CN111167518A - Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof - Google Patents

Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof Download PDF

Info

Publication number
CN111167518A
CN111167518A CN202010009115.2A CN202010009115A CN111167518A CN 111167518 A CN111167518 A CN 111167518A CN 202010009115 A CN202010009115 A CN 202010009115A CN 111167518 A CN111167518 A CN 111167518A
Authority
CN
China
Prior art keywords
uio
catalyst
cuzn
carbon dioxide
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010009115.2A
Other languages
Chinese (zh)
Inventor
邵霞
宋清政
俞俊
高宁
韩颖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Technology
Original Assignee
Shanghai Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Technology filed Critical Shanghai Institute of Technology
Priority to CN202010009115.2A priority Critical patent/CN111167518A/en
Publication of CN111167518A publication Critical patent/CN111167518A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • C07C29/15—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 oxides of carbon exclusively
    • C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及一种二氧化碳加氢合成甲醇的催化剂及其制备方法。所用主要原料为Cu(NO3)2·3H2O,Zn(NO3)2·6H2O，四氯化锆，对苯二甲酸，N,N‑二甲基甲酰胺和盐酸。所述的制备方法为共沉淀法，将UiO‑66添加到Cu和Zn盐溶液中，滴加碳酸钠溶液至pH为7，再经老化过滤。本发明所述的催化剂特点在于UiO‑66将Cu颗粒包裹，能有效防止Cu颗粒聚集，催化剂稳定性显著提高，甲醇的选择性和二氧化碳转化率也有一定程度提高。The invention relates to a catalyst for synthesizing methanol by hydrogenation of carbon dioxide and a preparation method thereof. The main raw materials used are Cu(NO 3 ) 2 ·3H 2 O, Zn(NO 3 ) 2 ·6H 2 O, zirconium tetrachloride, terephthalic acid, N,N-dimethylformamide and hydrochloric acid. The preparation method is a co-precipitation method. UiO-66 is added to the Cu and Zn salt solution, the sodium carbonate solution is added dropwise to pH 7, and then filtered through aging. The catalyst of the invention is characterized in that UiO-66 wraps the Cu particles, which can effectively prevent the Cu particles from agglomerating, the stability of the catalyst is significantly improved, and the selectivity of methanol and the conversion rate of carbon dioxide are also improved to a certain extent.

Description

Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof
Technical Field
The invention relates to a catalyst for synthesizing methanol by carbon dioxide hydrogenation and a preparation method thereof, belonging to the field of catalysts.
Background
After the industrial revolution, fossil energy is exploited in large quantities, and then a large amount of carbon is released into the atmosphere, the global average temperature rises by 1.02 ℃ in 2015 compared with that before the industrial revolution, the global average temperature rises by 0.85 ℃ in 1980 to 2012, the global average temperature rises by more than 2 ℃, human beings lose control over global climate, the paris agreement signed in 2016 tries to control the global average temperature rise within 1.5 ℃ in the century, and China is CO in the world at present2The emission of carbon dioxide is urgently controlled in the first major country, hydrogen can be produced by dissociating water by utilizing solar energy and other forms of renewable energy sources, and other large quantities of consumed chemicals are synthesized by utilizing the hydrogenation catalysis of the carbon dioxide, so that the method is also an important method for solving the greenhouse effect.
Methanol exists in liquid form at normal temperature, is a novel clean energy source, can be combusted, and utilizes CO2Hydrogenation for synthesizing methanol, and the methanol can be combusted to produce CO2This is a complete carbon cycle with little environmental impact, the most studied CO at present2The catalyst for synthesizing methanol by hydrogenation is concentrated on a CuZnO system, the CuZnAl catalyst is widely used for preparing methanol by carbon dioxide hydrogenation in industry, the defects are obvious, the problems of low methanol selectivity, easy inactivation of the catalyst and the like are faced, and subsequent researchers load Cu and ZnO on ZrO2On the carrier, the catalyst activity is improved to a certain extent, for example, the Chinese academy of sciences, large-linkage chemico-physical research institute CN107008332A, reports different Cu: zn: al: compared with the traditional CuZnAl and CuZnZr catalysts, the activity of the CuZnAlZr catalyst with the Zr ratio is obviously improved, and the yield of methanol of the catalyst with the optimal ratio reaches 25.3 percent under the reaction condition of 4.8 MPa. For UiO-66 is mostly used as an adsorbent, for example, the Unionidae institute CN 108084453A reports that UiO-66 metal organic framework material pore diameter diffusion and is used as an adsorbent for treating organic dye wastewater, which also shows that UiO-66 has more excellent adsorption capacity in a certain aspect, and has more excellent structural stability different from other MOFs materials, of course UiO-66 also has certain application in catalysis,for example, CN 107987281A of university of Jiangsu university supports Cu on modified UiO-66, Cu-UiO-66 is prepared by an impregnation method and is used for preparing methanol from synthesis gas, the catalyst shows excellent carbon conversion capacity, the catalyst is greatly different from the catalyst researched by us, the catalyst is prepared by simply impregnating Cu on the surface of the UiO-66 by the impregnation method, the Cu and ZnO are wrapped by the UiO-66 by a coprecipitation method, and the influence of carrier modification on the preparation of methanol from catalytic synthesis gas is mainly researched in the research direction, the activity of the preparation of methanol from catalytic carbon dioxide hydrogenation is improved, the catalyst is more likely to be popularized, and the application of the UiO-66 serving as a carrier for preparing methanol from carbon dioxide hydrogenation is only reported.
Disclosure of Invention
The invention aims to provide a catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and a preparation method thereof.
In order to achieve the aim, the invention provides a catalyst CuZn/UiO-66 for synthesizing methanol by hydrogenating carbon dioxide, which is characterized in that Cu and Zn are loaded on the UiO-66, wherein the mass of the Cu and the Zn accounts for 5-55% of the total mass of the catalyst, and the mass ratio of the Cu: zn is 1:1 to 4: 1.
The invention also provides a preparation method of the catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation, which is characterized by comprising the following steps:
(1) preparing a Cu and Zn salt water solution with the concentration of 0.1-0.5 mol/L, adding UiO-66 to obtain a mixed solution, and carrying out coprecipitation at the temperature of 60-90 ℃, wherein the concentration of UiO-66 in the mixed solution is 0.1-0.2 g/mL; preparing 0.5-1 mol/L sodium carbonate aqueous solution, dropwise adding the sodium carbonate aqueous solution into the mixed solution, controlling the pH value to be 7-8, aging the obtained precipitate for 2-4 h, and filtering to obtain a CuZn/UiO-66 precipitate precursor;
(2) drying the CuZn/UiO-66 precipitate precursor obtained in the step (1) at the temperature of 80-110 ℃ for 10-16 h, roasting at the temperature of 250-400 ℃ for 2-4 h, and screening 40-80 mesh particles to obtain the catalyst CuZn/UiO-66 for synthesizing methanol by hydrogenating carbon dioxide.
Preferably, the preparation of UiO-66 in the step (1) comprises: adding zirconium tetrachloride and terephthalic acid into a mixed solution of N, N-dimethylformamide and hydrochloric acid, and ultrasonically dissolving; and (3) placing the mixed solution at 80-110 ℃, preserving heat for 24 hours, cooling to room temperature, washing with terephthalic acid and methanol for 6 times, placing the obtained solid powder at room temperature, airing, and placing the aired solid powder in an oven at 80-110 ℃ for drying for 12-16 hours to obtain the UiO-66 material.
Compared with the prior art, the invention has the beneficial effects that:
the catalyst provided by the invention is used for preparing methanol by carbon dioxide hydrogenation, the activity is obviously improved, the optimal 45% CuZn/UiO-66 catalyst has a space velocity of 3000mL/(h g) at 3MPa, the carbon dioxide conversion rate reaches 19.69%, the methanol selectivity reaches 49.61%, the carbon dioxide conversion rate of the traditional CuZnZr catalyst reaches 15.77%, the methanol selectivity reaches 40.39%, the UiO-66 catalyst is used as a carrier, the effect is obviously improved, and the stability is also excellent.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The preparation method of UiO-66 in each embodiment of the invention is as follows:
step 1: adding 3g of zirconium tetrachloride and 2.95g of terephthalic acid into 384mL of a mixed solution of N, N-dimethylformamide and hydrochloric acid, wherein the volume ratio of the N, N-dimethylformamide to the hydrochloric acid is 15:1, the concentration of the hydrochloric acid is 0.77mol/L, and carrying out ultrasonic dissolution;
step 2: and (3) placing the mixed solution at 80-110 ℃, preserving heat for 24 hours, cooling to room temperature, washing with terephthalic acid and methanol for 6 times, placing the obtained solid powder at room temperature, airing, and placing the aired solid powder in an oven at 80-110 ℃ for drying for 12-16 hours to obtain the UiO-66 material.
The activity evaluation of the catalyst in each embodiment of the invention on the synthesis of methanol by hydrogenation of carbon dioxide is carried out on a pressurized fixed bed continuous flow reactor-GC combined system:
the oxide precursor before reaction is 10 vol% H2/N2Reducing for 2 hours under normal pressure at 300 ℃, and switching the gas to 64.5 percent H after the reduction is finished2-23.5％CO2-12％N2The reaction pressure of the raw material gas is 3MPa, the reaction temperature is 200-300 ℃, the space velocity is 1500-6000 mL/(h g), and the detection is carried out after the reaction gas is introduced and the reaction is maintained for 3 hours.
Example 1
The embodiment provides a preparation method of a catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation, which comprises the following specific steps:
0.284g of Cu (NO3) was weighed out2·3H2O and 0.137g Zn (NO)3)2·6H2Preparing 20mL of aqueous solution, adding 2g of UiO-66 carrier, placing the mixed solution on a magnetic stirrer, stirring for 1 hour, placing the stirred solution in a water bath kettle at 60 ℃ after stirring, preparing 50mL of 0.5mol/L sodium carbonate aqueous solution, slowly adding the sodium carbonate aqueous solution into the mixed solution until the pH value is 7, standing and aging the solution in a water bath at 60 ℃ for 3 hours after precipitation is finished, carrying out suction filtration and washing for 5 times, drying the solution at 80 ℃, roasting the solution at 300 ℃ for 4 hours to obtain a catalyst oxide precursor, and screening a 40-80-mesh catalyst for activity evaluation, wherein the prepared catalyst is a 5% CuZn/UiO-66 catalyst, and the molar ratio of Cu in the catalyst is as follows: zn ═ 5: 2.
The activity evaluation of the catalyst is carried out on a fixed bed reactor, 0.3g of the screened catalyst is weighed, 0.5g of quartz sand is mixed into the catalyst, the catalyst is placed into a stainless steel reaction tube with the diameter of 5mm, before the reaction, the catalyst is placed under the normal pressure, the reduction is carried out for 2 hours at the temperature of 300 ℃ in the atmosphere of reducing gas (10 vol% H2/N2) with the flow rate of 46.5mL/min, the catalyst is cooled to 240 ℃ after the reduction is finished, and the temperature is switched to raw material gas (64.5% H22-23.5％CO2-12％N2) The reaction is carried out under the conditions of increasing the pressure to 3MPa and GHSV of 3000mL/(h g), and the activity of the catalyst after 3-5 hours of reaction is taken as test data of the activity of the catalyst shown in Table 1.
Example 2
0.953g of Cu (NO) was taken3)2·3H2O and 0.461g Zn (NO)3)2·6H2O, salt with the preparation concentration of 0.2-0.5 mol/L2g of UiO-66 support were added to the aqueous solution. The other preparation and evaluation were the same as in example 1, and the catalyst prepared was a 15% CuZn/UiO-66 catalyst, and the activity evaluation is shown in Table 1.
Example 3
1.8g of Cu (NO)3)2·3H2O and 0.87g Zn (NO)3)2·6H2And O, preparing a saline solution with the concentration of 0.2-0.5 mol/L, and adding 2g of UiO-66 carrier. The other preparation and evaluation were the same as in example 1, and the catalyst prepared was a 25% CuZn/UiO-66 catalyst, and the activity evaluation is shown in Table 1.
Example 4
1.454g of Cu (NO)3)2·3H2O and 0.703g Zn (NO)3)2·6H2And O, preparing a saline solution with the concentration of 0.2-0.5 mol/L, and adding 1g of UiO-66 carrier. The other preparation and evaluation were the same as in example 1, and the catalyst prepared was a 35% CuZn/UiO-66 catalyst, and the activity evaluation is shown in Table 1.
Example 5
2.21g of Cu (NO)3)2·3H2O and 1.068g Zn (NO)3)2·6H2And O, preparing a saline solution with the concentration of 0.2-0.5 mol/L, and adding 1g of UiO-66 carrier. The other preparation and evaluation were the same as in example 1, and the catalyst prepared was a 45% CuZn/UiO-66 catalyst, and the activity evaluation is shown in Table 1.
Example 6
3.301g of Cu (NO)3)2·3H2O and 1.596g Zn (NO)3)2·6H2And O, preparing a saline solution with the concentration of 0.2-0.5 mol/L, and adding 1g of UiO-66 carrier. The other preparation and evaluation were the same as in example 1, and the catalyst prepared was a 55% CuZn/UiO-66 catalyst, and the activity evaluation is shown in Table 1.
Example 7 (comparative example)
1.547g of Cu (NO) was taken3)2·3H2O and 1.869g Zn (NO)3)2·6H2And O, preparing a saline solution with the concentration of 0.2-0.5 mol/L, and adding 1g of UiO-66 carrier. Other preparation and evaluation were the same as in example 1, and the molar ratio of Cu: zn is 1:1, and the prepared catalyst is45% CuZn/UiO-66 (Cu: Zn ═ 1:1) catalyst, the activity evaluations are given in Table 1.
Example 8 (comparative example)
2.475g of Cu (NO)3)2·3H2O and 0.748g Zn (NO)3)2·6H2And O, preparing a saline solution with the concentration of 0.2-0.5 mol/L, and adding 1g of UiO-66 carrier. Other preparation and evaluation were the same as in example 1, and the molar ratio of Cu: zn 4:1, 45% CuZn/UiO-66 (Cu: Zn 4:1) catalyst was prepared and activity evaluations are given in table 1.
Example 9
4.363g of Cu (NO) was taken3)2·3H2O、2.109g Zn(NO3)2·6H2O、3.264g Zr(NO3)4·5H2Preparing a salt water solution with the concentration of 0.2-0.5 mol/L of O, and preparing and evaluating the salt water solution as the same as the salt water solution in the example 1, wherein the molar ratio of Cu: zn: zr is 5:2:3, and the catalyst prepared is Cu5Zn2Zr3The catalyst, activity evaluation is shown in table 1.
Example 10
The CuZn/UiO-66 catalyst is prepared by an impregnation method, and 1.454g of Cu (NO) is taken3)2·3H2O and 0.703g Zn (NO)3)2·6H2Adding O into 10mL of deionized water, stirring and dissolving, adding 1g of UiO-66 carrier, stirring for 30 minutes to fully disperse the metal nitrate precursor on the surface of the UiO-66, then placing the mixture into an oven at 80 ℃ for drying, roasting at 300 ℃ for 4 hours to obtain a catalyst oxide precursor, screening a 40-80-mesh catalyst for activity evaluation, wherein the prepared catalyst is a 35% CuZn/UiO-66-IP catalyst, and the molar ratio of Cu in the catalyst is as follows: zn ═ 5: 2.
TABLE 1 results of catalyst activity
Figure BDA0002356472560000051
Figure BDA0002356472560000061
GHSV＝3000mL/(g h)。
In conclusion, the Cu and ZnO loaded catalyst has more excellent activity in UiO-66, and as can be seen from the table above, compared with the catalyst prepared by the impregnation method, the catalyst prepared by the coprecipitation method has higher activity and better stability, and the influence of different Cu and Zn loading amounts on the catalysis is researched, and the catalytic activity shows volcano deformation along with the increase of the loading amount, and the catalyst activity is optimal when the Cu and Zn loading amounts are 35-45%.

Claims (3)

1.一种二氧化碳加氢合成甲醇催化剂CuZn/UiO-66，其特征在于，将Cu和Zn负载在UiO-66上，其中Cu和Zn质量占总催化剂质量的5％～55％，其中Cu：Zn＝1:1～4:1。1. a carbon dioxide hydrogenation synthesis methanol catalyst CuZn/UiO-66, is characterized in that, Cu and Zn are supported on UiO-66, and wherein Cu and Zn quality account for 5%～55% of total catalyst quality, wherein Cu: Zn=1:1～4:1. 2.权利要求1所述的二氧化碳加氢合成甲醇催化剂CuZn/UiO-66的制备方法，其特征在于，包括以下步骤：2. the preparation method of carbon dioxide hydrogenation synthesis methanol catalyst CuZn/UiO-66 according to claim 1, is characterized in that, comprises the following steps: (1)配置Cu和Zn盐水溶液，浓度为0.1～0.5mol/L，加入UiO-66得到混合溶液于60～90℃下共沉淀，其中混合溶液中UiO-66的浓度为0.1～0.2g/mL；配制0.5～1mol/L的碳酸钠水溶液，滴加到上述混合溶液中，控制pH＝7～8，得到沉淀物老化2～4h，过滤得到CuZn/UiO-66沉淀前驱体；(1) Prepare a Cu and Zn salt solution with a concentration of 0.1-0.5mol/L, add UiO-66 to obtain a mixed solution and co-precipitate at 60-90°C, wherein the concentration of UiO-66 in the mixed solution is 0.1-0.2g/ mL; prepare 0.5～1mol/L sodium carbonate aqueous solution, add dropwise to the above mixed solution, control pH=7～8, get the precipitate to be aged for 2～4h, filter to obtain the CuZn/UiO-66 precipitation precursor; (2)将步骤(1)所得的CuZn/UiO-66沉淀前驱体于80～110℃干燥10～16h，250～400℃焙烧2～4h，筛选40～80目颗粒，得到二氧化碳加氢合成甲醇催化剂CuZn/UiO-66。(2) The CuZn/UiO-66 precipitation precursor obtained in step (1) is dried at 80-110 °C for 10-16 h, calcined at 250-400 °C for 2-4 h, and screened for 40-80 mesh particles to obtain carbon dioxide hydrogenation to synthesize methanol Catalyst CuZn/UiO-66. 3.如权利要求2所述的二氧化碳加氢合成甲醇催化剂CuZn/UiO-66的制备方法，其特征在于，所述步骤(1)中UiO-66的制备包括：将四氯化锆、对苯二甲酸，加入到N,N-二甲基甲酰胺和盐酸混合溶液中，超声溶解；将混合溶液放于80～110℃下，保温24小时后冷却到室温，用对苯二甲酸和甲醇洗涤6次，将得到的固体粉末放于室温晾干，将晾干后的固体粉末放于80～110℃烘箱内干燥12～16小时，得到UiO-66材料。3. the preparation method of carbon dioxide hydrogenation synthesis methanol catalyst CuZn/UiO-66 as claimed in claim 2, is characterized in that, in described step (1), the preparation of UiO-66 comprises: zirconium tetrachloride, p-benzene Diformic acid was added to the mixed solution of N,N-dimethylformamide and hydrochloric acid, and dissolved by ultrasonic; the mixed solution was placed at 80 to 110 °C, kept at 80 to 110 °C, cooled to room temperature for 24 hours, and washed with terephthalic acid and methanol. 6 times, the obtained solid powder is dried at room temperature, and the dried solid powder is dried in an oven at 80-110° C. for 12-16 hours to obtain UiO-66 material.
CN202010009115.2A 2020-01-06 2020-01-06 Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof Pending CN111167518A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010009115.2A CN111167518A (en) 2020-01-06 2020-01-06 Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010009115.2A CN111167518A (en) 2020-01-06 2020-01-06 Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111167518A true CN111167518A (en) 2020-05-19

Family

ID=70619185

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010009115.2A Pending CN111167518A (en) 2020-01-06 2020-01-06 Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111167518A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111514938A (en) * 2020-06-08 2020-08-11 中国华能集团有限公司 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
CN112121805A (en) * 2020-09-28 2020-12-25 上海应用技术大学 A kind of carbon dioxide hydrogenation catalyst to synthesize methanol and its preparation and application
CN112371188A (en) * 2020-11-03 2021-02-19 宁波诺丁汉新材料研究院有限公司 Preparation method of efficient methanation nano catalyst
CN112892598A (en) * 2021-01-26 2021-06-04 烟台市友利化工科技有限公司 Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst
CN114160104A (en) * 2021-11-29 2022-03-11 昆岳互联环境技术(江苏)有限公司 Kiln flue gas CO2Trapping and utilizing coupling material and application thereof
CN118649710A (en) * 2024-08-15 2024-09-17 山东海化集团有限公司 A mesoporous UiO-67 coated Zn or Cu particle catalyst and its preparation method and application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4535071A (en) * 1983-05-16 1985-08-13 Sud Chemie Aktiengesellschaft Catalyst for methanol synthesis and method of preparing the catalyst
CN101513615A (en) * 2009-03-28 2009-08-26 大连理工大学 Carbon dioxide-synthesized methanol catalyst and preparation method thereof
CN102000578A (en) * 2010-09-29 2011-04-06 大连理工大学 Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof
CN107008332A (en) * 2016-01-27 2017-08-04 中国科学院大连化学物理研究所 A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application
CN108889303A (en) * 2018-07-20 2018-11-27 太原理工大学 The support type high dispersive copper-based catalysts and preparation method of carbon dioxide methanol and application
CN110433864A (en) * 2019-07-11 2019-11-12 厦门大学 A kind of preparation and its application of MOF supported bi-metallic type catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4535071A (en) * 1983-05-16 1985-08-13 Sud Chemie Aktiengesellschaft Catalyst for methanol synthesis and method of preparing the catalyst
CN101513615A (en) * 2009-03-28 2009-08-26 大连理工大学 Carbon dioxide-synthesized methanol catalyst and preparation method thereof
CN102000578A (en) * 2010-09-29 2011-04-06 大连理工大学 Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof
CN107008332A (en) * 2016-01-27 2017-08-04 中国科学院大连化学物理研究所 A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application
CN108889303A (en) * 2018-07-20 2018-11-27 太原理工大学 The support type high dispersive copper-based catalysts and preparation method of carbon dioxide methanol and application
CN110433864A (en) * 2019-07-11 2019-11-12 厦门大学 A kind of preparation and its application of MOF supported bi-metallic type catalyst

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111514938A (en) * 2020-06-08 2020-08-11 中国华能集团有限公司 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
CN111514938B (en) * 2020-06-08 2021-12-14 中国华能集团有限公司 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
WO2021249403A1 (en) * 2020-06-08 2021-12-16 中国华能集团清洁能源技术研究院有限公司 Catalyst for preparing methanol by means of hydrogenation of carbon dioxide, and preparation method therefor
CN112121805A (en) * 2020-09-28 2020-12-25 上海应用技术大学 A kind of carbon dioxide hydrogenation catalyst to synthesize methanol and its preparation and application
CN112371188A (en) * 2020-11-03 2021-02-19 宁波诺丁汉新材料研究院有限公司 Preparation method of efficient methanation nano catalyst
CN112892598A (en) * 2021-01-26 2021-06-04 烟台市友利化工科技有限公司 Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst
CN112892598B (en) * 2021-01-26 2022-05-24 烟台市友利化工科技有限公司 Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst
CN114160104A (en) * 2021-11-29 2022-03-11 昆岳互联环境技术(江苏)有限公司 Kiln flue gas CO2Trapping and utilizing coupling material and application thereof
CN118649710A (en) * 2024-08-15 2024-09-17 山东海化集团有限公司 A mesoporous UiO-67 coated Zn or Cu particle catalyst and its preparation method and application

Similar Documents

Publication Publication Date Title
CN111167518A (en) Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof
CN101879448B (en) Regular structure catalyst for hydrogenation of oxalate to ethylene glycol and preparation method thereof
CN110327933B (en) Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof
CN101584986A (en) Method for preparing methanol synthesizing catalyst
CN106582655A (en) Method for preparing high-dispersion easy-reduction loaded nickel-aluminum catalyst
CN103566949B (en) By the copper-based catalysts and preparation method thereof of preparing ethylene glycol by using dimethyl oxalate plus hydrogen and glycol monoethyl ether
CN114272950A (en) A kind of CH4, CO2 reforming to prepare synthesis gas catalyst and its preparation method and application
CN102716749A (en) A catalyst for co-hydrogenation of CO and CO2 to synthesize methanol modified by additives
CN110102294A (en) Composite oxide supported Pd base catalyst and its preparation method and application
WO2021042874A1 (en) Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof
CN101693203A (en) Method for preparing Ni base catalyst for methane portion oxidation synthesis gas
CN113694929B (en) Supported single-atom copper-based metal oxide catalyst, and preparation method and application thereof
CN114160143B (en) CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof
CN114853567A (en) A kind of carbon dioxide conversion to prepare low carbon alcohol catalyst and its preparation method and application
CN113751062A (en) Porous copper-based catalyst for hydrogenation of carbon dioxide to ethanol and preparation method thereof
CN113058613A (en) Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof
CN115999611B (en) Magnesium-nitrogen co-doped titanium dioxide supported palladium-indium bimetallic catalyst and preparation method and application thereof
CN114054034A (en) Multi-element copper-based non-noble metal hydrogenation catalyst, and preparation method and application thereof
CN115318298B (en) Copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof
CN117181232A (en) CuZnCeO x Preparation of nano rod catalyst and CO under photo-thermal synergistic catalysis 2 Application in reduction
CN109999799B (en) Preparation method, performance test method and application of zirconium-containing supported nano ruthenium catalyst
CN114984989A (en) Preparation method and application of catalyst for generating 1,4 cyclohexanedimethanol from diethylene glycol terephthalate by one-step method
CN113828309A (en) A catalyst for hydrogenating carbon dioxide to synthesize methanol and its preparation and application
CN114602449A (en) A kind of ZnZrO2 surface solid solution catalyst and its preparation method and application
CN113398918A (en) Catalyst for synthesizing methyl mercaptan and preparation and application methods thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200519