CN114452991A - Multi-additive doped supported catalyst, preparation method and application - Google Patents
Multi-additive doped supported catalyst, preparation method and application Download PDFInfo
- Publication number
- CN114452991A CN114452991A CN202011136788.0A CN202011136788A CN114452991A CN 114452991 A CN114452991 A CN 114452991A CN 202011136788 A CN202011136788 A CN 202011136788A CN 114452991 A CN114452991 A CN 114452991A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- raney
- doped
- solution
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000654 additive Substances 0.000 title abstract description 15
- 229910052709 silver Inorganic materials 0.000 claims abstract description 67
- 239000002245 particle Substances 0.000 claims abstract description 65
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004332 silver Substances 0.000 claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 239000002861 polymer material Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229920000620 organic polymer Polymers 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 52
- 239000000843 powder Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 235000019439 ethyl acetate Nutrition 0.000 claims description 24
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 15
- 239000004033 plastic Substances 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- 229920001169 thermoplastic Polymers 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 229920002292 Nylon 6 Polymers 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- AYKOTYRPPUMHMT-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag] AYKOTYRPPUMHMT-UHFFFAOYSA-N 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 79
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 32
- 238000005303 weighing Methods 0.000 description 19
- 229910001961 silver nitrate Inorganic materials 0.000 description 16
- 238000001914 filtration Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000004416 thermosoftening plastic Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- CYBIXTWDGDWNDH-UHFFFAOYSA-N [N].[Mo].[C] Chemical compound [N].[Mo].[C] CYBIXTWDGDWNDH-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012633 leachable Substances 0.000 description 3
- 229940040102 levulinic acid Drugs 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007723 die pressing method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- UDBXMVWPBSRJIQ-UHFFFAOYSA-N [Cu]N=[Mo] Chemical compound [Cu]N=[Mo] UDBXMVWPBSRJIQ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 239000003086 colorant Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction 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
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- B01J25/00—Catalysts of the Raney type
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
- 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
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a multi-additive doped supported catalyst, a preparation method and application. The catalyst comprises: the organic polymer material carrier and nitrogen and multiple metal doped Raney alloy particles loaded on the surface of the organic polymer material carrier; the multiple metal-doped Raney alloy particles comprise Raney metal copper, aluminum, silver and auxiliary metal; the auxiliary metal is at least one of Ba, Mo, Cr, Ti, Fe, Pt, Pd, Rh, Ru, Mn and Co; preferably at least one of Mo, Fe and Co. The supported catalyst of the invention can realize higher catalytic activity at lower reaction temperature. Under the same reaction condition, the multi-additive doped composite catalyst is beneficial to improving the activity and the selectivity of the catalyst.
Description
Technical Field
The invention relates to the technical field of ethanol preparation, and further relates to a multi-additive doped supported catalyst, a preparation method and application in preparation of ethanol by acetate hydrogenation.
Background
The ethanol has wide application range, and can be widely applied to the industries of food, chemical industry, medicine, dye, fuel, national defense and the like. Ethanol is a good solvent, and is commonly used for the extraction of pigments in plants or medicinal components therein. Ethanol with 75% volume fraction is commonly used as medical disinfectant in medical treatment. As an important chemical raw material, ethanol can be used for preparing chemical raw materials such as acetaldehyde, diethyl ether, ethyl acetate, ethylamine and the like, and also can be used for preparing products such as dye, paint, detergent and the like. In addition, ethanol is an important clean energy source and has the characteristics of high oxygen content, high vaporization latent heat, good antiknock performance and the like.
The traditional ethanol production technologies mainly comprise an ethylene hydration method, a biological fermentation method and a method for preparing alcohol by hydrogenating carboxylic ester. Wherein, the ethylene hydration method is a petroleum route which adopts petroleum cracking product ethylene as raw material and obtains ethanol through hydration. The biological fermentation method is a biological fermentation method which takes various sugar-containing agricultural products, agricultural and forestry byproducts and wild plants as raw materials and converts disaccharide and polysaccharide into monosaccharide and further into ethanol through hydrolysis and fermentation. The carboxylic ester hydrogenation reaction refers to the preparation of ethanol by using acetic acid or acetic ester hydrogenation, and the prior acetic acid or acetic ester production technology is mature and low in price, so that the preparation of ethanol by acetic ester hydrogenation is a valuable industrial approach and is widely concerned.
Chinese patent CN86105765A discloses a process for the hydrogenation of carboxylic esters to alcohols by hydrogenating the carboxylic esters in the presence of a catalyst comprising copper and at least one molybdenum, lanthanide or actinide metal at elevated temperature, pressure or pressure to produce alcohols.
U.S. Pat. Nos. 5,168, 5021589A, 4892955, 4892955A and 4346240A each disclose a technique for preparing an alcohol by hydrogenating a carboxylic ester under homogeneous conditions using catalysts such as Ru and Rh.
Chinese patents CN1275689A and CN1974510A disclose methods for preparing alcohol by homogeneous hydrogenation of fatty acid and derivatives thereof on Ru-based catalyst and liquid-solid phase hydrogenation, respectively.
These techniques involve expensive metals and the reaction conditions are also harsh.
