CN112569944A - NiCu alloy hydrogenation catalyst, preparation method and application thereof - Google Patents
NiCu alloy hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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- CN112569944A CN112569944A CN202011462072.XA CN202011462072A CN112569944A CN 112569944 A CN112569944 A CN 112569944A CN 202011462072 A CN202011462072 A CN 202011462072A CN 112569944 A CN112569944 A CN 112569944A
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- nicu alloy
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- hydrogenation catalyst
- aldehyde
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 106
- 229910003322 NiCu Inorganic materials 0.000 title claims abstract description 68
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 68
- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 54
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 230000004048 modification Effects 0.000 claims abstract description 33
- 238000012986 modification Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 7
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 23
- 150000001299 aldehydes Chemical class 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- -1 carbon aldehyde Chemical class 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 claims description 10
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 claims description 8
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 claims description 8
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002048 multi walled nanotube Substances 0.000 claims description 8
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- MMFCJPPRCYDLLZ-CMDGGOBGSA-N (2E)-dec-2-enal Chemical compound CCCCCCC\C=C\C=O MMFCJPPRCYDLLZ-CMDGGOBGSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- MMFCJPPRCYDLLZ-UHFFFAOYSA-N dec-2-enal Natural products CCCCCCCC=CC=O MMFCJPPRCYDLLZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- KMPQYAYAQWNLME-UHFFFAOYSA-N undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 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
- 229910001453 nickel ion Inorganic materials 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
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 claims 2
- 230000004913 activation Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- 239000004439 Isononyl alcohol Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
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- Condensed Matter Physics & Semiconductors (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a NiCu alloy hydrogenation catalyst, a preparation method and application thereof. The catalyst comprises a carrier, and a main active component and a modification auxiliary agent which are loaded on the carrier, wherein the main active component and the modification auxiliary agent are uniformly distributed on the surface of the carrier, the main active component is NiCu alloy, and the modification auxiliary agent is a carbon nano tube. The preparation method comprises the following steps: and dropwise adding a mixed metal salt solution containing active component metal salts and carrier metal salts and alkali liquor into the modification auxiliary agent solution together to form a mixed solution, and then carrying out precipitation, aging, roasting and reduction treatment to obtain the carbon nanotube modified NiCu alloy hydrogenation catalyst. The NiCu alloy catalyst modified by the carbon nano tube has a hydrotalcite precursor structure, and the modification of the carbon nano tube can promote the dispersion of active metal of the catalyst, improve the reducibility of the active metal and the adsorption and activation of raw materials, so that the high-carbon-aldehyde high-conversion-rate high-selectivity hydrogenation is realized.
Description
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a carbon nano tube modified NiCu alloy hydrogenation catalyst for preparing high-carbon alcohol by liquid-phase hydrogenation of high-carbon aldehyde, a preparation method thereof and application thereof in preparing high-carbon alcohol by liquid-phase hydrogenation, belonging to the technical field of chemical industry.
Background
Higher alcohols refer to alcohols having six or more carbon atoms, which are the main basic materials for synthesizing surfactants, detergents, plasticizers and other various fine chemicals, and the subsequent processed products are widely used in the fields of textile, paper making, food, medicine, etc. World market demand is at 1500 million/a, increasing at a rate of around 10% per year. A series of olefin products are produced in the petroleum refining process, the olefin hydroformylation reaction is an important source of aldehyde, the catalytic hydrogenation of the aldehyde is an important method for synthesizing alcohol, and the reaction process for preparing the alcohol from the olefin is as follows:
the preparation of alcohol by aldehyde hydrogenation mainly comprises gas phase hydrogenation and liquid phase hydrogenation. In the gas phase hydrogenation process, a copper-based catalyst is often adopted, and other auxiliary agents are added for modification, and the modification is usually carried out at the high temperature of 180 ℃ and 250 ℃. For example, Chinese patent CN1883795A discloses a method for preparing higher alcohols by hydrogenation of Cu-Zn-Al vapor phase aldehydes, the catalyst adopts a step coprecipitation method, the conversion rate and selectivity of hydrogenation of octenal and n-butyraldehyde can both reach more than 99%, but the volume ratio of hydrogen aldehyde in the reaction process is 8000: 1, the hydrogen consumption is too large, and the reaction space velocity is low (less than or equal to 0.5 h)-1)。
Liquid phase hydrogenation is widely used for hydrogenation of high carbon aldehyde with the characteristics of low energy consumption, high product purity and the like. The liquid phase hydrogenation process generally uses a nickel-based catalyst or a noble metal supported catalyst. Chinese patent CN104945225A discloses a method for preparing alcohol by liquid phase hydrogenation of decenal, in which Raney alloy as main active component including Raney metallic nickel and leachable element (at least one selected from aluminum, zinc and silicon) and promoter Mo, Cr, Ti, Fe, Pt, Pd, Ph and Pu (at least one) are dispersed in continuous phase carbon, the conversion rate of the prepared catalyst can reach 99.99% at most, and the selectivity can reach 98.2% at most, but the preparation mode of the catalyst can cause the active component to be unevenly distributed in the continuous phase, the volume ratio of reaction hydrogen and decenal is as large as 10000: 1 at most, and the reaction space velocity is lower (less than or equal to 1.0 h) at most-1). Chinese patent CN110560053A discloses that a composite oxide is used as a carrier (including a silicon-aluminum and titanium-aluminum composite carrier or an alumina carrier), a load Ru is used as a catalyst, a modification auxiliary agent (including one or more of Cu, Ni, Cs, Ba, Mg and Zn) is added to catalyze hydrogenation of various aldehydes to prepare alcohol, the catalyst takes a noble metal Ru as a main active component, the cost is high, and the aldehydes are difficult to completely convert. U.S. Pat. No. 4, 6239318, 1 discloses a pair C5-C24The application of catalyst for selective hydrogenation of olefin hydroformylation distillate. The patent takes Cu, Ni and Cr as active components of a catalyst, and aldehyde in a mixed solution is hydrogenated under the reaction conditions of 140 ℃ and 180 ℃ and 1.5-2.5 MPa. The catalyst used in the patent contains metal Cr with high toxicity, the reaction temperature is high, high-carbon aldehyde is not completely converted, and the quality of downstream products is influenced.
Disclosure of Invention
The invention mainly aims to provide a carbon nano tube modified NiCu alloy hydrogenation catalyst for preparing high-carbon alcohol by high-carbon aldehyde liquid-phase hydrogenation and a preparation method thereof, so as to overcome the defects of the prior art.
The invention also aims to provide the application of the NiCu alloy hydrogenation catalyst in the preparation of high-carbon alcohol by high-carbon aldehyde liquid-phase hydrogenation.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a NiCu alloy hydrogenation catalyst, which comprises a carrier, and a main active component and a modification auxiliary agent which are loaded on the carrier, wherein the main active component and the modification auxiliary agent are uniformly distributed on the surface of the carrier, the main active component is NiCu alloy, and the modification auxiliary agent is a carbon nano tube.
In some preferred embodiments, the content of the main active component in the NiCu alloy hydrogenation catalyst is 35-75 wt%, and the mass ratio of Ni to Cu in the NiCu alloy is 3: 1-15: 1.
In some preferred embodiments, the content of the modification auxiliary agent in the NiCu alloy hydrogenation catalyst is 1-15 wt%.
The embodiment of the invention also provides a preparation method of the NiCu alloy hydrogenation catalyst, which comprises the following steps: and preparing the NiCu alloy hydrogenation catalyst by adopting a coprecipitation method.
In some preferred embodiments, the preparation method specifically comprises:
and dropwise adding a mixed metal salt solution containing the metal salt of the active component and the metal salt of the carrier and alkali liquor into the modified auxiliary agent solution together to form a mixed solution, and then carrying out precipitation, aging, roasting and reduction treatment to obtain the NiCu alloy hydrogenation catalyst.
In some preferred embodiments, the temperature of the aging treatment is 80-100 ℃ and the time is 4-24 h.
In some preferred embodiments, the process conditions of the calcination treatment include: the adopted atmosphere is inert atmosphere, the roasting treatment temperature is 400-650 ℃, and the roasting treatment time is 3-6 h.
In some preferred embodiments, the process conditions of the reduction treatment include: the adopted atmosphere is a reducing atmosphere, the temperature of reduction treatment is 400-600 ℃, the time is 2-8 h, and the flow rate of reducing gas adopted by each gram of catalyst is 20-100 mL/min.
The embodiment of the invention also provides the application of the NiCu alloy hydrogenation catalyst in the preparation of high-carbon alcohol by hydrogenation of high-carbon aldehyde.
