CN108579747A - A kind of preparation method of fructose hydrogenation copper base catalyst - Google Patents
A kind of preparation method of fructose hydrogenation copper base catalyst Download PDFInfo
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- CN108579747A CN108579747A CN201810168607.9A CN201810168607A CN108579747A CN 108579747 A CN108579747 A CN 108579747A CN 201810168607 A CN201810168607 A CN 201810168607A CN 108579747 A CN108579747 A CN 108579747A
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- copper
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- catalyst
- mantoquita
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000010949 copper Substances 0.000 title claims abstract description 44
- 229930091371 Fructose Natural products 0.000 title claims abstract description 34
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 34
- 239000005715 Fructose Substances 0.000 title claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 150000001879 copper Chemical class 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 230000001376 precipitating effect Effects 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 46
- 239000000725 suspension Substances 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 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
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 abstract description 31
- 229930195725 Mannitol Natural products 0.000 abstract description 31
- 239000000594 mannitol Substances 0.000 abstract description 31
- 235000010355 mannitol Nutrition 0.000 abstract description 31
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 229960002737 fructose Drugs 0.000 description 28
- 238000010792 warming Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 239000003643 water by type Substances 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000969 carrier Substances 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- 239000012670 alkaline solution Substances 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000000214 mouth Anatomy 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- PJVXUVWGSCCGHT-ZPYZYFCMSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;(3s,4r,5r)-1,3,4,5,6-pentahydroxyhexan-2-one Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO PJVXUVWGSCCGHT-ZPYZYFCMSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 208000009304 Acute Kidney Injury Diseases 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 208000010412 Glaucoma Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 206010020852 Hypertonia Diseases 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 208000033626 Renal failure acute Diseases 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 201000011040 acute kidney failure Diseases 0.000 description 1
- 208000012998 acute renal failure Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007910 chewable tablet Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- 235000019534 high fructose corn syrup Nutrition 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000013215 result calculation Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/394—
-
- 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
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
-
- 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
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07C29/143—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 ketones
- C07C29/145—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 ketones with hydrogen or hydrogen-containing gases
Abstract
The invention discloses a kind of preparation method and applications of fructose hydrogenation copper base catalyst, and catalyst is prepared using deposition-precipitation method.Precursor substance is made using different alkaline precipitating agents, copper salt solution, oxide carrier.After being filtered, washed, drying, precursor substance is pulverized.Under air atmosphere, oxide is formed in Muffle kiln roasting with 300 450 DEG C of temperature.Then it is transferred in tube furnace, in atmosphere of hydrogen, is restored with 200 300 DEG C of temperature, form carried copper-base catalyst.A certain amount of copper-based catalysts produced by the present invention, water, organic solvent and fructose reaction is taken to can be prepared by mannitol.Copper-based catalysts dispersion degree produced by the present invention is high, particle is small, there is higher catalytic activity.Copper-based catalysts prepared by the present invention apply to fructose Hydrogenation for mannitol, and hydroconversion condition mitigates, and catalyst stability and selectivity are good, and catalyst preparation is of low cost, there is very high application value.
Description
Technical field
The present invention relates to the preparing technical fields of mannitol, and in particular to a kind of preparation of fructose hydrogenation copper base catalyst and
Using.
Background technology
Mannitol is a kind of hexitol, pleasantly sweet because absorbing heat when dissolving, has comfort sense to oral cavity, therefore is widely used in and sobers up
The manufacture of the chewable tablets such as freshener in medicine, mouth.The tissue dewatering agent of it or a kind of hypertonicity is clinically applied to treatment brain water
Swollen, glaucoma；Prevent acute renal failure, accelerates the excretion of poisonous substance and drug from kidney；It is used as blood vessel expansion in hypertension therapeutic
Open agent.In recent years, due to being applied in the diversification of medical treatment, food, cosmetics etc., the demand to mannitol greatly increases.
The yield for how improving mannitol, requires further study.
