CN107970932A - A kind of catalytic cellulose converts polynary alcohol catalyst and preparation method thereof and application method - Google Patents
A kind of catalytic cellulose converts polynary alcohol catalyst and preparation method thereof and application method Download PDFInfo
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- CN107970932A CN107970932A CN201711183119.7A CN201711183119A CN107970932A CN 107970932 A CN107970932 A CN 107970932A CN 201711183119 A CN201711183119 A CN 201711183119A CN 107970932 A CN107970932 A CN 107970932A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 106
- 239000001913 cellulose Substances 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 32
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 239000002048 multi walled nanotube Substances 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910020628 SiW12O40 Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 239000012047 saturated solution Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 241000370738 Chlorion Species 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 230000000640 hydroxylating effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 7
- 230000009466 transformation Effects 0.000 abstract description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 81
- 239000000047 product Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010905 bagasse Substances 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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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
- B01J23/76—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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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
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Abstract
The invention belongs to polyalcohol catalyst field, and in particular to a kind of catalytic cellulose converts polynary alcohol catalyst and preparation method thereof and application method.The present invention is using carbon carrier as catalyst carrier, using two-step method first in its area load heteropoly acid, supported active metals component on this basis again, two kinds of functions of catalyzing hydrolysis and catalytic hydrogenation are concentrated on into a kind of catalyst, the hydrolysis of cellulose and hydrogenation are concentrated on into primary first-order equation process during use, cellulose has been simplified to the step of converting of polyalcohol, has improved transformation efficiency.The specific surface area of catalyst of catalytic cellulose conversion polyalcohol of the present invention is big, and heat endurance is good, and loss of active component is few, and cellulose high conversion rate, catalyst is easily separated with reaction product, can be recycled, and is a kind of green catalyst of good performance.The preparation process and use process of the polynary alcohol catalyst of catalytic cellulose conversion of the present invention are simple, and non-environmental-pollution is low for equipment requirements.
Description
Technical field
The invention belongs to catalytic cellulose to convert polyalcohol catalyst field, and in particular to a kind of catalytic cellulose conversion is more
First alcohol catalyst and preparation method thereof and application method.
Background technology
As the increasingly reduction of fossil resources and environmental problem constantly deteriorate, biomass resource is because of its recyclability, dioxy
Changing the good environment effects such as carbon zero-emission becomes the focus of global concern.Cellulose is widely present in agriculture as non-cereal crops
Woods discarded object, such as maize straw, bagasse and discarded sawdust, are biomass resources most abundant on the earth, annual output
More than 100,000,000,000 tons.Cellulose is a kind of straight-chain polysaccharide macromolecule formed by β-D-Glucose by β -1,4- glucosides key connections
Compound.By chemical catalysis means, cellulose through hydrolyze hydrogenation coupled reaction can be converted into polyalcohol, as sorbierite, glycerine,
Ethylene glycol and propane diols etc., these polyalcohols be considered as a new generation greening platform compound, available for production bio-fuel-oil,
Chemicals etc..
The reaction process of cellulose conversion polyalcohol includes：(1) hydrolysis of cellulose；(2) hydrolysate is hydrogenated to more
First alcohol.Method for transformation main at present is that, first with inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, heteropoly acid, hydrolyzes cellulose
It is then rapid Hydrogenation under Ru, Ni isoreactivity metallic catalyst catalytic action in carrying active component into monose and oligosaccharide
Obtain polyalcohol.There is the problem of acid separation and recovery in this method, in addition, reaction temperature is higher, acid under the high temperature conditions, to anti-
Answer the requirement of equipment very high.
The content of the invention
To solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of catalytic cellulose convert polynary alcohol catalyst and
Its preparation method and application method.
Technical solution of the present invention：
It is carried heteropoly acid and activity at the same time on the carbon carrier that a kind of catalytic cellulose of the present invention, which converts polynary alcohol catalyst,
Metal salt is made, and the carbon carrier is carbon nanotubes, and the heteropoly acid is H4SiW12O40、H3PW12O40One or both of
Mixture, the active metal salt are RuCl3Or Ni (NO3)2·6H2One or both of O.
