CN1036711A - 甲醇离解催化剂的二氧化碳焙烧 - Google Patents
甲醇离解催化剂的二氧化碳焙烧 Download PDFInfo
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- CN1036711A CN1036711A CN89102145A CN89102145A CN1036711A CN 1036711 A CN1036711 A CN 1036711A CN 89102145 A CN89102145 A CN 89102145A CN 89102145 A CN89102145 A CN 89102145A CN 1036711 A CN1036711 A CN 1036711A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000010949 copper Substances 0.000 title claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 22
- 238000010494 dissociation reaction Methods 0.000 title claims abstract description 20
- 230000005593 dissociations Effects 0.000 title claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 8
- 239000001569 carbon dioxide Substances 0.000 title claims description 8
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 208000018459 dissociative disease Diseases 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- -1 for example Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000382353 Pupa Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910018594 Si-Cu Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910008465 Si—Cu Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910000019 calcium carbonate 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
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 230000002475 laxative effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- 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
- B01J23/72—Copper
-
- 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
-
- 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
- B01J23/8926—Copper and noble metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种制备含铜甲醇离解催化剂的改进方法，该方
法通过沉淀含铜催化剂前体，焙烧和还原该前体，其
改进在于在CO2气氛中进行前体的焙烧。
Description
使用最广泛的甲醇离解催化剂含有与其它过渡金属或其氧化物或与碱土金属或其氧化物紧密缔合的铜或氧化铜。这些甲醇离解催化剂的制备通常包括将所有组份（除了也许有的二氧化硅以外）由可溶性金属盐（例如，硝酸盐）的一般溶液中共沉淀，以产生作为沉淀物的密切缔合的不溶性盐。
所得到的沉淀物通常进行焙烧，也就是，充分加热以除水份，有机溶剂和盐类，并使催化剂具有一定程度的结构完整性。焙烧一般是在高温（200℃～700℃）进行。更高的温度会引起催化剂的烧结，由于表面积减少而伴随有活性的损失。氧化气氛，例如，空气或氧，促进各种金属盐变为它们各自的金属氧化物。在许多情况下，金属氧化物是催化活性的。而对其它催化剂，金属氧化物可以还原，例如用氢，而形成活性催化剂。
焙烧气氛的选择取决于要处理的催化剂。Stiles（催化剂制备，Marcel Dekker，纽约）公开了焙烧催化剂的气氛可以是蒸汽、氧、二氧化碳、氮、氢或一氧化碳，但是没有给出选择最佳焙烧气氛的准则。
