CN110882686B - Monolithic catalyst for preparing dimethyl carbonate by direct synthesis method, preparation method and direct synthesis method of dimethyl carbonate - Google Patents
Monolithic catalyst for preparing dimethyl carbonate by direct synthesis method, preparation method and direct synthesis method of dimethyl carbonate Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
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- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 14
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 22
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J35/56—
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- B01J35/61—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
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Abstract
The invention discloses an integral catalyst for preparing dimethyl carbonate by a direct synthesis method, a preparation method and the direct synthesis method of dimethyl carbonate, wherein the catalyst consists of a cerium-based composite oxide coating and a cordierite honeycomb ceramic matrix, wherein cerium ammonium nitrate and lanthanum nitrate are used as raw materials, urea is used as a precipitator, a composite material is prepared by a coprecipitation method, then the obtained composite material is mixed with an alumina ball mill and is roasted to form a composite oxide powder catalyst, and finally the prepared composite oxide powder catalyst is coated on the cordierite honeycomb ceramic matrix to form the required integral catalyst; the invention places the monolithic catalyst in the center of the steel tube of the continuous fixed bed reactor, and then liquid CH is put in the heating environment 3 OH is pumped to a preheater to be gasified and is mixed with CO by a high-pressure constant-flow pump 2 Premixing; CH in the reaction gas 3 OH and CO 2 The molar ratio of the dimethyl carbonate to the dimethyl carbonate is 1 to 3, and the dimethyl carbonate is obtained after the reaction is carried out for 2 to 6 hours. The invention provides a novel catalyst and a preparation method thereof, which can improve the production efficiency.
Description
Technical Field
The invention relates to the technical field of preparation of nano metal catalysts, in particular to a catalyst for preparing dimethyl carbonate by a direct synthesis method, a preparation method and the direct synthesis method of the dimethyl carbonate.
Background
With the development of society, the emission of carbon dioxide is also gradually increased, and carbon dioxide is a main gas causing greenhouse effect and is also a potential carbon source. Thus converting the greenhouse effect gas CO 2 The carbon resource is effectively fixed and recycled, and has important significance for relieving the crisis of the carbon resource, protecting the environment and the like.
Dimethyl Carbonate (CH) 3 OCOOCH 3 Abbreviated as DMC) is a widely used green chemical raw material, has very active chemical properties, and can participate in various chemical reactions such as methylation, carboxylation, methoxylation and the like. DMC can also be used as a low-toxicity green solvent in organic synthesis and clean production, instead of phosgene as a carbonylation agent in the synthesis of carbonic acid derivatives, instead of dimethyl sulfate as a methylation agent in methylation reactions. DMC is widely used in many fields, has very wide market prospect. There are many kinds of production processes of dimethyl carbonate, and the main method for synthesizing dimethyl carbonate comprises the following steps: phosgene process, methanol oxidative carbonylation process, ester exchange process (for example, chinese patents CN201410300187.7, CN201210226548.9,CN 201110415385.4), urea alcoholysis (as described in chinese patent No. cn201410585479. X), electrochemical synthesis, and direct synthesis of methanol and carbon dioxide.
Among the above methods, the phosgene process was the earliest developed classical method for preparing dimethyl carbonate, but the conventional production route of the phosgene process was gradually eliminated due to the high toxicity and corrosiveness of phosgene and the environmental problems of the emission of various other pollutants. Methanol liquid phase oxidative carbonylation, methanol gas phase oxidative carbonylation, and transesterification processes have all been commercialized, but industrial production has found that these processes have some inherent drawbacks. The liquid-phase oxidation carbonylation method of methanol adopts CuCl as a catalyst, has certain corrosivity to production equipment, and has CH in the whole system 3 OH、CO、O 2 The proportion of the mixed gas of the three gases is changed along with the reaction, and when the mixed gas reaches an explosion value, great safety threat is generated; the methanol gas-phase carbonylation method has higher danger coefficient of the reaction because the reaction raw material relates to toxic gas CO, and is not suitable for large-scale industrial popularization; most of the reaction processes related to the ester exchange method are reversible, so that the reaction yield is low under thermodynamic limitation conditions, and meanwhile, a large number of byproducts are generated in the reaction, so that the later separation and purification are difficult. Therefore, synthetic methods developed in laboratories, such as electrochemical synthesis and direct synthesis, have been receiving much attention. Compared with the electrochemical synthesis method, the direct synthesis method has simpler equipment requirement, no complex process flow requirement, obvious economic advantage and easy industrial popularization, and attracts the wide attention of a large number of researchers at home and abroad. However, CO 2 As one of the main raw materials of the reaction, the chemical property is extremely stable, the activation is difficult in the reaction, and a proper catalyst needs to be added to solve the problem of CO 2 The problem of difficulty in activation; however, this reaction usually produces a large amount of water as a by-product, which is liable to cause deactivation of the catalyst due to water poisoning, and therefore, suitable catalysts and reaction equipment are selected to realize CO 2 Rapid activation and timely removal of byproduct water is central to conducting this study.