At present, copper catalysts prepared by a precipitation method or an impregnation method are oxide carrier catalysts, most of the carriers are alumina and silica carriers, more byproducts appear in the reaction due to the obvious acidity of the alumina carrier, and most of acetate hydrogenation catalysts select the silica carrier with lower acidity. Silica supports have their own advantages, but their low strength also limits the application of catalysts, and their thermal conductivity is far inferior to that of aluminum-containing supports, and copper grains are easily aggregated to cause a decrease in catalyst activity.
The raney copper alloy catalyst has been described as a novel catalyst and is industrially used mainly as a catalyst for the reaction of producing acrylamide by the hydration of acrylonitrile. Chinese patent CN102603681A describes a method for liquid-phase furfural hydrogenation reaction by using raney copper alloy catalyst powder, wherein the catalyst is raney copper alloy catalyst powder, and the conversion rate for liquid-phase furfural hydrogenation is 97%. Chinese patent CN102617519A introduces a method for preparing gamma-valerolactone by using Raney copper alloy catalyst powder for hydrogenation of levulinic acid, wherein the catalyst is the Raney copper alloy catalyst powder, the catalyst has both a hydrogenation function and a intramolecular esterification ring-closing function, and can realize the preparation of the gamma-valerolactone by hydrogenation of the levulinic acid, and the conversion rate of the levulinic acid is as high as 99.8%. Raney copper alloy powders, although having a high conversion, have major disadvantages due to the powder catalyst, such as the distribution of the catalyst in the reactor and the necessity to separate the powder during the reaction, typically by filtration, which requires elaborate and expensive processing techniques.
Chinese patent CN1272835A describes a method for preparing 1, 6-hexanediol, wherein the catalyst is a catalyst containing copper, manganese and aluminum as basic components, and as a comparative example, a raney copper flake catalyst has a catalytic activity of 97% in a reaction for preparing 1, 6-hexanediol, but the catalytic activity and selectivity are lower than those of a catalyst obtained by a coprecipitation method containing copper, manganese and aluminum as basic components. The problem that powder alloy catalyst is retrieved in the reaction can effectively be solved to block raney copper catalyst, but most alloy all is wrapped up inside the alloy and can't really play catalytic action, leads to the low-usage of copper, has caused economic loss. Particularly, the bulk raney copper catalyst is irregular in shape, and cavities and bridges may occur during filling to cause bias flow and channeling, so that adverse conditions such as unstable bed pressure easily occur.
In conclusion, the selection of a catalyst which has both high conversion rate of acetic ester and high selectivity of ethanol is a problem which needs to be solved urgently in the preparation of ethanol by hydrogenation of acetic ester at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a multi-additive doped supported catalyst, a preparation method and application in preparation of ethanol by hydrogenation of acetic ester. Solves the problems of low acetic ester hydrogenation conversion rate and selectivity and the like in the prior art.
One of the objects of the present invention is to provide a supported catalyst doped with multiple promoters.
The catalyst comprises: the organic polymer material carrier and nitrogen and various metal-doped Raney alloy particles loaded on the surface of the organic polymer material carrier;
the multiple metal-doped Raney alloy particles comprise Raney metal copper, aluminum, silver and auxiliary metal;
the auxiliary metal is at least one of Ba, Mo, Cr, Ti, Fe, Pt, Pd, Rh, Ru, Mn and Co; preferably at least one of Mo, Fe and Co; more preferably Mo.
In a preferred embodiment of the present invention,
based on the total weight of the catalyst 100%,
in a further preferred embodiment of the present invention,
based on the total weight of the catalyst 100%,
the invention also aims to provide a preparation method of the supported catalyst doped with multiple auxiliary agents.
The method comprises the following steps:
(a) mixing copper powder, aluminum powder, auxiliary metal powder and N-containing precursor powder, and calcining under the protection of inert atmosphere to obtain auxiliary metal doped Raney alloy particles;
(b) preparing a supported Raney copper catalyst from an organic high polymer material carrier and Raney alloy particles;
(c) activating the supported Raney copper catalyst by using an alkali solution;
(d) preparing soluble organic amine, silver salt and water into silver source solution;
(e) adding the supported Raney copper catalyst into deionized water to form a suspension solution, dropwise adding a silver source solution into the suspension solution of the supported Raney copper catalyst, and reacting and washing to obtain the multi-assistant doped supported catalyst.
In a preferred embodiment of the present invention,
a step (a) of, after the step (a),
the weight ratio of the copper powder to the aluminum powder is 1: 99-10: 1, preferably 1: 10-4: 1;
the dosage of the auxiliary metal powder is 0.01-10 wt% of the total weight of the metal powder;
the dosage of the nitrogen-containing precursor powder is 0.1 to 20 weight percent of the total weight of the metal powder.
In a preferred embodiment of the present invention,
the nitrogen-containing precursor is a nitrogen-containing organic matter; preferably at least one of urea, cyanamide, dicyandiamide, melamine, pyrrole, pyridine and melamine formaldehyde resin; and/or the presence of a gas in the gas,
the calcination temperature is 400-1200 ℃, preferably 600-950 ℃.
In a preferred embodiment of the present invention,
a step (b) of, after the step (c),
the organic polymer material is plastic or a modified product thereof, and the plastic comprises thermosetting plastic and thermoplastic plastic; preferably, the plastic is selected from at least one of polyolefin resin, polyamide resin, polystyrene, epoxy resin and phenolic resin, more preferably at least one of polypropylene, nylon-6, nylon-66, polystyrene, phenolic resin and epoxy resin;
the auxiliary metal-doped Raney alloy particles are loaded on the surface of the carrier in a form of being partially embedded into the organic high polymer material carrier;
the preparation is that the organic polymer material coated by the Raney alloy particles is molded under the condition of the forming and processing temperature of the organic polymer material or the uncured and shaped condition.
