CN114433242B - Embedded copper oxide nanotube catalyst - Google Patents

Embedded copper oxide nanotube catalyst Download PDF

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CN114433242B
CN114433242B CN202011526635.7A CN202011526635A CN114433242B CN 114433242 B CN114433242 B CN 114433242B CN 202011526635 A CN202011526635 A CN 202011526635A CN 114433242 B CN114433242 B CN 114433242B
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catalyst
copper oxide
oxide nanotube
embedded copper
drying
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CN114433242A (en
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刘野
赵亮
王岩
于庆志
党雷
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • 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
    • C07C29/147—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 carboxylic acids or derivatives thereof
    • C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

An embedded copper oxide nanotube catalyst prepared by the method comprising: cuCl is added 2 Dissolving in deionized water, heating, and stirring to form Cu (OH) 2 Sol, naturally cooling; washing the resin catalyst, drying, and immersing in Cu (OH) 2 And (3) soaking in the sol under the condition of maintaining negative pressure, filtering, drying and calcining to obtain the embedded copper oxide nanotube catalyst. The catalyst of the invention has a copper oxide nanotube structure with uniform and continuous aperture, is different from a 'punctiform' active center formed by a common dipping method, and has higher concentration and adsorption effect on the part of the reactive active center due to the gas-sensitive property and the space limiting effect of the copper oxide nanotube, so that the catalyst has stronger catalytic activity, high mutual contact efficiency and mass transfer efficiency between reaction materials, higher reaction conversion rate and product selectivity, and good stability.