For preparing dimethyl carbonate by direct synthesisCatalyst, ceO 2 Due to the abundant acid-base sites and oxygen vacancies, the method has attracted the attention of researchers. In 1999, tomishige et al (K Tomishige, et al, catal. Lett.,1999,58,225-229.) first initiated CeO 2 Application as catalyst to CO 2 And CH 3 The reaction of OH directly to DMC, although not at that moment with high yield, finds that the acid-base position on the catalyst surface is related to the performance of the catalyst. In 2006, yoshida et al (Yoshida, et al, catal Total., 2006,115,95-101.) for CO 2 And CH 3 CeO in reaction for directly synthesizing DMC by OH 2 And ZrO 2 By comparison of the catalytic effects of (A) and (B), ceO was found 2 Has a catalytic activity higher than that of ZrO 2 This is because of CeO 2 Simultaneously has an acid-base center, and the acid position can activate CH 3 OH, basic site can activate CO 2 Therefore, good catalytic performance is exhibited. However, ceO 2 Poor thermal stability, easy sintering at high temperature, greatly shortened catalyst life and reduced catalyst performance, on the other hand, pure CeO 2 The acid-base active sites that can be provided are limited. Studies have shown that (G.A. Turko, et al. Kinet. Catal.,2005,46,884-890), in CeO 2 Adding some other metal ions such as Zr 4+ 、La 3+ 、Ti 4+ 、Y 3+ Etc. to make it into CeO 2 Forms a solid solution in the crystal lattice of (A), can greatly improve CeO 2 Thermal stability, redox properties and oxygen storage properties. Therefore, researchers began to resort to working with CeO 2 Doping other metal ions to CeO 2 The catalyst undergoes a series of modifications. At present, ceMO is concerned δ Studies on (M = Zr, ti, ca, etc.) solid solutions have been reported in large numbers. Liu et al (b.liu, et al, acs cat., 2018,8 2 Nanorods, the influence of the amount of Zr doped on the lattice structure, microstructure, amount of oxygen vacancies and catalytic activity of DMC synthesis was investigated. The research result shows that the Zr providing the highest oxygen vacancy amount 0.1 CeO 2 The nanorods showed the highest DMC synthesis activity (DMC yield =14.2 mmol. Multidot.g) cat -1 ，CH 3 OH conversion =0.65%). Z.W.Fu et al (Z.W.Fu, et al. ACS omega.,2018,3,198-207.) investigated TiO in ceria nanorods 2 The effect of the doping ratio and various reaction conditions on the catalytic performance was found to be TiO 2 The introduction of the cerium dioxide nano-rod can greatly improve the catalytic performance of the cerium dioxide nano-rod because the cerium dioxide nano-rod has more surface acidic basic sites. Ti 0.04 Ce 0.96 O 2 The nanorod catalyst has the advantage of being superior to pure CeO 2 And other Ce 1-x Ti x O 2 The catalytic performance of the nano-rod is optimized under the optimal reaction conditions (140 ℃,1.0MPa, 360h) -1 ) Lower, ti 0.04 Ce0 .96 O 2 The nanorod catalyst has the highest catalytic performance, and CH is contained in a fixed bed reactor 3 The OH conversion was 5.38% and the DMC selectivity was 83.1%. Liu et al (b.liu, et al.new jchem.,2017,41 2 Based catalyst, research results show that CaO and CeO are used as catalyst 2 The interaction of the catalyst improves the acid-base property