其中沉淀剂由碳酸钠组成的连续工艺中,温度优选在40-60℃范围内。
在老化反应器内的pH在老化步骤期间可以变化。在老化反应器内的平均pH优选维持在6-11,更优选7-10,最优选8-10范围内。
可分批(即,不连续)、连续和半连续地(例如,根据阶式(cascade)方法)进行沉淀步骤以及老化步骤。
可在一个或更多个反应器内进行老化步骤,(总)的平均停留时间维持在10-180分钟,优选30-150分钟,更优选30-70分钟。若使用大于一个的老化反应器,则条件可以相同或不同。或者,可在一个反应器内充分老化产物,然后在其中没有进一步发生老化的条件下,流动到储存容器内。“充分老化”是指基本上所有的铝化合物已经沉淀,优选以钴铝化合物形式沉淀。例如,老化反应器可将其中基本上所有的铝已经反应形成钴铝化合物的产物排放到在室温(约20℃)下操作的搅拌罐内。
与同时共沉淀的前体相比,涉及单独沉淀和老化步骤的本发明方法导致粒度和粒度分布更加适合于过滤的催化剂前体。改进的可过滤性在其中高度希望更加有效的催化剂回收的氢化工艺和烃的费托合成中均是相当重要的。
从老化反应器中回收的固体材料优选用水洗涤,所述水任选地含有一些碱或表面活性材料,例如非离子表面活性剂。此外,可有利地在洗涤期间使用有机溶剂,例如丙酮。优选用低于200℃的热空气进行干燥。优选喷雾干燥,但冻干也是合适的。
在通过还原来活化催化剂之前,可使用本领域技术人员已知的方法,将干燥的组合物视需要形成为适合于催化剂所意欲应用的工艺用的成型单元。成型单元可以是球形、粒料、圆柱体、圆环、或者多孔粒料,它们可以具有例如多叶片或者有波纹的苜蓿叶形截面。
可通过在升高的温度下,使含氢气体,例如氢气、合成气或者氢气与氮气、甲烷或其它惰性气体的混合物在干燥的催化剂组合物上流过,例如通过在150-600℃范围内的温度下,优选250-600℃下,或者150-500℃,优选300-500℃下经1-24小时,使含氢气体在组合物上流过,从而进行还原。可在大气压或者最多与约25bar的更高的压力下进行还原。
处于还原状态下的催化剂可能难以处理,这是因为它们可与空气中的氧自发反应,这可导致非所需的自加热和活性损失。因此,可在还原之后用含氧气体,常常在二氧化碳和/或氮气中的空气或者氧气钝化适合于氢化反应的还原的催化剂。钝化提供薄的保护层,所述保护层足以防止与空气非所需的反应,但一旦将催化剂安装在氢化工艺内时,通过用含氢气体处理容易除去。对于适合于费托工艺的催化剂来说,不优选钝化,而优选通过用合适的隔离涂层封装还原的催化剂颗粒来保护还原的催化剂。在费托催化剂的情况下,它可合适地为FT-烃蜡。或者,可提供未还原状态下的催化剂,并用含氢气体就地还原。
不管选择哪一路线,本发明的催化剂提供非常高的钴表面积。当在425℃下还原时,催化剂具有至少30m2/g(还原的)催化剂的钴表面积,这通过此处所述的氢气化学吸附技术来测量。优选钴的表面积大于35m2/g(还原的)催化剂,更优选至少40m2/g(还原的)催化剂。
通过氢气化学吸附来测定钴的表面积。优选的方法如下所述:首先使约0.2-0.5g样品材料脱气,并通过在流动的氦气中以10℃/min加热到140℃,并在140℃下保持60分钟,从而干燥。然后通过在50ml/min的氢气流速下,以3℃/min的速度从140℃加热到425℃,然后在相同的氢气流速下将其保持在425℃下6小时,从而还原经脱气和干燥的样品。在还原之后和在真空下,以10℃/min加热样品到450℃,并在这些条件下保持2小时。然后冷却样品到150℃并在真空下进一步保持30分钟。在150℃下,使用纯的氢气进行化学吸附分析。使用自动分析程序,测量在100mmHg一直到760mmHg的氢气压力范围内的全部等温线。进行2次分析;第一次测量“总”的氢气吸收量(即,包括化学吸附的氢气和物理吸附的氢气),并紧跟着在第一次分析之后,将样品置于真空(<5mmHg)下30分钟,然后反复该分析方法,测量物理吸附的吸收量。然后将线性回归线应用到“总”的吸收量数据上并往外回推至0压力,计算化学吸附的气体体积(V)。
在所有情况下,使用下述方程式计算钴的表面积:
Co的表面积=(6.023×1023×V×SF×A)/22414
其中V=H2的吸收量(ml/g)
SF=化学计量因子(对于在Co上H2的化学吸附来说,认为是2)