Correspondingly, the embodiment of the invention also provides a method for preparing high-carbon alcohol by continuously hydrogenating high-carbon aldehyde, which comprises the following steps:
continuously inputting an aldehyde-alcohol mixed solution containing high-carbon aldehyde and organic alcohol into a fixed bed reactor filled with the NiCu alloy hydrogenation catalyst in a hydrogen atmosphere to carry out liquid-phase hydrogenation reaction to prepare the high-carbon alcohol.
In some preferred embodiments, the process conditions for the hydrogenation reaction include: the temperature is 80-150 ℃, the pressure is 1-4 MPa, and the feeding volume space velocity is 1-8 h-1The molar ratio of the hydrogen to the high-carbon aldehyde is 4: 1-30: 1.
Further, the high-carbon aldehyde includes any one or a combination of two or more of hexanal, heptanal, octanal, n-nonanal, isononanal, decanal, decenal, undecalanal, and the like, but is not limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
1) the carbon nanotube modified NiCu alloy hydrogenation catalyst provided by the invention adopts the synergistic effect of Ni and Cu nanoparticles and the carbon nanotube, shows excellent catalytic effect, can efficiently catalyze aldehyde and hydrogen to react to generate corresponding alcohol, has high conversion rate (more than 99.5%), few ethers, esters and aldehyde condensation byproducts in the product, and has high product selectivity (more than 99%);
2) the carbon nanotube modified NiCu alloy hydrogenation catalyst provided by the invention has a hydrotalcite precursor structure, and the modification of the carbon nanotube can promote the dispersion of active metal of the catalyst, improve the reducibility of the active metal and the adsorption and activation of raw materials, so that the high-conversion-rate and high-selectivity hydrogenation of high-carbon aldehyde is realized;
3) the carbon nanotube modified NiCu alloy hydrogenation catalyst for preparing high-carbon alcohol by high-carbon aldehyde liquid-phase hydrogenation, which is provided by the invention, has the advantages of high activity and high stability, is simple in preparation method, low in production cost, good in catalyst stability, difficult to sinter and deposit carbon, capable of effectively catalyzing aldehyde and hydrogen to react to generate corresponding alcohol, and carrying out high-activity and high-selectivity hydrogenation under mild reaction conditions to obtain target high-carbon alcohol;
4) the carbon nano tube modified NiCu alloy hydrogenation catalyst provided by the invention has a wide application range and can be used for producing various high-carbon alcohols.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1 and 2 are XRD and TEM representations of a carbon nanotube-modified NiCu alloy hydrogenation catalyst obtained in example 1 of the present invention;
FIG. 3 is a schematic diagram showing the continuous operation stability of a carbon nanotube-modified NiCu alloy hydrogenation catalyst for liquid-phase hydrogenation of high carbon aldehyde to prepare high carbon alcohol in example 9 of the present invention.
Detailed Description
In order to overcome the defects of the existing hydrogenation catalyst, the inventor of the invention provides a technical scheme of the invention through long-term research and a great deal of practice. The invention mainly provides a catalyst for preparing high-carbon alcohol by high-carbon aldehyde liquid-phase hydrogenation, and a preparation method and application thereof. The catalyst comprises a carrier, and a main active component and a modification auxiliary agent which are loaded on the carrier. The main active component is NiCu alloy, the modification auxiliary agent is carbon nano tube, and the carrier is Al2O3. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of an embodiment of the present invention provides a carbon nanotube modified NiCu alloy hydrogenation catalyst, including a carrier, and a main active component and a modification auxiliary agent loaded on the carrier, where the main active component and the modification auxiliary agent are uniformly distributed on a surface of the carrier, the main active component is a NiCu alloy, and the modification auxiliary agent is a carbon nanotube.
In some preferred embodiments, the content of the main active component in the carbon nanotube modified NiCu alloy hydrogenation catalyst is 35-75 wt%, and the mass ratio of Ni to Cu in the NiCu alloy is 3: 1-15: 1.
In some preferred embodiments, the content of the modification auxiliary agent in the carbon nanotube modified NiCu alloy hydrogenation catalyst is 1-15 wt%.
In some preferred embodiments, the carbon nanotube is a multi-walled carbon nanotube, the multi-walled carbon nanotube has an outer diameter of 5 to 20nm, an inner diameter of 2 to 5nm, a tube length of 2 to 30 μm, and a specific surface area of more than 200m2/g。
Furthermore, the NiCu alloy hydrogenation catalyst has a hydrotalcite precursor structure.
Further, the carrier is Al2O3But is not limited thereto. This application uses Al2O3The purpose of the (trivalent metal) as a support is to form a hydrotalcite structure.