In a preferred embodiment of the present invention,
step (c), the alkali solution is sodium hydroxide solution or potassium hydroxide solution;
the concentration of the alkali solution is 0.5-30 wt%; and/or the presence of a gas in the gas,
the activation temperature is 25-95 ℃; the activation time is 5 min-72 h.
In a preferred embodiment of the present invention,
in the step (d), the molar ratio of the organic amine to the silver is 2-10: 1;
the soluble organic amine is one or a combination of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, diethylamine, isopropylamine, aniline, N-dimethylaniline, dodecylamine, triethylenediamine, cyclohexylamine and hexamethylenetetramine;
in a preferred embodiment of the present invention,
step (e), the mass of the silver in the silver source solution is 0.2-1 wt% of that of the supported Raney copper catalyst; and/or the presence of a gas in the gas,
the reaction time is 0.5-3 h.
The invention also aims to provide the application of the multi-additive doped supported catalyst in the preparation of ethanol by acetate hydrogenation.
In the presence of hydrogen, the reaction temperature is 100-200 ℃, the reaction pressure is 1.0-5.0 MPa, and the liquid space velocity of acetic ester is 0.1-2 h-1Under the condition that the molar ratio of hydrogen to acetic ester is 15-50, enabling acetic ester to contact a supported catalyst doped with multiple auxiliaries in a fixed bed reactor to prepare ethanol; the preferable reaction temperature is 150-200 ℃, and the reaction pressure is 2.0-4.0 MPa.
Wherein the supported catalyst doped with multiple auxiliary agents is the catalyst of one object of the invention or the catalyst obtained by the method of the two objects of the invention.
The invention can adopt the following technical scheme:
the method for preparing the ethanol by hydrogenating the acetic ester is characterized in that in the presence of hydrogen, the reaction temperature is 100-200 ℃, the reaction pressure is 1.0-5.0 MPa, and the liquid airspeed of the acetic ester is 0.1-2 h-1Under the condition that the molar ratio of hydrogen to acetic ester is 15-50, enabling the acetic ester to contact a multi-additive doped supported catalyst in a fixed bed reactor to prepare ethanol; the preferable reaction temperature is 150-200 ℃, and the reaction pressure is 2.0-4.0 MPa.
The multi-additive doped supported catalyst comprises an organic polymer material carrier and nitrogen and a plurality of metal doped Raney alloy particles loaded on the surface of the organic polymer material carrier, wherein the Raney alloy comprises Raney metal copper, aluminum, silver and additive metal.
The Raney alloy particles are loaded on the surface of a carrier in a form of being partially embedded into an organic high polymer material carrier. The phrase "the particles of the raney alloy are partially embedded in the support of the organic polymer material" means that each particle of the raney alloy has a portion embedded in the support.
The part of the Raney alloy particles is embedded into the organic polymer material carrier by molding the carrier coated by the Raney alloy particles at the carrier molding processing temperature or under the uncured shaping condition. Under the double action of heat and pressure, the carrier of organic polymer material is softened and deformed, the Raney alloy particles are partially pressed into the softened carrier, the softened carrier overflows around the particles while the particles are partially pressed, the overflowing carrier not only plays a role of firmly fixing the particles, but also presses other particles into the surface of the overflowing carrier, and the steps are repeated, so that the Raney alloy particles are partially pressed into all the surfaces of the carrier which can be pressed. As described above, the present invention effectively utilizes the surface area of the carrier, so that the active metal content supported by the catalyst is high. In addition, because the particles of the Raney alloy are partially embedded in the carrier, the carrier around the particles serves as a firm fixture, so that the catalyst has good stability.
The raney alloy includes raney metal, a promoter metal and a leachable element. "Raney metal" means a metal that is insoluble when activated by Raney process, and most typically the Raney metal is at least one of nickel, cobalt, copper and iron. "leachable element" refers to an element that dissolves when activated by the raney process, and typically is aluminum. The raney alloy is preferably a copper aluminum alloy.
The nitrogen-containing Raney alloy is prepared by a carbonization method, and is specifically prepared by mixing an active metal and a precursor containing the active metal and then carbonizing the mixture in an inert atmosphere. Wherein the weight ratio of raney metal to leachable elements is 1: 99-10: 1, preferably in a weight ratio of 1: 10-4: 1. the nitrogen-containing precursor comprises urea, cyanamide, dicyandiamide, melamine, pyrrole, pyridine, melamine formaldehyde resin and other nitrogen-containing organic matters, and the usage amount of the nitrogen-containing precursor is 0.1-20% of the total weight of the metal powder. In order to improve the activity or selectivity of the catalyst, the Raney alloy can also be introduced with an auxiliary metal, wherein the auxiliary metal is at least one of Ba, Mo, Cr, Ti, Fe, Pt, Pd, Rh, Ru, Mn and Co; forming the multi-component Raney alloy.