Currently, industrial production mannitol mainly there are two kinds of techniques in the world, one is using kelp as raw material, seaweed is being produced
While hydrochlorate, the kelp-soaking liquid after iodine will be carried, through multiple concentrate, removal of impurities, ion-exchange, evaporation and concentration, crystallisation by cooling and obtain；One
Kind is made by catalytic hydrogenation using sucrose, glucose, fructose as raw material.The former cost is higher, thus, the side of catalytic hydrogenation
It is current industrial main method that method, which prepares mannitol,.Mannitol can be former with fructose or Glucose-Fructose mixture
Material is made using Raney's nickel as catalyst to catalyzing hydrogenating, but selectivity is low, and yield is generally 45%.Heinen A W,
Peters J A, Van B H et al. by promoting Pd/C and Pt/C loaded noble metal catalysts Hydrogenation for mannitol with Sn,
It is selectively 60%, yield 56%.But noble metal catalyst, it is expensive.Zhu Jianliang etc. using copper-based the study found that urged
Agent catalysis fructose prepares mannitol, and the selectivity of reaction can reach 70%, and mannitol yield is 46%.Zhang J,Wu
S, Liu Y et al. carries out fructose using magnetic catalyst Ni/Cu/Al/Fe hydrotalcite-based compounds and adds hydrogen.It is sweet on magnetic catalyst
The desirable yield for revealing alcohol is 56.9%.In summary, the preparation condition of the property and catalyst of metal and carrier is in mannitol
It plays an important role in selective hydrogenation.Copper-based catalysts are applied to fructose because of its higher mannitol selectivity
Hydrogenation is for mannitol.However, existing copper-based catalysts for fructose Hydrogenation for mannitol, generally existing activity it is not high or
The problem of severe reaction conditions, need to be improved and be optimized.
Invention content
Insufficient existing for current catalyst to solve, the purpose of the present invention is to provide a kind of dispersion degree height, metallic particles
The small copper-based catalysts for having greater activity；Mannitol is prepared under catalyst action prepared by this method, reaction condition is mild, former
Expect conversion ratio and mannitol high selectivity.
In order to realize that above-mentioned target, the present invention adopt the following technical scheme that
A kind of preparation method of fructose hydrogenation copper base catalyst, includes the following steps：
(1) mantoquita is added in deionized water and is dissolved, form the copper salt solution A of a concentration of 0.2~0.6mol/L；
(2) alkaline precipitating agent is dissolved in deionized water, forms the solution C of a concentration of 0.4~1.2mol/L；
(3) at a temperature of 50~70 DEG C, simultaneously by copper salt solution A obtained by step (1) and acquired solution C in step (2)
It is added dropwise in solid phase carrier, is uniformly mixed under stiring after being added dropwise, it is 6~9 to adjust pH value；Keep temperature constant, aging 2
~8h forms slurries D；The amount of substance of the solution C in terms of alkaline precipitating agent with copper salt solution A in terms of mantoquita is than 1：1~2；
The mass ratio of the solid phase carrier and mantoquita in the copper salt solution A is 1~5：1 (preferably 2：1)；
(4) gained slurries D is filtered while hot, is washed with deionized 3~5 times, acid ion is removed, at 80~100 DEG C
At a temperature of dry 9~12h, obtain catalyst precarsor substance E；
(5) by gained catalyst precarsor substance E grind into powder, with 300~450 DEG C of temperature calcination 2 in Muffle furnace
~8 hours, soild oxide F is formed in air atmosphere；
(6) obtained solid oxide F is put into tube furnace, is passed through hydrogen, temperature is controlled at 200 DEG C~300 DEG C, reduction
2~4h forms carried copper-base catalyst, i.e., the described fructose hydrogenation copper base catalyst after natural cooling.
Further, it can also be carried out as follows in abovementioned steps (3)：The step (3) is first in the middle gained copper of step (1)
Solid phase carrier is added in salting liquid A, forms suspension B；Again at a temperature of 50~70 DEG C, acquired solution C in step (2) is instilled
In gained suspension B or by acquired solution C in gained suspension B instillation steps (2), it is uniformly mixed under stiring after being added dropwise,
It is 6~9 to adjust pH value；Keep temperature constant, 2~8h of aging forms slurries D；The solution C is in terms of alkaline precipitating agent and mantoquita
The amount of substance of the solution A in terms of mantoquita is than 1：1~2；The mass ratio of the solid phase carrier and mantoquita in the copper salt solution A is 1
~5：1.
Further, in abovementioned steps (3), solution C is preferably added drop-wise in suspension B by dropwise addition mode.