A=一个钴原子占据的面积(认为是0.0662nm2)
在Operators Manual for the Micromeretics ASAP 2010 ChemiSystem V2.01,Appendix C,Part No.201-42808-01,1996年10月中公开了这一方程式。
该催化剂可用于氢化反应和用于烃的费托合成。
典型的氢化反应包括分别氢化醛和腈成醇和胺,以及氢化环芳族化合物或者不饱和烃。本发明的催化剂尤其适合于氢化不饱和有机化合物,尤其油、脂肪、脂肪酸和脂肪酸衍生物,例如腈。典型地通过在高压釜中,在环境或者升高的温度下,在钴-催化剂存在下,用含氢气体处理待氢化的化合物,以连续或者分批的方式进行这种氢化反应,例如可在80-250℃下和在范围为0.1-5.0×106Pa的压力下,用氢气进行氢化。
烃的费托合成是众所周知的。费托合成将一氧化碳和氢气的混合物转化成烃。一氧化碳和氢气的混合物典型地为氢气:一氧化碳之比范围为1.7-2.5:1的合成气。可使用一个或更多个搅拌的淤浆相反应器、泡罩塔反应器、环管反应器或流化床反应器,以连续或者分批的工艺进行该反应。可在范围为0.1-10MPa的压力下和范围为150-350℃的温度下操作该工艺。对于连续操作来说,气体时空速度(GHSV)范围为100-25000h-1。本发明的催化剂因其高的钴表面积/g催化剂,因此尤其有用。
参考下述实施例进一步阐述本发明。
实施例1:催化剂的制备
Al:Co摩尔比=0.21:1。分别以1500和860ml/h的流速,将Co(NO3)2水合物(35g Co/升)和无水Na2CO3(67g/升)/NaOH(25g/升)混合物的水溶液连续泵送到剧烈搅拌的沉淀反应器内,在此在35℃的温度下沉淀氢氧化钴/碳酸钴。在这一反应器内悬浮液的pH为9.5。在这一沉淀反应器(体积100ml)内,悬浮液的平均停留时间为0.5分钟。然后将该悬浮液连续转移到其中温度为70℃的老化反应器(体积5000ml)中。同时,将适量铝离子以铝酸钠(10g Al/升)形式,在490ml/h的速度下连续计量加入到这一反应器内。另外,将1150ml/h的水计量加入到这一反应器内。随后将悬浮液连续转移到其中温度为60℃的第二个老化反应器内。
在第一个老化反应器内悬浮液的pH为9.5,和在第二个老化反应器内为9.5。在第一和第二个老化反应器内液体的体积保持恒定。
继续老化直到至少大部分的铝形成钴-铝化合物。终止老化步骤,并过滤来自第二个老化反应器的悬浮液。过滤速度为约1升/min。用蒸馏水洗涤如此获得的滤饼。喷雾干燥洗过的滤饼。通过如上所述的氢气化学吸附,在还原的催化剂上测定钴的表面积。使用MalvernMastersizerTM,测量在还原之前催化剂的粒度。使用本领域技术人员已知的方法,通过氮气物理吸附,测量未还原和还原的催化剂的BET表面积和孔体积。使用吸附分支(branch)测定孔体积,和由(4×孔体积)/BET表面积,计算孔径。表1中给出了结果。
对比例A
根据实施例1所述的工序,通过使用1g Al/升的铝酸钠溶液,使用Al/Co原子比为0.02,制备催化剂。表1中给出了结果。
表1
催化剂 | 实施例1 | 对比例A |
Co含量未还原的催化剂(wt%) | 44.3 | 36.6 |
Co含量还原的催化剂(wt%) | 82.0 | 98.9 |
Co表面积(m<sup>2</sup>/g还原的催化剂) | 42.0 | 11.2 |
Co表面积(m<sup>2</sup>/g还原的催化剂内的钴) | 51.2 | 11.3 |
BET表面积未还原的催化剂(m<sup>2</sup>/g) | 96.8 | NM |
BET表面积还原的催化剂(m<sup>2</sup>/g) | 95.7 | NM |
孔体积未还原的催化剂(cm<sup>3</sup>/g) | 0.51 | NM |
孔体积还原的催化剂(cm<sup>3</sup>/g) | 0.36 | NM |
平均孔径未还原的催化剂(埃) | 211 | NM |
平均孔径还原的催化剂(埃) | 150 | NM |
粒度未还原的催化剂(微米)D(v,0.1)D(v,0.5)D(v,0.9) | 4.012.623.1 | 2.713.328.8 |