The organic polymer material is preferably plastic or a modified product thereof, and the plastic comprises thermosetting plastic and thermoplastic plastic. The specific plastic comprises: polyolefin, poly-4-methyl-1-pentene, polyamide resin (e.g., nylon-5, nylon-12, nylon-6/6, nylon-6/10, nylon-11), polycarbonate resin, linear polyester obtained by polycondensation of homo-and/or co-polyoxymethylene, saturated dibasic acid and dihydric alcohol, aromatic ring polymer (polymer whose molecule consists only of aromatic rings and linking groups, such as polyphenyl, polyphenylene ether, polyphenylene sulfide, polyarylsulfone, polyaryl ketone, polyaryl ester, aromatic polyamide), heterocyclic polymer (polymer material whose molecular main chain has heterocyclic rings in addition to aromatic rings, such as polybenzimidazole), fluorine-containing polymers, acrylic resins, urethanes, epoxy resins, phenol resins, urea resins, melamine resins, and the like. At least one of polyolefin resin, polyamide resin, polystyrene, epoxy resin and phenol resin is preferable, and at least one of polypropylene, nylon-6, nylon-66, polystyrene, phenol resin and epoxy resin is more preferable.
The plastic modified product refers to a modified product obtained by using an existing plastic modification method. Plastic modification methods include, but are not limited to, the following: graft modification of polar or non-polar monomers or polymers thereof; the material is modified by melt blending with inorganic or organic reinforcing materials, toughening materials, stiffening materials, heat resistance increasing materials and the like.
The preparation method of the supported catalyst comprises the following steps: and under the condition of the forming processing temperature of the organic polymer material or the uncured shaping condition, the organic polymer material coated by the Raney alloy particles is molded.
The specific preparation method is slightly different for different organic polymer material carriers.
When the carrier is a thermoplastic organic polymer material, the following method (i) or (ii) can be specifically selected:
method (i):
(1) processing the thermoplastic carrier into particles of any shape according to the size required by the fixed bed catalyst or the fluidized bed catalyst;
(2) placing the carrier particles in the Raney alloy particles, namely, the carrier is completely coated by the Raney alloy particles;
(3) and under the condition of corresponding thermoplastic carrier forming processing temperature, placing the thermoplastic carrier in the Raney alloy particles by die pressing, partially pressing the Raney alloy particles into the thermoplastic carrier particles to load the Raney alloy particles on the surfaces of the thermoplastic carrier particles and partially embed the Raney alloy particles into the carrier, cooling and sieving to obtain the granular supported catalyst.
The particle size of the particulate supported catalyst is based on the particle size that can meet the requirements of a fixed bed catalyst or a fluidized bed catalyst. The shape of the particles may be any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder, tooth shape or a combination of the above shapes, etc., preferably spherical, ring, tooth shape, cylindrical or a combination of the above shapes. The thermoplastic carrier particles can be shaped from powder or can be used directly as commercially available shaped thermoplastic carrier particles.
Or method (ii):
(1) processing the thermoplastic carrier into a sheet with the thickness required by the fixed bed catalyst or the fluidized bed catalyst;
(2) uniformly coating the surface of the obtained carrier sheet with the Raney alloy particles;
(3) the method comprises the steps of carrying out die pressing on a sheet material coated by the Raney alloy particles under the common molding processing temperature condition of a corresponding thermoplastic carrier, pressing part of the Raney alloy particles into the carrier sheet material, cooling, processing the carrier sheet material with the Raney alloy particles loaded on the surface into particles with required shape and size by cutting, stamping or crushing and other methods by adopting any available processing equipment, and finally obtaining the granular supported catalyst.
The thermoplastic carrier described in method (i) or method (ii) may incorporate additives commonly used in plastics processing such as antioxidants, secondary antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, softeners, antiblocking agents, blowing agents, dyes, pigments, waxes, extenders, organic acids, flame retardants, and coupling agents. The dosage of the used auxiliary agent is conventional dosage or is adjusted according to the requirements of actual conditions.
When the support is a thermosetting organic polymer material support, the following method (iii) or (iv) can be specifically selected for preparation:
method (iii):
(1) preparing a proper curing system according to a common curing formula of a thermosetting carrier, wherein a liquid system can be directly and uniformly stirred; the powdery solid system can be directly and uniformly blended; the granular solid system can be pulverized by any pulverizing equipment commonly used in industry and then uniformly blended.
(2) Adding Raney alloy powder into a die with any cavity shape which can meet the particle size required by a fixed bed catalyst or a fluidized bed catalyst, then adding the prepared uncured thermosetting organic high polymer material, then adding the Raney alloy powder, carrying out partial curing and shaping under the common curing condition, then carrying out mould pressing and curing on the partially cured and shaped granular carrier coated with the Raney alloy powder by any available organic high polymer material processing equipment, and sieving after complete curing to obtain the granular supported catalyst;
or method (iv):
(1) preparing a proper curing system according to a common curing formula of the thermosetting organic high polymer material, wherein a liquid system can be directly and uniformly stirred; the powdery solid system can be directly and uniformly blended; the granular solid system can be pulverized by any pulverizing equipment commonly used in industry and then uniformly blended.
(2) Under the common curing condition, the prepared thermosetting organic polymer material system is molded into a sheet by any available equipment, the sheet is not cured completely, the thickness is determined by the size of a fixed bed catalyst or a fluidized bed catalyst, the upper surface and the lower surface of the sheet are uniformly coated with Raney alloy powder, the sheet is molded continuously until the sheet is cured completely, the Raney alloy powder is partially pressed into a thermosetting carrier, and the surface of the thermosetting carrier sheet is loaded by the Raney alloy powder, so that the loaded catalyst is obtained.
