CN113398912A - Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate - Google Patents
Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate. The catalyst is a ternary composite metal oxide catalyst, and is prepared by high-temperature roasting of ternary layered composite metal hydroxide containing transition metal and rare earth metal elements. The catalyst has more surface acid-base active sites. The rare earth metal element is doped in the layered composite metal hydroxide, so that the dispersity of the catalytic active metal can be improved, surface vacancies and defects are easily formed after high-temperature roasting, and the layered composite metal hydroxide contains 4f orbitals which are not filled with electrons and can be used as an electron transfer path of catalytic reaction, and the dissolution of the active metal in a reaction liquid can be reduced in the catalytic reaction process, so that the activity and the stability of the catalyst for catalyzing the alcoholysis of methyl carbamate to synthesize the dimethyl carbonate are improved. The catalyst has a good application prospect in the field of synthesizing dimethyl carbonate by a urea alcoholysis method, the raw materials are cheap, and the preparation method and the operation are simple, so that the catalyst is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of synthesizing dimethyl carbonate by a methyl carbamate alcoholysis method, and particularly relates to a catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate.
Technical Field
Dimethyl carbonate (DMC) contains methyl, methoxy, carbonyl functional groups in the molecule, and is therefore a good methylating, carbonylating and methoxylating reagent. DMC is used as chemical raw material, so that a plurality of organic compounds with high added value can be synthesized, and the DMC is expected to replace phosgene (COCl)2) And highly toxic organic synthesis raw materials such as dimethyl sulfate (DMS) and the like, and therefore, the DMS is an important intermediate for organic synthesis. Meanwhile, the product has good physical and chemical properties and low toxicity, can be applied to various fields, and is a clean and green chemical. In recent years, the demand for DMC in the market has been increasing, and the price of DMC has also been rising.
The current DMC synthesis methods mainly comprise a phosgene method, an ester exchange method and CO2Direct methanol synthesis and urea alcoholysis. The phosgene method has mature process flow, but the method is eliminated because the used raw material is the highly toxic phosgene and the product contains HCl which is corrosive; DMC prepared by ester exchange method has high yield and selectivity, but because the process flow is complex and the raw material price is expensive, the method has less application in industry; CO 22The direct synthesis of methanol is due to raw material CO2The former three methods have their disadvantages because of the low activity and the formation of water in the product, which forms a methanol-DMC-water ternary system that is difficult to separate. The raw materials applied to the urea alcoholysis method are cheap urea and methanol, and the method has the characteristics of simple process, green and environment-friendly product, no water in the product, easy separation and the like and is always a hot point of research.
The reaction system for synthesizing DMC by urea alcoholysis method is divided into two steps: the first step is that urea and methanol react to generate an intermediate product Methyl Carbamate (MC), and the reaction of the first step can obtain higher selectivity of MC without the presence of a catalyst; the second step is that MC further reacts with methanol to generate DMC, and the reaction is a speed control step of synthesizing DMC system by urea alcoholysis method, and needs a catalyst with better performance to participate. In the second step, there are many side reactions in the system, such as self-decomposition of MC and further reaction of the produced DMC with MC to produce N-methyl carbamate (NMMC), so finding a catalyst with better performance and simple preparation method has been receiving extensive attention.
CN200810101782.2 reports on gamma-Al2O3The catalyst is a carrier, and a surfactant is added to adjust the size of active grains, so that the stability of synthesizing DMC by catalyzing alcoholysis of urea is high, and the yield of DMC is high; CN200410012504.1 adopts active carbon and gamma-Al2O3The catalyst is prepared by loading active components such as alkali metal and the like as a carrier, and is applied to a catalytic rectification reactor to prepare DMC, so that the yield of DMC can be further improved, the reaction activity and stability are higher, and byproducts are less; CN201310499274.5 discloses a supported catalyst for preparing DMC from urea and methanol, which has high activity and stability for catalyzing the synthesis of DMC from urea and methanol; CN201110099602.3 adopts molecular sieve to load Fe2O3The catalyst is simple to prepare and easy to separate from a reaction system, a cocatalyst or a cocatalyst is not required to be added, the DMC yield can reach 36.7%, and the selectivity can also reach 97.4%.