In some preferred embodiments, the NiCu alloy hydrogenation catalyst has a nickel-copper alloy grain size below 6 nm.
The design mechanism of the invention is as follows: the carbon nanotube modified NiCu alloy hydrogenation catalyst provided by the invention adopts the synergistic effect of Ni and Cu nanoparticles and the carbon nanotube, shows excellent catalytic effect, can efficiently catalyze aldehyde and hydrogen to react to generate corresponding alcohol, has high conversion rate (more than 99.5%), few ethers, esters and aldehyde condensation byproducts in the product, and has high product selectivity (more than 99%).
In conclusion, the carbon nanotube modified NiCu alloy hydrogenation catalyst provided by the invention has a hydrotalcite precursor structure, and the modification of the carbon nanotube can promote the dispersion of active metal of the catalyst, improve the reducibility of the active metal and the adsorption and activation of raw materials, so that the hydrogenation with high carbon aldehyde, high conversion rate and high selectivity can be realized.
In another aspect of the embodiments of the present invention, there is provided a method for preparing the carbon nanotube modified NiCu alloy hydrogenation catalyst, including: and preparing the carbon nano tube modified NiCu alloy hydrogenation catalyst by adopting a coprecipitation method.
In some preferred embodiments, the preparation method specifically comprises:
and dropwise adding a mixed metal salt solution containing the metal salt of the active component and the metal salt of the carrier and alkali liquor into the modification auxiliary agent solution together to form a mixed solution, and then carrying out precipitation, aging, roasting and reduction treatment to obtain the carbon nanotube modified NiCu alloy hydrogenation catalyst.
In some preferred embodiments, the total concentration of the metal nickel ions, copper ions and the support metal salt in the mixed metal salt solution is 0.1-1.0 mol/L.
In some preferred embodiments, the active component metal salt contained in the mixed metal salt solution includes nickel salts and copper salts.
Further, the nickel salt includes nickel nitrate, nickel sulfate, etc., but is not limited thereto.
Further, the copper salt includes copper nitrate, copper sulfate, etc., but is not limited thereto.
Further, the metal salt of the carrier includes aluminum nitrate, aluminum sulfate, etc., but is not limited thereto.
In some preferred embodiments, the lye comprises a hydroxide solution and/or a carbonate solution or the like.
Further, the alkali solution may be any one or a combination of two or more of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution, a potassium carbonate solution, and the like, but is not limited thereto.
Further, the concentration of the hydroxide solution is 2-6 mol/L, and the concentration of the carbonate solution is 0.4-2 mol/L.
In some preferred embodiments, the modification aid solution comprises carbon nanotubes and deionized water, and the content of the carbon nanotubes in the modification aid solution is 1-10 wt%.
Further, the carbon nanotube is treated by acid, the acid adopted in the acid treatment is concentrated nitric acid, and the acid treatment time is 2-8 h, namely, the carbon nanotube is treated by the concentrated nitric acid for 2-8 h before use, and can also be directly used without treatment.
In some preferred embodiments, the pH value of the mixed solution is maintained at 9.0-11 during the precipitation treatment.
In some preferred embodiments, the temperature of the aging treatment is 80-100 ℃ and the time is 4-24 h.
In some preferred embodiments, the process conditions of the calcination treatment include: the adopted atmosphere is inert atmosphere, the roasting treatment temperature is 400-650 ℃, and the roasting treatment time is 3-6 h.
Further, the inert atmosphere includes a nitrogen or argon atmosphere, etc., but is not limited thereto.
In some preferred embodiments, the process conditions of the reduction treatment include: the adopted atmosphere is a reducing atmosphere, the temperature of reduction treatment is 400-600 ℃, the time is 2-8 h, and the flow rate of reducing gas adopted by each gram of catalyst is 20-100 mL/min.
Further, the reducing atmosphere is a hydrogen atmosphere.
The carbon nano tube modified NiCu alloy hydrogenation catalyst for preparing high-carbon alcohol by high-carbon aldehyde liquid-phase hydrogenation, which is provided by the invention, has the advantages of high activity and high stability, is simple in preparation method, low in production cost, good in catalyst stability, difficult to sinter and deposit carbon, capable of effectively catalyzing aldehyde and hydrogen to react to generate corresponding alcohol, and high-activity and high-selectivity hydrogenation is carried out under mild reaction conditions to obtain the target high-carbon alcohol.
In another aspect of the embodiments of the present invention, there is also provided a use of the foregoing carbon nanotube modified NiCu alloy hydrogenation catalyst in the preparation of higher alcohols by continuous hydrogenation of higher aldehydes.
Accordingly, another aspect of the embodiments of the present invention also provides a method for preparing a higher alcohol by continuously hydrogenating a higher aldehyde, comprising:
continuously inputting an aldehyde-alcohol mixed solution containing high-carbon aldehyde and organic alcohol into a fixed bed reactor filled with the carbon nano tube modified NiCu alloy hydrogenation catalyst in a hydrogen atmosphere to carry out liquid phase hydrogenation reaction to prepare the high-carbon alcohol.
In some preferred embodiments, the process conditions for the hydrogenation reaction include: the temperature is 80-150 ℃, the pressure is 1-4 MPa, and the feeding volume space velocity is 1-8 h-1The molar ratio of the hydrogen to the high-carbon aldehyde is 4: 1-30: 1.
Further, the reaction of the invention is carried out in a fixed bed, and the reaction time is not fixed but is more than 8 h.
Further, the high-carbon aldehyde includes any one or a combination of two or more of hexanal, heptanal, octanal, n-nonanal, isononanal, decanal, decenal, undecalanal, and the like, but is not limited thereto.
Further, the organic alcohol includes ethanol, higher alcohols corresponding to higher aldehydes, and the like, but is not limited thereto. For example, ethanol, 2-ethylhexanol, isononyl alcohol, etc. can be mentioned.
Further, the mass ratio of the high-carbon aldehyde to the organic alcohol in the aldehyde-alcohol mixed solution is 1: 1-20.
Further, in the method, the conversion rate of the high-carbon aldehyde is more than 99.5%, and the product selectivity is more than 99%.
The technical solution of the present invention will be described below with reference to specific examples and drawings. It is to be understood that one or more method steps recited herein do not preclude the presence or addition of additional method steps before or after the recited combination of steps or intervening method steps between the explicitly recited steps; it should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying individual method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, nor is it intended that changes or modifications in the relative relationship thereto, without materially changing the technical details, be regarded as the scope of the invention in which the invention may be practiced.
In the following examples, qualitative and quantitative analysis was carried out by gas chromatography using an Aglient 7890A GC-FID (hydrogen flame detector, nitrogen as carrier gas), a capillary chromatography column of HP-5 type (5% Phenyl Methyl Siloxan, 50 m.times.0.32 mm.times.2.0. mu.m).
Example 1: preparation and characterization of carbon nanotube modified NiCu alloy hydrogenation catalyst
Pretreatment of carbon nanotubes
Weighing 10.0g of commercial multi-walled carbon nanotubes, pouring into a round-bottom flask, adding 100ml of concentrated nitric acid, placing in an oil bath at 90 ℃, refluxing for 4-24h under vigorous stirring, cooling to room temperature, filtering, washing with deionized water to neutrality, and drying at 110 ℃ for later use.
Preparation of carbon nano tube modified NiCu alloy hydrogenation catalyst
Weighing active metals Ni, Cu and carrier Al according to proportion at room temperature2O3Adding deionized water into the metal salt to prepare a solution A with the total concentration of metal ions being 0.5 mol/L; the concentration of NaOH is 4mol/L, Na2CO3Mixed alkali B with the concentration of 1 mol/L; adding the carbon nano tube which is treated by acid in a reaction tank according to a certain proportion, adding deionized water (the adding amount is 100 times of the mass of the carbon nano tube), fully stirring and uniformly mixing, then dropwise adding a salt solution A and an alkali solution B into the reaction tank under rapid stirring, keeping the pH value of the precipitation process at 9.0-11, raising the temperature to 80 ℃ after the precipitation is finished, aging for 4h, filtering after the aging is finished, and washing with the deionized water until the filtrate is neutral. The filter cake was dried at 110 ℃ for 12h and calcined at 500 ℃ for 4h in a nitrogen atmosphere. The tablets were sieved to 20-40 mesh catalyst particles and 4g were packed in a fixed bed reactor. Finally, heating to 550 ℃ in a hydrogen atmosphere (flow rate is 80-100mL/min), and reducing for 4h to obtain the activated catalyst.
The catalyst powder prepared above was subjected to XRD and transmission electron microscopy characterization (TEM) after reduction activation under the same conditions, and fig. 1 and 2 are XRD and TEM characterization images of the representative catalyst (No. 2) in table 1 of this example, respectively. The different catalyst compositions and the grain sizes of the metallic nickel-copper alloys are shown in table 1. The catalyst has good dispersibility, and the grain size of the metal nickel-copper alloy is below 6 nm.
TABLE 1 catalyst Synthesis conditions, compositions and characterization results
*The Arabic numerals in the front of the active metal and the auxiliary agent represent the mass percentage, and the rest is A12O3。
Example 2
The preparation process and composition of the carbon nanotube modified NiCu alloy hydrogenation catalyst in this example are the same as those of the catalyst (No. 2), except that the concentration of the metal salt solution A is 1.0moL/L, the catalyst is aged at 100 ℃ for 4h, washed, dried, and then calcined at 650 ℃ for 3h in nitrogen atmosphere, and reduced and activated at 600 ℃ for 2h to obtain the catalyst (No. 6), and XRD characterization results show that the grain size of the metal nickel-copper alloy in the reduced and activated catalyst is 5.8 nm.
Example 3
The preparation process and the composition of the carbon nanotube modified NiCu alloy hydrogenation catalyst in this example are the same as those of the catalyst (No. 2), except that the concentration of the metal salt solution A is 0.1moL/L, the catalyst is aged at 80 ℃ for 24h, washed, dried, and then calcined at 400 ℃ for 6h in a nitrogen atmosphere, and reduced and activated at 400 ℃ for 8h to obtain the catalyst (No. 7), and XRD characterization results show that the grain size of the metal nickel-copper alloy in the reduced and activated catalyst is 4.0 nm.
Example 4
The preparation process and composition of the carbon nanotube modified NiCu alloy hydrogenation catalyst in this example are the same as those in example 2 except that 6mol/L NaOH and 0.4mol/L Na are substituted2CO3Instead of 4mol/L NaOH and 1mol/L Na2CO3The catalyst (No. 8) was obtained, and XRD characterization showed that the grain size of the metallic nickel-copper alloy in the reduction-activated catalyst was 5.2 nm.
Example 5
The preparation process and composition of the carbon nanotube modified NiCu alloy hydrogenation catalyst in this example are the same as those in example 2, except that the catalyst is aged at 90 ℃ for 6h, washed, dried, and then calcined at 600 ℃ for 3h, and reduced and activated at 600 ℃ for 4h, the flow rate of hydrogen atmosphere is 20-80mL/min, the catalyst (number 9) is obtained, and XRD characterization results show that the grain size of the metallic nickel-copper alloy in the reduced and activated catalyst is 4.5 nm.
Example 6
The preparation process and composition of the carbon nanotube modified NiCu alloy hydrogenation catalyst in this example are the same as those in example 2, except that 2mol/L Na2CO3Instead of 4mol/L NaOH and 1mol/L Na2CO3The mixed alkali is calcined in the argon atmosphere, the pH value in the precipitation process is controlled to be 9.0, the catalyst (number 10) is obtained, and XRD (X-ray diffraction) characterization results show that the grain size of the metal nickel-copper alloy in the reduction activation catalyst is 4.7 nm.
Example 7
The reaction performance of different catalysts for catalyzing hydrogenation of high-carbon aldehyde to prepare high-carbon alcohol.
Preparing reaction liquid of at least one of hexanal, heptanal, octanal, n-nonanal, isononanal, decanal, decenal and undecanal and organic alcohol according to the mass ratio of the raw material aldehyde to the organic alcohol of 1: 5. Pumping the prepared high-carbon aldehyde reaction solution into a fixed bed reactor through a high-pressure constant flow pump, and reacting at the temperature of 90 ℃ and H2Pressure 3MPa, H2The mol ratio of the high carbon aldehyde to the high carbon aldehyde is 10: 1 and the space velocity of the feeding volume is 2.0h-1The hydrogenation reaction performance of NiCu alloy hydrogenation catalysts modified by different carbon nano tubes is researched under the condition, and a sample after 8 hours of stabilization is taken for gas chromatography analysis. The results in table 2 show that the yields of the target higher alcohols are all above 99%, and the highest yield can reach 100%, which indicates that the catalyst synthesized by the invention can efficiently catalyze the hydrogenation reaction of higher aldehydes.
TABLE 2 high alcohol Performance from hydrogenation of high carbon aldehyde catalyzed by different catalysts
Comparative example 1
Preparation of 30Ni5Cu-Al according to the method of catalyst (No. 3)2O3(preparation Process without addition of modificationSexual assistant solution, catalyst No. 11), 35Ni-Al2O3(No modifying assistant solution and copper salt are added in the preparation process, the catalyst is numbered 12) and 35Cu-Al2O3(No. 13 catalyst without adding modifying assistant solution and nickel salt). The influence of the three catalysts and the catalyst No. 3 on the performance of the hydrogenation of isononanol to isononanol was examined according to the reaction conditions of example 5, and a sample after 8 hours of settling was taken for gas chromatography analysis, and the results are shown in Table 3.
TABLE 3 Performance of catalyst of comparative example 1 for hydrogenation of higher aldehyde to higher alcohol
| Catalyst numbering | Conversion (%) | Selectivity (%) |
| 3 | 99.9 | 99.9 |
| 11 | 96.9 | 97.3 |
| 12 | 90.1 | 93.5 |
| 13 | 91.6 | 92.6 |
From the results in tables 2 and 3, it can be seen that the Ni and Cu hydrogenation catalysts alone have lower activity than NiCu alloy hydrogenation catalysts, while the carbon nanotube modified NiCu alloy hydrogenation catalysts can further improve the activity and selectivity of the catalysts than the unmodified NiCu alloy hydrogenation catalysts. The NiCu alloy catalyst modified by the carbon nano tube not only has a hydrotalcite precursor structure, but also can promote the dispersion of active metals Ni and Cu of the catalyst, improve the reducibility of the active metals and the adsorption and activation capacity of raw materials, and realize high-carbon-aldehyde high-conversion-rate high-selectivity hydrogenation.
EXAMPLE 8 hydrogenation of n-nonanal to n-nonanol under different reaction conditions
The catalyst (No. 2) is used for researching the reaction temperature and H of isononanal isononyl alcohol solutions with different mass ratios2Pressure, isononanal mass space velocity, H2The hydrogenation performance was affected by the molar ratio to isononanal, and the results are shown in table 4, after 8h of settling, the sample was taken for gas chromatography analysis. Therefore, under the mild reaction conditions of the invention, such as the temperature of not higher than 130 ℃ and the pressure of not higher than 4MPa, the high-yield (> 96%) synthesis of the isononyl alcohol can be conveniently realized by adjusting the reaction process parameters.
TABLE 4 hydrogenation performance of catalyst (No. 2) under different reaction conditions
Example 9 continuous reaction stability study of catalyst
The mass ratio of isononanal to isononanol is 1: 9, the reaction liquid is heated at 90 ℃ and 3MPa H2Pressure, 3.0h-1Volume space velocity, H2The continuous reaction stability of the catalyst (No. 2) was investigated at a molar ratio of isononanal of 20: 1, and samples were taken every 6-10h for gas chromatography. The results in FIG. 3 show that the catalyst maintains good stability, and the conversion rate of isononanal and the selectivity of isononanol are basically maintained above 99% after running for 500 hours.
In conclusion, the carbon nanotube modified NiCu alloy hydrogenation catalyst provided by the invention has a hydrotalcite precursor structure, and the modification of the carbon nanotube can promote the dispersion of active metal of the catalyst, improve the reducibility of the active metal and the adsorption and activation of raw materials, so that the hydrogenation with high carbon aldehyde, high conversion rate and high selectivity is realized; meanwhile, the preparation method is simple, the production cost is low, the catalyst is good in stability and not easy to sinter and deposit carbon, the corresponding alcohol can be effectively generated by the reaction of aldehyde and hydrogen, and the target high-carbon alcohol is obtained by high-activity and high-selectivity hydrogenation under mild reaction conditions.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. The NiCu alloy hydrogenation catalyst is characterized by comprising a carrier, and a main active component and a modification auxiliary agent which are loaded on the carrier, wherein the main active component and the modification auxiliary agent are uniformly distributed on the surface of the carrier, the main active component is NiCu alloy, and the modification auxiliary agent is a carbon nano tube.
2. The NiCu alloy hydrogenation catalyst of claim 1, wherein: the content of a main active component in the NiCu alloy hydrogenation catalyst is 35-75 wt%, and the mass ratio of Ni to Cu in the NiCu alloy is 3: 1-15: 1; and/or the content of the modification auxiliary agent in the NiCu alloy hydrogenation catalyst is 1-15 wt%.