The preparation method step that a kind of catalytic cellulose of the present invention converts polynary alcohol catalyst is as follows：
Step 1：Heteropoly acid saturated solution is prepared, carbon carrier is added in heteropoly acid saturated solution, at a certain temperature
Ultrasonic immersing is carried out, carbon carrier taking-up drains away the water after completing ultrasonic immersing, is dried in vacuo, the carbon that carried heteropoly acid is made carries
Body；
Step 2：Active metal salt is configured to the stablizing solution of certain mass concentration；
Step 3：The carbon carrier for the carried heteropoly acid that step 1 is obtained adds active metal salt solution made from step 2
In, ultrasonic immersing at a certain temperature, the collected by suction carbon carrier of carried heteropoly acid and active metal salt at the same time after dipping,
It is dried in vacuo after the carbon carrier is washed with deionized, the carbon carrier is carried out at a certain temperature using reducing gas
Reduction treatment, completes reduction treatment postcooling to room temperature, obtains catalytic cellulose and convert polynary alcohol catalyst.
Further, heteropoly acid described in step 1 is H4SiW12O40、H3PW12O40One or both of mixture；Institute
It is carbon nanotubes to state carbon carrier；The ultrasonic immersing is ultrasonic immersing 20-180min at 60-120 DEG C；The vacuum drying is
50-120 DEG C of vacuum drying 12h.
Further, the carbon nanotubes is short hydroxyl multi-walled carbon nano-tube or short functionalized multi-wall carbonnanotubes, its
In short hydroxyl multi-walled carbon nano-tube purity>98%, outer diameter length 20nm-30nm, 30nm-50nm,>50nm, interior path length
It is 0.5-2 μm to spend for 5-15nm, length, specific surface area>90m2/g、>110m2/g、>160m2/ g, contained-OH mass fractions are
0.71wt% -1.76wt%；The purity of wherein short functionalized multi-wall carbonnanotubes>98%, outer diameter length 20nm-30nm,
30nm-50nm、>50nm, interior electrical path length are 5-15nm, and length is 0.5-2 μm, specific surface area>90m2/g、>170m2/g、>
200m2/ g, contained-COOH mass fractions are 0.49wt%-2.0wt%.
Further, active metal salt described in step 2 is RuCl3Or Ni (NO3)2·6H2One or both of O, institute
It is 0.1-30% to state active metal salt solution mass concentration.
Further, active metal salt solution described in step 2 is RuCl3With Ni (NO3)2·6H2During O mixed solutions, institute
State mixed solution to be the RuCl for being 0.1-30% by mass concentration3Solution and Ni (NO3)2·6H2O solution is 1- by volume
16:4 ratio is formulated.
Further, ultrasonic immersing described in step 3 is 45 DEG C of ultrasonic immersing 20-240min；The deionized water washing time
Number is 5-8 times, when containing RuCl in active metal salt solution made from step 23When, wash into deionized water cleaning solution and examine
Untill not detecting chlorion；The vacuum drying time is 24h；The reducing gas is that volume ratio is 1:1 nitrogen and hydrogen
Mixed gas；The reduction treatment is reductase 12-8h at a temperature of 150-600 DEG C, and reducing gas flow is 150mL/min；It is described
Be cooled to room temperature is cooled down in hydrogen atmosphere.
The application method that a kind of catalytic cellulose of the present invention converts polynary alcohol catalyst is by a certain percentage by catalysis fibre
Element converts polynary alcohol catalyst, cellulose and deionized water and is added in autoclave, uses high pure nitrogen after sealing at room temperature
Air in replacement reaction kettle, the high-purity hydrogen of certain pressure intensity is passed through into autoclave, in certain reaction temperature and stirring
Hydrogenation reaction is hydrolyzed under speed；After reaction, product liquid is collected, the product liquid is that polyalcohol mixing is molten
Liquid.
Further, the cellulose is dried in vacuo the cellulose obtained by 2-30h at a temperature of being 40-80 DEG C；The fiber
The mass ratio that element converts polynary alcohol catalyst with catalytic cellulose is 3-20:1；The quality volume of the cellulose and deionized water
Than for 1g:10-60mL.
Further, the pressure of the high-purity hydrogen is 3-10MPa, and the temperature of the hydrolysis hydrogenation reaction is 120-300
DEG C, mixing speed 100-300rpm, reaction time 2-24h.
Beneficial effects of the present invention：
1st, catalytic cellulose conversion polyalcohol specific surface area of catalyst of the present invention is big, and heat endurance is good, loss of active component
Few, cellulose high conversion rate, catalyst is easily separated with reaction product, can be recycled, and is a kind of green catalysis of good performance
Agent.
