CN111229236B - Graphene-supported Cu/ZnO catalyst and preparation method and application thereof - Google Patents
Graphene-supported Cu/ZnO catalyst and preparation method and application thereof Download PDFInfo
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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- 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
Abstract
The invention relates to a graphene-supported Cu/ZnO catalyst, and a preparation method and application thereof, and belongs to the field of organic catalysis. The invention is characterized in that the catalyst is prepared by adopting a parallel flow precipitation method, compared with the common precipitation method, the active site Cu has smaller particle size and dispersibility, and the Cu 2+ With Zn 2+ The co-precipitation of the graphene and the addition of the graphene can better exert the synergistic catalytic effect, have low-temperature activity on target reaction and have high selectivity on the product methyl formate.
Description
Technical Field
The invention relates to a graphene-supported Cu/ZnO catalyst, and a preparation method and application thereof, and belongs to the field of organic catalysis.
Background
Methyl formate is a very important chemical intermediate and can be directly used as a solvent, a preservative and a gasoline additive. The methyl formate can be used as raw material to prepare high value-added fine chemicals such as formamide, hydrocyanic acid, N-methyl formamide, N-dimethyl formamide, methyl glycolate, methyl acrylate and the like.
In early industries, the production process of methyl formate mainly comprises the following steps: direct esterification of formic acid and methanol, methanol carbonylation and synthesis of synthesis gas. Among them, the esterification method has been eliminated due to the disadvantages of the process lag, serious equipment corrosion, etc. The synthesis gas method has the advantages of easily available raw materials, high reaction pressure and low single pass yield of methyl formate. The methanol carbonylation method has the advantages of good benefit and high purity requirement on raw materials methanol and CO.
The production of methanol is inferior to the basic raw materials such as ethylene, propylene, pure benzene and the like in the world, the production of the methanol is based on C1 chemistry, the production of the methanol in the world is based on natural gas, china is a country rich in coal, lean in gas and less in oil, the production of the methanol is based on coal, but with the improvement of a process route, the performance of a catalyst for synthesizing the methanol is improved, and the productivity and the yield of the methanol in the country are seriously excessive, so that the methanol becomes an important bottleneck in the methanol industry.
The method solves the problem of excessive methanol market and breaks the technical barrier in the aspect of methyl formate production in the aspect of the process route of preparing methyl formate by one step of methanol dehydrogenation; from the economic benefit, the conversion of methanol with low added value into methyl formate with high added value has largerIs a benefit space of (1); the method has the advantages of single raw material, short process flow, low equipment investment, and CO and H as byproducts 2 Is a raw material for synthesizing methanol. As early as 1988, mitsubishi gas chemical company (MGC) in japan realized industrialization of the technology for the first time in the world. In China, the southwest chemical industry institute develops an industrial device for annual production of 2kt, the methanol conversion rate is 30-40%, the methyl formate selectivity reaches about 70%, and the methyl formate yield is 20-30%. However, the common CuSiO-based and CuCrO-based catalysts in domestic technology need a higher reaction temperature of 250-300 ℃, and in addition, the chromium-containing system catalyst has certain toxicity and is not friendly to the environment.
Therefore, research on the preparation of methyl formate by catalyzing the dehydrogenation of methanol with a copper-based catalyst is always an important direction in the field. The copper-based catalyst with high activity, high methyl formate selectivity, stable catalytic performance, long service life and environmental friendliness is the focus of research.
Disclosure of Invention
The invention aims to develop a dehydrogenation catalyst with high activity, high selectivity and stable catalytic performance and catalytic activity at a relatively low temperature, which is used for preparing methyl formate by a one-step method of catalytic methanol dehydrogenation.
The reaction is gas-solid phase catalytic reaction, and the reaction is carried out in a miniature fixed bed reaction device under the condition of gas phase normal pressure.
The invention is realized by the following technical scheme:
in the graphene-supported Cu/ZnO catalyst, the Cu loading amount is 5-10wt.%, the molar ratio of Cu to ZnO is 2:1-1:2, and the rest is carrier graphene.
The preparation method of the graphene-supported Cu and ZnO bimetallic catalyst comprises the following specific steps:
step 1, preparing a catalyst matrix: preparing ammonia water solution for standby; cu (NO) 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 Preparing mixed aqueous solution for later use; firstly, weighing graphene and deionized water, mixing, performing ultrasonic dispersion in an ultrasonic machine, and then putting into a 65 ℃ water bath kettle for violent treatmentStirring, and simultaneously dropwise adding Cu (NO) 3 ) 2 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 The mixed solution of O and the ammonia solution, and the dropping speed of the ammonia solution is controlled to ensure that the pH value of the reaction solution is stabilized at 7.0+/-0.2; after the addition, the reaction solution was aged for 2 hours under vigorous stirring; filtering the precipitate, washing with deionized water, drying at 100deg.C for 24 hr, grinding the dried sample into powder, and concentrating at 450deg.C under N 2 Roasting for 4 hours in the atmosphere; pressing the roasted powder into slices under 10MPa, sieving to obtain 30-40 mesh particles, and preparing the catalyst matrix.
Step 2, activating treatment of a parent catalyst: with the parent catalyst in H 2 And N 2 The mixed gas of (2) is subjected to reduction activation pretreatment. At normal pressure, the temperature is programmed to rise from room temperature to 300 ℃ at 5 ℃/min, and H in the mixed gas in the process 2 The volume fraction is 10%; heating to 300 ℃ and then adding H into the mixed gas 2 The volume fraction is adjusted to 30 percent, and the mixture is reduced for 4 hours at 300 ℃; and obtaining the reduced catalyst, namely the Cu/ZnO/graphene catalyst.
In step 1, the concentration of the aqueous ammonia solution was 0.5mol L -1 。
Activity test of catalyst:
methanol is used as a raw material, the raw material is gasified and then enters a reactor loaded with a Cu/ZnO/graphene catalyst for reaction, continuous sampling is carried out at a given temperature, and liquid phase products are collected by condensation.
The vaporization temperature of raw material methanol is 160 ℃, the length of a reactor is 20cm, the inner diameter is 0.5cm, and the loading amount of Cu/ZnO/graphene catalyst is 5g; the flow rate of the methanol is 6mL/h, and the methanol is pumped by a constant flow pump without carrier gas. The reaction is carried out at normal pressure, the given temperatures are 160-240 ℃ respectively, and lh is sampled continuously at the given temperatures.
The beneficial effects are that:
the invention is characterized in that the catalyst is prepared by adopting a parallel flow precipitation method, compared with the common precipitation method, the active site Cu has smaller particle size and dispersibility, and the Cu 2+ With Zn 2+ The co-precipitation of the graphene and the addition of the graphene can better exert the synergistic catalytic effect, has low-temperature activity on target reaction and yieldMethyl formate has high selectivity. For example, with the catalyst of the present invention, the single pass conversion of methanol is as high as 85%, the selectivity of methyl formate is 92% and the yield of methyl formate is 78% at a reaction temperature of 240 ℃ under normal pressure. The single pass yield of methyl formate is much higher than that of methyl formate catalyst prepared by dehydrogenation of methanol at home and abroad, and is more than 2-3 times of that of methyl formate catalyst.
Detailed Description
Example 1
Preparation of the catalyst the loading of Cu was 10wt.%, and the molar ratio of Cu to ZnO was 2:1.
The Cu/ZnO/graphene catalyst is prepared by a coprecipitation method: preparation of 0.5mol L -1 For later use, 2.5346g of Cu (NO) 3 ) 2 ·3H 2 O and 1.5605g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 80mL of deionized water for standby; 5.5731g of graphene is weighed and mixed with 240mL of deionized water, and after ultrasonic dispersion is carried out for 30 minutes, a graphene suspension is obtained and is put into a water bath kettle at 65 ℃ for vigorous stirring. Cu (NO) 3 ) 2 ·3H 2 O/Zn(NO 3 ) 2 ·6H 2 The mixed aqueous solution of O and the ammonia solution are simultaneously dripped into the graphene suspension, and the pH value of the reaction solution is stabilized at 7.0+/-0.2 in the dripping process; aging the reaction solution for 2 hours under intense stirring, and filtering and washing the precipitate with deionized water; the washed sample was dried at 100deg.C for 24 hours, the dried sample was ground to a powder, N at 450deg.C 2 Roasting for 4 hours in the atmosphere; pressing the roasted powder into a sheet shape under the pressure of 10MPa, sieving the sheet shape into particles with the size of 30-40 meshes, and preparing a catalyst matrix;
and (3) activating pretreatment of a catalyst:
adopting a fixed bed reactor, filling 5g of catalyst, gasifying raw material methanol, and then entering a stainless steel tubular reactor (length 20cm, inner diameter 0.5 cm) for reaction; the catalyst precursor is first treated with H prior to activity testing 2 /N 2 (100 ml/min) the mixture is subjected to reduction activation, and the temperature is programmed to be 300 ℃ at 5 ℃ per min under normal pressure, and H in the mixture is in the process 2 The volume fraction is 10%; after heating to 300 ℃, H is added 2 Volume ofThe fraction was adjusted to 30% and reduced at 300℃for 4h. The catalyst prepared had a Cu loading of 10wt.% and a Cu/ZnO molar ratio of 2:1.
