CN108786815B - Mesoporous carbon-based catalyst and application thereof in polyether amine synthesis - Google Patents
Mesoporous carbon-based catalyst and application thereof in polyether amine synthesis Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 31
- 229920000570 polyether Polymers 0.000 title claims abstract description 31
- 150000001412 amines Chemical class 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 8
- 238000005470 impregnation Methods 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 238000004176 ammonification Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 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 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- PAWSVPVNIXFKOS-UHFFFAOYSA-N 2-aminobut-2-enoic acid zwitterion Chemical compound CC=C([NH3+])C([O-])=O PAWSVPVNIXFKOS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
- C08G65/3255—Ammonia
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- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Polyethers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a mesoporous carbon-based catalyst and application thereof in polyether amine synthesis. The catalyst takes CMK-3 mesoporous carbon as a substrate, one or more metals of Ni, Ru or Cu are loaded on the surface of the catalyst by an impregnation method, and the catalyst is used after reduction. The catalyst can efficiently catalyze polyether glycol with the number average molecular weight of 200-5000 for ammonification and hydrogenation to synthesize polyether amine, wherein the primary amine rate can reach more than 95%. The carrier has the characteristics of uniform mesopores and higher specific surface, so that hydrogen, ammonia and polyether polyol can be well mixed in a pore channel in the reaction process, the required hydrogen pressure is low, the applicable substrate has wide molecular weight, the catalyst is low in use amount, the thermal stability is good, and the service life of the catalyst is long.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a mesoporous carbon-based catalyst and application thereof in polyether amine synthesis.
Background
The polyether amine is a polymer with a main chain of a polyether structure and an active functional group at the tail end of the polymer as an amino group. Because of the adjustability of a series of properties such as reactivity, toughness, viscosity and hydrophilicity of the polyetheramine and the possibility of the amine group to react with various compounds, the special molecular structure of the polyetheramine endows the polyetheramine with excellent comprehensive properties, and the current commercial polyetheramines comprise a series of products which are monofunctional, difunctional and trifunctional and have the molecular weight of 200 to 5000. The polyurea epoxy resin curing agent is widely applied to the fields of polyurea spraying, large-scale composite material preparation, epoxy resin curing agent and the like. The synthesis method of polyether amine mainly comprises a high-pressure catalytic ammoniation method, a leaving group method, an amino butenoic acid esterification method, a polyether nitrile alkylation method and the like. The method for synthesizing the polyether amine by the catalytic ammoniation method has the advantages of stable product quality, better environmental protection requirement conformity and the like, and is the main method for industrially producing the polyether amine at present. Most of the catalysts used in the current catalytic ammoniation method are catalysts such as framework series, for example, the catalyst disclosed in patent US3128311 is framework nickel, and in patent CN 105713191 a, the catalyst is selected from at least one of raney nickel, raney cobalt, raney copper, raney iron and raney nickel cobalt. However, the skeleton series still have low total amine value and low primary amine rate. Low universality of molecular weight and the like
The mesoporous carbon is a non-silicon-based mesoporous material with high specific surface area (up to 2500 m)2Per gram) and pore volume (up to 2.25cm3And/g) are highly expected to be applied to catalyst carriers, hydrogen storage materials, electrode materials and the like, and therefore, the catalyst is highly regarded by people. Compared with pure mesoporous silicon materials, mesoporous carbon materials exhibit special properties: the specific surface area and the porosity are high; the aperture size is adjustable within a certain range; the mesoporous shape is various, and the pore wall composition, structure and property are adjustable; high thermal stability and hydrothermal stability can be obtained by optimizing synthesis conditionsSex; simple synthesis, easy operation and no physiological toxicity. The CMK-3 type mesoporous carbon is a mesoporous carbon material prepared by using SBA-15 as a hard template method, and has an ordered mesoporous pore channel structure, the pore size is 3.9nm, and the specific surface area is 1500 m-2Within the range of/g, the pore volume is between 0.7 and 1.5 cc/g. The ordered mesoporous structure provides an internal reaction site for reaction, and the longer pore structure better restricts the diffusion of a reaction substrate, so that the reaction is more complete, and the product has higher primary amine rate.
Disclosure of Invention
The invention provides a mesoporous carbon-based catalyst and application thereof in polyether amine synthesis. The invention takes CMK-3 as a substrate, and active metal is loaded on the surface of the substrate as a catalyst. The invention utilizes mesoporous pore canals with ordered mesoporous carbon as reaction sites, restricts the diffusion of reaction substrates, is beneficial to complete reaction, and thus, the product has higher primary amine rate.