Description

Embedded copper oxide nanotube catalyst
Technical Field
The invention relates to an embedded copper oxide nanotube catalyst which is used for producing 1, 6-hexanediol by catalyzing ester hydrogenation.
Background
1, 6-Hexanediol (HDO) is a novel fine chemical product with unique performance, can be mixed with various organic chemicals in any proportion, has no corrosiveness, can derive a series of novel fine chemicals, and has wider and wider application in the fields of polyurethane, polyester, coiled material coating, photo-curing and the like. For example: the modified resin is applied to polyurethane elastomer, and the 1, 6-hexanediol is used for modifying the polyurea aldehyde elastomer, so that the modified resin has excellent mechanical strength, water resistance, heat resistance and oxidation resistance; for polycarbonate, 1, 6-hexanediol is reacted with dimethyl carbonate to give polycarbonate, which can be made into fibers and films; when the flame-retardant polyester plasticizer is applied to the polyester plasticizer, the traditional ester plasticizer has certain defects in the process of manufacturing the flame-retardant plastic polyvinyl chloride, and the polyester plasticizer prepared from 1, 6-hexanediol and related substances just compensates and improves the defects; the modified acrylic acid ester plasticizer is applied to acid ester plasticizers, and improves the water resistance and oil resistance of the acid ester plasticizers; the pesticide can be applied to pesticide pyrethrin and the like.
The main preparation methods of the 1, 6-hexanediol comprise an adipic acid esterification method, a hydrogenation method, an adipic acid direct hydrogenation method, an acrylic acid method, a hydroformylation method and the like. Although there are various technical routes for preparing 1, 6-hexanediol, these technical routes are not all suitable for industrial production. The adipic acid direct hydrogenation method has high acid resistance requirements on catalysts and equipment; dimerization of acrylic esters followed by hydrogenation to give 1, 6-hexanediol provides a process for the preparation of 1, 6-hexanediol from lower hydrocarbons (C3), but is currently still in the laboratory exploration phase; the hydroformylation method is used for preparing the 1, 6-hexanediol, so that the selectivity is low; the epoxybutadiene method has the advantages of complicated reaction process and rare raw materials. Therefore, the more mature 1, 6-hexanediol production method is also an adipic acid esterification and hydrogenation method.
Patent CN102372604A discloses a method for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, wherein oxide-supported noble metal is used as a catalyst, the reaction is carried out in an autoclave, and the reaction is discontinuous and the cost of the catalyst is highHigher, the impurity separation is difficult, and the conversion rate and selectivity of the product are lower. Patent CN111659375A discloses a catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, a preparation method and application thereof, wherein the method uses SiO 2 /ZrO 2 The catalyst is used as a carrier, noble metal ruthenium or iridium is used as an active component, the preparation process is complex, the catalyst cost is high, and a large amount of organic solvents are used in the preparation process, so that environmental pollution is easy to cause.
Therefore, the existing method for preparing the 1, 6-hexanediol by ester hydrogenation has the problems of low reaction conversion rate, poor product selectivity, difficult separation of products and catalyst impurities and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an embedded copper oxide nanotube catalyst which adopts a resin catalyst as a template to form copper oxide nanotubes in situ in the pore canal of the catalyst, is applied to the hydrogenation of ester to produce 1, 6-hexanediol, has higher reaction efficiency and reaction conversion rate, has higher product selectivity and obtains better reaction effect.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the technical object of the first aspect of the present invention is to provide a method for preparing an embedded copper oxide nanotube catalyst, comprising the following steps:
(1) Washing the resin catalyst, and drying for later use;
(2) CuCl is added 2 Dissolving in deionized water, heating, and stirring to form Cu (OH) 2 Sol, naturally cooling and then standby;
(3) Impregnating the resin catalyst obtained in the step (1) with Cu (OH) in the step (2) 2 And (3) soaking in the sol under the condition of maintaining negative pressure, filtering, drying and calcining to obtain the embedded copper oxide nanotube catalyst.
In one embodiment of the present invention, the embedded copper oxide nanotube catalyst obtained in step (3) accounts for 10% to 30%, preferably 7% to 12% of the total weight of the catalyst, based on the weight of copper oxide.
In the present inventionIn one embodiment, the resin catalyst in step (1) is a polystyrene resin catalyst having an average diameter of 0.5 to 1.2mm, preferably 0.8 to 1.0mm; the average specific surface area is 600-1000 cm 2 Preferably 700 to 900cm 2 The average pore diameter per gram is 5 to 30nm, preferably 10 to 20nm, and the average pore volume is 0.01 to 0.1mL/g, preferably 0.03 to 0.05mL/g.
In one embodiment of the present invention, the number of times of washing in the step (1) is 3 to 5, the solvent used for washing is 95% absolute ethanol, the washing temperature is 20 to 50 ℃, preferably 30 to 35 ℃, and the drying temperature is 50 to 100 ℃, preferably 60 to 70 ℃.
In one embodiment of the present invention, the CuCl of step (2) 2 CuCl in solution 2 The mass percentage concentration of the catalyst is 10-30wt%, the heating temperature is 90-100deg.C, the stirring revolution is 100-350 r/min, and preferably 200-250 r/min until the solution changes color to form sol, heating and stirring are stopped, and natural cooling is performed.
In one embodiment of the present invention, the impregnation time in step (3) is 1 to 3 hours and the impregnation pressure is 1.0 to 10.0kPa, preferably 1.5 to 3.0kPa.
In one embodiment of the present invention, the drying temperature in step (3) is 30 to 40 ℃, the drying time is 12 to 24 hours, the calcination temperature is 150 to 200 ℃, and the calcination time is 1 to 3 hours.
The technical purpose of the second aspect of the invention is to provide the embedded copper oxide nanotube catalyst prepared by the method. The invention adopts a styrene resin catalyst as a template, and impregnates the catalyst under the condition of negative pressure to ensure Cu (OH) 2 The sol enters into a pore canal of the resin catalyst, and is filtered, dried and calcined to obtain the embedded copper oxide nanotube catalyst. The method forms a copper oxide nanotube structure with uniform and continuous pore diameter in the resin catalyst, is different from a 'punctiform' active center formed by a common dipping method, and ensures that the reactive gas has higher concentration and adsorption effect in the local part of the reactive active center due to the gas-sensitive property and the space confinement effect of the copper oxide nanotubeTherefore, the catalyst has stronger catalytic activity, high mutual contact efficiency and mass transfer efficiency between reaction materials, higher reaction conversion rate and product selectivity, and good stability.
The technical purpose of the third aspect of the invention is to provide application of the embedded copper oxide nanotube catalyst, wherein the embedded copper oxide nanotube catalyst is used for catalyzing the reaction of preparing 1, 6-hexanediol by hydrogenating dimethyl adipate.
In the above application, the dimethyl adipate hydrogenation reaction conditions were as follows: the reaction temperature is 180-260 ℃, preferably 190-200 ℃; the reaction pressure is 2-8 MPa, preferably 3-6 MPa, and the volume airspeed of the dimethyl adipate is 0.2-2: 1, preferably 0.5 to 1:1, molar ratio of hydrogen ester is 150:1 to 350:1, preferably 200:1 to 300:1.
compared with the prior art, the invention has the following advantages:
(1) The embedded copper oxide nanotube catalyst of the invention adopts a styrene resin catalyst as a template, and is impregnated with Cu (OH) under the condition of negative pressure 2 The sol enters into a pore canal of a resin catalyst, and is filtered, dried and calcined to obtain an embedded copper oxide nanotube catalyst; the embedded copper oxide nanotubes have better continuity and form stronger reactive centers.