3. The NiCu alloy hydrogenation catalyst of claim 1, wherein: the carbon nano tube is a multi-walled carbon nano tube, the outer diameter of the multi-walled carbon nano tube is 5-20 nm, the inner diameter of the multi-walled carbon nano tube is 2-5 nm, the length of the multi-walled carbon nano tube is 2-30 mu m, and the specific surface area of the multi-walled carbon nano tube is more than 200m2(ii)/g; and/or, the carrier is Al2O3(ii) a And/or the NiCu alloy hydrogenation catalyst has a hydrotalcite precursor structure;
and/or the grain size of the nickel-copper alloy in the NiCu alloy hydrogenation catalyst is below 6 nm.
4. A process for the preparation of a NiCu alloy hydrogenation catalyst according to any of the claims 1 to 3, characterized in that it comprises: and preparing the NiCu alloy hydrogenation catalyst by adopting a coprecipitation method.
5. The preparation method according to claim 4, characterized by specifically comprising:
and dropwise adding a mixed metal salt solution containing the metal salt of the active component and the metal salt of the carrier and alkali liquor into the modified auxiliary agent solution together to form a mixed solution, and then carrying out precipitation, aging, roasting and reduction treatment to obtain the NiCu alloy hydrogenation catalyst.
6. The method of claim 5, wherein: the total concentration of metal nickel ions, copper ions and carrier metal salts in the mixed metal salt solution is 0.1-1.0 mol/L; preferably, the active component metal salt contained in the mixed metal salt solution comprises nickel salt and copper salt; preferably, the nickel salt comprises nickel nitrate and/or nickel sulfate; preferably, the copper salt comprises copper nitrate and/or copper sulfate;
and/or the metal salt of the support comprises aluminum nitrate and/or aluminum sulfate;
and/or the alkali liquor comprises a hydroxide solution and/or a carbonate solution, preferably comprises any one or the combination of more than two of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and a potassium carbonate solution; preferably, the concentration of the hydroxide solution is 2-6 mol/L, and the concentration of the carbonate solution is 0.4-2 mol/L;
and/or the modification auxiliary agent solution comprises carbon nano tubes and deionized water, wherein the content of the carbon nano tubes in the modification auxiliary agent solution is 1-10 wt%; preferably, the carbon nanotubes are acid-treated carbon nanotubes; preferably, the acid adopted for the acid treatment is concentrated nitric acid, and the time for the acid treatment is 2-8 h.
7. The method of claim 5, wherein: the pH value of the mixed solution during the precipitation treatment is 9.0-11; and/or the temperature of the aging treatment is 80-100 ℃, and the time is 4-24 hours; and/or the roasting treatment process conditions comprise: the adopted atmosphere is inert atmosphere, the roasting treatment temperature is 400-650 ℃, and the roasting treatment time is 3-6 h; preferably, the inert atmosphere comprises a nitrogen or argon atmosphere; and/or the process conditions of the reduction treatment comprise: the adopted atmosphere is a reducing atmosphere, the temperature of reduction treatment is 400-600 ℃, the time is 2-8 h, and the flow rate of reducing gas adopted by each gram of catalyst is 20-100 mL/min; preferably, the reducing atmosphere is a hydrogen atmosphere.
8. Use of the NiCu alloy hydrogenation catalyst of any of claims 1 to 3 for the hydrogenation of higher aldehydes to higher alcohols.
9. A method for preparing high-carbon alcohol by continuously hydrogenating high-carbon aldehyde is characterized by comprising the following steps:
continuously feeding an aldol mixed solution containing a higher carbon aldehyde and an organic alcohol into a fixed bed reactor filled with the NiCu alloy hydrogenation catalyst according to any one of claims 1 to 3 in a hydrogen atmosphere to carry out a liquid phase hydrogenation reaction to obtain a higher carbon alcohol.
10. The method of claim 9, wherein: the process conditions of the hydrogenation reaction comprise: the temperature is 80-150 ℃, the pressure is 1-4 MPa, and the feeding volume space velocity is 1-8 h-1The molar ratio of the hydrogen to the high-carbon aldehyde is 4: 1-30: 1;
and/or the high-carbon aldehyde comprises any one of hexanal, heptanal, octanal, n-nonanal, isononanal, decanal, decenal and undecanal;
and/or the organic alcohol comprises ethanol and a higher alcohol corresponding to a higher aldehyde;
and/or the mass ratio of the high-carbon aldehyde to the organic alcohol in the aldehyde-alcohol mixed solution is 1: 1-20;
and/or the conversion rate of the high-carbon aldehyde in the method is more than 99.5 percent, and the product selectivity is more than 99 percent.
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