Further, in abovementioned steps (1), the mantoquita is one or both of copper nitrate, copper chloride, preferably nitric acid
Copper.
Further, the solid phase carrier is AI2O3、ZrO2、ZnO、CeO2, activated carbon, TiO2In it is one or more, preferably
For activated carbon.
Further, in abovementioned steps (2), the alkaline precipitating agent is sodium carbonate, potassium carbonate, potassium hydroxide, sodium bicarbonate
In one or more, preferably potassium carbonate.
Further, in abovementioned steps (6), the flow control of the hydrogen is in 50~70cm3/min。
The present invention also provides the methods using the fructose hydrogenation copper base catalyst preparation mannitol, including walk as follows
Suddenly：
(A) deionized water, organic solvent, fructose and the fructose hydrogenation copper base catalyst are added in autoclave, it will
Autoclave seals, and is replaced 3~7 times with hydrogen；
(B) when the temperature of autoclave rises to 50~100 DEG C of reaction temperature, hydrogen make-up makes the pressure of reaction kettle reach
1~5MPa, turn on agitator are reacted, and the reaction time is 8~15h；
(C) after reaction, when temperature of reaction kettle is cooled to 30~40 DEG C, product and catalyst in kettle are taken out, is filtered,
After drying, hybrid solid is obtained, after gained hybrid solid is dissolved, by Crystallization Separation, by-product is removed, is obtained after dry sweet
Reveal alcohol product.
Preferably, (solvent is the mixture of organic solvent and deionized water, mass ratio 6 to solvent in step (A):4), fruit
Sugar and the mass ratioes of copper-based catalysts are：(150~230):(10~60):(1~6).
It is highly preferred that organic solvent is one or more in propylene glycol, ethyl alcohol, isopropanol in step (A).
It is highly preferred that the rotating speed of blender is 500~800r/min in step (B).
It is highly preferred that the mode of Crystallization Separation described in step (C) is multiple condensing crystallizing.
More preferably, hybrid solid described in step (C) is dissolved in ethanol solution.
The invention has the beneficial effects that：The present invention can be prepared that a kind of dispersion degree is high, metallic particles is small, has higher work
The copper-based catalysts of property；This method prepare catalyst action under prepare mannitol, reaction condition is mild, feed stock conversion and
Mannitol high selectivity, and reaction process is environmentally protective.
Description of the drawings
Fig. 1-3 is the TEM figures of catalyst prepared by embodiment 3.
Specific implementation mode
Specific introduce is made to the present invention in conjunction with following specific examples.
Embodiment 1
The preparation method of fructose hydrogenation copper base catalyst includes the following steps：
1, by 5g Cu (NO3)2.3H2O, which is added in 100mL deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+'s
Molar concentration is 0.2mol/L；10g absorbent charcoal carriers are added into copper salt solution A, form suspension B；
2, by precipitating reagent 2g NaHCO3It is added in 50mL deionized waters and dissolves, form alkaline solution C；Solution C it is mole dense
Degree is 0.8mol/L；
3, at a temperature of 60 DEG C, solution C is all instilled in suspension B, stirs evenly, adjusts in 250mL three-necked flasks
It is 7 to save pH value.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 2
The preparation process of the present embodiment and embodiment 1 are substantially similar, and the main distinction is step 2 neutral and alkali precipitating reagent, tool
Steps are as follows for body：
1, by 5g Cu (NO3)2.3H2O, which is added in 100ml deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+'s
Molar concentration is 0.2mol/L；10g absorbent charcoal carriers are added into copper salt solution A, form suspension B；
2, by precipitating reagent 2.15gNa2CO3It is dissolved in 50ml deionized waters, forms alkaline solution C；Solution C it is mole dense
Degree is 0.4mol/L.
3, at a temperature of 60 DEG C, solution C is all instilled in suspension B, stirs evenly, adjusts in 250mL three-necked flasks
It is 7 to save pH value.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 3
The preparation process of the present embodiment and embodiment 2 are substantially similar, and the main distinction is step 2 neutral and alkali precipitating reagent, tool
Steps are as follows for body：
1, by 5gCu (NO3)2.3H2O, which is added in 100ml deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+'s
Molar concentration is 0.2mol/L；10g absorbent charcoal carriers are added into copper salt solution A, form suspension B；
2, by 2.8g precipitating reagents K2CO3It is dissolved in 50ml deionized waters, forms alkaline solution C；The molar concentration of solution C
For 0.4mol/L.