2nd, catalytic cellulose of the present invention converts polynary alcohol catalyst and concentrates on two kinds of functions of catalyzing hydrolysis and catalytic hydrogenation
A kind of catalyst, primary first-order equation process is concentrated on during use by the hydrolysis of cellulose and hydrogenation, has simplified cellulose to more
The step of converting of first alcohol, improves transformation efficiency.
3rd, catalytic cellulose of the present invention converts the preparation process of polynary alcohol catalyst and simple, no environment using process
Pollution, it is low for equipment requirements, meet the requirement of Green Chemistry, application prospect is good, is converted using catalytic cellulose of the present invention more
First alcohol catalyst carries out the preparation of polyalcohol, can mitigate the pressure for preparing polyalcohol using fossil as raw material for a long time, raw materials for production
It is renewable, it can improve the ecological environment and reduce the discharge of carbon dioxide, there is significant Social benefit and economic benefit.
Brief description of the drawings
Fig. 1 is the preparation method and application method process flow chart that catalytic cellulose of the present invention converts polynary alcohol catalyst.
Embodiment
Technical scheme is described further with reference to embodiment, but is not limited thereto, it is every right
Technical solution of the present invention technical scheme is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention, should all contain
Cover in protection scope of the present invention.
Embodiment 1
Catalytic cellulose provided in this embodiment convert polynary alcohol catalyst be on the carbon carrier at the same time carried heteropoly acid and
Active metal salt is made, and the carbon carrier is carbon nanotubes, and the heteropoly acid is H4SiW12O40、H3PW12O40In one kind or two
The mixture of kind, the active metal salt is RuCl3Or Ni (NO3)2·6H2One or both of O.
The preparation method step that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst is as follows：
Step 1：Prepare H4SiW12O40、H3PW12O40One or both of saturated solution, carbon nanotubes carbon carrier is added
Enter into above-mentioned heteropoly acid saturated solution, the ultrasonic immersing 20-180min at 60-120 DEG C, by carbon carrier after completion ultrasonic immersing
Taking-up drains away the water, 50-120 DEG C of vacuum drying 12h, and the carbon carrier of carried heteropoly acid is made；
The carbon nanotubes is short hydroxyl multi-walled carbon nano-tube or short functionalized multi-wall carbonnanotubes, wherein short hydroxylating
The purity of multi-walled carbon nanotube>98%, outer diameter length 20nm-30nm, 30nm-50nm,>50nm, interior electrical path length are 5-15nm,
Length is 0.5-2 μm, specific surface area>90m2/g、>110m2/g、>160m2/ g, contained-OH mass fractions for 0.71wt%-
1.76wt%；The purity of wherein short functionalized multi-wall carbonnanotubes>98%, outer diameter length 20nm-30nm, 30nm-50nm,>
50nm, interior electrical path length are 5-15nm, and length is 0.5-2 μm, specific surface area>90m2/g、>170m2/g、>200m2/ g, contained-
COOH mass fractions are 0.49wt%-2.0wt%.
Step 2：By RuCl3Or Ni (NO3)2·6H2It is 0.1-30%'s that one or both of O, which is configured to mass concentration,
Stablizing solution；The active metal salt solution is RuCl3With Ni (NO3)2·6H2During O mixed solutions, the mixed solution be by
Mass concentration is the RuCl of 0.1-30%3Solution and Ni (NO3)2·6H2O solution is 1-16 by volume:4 ratio is prepared
Form.
Step 3：The carbon carrier for the carried heteropoly acid that step 1 is obtained adds active metal salt solution made from step 2
In, 45 DEG C of ultrasonic immersing 20-240min, the carbon of carried heteropoly acid and active metal salt carries collected by suction at the same time after dipping
Body, vacuum drying 24h after the carbon carrier is washed with deionized 5-8 times, is 1 using volume ratio:1 nitrogen and hydrogen
Mixed gas carries out reduction treatment 2-8h, reducing gas stream at a temperature of 150-600 DEG C as reducing gas to the carbon carrier
Measure as 150mL/min, be cooled to room temperature after completing reduction treatment in hydrogen atmosphere, obtain catalytic cellulose conversion polyalcohol and urge
Agent.Ultrasonic immersing method can be such that active ingredient is uniformly dispersed in solution, lift the effect of dip loading.