(3) The obtained supported catalyst is processed into particles which can be used in a fixed bed or a fluidized bed reaction by cutting, stamping or crushing and the like by any available organic polymer material processing equipment, the particle size of the particles is based on the particle size which can meet the requirement of the fixed bed catalyst or the fluidized bed catalyst, the shape of the particles can be any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder, tooth shape or the combination of the shapes, and the like, and the preferred shape is spherical, annular, tooth shape, cylindrical or the combination of the shapes.
In the preparation of the thermosetting organic polymer material curing system according to the method (iii) or the method (iv), optionally, one or more additives selected from the group consisting of: cure accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, drip retardants, antiblock agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release aids, nucleating agents, and the like. The dosage of the used additives is conventional dosage or is adjusted according to the requirements of actual conditions.
The catalyst obtained according to the above process can be easily activated, the activation conditions being generally: dissolving out aluminum by using 0.5-30 wt% of alkali solution at 25-95 ℃, wherein the alkali solution is preferably NaOH or KOH, and the treatment time of the alkali solution is about 5 min-72 h.
The loading amount of the Raney metal copper in the activated catalyst can be easily controlled by controlling the adding amount of the Raney alloy in the preparation process of the catalyst and/or controlling the activation degree of the catalyst. For example, an activated supported catalyst having a copper loading of 60 to 80 wt% can be obtained, and a Raney metal loading of 60 to 70 wt% is more preferable.
The acetate is selected from methyl acetate or ethyl acetate, the source of the acetate is a condensed liquid phase after acetic acid is directly hydrogenated in a reactor, and the main body of the acetate is ethanol and water and contains trace ethyl acetate.
The invention has the beneficial effects that:
(1) the supported catalyst carrier is plastic, the content of acidic oxides in the catalyst is obviously reduced compared with the traditional oxide carrier, and the generation of byproducts is effectively reduced.
(2) The catalyst has a regular shape, so that adverse conditions that the block alloy catalyst is likely to have cavities and bridges in filling due to irregular shape, bias flow and channeling are caused, and the pressure of a bed layer is unstable are avoided effectively. And the catalyst does not have a high-temperature treatment process in the preparation process, so that the service life of the catalyst and the service life of a reaction device are effectively prolonged.
(3) The preparation method of the N-containing Raney alloy is to mix active metal and nitrogen-containing precursor and then prepare the N-containing Raney alloy by a carbonization method, and the Raney copper catalyst doped with multiple additives can be realized by the method. Furthermore, the inventors have found that the interaction of the promoter metal and Ag makes the copper crystallites in the catalyst more dispersed, and thus the activity and selectivity are significantly improved.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
(1) Carbonizing 20g of melamine, 545g of copper powder, 468g of aluminum powder and 50g of molybdenum powder in a tubular high-temperature electric furnace at the temperature rise rate of 10 ℃/min and the furnace temperature of 650 ℃, keeping for 3h, and under the protection of nitrogen, wherein the flow rate is 200 mL/min;
(2) weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in the alloy powder in the step (1), molding for 10min at 220 ℃ and 7MPa by using a flat-plate vulcanizer, taking out, cooling, sieving, screening out spherical particles, completely covering the surfaces of the particles with copper-aluminum alloy powder, thus obtaining a supported catalyst, and weighing 210 g;
(3) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain the molybdenum-nitrogen carbon raney copper catalyst, adding water to prepare a catalyst suspension, and storing for later use.
(4) Preparing a silver source solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(5) Weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL (the content of silver is 15mg, and the weight accounts for 0.10 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver, molybdenum and nitrogen doped supported Raney's copper catalyst (Cu65.2 wt%, Mo 6.0%, Al 20.3 wt%, Ag 0.1 wt%, and N0.7 wt%).
Example 2
(1) Fully mixing 40g of melamine formaldehyde resin, 545g of copper powder, 468g of aluminum powder and 100g of molybdenum powder by using a high-speed stirrer, carbonizing in a tubular high-temperature electric furnace at the heating rate of 10 ℃/min and the furnace temperature of 650 ℃, keeping for 3h, and protecting with nitrogen at the flow rate of 200 mL/min;
(2) weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in the alloy powder in the step (1), molding for 10min at 220 ℃ and 7MPa by using a flat-plate vulcanizer, taking out, cooling, sieving, screening out spherical particles, completely covering the surfaces of the particles with copper-aluminum alloy powder, thus obtaining a supported catalyst, and weighing 210 g;
(3) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), filtering the solution after the activation temperature is 80 ℃ and 3.5 hours, washing the solution to be nearly neutral to obtain a Raney's copper molybdenum nitrogen carbide catalyst, adding water to prepare a catalyst suspension, and storing the suspension for later use;
(4) preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, and dropwise adding 1.9mL of triethanolamine solution (density: 1.1g/mL of triethanolamine) into 10mL of deionized water to prepare a uniform solution. The molar ratio of triethanolamine to silver was 4: 1, dropwise adding a solution of triethanolamine into a silver nitrate solution to form a transparent and uniform solution, and quantitatively accommodating the solution in a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(5) Weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL (the content of silver is 15mg, and the weight accounts for 0.10 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 3h, filtering, and washing to obtain the silver, molybdenum and nitrogen doped supported Raney's copper catalyst (Cu 63.1 wt%, Mo 10.6%, Al 20.0 wt%, Ag 0.1 wt%, and N1.4 wt%).