of the surface of the catalyst and the surface oxygen vacancy amount, and the increase of the oxygen vacancy enhances the CO pairing of the catalyst 2 Adsorption of (3). Ca under the reaction conditions of 3MPa and 140 DEG C 1.5 The DMC yield of the Ce sample was highest (2.47 mmol. Multidot.g) -1 ). The catalysts used in these documents are all particulate catalysts, and the use of these particulate catalysts in the reaction has the same problem-CH 3 The low OH conversion (typically 2-6%) severely hampers the application and spread of particulate cerium-based catalysts for the direct synthesis of DMC. After analyzing the reason, we conclude that the water is mainly caused by the accumulation of the byproduct water generated by the reaction, and the byproduct water cannot be removed in time in the catalytic process of the reaction kettle or the fixed bed reactor, so that the reaction equilibrium moves to the left (Le Chatelier principle). Thus, dehydrating agents (e.g. 2-cyanopyridines) are those which achieve high CH 3 OH conversion is necessary. S.P.Wang et al (S.P.Wang, et al. Chinese Chem Lett.,2015,26,1096-1100.) studied the use of 2-cyanopyridine and its derivatives in CeO 2 In situ hydrolysis on CO 2 And CH 3 Influence of OH on the Synthesis of dimethyl carbonate (DMC). The results show that the DMC yield after addition of 2-cyanopyridine had exceeded 12.8mmol g cat -1 Greatly increased to 378.5 mmol/g cat -1 . However, dehydrating agents are generally expensive and cause great harm to the environment. Therefore, it would be very valuable to develop cost-effective and less toxic accelerators under the concept of "green chemistry". The monolithic catalyst has the advantages of large specific surface area, low pressure drop, excellent mechanical property and good thermal stability when being compressed into corresponding granular catalyst, and is introduced into the reaction system and Ce 1-x La x O δ -Al 2 O 3 Formation of composite oxide Ce 1-x La x O δ -Al 2 O 3 The monolithic catalyst is expected to greatly improve CH 3 OH conversion and DMC yield. Thus, the applicant filed a prior application with application number 201910863440.2, but this is only an attempt and needs to explore further possibilities to find a more efficient solution.
Disclosure of Invention
Aiming at the defects of the existing granular catalyst for preparing the dimethyl carbonate by the direct synthesis method, the invention provides an integral catalyst for preparing the dimethyl carbonate by the direct synthesis method, which is used for directly synthesizing the dimethyl carbonate in a continuous fixed bed reactor.
The purpose of the invention is realized by the following technical scheme:
an integrated catalyst for preparing dimethyl carbonate by direct synthesis is prepared from Ce 1-x La x O δ -Al 2 O 3 The composite oxide coating and the cordierite honeycomb ceramic substrate. The Ce 1-x La x O δ -Al 2 O 3 The composite oxide is coated on a cordierite honeycomb ceramic matrix after ball milling and pulping to form Ce 1-x La x O δ -Al 2 O 3 A monolithic catalyst. In the catalyst, the molar ratio of cerium dioxide to lanthanum oxide is 0.99-0.80 1-x La x O δ 1wt% of the mass of the composite material.