The application method that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst is by cellulose and catalysis fibre
The mass ratio that element converts polynary alcohol catalyst is 3-20:1st, cellulose and the mass volume ratio of deionized water are 1g:10-60mL's
Catalytic cellulose converts polynary alcohol catalyst by ratio, the cellulose obtained by 2-30h is dried in vacuo at a temperature of 40-80 DEG C and go from
Sub- water is added in the stainless steel autoclave with polytetrafluoroethyllining lining, and the addition of deionized water must not exceed stainless
The 2/3 of steel autoclave solvent, uses the air in high pure nitrogen replacement reaction kettle, into autoclave at room temperature after sealing
The high-purity hydrogen of 3-10MPa is passed through, at a temperature of 120-300 DEG C, hydrogenation reaction is hydrolyzed with 100-300rpm mixing speeds,
Reaction time is 2-24h, after reaction, collects product liquid, the product liquid is polynary mixed alkoxide solution.
Embodiment 2
It is same on short hydroxyl multi-walled carbon nano-tube that catalytic cellulose provided in this embodiment, which converts polynary alcohol catalyst I,
When load H3PW12O40And RuCl3It is made.
The preparation method step that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst I is as follows：
Step 1：Prepare H3PW12O40Saturated solution, adds short hydroxyl multi-walled carbon nano-tube as carbon carrier
H3PW12O40In saturated solution, the ultrasonic immersing 60min at 90 DEG C, by short hydroxyl multi-walled carbon nano-tube after completion ultrasonic immersing
Taking-up drains away the water, and 90 DEG C of vacuum drying 12h, are made load H3PW12O40Short hydroxyl multi-walled carbon nano-tube；
The purity of the short hydroxyl multi-walled carbon nano-tube>98%, outer diameter length 20nm-30nm, 30nm-50nm,>
50nm, interior electrical path length are 5-15nm, and length is 0.5-2 μm, specific surface area>90m2/g、>110m2/g、>160m2/ g, contained-OH
Mass fraction is 0.71wt% -1.76wt%；
Step 2：By RuCl3It is configured to the stablizing solution 100mL that mass concentration is 7%；
Step 3：H will be loaded made from step 13PW12O40Short hydroxyl multi-walled carbon nano-tube add step 2 be made
RuCl3In solution, 45 DEG C of ultrasonic immersing 60min, filter after dipping, collect and load H at the same time3PW12O40And RuCl3It is short
Hydroxyl multi-walled carbon nano-tube, the short hydroxyl multi-walled carbon nano-tube is washed with deionized into deionized water cleaning solution
24h is dried in vacuo after can't detect chlorion, is 1 using volume ratio:1 nitrogen and the mixed gas of hydrogen are as reducing gas
To described while load H at a temperature of 180 DEG C3PW12O40And RuCl3Short hydroxyl multi-walled carbon nano-tube carry out reduction treatment
6h, reducing gas flow are 150mL/min, are cooled to room temperature after completing reduction treatment in hydrogen atmosphere, obtain catalysis fibre
Element converts polynary alcohol catalyst I.
The application method that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst I be by 1.5g at a temperature of 65 DEG C
Cellulose, 0.5g catalytic celluloses obtained by vacuum drying 3h convert polynary alcohol catalyst I and 30mL deionized waters are added to band
Have in the 100mL stainless steel autoclaves of polytetrafluoroethyllining lining, at room temperature with high pure nitrogen replacement reaction kettle after sealing
Air, the high-purity hydrogen of 5MPa is passed through into autoclave, at a temperature of 150 DEG C, water is carried out with 150rpm mixing speeds
Hydrogenation reaction is solved, reaction time 8h, after reaction, collects product liquid, the product liquid is that polyalcohol mixing is molten
Liquid, product liquid use high performance liquid chromatography qualitative and quantitative analysis, obtain each Product yields；
Obtained solid part is unreacted cellulose and catalyst after reaction, and solid portion is washed with deionized water
85 DEG C of vacuum drying 5h, weigh after washing 6 times, and it is cellulose quality after reacting that gained weight, which subtracts catalyst weight,；
Cellulose conversion ratio and polyalcohol yield are calculated using equation below：
Cellulose quality before cellulose conversion ratio=(cellulose quality after cellulose quality-reaction before reaction)/reaction ×
100%；
Polyalcohol yield=gained polyol quality/(cellulose quality after cellulose quality-reaction before reaction) ×
100%.