在现有技术的某些参考文献中，气氛是专指“空气”的，但更一般地说，用于制备甲醇离解催化剂的焙烧气氛的性质是不明确的。美国专利4431566公开了一个甲醇催化转化成氢和一氧化碳的方法，所使用的催化剂是由氧化铝作载体材料而在载体材料上载有镍和钾。该催化剂的制备包括在一种氧气氛中进行焙烧。
本发明提供一种制备含铜的甲醇离解催化剂方法的改进，该方法通过（a）将含有至少一种铜盐的金属盐水溶液与一种任选的含硅源的碱溶液相混合，以沉淀含铜催化剂前体，（b）回收沉淀的前体，（c）在高温下焙烧所回收的前体，和（d）还原焙烧的前体，其改进包括在二氧化碳气氛中进行焙烧所回收的前体。
在制备甲醇离解催化剂的典型工艺中，在碳酸钠水溶液中分散的二氧化硅中慢慢地加入一种金属盐水溶液并剧烈搅拌。在某些情况下，可用碳酸钙、氢氧化钙或氢氧化钠的浆料或溶液代替碳酸钠水溶液。在完全沉淀和混合后，过滤浆料以除去过量的液体，然后用热水洗涤以除去沉淀过程的副产品。为了在干燥过程中使硬烧结块的形成减少至最小程度，该湿产物可以用丙酮再次成浆，然后在部分真空下进行干燥。根据本发明，所得到的催化剂前体是在二氧化碳气氛中，10千巴（KPa）～5×103千巴的压力和150℃～600℃的温度条件下加热至少20分钟，一般3小时，以焙烧催化剂，从而使各种金属盐转变成它们各自的金属氧化物。在其用于甲醇离解反应之前，焙烧的催化剂要在N2/H2或CO气氛中进行还原。
通常，在焙烧期催化剂前体的损失约为其重量的23%，而在还原期约增加8%。因此，装入反应器、管子或炉中的样品量，要随着制备步骤进行调节，使所有催化剂样品在甲醇离解反应开始时，都具有大致相同的重量。
一般，将大约2.0克焙烧的催化剂（-12、+20目）装入外径3/8吋（0.953厘米）的Ni-Cr-Fe-Mn-Si-Cu合金制的U型反应器管中，该管子在砂浴内加热。将几克碳化硅装填在催化剂床的顶部，以填充反应器容积。反应器系统包括在分开的砂浴中的两个平行反应器。在用于甲醇离解反应之前，焙烧的催化剂通过在250℃和200千巴条件下在100sccm流速的N2/H2（95/5）气氛中加热约3小时而进行还原。
焙烧期间选用的CO2压力是100千巴～500千巴，选用的焙烧温度是200℃～400℃;最好的温度是300℃～350℃。
在下面的描述中，所有催化剂的组成是以过渡金属、碱土金属和硅（如果存在）的总量的重量百分数来表示的。
甲醇离解催化剂的铜含量，按重量为5%到100%，最好是20%～90%。该催化剂也可以含有一种或多种选自以下的过渡金属或碱土金属或其氧化物或氢氧化物：铬、钼、钨、锰、镍、铼、铁、钌、锇、钯、金、锌、汞、镁、钙、钡和锶。优先的金属砑蛹潦歉酰?%～75%）、锰（1%～5%）和碱土元素（1%～15%）。
催化剂也可以含有以二氧化硅、硅酸盐或硅酸的形式存在的硅。硅的存在量是不严格的。硅可以是催化剂的小组成，小到0.1%，或者它可以是催化剂的主要成份，并用作催化剂的支持体。催化剂最好含有0.1%～15%的二氧化硅。
适宜的过渡金属源包括不含有能使催化剂中毒的元素，如卤素或硫，的水溶性金属盐。合适的过渡金属源的实例是硝酸盐、醋酸盐、草酸盐和胺碳酸盐。最好的是硝酸盐。
同样，适宜的碱土金属源包括不含卤素或硫的碱土金属盐。适宜的碱土金属盐的实例是醋酸盐、苯甲酸盐、丁酸盐、碳酸盐、柠檬酸盐、甲酸盐、乳酸盐、硝酸盐、亚硝酸盐、氧化物、丙酸盐、水杨酸盐、硅酸盐和戊酸盐。最好的是硝酸盐。
适宜的二氧化硅源包括，例如，硅酸钠、二氧化硅水溶胶、硅胶、二氧化硅溶胶和硅酸。优先的二氧化硅源是一种二氧化硅颗粒的水性胶状分散体。合适的工业用二氧化硅源包括LudoxTM胶体二氧化硅（可从Dupont买到）和CabosilTM（可从Cabot公司买到）。
甲醇离解反应通常在250℃、2个大气压（200千巴）下进行;流量是定在17.5、35或105sccm而变化的。
反应产物是通过两个串联的、并装有热传导率检测器的气体色谱仪而进行分析。CO2、甲醇、甲基甲酸酯、二甲醚、水和其他高沸产物是在第一个色谱柱（GC）（80/100 Porapak T，1/8″×8′的装填柱）中分离和分析的，该柱是在温度程序模以8℃/分速率升温到100℃～160℃中进行操作。气体产物，如CO、H2和甲烷是在70℃下运行的第二个柱（5A分子筛、1/8″×8′装填柱）中进行分离和分析的。用于两个色谱仪中的载气是39sccm流量的含8.5%H2的He气体。
甲醇的转化率是以送入反应器的每摩尔甲醇中所转化的甲醇摩尔数来表示。CO和氢是主要产物，其它产物包括少量的CO2、二甲醚、甲基甲酸酯和痕量的水和甲烷。
对CO的选择性是以每摩尔反应的甲醇所产生的CO摩尔数来表示。
在用于甲醇离解反应的最初几个小时期间，催化剂的活性稍有降低。列于表2的转化率和选择性的值是在“准稳定”条件下，也就是在反应14～20小时后进行比较的。
催化剂前体的组成综述于表1。焙烧条件综述于表2。甲醇离解结果综述于表3。
实施例1-4：CO2-焙烧的催化剂1-4和比较催化剂A-F的制备。