(2) The copper oxide nanotube formed in the catalyst has good gas sensitivity and space confinement effect, so that the reactive gas has high concentration and adsorption effect in the local part of the reactive center, the catalyst has high catalytic activity, the mutual contact efficiency and mass transfer efficiency between the reaction materials are high, the reaction conversion rate and the product selectivity are high, and the catalyst has good stability.
Detailed Description
The specific embodiments of the present invention are as follows: preparing an embedded copper oxide nanotube catalyst, performing ester hydrogenation reaction on a fixed bed continuous reaction device with the embedded copper oxide nanotube catalyst, introducing reaction materials into the reactor from the top of the reactor under certain process conditions, performing ester hydrogenation reaction under the action of the embedded copper oxide nanotube catalyst, allowing reaction products to flow out from the bottom of the reactor, and performing sampling analysis.
The following describes specific embodiments of the present invention in detail with reference to examples. Unless otherwise specified, the following examples and comparative examples are given in% by mass.
Example 1
In this example, an embedded copper oxide nanotube catalyst was prepared and applied to the esterification of adipic acid and methanol to prepare 1, 6-hexanediol:
preparing an embedded copper oxide nanotube catalyst:
(1) Measuring 100mL of resin catalyst, measuring 300mL of absolute ethyl alcohol with the concentration of 95%, washing 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 60g of CuCl 2 Dissolving in 300g deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(3) Impregnating the resin catalyst obtained in the step (1) in the sol obtained in the step (2), impregnating for 3 hours under the condition of the pressure of 1.8kPa, drying for 12 hours at the temperature of 40 ℃ after filtering, and calcining for 2 hours at the temperature of 200 ℃ to obtain the embedded copper oxide nanotube catalyst, wherein copper oxide accounts for 9.1% of the total weight of the catalyst by weight.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor with an embedded copper oxide nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 200 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 0.8h -1 The molar ratio of the hydrogen ester is 200:1 and the reaction results are shown in Table 1.
Example 2
Preparing an embedded copper oxide nanotube catalyst:
(1) Measuring 100mL of resin catalyst, measuring 300mL of absolute ethyl alcohol with the concentration of 95%, washing 3 times at 30 ℃, and drying for 12 hours at 60 ℃ for later use;
(2) 70g of CuCl 2 Dissolving in 300g deionized water, reacting at 95 ℃ under the condition of stirring revolution of 200r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(3) Impregnating the resin catalyst obtained in the step (1) in the sol obtained in the step (2), impregnating for 3 hours under the condition of the pressure of 1.7kPa, drying for 12 hours at the temperature of 40 ℃ after filtering, and calcining for 2 hours at the temperature of 200 ℃ to obtain the embedded copper oxide nanotube catalyst, wherein copper oxide accounts for 8.6% of the total weight of the catalyst by weight.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor with an embedded copper oxide nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 210 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 1.0h -1 The molar ratio of the hydrogen ester is 250:1 and the reaction results are shown in Table 1.
Example 3
Preparing an embedded copper oxide nanotube catalyst:
(1) Measuring 100mL of resin catalyst, measuring 300mL of absolute ethyl alcohol with the concentration of 95%, washing 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 75g of CuCl 2 Dissolving in 300g deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(3) Impregnating the resin catalyst obtained in the step (1) in the sol obtained in the step (2), impregnating for 3 hours under the condition of the pressure of 1.5kPa, drying for 12 hours at the temperature of 40 ℃ after filtering, and calcining for 2 hours at the temperature of 200 ℃ to obtain the embedded copper oxide nanotube catalyst, wherein copper oxide accounts for 8.4% of the total weight of the catalyst by weight.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor with an embedded copper oxide nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 220 ℃, the reaction pressure is 6MPa, and the volume space velocity of the dimethyl adipate is 0.8h -1 The molar ratio of the hydrogen ester is 250:1 and the reaction results are shown in Table 1.
Example 4
Preparing an embedded copper oxide nanotube catalyst:
(1) Measuring 100mL of resin catalyst, measuring 300mL of absolute ethyl alcohol with the concentration of 95%, washing 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 65g of CuCl 2 Dissolving in 300g deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(3) Impregnating the resin catalyst obtained in the step (1) in the sol obtained in the step (2), impregnating for 3 hours under the condition of the pressure of 1.6kPa, drying for 12 hours at the temperature of 40 ℃ after filtering, and calcining for 2 hours at the temperature of 200 ℃ to obtain the embedded copper oxide nanotube catalyst, wherein copper oxide accounts for 9.7% of the total weight of the catalyst by weight.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor with an embedded copper oxide nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 220 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 1.0h -1 The molar ratio of the hydrogen ester is 250:1 and the reaction results are shown in Table 1.
Example 5
Preparing an embedded copper oxide nanotube catalyst:
(1) Measuring 100mL of resin catalyst, measuring 300mL of absolute ethyl alcohol with the concentration of 95%, washing 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 60g of CuCl 2 Dissolving in 300g deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(3) Impregnating the resin catalyst obtained in the step (1) in the sol obtained in the step (2), impregnating for 3 hours under the condition of the pressure of 1.8kPa, drying for 12 hours at the temperature of 40 ℃ after filtering, and calcining for 2 hours at the temperature of 200 ℃ to obtain the embedded copper oxide nanotube catalyst, wherein copper oxide accounts for 10.1% of the total weight of the catalyst by weight.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor with an embedded copper oxide nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 220 ℃, the reaction pressure is 4MPa, and the volume space velocity of the dimethyl adipate is 1.5h -1 The molar ratio of the hydrogen ester is 300:1 and the reaction results are shown in Table 1.
Example 6
Preparing an embedded copper oxide nanotube catalyst:
(1) Measuring 100mL of resin catalyst, measuring 300mL of absolute ethyl alcohol with the concentration of 95%, washing 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 80g of CuCl 2 Dissolving in 300g deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(3) Impregnating the resin catalyst obtained in the step (1) in the sol obtained in the step (2), impregnating for 3 hours under the condition of 1500Pa, drying for 12 hours at 40 ℃ after filtering, and calcining for 2 hours at 200 ℃ to obtain the embedded copper oxide nanotube catalyst, wherein copper oxide accounts for 10.5% of the total weight of the catalyst by weight.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor with an embedded copper oxide nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 210 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 0.8h -1 The molar ratio of the hydrogen ester is 200:1 and the reaction results are shown in Table 1.
Comparative example 1
In the hydrogenation reaction process of dimethyl adipate, the catalyst used is a supported CuO/resin catalyst, copper oxide accounts for 11.2% of the total weight of the catalyst by weight, other conditions are the same as in example 4, and the reaction results are shown in Table 1.
Comparative example 2
In the hydrogenation reaction process of dimethyl adipate, the catalyst used is a supported CuO/alumina catalyst, copper oxide accounts for 9.8% of the total weight of the catalyst by weight, other conditions are the same as in example 4, and the reaction results are shown in Table 1.
Table 1 reaction results (conversion in moles) for the examples