Methyl formate is prepared by gas phase dehydrogenation of methanol:
pumping raw material methanol into a miniature gas-solid phase reaction device at a flow rate of 6mL/h by using a constant flow pump, vaporizing liquid-phase methanol in a vaporization chamber at 160 ℃ and then entering a reactor for reaction, condensing and recycling a liquid-phase product after the reaction by an ethanol condensing device (-18+/-2 ℃), evacuating a gas-phase product, and carrying out the whole reaction under normal pressure; the reaction temperatures are respectively 160, 180, 200, 220 and 240 ℃ and l h are continuously sampled at a given temperature; the liquid phase product and the gas phase product were analyzed by two gas chromatographs (equipped with FID and TCD detectors, respectively), the flow rate of the gas phase product was calibrated by a soap foam flowmeter, and the results of the test were calculated and shown in table 1.
TABLE 1 Cu (2)/ZnO (1)/graphene catalyzed methanol dehydrogenation feed conversion and reaction product selectivity and yield
Example 2
As in example 1, the Cu loading was kept at 10wt.%, the molar ratio of Cu to ZnO was adjusted to 1:1; 2.5346g Cu (NO) was weighed out 3 ) 2 ·3H 2 O，3.1210g Zn(NO 3 ) 2 ·6H 2 O and 5.1462g graphene. The results obtained are shown in Table 2.
TABLE 2 Cu (1)/ZnO (1)/graphene catalyzed methanol dehydrogenation feed conversion and reaction product selectivity and yield
Example 3
As in example 1, the Cu loading was kept at 10wt.%, the molar ratio of Cu to ZnO was adjusted to 1:2; 2.5346g Cu (NO) was weighed out 3 ) 2 ·3H 2 O，6.2420g Zn(NO 3 ) 2 ·6H 2 O and 4.2925g graphene. The results obtained are shown in Table 3.
TABLE 3 Cu (1)/ZnO (2)/graphene catalyzed methanol dehydrogenation feed conversion and reaction product selectivity and yield
Example 4
As in example 1, the Cu loading was kept at 5wt.%, the molar ratio of Cu to ZnO was adjusted to 1:1; 1.2006g Cu (NO) was weighed out 3 ) 2 ·3H 2 O，1.4783g Zn(NO 3 ) 2 ·6H 2 O and 5.5955g graphene. The results obtained are shown in Table 4.
TABLE 4 Cu (1)/ZnO (1)/graphene catalyzed methanol dehydrogenation feed conversion and reaction product selectivity and yield
Comparative example 1
As in example 1, the Cu loading was kept at 10wt.%, no graphene was incorporated; 2.5346g Cu (NO) was weighed out 3 ) 2 ·3H 2 O, and 21.9334g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL deionized water, cu (NO 3 ) 2 ·3H 2 O/Zn(NO 3 ) 2 ·6H 2 The mixed aqueous solution of O and the aqueous ammonia solution were simultaneously added dropwise to stabilize the pH of the mixture at 7.0.+ -. 0.2, and the subsequent operations were the same as in example 1, and the results obtained are shown in Table 5.
TABLE 5 Cu/ZnO catalyzed methanol dehydrogenation feed conversion and reaction product selectivity and yield
Comparative example 2
As in example 1, the Cu loading was kept at 10wt.%, no ZnO was incorporated; 2.5346g Cu (NO) was weighed out 3 ) 2 ·3H 2 O, and 6.0000g graphene. The results obtained are shown in Table 6.
Cu/graphene catalyzed methanol dehydrogenation feedstock conversion and reaction product selectivity and yield
Claims (4)
1. The preparation method of the graphene loaded Cu/ZnO catalyst is characterized by comprising the following specific steps:
step 1, preparation of a catalyst matrix: preparing ammonia water solution for standby; cu (NO) 3 ) 2 •3H 2 O、Zn(NO 3 ) 2 •6H 2 Preparing mixed aqueous solution for later use; firstly, weighing graphene, mixing with deionized water, performing ultrasonic dispersion in an ultrasonic machine, then placing into a water bath kettle, vigorously stirring, and simultaneously dropwise adding Cu (NO) 3 ) 2 •3H 2 O and Zn (NO) 3 ) 2 •6H 2 Mixing the aqueous solution of O and the aqueous ammonia solution, and controlling the dropping speed of the aqueous ammonia solution to ensure that the pH value of the reaction solution is stabilized at 7.0+/-0.2; after the addition, the reaction solution is aged under intense stirring; filtering the precipitate, washing with deionized water, drying, grinding the dried sample into powder, and roasting; pressing the roasted powder into a sheet shape by applying pressure, and sieving to prepare a catalyst matrix;
step 2, activating treatment of a catalyst matrix: with catalyst precursor in H 2 And N 2 Carrying out reduction activation pretreatment in the mixed gas of (a); at normal pressure, the temperature is programmed to rise from room temperature to 300 ℃, H in the mixed gas in the process 2 The volume fraction is 10%; after heating to 300 ℃, H in the mixed gas 2 The volume fraction is adjusted to 30 percent, and the mixture is reduced for 4 hours at 300 ℃; and obtaining the reduced catalyst, namely the graphene-supported Cu/ZnO catalyst.
2. The method for preparing a graphene-supported Cu/ZnO catalyst as defined in claim 1, wherein in step 1, the concentration of the aqueous ammonia solution is 0.5mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the water bath kettle is 65 ℃; aging time is 2h; drying at 100 ℃ for 24 hours; calcination means N at 450 DEG C 2 Roasting for 4 hours in the atmosphere; the pressure applied by pressing into a sheet is 10MPa; sieving to obtain 30-40 mesh granule; in step 2, the temperature programming from room temperature to 300℃was performed at a rate of 5℃per minute.
3. The method for preparing the graphene-supported Cu/ZnO catalyst according to claim 1, wherein the graphene-supported Cu/ZnO catalyst has a Cu loading amount of 10wt.%, a molar ratio of Cu to ZnO of 1:1, and the balance being supported graphene.
4. The use of the graphene-supported Cu/ZnO catalyst prepared by the preparation method according to claim 1, wherein the catalyst is used as a dehydrogenation catalyst for preparing methyl formate by a catalytic methanol dehydrogenation one-step method; taking methanol as a raw material, gasifying the raw material, then, entering a reactor loaded with a graphene loaded Cu/ZnO catalyst for reaction, continuously sampling at a given temperature, and condensing and collecting a liquid-phase product; the vaporization temperature of raw material methanol is 160 ℃, the length of the reactor is 20cm, the inner diameter is 0.5 and cm, and the loading amount of the graphene loaded Cu/ZnO catalyst is 5g; the flow rate of methanol was 6mL/h, the reaction was carried out at a given temperature of 240℃under normal pressure with no carrier gas, and l h was sampled continuously at the given temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182307A (en) * | 2013-03-05 | 2013-07-03 | 华南理工大学 | Cu-doped ZnO/graphene composite photocatalyst and preparation method thereof |
| CN107519884A (en) * | 2017-08-28 | 2017-12-29 | 江苏大学 | A kind of method that catalyst methanol dehydrogenation prepares methyl formate |
| CN107522617A (en) * | 2017-08-28 | 2017-12-29 | 江苏大学 | A kind of method that catalysis methanol dehydrogenation prepares methyl formate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182307A (en) * | 2013-03-05 | 2013-07-03 | 华南理工大学 | Cu-doped ZnO/graphene composite photocatalyst and preparation method thereof |
| CN107519884A (en) * | 2017-08-28 | 2017-12-29 | 江苏大学 | A kind of method that catalyst methanol dehydrogenation prepares methyl formate |
| CN107522617A (en) * | 2017-08-28 | 2017-12-29 | 江苏大学 | A kind of method that catalysis methanol dehydrogenation prepares methyl formate |
Non-Patent Citations (2)
| Title |
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| Enhanced photo-induced catalytic activity of Cu ion doped ZnO-Graphene ternary nanocomposite for degrading organic dyes;Rosalin Beura等;《Journal of Water Process Engineering》;20190928;第32卷;全文 * |
| 纳米氧化锌及其复合材料光催化去除水中低浓度氨氮研究;张婉;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20170715(第07期);全文 * |
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