催化剂1的前体是通过下法制备的：将500毫升Cu（NO3）2·3H2O（76.25克）、Cr（NO2）3·9H2O（51.25克）和Mn（NO3）2（3.6克，50～52%重量）的水溶液加入到一分液漏斗中。漏斗安置在一个标准的1250cc Hamilton Beach食品搅拌器的玻璃混合罐上面，该混合罐装有400毫升SiO2（1.52克、CabosilTM）和Na2CO3（70克）的水溶液浆料。连接在漏斗出口的是一个外径10毫米的玻璃管，该玻璃管的长度足以向下通过罐盖而伸到搅拌器浆叶的1/2吋内。将溶液在15～30分钟内从漏斗加到搅拌器的快速搅拌的浆料中。所得沉淀过滤而分离，并用热水洗涤直到中性（pH6～7）为止。得到的粉末转入一清洁的搅拌器，用丙酮再次成浆，重复过滤和洗涤过程。得到的自由流动粉末是用丙酮再次成浆，然后在60℃的旋转蒸发器中干燥而获得粒状的粉末。
将催化剂前体颗粒（-12、+20目大小范围内）进行焙烧，然后在N2/H2（95/5）气氛中还原。用于实施例3-4和比较例A-F的前体的制备主要是按对催化剂Ⅰ的前体的描述进行的。催化剂2是通过将催化剂1的前体再压制然后粉碎而得到的。
实施例5：CO2-焙烧的催化剂5和比较催化剂G-H的制备。
催化剂前体是按催化剂1-3而制备的，除了用LudoxTMHS-40（3.8克）代替CabosilTM作为二氧化硅的水性胶状分散体。
实施例6：CO2焙烧的催化剂6和比较催化剂Ⅰ的制备。
催化剂前体是根据催化剂1-4方法制备的，除了省去CabosilTM的水性二氧化硅胶状分散体。
实施例7：CO2-焙烧的催化剂7和比较催化剂J的制备
催化剂前体是这样制备的：将500毫升Cu（NO3）2·3H2O（27.33克）和Zn（NO3）2·6H2O（76.76克）的水溶液加到在500毫升水中的Na2CO3（50克）的剧烈搅拌的溶液中。将浆料在塑料烧杯中放置4小时，然后过滤，所得到的固体用水好好洗涤。固体用丙酮成浆，过滤并干燥后获得自由流动的粉末。
实施例8：CO2-焙烧的催化剂8和催化剂K-L的制备
催化剂前体是这样制备的：将400毫升的Cu（NO3）2·3H2O（59.185克），Cr（NO3）3·9H2O（31.95克）和Ba（NO3）2（5.11克）的水溶液加到在400毫升水中的CabosilTM（1.52克）和NaOH（18克）的快速搅拌的溶液中。得到的固体按实施例1-4所描述的进行洗涤、过滤和干燥。
实施例9：CO2-焙烧的催化剂9和比较催化剂M的制备
通过重复实施例7中所描述的步骤制备催化剂前体，金属盐溶液中是使用Cu（NO3）2·3H2O（72.8克）、Cr（NO3）3·9H2O（47.36克）和Zn（NO3）2·6H2O（60.67克）。
表1.催化剂前体的组成a
催化剂 Cu Cr Mn Si Zn Ba
1-4，A-F 70.3 23.3 3.9 2.5 - -
5，G-H 70.3 23.4 3.9 2.4 - -
6.I 72.1 23.9 4.0 - - -
7，J 29.9 - - - 70.1 -
8，K-L 67.4 17.9 - 3.1 - 11.7
9b，Mb48 18 - - 33 -
a.这些组成是基于金属的重量%;
b.这些组成是基于金属氧化物的重量%。
表2 焙烧的条件
催化剂 气氛 温度℃ 压力 流量 容器类型
psia sccm
1 CO2300 30 5 反应器
A 空气 300 15 - 炉a
B 空气 300 30 100 反应器
2 CO2300 30 50 反应器
C MeOH 250 30 35 反应器
3 CO2300 30 20 反应器
4 CO2300 15 - 管b
D N2300 30 20 反应器
E 空气 300 30 20 反应器
F 真空 300 - - 炉
5 CO2300 30 5 反应器
G 空气 300 30 100 反应器
H H2/N2250 30 100 反应器
6 CO2300 15 - 管b
I 空气 300 15 - 管b
7 CO2300 30 47 反应器
J N2300 30 50 反应器
8 CO2250 15 - 炉a
K 真空 250 - - 炉a
L 真空 450 - - 炉a
9 CO2300 30 50 反应器
M N2/H2250 30 100 反应器
a.常用炉
b.外径2吋的石英管。
表3：甲醇离解催化剂的转化率和选择性
催化 焙烧气氛 温度 甲醇 离解f
剂 ℃ 流量sccm 转化率 选择性
1 CO2250 35 84.4 88.4
Ab空气 250 35 72.3 92.3
B 空气 250 35 81.7 89.4
2 CO2250 35 72.3 90.0
C MeOH 250 35 48.4 81.4
3 CO2250 35 90.6 91.5
4cCO2250 35 79.4 90.9
D N2250 35 75.9 91.9
E 空气 250 35 74.1 92.0
Fb真空 250 35 72.1 91.7
5 CO2250 35 65.1 90.5
G 空气 250 35 59.8 89.9
H H2/N2250 35 59.5 88.3
6dCO2250 17.5 66.5 91.3
Id空气 250 17.5 60.8 89.2
6dCO2274 17.5 85.2 93.3