TABLE 1 relevant catalyst literature and patents
The activity of the catalyst is mainly related to the number and the type of active sites on the surface of the catalyst, and a hydrotalcite-like compound (LDHs) is used as a precursor, and the composite metal oxide (LDO) catalyst obtained by roasting can better meet the condition. The catalytic effect of the prepared ZnAlLa-LDO catalyst is excellent, the phenomenon shows that Zn, Al and La elements have a synergistic effect in the catalytic reaction process, and the catalyst exposes more acidic and alkaline active sites due to partial dissolution of the Zn element in the reaction process.
TABLE 2 comparison of the number of active sites on the surface of ZnAlLa-LDO and ZnAl-LDO catalysts
Aiming at solving the problem of more side reactions in a reaction system of MC and methanol, rare earth metal elements are doped into layered composite hydroxide with a hydrotalcite-like structure through reasonable design optimization, and the hydrotalcite-like base composite metal oxide catalyst is further prepared through roasting. In the presence of this catalyst, the selectivity of DMC is higher compared to the catalyst systems already reported. The rare earth metal element contains 4f orbitals which are not filled with electrons, so that the rare earth metal element can be used as an electron transfer path of catalytic reaction. Research shows that rare earth metal elements doped in the catalyst can improve the dispersity of the catalytically active metal and easily form surface vacancies and defects.
Disclosure of Invention
The invention solves the technical problem of providing a catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate through a designed catalyst preparation scheme. The composite catalyst is doped with rare earth metal elements, so that the structure of the catalyst is stabilized, and more electron transfer paths are provided. In addition, the catalyst is applied to a reaction system for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate, and shows excellent catalytic activity. Meanwhile, the preparation process flow of the catalyst is simple and convenient, no toxic and harmful substances are generated, and the catalyst is suitable for large-scale industrial production.
The technical scheme adopted by the invention is as follows:
a catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate, the catalyst comprising:
(1) the catalyst is composite metal oxide, and the active metal elements comprise transition metal elements and rare earth metal elements;
(2) the catalyst precursor is of a layered structure, after high-temperature roasting, the layered structure is partially collapsed, and more acidic and alkaline active sites are exposed on the surface of the composite metal oxide catalyst.
The catalyst is characterized in that in the step (1), the transition metal element can be Zn or Fe.
The catalyst, characterized in that (1), the rare earth metal element may be La.
The catalyst is characterized in that in the step (1), the composite metal oxide is prepared by oxidizing layered composite metal hydroxide under a high-temperature roasting condition, and the collapse degree of the laminated plate structure can be controlled by adjusting the roasting temperature and the roasting time.
The preparation method of the catalyst is characterized by comprising the following steps:
(1) dissolving metal nitrate in deionized water, performing ultrasonic treatment to form a mixed solution, adding the mixed solution of the nitrate into a urea solution, stirring and refluxing the mixed solution at a certain temperature, aging at room temperature, performing suction filtration, washing and drying to obtain a catalyst precursor.
(2) Grinding the catalyst precursor into powder, and then placing the powder into a muffle furnace to be roasted at a high temperature for a certain time to finally obtain the catalyst.
In the preparation method, in the step (1), the molar ratio of the rare earth metal to the transition metal element is 0-4.
In the preparation method, in the step (1), the molar ratio of the urea to the nitrate radical is 1-4.
In the preparation method, in the step (1), the stirring speed is 500-1200rpm, the reaction temperature is 85-100 ℃, and the reaction time is 6-10 h.
In the preparation method, in the step (2), the roasting temperature is 100-.
The catalyst is applied, and the molar ratio of the reactants of the catalytic reaction, namely methanol and MC is 0-40.
The application of the catalyst, the dosage of the catalyst is 0.1-10 wt.%.
