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 PDFInfo
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- 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
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Abstract
The invention relates to a catalyst for synthesizing methanol by carbon dioxide hydrogenation and a preparation method thereof. The main raw material is Cu (NO)3)2·3H2O,Zn(NO3)2·6H2O, zirconium tetrachloride, terephthalic acid, N-dimethylformamide and hydrochloric acid. The preparation method is a coprecipitation method, and comprises the steps of adding UiO-66 into a Cu and Zn salt solution, dropwise adding a sodium carbonate solution until the pH value is 7, and then aging and filtering. The catalyst provided by the invention has the characteristics that the UiO-66 wraps the Cu particles, the Cu particles can be effectively prevented from being aggregated, the stability of the catalyst is obviously improved, and the selectivity of methanol and the conversion rate of carbon dioxide are also improved to a certain extent.
Description
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
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. A catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation is characterized in that Cu and Zn are loaded on the UiO-66, wherein the mass of Cu and Zn accounts for 5-55% of the total mass of the catalyst, and the mass ratio of Cu: zn is 1:1 to 4: 1.
2. The preparation method of the catalyst CuZn/UiO-66 for synthesizing methanol by hydrogenating carbon dioxide as claimed in claim 1, which comprises 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.
3. The method for preparing the catalyst CuZn/UiO-66 for synthesizing methanol by hydrogenating carbon dioxide according to claim 2, wherein the preparation of UiO-66 in the step (1) comprises the following steps: 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.
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Cited By (5)
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| 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 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation and application thereof |
| 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 |
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| 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 |
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