The cellulose of certain mass is supplemented after to hydrolysis hydrogenation reaction in remaining cellulose and catalyst, makes cellulose material
Measure as 1.5g, the application method that polynary alcohol catalyst is converted by catalytic cellulose provided in this embodiment carries out repeating hydrolysis hydrogenation
Experiment, test catalytic cellulose convert the catalytic activity that can be recycled of polynary alcohol catalyst.
Embodiment 3
Catalytic cellulose conversion polyalcohol catalyst II provided in this embodiment is on short hydroxyl multi-walled carbon nano-tube
Load H at the same time3PW12O40、RuCl3With Ni (NO3)2·6H2O is made.
A kind of preparation method step of catalytic cellulose conversion polyalcohol catalyst II of the present embodiment is as follows：
Step 1：Prepare H3PW12O40Saturated solution, adds short hydroxyl multi-walled carbon nano-tube as carbon carrier
H3PW12O40In saturated solution, the ultrasonic immersing 60min at 90 DEG C, by short hydroxyl multi-walled carbon nano-tube after completion ultrasonic immersing
Taking-up drains away the water, and 90 DEG C of vacuum drying 12h, are made load H3PW12O40Short hydroxyl multi-walled carbon nano-tube；
The purity of the short hydroxyl multi-walled carbon nano-tube>98%, outer diameter length 20nm-30nm, 30nm-50nm,>
50nm, interior electrical path length are 5-15nm, and length is 0.5-2 μm, specific surface area>90m2/g、>110m2/g、>160m2/ g, contained-OH
Mass fraction is 0.71wt% -1.76wt%；
Step 2：By RuCl3The stablizing solution 50mL that mass concentration is 4% is configured to, by Ni (NO3)2·6H2O is configured to
Mass concentration is 6% stablizing solution 50mL, the two kinds of solution by volume 1 that will be prepared number:1 is uniformly mixed；
Step 3：H will be loaded made from step 13PW12O40Short hydroxyl multi-walled carbon nano-tube add step 2 be made
RuCl3With Ni (NO3)2·6H2In O mixed solutions, 45 DEG C of ultrasonic immersing 90min, filter after dipping, collect negative at the same time
Carry H3PW12O40、RuCl3With Ni (NO3)2·6H2The short hydroxyl multi-walled carbon nano-tube of O, by the short hydroxylating multi-wall carbon nano-tube
Pipe is washed with deionized into deionized water cleaning solution can't detect chlorion after be dried in vacuo 24h, using volume ratio be 1:1
Nitrogen and hydrogen mixed gas as reducing gas at a temperature of 500 DEG C to described while load H3PW12O40And RuCl3's
Short hydroxyl multi-walled carbon nano-tube carries out reduction treatment 6h, and reducing gas flow is 150mL/min, in hydrogen after completion reduction treatment
It is cooled to room temperature in gas atmosphere, obtains catalytic cellulose conversion polyalcohol catalyst II.
A kind of application method of catalytic cellulose of the present embodiment conversion polyalcohol catalyst II be by 1g at a temperature of 50 DEG C
Cellulose, 0.2g catalytic celluloses conversion polyalcohol catalyst II and 60mL deionized waters obtained by vacuum drying 2h are added to band
Have in the 100mL stainless steel autoclaves of polytetrafluoroethyllining lining, at room temperature with high pure nitrogen replacement reaction kettle after sealing
Air, the high-purity hydrogen of 7MPa is passed through into autoclave, at a temperature of 200 DEG C, water is carried out with 150rpm mixing speeds
Hydrogenation reaction is solved, reaction time 3h, after reaction, collects product liquid, the product liquid is that polyalcohol mixing is molten
Liquid.
Test what cellulose conversion ratio, polyalcohol yield and catalyst can be recycled according to the same manner as in Example 2
Catalytic activity.
Embodiment 4
It is on short hydroxyl multi-walled carbon nano-tube that catalytic cellulose provided in this embodiment, which converts polynary alcohol catalyst III,
Load H at the same time4SiW12O40With Ni (NO3)2·6H2O is made.