NM=没有测量
实施例2:催化剂的制备
重复实施例1的催化剂制备方法,其中改变Co:Al之比以及反应和老化容器内的pH。分析结果如下所述:
催化剂 | 2a | 2b | 2c | 2d | 2e |
Al∶Co之比 | 0.23 | 0.21 | 0.22 | 0.22 | 0.33 |
pH沉淀反应器 | 8.1 | 7.9 | 10.3 | 8.0 | 7.0 |
pH老化容器1 | 8.3 | 8.0 | 10.6 | 8.9 | 9.2 |
pH老化容器2 | 8.3 | 8.1 | 10.6 | 8.9 | 9.2 |
Co含量(wt%)未还原的催化剂 | 44.5 | 45.2 | 44.6 | 44.3 | 41.3 |
Co含量(wt%)还原的催化剂 | 78.8 | 80.4 | 77.3 | 76.0 | 76.1 |
Co表面积(m<sup>2</sup>/g还原的催化剂内的钴) | 58.1 | 54.7 | 58.3 | 43.7 | 61.5 |
Co表面积(m<sup>2</sup>/g还原的催化剂) | 45.8 | 44.0 | 45.1 | 33.2 | 46.8 |
BET表面积(m<sup>2</sup>/g)未还原的催化剂 | 128.5 | 146.6 | 116.0 | 103.0 | 92.8 |
粒度(微米)未还原的催化剂D50(vol) | 10.0 | 13.2 | 12.7 | 10.8 | 11.1 |
对于3:1的Co/Al来说,实现最高的Co表面积。
实施例3:催化剂的制备
分别以1500和860ml/h的流速将硝酸钴的水溶液和含NaOH/和/或Na2CO3的沉淀剂水溶液连续泵送到剧烈搅拌的沉淀反应器内(一直到1500rpm),在此在20-45℃的温度下沉淀氢氧化钴/碳酸钴。在这一沉淀反应器(体积约15ml)内,悬浮液的平均停留时间为约0.5分钟。然后将该悬浮液连续转移到搅拌的老化反应器(体积5000ml,搅拌速度100-450rpm)中,并允许75-25分钟的老化时间(或者,在一些实验中,使用3000ml容器)。借助恒温控制的水浴来控制老化反应器的温度。同时,将适量铝离子以铝酸钠形式连续计量加入到这一反应器内。随后,在室温(约20℃)下,将该悬浮液连续转移到非搅拌的储存罐内。随后用1500ml软化水洗涤来自储存罐的悬浮液并过滤。在110℃下干燥如此获得的滤饼过夜或者喷雾干燥。通过如上所述的氢气化学吸附,在还原的催化剂上测定钴的表面积。
a)pH的影响。在第一系列的实验中,通过在沉淀剂溶液中,在70℃下老化70分钟的同时,在0.3的Al:Co之比下,使用不同量的碳酸钠和氢氧化钠,改变老化反应器内的pH。(0.0表示所有的沉淀剂是碳酸钠和1.0表示沉淀剂为50:50(摩尔)的氢氧化钠和碳酸钠)。结果如下所述:
b)
pH | NaOH/Na<sub>2</sub>CO<sub>3</sub>摩尔比 | 干燥方法 | BET SAm2/g | 孔体积cm<sup>3</sup>/g | 孔径(埃) | Co表面积(m<sup>2</sup>/g还原的催化剂) |
6.5 | 0.0 | 烘箱 | 136.1 | 0.47 | 138 | 32.8 |
6.5 | 0.5 | 喷雾干燥 | 150.5 | 0.54 | 144 | 44.2 |
7.7 | 0.75 | 喷雾干燥 | 101.3 | 0.38 | 150 | 43.4 |
9.8 | 1.0 | 喷雾干燥 | 153.8 | 0.66 | 172 | 45.2 |
所有催化剂得到>30m2/g还原的催化剂的Co表面积,且结果表明,通过增加沉淀剂溶液内NaOH浓度来增加pH导致较高的钴表面积。优选地,NaOH/Na2CO3的摩尔比≥0.5:1,更优选1:1和pH为8-10。
b)Al:Co之比的影响。采用不同含量的Al和Co溶液和在约60℃的老化温度下70分钟,进行一系列实验。全部烘箱干燥沉淀的催化剂前体。在较低的钴含量(Co:Al=1.5:1和1.02:1)下制备对比例(星号*),它表明与本发明的催化剂相比,钴的表面积和BET表面积均低。
结果如下所述:
Al/Co(mol/mol) | 老化温度(℃) | 老化pH | NaOH/Na<sub>2</sub>CO<sub>3</sub>摩尔比 | BET SAm<sup>2</sup>/g | 孔体积cm<sup>3</sup>/g | 孔径(埃) | Co SA(m<sup>2</sup>/g还原的催化剂) |
0.30 | 60 | 6.1 | 0 | 42.6 | |||
*0.66 | 62 | 6.4 | 0 | 64.3 | 0.40 | 249 | 26.0 |
*0.98 | 62 | 7.0 | 0 | 74.5 | 0.46 | 247 | 23.4 |
c)老化温度的影响。在Al:Co=0.3和不同的老化反应器温度/时间下进行一系列实验。在老化过程中的pH低,这是因为碳酸钠用作唯一的沉淀剂。结果如下所述:
老化温度(℃) | 老化时间(min) | 干燥方法 | pH | NaOH/Na<sub>2</sub>CO<sub>3</sub> | BET SAm<sup>2</sup>/g | 孔体积cm<sup>3</sup>/g | 孔径(埃) | Co表面积(m<sup>2</sup>/g还原的催化剂) |
70 | 70 | 烘箱 | 6.5 | 0 | 136.1 | 0.47 | 138 | 32.8 |
60 | 70 | 喷雾干燥 | 6.0 | 0 | 112.9 | 0.55 | 195 | 37.0 |
55 | 30 | 喷雾干燥 | 6.5 | 0 | 217.6 | 0.56 | 103 | 46.5 |
50 | 30 | 喷雾干燥 | 6.6 | 0 | 186.4 | 0.51 | 109 | 48.8 |
40 | 30 | 烘箱 | 6.8 | 0 | 137 | 0.33 | 96 | 34.3 |
结果表明,在这些条件下,最佳的温度范围为约50℃。
d)老化时间的影响。在Al:Co=0.3、沉淀反应器T=35℃、老化反应器T=40或70℃和增加的老化时间25-70分钟下进行一系列实验。结果如下所述:
老化温度(℃) | 老化时间(min) | pH | 老化搅拌速度 | 干燥方法 | BET SAm<sup>2</sup>/g | 孔体积cm<sup>3</sup>/g | 孔径(埃) | Co表面积(m<sup>2</sup>/g还原的催化剂) |
70 | 70 | 6.5 | 350 | 烘箱 | 136.1 | 0.47 | 138 | 32.8 |
70 | 37 | 6.5 | 350 | 喷雾干燥 | 145.0 | 0.48 | 132 | 44.5 |
70 | 25 | 6.2 | 350 | 烘箱 | 150.2 | 0.37 | 98 | 31.7 |
40 | 30 | 6.9 | 200 | 烘箱 | 137.0 | 0.33 | 96 | 34.3 |
40 | 40 | 9.9 | 200 | 烘箱 | 33.2 | |||
40 | 50 | 9.9 | 200 | 烘箱 | 33.1 |
结果表明,所有Co表面积高于30m2/g还原的催化剂,和对于70℃老化35-40分钟来说,实现最高的Co表面积。
e)Mn促进剂的影响,混合硝酸锰与起始的硝酸钴溶液。用下述组成制备催化剂。
Al/Co原子比 | 预期的Co/Mn | 实验的Co/Mn | (Al+Mn)/Co | Al/(Co+Mn) |
0.24 | 80 | 80.75 | 0.25 | 0.23 |
0.19 | 20 | 19.28 | 0.24 | 0.18 |
0.19 | 10 | 12.27 | 0.27 | 0.17 |
0.24 | 5 | 11.81 | 0.32 | 0.22 |
0.24 | 5 | 11.91 | 0.32 | 0.22 |
老化温度为50℃,老化时间为30分钟,在老化反应器内的搅拌速度为200rpm。50:50(摩尔)的NaOH/Na2CO3用作沉淀剂,和对于所有催化剂来说,在老化反应器内的平均pH为8.2。结果如下所述:
备注 | 干燥方法 | BET SAm<sup>2</sup>/g | 孔体积cm<sup>3</sup>/g | 孔径(埃) | Co表面积(m<sup>2</sup>/g还原的催化剂) |
1/80Mn/Co | 烘箱 | 165.1 | 0.71 | 172 | 48.6 |