Id空气 274 17.5 68.5 91.7
7 CO2250 35 19.5 77.5
J N2250 35 9.8 67.2
8bCO2250 35 80.0 93.0
Kb真空 250 35 73.8 91.0
Le真空 250 35 65.6 90.6
表3（续）：甲醇离解催化剂的转化率和选择性
催化 焙烧气氛 温度 甲醇 离解f
剂 ℃ 流量sccm 转化率 选择性
8bCO2274 105 73.2 92.5
Kb真空 274 105 61.9 89.2
Le真空 274 105 58.8 86.8
9 CO2250 35 18.9 55.3
M N2/H2250 35 15.2 42.6
a.反应器含有由2.6克催化剂前体所得的焙烧、还原的催化剂，除另有注明的以外。
b.炉中装有2.0克焙烧的催化剂。
c.管中装有1.8克还原的催化剂。
d.管中装有0.9克还原的催化剂。
e.炉中装有1.8克焙烧的催化剂。
f.对那些在250℃下进行的反应，它反应压力是2个大气压;而对那些在274℃下进行的反应，其反应压力是3个大气压。
Claims (4)
1、一种含铜的甲醇离解催化剂的制备方法，通过：
(a)将含有至少一种铜盐的金属盐水溶液与任选的含硅源的碱溶液混合，以沉淀含铜催化剂前体；
(b)回收(a)沉淀的前体；
(c)在高温下焙烧(b)所回收的前体；
(d)还原(c)焙烧的前体；
其改进包括在二氧化碳气氛中进行(c)的焙烧。
2、根据权利要求1的方法，其特征在于，二氧化碳气氛是在10千巴～5000千巴的压力和150℃～600℃的温度范围。
3、根据权利要求1的方法，其特征在于，二氧化碳气氛是在100千巴～500千巴的压力和200℃～400℃的温度。
4、根据权利要求1的方法，其特征在于，二氧化碳气氛是在100千巴～500千巴的压力和300℃～350℃的温度。
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| Application Number | Priority Date | Filing Date | Title |
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| US07/164,453 US4826798A (en) | 1988-03-04 | 1988-03-04 | Carbon dioxide calcination of methanol dissociation catalysts |
| US164,453 | 1988-03-04 |
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| EP (1) | EP0331466B1 (zh) |
| JP (1) | JPH01281146A (zh) |
| KR (1) | KR890014161A (zh) |
| CN (1) | CN1019550B (zh) |
| AR (1) | AR243098A1 (zh) |
| AT (1) | ATE68995T1 (zh) |
| AU (1) | AU607054B2 (zh) |
| BR (1) | BR8900991A (zh) |
| DE (1) | DE68900369D1 (zh) |
| ES (1) | ES2027063T3 (zh) |
| GR (1) | GR3003041T3 (zh) |
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| CN110327933A (zh) * | 2019-07-25 | 2019-10-15 | 常州北化澳联环保科技有限公司 | 二氧化碳加氢制备甲醇的催化剂及其制备方法和应用 |
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| US5622907A (en) * | 1989-04-28 | 1997-04-22 | Electric Power Research Institute, Inc. | Post-reducing treatment of alcohol synthesis catalysts with carbon dioxide |
| US5106810A (en) * | 1989-06-29 | 1992-04-21 | E. I. Du Pont De Nemours And Company | Methanol dissociation catalysts |
| US20040082927A1 (en) * | 2002-10-28 | 2004-04-29 | Wade Littleton | Powder dispensing pouch for mens and boys underwear |
| US20090042723A1 (en) * | 2007-02-06 | 2009-02-12 | Kun Wang | Process for preparing mixed metal oxide catalysts |
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| CA544891A (en) * | 1957-08-13 | L. Tollefson Eric | Conditioning of silver base catalysts for the oxidation of ethylene | |
| US2794784A (en) * | 1953-01-21 | 1957-06-04 | Air Reduction | Copper-containing catalysts |
| DE2115860A1 (en) * | 1971-04-01 | 1972-10-12 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Catalysts for ammonia synthesis - contg iron oxide, aluminium (hydr)oxide and calcium or magnesium (hydr)oxide |
| GB1561635A (en) * | 1975-11-04 | 1980-02-27 | Ici Ltd | Catalyst and chemicalprocesses such as carbon monoxide shift |
| US4226839A (en) * | 1978-07-21 | 1980-10-07 | The United States Of America As Represented By The Administrator Of The U.S. Environmental Protection Agency | Activation of calcium oxide as a sorbent |
| JPS5910256B2 (ja) * | 1979-11-12 | 1984-03-07 | 三菱瓦斯化学株式会社 | メタノ−ル合成触媒の製造法 |
| EP0055311B1 (en) * | 1980-12-30 | 1986-05-07 | Exxon Research And Engineering Company | Catalysts and hydrocarbon treating processes utilizing the same |
| JPS6045939B2 (ja) * | 1981-03-04 | 1985-10-12 | 工業技術院長 | 水素及び一酸化炭素製造のためのメタノ−ル分解用触媒 |
| JPS5990633A (ja) * | 1982-11-12 | 1984-05-25 | Nitto Chem Ind Co Ltd | アンチモン含有金属酸化物触媒の製造法または活性化法 |
| NO154486C (no) * | 1984-04-12 | 1986-10-01 | Norsk Hydro As | Katalysator og dens anvendelse for spalting av metanol. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110327933A (zh) * | 2019-07-25 | 2019-10-15 | 常州北化澳联环保科技有限公司 | 二氧化碳加氢制备甲醇的催化剂及其制备方法和应用 |
| CN110327933B (zh) * | 2019-07-25 | 2022-09-20 | 甄崇礼 | 二氧化碳加氢制备甲醇的催化剂及其制备方法和应用 |
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| ES2027063T3 (es) | 1992-05-16 |
| NZ228199A (en) | 1990-04-26 |
| AR243098A1 (es) | 1993-07-30 |
| US4826798A (en) | 1989-05-02 |
| EP0331466A1 (en) | 1989-09-06 |
| KR890014161A (ko) | 1989-10-23 |
| DE68900369D1 (de) | 1991-12-05 |
| CN1019550B (zh) | 1992-12-23 |
| JPH01281146A (ja) | 1989-11-13 |
| BR8900991A (pt) | 1989-10-24 |
| ATE68995T1 (de) | 1991-11-15 |
| MY103834A (en) | 1993-09-30 |
| AU607054B2 (en) | 1991-02-21 |
| MX166325B (es) | 1992-12-29 |
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