Ce for preparing dimethyl carbonate by direct synthesis method 1-x La x O δ -Al 2 O 3 The preparation method of the monolithic catalyst comprises the following steps:
s1, weighing a certain mass of (NH) according to a specific molar ratio 4 ) 2 Ce(NO 3 ) 6 、La(NO 3 ) 3 ·6H 2 O and urea are respectively and completely dissolved by 500mL of deionized water to form the solution containing Ce 4+ 、La 3+ And urea solution of (2), containing Ce 4+ 、La 3+ Respectively transferring the solution and the urea solution into a 1000mL three-neck flask, uniformly mixing, carrying out coprecipitation reaction for 4-6 h under the conditions of mechanical stirring and water bath heating at 80-100 ℃, and collecting precipitates generated by the reaction;
s2, filtering and washing the reaction product, mashing the obtained filter cake, adding a proper amount of deionized water to prepare emulsion, adding a polyethylene glycol solution accounting for 10-50 wt% of the total mass of the obtained reaction product, mixing, spray drying, controlling the average particle size of the powder to be 5-10 microns, and finally vacuum drying the catalyst powder at 60-100 ℃ for more than 12 hours to obtain Ce 1-x La x O δ A composite material;
s3, the Ce prepared in the step S2 1-x La x O δ Composite material and Al with certain mass 2 O 3 Ball milling and mixing the powder, then roasting for 1-2 h at 150-200 ℃ in the air or oxygen atmosphere, and then roasting for 3-5 h at 400-500 ℃ in the air or oxygen atmosphere to obtain the formed Ce 1-x La x O δ -Al 2 O 3 A composite oxide powder catalyst;
s4, preparing Ce prepared in step S3 1-x La x O δ -Al 2 O 3 Ball-milling a composite oxide powder catalyst, 2-5 wt% of glacial acetic acid and a proper amount of deionized water according to a ball mill to prepare slurry, soaking a cordierite honeycomb ceramic matrix in the slurry, blowing off redundant catalyst slurry by using compressed air, drying the cordierite honeycomb ceramic matrix coated with the slurry for 3-4 h at 70-80 ℃, roasting at 150-200 ℃ for 1-2 h in the air or oxygen atmosphere, and roasting at 400-500 ℃ for 2-5 h in the air or oxygen atmosphere to obtain Ce 1-x La x O δ -Al 2 O 3 A monolithic catalyst.
By using Ce 1-x La x O δ -Al 2 O 3 Monolithic catalyst for catalyzing CO 2 And CH 3 The method for directly synthesizing dimethyl carbonate by OH comprises the following steps: ce is mixed 1-x La x O δ -Al 2 O 3 Putting the monolithic catalyst into a steel pipe of a continuous fixed bed reactor, and introducing CO for 5min 2 Other gases in the reaction system are removed, then the temperature is raised, and liquid CH is added when the temperature of the system reaches 100-180 DEG C 3 OH is transported to a preheater for gasification treatment by a high-pressure constant flow pump, the reaction pressure is controlled to be 1.2-3.0 Mpa, and CH is contained in the reaction gas 3 OH and CO 2 At a gas flow rate of 2880g, in a molar ratio of 1 to 3 cat -1 h -1 And after reacting for 2-6 h, the reaction gas mixture passes through a gas chromatograph to realize the online detection of the contents of reactants and products.
Compared with the prior art, the invention has the advantages that:
1. the invention adopts Ce with excellent oxygen storage performance, high specific surface area, abundant acid-base sites and other characteristics 1-x La x O δ -Al 2 O 3 Preparing composite oxide powder catalyst, preparing the powder catalyst into catalyst slurry by adopting a special coating technology, and coating the catalyst slurry on cordierite honeycomb ceramics to prepare high-performance Ce 1-x La x O δ -Al 2 O 3 Monolithic catalyst suitable for direct synthesis of dimethyl carbonate in a fixed bed reactor. La 2 O 3 Doping into CeO 2 Formation of Ce in the crystal lattice 1-x La x O δ The specific surface area of the catalyst can be increased, and the concentration of oxygen vacancies and acid-base sites of the catalyst is increased, so that more active sites are provided for catalytic reaction, and the contact frequency of reactants and the active sites is increased. The Ce 1-x La x O δ -Al 2 O 3 The monolithic catalyst exhibits superior catalytic performance compared to conventional particulate catalysts because the monolithic catalyst can achieve reactantsThe rapid removal of the catalyst promotes the forward movement of the reaction, realizes the process strengthening and further improves the catalytic performance. Experimental results show that the catalyst has excellent catalytic performance and stability. Ce prepared by the invention 1-x La x O δ -Al 2 O 3 Compared with the particle catalyst, the monolithic catalyst has obviously improved reactant conversion rate and product yield. CH (CH) 3 The highest OH conversion is up to 22% and DMC yield is up to 18%, which is mainly benefited by Ce 1-x La x O δ -Al 2 O 3 The monolithic catalyst is more beneficial to fully contacting active particles with reactants, and can discharge generated byproduct water to a reaction system in time so as to be beneficial to forward reaction, thereby achieving the purposes of high activity and high stability.
2. Ce of the invention 1-x La x O δ -Al 2 O 3 The composite oxide powder catalyst is prepared by adopting a coprecipitation method, ce 1- x La x O δ -Al 2 O 3 The monolithic catalyst is prepared by adopting an immersion method, is simple and easy to operate, is convenient for carrying out comparison experiments, and systematically studies the influence of the preparation conditions of the catalyst on the catalytic performance of the catalyst.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and that those skilled in the art can also derive other related drawings based on these drawings without inventive effort.
FIG. 1 shows CeO 2 -Al 2 O 3 Powder catalyst and Ce obtained in examples 2 and 4 of the invention 0.90 La 0.10 O δ -Al 2 O 3 、Ce 0.80 La 0.20 O δ -Al 2 O 3 XRD pattern of the powder catalyst.
FIG. 2 shows CeO 2 -Al 2 O 3 Powder ofCatalyst and Ce obtained in examples 2 and 4 of the invention 0.90 La 0.10 O δ -Al 2 O 3 、Ce 0.80 La 0.20 O δ -Al 2 O 3 TEM pictures of the powder catalyst.
FIG. 3 shows Ce obtained in example 1 of the present invention 0.95 La 0.05 O δ -Al 2 O 3 Monolithic catalyst and Ce obtained in example 5 0.95 La 0.05 O δ -Al 2 O 3 Activity comparison of the granular catalyst.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, and it should be understood that the preferred embodiments described herein are merely for the purpose of illustrating and explaining the present invention and are not intended to limit the present invention. Advantages and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Example 1
Preparation of 5% lanthanum oxide doped Ce 0.95 La 0.05 O δ -Al 2 O 3 Monolithic catalyst (ceria to lanthanum oxide molar ratio 0.95. The method comprises the following steps:
15.000g (NH) were weighed in a molar ratio of 0.95 4 ) 2 Ce(NO 3 ) 6 And 0.624g La (NO) 3 )·6H 2 And O, stirring and dissolving the mixture in a proper amount of deionized water to obtain a nitrate precursor mixed solution, and stirring and dissolving 70g of urea in a proper amount of deionized water, wherein the total amount of the deionized water used in the two dissolving processes is 500mL. Sequentially transferring the nitrate precursor mixed solution and the urea solution into a 1000mL three-neck flask, heating the mixed solution and the urea solution to 80-100 ℃ (preferably 90 ℃) in a water bath under the condition of mechanical stirring for reaction, keeping the temperature for 4-6 h (preferably 5 h) until the pH value reaches 8-9, naturally cooling the mixed solution to room temperature after the reaction is completed, filtering and washing a reaction product, mashing the obtained filter cake, adding deionized water to prepare emulsion, adding a polyethylene glycol solution containing 1.7097g of polyethylene glycol for size mixing, performing spray drying, controlling the average particle size of the powder to be 5 microns, and preparing the mixed solution into a powderVacuum drying the obtained powder at 80 deg.C for more than 12h to obtain Ce 0.95 La 0.05 O δ A composite material.
Ce prepared by the above experiment 0.95 La 0.05 O δ Ball milling and mixing the composite material with 0.0570g of alumina powder, then roasting for 1h at 150 ℃ in the atmosphere of air or oxygen (the roasting effect of oxygen is better, and the economic cost of air is lower), and then roasting for 2-5 h (preferably 4 h) at 400-500 ℃ (preferably 400 ℃), so as to obtain Ce with the diameter of 5-10 nm 0.95 La 0.05 O δ -Al 2 O 3 A powder catalyst. Is named as Pow-Ce 0.95 La 0.05 O δ -Al 2 O 3 。
4g of Pow-Ce prepared in the above experiment was taken 0.95 La 0.05 O δ -Al 2 O 3 Ball-milling 0.32mL of 25wt% glacial acetic acid and a proper amount of deionized water to prepare slurry, then soaking cordierite honeycomb ceramic in the slurry, blowing out redundant slurry by using compressed air, finally drying the substrate coated with the slurry at 80 ℃ for 3h, then roasting at 150 ℃ for 1h in air atmosphere, and finally roasting at 400 ℃ for 4h to obtain Ce 0.95 La 0.05 O δ -Al 2 O 3 Monolithic catalyst, named Mon-Ce 0.95 La 0.05 O δ -Al 2 O 3 And is marked as Cat 1.
Example 2
10wt% of Ce doped with lanthanum oxide 0.90 La 0.10 O δ -Al 2 O 3 The preparation of the monolithic catalyst (noted Cat 2) was identical to that of example 1, except that: the amounts of each precursor and polyethylene glycol were varied, and the specific amounts are shown in table 1.
Example 3
The doping amount of lanthanum oxide is 15wt% of Ce 0.85 La 0.15 O δ -Al 2 O 3 The monolithic catalyst (designated Cat 3) was prepared by the same procedure as in example 1, except that: the amounts of each precursor and polyethylene glycol were varied, and the specific amounts are shown in table 1.
Example 4
The doping amount of lanthanum oxide is 20wt% of Ce 0.80 La 0.20 O δ -Al 2 O 3 The monolithic catalyst (noted Cat 4) was prepared in the same manner as in example 1, except that: the amounts of each precursor and polyethylene glycol were varied, and the specific amounts are shown in table 1.
Example 5
5wt% of Ce doped with lanthanum oxide 0.95 La 0.05 O δ -Al 2 O 3 The preparation of the particulate catalyst was the same as the preparation of the monolithic catalyst of example 1, except that: synthesized Ce 0.95 La 0.05 O δ -Al 2 O 3 The composite oxide powder catalyst is directly tabletted by a tablet machine and sieved (40-60 meshes) to obtain Ce 0.95 La 0.05 O δ -Al 2 O 3 A particulate catalyst, noted Cat 5.
TABLE 1 preparation of different doping amounts of Ce 1-x La x O δ Dosage parameter of each raw material component of catalyst
| Examples | Ammonium cerium nitrate | Lanthanum nitrate | Urea | Alumina oxide | Polyethylene glycol | Glacial acetic acid |
| Example 2 (Cat 2) | 15.0000g | 1.3160g | 70.0000g | 0.0570g | 1.7097g | 0.32mL |
| Example 3 (Cat 3) | 15.0000g | 2.0910g | 70.0000g | 0.0628g | 1.8846g | 0.32mL |
| Example 4 (Cat 4) | 15.0000g | 2.9620g | 70.0000g | 0.0694g | 2.0812g | 0.32mL |
Ce 1-x La x O δ -Al 2 O 3 Monolithic catalyst for catalyzing CO 2 And CH 3 The method for directly synthesizing dimethyl carbonate by OH comprises the following steps:
CH 3 OH and CO 2 The reaction for direct synthesis of DMC was carried out in a continuous fixed bed reactor. Ce prepared in examples 1 to 4 1-x La x O δ -Al 2 O 3 (x =0.05,0.10,0.15,0.20) the monolithic catalysts were placed in steel tube reactors at 140 ℃, 2.4MPa and 2880g of space velocity cat -1 h -1 (nCH 3 OH:nCO 2 = 2:1), and the composition of the product was analyzed and detected on-line using an Agilent GC7890B gas chromatograph. The test results are shown in Table 2. (in the table, C CH3OH Represents CH 3 OH conversion, S DMC Denotes the selectivity to dimethyl carbonate, Y DMC Represents the yield of dimethyl carbonate. )
TABLE 2 CeO 2 -Al 2 O 3 Comparison of the Activity of the monolithic catalysts with the monolithic catalysts prepared in examples 1 to 4
Ce prepared in example 1 0.95 La 0.05 O δ -Al 2 O 3 Monolithic catalyst and Ce prepared in example 5 0.95 La 0.05 O δ -Al 2 O 3 The granular catalysts are respectively arranged in a steel tube reactor, the temperature is 140 ℃, the pressure is 2.4MPa, and the space velocity is 2880g cat -1 h -1 (nCH 3 OH：nCO 2 = 2:1) under the reaction conditions, the product was detected on-line. The composition of the product was analyzed using an Agilent GC7890B gas chromatograph. In addition, the activity of the monolithic catalyst prepared by the present invention was compared with the particulate catalyst prepared by the present invention and the particulate catalyst commonly used in the literature, and the results are shown in table 3.
TABLE 3 comparison of monolithic catalyst to granular catalyst Activity
As can be seen from Table 2, with CeO 2 -Al 2 O 3 Integral typeCompared with the catalyst, ce doped with lanthanum oxide 1-x La x O δ -Al 2 O 3 Monolithic catalyst catalyzed CH 3 OH and CO 2 The activity of direct synthesis of DMC is obviously improved. Wherein, when the doping amount of lanthanum oxide is 5 percent, the corresponding Ce 0.95 La 0.05 O δ -Al 2 O 3 The catalytic activity of the monolithic catalyst is the best. As can be seen from Table 3, the monolithic catalyst prepared in accordance with the present invention (No. 1) catalyzes CO in comparison with the particulate catalyst prepared in accordance with the present invention (No. 2) and the particulate catalysts commonly used in the literature (No. 3 to 5) 2 And CH 3 The direct synthesis of DMC from OH has the best catalytic activity. Under the experimental conditions, the CH of the catalytic reaction 3 The OH conversion rate is as high as 22%, and the DMC yield is as high as 18%. The catalyst slurry in the monolithic catalyst is uniformly distributed on the cordierite honeycomb ceramic matrix, so that the catalyst slurry is more beneficial to fully contacting active particles with reactants. Meanwhile, by using the continuous fixed bed reactor in a matching way, byproduct water generated by the reaction can be discharged out of the reaction system in time, and the forward reaction is facilitated, so that the effects of high activity and high stability of the catalytic reaction are achieved.
FIG. 1 and FIG. 2 show CeO, respectively 2 -Al 2 O 3 Powder catalyst and Ce prepared in examples 2 and 4 of the invention 1-x La x O δ -Al 2 O 3 XRD pattern and TEM picture of the powder catalyst. As can be derived from FIG. 1, la 2 O 3 Successfully dope into CeO 2 Form Ce in the crystal lattice 1-x La x O δ -Al 2 O 3 A composite oxide; as can be seen from FIG. 2, ceO 2 -Al 2 O 3 (FIG. 2 (a)) and Ce 1-x La x O δ -Al 2 O 3 (FIGS. 2 (b, c)) are all spherical nanoparticles with uniform morphology. However, after further particle size analysis we found that La is accompanied by La 2 O 3 Doping and increase of doping amount of (3), formed Ce 1-x La x O δ -Al 2 O 3 Particle size of (D) is smaller than that of CeO 2 -Al 2 O 3 Is reduced, mainly due to La 2 O 3 Is doped into CeO 2 Causing lattice contraction in the crystal lattice. FIG. 3 shows Ce prepared in example 1 of the present invention 0.95 La 0.05 O δ -Al 2 O 3 Monolithic catalyst and Ce prepared according to the invention in example 5 0.95 La 0.05 O δ -Al 2 O 3 Activity comparison of the granular catalyst. As can be seen from FIG. 3, ce 1-x La x O δ -Al 2 O 3 The catalytic activity of the monolithic catalyst is obviously higher than that of Ce 1-x La x O δ -Al 2 O 3 A particulate catalyst.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A method for directly synthesizing dimethyl carbonate is characterized in that Ce is adopted 1-x La x O δ -Al 2 O 3 Monolithic catalyst for catalyzing CO 2 And CH 3 OH is prepared by reacting Ce 1-x La x O δ -Al 2 O 3 Putting the monolithic catalyst into a steel pipe of a continuous fixed bed reactor, and introducing CO firstly 2 Removing other gases in the reaction system, starting heating the system after 5min, and heating the liquid CH when the temperature of the system rises to 100-180 DEG C 3 OH is transported to a preheater for gasification treatment by a high-pressure constant flow pump, the reaction pressure is controlled to be 1.2-3.0 MPa, and CH is contained in the reaction gas 3 OH and CO 2 Is 1 to 3, the gas flow rate is controlledIs 2880g cat -1 h -1 (ii) a After reacting for 2-6 h, the reaction gas mixture passes through a gas chromatograph to realize the online detection of the components and the content of each component of the product;
the Ce 1-x La x O δ -Al 2 O 3 The monolithic catalyst is prepared from Ce 1-x La x O δ -Al 2 O 3 A composite oxide coating and a cordierite honeycomb ceramic substrate; the preparation method comprises the following steps: doping lanthanum oxide into the crystal lattice of cerium dioxide to form Ce 1-x La x O δ Composite material, ce 1- x La x O δ The Ce is formed by ball milling and mixing the composite material and alumina powder and then roasting and molding 1-x La x O δ -Al 2 O 3 Composite oxide powder catalyst, last Ce 1-x La x O δ -Al 2 O 3 The composite oxide powder catalyst is coated on a cordierite honeycomb ceramic matrix after ball milling and pulping to form Ce 1-x La x O δ -Al 2 O 3 A monolithic catalyst;
in the monolithic catalyst, the molar ratio of cerium dioxide to lanthanum oxide is 0.99-0.80 1-x La x O δ 1wt% of the mass of the composite material.
2. Ce for preparing dimethyl carbonate by direct synthesis method 1-x La x O δ -Al 2 O 3 The preparation method of the monolithic catalyst is characterized by comprising the following preparation steps:
s1, weighing a certain mass of (NH) according to a specific molar ratio 4 ) 2 Ce(NO 3 ) 6 、La(NO 3 ) 3 ·6H 2 Dissolving O and urea completely in 500mL of deionized water, and adding Ce 4+ 、La 3+ The solution is mixed with urea solution, the coprecipitation reaction is carried out by mechanical stirring under the heating of water bath, and after the reaction is finished, the precipitate generated by the reaction is collected;
s2, filtering the reaction product,Washing, adding polyethylene glycol solution accounting for 10-50 wt% of the total mass of the obtained reaction product, mixing, spray drying, controlling the average particle size of the powder to be 5-10 microns, and finally, carrying out vacuum drying on the catalyst powder to obtain Ce 1-x La x O δ A composite material;
s3, preparing Ce prepared in the step S2 1-x La x O δ Composite powder and Al of a certain mass 2 O 3 Ball milling and mixing the powder, and then continuously roasting for two times at a given temperature and a given atmosphere to obtain the formed Ce 1-x La x O δ -Al 2 O 3 A composite oxide powder catalyst;
s4, ce prepared in the step S3 1-x La x O δ -Al 2 O 3 Ball-milling composite oxide powder catalyst, glacial acetic acid and deionized water in a certain proportion by a ball mill to prepare slurry, soaking the cordierite honeycomb ceramic substrate in the slurry, blowing off redundant catalyst slurry by compressed air, and finally drying and roasting the cordierite honeycomb ceramic substrate coated with the slurry to obtain Ce 1-x La x O δ -Al 2 O 3 A monolithic catalyst.
3. The Ce as claimed in claim 2 for preparing dimethyl carbonate by direct synthesis 1-x La x O δ -Al 2 O 3 The preparation method of the monolithic catalyst is characterized in that in the step S1, the water bath heating temperature is 80-100 ℃, and the water bath heating time is 4-6 h.
4. The Ce as claimed in claim 2 for preparing dimethyl carbonate by direct synthesis 1-x La x O δ -Al 2 O 3 The preparation method of the monolithic catalyst is characterized in that in the step S2, the temperature of vacuum drying is 60-100 ℃, and the time of vacuum drying is more than 12 h.
5. A process for the preparation of the compound of claim 2 by direct synthesisCe of dimethyl carbonate 1-x La x O δ -Al 2 O 3 The preparation method of the monolithic catalyst is characterized in that the roasting atmosphere in the step S3 is air or oxygen, and the twice roasting conditions are that the roasting is carried out for 1-2 hours at the temperature of 100-150 ℃ and for 3-5 hours at the temperature of 400-500 ℃ in sequence.
6. The Ce as claimed in claim 2 for preparing dimethyl carbonate by direct synthesis 1-x La x O δ -Al 2 O 3 The preparation method of the monolithic catalyst is characterized in that in the step S4, a cordierite honeycomb ceramic substrate is soaked in slurry, then the substrate is taken out, redundant slurry is blown off by compressed air, and then drying and roasting are carried out to obtain Ce 1-x La x O δ -Al 2 O 3 A monolithic catalyst; the drying and roasting processes are as follows: drying the substrate coated with the slurry at 70-80 ℃ for 3-4 h, then roasting at 150-200 ℃ for 1-2 h, and then roasting at 400-500 ℃ for 2-5 h.
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