1/80Mn/Co | 喷雾干燥 | 144.0 | 0.80 | 222 | 44.1 |
1/20Mn/Co | 喷雾干燥 | 35.5 | |||
1/10Mn/Co | 喷雾干燥 | 34.4 | |||
1/5Mn/Co | 喷雾干燥 | 126.3 | 0.48 | 152 | 43.3 |
1/5Mn/Co | 喷雾干燥 | 158.3 | 0.60 | 152 | 45.4 |
可预期当Mn的含量增加时,锰之比的系列实验引起钴表面积/g还原的催化剂下降。确实观察到这一结果,例外是1/5之比。认为Mn是改进催化剂选择性的促进剂。
f)还原温度Co表面积的影响。在下述条件下制备催化剂前体:Al/Co原子比=0.3;NaOH/Na2CO3摩尔比=1:1,沉淀反应器温度=35℃,老化反应器温度=50℃;老化反应器的搅拌速度=200rpm,和沉淀反应器=1500rpm;老化时间30分钟;烘箱干燥洗涤过的沉淀。
在不同温度下,在纯氢气物流下还原没有焙烧的催化剂前体,并在150℃下使用以上所述的化学吸附方法测量Co表面积。
还原温度(℃) | Co表面积(m<sup>2</sup>/g还原的催化剂) | 还原时的重量损失(%w/w) |
380 | 53.2 | 65 |
425 | 51.1 | 66 |
480 | 47.9 | 67 |
结果表明,在380-480℃下,优选在较低温度下,发生可接受的还原。这一发现与Khassin等人的教导相反,Khassin等人认为,对于同时共沉淀的Co-Al催化剂来说,较高的还原温度得到较高的钴表面积。
实施例4:催化剂测试
在250℃下,在空气中焙烧根据实施例3的方法制备的催化剂前体5小时。焙烧时的重量损失为52.9%w/w。将0.1g焙烧过的材料分散在1.0g50-100微米的惰性碳化硅内,并置于实验室管状(4mm内径)反应器内。使用99%氢气、1%Ar,在380℃/9小时下还原前体,然后冷却到100℃,并使氢气和一氧化碳的混合物(H2:CO=2:1)在催化剂上流过。在16小时内,温度增加到195℃,然后在这一温度下保持一段时间,之后升高温度到210℃,保持90-150小时。压力为20bar。维持原料气体混合物的空间速度,以便实现约30%的转化率。使用已知方法,在线使用气相色谱,在100-150小时之间测定产物气体组成。分析产物气体物流中的CO2和甲烷(CH4)副产物以及所需的C5+烃产物。
使用标准催化剂进行对比实验,所述标准催化剂在还原之前包括在氧化铝载体上浸渍的20wt%的Co和1wt%的Re。通过用硝酸钴和高铼酸铵的溶液浸渍γ氧化铝(Puralox HP 14/150),并在200℃下焙烧1小时之前,在110℃下烘箱干燥分离的固体6.5小时,从而制备标准催化剂。在1.0g SiC内添加0.2g催化剂。对于这两种催化剂来说,还原和反应条件是相同的。
通过观察得到所需转化率所要求的相对催化剂组成和空间速度,可计算本发明催化剂的相对活性。结果如下所述:
标准催化剂 | 实施例4的催化剂 | |
未还原(氧化)的催化剂重量(g) | 0.203 | 0.104 |
还原温度(℃) | 380 | 380 |
还原时间(min) | 540 | 540 |
还原空间速度(1/h.kg) | 9754 | 19038 |
还原时的重量损失(%) | 17.7 | 27.7 |
Co表面积(m<sup>2</sup>/g还原的催化剂) | 14.9 | |
反应温度(℃) | 210 | 210 |
压力(bar) | 20 | 20 |
空间速度(1/h.kg)(基于未还原的催化剂) | 8867 | 17308 |
所测量的转化率(基于起始的Ar%) | 33.2 | 30.2 |
相对活性(未还原的催化剂) | 1.0 | 1.8 |
相对活性(还原的催化剂) | 1.0 | 2.0 |
CO<sub>2</sub>(%) | 0.213 | 0.257 |
CH<sub>4</sub>(%) | 7.16 | 7.81 |
C5+(%) | 86.3 | 85.9 |
结果表明,对于本发明的催化剂来说具有高得多的活性和相当的选择性。
Claims (14)