Example 3
(1) Fully mixing 10g of melamine formaldehyde resin, 545g of copper powder, 468g of aluminum powder and 75g of molybdenum powder by using a high-speed stirrer, carbonizing in a tubular high-temperature electric furnace at the heating rate of 10 ℃/min and the furnace temperature of 900 ℃, keeping for 2h, and protecting with nitrogen at the flow rate of 200 mL/min;
(2) weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in the alloy powder in the step (1), molding for 10min at 220 ℃ and 7MPa by using a flat-plate vulcanizer, taking out, cooling, sieving, screening out spherical particles, completely covering the surfaces of the particles with copper-aluminum alloy powder, thus obtaining a supported catalyst, and weighing 210 g;
(3) preparing 500mL of 10 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 65 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain a molybdenum-nitrogen carbon raney copper catalyst, adding water to prepare a catalyst suspension, and storing for later use;
(4) preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(5) Weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL (the content of silver is 15mg, and the weight accounts for 0.10 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver, molybdenum and nitrogen doped Raney nickel carbide catalyst (Cu 64.2 wt%, Mo 8.0%, Al 20 wt%, Ag 0.1 wt%, and N0.3 wt%).
Example 4
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 20mL (the content of silver is 60mg, and the weight accounts for 0.4 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver, molybdenum and nitrogen doped Raney nickel carbide catalyst (Cu65.2wt%, Mo 6.0%, Al 20.3 wt%, Ag 0.4 wt%, and N0.7 wt%).
Example 5
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 30mL (the content of silver is 90mg, and the silver accounts for 0.6 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver, molybdenum and nitrogen doped Raney's copper carbide catalyst (Cu65.2 wt%, Mo6.0%, Al 20.3 wt%, Ag 0.6 wt%, and N0.7 wt%).
Example 6
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 0.5mL (the content of silver is 1.5mg, and accounts for 0.01 wt% of the mass of the added catalyst) of the silver source solution obtained in the step (5), reacting for 2 hours, and filtering and washing to obtain the silver, molybdenum and nitrogen doped Raney's copper carbide catalyst (Cu65.2wt%, Mo 6.0%, Al 20.3 wt%, Ag 0.01 wt%, and N0.7 wt%).
Example 7
The process of preparation example 1 was followed, except that step (6) was carried out as follows:
weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 50mL of silver source solution (the content of silver is 150mg, and accounts for 1 wt% of the mass of the added catalyst) obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver, molybdenum and nitrogen doped Raney's copper carbide catalyst (Cu65.2 wt%, Mo 6.0%, Al 20.3 wt%, Ag 1.0 wt%, and N0.7 wt%).
Example 8
The process of example 1 is followed except that step (5) is carried out as follows:
preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until being dissolved, 1.2mL of isopropylamine solution (density: 0.7g/mL of isopropylamine) is dripped into 10mL of deionized water to prepare uniform solution. The molar ratio of isopropylamine to silver is 2: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and setting the solution in a 200mL volumetric flask to form a silver source solution of 3.0mgAg/mL (the catalyst content is Cu65.2 wt%, Mo 6.0%, Al 20.3 wt%, Ag 0.1 wt%, N0.7 wt%).
Example 9
The process of preparation example 1 was followed except that step (5) was carried out as follows:
preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until being dissolved, 1.2mL of isopropylamine solution (density: 0.7g/mL of isopropylamine) is dripped into 10mL of deionized water to prepare uniform solution. The molar ratio of isopropylamine to silver was 10: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution. The catalyst comprises 65.2 wt% of Cu, 6.0 wt% of Mo, 20.3 wt% of Al, 0.1 wt% of Ag and 0.7 wt% of N.
Comparative example 1
(1) Carbonizing 20g of melamine, 545g of copper powder, 468g of aluminum powder and 50g of molybdenum powder in a tubular high-temperature electric furnace at the temperature rise rate of 10 ℃/min and the furnace temperature of 650 ℃, keeping for 3h, and under the protection of nitrogen, wherein the flow rate is 200 mL/min;
(2) weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in the alloy powder in the step (1), molding for 10min at 220 ℃ and 7MPa by using a flat-plate vulcanizer, taking out, cooling, sieving, screening out spherical particles, completely covering the surfaces of the particles with copper-aluminum alloy powder, thus obtaining a supported catalyst, and weighing 210 g;
(3) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain the molybdenum-nitrogen carbon raney copper catalyst, adding water to prepare a catalyst suspension, and storing for later use. (Cu65.2 wt%, Mo 6.0%, Al 20.3 wt%, N0.7 wt%).
Comparative example 2
(1) Carbonizing 20g of melamine, 500g of copper powder and 398g of aluminum powder in a tubular high-temperature electric furnace at the temperature rising rate of 10 ℃/min and the furnace temperature of 650 ℃ for 3h under the protection of nitrogen and at the flow rate of 200 mL/min;
(2) weighing 50g of nylon-6 particles (ba ling petrochemical, BL2340-H) in the alloy powder in the step (1), molding for 10min at 220 ℃ and 7MPa by using a flat-plate vulcanizer, taking out, cooling, sieving, screening out spherical particles, completely covering the surfaces of the particles with copper-aluminum alloy powder, thus obtaining a supported catalyst, and weighing 210 g;
(3) preparing 500mL of 20 weight percent NaOH aqueous solution by using deionized water, adding 100mL of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4h, washing to be nearly neutral to obtain the molybdenum-nitrogen carbon raney copper catalyst, adding water to prepare a catalyst suspension, and storing for later use.
