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CN111659375B - Catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, and preparation method and application thereof - Google Patents

Catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, and preparation method and application thereof Download PDF

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CN111659375B
CN111659375B CN202010433632.2A CN202010433632A CN111659375B CN 111659375 B CN111659375 B CN 111659375B CN 202010433632 A CN202010433632 A CN 202010433632A CN 111659375 B CN111659375 B CN 111659375B
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carrier
catalyst
active component
dimethyl adipate
hexanediol
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CN111659375A (en
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代淑梅
吴超勇
李秋园
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Tangshan Zhongrong Technology Co ltd
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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
    • B01J23/894—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 rare earths or actinides
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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

The application discloses a catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, which consists of a carrier and active components dispersed and loaded on the carrier; the active component consists of a first active component and a second active component, wherein the first active component is ruthenium and/or iridium, and the second active component is copper chromite; the carrier is lanthanum-doped SiO 2 /ZrO 2 A carrier; the carrier is of a mesoporous structure, and the pore size of the carrier is 10-50 nm. The catalyst of the application not only has the advantages of high conversion rate of dimethyl adipate and strong selectivity of 1, 6-hexanediol, but also has the excellent performances of large specific surface area, high active component carrying capacity, stable performance and long service life. The application also discloses a preparation method and application of the catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate.

Description

Catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, and preparation method and application thereof
Technical Field
The application relates to the technical field of hydrogenation catalysts, in particular to a catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, a preparation method and application thereof.
Background
The 1, 6-hexanediol is a new growing important fine chemical raw material, and the product has excellent high-end special application properties such as environmental protection, thermal processing, weather resistance and the like, is an environmental-friendly chemical raw material without environmental pollution, and is known as a new foundation stone for organic synthesis. The modified polyester fiber has wide application in the fields of high-end environment-friendly coating, biodegradable polyester, high-grade synthetic fiber, high-grade mechanical products such as automobile components and the like.
CN201310512632.1 discloses a four-component catalyst of active components Ru, re, in and Ir for catalytic synthesis of 1, 6-hexanediol, the composition of the active components is complex, and the yield of adipic acid is low; CN201910891013.5 discloses a catalyst for producing 1, 6-hexanediol by hydrogenation of adipic acid ester, which takes CuO as main active component, znO as auxiliary component and Al modified by alkaline earth metal oxide 2 O 3 The material is a carrier; the catalyst has low treatment capacity and high molar ratio of hydrogen ester in the reaction process.
In view of the foregoing, there is a need to develop a more optimized catalyst for the hydrogenation of dimethyl adipate to 1, 6-hexanediol that ameliorates the shortcomings of the prior art.
Disclosure of Invention
In view of the defects of the prior art, the application provides the catalyst for preparing the 1, 6-hexanediol by hydrogenating the dimethyl adipate and the preparation method thereof, so as to solve the problems of low performance, short service life, low unit treatment capacity of the dimethyl adipate and the like of the existing catalyst for preparing the 1, 6-hexanediol by hydrogenating the dimethyl adipate, further improve the economy of preparing the 1, 6-hexanediol by hydrogenating the dimethyl adipate, reduce the production and operation cost and be more beneficial to large-scale popularization and application of the process route.
The application also provides application of the catalyst for preparing the 1, 6-hexanediol by hydrogenating the dimethyl adipate, so that the catalytic efficiency of the catalyst is furthest exerted in the process of preparing the 1, 6-hexanediol by hydrogenating the dimethyl adipate, and the conversion rate of the dimethyl adipate and the selectivity of the 1, 6-hexanediol are improved.
In order to achieve the above purpose, the application adopts the following technical scheme:
the catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate comprises a carrier and active components which are dispersedly supported on the carrier; the active component consists of a first active component and a second active component, wherein the first active component is ruthenium and/or iridium, and the second active component is copper chromite; the carrier is a lanthanum-doped SiO2/ZrO2 carrier; the carrier is of a mesoporous structure, and the pore size of the carrier is 10-50 nm.
The inside of the carrier of the application presents a highly ordered three-dimensional pore canal structure, the active component has high carrying capacity and good dispersibility, and the mass airspeed of the catalyst is improved, namely the catalytic efficiency of the active component per unit mass is improved; the catalyst carrier also has good high thermal stability and hydrothermal stability, and the service life of the catalyst is prolonged.
The catalyst carrier of the application is prepared by SiO 2 And ZrO(s) 2 Is taken as a carrier together and doped with lanthanum hetero atoms, and the existence of the lanthanum hetero atoms extendsThe residence time of the hydrogen in the catalyst is prolonged, the reaction ratio of the hydrogen and the dimethyl adipate is optimized, and when the reaction ratio of the hydrogen and the dimethyl adipate is smaller, the higher catalytic reaction activity can be achieved; the improvement of the carrier reduces the ventilation of hydrogen in the reaction process and reduces the cost of preparing 1, 6-hexanediol by hydrogenating dimethyl adipate.
As a preferable technical scheme, the content of the active component is 20-35 wt% and the content of the carrier is 65-80 wt%.
As a preferable technical scheme, the mass ratio of the first active component to the second active component is 1:10 to 25. The double-active-component catalyst not only ensures that the catalyst has excellent performances of high conversion rate of dimethyl adipate and high selectivity of 1, 6-hexanediol, but also reduces the preparation cost of the catalyst by optimizing the ratio of the two active components.
As a preferable technical scheme, the mesoporous volume of the carrier is 0.55-0.86 cm 3 And/g. The high mesoporous volume of the carrier ensures that the catalyst has huge specific surface area, increases the contact area of active components and reaction raw materials, and improves the treatment capacity of the catalyst.
The preparation method of the catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate comprises the following steps:
s1, preparation of a carrier: dissolving lanthanum nitrate, sodium silicate and zirconium nitrate in deionized water to prepare a mixed solution A; in ice water bath, slowly dropwise adding the mixed solution A into the ice water bath, wherein the metering ratio is 1:1, controlling the pH value to 8-10 after the dripping is completed, and obtaining alkaline silica sol; then adding polyoxyethylene-polystyrene block copolymer and a proper amount of toluene, stirring and mixing uniformly, standing and aging for 4-12 h, filtering, washing and drying to obtain regular composite microspheres; vacuum drying the composite microsphere for 0.5-3 h at the temperature of 80-120 ℃, and roasting in a muffle furnace at 450-550 ℃ for 3-6 h to obtain the carrier with a mesoporous structure;
s2, carrier impregnation: preparing a nitrate solution of ruthenium and/or iridium and a copper chromite solution according to the weight ratio to form an active component solution; soaking the carrier prepared in the step S1 in a mixed solution consisting of cage-type polysilsesquioxane and active component solution to enable the active component to be uniformly attached to the carrier, and taking out after soaking for 1-10 hours; the nitrate solution of ruthenium and/or iridium is a ruthenium nitrate and/or iridium nitrate aqueous solution with the mass concentration of 20 wt%; the copper chromite solution comprises the following components in percentage by mass: 3, copper chromite and hydrochloric acid solution (the metering ratio is 1:1); the cage polysilsesquioxane is octaamino cage polysilsesquioxane or methacryloxypropyl cage polysilsesquioxane. The addition amount of the cage-type polysilsesquioxane accounts for 0.1-1% of the total mass of the mixed solution; the octaamino cage polysilsesquioxane is that the substituents of 8 vertex angles of the cage polysilsesquioxane are all substituents with functional groups of amino; the methacryloxypropyl cage-shaped polysilsesquioxane is an organic-inorganic hybrid nano cage-shaped structure and has the characteristics of low shrinkage, high permeability, high hardness, high wear resistance and the like.
S3, preparation of a catalyst: and (3) drying, forming and secondarily roasting the carrier subjected to the impregnation treatment in the step (S2) to obtain the catalyst.
As a preferable technical scheme, in step S1, the mass ratio of lanthanum nitrate, sodium silicate, zirconium nitrate and deionized water is 0.3-1: 5-15: 0.8 to 1.8:50 to 100.
In a preferred embodiment, in step S1, the amount of the polyoxyethylene-polystyrene block copolymer added is 5 to 10% of the amount of the alkaline silica sol. The polyoxyethylene-polystyrene block copolymer plays a role of a template agent in the preparation process of the mesoporous structure carrier.
As a preferable technical solution, in step S3, the drying conditions are as follows: the time is 2-24 h, and the temperature is 100-150 ℃; the roasting conditions are as follows: the time is 3-15 h, and the temperature is 500-700 ℃.
The application of the catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate comprises the steps of filling the catalyst prepared by the method into a tubular fixed bed reactor, wherein the operation condition of the reactor is as follows: the reaction temperature is 150-250 ℃, and the reaction pressure is2.5 MPa-5 MPa, and the liquid airspeed of dimethyl adipate is 1.5h -1 ～3.0h -1 The molar ratio of the hydrogen to the dimethyl adipate is 80-150:1.
The application has the beneficial effects that:
the catalyst for preparing the 1, 6-hexanediol by hydrogenating the dimethyl adipate adopts noble metal and non-noble metal as active components, the use amount of the noble metal is small, the catalytic reaction activity is high, the conversion rate of the dimethyl adipate reaches 97%, and the selectivity of the 1, 6-hexanediol reaches 98%.
The catalyst for preparing 1, 6-hexanediol by hydrogenating adipic acid dimethyl ester has the advantages that the carrier has high mesoporous characteristic, the inside of the catalyst presents a highly ordered three-dimensional pore structure, the active component has high carrying capacity and good dispersibility, and the unit processing capacity of the catalyst to adipic acid dimethyl ester is improved.
The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate has good high thermal stability and hydrothermal stability, and the service life of the catalyst is prolonged.
The application relates to a catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, which uses SiO 2 And ZrO(s) 2 The catalyst is a common carrier and doped with lanthanum heteroatom, so that the reaction ratio of hydrogen and dimethyl adipate is optimized, and when the molar ratio of hydrogen to dimethyl adipate is 120-150:1, the higher catalytic reaction activity can be achieved.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the application. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate of the embodiment consists of a carrier and active components which are dispersed and loaded on the carrier; the active component consists of a first active component and a second active component, wherein the first active component is ruthenium, and the second active component is copper chromite; the carrier is lanthanum-doped SiO 2 /ZrO 2 A carrier; the carrier is a mediumPore structure with pore size of 10-50 nm.
The active component content was 29wt% and the carrier content was 71wt%.
The mass ratio of the first active component to the second active component is 1:16.
the preparation method of the catalyst comprises the following steps:
s1, preparation of a carrier: dissolving lanthanum nitrate, sodium silicate and zirconium nitrate in deionized water to prepare a mixed solution A; in ice water bath, slowly dropwise adding the mixed solution A into the ice water bath, wherein the metering ratio is 1:1, controlling the pH value to 9 after the dripping is completed, and obtaining alkaline silica sol; then adding polyoxyethylene-polystyrene block copolymer and a proper amount of toluene, stirring and mixing uniformly, standing and aging for 8 hours, filtering, washing and drying to obtain regular composite microspheres; vacuum drying the composite microsphere for 1.5h at the temperature of 100 ℃, and roasting in a muffle furnace at the temperature of 500 ℃ for 4h to obtain the carrier with a mesoporous structure;
the mass ratio of the lanthanum nitrate to the sodium silicate to the zirconium nitrate to the deionized water is 0.6:10:1.4:80; the addition amount of the polyoxyethylene-polystyrene block copolymer accounts for 8% of the alkaline silica sol;
s2, carrier impregnation: preparing a ruthenium nitrate solution and a copper chromite solution according to the weight ratio to form an active component solution; soaking the carrier prepared in the step S1 in a mixed solution consisting of octaamino cage-type polysilsesquioxane and active component solution to enable the active component to be uniformly attached to the carrier, and taking out after soaking for 6 hours; the addition amount of the octaamino cage polysilsesquioxane accounts for 0.5% of the total mass of the mixed solution;
s3, preparation of a catalyst: and (3) drying, forming and secondarily roasting the carrier subjected to the impregnation treatment in the step (S2) to obtain the catalyst. The drying conditions are as follows: the time is 10 hours, and the temperature is 120 ℃; the roasting conditions are as follows: the time was 10h and the temperature was 600 ℃.
The catalyst prepared in this example was packed in a tubular fixed bed reactor and subjected to hydrogenation of dimethyl adipate to give 1, 6-hexanediol, provided withSetting the reaction temperature at 200 deg.c, the reaction pressure at 3.5MPa and the liquid space velocity of dimethyl adipate for 2.2 hr -1 The molar ratio of the hydrogen to the dimethyl adipate is 120:1; the reaction results show that the conversion rate of the dimethyl adipate reaches 93 percent, and the selectivity of the 1, 6-hexanediol reaches 94 percent.
Example 2
The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate of the embodiment consists of a carrier and active components which are dispersed and loaded on the carrier; the active component consists of a first active component and a second active component, wherein the first active component is iridium, and the second active component is copper chromite; the carrier is lanthanum-doped SiO 2 /ZrO 2 A carrier; the carrier is of a mesoporous structure, and the pore size of the carrier is 10-50 nm.
The active component content was 35wt% and the carrier content was 65wt%.
The mass ratio of the first active component to the second active component is 1:10.
the preparation method of the catalyst comprises the following steps:
s1, preparation of a carrier: dissolving lanthanum nitrate, sodium silicate and zirconium nitrate in deionized water to prepare a mixed solution A; in ice water bath, slowly dropwise adding the mixed solution A into the ice water bath, wherein the metering ratio is 1:1, controlling the pH value to 8 after the dripping is completed, and obtaining alkaline silica sol; then adding polyoxyethylene-polystyrene block copolymer and a proper amount of toluene, stirring and mixing uniformly, standing and aging for 4 hours, filtering, washing and drying to obtain regular composite microspheres; vacuum drying the composite microsphere for 0.5h at the temperature of 120 ℃, and roasting in a muffle furnace at 450 ℃ for 6h to obtain the carrier with a mesoporous structure;
the mass ratio of the lanthanum nitrate to the sodium silicate to the zirconium nitrate to the deionized water is 0.3:5:0.8:50; the addition amount of the polyoxyethylene-polystyrene block copolymer is 5% of that of the alkaline silica sol;
s2, carrier impregnation: preparing an iridium nitrate solution and a copper chromite solution according to the weight ratio to form an active component solution; soaking the carrier prepared in the step S1 in a mixed solution consisting of octaamino cage-type polysilsesquioxane and active component solution to enable the active component to be uniformly attached to the carrier, and taking out the carrier after soaking for 3 hours; the addition amount of the octaamino cage polysilsesquioxane accounts for 0.1% of the total mass of the mixed solution;
s3, preparation of a catalyst: and (3) drying, forming and secondarily roasting the carrier subjected to the impregnation treatment in the step (S2) to obtain the catalyst. The drying conditions are as follows: the time is 4 hours, and the temperature is 100 ℃; the roasting conditions are as follows: the time was 5h and the temperature was 650 ℃.
The catalyst prepared in the example is filled in a tubular fixed bed reactor, and is subjected to hydrogenation reaction to prepare 1, 6-hexanediol, wherein the reaction temperature is set to be 150 ℃, the reaction pressure is set to be 2.5MPa, and the liquid space velocity of dimethyl adipate is set to be 1.5h -1 The molar ratio of the hydrogen to the dimethyl adipate is 80:1; the reaction results show that the conversion rate of the dimethyl adipate reaches 92 percent, and the selectivity of the 1, 6-hexanediol reaches 94 percent.
Example 3
The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate of the embodiment consists of a carrier and active components which are dispersed and loaded on the carrier; the active component consists of a first active component and a second active component, wherein the first active component is ruthenium, and the second active component is copper chromite; the carrier is lanthanum-doped SiO 2 /ZrO 2 A carrier; the carrier is of a mesoporous structure, and the pore size of the carrier is 10-50 nm.
The active component content is 20wt%, and the carrier content is 80wt%.
The mass ratio of the first active component to the second active component is 1:25.
the preparation method of the catalyst comprises the following steps:
s1, preparation of a carrier: dissolving lanthanum nitrate, sodium silicate and zirconium nitrate in deionized water to prepare a mixed solution A; in ice water bath, slowly dropwise adding the mixed solution A into the ice water bath, wherein the metering ratio is 1:1, controlling the pH value to be 10 after the completion of dropwise adding to obtain alkaline silica sol; then adding polyoxyethylene-polystyrene block copolymer and a proper amount of toluene, stirring and mixing uniformly, standing and aging for 12 hours, filtering, washing and drying to obtain regular composite microspheres; vacuum drying the composite microsphere for 0.5h at the temperature of 120 ℃, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the carrier with a mesoporous structure;
the mass ratio of lanthanum nitrate to sodium silicate to zirconium nitrate to deionized water is 1:15:1.8:100; the addition amount of the polyoxyethylene-polystyrene block copolymer accounts for 10% of the alkaline silica sol;
s2, carrier impregnation: preparing a ruthenium nitrate solution and a copper chromite solution according to the weight ratio to form an active component solution; soaking the carrier prepared in the step S1 in a mixed solution consisting of methacryloxypropyl cage-shaped polysilsesquioxane and an active component solution to enable the active component to be uniformly attached to the carrier, and taking out after soaking for 10 hours; the adding amount of the methacryloxypropyl cage-shaped polysilsesquioxane accounts for 1% of the total mass of the mixed solution; the methacryloxypropyl cage polysilsesquioxane is available from Guangzhou New technology Co., ltd and has a CAS number of 622404-27-7;
s3, preparation of a catalyst: and (3) drying, forming and secondarily roasting the carrier subjected to the impregnation treatment in the step (S2) to obtain the catalyst. The drying conditions are as follows: the time is 24 hours, and the temperature is 150 ℃; the roasting conditions are as follows: the time was 15h and the temperature was 500 ℃.
The catalyst prepared in the example is filled in a tubular fixed bed reactor, and is subjected to hydrogenation reaction to prepare 1, 6-hexanediol, wherein the reaction temperature is set to 250 ℃, the reaction pressure is 5MPa, and the liquid space velocity of dimethyl adipate is 3.0h -1 The molar ratio of the hydrogen to the dimethyl adipate is 150:1; the reaction results show that the conversion rate of the dimethyl adipate reaches 91 percent and the selectivity of the 1, 6-hexanediol reaches 92 percent.
Example 4
The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate of the embodiment consists of a carrier and active components which are dispersed and loaded on the carrier; the active component is composed of a first active component and a second active componentThe first active component is iridium, and the second active component is copper chromite; the carrier is lanthanum-doped SiO 2 /ZrO 2 A carrier; the carrier is of a mesoporous structure, and the pore size of the carrier is 10-50 nm.
The active component content was 25wt% and the carrier content was 75wt%.
The mass ratio of the first active component to the second active component is 1:20.
the preparation method of the catalyst comprises the following steps:
s1, preparation of a carrier: dissolving lanthanum nitrate, sodium silicate and zirconium nitrate in deionized water to prepare a mixed solution A; in ice water bath, slowly dropwise adding the mixed solution A into the ice water bath, wherein the metering ratio is 1:1, controlling the pH value to 9 after the dripping is completed, and obtaining alkaline silica sol; then adding polyoxyethylene-polystyrene block copolymer and a proper amount of toluene, stirring and mixing uniformly, standing and aging for 6 hours, filtering, washing and drying to obtain regular composite microspheres; vacuum drying the composite microsphere for 1.5h at 90 ℃, and roasting in a muffle furnace at 500 ℃ for 4h to obtain the carrier with a mesoporous structure;
the mass ratio of the lanthanum nitrate to the sodium silicate to the zirconium nitrate to the deionized water is 0.7:12:1.5:70; the addition amount of the polyoxyethylene-polystyrene block copolymer accounts for 6% of the alkaline silica sol;
s2, carrier impregnation: preparing an iridium nitrate solution and a copper chromite solution according to the weight ratio to form an active component solution; soaking the carrier prepared in the step S1 in a mixed solution consisting of octaamino cage-type polysilsesquioxane and active component solution to enable the active component to be uniformly attached to the carrier, and taking out after soaking for 8 hours; the addition amount of the octaamino cage polysilsesquioxane accounts for 0.6% of the total mass of the mixed solution;
s3, preparation of a catalyst: and (3) drying, forming and secondarily roasting the carrier subjected to the impregnation treatment in the step (S2) to obtain the catalyst. The drying conditions are as follows: the time is 12 hours, and the temperature is 120 ℃; the roasting conditions are as follows: the time was 12h and the temperature was 650 ℃.
The catalyst prepared in the example is filled in a tubular fixed bed reactor, and is subjected to hydrogenation reaction to prepare 1, 6-hexanediol, wherein the reaction temperature is set to be 200 ℃, the reaction pressure is set to be 4MPa, and the liquid space velocity of dimethyl adipate is set to be 2.5h -1 The molar ratio of the hydrogen to the dimethyl adipate is 130:1; the reaction results show that the conversion rate of the dimethyl adipate reaches 93 percent, and the selectivity of the 1, 6-hexanediol reaches 94 percent.
Comparative example 1
The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate of this comparative example has the same structure, composition and preparation method as example 1, but is mainly different in that the catalyst carrier of this comparative example is not doped with lanthanum and is only SiO 2 /ZrO 2 A carrier.
The catalysts prepared in examples 1 to 4 and comparative example 1 were subjected to performance test, and the performance results are shown in Table 1:
mesoporous pore volume test: measuring by adopting a nitrogen adsorption and desorption method;
high thermal stability test: the catalysts prepared in examples 1 to 4 and comparative example 1 were heated at a high temperature of 400℃for 168 hours, and then subjected to a test of dimethyl adipate conversion and 1, 6-hexanediol selectivity under the same conditions, and then the decrease rates of dimethyl adipate conversion and 1, 6-hexanediol selectivity before and after heating were used as evaluation indexes of high temperature stability, respectively;
hydrothermal stability test: the catalysts prepared in examples 1 to 4 and comparative example 1 were continuously heated at 100℃for 24 hours, and then tested for dimethyl adipate conversion and 1, 6-hexanediol selectivity under the same conditions, and then the dimethyl adipate conversion and 1, 6-hexanediol selectivity decrease rate before and after heating were used as evaluation indexes of water temperature stability, respectively;
the foregoing has shown and described the basic principles, principal features and advantages of the application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present application, and various changes and modifications may be made therein without departing from the spirit and scope of the application, which is defined by the appended claims.

Claims (8)

1. The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate is characterized by comprising a carrier and active components which are dispersedly supported on the carrier; the active component consists of a first active component and a second active component, wherein the first active component is ruthenium and/or iridium, and the second active component is copper chromite; the carrier is a lanthanum-doped SiO2/ZrO2 carrier; the carrier is of a mesoporous structure, and the pore size of the carrier is 10-50 nm;
the preparation method of the catalyst comprises the following steps:
s1, preparation of a carrier: dissolving lanthanum nitrate, sodium silicate and zirconium nitrate in deionized water to prepare a mixed solution A; in ice water bath, slowly dropwise adding the mixed solution A into the ice water bath, wherein the metering ratio is 1: 1. controlling the pH value to 8-10 after the completion of the dropwise addition to obtain alkaline silica sol; then adding polyoxyethylene-polystyrene block copolymer and a proper amount of toluene, stirring and mixing uniformly, standing and aging for 4-12 h, filtering, washing and drying to obtain regular composite microspheres; vacuum drying the composite microsphere for 0.5-3 h at the temperature of 80-120 ℃ and roasting in a muffle furnace at 450-550 ℃ for 3-6 h to obtain the carrier with a mesoporous structure;
s2, carrier impregnation: preparing a nitrate solution of ruthenium and/or iridium and a copper chromite solution according to the weight ratio to form an active component solution; soaking the carrier prepared in the step S1 in a mixed solution consisting of cage-type polysilsesquioxane and active component solution to enable the active component to be uniformly attached to the carrier, and taking out after soaking for 1-10 hours;
s3, preparation of a catalyst: and (3) drying, forming and secondarily roasting the carrier subjected to the impregnation treatment in the step (S2) to obtain the catalyst.
2. The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate according to claim 1, wherein the content of the active component is 20-35 wt% and the content of the carrier is 65-80 wt%.
3. The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate according to claim 1, wherein the mass ratio of the first active component to the second active component is 1:10 to 25.
4. The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate according to claim 1, wherein the mesoporous volume of the carrier is 0.55-0.86 cm3/g.
5. The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate according to claim 1, wherein in the step S1, the mass ratio of lanthanum nitrate, sodium silicate, zirconium nitrate and deionized water is 0.3-1: 5-15: 0.8 to 1.8:50 to 100.
6. The catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate according to claim 1, wherein in the step S1, the addition amount of the polyoxyethylene-polystyrene block copolymer is 5 to 10% of that of the basic silica sol.
7. The catalyst for the hydrogenation of dimethyl adipate to 1, 6-hexanediol according to claim 1, wherein in step S3, the drying conditions are: the time is 2-24 h, and the temperature is 100-150 ℃; the roasting conditions are as follows: the time is 3-15 h, and the temperature is 500-700 ℃.
8. Use of a catalyst according to any one of claims 1 to 7 packed in a tubular fixed bed reactor, the reactor operating conditions: the reaction temperature is 150-250 ℃, the reaction pressure is 2.5-5 MPa, the liquid airspeed of the dimethyl adipate is 1.5h < -1 > -3.0 h < -1 >, and the molar ratio of hydrogen to the dimethyl adipate is 80-150:1.
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