1.一种烃的费托合成方法,该方法包括使一氧化碳和氢气的混合物在粒状催化剂的存在下反应的步骤,该粒状催化剂包括钴与铝的原子比范围为10:1-2:1的承载在钴-铝化合物上的钴化合物,当在425℃下被还原时,该粒状催化剂具有至少30m2/g催化剂的钴表面积,这通过在150℃下的氢气化学吸附来测量,其中该催化剂通过包括下述的步骤制备:
(i)使用过量的碱沉淀剂,由钴盐的水溶液沉淀不可溶的钴化合物,
(ii)添加可溶的铝化合物,
(iii)老化所得的悬浮形式的沉淀物,
(iv)回收并干燥该催化剂组合物,和
(v)通过使用含氢气体的还原来活化该催化剂。
2.权利要求1的方法,进一步包括焙烧干燥的催化剂组合物的步骤。
3.权利要求1或2的方法,其中钴盐是硝酸盐、硫酸盐、乙酸盐、氯化物或甲酸盐。
4.权利要求1或2的方法,其中钴盐是硝酸钴。
5.权利要求1或2的方法,其中沉淀剂是碱金属氢氧化物、碱金属碳酸盐、碱金属碳酸氢盐、氢氧化铵、碳酸铵、碳酸氢铵或其混合物。
6.权利要求1或2的方法,其中沉淀剂是氢氧化钠、碳酸钠或其混合物。
7.权利要求1或2的方法,其中在7-10范围内的pH下,在低于50℃的温度下进行沉淀。
8.权利要求1或2的方法,其中可溶的铝化合物是硝酸铝、铝酸钠或至少部分溶解在过量碱内的氧化铝。
9.权利要求1或2的方法,其中可溶的铝化合物是铝酸钠。
10.权利要求1或2的方法,其中进行老化,直到>50%的铝为钴铝化合物形式。
11.权利要求1或2的方法,其中在6-11范围内的pH下,在10-100℃范围内的温度下进行老化。
12.权利要求1或2的方法,其中用于烃的费托合成的一氧化碳和氢气的混合物是氢气:一氧化碳之比范围为1.7-2.5:1的合成气。
13.权利要求1或2的方法,其中烃的费托合成使用一个或更多个搅拌的淤浆相反应器、泡罩塔反应器、环管反应器或流化床反应器,以连续或者分批的工艺进行。
14.权利要求1或2的方法,其中烃的费托合成在范围为0.1-10MPa的压力下和范围为150-350℃的温度下操作。
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BRPI0705939A2 (pt) * | 2007-10-29 | 2009-06-23 | Petroleo Brasileiro Sa | processo para a produção de catalisadores hìbridos para a sìntese de fischer-tropsch e catalisador hìbrido produzido de acordo com o processo |
GB0806148D0 (en) * | 2008-04-04 | 2008-05-14 | Johnson Matthey Plc | Process for preparing catalysts |
US8148292B2 (en) * | 2008-07-25 | 2012-04-03 | Exxonmobil Research And Engineering Company | Preparation of high activity cobalt catalysts, the catalysts and their use |
KR101018660B1 (ko) * | 2009-12-22 | 2011-03-04 | 금호석유화학 주식회사 | 다중벽 탄소나노튜브 제조용 촉매조성물 |
DE102010021792B4 (de) * | 2010-05-27 | 2022-03-31 | Clariant Produkte (Deutschland) Gmbh | Katalysatoren und Verfahren zu deren Herstellung |
RU2445161C1 (ru) * | 2010-08-19 | 2012-03-20 | Общество с ограниченной ответственностью "СинТоп" | Способ активации кобальтового катализатора синтеза фишера-тропша |
RU2551433C1 (ru) | 2011-04-28 | 2015-05-27 | Сэсол Текнолоджи (Проприетери) Лимитед | Катализаторы |
RU2458736C1 (ru) * | 2011-05-10 | 2012-08-20 | Учреждение Российской академии наук Институт катализа им. Г.К. Борескова Сибирского отделения РАН | Катализатор и способ получения углеводородов из монооксида углерода и водорода (варианты) |
CN103387246A (zh) * | 2012-05-09 | 2013-11-13 | 中节能六合天融环保科技有限公司 | 一种适用于亚硫酸镁快速氧化生成硫酸镁的处理工艺 |
CN104307512A (zh) * | 2014-10-14 | 2015-01-28 | 武汉大学苏州研究院 | 一种负载型钯催化剂及其制备方法和应用 |
US10066169B2 (en) * | 2015-07-14 | 2018-09-04 | Research & Business Foundation Sungkyunkwan University | Mesoporous cobalt-metal oxide catalyst for Fischer-Tropsch synthesis reactions and a preparing method thereof |
CN106582658A (zh) * | 2015-10-19 | 2017-04-26 | 神华集团有限责任公司 | 一种费托合成铁基催化剂的制备方法 |
FR3044005B1 (fr) * | 2015-11-23 | 2017-12-15 | Ifp Energies Now | Procede de synthese d'hydrocarbures a partir de gaz de synthese en presence d'un catalyseur a base de cobalt piege dans une matrice oxyde mesoporeuse et obtenu a partir d'au moins un precurseur monomerique |
WO2018206716A1 (en) * | 2017-05-12 | 2018-11-15 | Basf Se | Precipitation catalyst for the hydrogenation of ethyl acetate containing copper on zirconia |
WO2019180013A1 (en) * | 2018-03-20 | 2019-09-26 | Shell Internationale Research Maatschappij B.V. | Preparation of a cobalt-containing catalyst |
CN115297962A (zh) * | 2020-03-24 | 2022-11-04 | 巴斯夫公司 | 催化剂组合物及其制备和使用方法 |
WO2023164163A2 (en) * | 2022-02-24 | 2023-08-31 | West Virginia University Board of Governors on behalf of West Virginia University | Methods and compositions for chemical looping ammonia synthesis at low pressure |
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CN114870856A (zh) * | 2022-06-14 | 2022-08-09 | 扬州大学 | 钴锰复合氧化物催化剂及其制备方法和应用 |
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