(4) Preparing a silver source solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(5) And (3) weighing 30mL (about 15g) of the sample obtained in the step (4), adding the sample into 50mL of aqueous solution, dropwise adding 5mL of silver source solution (the silver content is 15mg, and the silver content accounts for 0.10 wt% of the mass of the added catalyst) obtained in the step (5), reacting for 2h, filtering, and washing to obtain the silver and nitrogen doped supported Raney copper catalyst.
(Cu 65.2wt％,Al 20.3wt％,Ag 0.1wt％N 0.9wt％)。
Acetate hydrogenation reaction performance test
The catalyst reaction performance is evaluated by using fixed bed acetic ester gas phase hydrogenation, 40ml of catalyst is loaded into a fixed bed reactor, the reaction temperature is 180 ℃, the pressure is 3.0Mpa, the molar ratio of hydrogen to acetic ester is 37, and the liquid airspeed of ethyl acetate is 0.25h-1The reaction product was quantified using gas chromatography with FID as the chromatographic detector. Table 1 shows the results of the analysis of samples taken at a reaction time of 80 hours.
Table 1 acetic ester hydrogenation test results
As can be seen from the evaluation results, the supported catalyst of the invention can realize higher catalytic activity at lower reaction temperature. Under the same reaction condition, the multi-additive doped composite catalyst is beneficial to improving the activity and the selectivity of the catalyst.
Claims (11)
1. A supported, multi-promoter doped catalyst characterized by:
the catalyst comprises: the organic polymer material carrier and nitrogen and various metal-doped Raney alloy particles loaded on the surface of the organic polymer material carrier;
the multiple metal-doped Raney alloy particles comprise Raney metal copper, aluminum, silver and auxiliary metal;
the auxiliary metal is at least one of Ba, Mo, Cr, Ti, Fe, Pt, Pd, Rh, Ru, Mn and Co; preferably at least one of Mo, Fe and Co.
2. The multi-promoter doped supported catalyst of claim 1, wherein:
based on the total weight of the catalyst 100%,
3. the supported, multi-promoter doped catalyst of claim 2, wherein:
based on the total weight of the catalyst of 100 percent,
4. a process for preparing a catalyst as claimed in any one of claims 1 to 3, characterized in that it comprises:
(a) mixing copper powder, aluminum powder, auxiliary metal powder and N-containing precursor powder, and calcining under the protection of inert atmosphere to obtain auxiliary metal doped Raney alloy particles;
(b) preparing a supported Raney copper catalyst from an organic high polymer material carrier and Raney alloy particles;
(c) activating the supported Raney copper catalyst by using an alkali solution;
(d) preparing soluble organic amine, silver salt and water into silver source solution;
(e) adding the supported Raney copper catalyst into deionized water to form a suspension solution, dropwise adding a silver source solution into the suspension solution of the supported Raney copper catalyst, and reacting and washing to obtain the multi-assistant doped supported catalyst.
5. The method of claim 4, wherein:
a step (a) of, after the step (a),
the weight ratio of the copper powder to the aluminum powder is 1: 99-10: 1, preferably 1: 10-4: 1;
the dosage of the auxiliary metal powder is 0.01-10 wt% of the total weight of the metal powder; preferably 5 to 10 wt%;
the dosage of the nitrogen-containing precursor powder is 0.1 to 20 weight percent of the total weight of the metal powder; preferably 0.3 to 5 wt%.
6. The method of claim 4, wherein:
the nitrogen-containing precursor is a nitrogen-containing organic matter; preferably at least one of urea, cyanamide, dicyandiamide, melamine, pyrrole, pyridine and melamine formaldehyde resin; and/or the presence of a gas in the gas,
the calcination temperature is 400-1200 ℃, preferably 600-950 ℃.
7. The method of claim 4, wherein:
a step (b) of, after the step (c),
the organic polymer material is plastic or a modified product thereof, and the plastic comprises thermosetting plastic and thermoplastic plastic; preferably, the plastic is selected from at least one of polyolefin resin, polyamide resin, polystyrene, epoxy resin and phenolic resin, more preferably at least one of polypropylene, nylon-6, nylon-66, polystyrene, phenolic resin and epoxy resin;
the auxiliary metal-doped Raney alloy particles are loaded on the surface of the carrier in a form of being partially embedded into the organic high polymer material carrier;
the preparation is that the organic polymer material coated by the Raney alloy particles is molded under the condition of the forming and processing temperature of the organic polymer material or the uncured and shaped condition.
8. The method of claim 4, wherein:
step (c), the alkali solution is sodium hydroxide solution or potassium hydroxide solution;
the concentration of the alkali solution is 0.5-30 wt%; and/or the presence of a gas in the gas,
the activation temperature is 25-95 ℃; the activation time is 5 min-72 h.
9. The method of claim 4, wherein:
in the step (d), the molar ratio of the organic amine to the silver is 2-10: 1;
the soluble organic amine is one or a combination of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, ethylenediamine, butylamine, diethylamine, isopropylamine, aniline, N-dimethylaniline, dodecylamine, triethylenediamine, cyclohexylamine and hexamethylenetetramine.
