CN109107583A - 一种丁炔二醇半加氢双金属催化剂及其制备方法与应用 - Google Patents
一种丁炔二醇半加氢双金属催化剂及其制备方法与应用 Download PDFInfo
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- CN109107583A CN109107583A CN201810604825.2A CN201810604825A CN109107583A CN 109107583 A CN109107583 A CN 109107583A CN 201810604825 A CN201810604825 A CN 201810604825A CN 109107583 A CN109107583 A CN 109107583A
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- butynediols
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000010953 base metal Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 abstract description 15
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052594 sapphire Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JNODDICFTDYODH-UHFFFAOYSA-N 2-hydroxytetrahydrofuran Chemical compound OC1CCCO1 JNODDICFTDYODH-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000005574 cross-species transmission Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000011726 vitamin B6 Substances 0.000 description 1
- 235000019158 vitamin B6 Nutrition 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or 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
- 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
- B01J37/16—Reducing
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种丁炔二醇半加氢双金属催化剂及其制备方法与应用,所述催化剂以贵金属‑非贵金属为活性组分,其通式可表达为M1‑M2‑M2O/S,式中M1代表Pd、Ru、Pt或Au中的一种,M2代表Ni、Cu、Fe或Co中的一种,S代表惰性载体;所述催化剂组成中M1的重量比为0.1%~1%,M2的总重量比为0.5%~10%,余量为载体。所述催化剂应用于1,4‑丁炔二醇选择性半加氢的反应中,反应转化率高达100%,产物丁烯二醇的选择性也高达100%,这在很大程度上减少了后续产品分离中的许多阻碍;并且反应在常温常压下进行即可,条件温和,与以往的高温高压反应条件相比,大大降低了对反应设备的要求及危险性,从而大大降低了设备费用和生产成本。
Description
技术领域
本发明属于催化技术领域,具体涉及一种丁炔二醇半加氢双金属催化剂及其制备方法与应用。
背景技术
1,4-丁烯二醇(B2D)可广泛用于医药产品维生素B6和农药硫丹等的生产,少量用作聚合物生产,因此极具商业应用价值。目前工业上合成1,4-丁烯二醇的方式主要是通过对1,4-丁炔二醇的选择性半加氢制备的。
1,4-丁炔二醇是基于煤化工和甲醇工艺而生产的一种上游产品,具有较高的附加值,其加氢过程主要分为两类反应:半加氢反应和完全加氢反应,在加氢过程中还会发生一些副反应,例如:氢解反应和异构化反应等。
通常1,4-丁炔二醇加氢过程使用的催化剂分为非金属催化剂如Cu、Ni、Fe、Co和贵金属催化剂如Pd、Pt、Ag、Rh、Au。非金属催化剂价格便宜易得,但反应条件较苛刻,温度,氢气压力要求较高,如工业生产中温度一般在150℃以上,并且副产物绿油等较多,导致催化剂稳定性较差,进一步加剧了生产成本。而贵金属催化剂价格较昂贵,但反应条件比较温和,反应温度压力也不高,常见反应温度在60—100℃,压力在1.5bar左右,其催化选择性好,不会造成后续分离困难和原子经济性差的问题。公开号为106040246A的中国专利公开了一种用于1,4-丁炔二醇半加氢的镍基催化剂及其制备方法,其活性组分为金属镍、金属铜和金属锌,载体为二氧化硅。其催化剂反应温度达150℃,反应压力达2.5Mpa,选择性与转化率均对后续分离造成困难且对反应设备要求较高。
因此,设计一种贵金属用量低且能在较低温度和压力下高效催化1,4-丁炔二醇半加氢的催化剂是非常有必要的。
发明内容
本发明的目的在于提供一种丁炔二醇半加氢双金属催化剂及其制备方法与应用,本发明的解决方案是:
一种丁炔二醇半加氢双金属催化剂,其特征在于,所述催化剂以贵金属-非贵金属为活性组分,其通式可表达为M1-M2-M2O/S,式中M1代表Pd、Ru、Pt或Au中的一种,M2代表Ni、Cu、Fe或Co中的一种,S代表惰性载体;;所述催化剂组成中M1的重量比为0.1%~1%,M2的重量比为0.5%~10%,余量为载体。
优选地,所述惰性载体为活性炭、炭黑、椰壳炭、二氧化硅、α-氧化铝、碳化硅或SBA-15分子筛中的一种。
一种丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,具体步骤如下:
1)将非贵金属前驱盐和聚乙烯吡咯烷酮(PVP)加入到水和乙醇组成的混合溶剂中、搅拌均匀后使用碱性溶液调节pH值至9~14得混合溶液;
2)往步骤1)制得的混合溶液中加入还原剂搅拌均匀,然后加入惰性载体并继续搅拌得混合物,所得混合物密封后继续搅拌,过滤后,洗涤所得固体,干燥后制得固体粉末;
3)将步骤2)制得的固体粉末加入到含贵金属前驱盐溶液中,搅拌后过滤,所得固体经洗涤干燥后制得固体粉末A;
4)将步骤3)制得的固体粉末A在由氮气和氢气组成的混合气中焙烧即可制得所述丁炔二醇半加氢双金属催化剂。
优选地,步骤1)所述的非贵金属前驱盐选自硝酸亚铁、硫酸亚铁、氯化亚铁、醋酸亚铁、氯化钴、硝酸钴、硫酸钴、氯化镍、硝酸镍、硫酸镍、醋酸镍、氯化铜、硝酸铜、硫酸铜或醋酸铜中的一种或几种。
优选地,步骤1)所述的碱性溶液选自氢氧化钾溶液、氢氧化钠溶液或氨水中的一种。
优选地,步骤1)所述的还原剂选自水合肼、硼氢化钠或硼氢化钾中的一种。
优选地,步骤3)所述的含贵金属的前驱盐选自氯化钯、氯化钌、氯铂酸或氯铂酸中的一种。
优选地,步骤4)所述的焙烧温度为300~500℃,焙烧时间为2~5h。
优选地,步骤4)所述的混合气中氮气和氢气的体积比为:9:1
一种将丁炔二醇半加氢双金属催化剂应用于丁炔二醇半加氢制丁烯二醇的方法,其特征在于,包括如下步骤:将催化剂、1,4-丁炔二醇和水加入到反应釜中维持反应温度为30℃,反应压力为1bar,反应结束即可制备得到1,4-丁烯二醇。
本发明的原理是:本发明的催化剂采用化学还原法和化学置换法合成具备小岛状结构(朱丽华.Ru-TM/TMO/C催化剂纳米结构的设计,制备及其催化芳烃加氢性能的研究[D].厦门大学博士学位论文.2014.)的双金属催化剂,其活性组分第一金属为贵金属Pd、Ru、Pt或Au,第二金属为Ni、Cu、Fe或Co等非贵金属;此外,催化剂选择惰性载体来避免异构化反应和深度加氢反应的发生,从而可提高丁烯二醇的选择性,这是因为含有酸性位点的普通载体会大量吸附丁炔二醇,并促使异构化反应发生而生成正丁醇、2-羟基四氢呋喃等异构化产物,因而降低对丁烯二醇的选择性。在催化剂制备过程中,首先使用水合肼等还原剂将第二金属还原后进行化学置换引入第一金属,其中,Pd、Ru、Pt或Au可负载于第二金属纳米颗粒的催化剂;在催化反应过程中,第一金属Pd、Ru、Pt或Au可优先吸附和活化H2,但由于第一金属活性位较小而不会活化底物BYD分子;而第二金属氧化物带有正电荷空穴,可通过亲电吸附作用活化BYD分子;同时第二金属起着氢溢流作用“桥梁”,可将活化了的H﹡物种转移至活化了的BYD上从而发生加氢反应,将底物BYD选择性氧化为1,4-丁烯二醇。
相对于现有的丁炔二醇半加氢催化剂及其制备方法,本发明的优点如下:
(1)本发明的催化剂是采用化学还原法和化学置换法制备的,所制备的催化剂在较高活性组分负载量下还能保持很高的分散度,此外,所制备的催化剂还具有很高的比表面积与孔径,因而可在1,4-丁炔二醇选择性半加氢的反应中表现出高的活性与完美的选择性,且具有很长的使用寿命。
(2)本发明所制备的催化剂应用于1,4-丁炔二醇选择性半加氢的反应,反应转化率可高达100%,选择性达到100%;并且反应在常温常压下进行,条件温和,与现有的高温高压反应条件相比,大大降低了对反应设备的要求及危险性,也大大降低了设备费用和生产成本。
具体实施方式
下面进一步结合实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,示例中具体的质量、反应时间和温度、工艺参数等也仅是合适范围中的一个示例,本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。实施例中未注明具体技术或条件者,均为按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市场购买的常规产品。
实施例1
催化剂的制备:
(1)将0.0505g NiCl2·6H2O和0.3g PVP-K30加入锥形瓶中,加入82.5mL超纯水与12.5mL乙醇组成的混合溶剂进行溶解,搅拌10min,加入NaOH溶液调节混合溶液的pH值至9-14之间;
(2)加入25.0mL 85wt%水合肼并搅拌10min;
(3)加入2.5gα-Al2O3并继续搅拌10min;
(4)将锥形瓶中的混合物转移至水热合成釜中(胶带密封),室温下磁力搅拌18h后过滤,所得固体用乙醇和超纯水洗涤后在60℃真空干燥6h,碾碎后得固体粉末;
(5)移取PdCl2溶液10.6mL(浓度为0.00118gPd/mL水)于250mL锥形瓶中,将步骤(4)制得的固体粉末2.545g加入到10.6mL(浓度为1.18mgPd/mL水)的PdCl2溶液中并加入超纯水至溶液体积为200mL,所得混合物常温下磁力搅拌18.5h后过滤,所得固体用乙醇和超纯水洗涤后在60℃真空干燥6h,碾碎后得固体粉末;
(6)将步骤(5)中制得的固体粉末装入有石英管的管式炉中,在流量为50mL·min-190%N2/10%H2中300℃焙烧5h,升温速率为2℃·min-1,焙烧结束后冷却至室温即可制得催化剂0.5%Pd-0.5%Ni/α-Al2O3
考评条件:
在耐压反应瓶中进行催化反应,反应温度为30℃,反应压力为一个1bar,催化剂投料为0.5g,反应底物1,4-丁炔二醇投料为6g,溶剂水为20ml,连续反应4h后取样检测加氢产物的含量,计算反应底物的转化率及产物的选择性,考评结果见表1.
实施例2
取2.5g SiO2载体替代α-Al2O3载体,焙烧温度调整为500℃,焙烧时间调整为3h,其余条件同实施例1即可制得催化剂0.5%Pd-0.5%Ni/SiO2。考评条件同
实施例1,考评结果见表1.
实施例3
取2.5g椰壳炭载体替代α-Al2O3载体,其余步骤同实施例1即可制得催化剂0.5%Pd-0.5%Ni/椰壳炭。考评条件同实施例1,考评结果见表1.
实施例4
取2.5g炭黑载体替代α-Al2O3载体,其余步骤同实施例1即可制得催化剂0.5%Pd-0.5%Ni/CNTs。考评条件同实施例1,考评结果见表1.
实施例5
取2.5g碳化硅载体替代α-Al2O3载体,其余步骤同实施例1即可制得催化剂0.5%Pd-0.5%Ni/碳化硅。考评条件同实施例1,考评结果见表1.
实施例6
取2.5g SBA-15分子筛载体替代Al2O3载体,其余步骤同实施例1即可制得催化剂0.5%Pd-0.5%Ni/SBA-15。考评条件同实施例1,考评结果见表1.
表1不同载体的丁炔二醇半加氢双金属催化剂催化性能
实施例7
催化剂制备参照实施例1,水合肼变为硼氢化钠,PdCl2溶液用量变为2.12ml。其余条件相同,制得催化剂0.1%Pd-0.5%Ni/α-Al2O3。考评条件同实施例1,考评结果见表2.
实施例8
催化剂制备参照实施例1,水合肼变为硼氢化钾,PdCl2溶液用量变为21.2ml。其余条件相同,制得催化剂1%Pd-0.5%Ni/α-Al2O3。考评条件同实施例1,考评结果见表2.
实施例9
催化剂制备参照实施例1,NiCl2·6H2O用量变为1.01g,NaOH溶液变为KOH溶液。其余条件相同,制得0.5%Pd-10%Ni/α-Al2O3。考评条件同实施例1,考评结果见表2.
实施例10
催化剂制备参照实施例1,NiCl2·6H2O变为Co(NO3)2·6H2O,用量变为0.0617g,其余条件相同,制得0.5%Pd-0.5%Co/α-Al2O3。考评条件同实施例1,考评结果见表2.
实施例11
催化剂制备参照实施例1,NiCl2·6H2O变为Cu(NO3)2·3H2O,用量变为0.0475g,。其余条件相同,制得0.5%Pd-0.5%Cu/α-Al2O3。考评条件同实施例1,考评结果见表2.
表2不同非贵金属及含量的双金属催化剂催化性能
实施例12
催化剂制备参照实施例1,将PdCl2溶液换做2.5mL 5mg/mL(以Pd离子浓度计)PtCl4溶液。其余条件相同,制得0.5%Pt-0.5%Ni/α-Al2O3催化剂。考评条件同实施例1,考评结果见表3.
实施例13
催化剂制备参照实施例1,将PdCl2溶液换做2.5mL 5mg/mL(以Au离子浓度计)AuCl3·HCl·4H2O溶液。其余条件相同,制得0.5%Au-0.5%Ni/α-Al2O3催化剂。考评条件同实施例1,考评结果见表3.
实施例14
催化剂制备参照实施例1,将PdCl2溶液换做2.5mL 5mg/mL(以Ru离子浓度计)RuCl3溶液。其余条件相同,制得0.5%Ru-0.5%Ni/α-Al2O3催化剂。考评条件同实施例1,考评结果见表3.
表3含不同贵金属的双金属催化剂催化性能
实施例14
催化剂制备参照实施例1,将NiCl2·6H2O换做CuSO4·5H2O。其余条件相同,制得0.5%Pd-0.5%Cu/α-Al2O3催化剂。考评条件同实施例1,考评结果见表4.
实施例15
催化剂制备参照实施例1,将NiCl2·6H2O换做FeSO4·7H2O。其余条件相同,制得0.5%Pd-0.5%Fe/α-Al2O3催化剂。考评条件同实施例1,考评结果见表4.
实施例16
催化剂制备参照实施例1,将NiCl2·6H2O换做CoCl2·6H2O。其余条件相同,制得0.5%Pd-0.5%Co/α-Al2O3催化剂。考评条件同实施例1,考评结果见表4.
表4含不同非贵金属的双金属催化剂催化性能
Claims (10)
1.一种丁炔二醇半加氢双金属催化剂,其特征在于,所述催化剂以贵金属-非贵金属为活性组分,其通式可表达为M1-M2-M2O/S,式中M1代表Pd、Ru、Pt或Au中的一种,M2代表Ni、Cu、Fe或Co中的一种,S代表惰性载体;所述催化剂组成中M1的重量比为0.1%~1%,M2的重量比为0.5%~10%,余量为载体。
2.如权利要求1所述的丁炔二醇半加氢双金属催化剂,其特征在于,所述惰性载体为活性炭、炭黑、椰壳炭、二氧化硅、α-氧化铝、碳化硅或SBA-15分子筛中的一种。
3.一种如权利要求1所述的丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,具体步骤如下:
1)将非贵金属前驱盐和聚乙烯吡咯烷酮(PVP)加入到水和乙醇组成的混合溶剂中、搅拌均匀后使用碱性溶液调节pH值至9~14得混合溶液;
2)往步骤1)制得的混合溶液中加入还原剂搅拌均匀,然后加入惰性载体并继续搅拌得混合物,所得混合物密封后继续搅拌,过滤后,洗涤所得固体,干燥后制得固体粉末;
3)将步骤2)制得的固体粉末加入到含贵金属的前驱盐溶液中,搅拌后过滤,所得固体经洗涤干燥后制得固体粉末A;
4)将步骤3)制得的固体粉末A在由氮气和氢气组成的混合气中焙烧即可制得所述丁炔二醇半加氢双金属催化剂。
4.如权利要求3所述的丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,步骤1)所述的非贵金属前驱盐选自硝酸亚铁、硫酸亚铁、氯化亚铁、醋酸亚铁、氯化钴、硝酸钴、硫酸钴、氯化镍、硝酸镍、硫酸镍、醋酸镍、氯化铜、硝酸铜、硫酸铜或醋酸铜中的一种或几种。
5.如权利要求3所述的丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,步骤1)所述的碱性溶液选自氢氧化钾溶液、氢氧化钠溶液或氨水中的一种。
6.如权利要求3所述的丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,步骤1)所述的还原剂选自水合肼、硼氢化钠或硼氢化钾中的一种。
7.如权利要求3所述的丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,步骤3)所述的含贵金属的前驱盐选自氯化钯、氯化钌、氯铂酸或氯金酸中的一种。
8.如权利要求3所述的丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,步骤4)所述的焙烧温度为300~500℃,焙烧时间为2~5h。
9.如权利要求3所述的丁炔二醇半加氢双金属催化剂的制备方法,其特征在于,步骤4)所述的混合气中氮气和氢气的体积比为:9:1。
10.一种将如权利要求1所述的丁炔二醇半加氢双金属催化剂应用于丁炔二醇半加氢制丁烯二醇的方法,其特征在于,包括如下步骤:将催化剂、1,4-丁炔二醇和水加入到反应釜中维持反应温度为30℃,反应压力为1bar,反应结束即可制备得到1,4-丁烯二醇。
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CN110743590A (zh) * | 2019-10-21 | 2020-02-04 | 西安凯立新材料股份有限公司 | 一种合成维生素a中间体用高选择性催化剂及其制备方法 |
CN113101928A (zh) * | 2021-04-23 | 2021-07-13 | 上海润颉生物医药科技有限公司 | 1,4-丁炔二醇制备1,4-丁烯二醇用催化剂及其制备方法和应用 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110743590A (zh) * | 2019-10-21 | 2020-02-04 | 西安凯立新材料股份有限公司 | 一种合成维生素a中间体用高选择性催化剂及其制备方法 |
CN110743590B (zh) * | 2019-10-21 | 2023-01-24 | 西安凯立新材料股份有限公司 | 一种合成维生素a中间体用高选择性催化剂及其制备方法 |
CN113101928A (zh) * | 2021-04-23 | 2021-07-13 | 上海润颉生物医药科技有限公司 | 1,4-丁炔二醇制备1,4-丁烯二醇用催化剂及其制备方法和应用 |
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