The invention has the following characteristics:
the catalyst is prepared by doping rare earth metal elements in hydrotalcite-like layered hydroxide and further roasting at high temperature. The catalyst has more reaction active sites. The preparation method of the catalyst is cheap, simple to operate and suitable for large-scale production.
The catalyst is applied to the catalytic reaction of synthesizing dimethyl carbonate by alcoholysis of methyl carbamate, and has the following advantages:
(1) because the catalyst contains rare earth metal elements which contain 4f orbitals which are not filled with electrons, the rare earth metal elements can be used as electron transfer paths of catalytic reaction, so that the catalytic activity of the catalyst is greatly improved compared with other types of catalysts.
(2) The catalyst has a higher number of active sites on the surface, which enables more reactants to be activated when participating in a catalytic reaction, and therefore the catalytic activity of the catalyst is higher.
Drawings
FIG. 1 shows the X-ray single crystal diffraction pattern (XRD) of (3-1-0.9) ZnAlLa-LDO-700 and its hydrotalcite-like precursor.
FIG. 2 shows N of (3-1-0.9) ZnAlLa-LDO-7002Adsorption and desorption curve chart.
FIG. 3 shows CO of (3-1-0.9) ZnAlLa-LDO-7002-TPD profile.
FIG. 4 shows NH of (3-1-0.9) ZnAlLa-LDO-7003-TPD profile.
Detailed description of the invention
The present invention will be further described with reference to the following examples.
Example 1: a preparation method of a composite metal oxide catalyst ZnAlLa-LDO. Weighing a certain amount of urea to be dissolved in 100mL of deionized water, and marking as a solution A; weighing Zn (NO) according to the molar ratio of Zn to Al to La of 3:1:0.93)2、Al(NO3)3、La(NO3)3Dissolving in 100mL of deionized water, marking as solution B, and carrying out ultrasonic treatment on the solution A and the solution B for 30min to fully dissolve the solutions. Then, the solution A and the solution B were transferred to a 500mL three-necked flask, and heated at a temperature of 95 ℃ for 8 hours with stirring at a speed of 600 rad/min. And after the reaction is finished, carrying out suction filtration and separation on the obtained solid-liquid mixture, drying a solid sample at 85 ℃ for 12h, and grinding the solid sample into powder, wherein the obtained sample is marked as ZnAlLa-LDHs. ZnAlLa-LDHs is placed in a muffle furnace to be roasted at the roasting temperature of 700 ℃ for 6 hours, so that the composite metal hydroxide is oxidized into the composite metal oxide, and the obtained sample is marked as (3-1-0.9) ZnAlLa-LDO-700。
Comparative example 1: the catalyst was commercial ZnO and was not further treated prior to use.
Comparative example 2: the preparation method is the same as that of example 1, except that NO La (NO) is added to the solution B during the preparation of the catalyst3)3The calcination temperature was 600 ℃ and the obtained sample was designated as (3-1) ZnAl-LDO-600.
Comparative example 3: the preparation method is the same as that of example 1, and the difference is that in the preparation process of the catalyst, the solution B is a solution with the molar ratio of Zn, Al and Fe of 3:1:0.5, the roasting temperature of a muffle furnace is 600 ℃, and the obtained sample is marked as (3-1-0.5) ZnAlFe-LDO-600.
Example 2: the preparation method is the same as that of example 1, and the difference is that in the preparation process of the catalyst, the solution B is a solution with the molar ratio of Zn, Al and La of 3:1:0.5, the roasting temperature of a muffle furnace is 600 ℃, and the obtained sample is marked as (3-1-0.5) ZnAlLa-LDO-600.
Example 3: the preparation method is the same as that of example 1, and the difference is that in the preparation process of the catalyst, the roasting temperature of a muffle furnace is 600 ℃, and the obtained sample is marked as (3-1-0.9) ZnAlLa-LDO-600.