Claims (16)

1. The preparation process of embedded copper oxide nanotube catalyst includes the following steps:
(1) Washing a resin catalyst, and drying for later use, wherein the average pore diameter of the resin catalyst is 5-30 nm;
(2) CuCl is added 2 Dissolving in deionized water, heating, and stirring to form Cu (OH) 2 Sol, naturally cooling and then standby;
(3) Impregnating the resin catalyst obtained in the step (1) with Cu (OH) in the step (2) 2 And (3) soaking in the sol under the condition of maintaining negative pressure, filtering, drying and calcining to obtain the embedded copper oxide nanotube catalyst.
2. The method of claim 1, wherein the embedded copper oxide nanotube catalyst comprises 7% to 30% by weight of copper oxide based on the total weight of the catalyst.
3. The method of claim 2, wherein the embedded copper oxide nanotube catalyst comprises 7-12% by weight of copper oxide based on the total weight of the catalyst.
4. The method according to claim 1, wherein the resin catalyst in step (1) is a polystyrene resin catalyst having an average diameter of 0.5 to 1.2mm.
5. The process according to claim 1, wherein the resin catalyst in step (1) has an average specific surface area of 600 to 1000cm 2 And/g, the average pore diameter is 10-20 nm, and the average pore volume is 0.01-0.1 mL/g.
6. The process according to claim 5, wherein the resin catalyst in step (1) has an average specific surface area of 700 to 900cm 2 Per gram, the average pore volume is 0.03-0.05 mL/g.
7. The process of claim 1, wherein in step (2) CuCl 2 CuCl in solution 2 The mass percentage concentration of (2) is 10-30wt%.
8. The process according to claim 1, wherein the heating temperature in step (2) is 90 to 100 ℃.
9. The method according to claim 1, wherein the immersion time in the step (3) is 1 to 3 hours.
10. The process according to claim 1, wherein the impregnation pressure in step (3) is 1.0 to 10.0kPa.
11. The process according to claim 10, wherein the impregnation pressure in step (3) is 1.5 to 3.0kPa.
12. The method according to claim 1, wherein the drying temperature in the step (3) is 30 to 40 ℃ and the drying time is 12 to 24 hours.
13. The method according to claim 1, wherein the calcination temperature in the step (3) is 150 to 200 ℃ and the calcination time is 1 to 3 hours.
14. An embedded copper oxide nanotube catalyst prepared by the method of any one of claims 1-13.
15. Use of the embedded copper oxide nanotube catalyst of claim 14 for catalyzing hydrogenation of dimethyl adipate to prepare 1, 6-hexanediol.
16. The use according to claim 15, wherein the dimethyl adipate hydrogenation conditions are as follows: the reaction temperature is 180-260 ℃, the reaction pressure is 2-8 MPa, and the volume airspeed of the dimethyl adipate is 0.2-2: 1, molar ratio of hydrogen ester is 150:1 to 350:1.
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