The preparation method step that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst III is as follows：
Step 1：Prepare H4SiW12O40Saturated solution, adds short functionalized multi-wall carbonnanotubes as carbon carrier
H4SiW12O40In saturated solution, the ultrasonic immersing 120min at 80 DEG C, by short carboxylated multi-wall carbon nano-tube after completion ultrasonic immersing
Pipe takes out and drains away the water, and 70 DEG C of vacuum drying 12h, are made load H4SiW12O40Short functionalized multi-wall carbonnanotubes；
The purity of the short functionalized multi-wall carbonnanotubes>98%, outer diameter length 20nm-30nm, 30nm-50nm,>
50nm, interior electrical path length are 5-15nm, and length is 0.5-2 μm, specific surface area>90m2/g、>170m2/g、>200m2/ g, contained-
COOH mass fractions are 0.49wt%-2.0wt%；
Step 2：By Ni (NO3)2·6H2O is configured to the stablizing solution 100mL that mass concentration is 10%；
Step 3：H will be loaded made from step 14SiW12O40Short functionalized multi-wall carbonnanotubes add step 2 be made
Ni(NO3)2·6H2In O mixed solutions, 45 DEG C of ultrasonic immersing 120min, filter after dipping, and collection loads at the same time
H4SiW12O40With Ni (NO3)2·6H2The short functionalized multi-wall carbonnanotubes of O, the short functionalized multi-wall carbonnanotubes are spent
24h is dried in vacuo after ion water washing 8 times, is 1 using volume ratio:1 nitrogen and the mixed gas of hydrogen are as reducing gas
To described while load H at a temperature of 300 DEG C4SiW12O40With Ni (NO3)2·6H2The short functionalized multi-wall carbonnanotubes of O carry out
Reduction treatment 7h, reducing gas flow are 150mL/min, are cooled to room temperature, obtain in hydrogen atmosphere after completing reduction treatment
Catalytic cellulose converts polynary alcohol catalyst III.
The application method that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst III be by 2g at a temperature of 75 DEG C
Cellulose, 0.2g catalytic celluloses obtained by vacuum drying 10h convert polynary alcohol catalyst III and 60mL deionized waters are added to
In 100mL stainless steel autoclaves with polytetrafluoroethyllining lining, high pure nitrogen replacement reaction kettle is used after sealing at room temperature
Interior air, the high-purity hydrogen of 9MPa is passed through into autoclave, at a temperature of 250 DEG C, is carried out with 200rpm mixing speeds
Hydrogenation reaction is hydrolyzed, reaction time 10h, after reaction, collects product liquid, the product liquid is polyalcohol mixing
Solution.
Test what cellulose conversion ratio, polyalcohol yield and catalyst can be recycled according to the same manner as in Example 2
Catalytic activity.
Embodiment 5
It is on short hydroxyl multi-walled carbon nano-tube that catalytic cellulose provided in this embodiment, which converts polynary alcohol catalyst IV,
Load H at the same time3PW12O40、H4SiW12O40、RuCl3With Ni (NO3)2·6H2O is made.
The preparation method step that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst IV is as follows：
Step 1：Prepare H3PW12O40And H4SiW12O40Mixing saturated solution, short functionalized multi-wall carbonnanotubes are made
H is added for carbon carrier3PW12O40And H4SiW12O40Mixing saturated solution in, the ultrasonic immersing 150min at 70 DEG C, is completed super
Short functionalized multi-wall carbonnanotubes are taken out after sound dipping and are drained away the water, 110 DEG C of vacuum drying 12h, are made and load at the same time
H3PW12O40And H4SiW12O40Short functionalized multi-wall carbonnanotubes；
The purity of the short functionalized multi-wall carbonnanotubes>98%, outer diameter length 20nm-30nm, 30nm-50nm,>
50nm, interior electrical path length are 5-15nm, and length is 0.5-2 μm, specific surface area>90m2/g、>170m2/g、>200m2/ g, contained-
COOH mass fractions are 0.49wt%-2.0wt%；
Step 2：By RuCl3The stablizing solution 80mL that mass concentration is 8% is configured to, by Ni (NO3)2·6H2O is configured to
Mass concentration is 12% stablizing solution 20mL, by prepared two kinds of solution by volume 4:1 is uniformly mixed；
Step 3：H is loaded while step 1 is made3PW12O40And H4SiW12O40Short functionalized multi-wall carbonnanotubes
Add step 2 and RuCl is made3With Ni (NO3)2·6H2In O mixed solutions, 45 DEG C of ultrasonic immersing 200min, take out after dipping
Filter, collects and loads H at the same time3PW12O40、H4SiW12O40、RuCl3With Ni (NO3)2·6H2The short functionalized multi-wall carbonnanotubes of O, will
The short functionalized multi-wall carbonnanotubes, which are washed with deionized into deionized water cleaning solution, can't detect vacuum after chlorion
Dry 24h, is 1 using volume ratio:1 nitrogen and the mixed gas of hydrogen as reducing gas at a temperature of 400 DEG C to described
Load H at the same time3PW12O40、H4SiW12O40、RuCl3With Ni (NO3)2·6H2The short functionalized multi-wall carbonnanotubes of O carry out also original place
4h is managed, reducing gas flow is 150mL/min, is cooled to room temperature after completing reduction treatment in hydrogen atmosphere, and it is fine to obtain catalysis
Dimension element converts polynary alcohol catalyst IV.
The application method that a kind of catalytic cellulose of the present embodiment converts polynary alcohol catalyst IV is in 80 DEG C of temperature by 2.5g
Cellulose, 0.5g catalytic celluloses obtained by lower vacuum drying 20h convert polynary alcohol catalyst IV and 50mL deionized waters add
Replaced and reacted with high pure nitrogen at room temperature into the 100mL stainless steel autoclaves with polytetrafluoroethyllining lining, after sealing
Air in kettle, the high-purity hydrogen of 6MPa is passed through into autoclave, at a temperature of 200 DEG C, with 250rpm mixing speeds into
Row hydrolysis hydrogenation reaction, reaction time 20h, after reaction, collects product liquid, the product liquid is that polyalcohol mixes
Close solution.
Test what cellulose conversion ratio, polyalcohol yield and catalyst can be recycled according to the same manner as in Example 2
Catalytic activity.
The performance parameter of catalyst made from embodiment 2- embodiments 5, catalytic cellulose conversion polyalcohol conversion ratio and
Polyalcohol yield, recyclable number are as shown in table 1：
Table 1：
The catalytic cellulose that it can be seen from data in table 1 prepared by preparation method of the present invention converts polynary alcohol catalyst ratio
Surface area is big, and heat endurance is good, and catalytic activity is good, and loss of active component is few, cellulose high conversion rate, catalyst and reaction product
It is easily separated, it can be recycled, it is free from environmental pollution, it is a kind of green catalyst of good performance.
Catalytic cellulose prepared by preparation method of the present invention converts polynary alcohol catalyst by catalyzing hydrolysis and catalytic hydrogenation two
Kind function concentrates on a kind of catalyst, and the hydrolysis of cellulose and hydrogenation are concentrated on primary first-order equation process during use, simplified
Step of converting of the cellulose to polyalcohol, improves transformation efficiency.Catalytic cellulose of the present invention converts polynary alcohol catalyst
Preparation process and use process are simple, and non-environmental-pollution is low for equipment requirements.
Claims (10)
1. a kind of catalytic cellulose converts polynary alcohol catalyst, it is characterised in that the catalyst is on the carbon carrier while loads
Heteropoly acid and active metal salt are made, and the carbon carrier is carbon nanotubes, and the heteropoly acid is H4SiW12O40、H3PW12O40In
One or two kinds of mixtures, the active metal salt is RuCl3Or Ni (NO3)2·6H2One or both of O.
2. a kind of catalytic cellulose converts the preparation method of polynary alcohol catalyst according to claim 1, it is characterised in that on
It is as follows to state preparation method step：
Step 1：Heteropoly acid saturated solution is prepared, carbon carrier is added in heteropoly acid saturated solution, is carried out at a certain temperature
Ultrasonic immersing, carbon carrier taking-up is drained away the water, be dried in vacuo, the carbon carrier of carried heteropoly acid is made after completing ultrasonic immersing；
Step 2：Active metal salt is configured to the stablizing solution of certain mass concentration；
Step 3：The carbon carrier for the carried heteropoly acid that step 1 is obtained is added in active metal salt solution made from step 2,
Ultrasonic immersing at a certain temperature, the collected by suction carbon carrier of carried heteropoly acid and active metal salt at the same time after dipping, will
The carbon carrier is dried in vacuo after being washed with deionized, and the carbon carrier is gone back at a certain temperature using reducing gas
Original place is managed, and is completed reduction treatment postcooling to room temperature, is obtained the catalyst of catalytic cellulose conversion polyalcohol.