The catalyst takes CMK-3 mesoporous carbon as a substrate, one or more metals of Ni, Ru or Cu are loaded on the surface of the catalyst by an impregnation method, and the catalyst is used after reduction.
The catalyst according to the invention is characterized in that it can be prepared according to the following steps: putting PVP-k90 water solution into a flask, adding one or more water soluble salts of Ni, Ru or Cu, stirring to dissolve, adding CMK-3, stirring to obtain suspension, heating to 30-60 deg.C, preferably 35 deg.C, and stirring for 1-12 hr, preferably 6 hr. Then NaBH is added4Stirring for 10-60min, filtering to obtain black solid, and drying to obtain the mesoporous carbon-based catalyst.
According to the invention, it is characterized in that: the mass fraction of the PVP-k90 aqueous solution is 0.5-30%, preferably 5%. The mass of the PVP-k90 aqueous solution is 5-100 times, preferably 9 times that of CMK-3.
The catalyst of claim 1, wherein: the total amount of Ni, Ru or Cu metal is 0.5-20% of CMK-3.
According to the invention, it is characterized in that: adding NaBH4The mass is 5 to 20 times, preferably 10 times the mass of the metal.
The use of the mesoporous carbon catalyst of claim 1 in the catalytic preparation of polyetheramines from polyether polyols.
According to the invention, it is characterized in that: the reaction is a kettle type reaction.
According to the invention, it is characterized in that: the polyether polyol has a number average molecular weight of 200-.
According to the invention, it is characterized in that: the reaction temperature is 100-300 ℃, preferably 220-250 ℃; the reaction time is 1-12h, preferably 4 h; the amount of the mesoporous carbon-based catalyst is 0.1-100% of the mass of the polyether polyol, and preferably 0.5-2%; the pressure of the reaction hydrogen is 1-20MPa, preferably 5-8 MPa; the weight ratio of polyether polyol to liquid ammonia is 1: 0.1 to 1, preferably 1: 0.2-0.5.
The invention has the beneficial effects that:
compared with the traditional barium hydroxide catalyst, the catalyst has the advantages of regular structure, high specific surface area, mesoporous structure which is beneficial to the mixing of the catalyst, the catalyst and the catalyst, low hydrogen pressure, wide applicable substrate molecular weight, low catalyst usage amount, good thermal stability and long service life of the catalyst.
The specific implementation mode is as follows:
the process provided by the present invention is described in detail below with reference to examples, but the present invention is not limited thereto in any way.
Drawings
Fig. 1 is a TEM electron micrograph of mesoporous carbon-based catalyst a.
Fig. 2 is a nitrogen adsorption and desorption curve of the mesoporous carbon-based catalyst a.
EXAMPLE 1 preparation of Material A
200g of PVP-k90 aqueous solution with the mass fraction of 10% was put into a flask, and 10g of Ni (NO) was added3) 2·6H2O, stirring until dissolved, adding 15g of CMK-3 powder, stirring to obtain a suspension, heating to 35 ℃, and stirring for 6 hours. Then 20g of NaBH was added4Stirring for 30min, filtering to obtain black solid, and drying to obtain the mesoporous carbon-based catalyst A.
EXAMPLE 2 preparation of Material B
200g of PVP-k90 aqueous solution with the mass fraction of 15% are put into a flask, and 5g of RuCl is added3·3H2O, stirring until dissolved, adding 10g of CMK-3 powder, stirring to obtain a suspension, heating to 40 ℃, and stirring for 8 hours. Then 20g of NaBH was added4Stirring for 40min, filtering to obtain black solid, and drying to obtain the mesoporous carbon-based catalyst B.
EXAMPLE 3 preparation of Material C
200g of a 15% PVP-k90 aqueous solution was placed in a flask, and 5g of Cu (NO) was added3) 2·3H2O, stirring until dissolved, adding 10g of CMK-3 powder, stirring to obtain a suspension, heating to 30 ℃, and stirring for 12 hours. Then 20g of NaBH was added4Stirring for 20min, filtering to obtain black solid, and drying to obtain the mesoporous carbon-based catalyst C.
EXAMPLE 4 preparation of Material D
200g of a 5% PVP-k90 aqueous solution was placed in a flask, and 2g of Ni (NO) was added3) 2·6H2O，3g Cu(NO3)2·3H2Stirring to dissolve O, adding 10g CMK-3 powder, stirring to obtain suspension, heating to 40 deg.C, and stirring for 12 hr. Then 30g of NaBH was added4Stirring for 60min, filtering to obtain black solid, and drying to obtain the mesoporous carbon-based catalyst D.
Example 5:
100g of polyether polyol with the number average molecular weight of 230 is added into a high-pressure synthesis kettle, 10g of catalyst A is added, 50g of liquid ammonia is injected after the high-pressure synthesis kettle is closed, stirring is started, the temperature is heated to 220 ℃, hydrogen is injected until the pressure is 8.0MPa, and the reaction is carried out for 4 hours. And separating liquid ammonia after the reaction is finished to obtain a product D230, wherein the total amine value of the obtained product is 8.7meq/g, and the primary amine rate is 99.8%.
Example 6:
100g of polyether polyol with the number average molecular weight of 403 is added into a high-pressure synthesis kettle, 10g of catalyst B is added, 100g of liquid ammonia is injected after the high-pressure synthesis kettle is closed, stirring is started, the temperature is heated to 260 ℃, hydrogen is injected until the pressure is 6.5MPa, and the reaction lasts for 8 hours. And separating liquid ammonia after the reaction is finished to obtain a product D403, wherein the total amine value of the obtained product is 6.8meq/g, and the primary amine rate is 99.2%.
Example 7:
100g of polyether polyol with the number average molecular weight of 2000 is added into a high-pressure synthesis kettle, 5g of catalyst C is added, 60g of liquid ammonia is injected after the high-pressure synthesis kettle is closed, stirring is started, the temperature is heated to 220 ℃, hydrogen is injected until the pressure is 6.0MPa, and the reaction lasts for 8 hours. And separating liquid ammonia after the reaction is finished to obtain a product D2000, wherein the total amine value of the obtained product is 1.05meq/g, and the primary amine rate is 99.1%.
Example 8:
100g of polyether polyol with the number average molecular weight of 5000 is added into a high-pressure synthesis kettle, 10g of catalyst D is added, 30g of liquid ammonia is injected after the high-pressure synthesis kettle is sealed, stirring is started, the temperature is heated to 200 ℃, hydrogen is injected until the pressure is 9.0MPa, and the reaction lasts for 12 hours. And after the reaction is finished, separating liquid ammonia to obtain a product D5000, wherein the total amine value of the obtained product is 0.54meq/g, and the primary amine rate is 99.8%.
Claims (9)
1. An application of a mesoporous carbon-based catalyst in preparation of polyether amine by catalyzing polyether polyol is characterized in that: the catalyst takes CMK-3 mesoporous carbon as a substrate, one or more than two metals of Ni, Ru or Cu are loaded on the surface of the catalyst by an immersion method, and the catalyst is used after reduction;
the catalyst is prepared according to the following steps:
adding PVP-k90 water solution into a container, adding one or more water-soluble salts of Ni, Ru or Cu, stirring to dissolve, adding CMK-3, stirring to obtain suspension, heating to 30-60 deg.C, and stirring for 1-12 hr; then NaBH is added4Stirring for 10-60min, filtering to obtain black solid, and drying to obtain mesoporous carbon-based catalyst;
the polyether polyol is mixed polyether polyol prepared by polymerization reaction of one or more of ethylene oxide, propylene oxide and butylene oxide; suitable for polyether polyol with the number average molecular weight of 200-;
the reaction temperature is 100-300 ℃; the reaction time is 1-12 h; the amount of the mesoporous carbon-based catalyst is 0.1-100% of the mass of the polyether polyol; the pressure of the reaction hydrogen is 1-20 MPa; the weight ratio of polyether polyol to liquid ammonia is 1: 0.1-1.
2. Use according to claim 1, characterized in that: the reaction temperature is 220-250 ℃; the reaction time is 4 h; the amount of the mesoporous carbon-based catalyst is 0.5-2% of the mass of the polyether polyol; the pressure of the reaction hydrogen is 5-8 MPa; the weight ratio of polyether polyol to liquid ammonia is 1: 0.2-0.5.
3. Use according to claim 1, characterized in that: the reaction is a kettle type reaction.
4. Use according to claim 1, characterized in that: heating to 35 ℃, and stirring for 6 h.
5. Use according to claim 1, characterized in that: the mass fraction of the PVP-k90 aqueous solution is 0.5-30%; the mass of the PVP-k90 aqueous solution is 5-100 times of that of CMK-3.
6. Use according to claim 5, characterized in that: the mass fraction of the PVP-k90 aqueous solution is 5%; the mass of the PVP-k90 aqueous solution is 9 times of that of CMK-3.
7. Use according to claim 1, characterized in that: the total amount of the Ni, Ru or Cu metal is CMK-30.5-20%.
8. Use according to claim 1, characterized in that: adding NaBH4The mass is 5-20 times of the metal mass.
9. Use according to claim 1, characterized in that: adding NaBH4The mass is 10 times the mass of the metal.
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