3, at a temperature of 60 DEG C, solution C is all instilled in suspension B, stirs evenly, adjusts in 250mL three-necked flasks
It is 7 to save pH value.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 4
The preparation process of the present embodiment and embodiment 3 are substantially similar, and the main distinction is step 2 neutral and alkali precipitating reagent, tool
Steps are as follows for body：
1, by 5gCu (NO3)2.3H2O, which is added in 100ml deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+'s
Molar concentration is 0.2mol/L；10g absorbent charcoal carriers are added into copper salt solution A, form suspension B；
2, precipitating reagent 2.3gKOH is dissolved in 50ml deionized waters, forms alkaline solution C；The molar concentration of solution C is
0.8mol/L。
3, at a temperature of 60 DEG C, solution C is all instilled in suspension B, stirs evenly, adjusts in 250mL three-necked flasks
It is 7 to save pH value.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 5
The preparation process of the present embodiment and embodiment 3 are substantially similar, and the main distinction is the mantoquita in step 1, specific to walk
It is rapid as follows：
1, by 2.7gCuCI2It is added in 100ml deionized waters and dissolves, form copper salt solution A；Cu in solution A2+It is mole dense
Degree is 0.2mol/L；10g absorbent charcoal carriers are added into copper salt solution A, form suspension B；
2, by precipitating reagent 2.8gK2CO3It is dissolved in 50ml deionized waters, forms alkaline solution C；The molar concentration of solution C
For 0.4mol/L.
3, at a temperature of 60 DEG C, solution C is all instilled in suspension B, stirs evenly, adjusts in 250mL three-necked flasks
It is 7 to save pH value.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 6
The preparation process of the present embodiment and embodiment 3 are substantially similar, and the main distinction is the titration mode in step 3, tool
Steps are as follows for body：
1, by 5gCu (NO3)2.3H2O, which is added in 100ml deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+'s
Molar concentration is 0.2mol/L；10g absorbent charcoal carriers are added into copper salt solution, form suspension B；
2, by 2.8g precipitating reagents K2CO3It is dissolved in 50ml deionized waters, forms alkaline solution C；The molar concentration of solution C
For 0.4mol/L.
3, at a temperature of 60 DEG C, suspension B is all instilled in solution C, stirs evenly, adjusts in 250mL three-necked flasks
It is 7 to save pH value.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 7
The preparation process of the present embodiment and embodiment 6 are substantially similar, and the main distinction is the titration mode in step 3, tool
Steps are as follows for body：
1, by 5gCu (NO3)2.3H2O, which is added in 50ml deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+Rub
You are a concentration of 0.4mol/L.
2, by precipitating reagent 2.8gK2CO3It is dissolved in 50ml deionized waters, forms alkaline solution C；The molar concentration of solution C
For 0.4mol/L.
3, at a temperature of 60 DEG C, solution A and solution C are instilled to the 50ml suspensions for being mixed with 10g absorbent charcoal carriers simultaneously
It in liquid, is stirred evenly in 250mL three-necked flasks, it is 7 to adjust pH value.After dripping, keep temperature constant, aging 2h is formed
Slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 8
The present embodiment is roughly the same with embodiment 3, and the main distinction is Cu2+Molar concentration, be as follows：
1, by 14.5gCu (NO3)2.3H2O, which is added in 100ml deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+
Molar concentration be 0.6mol/L；10g absorbent charcoal carriers are added into copper salt solution A, form suspension B；
2, by precipitating reagent 8.5g K2CO3It is dissolved in deionized water, forms alkaline solution C；The molar concentration of solution C is
1.2mol/L。
3, at a temperature of 60 DEG C, solution C is instilled in suspension B, is stirred evenly in 250mL three-necked flasks, adjust pH
Value is 7.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 9
The present embodiment uses different carriers, investigates influence of the carrier to experimental result, is as follows：
1, by 5g Cu (NO3)2.3H2O, which is added in 100ml deionized waters, to be dissolved, and copper salt solution A is formed；Cu in solution A2+'s
Molar concentration is 0.2mol/L；10g carriers (AI is added into copper salt solution A2O3、ZrO2、ZnO、CeO2, activated carbon, TiO2), shape
At suspension B；
2, by precipitating reagent 2.8g K2CO3It is dissolved in 50ml deionized waters, forms alkaline solution C；The molar concentration of solution C
For 0.4mol/L.
3, at a temperature of 60 DEG C, solution C is instilled in suspension B, is stirred evenly in 250mL three-necked flasks, adjust pH
Value is 7.After dripping, keep temperature constant, aging 2h forms slurries D；
4, slurries D is filtered while hot, is washed with deionized 5 times, remove acid ion.It is dry at a temperature of 85 DEG C
10h obtains catalyst precarsor E.
5, the catalyst precarsor substance E grind into powder that will be obtained, is warming up in Muffle furnace with the speed of 5 DEG C/min
425 DEG C of roasting 5h, form soild oxide F in air atmosphere.
6, soild oxide F is put into tube furnace, is passed through 20cm3The hydrogen of/min empties 30min.After excluding air,
285 DEG C are warming up to the speed of 5 DEG C/min, reductase 12 h.After natural cooling, carried copper-base catalyst is formed.
Embodiment 10
Take the copper-based catalysts prepared in above-described embodiment 1~9 of phase homogenous quantities to fructose Hydrogenation for mannitol, tool
Steps are as follows for body：
(1) it is according to the mass ratio of solvent, fructose and copper-based catalysts：230：20：1 will be added to after each material mixing
In 500ml autoclaves, wherein accurate measuring solvent 230ml (ethyl alcohol 140ml, deionized water 90ml), fructose 20g, cupper-based catalyst
Agent 1g.Autoclave is sealed, is replaced 5 times with hydrogen；
(2) hydrogen is passed through into autoclave makes the pressure of reaction kettle reach 4MPa, when the temperature liter of autoclave
To 100 DEG C of reaction temperature, turn on agitator is reacted.Reaction time is 12h；
(3) after reaction, when temperature of reaction kettle is cooled to 30 DEG C, product and catalyst in kettle are taken out.It filters, it is dry
Afterwards, hybrid solid is obtained.After solid is dissolved with ethyl alcohol, by Crystallization Separation, by-product is removed, mannitol production is obtained after dry
Product.
In order to preferably illustrate the present invention, the homemade catalyst in laboratory is changed into commercial copper-based catalysts, specific steps
It is similar with embodiment 10.
The fructose that the catalyst to catalyzing hydrogenating prepared by embodiment 1-8 using efficient liquid phase chromatographic analysis is obtained adds hydrogen to produce
Object.And according to the conversion ratio of Analysis result calculation fructose, the yield of the selectivity of copper-based catalysts and mannitol, correlated results is shown in
Table 1.The catalyst prepared in analysis embodiment 9 adds fructose the product of hydrogen, correlated results to be shown in Table 2.It is evaluated according to experimental result
Catalyst correlated performance.
Influence of the catalyst to the catalytic performance of fructose Hydrogenation mannitol obtained by 1 embodiment 1-8 of table
| Embodiment | Fructose converting rate | The selectivity of copper-based catalysts | The yield of mannitol |
| 1 | 88% | 65% | 57% |
| 2 | 94% | 67% | 63% |
| 3 | 98% | 79% | 78% |
| 4 | 75% | 64% | 48% |
| 5 | 90% | 68% | 61% |
| 6 | 80% | 66% | 52% |
| 7 | 95% | 75% | 71% |
| 8 | 80% | 65% | 52% |
| Commercial copper-based catalysts | 85% | 61% | 52% |
Influence of 2 embodiment of table, the 9 gained catalyst to the catalytic performance of fructose Hydrogenation mannitol
| Select carrier | Fructose converting rate | The selectivity of copper-based catalysts | The yield of mannitol |
| AI2O3 | 90% | 60% | 54% |
| ZrO2 | 96% | 66% | 63% |
| ZnO | 88% | 60% | 53% |
| CeO2 | 55% | 63% | 35% |
| Activated carbon | 98% | 79% | 78% |
| TiO2 | 85% | 62% | 53% |
By data analysis in embodiment 1-4 in table it is found that in the preparation process of catalyst, to be precipitated in embodiment 3
K is selected in agent2CO3, the copper-based catalysts effect of preparation is more preferable.
By data analysis in 1,5 it is found that in the preparation process of catalyst, Cu is selected with mantoquita in embodiment 3
(NO3)2.3H2O, the selective highest of conversion ratio and mannitol to fructose.
By data analysis in embodiment in table 1,6,7 it is found that in the preparation process of catalyst, coprecipitation mode is to implement
Select the copper-based catalysts effect that solution C is added drop-wise to the preparation of the dropwise addition method in suspension B more preferable in example 3.
By the experimental data in table 2 it is found that selecting activated carbon to be used as catalyst prepared by carrier, to the conversion ratio of fructose
With the selective highest of mannitol.
In conclusion preferably, the conversion ratio to fructose is for the catalytic performance of catalyst obtained and selectivity in embodiment 3
98%, and the yield of mannitol is up to 78%.
Claims (7)
1. a kind of preparation method of fructose hydrogenation copper base catalyst, it is characterised in that the preparation method includes the following steps：
(1) mantoquita is added in deionized water and is dissolved, form the copper salt solution A of a concentration of 0.2~0.6mol/L；
(2) alkaline precipitating agent is dissolved in deionized water, forms the solution C of a concentration of 0.4~1.2mol/L；
(3) at a temperature of 50~70 DEG C, copper salt solution A and acquired solution C in step (2) obtained by step (1) is instilled simultaneously
It into solid phase carrier, is uniformly mixed under stiring after being added dropwise, it is 6~9 to adjust pH value；Keep temperature constant, aging 2~
8h forms slurries D；The amount of substance of the solution C in terms of alkaline precipitating agent with copper salt solution A in terms of mantoquita is than 1：1~2；Institute
The mass ratio for stating solid phase carrier and mantoquita in the copper salt solution A is 1~5：1；
(4) gained slurries D is filtered while hot, is washed with deionized 3~5 times, acid ion is removed, in 80~100 DEG C of temperature
The lower dry 9~12h of degree, obtains catalyst precarsor substance E；
(5) by gained catalyst precarsor substance E grind into powder, with 300~450 DEG C of 2~8h of temperature calcination in Muffle furnace,
Soild oxide F is formed in air atmosphere；
(6) obtained solid oxide F is put into tube furnace, is passed through hydrogen, temperature control at 200 DEG C~300 DEG C, reductase 12~
4h forms carried copper-base catalyst, i.e., the described fructose hydrogenation copper base catalyst after natural cooling.
2. preparation method as described in claim 1, it is characterised in that：The step (3) is first in the middle gained mantoquita of step (1)
Solid phase carrier is added in solution A, forms suspension B；Again at a temperature of 50~70 DEG C, acquired solution C in step (2) is instilled into institute
It obtains in suspension B or by acquired solution C in gained suspension B instillation steps (2), is uniformly mixed under stiring after being added dropwise, adjusted
It is 6~9 to save pH value；Keep temperature constant, 2~8h of aging forms slurries D；The solution C is molten with mantoquita in terms of alkaline precipitating agent
The amount of substances of the liquid A in terms of mantoquita is than 1：1~2；In the solid phase carrier and the copper salt solution A mass ratio of mantoquita be 1~
5：1.
3. preparation method as claimed in claim 1 or 2, it is characterised in that：In step (1), the mantoquita is copper nitrate, chlorination
One or both of copper.
4. preparation method as claimed in claim 1 or 2, it is characterised in that：The solid phase carrier is AI2O3、ZrO2、ZnO、
CeO2, activated carbon, TiO2In it is one or more.
5. preparation method as claimed in claim 1 or 2, it is characterised in that：In step (2), the alkaline precipitating agent is carbonic acid
It is one or more in sodium, potassium carbonate, potassium hydroxide, sodium bicarbonate.
6. preparation method as claimed in claim 2, it is characterised in that：In step (3), dropwise addition mode is to be added drop-wise to solution C
In suspension B.
7. preparation method as claimed in claim 1 or 2, it is characterised in that：In step (6), the flow control of the hydrogen exists
50~70cm3/min。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115364856A (en) * | 2022-09-20 | 2022-11-22 | 西北工业大学 | Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof |
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Application publication date: 20180928 |