3. a kind of catalytic cellulose converts the preparation method of polynary alcohol catalyst according to claim 2, it is characterised in that step
A rapid heteropoly acid is H4SiW12O40、H3PW12O40One or both of mixture；The carbon carrier is carbon nanotubes；
The ultrasonic immersing is ultrasonic immersing 20-180min at 60-120 DEG C；The vacuum drying is 50-120 DEG C of vacuum drying 12h.
4. a kind of catalytic cellulose converts the preparation method of polynary alcohol catalyst according to claim 3, it is characterised in that institute
It is short hydroxyl multi-walled carbon nano-tube or short functionalized multi-wall carbonnanotubes to state carbon nanotubes, wherein short hydroxylating multi-wall carbon nano-tube
The purity of pipe>98%, outer diameter length 20nm-30nm, 30nm-50nm,>50nm, interior electrical path length are 5-15nm, length 0.5-
2 μm, specific surface area>90m2/g、>110m2/g、>160m2/ g, contained-OH mass fractions are 0.71wt% -1.76wt%；Wherein
The purity of short functionalized multi-wall carbonnanotubes>98%, outer diameter length 20nm-30nm, 30nm-50nm,>50nm, interior electrical path length
For 5-15nm, length is 0.5-2 μm, specific surface area>90m2/g、>170m2/g、>200m2/ g, contained-COOH mass fractions are
0.49wt%-2.0wt%.
5. a kind of catalytic cellulose converts the preparation method of polynary alcohol catalyst according to Claims 2 or 3, it is characterised in that
Active metal salt described in step 2 is RuCl3Or Ni (NO3)2·6H2One or both of O, the active metal salt solution matter
Amount concentration is 0.1-30%.
6. a kind of catalytic cellulose converts the preparation method of polynary alcohol catalyst according to claim 5, it is characterised in that step
Rapid two active metal salt solution is RuCl3With Ni (NO3)2·6H2During O mixed solutions, the mixed solution is dense by quality
Degree is the RuCl of 0.1-30%3Solution and Ni (NO3)2·6H2O solution is 1-16 by volume:4 ratio is formulated.
7. a kind of catalytic cellulose converts the preparation method of polynary alcohol catalyst according to claim 5, it is characterised in that step
Rapid three ultrasonic immersing is 45 DEG C of ultrasonic immersing 20-240min；The deionized water washing times are 5-8 times, work as step 2
Contain RuCl in obtained active metal salt solution3When, wash untill can't detect chlorion into deionized water cleaning solution；
The vacuum drying time is 24h；The reducing gas is that volume ratio is 1:1 nitrogen and the mixed gas of hydrogen；It is described to go back
Original place reason is reductase 12-8h at a temperature of 150-600 DEG C, and reducing gas flow is 150mL/min；Described be cooled to room temperature is in hydrogen
Cooled down in gas atmosphere.
8. a kind of catalytic cellulose converts the application method of polynary alcohol catalyst according to claim 1, it is characterised in that institute
It is that catalyst, cellulose and the deionized water of catalytic cellulose conversion polyalcohol are added to height by a certain percentage to state application method
Press in reaction kettle, a level pressure is passed through into autoclave with the air in high pure nitrogen replacement reaction kettle at room temperature after sealing
Strong high-purity hydrogen, hydrogenation reaction is hydrolyzed under certain reaction temperature and mixing speed；After reaction, liquid production is collected
Thing, the product liquid are polynary mixed alkoxide solution.
9. a kind of catalytic cellulose converts the application method of polynary alcohol catalyst according to claim 8, it is characterised in that institute
State the cellulose being dried in vacuo at a temperature of cellulose is 40-80 DEG C obtained by 2-30h；The cellulose and catalytic cellulose conversion are more
The mass ratio of the catalyst of first alcohol is 3-20:1；The cellulose and the mass volume ratio of deionized water are 1g:10-60mL.
10. a kind of catalytic cellulose converts the application method of polynary alcohol catalyst according to claim 8 or claim 9, its feature exists
It is 3-10MPa in the pressure of the high-purity hydrogen, the temperature of the hydrolysis hydrogenation reaction is 120-300 DEG C, and mixing speed is
100-300rpm, reaction time 2-24h.
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