10. The method of claim 4, wherein:
step (e), the mass of the silver in the silver source solution is 0.2-1 wt% of that of the supported Raney copper catalyst; and/or the presence of a gas in the gas,
the reaction time is 0.5-3 h.
11. Use of a catalyst according to any one of claims 1 to 3 or a catalyst obtained by a method according to any one of claims 4 to 10 in the preparation of ethanol by hydrogenation of acetate, wherein:
in the presence of hydrogen, the reaction temperature is 100-200 ℃, the reaction pressure is 1.0-5.0 MPa, and the liquid space velocity of acetic ester is 0.1-2 h-1Under the condition that the molar ratio of hydrogen to acetic ester is 15-50, enabling acetic ester to contact a supported catalyst doped with multiple auxiliaries in a fixed bed reactor to prepare ethanol; the preferable reaction temperature is 150-200 ℃, and the reaction pressure is 2.0-4.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011136788.0A CN114452991A (en) | 2020-10-22 | 2020-10-22 | Multi-additive doped supported catalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011136788.0A CN114452991A (en) | 2020-10-22 | 2020-10-22 | Multi-additive doped supported catalyst, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114452991A true CN114452991A (en) | 2022-05-10 |
Family
ID=81404121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011136788.0A Pending CN114452991A (en) | 2020-10-22 | 2020-10-22 | Multi-additive doped supported catalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114452991A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399605A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Method for preparing ethanol through acetate hydrogenation |
| CN105481648A (en) * | 2014-09-16 | 2016-04-13 | 中国石油化工股份有限公司 | Method for preparing ethanol through hydrogenation of acetate |
| CN106475115A (en) * | 2015-08-27 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of raney copper catalyst and its preparation method and application |
| CN109694303A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A method of four raffinate selective hydrogenation 1- butylene of carbon is carried out using silver carbonization raney copper catalyst |
| CN111085222A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-zinc carbon raney copper catalyst and preparation method and application thereof |
-
2020
- 2020-10-22 CN CN202011136788.0A patent/CN114452991A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399605A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Method for preparing ethanol through acetate hydrogenation |
| CN105481648A (en) * | 2014-09-16 | 2016-04-13 | 中国石油化工股份有限公司 | Method for preparing ethanol through hydrogenation of acetate |
| CN106475115A (en) * | 2015-08-27 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of raney copper catalyst and its preparation method and application |
| CN109694303A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A method of four raffinate selective hydrogenation 1- butylene of carbon is carried out using silver carbonization raney copper catalyst |
| CN111085222A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-zinc carbon raney copper catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11541376B2 (en) | Supported catalyst, its activated form, and their preparation and use | |
| CN105399605B (en) | A kind of method of acetate preparation of ethanol by hydrogenating | |
| CN105481630A (en) | Method for preparing 1-butene through selective hydrogenation of C4 distillate | |
| CN114436852B (en) | Method for preparing hexamethylenediamine by hydrogenation of adiponitrile | |
| CN101491762B (en) | Load hydrogenation catalyst for trickle bed and preparation method thereof | |
| CN104513121B (en) | A kind of method of preparing cyclohexane by hydrogenating benzene | |
| CN104945225B (en) | Method for preparing alcohol by decylenaldehyde hydrogenation | |
| CN105481648B (en) | A kind of method of acetate preparation of ethanol through hydrogenation | |
| CN107973681B (en) | Method for preparing cyclohexane by benzene hydrogenation | |
| CN111097446A (en) | Catalyst for preparing furfuryl alcohol by furfural liquid phase hydrogenation, preparation method and application thereof, and method for preparing furfuryl alcohol by furfural liquid phase hydrogenation | |
| CN114452991A (en) | Multi-additive doped supported catalyst, preparation method and application | |
| CN109694302B (en) | Method for preparing butylene by selective hydrogenation of carbon four raffinate with silver-doped supported Raney copper catalyst | |
| CN104418704A (en) | Method for refining glycol | |
| CN112745193B (en) | Method for preparing decanol by liquid-phase hydrogenation of decenal | |
| CN104513131B (en) | The method that decenal liquid-phase hydrogenatin prepares decyl alcohol | |
| CN104513135B (en) | A kind of method that decenal liquid-phase hydrogenatin prepares decyl alcohol | |
| CN112871171B (en) | Preparation method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate | |
| CN104513132B (en) | A kind of method of alcohol hydrogenation and removing trace aldehyde | |
| CN114452993A (en) | Preparation method of Raney copper carbide catalyst, catalyst and method for preparing ethanol by acetate hydrogenation | |
| CN112745187B (en) | Method for preparing cyclohexane by benzene hydrogenation | |
| CN104513134B (en) | N-butyl alcohol composition obtained through hydrogenation reaction of n-butyraldehyde | |
| CN112705219A (en) | Multi-additive doped Raney copper catalyst, preparation method and application | |
| CN111085223A (en) | Silver-loaded-zinc-doped Raney copper catalyst and preparation method and application thereof | |
| CN112707781A (en) | Method for preparing butylene by selective hydrogenation of C4 raffinate | |
| CN104557494A (en) | Method for synthesizing 3,5-heptadione and method for synthesizing 3,5-heptandiol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |