CN111420700A - Copper-doped composite catalyst and preparation method and application thereof - Google Patents

Copper-doped composite catalyst and preparation method and application thereof Download PDF

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CN111420700A
CN111420700A CN202010286379.2A CN202010286379A CN111420700A CN 111420700 A CN111420700 A CN 111420700A CN 202010286379 A CN202010286379 A CN 202010286379A CN 111420700 A CN111420700 A CN 111420700A
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catalyst
active component
copper
carbonate
doped composite
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CN111420700B (en
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魏天荣
孙苏红
陈坤
於国伟
薛耘芸
张小元
李善华
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Hubei Sanning Carbon Phosphorus Based New Material Industry Technology Research Institute Co ltd
Hubei Sanning Chemical Co Ltd
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Hubei Sanning Carbon Phosphorus Based New Material Industry Technology Research Institute Co ltd
Hubei Sanning Chemical Co Ltd
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a copper-doped composite catalyst and a preparation method and application thereof, wherein the active component of the catalyst comprises a first active component and/or a second active component, and the first active component is ZrO2Or MoO3A second active ingredientThe CuO is adopted, and the mass ratio of the first active component to the carrier is (5-30): (95-70), and the mass fraction of the second active component is 5-20 wt%. The preparation method comprises the steps of uniformly mixing zirconium oxide or molybdenum oxide serving as an active component with a carrier by nitric acid, then forming, drying at 30-150 ℃ for 1-10h, roasting at 200-700 ℃ for 1-24h, then soaking in a copper salt solution for 1-48h, drying at 70-120 ℃ for 1-10h, and roasting at 200-600 ℃ for 1-24h to obtain the novel catalyst for preparing the diphenyl carbonate by the disproportionation reaction. The catalyst has higher activity and selectivity for preparing diphenyl carbonate by disproportionation reaction of methyl phenyl carbonate, the conversion rate of the methyl phenyl carbonate can reach more than 60 percent, and the product selectivity is more than 99 percent.

Description

Copper-doped composite catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and relates to a copper-doped composite catalyst and a preparation method and application thereof.
Background
Diphenyl carbonate is an important organic intermediate, can synthesize a plurality of important organic compounds and high molecular materials, and can replace phosgene to react with bisphenol A to synthesize polycarbonate with excellent performance. At present, the most studied method for synthesizing diphenyl carbonate is the ester exchange method, including the ester exchange method of dimethyl carbonate and phenol, the ester exchange method of dimethyl oxalate and phenol, and the ester exchange method of carboxylic ester and dimethyl carbonate, wherein the method for synthesizing diphenyl carbonate by dimethyl carbonate and phenol is the main method.
In the disproportionation reaction stage, the catalyst for synthesizing diphenyl carbonate from methyl phenyl carbonate mainly comprises an organic titanium catalyst, an organic tin catalyst, a metal oxide composite catalyst and the like. In CN101491761A introduces a Pb-Cu composite oxide catalyst for disproportionation of methyl phenyl carbonate, which is prepared by a solution mixing method and a mechanical method, the highest yield of diphenyl carbonate exceeds 80 percent, the catalyst has poor mechanical strength, an active component lead is easy to run off, and the catalyst activity is reduced by repeated use. CN106140133B discloses a PbO/ZrO2The catalyst has the problems that the conversion rate of methyl phenyl carbonate reaches 76.6 percent, the yield of diphenyl carbonate reaches 76.1 percent, and active components are easy to lose. In "diphenyl carbonate synthesized by disproportionation of methylphenyl carbonate catalyzed by organotin compound" and "research on disproportionation of methylphenyl carbonate catalyzed by organotitanium compound", Wangselin et al studied organotin and organotitanium catalysts, respectively, wherein BuSnO (OH) catalyst in organotin has the best effect, the conversion rate of methylphenyl carbonate is up to 89.7%, and the selectivity and yield of diphenyl carbonate are 99.3% and 89.1%, respectively. In the organic titanium catalyst, tetraisopropyl titanate is used as a catalyst, the conversion rate of methyl phenyl carbonate reaches 90.3%, and the selectivity of diphenyl carbonate reaches 99.9%. "research on diphenyl carbonate and methyl phenyl carbonate synthesized by transesterification" in Xiyuanhong et al adopts Mg-Al hydrotalcite and isopropyl titanate as catalyst, and under the condition of reduced pressure of 600mmHg, the conversion rate of methyl phenyl carbonate is 63%, and the catalyst has the problem of poor repeatability.
Disclosure of Invention
The invention provides a copper-doped composite catalyst, a preparation method and application thereof, which can solve the problems of difficult separation, easy loss and difficult regeneration of the existing catalyst and have the advantages of high stability, easy separation and regeneration.
The technical scheme adopted by the invention is as follows:
the active component of the copper-doped composite catalyst comprises a first active component and/or a second active component, wherein the first active component is ZrO2Or MoO3The second active component is CuO, and the mass ratio of the first active component to the carrier is (5-30): (95-70), and the mass fraction of the second active component is 5-20 wt%.
Preferably, the support is an HZSM-5 molecular sieve.
The preparation method of the copper-doped composite catalyst comprises the following steps:
1) uniformly mixing the first active component and the carrier by using nitric acid, and then forming to obtain a catalyst intermediate A;
2) drying the catalyst intermediate A at 30-150 ℃ for 1-10h, and then roasting at 200-700 ℃ for 1-24h to obtain a catalyst intermediate B, namely a catalyst with an active component as a first active component;
3) the catalyst intermediate B is soaked in a copper salt solution for 1-48h, dried at 70-120 ℃ for 1-10h and then roasted at 200-600 ℃ for 1-24h to obtain the copper-doped composite catalyst, namely the catalyst with the active component comprising a first active component and a second active component.
Preferably, the concentration of the nitric acid of the step 1) is 5 to 30 wt%.
Preferably, the salt solution of copper in step 3) is copper nitrate, copper acetate or copper sulfate.
Preferably, when the catalyst in the step 1) is molded, the catalyst is made into a strip shape, the length of the strip shape is 0.5-1.5cm, and the diameter of the strip shape is 1-3 mm.
The catalyst or the catalyst prepared by the method is used for carrying out a methyl phenyl carbonate disproportionation reaction to prepare diphenyl carbonate.
Preferably, the pressure is 100-760mmHg, the catalyst is used in 0.01-0.1wt%, the reaction time is 1-8h, and the reaction temperature is 140-220 ℃ during the disproportionation reaction.
The diphenyl carbonate and dimethyl carbonate are generated by the disproportionation reaction of methyl phenyl carbonate, the yield of the diphenyl carbonate is directly influenced by the disproportionation reaction rate of the methyl phenyl carbonate, the method for improving the yield of the diphenyl carbonate breaks the reaction balance, removes the dimethyl carbonate and reduces the probability of reverse reaction on one hand, and the method for improving the yield of the diphenyl carbonate adds a feasible catalyst on the other hand, accelerates the reaction rate, reduces the reaction time and reduces the generation of byproducts.
The invention has the following beneficial effects:
1. the disproportionation reaction process of methyl phenyl carbonate needs a catalyst with a weak acid center, the HZSM-5 molecular sieve as a carrier has weak acid, medium strong acid and strong acid centers, molybdenum oxide contains the weak acid center, and copper oxide and zirconium oxide are amphoteric oxides and have both an acid center and a basic center, wherein the basic center can weaken the strong acid center of the molecular sieve carrier, so that the generation of byproducts caused by the over-strong acidity of the catalyst is avoided.
2. Copper is doped in the catalyst, so that on one hand, zirconium oxide and molybdenum oxide can be activated, and the catalytic activity of the catalyst is improved; on the other hand, the first active component can be dispersed by adopting a copper salt solution impregnation method, the dispersion degree of copper on the surface of the catalyst can be increased, the surface ion agglomeration is hindered, the dispersion degree and the catalytic circulation stability of the active component in the catalyst are improved, the sintering and agglomeration phenomena of the catalyst are effectively inhibited, and the catalytic activity of the catalyst is further improved.
3. The copper is doped in the catalyst, so that the synergistic effect of the molybdenum-copper or zirconium-copper serving as an active component can be increased, the specific surface area of the catalyst can be increased through the synergistic effect, and the pore structure of the catalyst can be changed, so that the catalytic activity of the catalyst is improved.
4. Nitric acid is added in the preparation of the catalyst to be used as a binder, so that the catalyst is molded, the strength of the catalyst is increased, and the loss of active components is avoided.
5. The catalyst molding can avoid the catalyst and the product from being mixed together, the later separation can be simpler, and the problems that the catalyst and the product are difficult to separate and regenerate are solved.
6. The method for preparing the catalyst has the advantages of simple operation, low cost and easy industrialization.
Detailed Description
The invention will be further elucidated with reference to the following examples.
Example 1
Using 15 wt% of nitric acid, and mixing ZrO with the mass fraction of 30%2And 70 percent of HZSM-5, then forming, drying for 5 hours at 50 ℃, roasting for 12 hours at 540 ℃, then soaking in 15 weight percent of copper nitrate solution for 24 hours, drying for 8 hours at 100 ℃, and roasting for 10 hours at 500 ℃ to obtain the novel catalyst 1.
The diphenyl carbonate was obtained by subjecting methyl phenyl carbonate to disproportionation reaction under reduced pressure under the above catalyst, at a pressure of 570mmHg, in an amount of 0.05 wt% catalyst, for 6 hours at a reaction temperature of 200 ℃ to obtain diphenyl carbonate, and the results are shown in Table 1.
Example 2
Using 15 wt% of nitric acid, and mixing the mixture with 30% of MoO in mass fraction3And 70 percent of HZSM-5, then forming, drying for 5 hours at 50 ℃, roasting for 12 hours at 540 ℃, then soaking in 15 weight percent of copper nitrate solution for 24 hours, drying for 8 hours at 100 ℃, and roasting for 10 hours at 500 ℃ to obtain the novel catalyst 2.
The reaction conditions were the same as in example 1, and the results are shown in Table 1.
Example 3
Using 15 wt% of nitric acid, and mixing ZrO with the mass fraction of 30%2And 70 percent of HZSM-5, then forming, drying for 5 hours at 50 ℃ and roasting for 12 hours at 540 ℃ to obtain the novel catalyst 3, wherein the length of the mixture is about 0.5cm, and the diameter of the mixture is about 1 mm.
The reaction conditions were the same as in example 1, and the results are shown in Table 1.
Example 4
Using 15 wt% of nitric acid, and mixing the mixture with 30% of MoO in mass fraction3And 70 percent of HZSM-5, then forming, drying for 5 hours at 50 ℃ and roasting for 12 hours at 540 ℃ to obtain the novel catalyst 4, wherein the length of the formed product is about 0.5cm, and the diameter of the formed product is about 1 mm.
The reaction conditions were the same as in example 1, and the results are shown in Table 1.
TABLE 1
Figure BDA0002448675040000041
As can be seen from Table 1, ZrO was used respectively2/HZSM-5、MoO3The catalyst HZSM-5 is used for carrying out disproportionation reaction, the conversion rate of methyl phenyl carbonate is more than 60%, the yield of diphenyl carbonate is more than 60%, after copper is added, the conversion rate of methyl phenyl carbonate is obviously increased, the yield of diphenyl carbonate is correspondingly increased, and the disproportionation reaction rate is accelerated by adding copper.
Example 5
Using 30wt% of nitric acid, and mixing ZrO with the mass fraction of 5%2And 95 percent of HZSM-5, then forming, drying for 2 hours at 100 ℃, roasting for 18 hours at 400 ℃, then soaking in 5 weight percent of copper acetate solution for 12 hours, drying for 10 hours at 70 ℃, and roasting for 15 hours at 550 ℃ to obtain the novel catalyst 5.
The diphenyl carbonate was obtained by subjecting methyl phenyl carbonate to disproportionation reaction under reduced pressure under the above catalyst, at a pressure of 115mmHg, in an amount of 0.01 wt% for 3 hours at a reaction temperature of 150 ℃ to obtain diphenyl carbonate, the results of which are shown in Table 2.
Example 6
Using 30wt% of nitric acid, and mixing ZrO with the mass fraction of 5%2And 95% HZSM-5, then forming, the length is about 1cm, the diameter is about 3mm, drying for 2h at 100 ℃, then roasting for 18h at 400 ℃, then soaking in 5 wt% copper sulfate solution for 12h, drying for 10h at 70 ℃, and then roasting for 15h at 550 ℃ to obtain the novel catalyst 6.
The reaction conditions were the same as in example 5, and the results are shown in Table 2.
Example 7
Using 30wt% of nitric acid, and mixing ZrO with the mass fraction of 5%2And 95% HZSM-5, then forming, the length is about 1cm, the diameter is about 3mm, drying for 2h at 100 ℃, then roasting for 18h at 400 ℃, then soaking in 5 wt% copper nitrate solution for 12h, drying for 10h at 70 ℃, and then roasting for 15h at 550 ℃ to obtain the novel catalyst 7.
The reaction conditions were the same as in example 5, and the results are shown in Table 2.
TABLE 2
Figure BDA0002448675040000051
As can be seen from Table 2, the catalysts using different copper sources have different catalytic activities, and under the same conditions, the catalyst using copper nitrate as the copper source has the highest activity, the highest conversion rate of methyl phenyl carbonate and the highest yield of diphenyl carbonate, indicating that the copper nitrate as the copper source has the best effect.
Example 8
Washing the surface of the novel catalyst 1 by using an absolute ethyl alcohol solution, drying for 6h at 100 ℃, and roasting for 5h at 540 ℃ to obtain a regenerated catalyst, which is marked as catalyst 8.
The reaction conditions were the same as in example 1, and the results are shown in Table 3.
Example 9
Washing the surface of the catalyst 8 with an absolute ethyl alcohol solution, drying at 100 ℃ for 6h, and roasting at 540 ℃ for 5h to obtain a regenerated catalyst, which is marked as catalyst 9.
The reaction conditions were the same as in example 1, and the results are shown in Table 3.
Example 10
Washing the surface of the catalyst 9 with an absolute ethanol solution, drying at 100 ℃ for 6h, and roasting at 540 ℃ for 5h to obtain a regenerated catalyst, which is marked as catalyst 10.
The reaction conditions were the same as in example 1, and the results are shown in Table 3.
TABLE 3
Figure BDA0002448675040000052
It can be seen from table 3 that the conversion rate of the disproportionation reaction of methyl phenyl carbonate is reduced by 1.8%, the selectivity of diphenyl carbonate is reduced by 0.1%, and the yield of diphenyl carbonate is reduced by 1.9% after catalyst 1 is reused 4 times.

Claims (8)

1. A copper-doped composite catalyst characterized by: the active component of the catalyst comprises a first active component and/or a second active component, wherein the first active component is ZrO2Or MoO3The second active component is CuO, and the mass ratio of the first active component to the carrier is (5-30): (95-70), and the mass fraction of the second active component is 5-20 wt%.
2. The copper-doped composite catalyst according to claim 1, characterized in that: the carrier is HZSM-5 molecular sieve.
3. A method for preparing the copper-doped composite catalyst according to any one of claims 1 to 2, characterized in that: the preparation method comprises the following steps:
1) uniformly mixing the first active component and the carrier by using nitric acid, and then forming to obtain a catalyst intermediate A;
2) drying the catalyst intermediate A at 30-150 ℃ for 1-10h, and then roasting at 200-700 ℃ for 1-24h to obtain a catalyst intermediate B, namely a catalyst with an active component as a first active component;
3) the catalyst intermediate B is soaked in a copper salt solution for 1-48h, dried at 70-120 ℃ for 1-10h and then roasted at 200-600 ℃ for 1-24h to obtain the copper-doped composite catalyst, namely the catalyst with the active component comprising a first active component and a second active component.
4. The method of claim 3, wherein: the concentration of the nitric acid in the step 1) is 5-30 wt%.
5. The method of claim 3, wherein: the salt solution of copper in the step 3) is copper nitrate, copper acetate and copper sulfate.
6. The method of claim 3, wherein: when the catalyst in the step 1) is molded, the catalyst is made into a strip shape, the length of the strip shape is 0.5-1.5cm, and the diameter of the strip shape is 1-3 mm.
7. The catalyst of any one of claims 1 to 2 or the catalyst prepared by the method of any one of claims 3 to 6 is used for the disproportionation of methyl phenyl carbonate to prepare diphenyl carbonate.
8. Use according to claim 7, characterized in that: during the disproportionation reaction, the pressure is 100-760mmHg, the catalyst dosage is 0.01-0.1wt%, the reaction time is 1-8h, and the reaction temperature is 140-220 ℃.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1168815A (en) * 1996-06-14 1997-12-31 杭州大学 Double component catalyst for directly synthesizing armoatic hydrocarbon by using methane as row material
CN110252274A (en) * 2019-06-14 2019-09-20 湖北三宁碳磷基新材料产业技术研究院有限公司 The preparation method of ester exchange synthesizing diphenyl carbonate catalyst
CN110818566A (en) * 2018-08-09 2020-02-21 中国科学院大连化学物理研究所 Method for preparing cyclopentanol from cyclopentene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1168815A (en) * 1996-06-14 1997-12-31 杭州大学 Double component catalyst for directly synthesizing armoatic hydrocarbon by using methane as row material
CN110818566A (en) * 2018-08-09 2020-02-21 中国科学院大连化学物理研究所 Method for preparing cyclopentanol from cyclopentene
CN110252274A (en) * 2019-06-14 2019-09-20 湖北三宁碳磷基新材料产业技术研究院有限公司 The preparation method of ester exchange synthesizing diphenyl carbonate catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SONG WANG等: "Dimethyl ether synthesis via CO2 hydrogenation over CuO–TiO2–ZrO2/HZSM-5 bifunctional catalysts" *

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