Example 4: comparative experiment of catalytic activity. The molar ratio of MC to methanol was 1:15 and the amount of catalyst was 1 wt.% in a 100mL autoclave with mechanical stirring. After filling, a certain amount of nitrogen is introduced into the reaction kettle for leak detection, and then the nitrogen is discharged to ensure that the reaction kettle maintains normal pressure. The reaction kettle is started to heat and stir, the temperature of the reaction kettle is raised to 180 ℃ within 30min, and the stirring speed is 600 rad/min. After reacting for 10h, the reaction kettle is placed in an ice water bath to be cooled to room temperature, the product is collected for centrifugal separation, and the liquid phase product is subjected to qualitative and quantitative analysis by gas chromatography. The conversion rate of MC and the selectivity of the main product DMC and the by-product NMMC are calculated. The results are shown in Table 3.
TABLE 3 comparison of catalytic effects of comparative and examples
Example 5: and (5) testing the stability of the catalyst. The experimental method is the same as the comparative experiment of catalytic activity, and the difference is that for the (3-1-0.9) ZnAlLa-LDO-700 catalyst, the optimized molar ratio of MC to methanol is 1:20, the optimized catalyst dosage is 0.8 wt%, the reaction temperature is 170 ℃, and the reaction time is 9 hours. The recovered catalyst was washed and dried, and then supplemented to the original ratio for catalytic reaction, and the results of catalytic stability thereof are shown in table 2.
TABLE 4 catalytic stability results
As shown in figure 2, the XRD spectrogram of the (3-1-0.9) ZnAlLa-LDO-700 precursor shows the characteristic diffraction peak of the hydrotalcite-like compound, which indicates that La can be doped into the crystal lattice of ZnAl-LDHs to form the ternary composite metal hydroxide; the XRD spectrogram of (3-1-0.9) ZnAlLa-LDO-700 does not show the characteristic diffraction peak of the hydrotalcite-like compound, which shows that the layered structure of the hydrotalcite-like compound collapses to form the composite metal oxide under the roasting of 700 ℃. As shown in Table 3, when (3-1-0.9) ZnAlLa-LDO-700 is used as a catalyst, the conversion rate of MC and the selectivity of DMC are highest, and the conversion rate of MC is greatly increased compared with that of (3-1) ZnAl-LDO-600, because in the process of preparing (3-1-0.9) ZnAlLa-LDO-700 catalyst, rare earth metal La is added into hydrotalcite-like compound, so that the number of empty electron orbitals in the catalyst is increased, which is beneficial to the transfer of electrons in the reaction process, and simultaneously, compared with (3-1) ZnAl-LDO-600 catalyst, the acid-base active sites on the surface of (3-1-0.9) ZnAlLa-LDO-700 catalyst are more, as shown in Table 2 and FIGS. 3 and 4. So that the catalytic activity of the catalyst is higher, and the conversion rate of MC and the selectivity of DMC are further improved.
From the aspect of catalyst stability, when (3-1-0.9) ZnAlLa-LDO-700 is used as a catalyst, the catalytic stability is superior to that of the (3-1) ZnAl-LDO-600 catalyst, and the catalytic activity after the catalyst is repeatedly used for three times is still higher than that of the newly prepared (3-1) ZnAl-LDO-600 catalyst. It was found from inductively coupled plasma emission spectroscopy (ICP) that the amount of Zn contained in the composite metal oxide decreased after the reaction, indicating that Zn dissolved as an active metal in the reaction liquid during the catalytic reaction and Zn element was detected in the reaction liquid (table 5), so the activity of the catalyst decreased with the increase of the number of repeated use due to the decrease in the content of Zn element. And the amount of Zn lost by the (3-1-0.9) ZnAlLa-LDO-700 catalyst after reaction is less than that of the (3-1) ZnAl-LDO-600 catalyst, so that the La element is added into the catalyst to effectively reduce the dissolution of Zn in a reaction system, thereby improving the catalytic reaction activity and the catalytic stability of the catalyst.
TABLE 5 ICP results
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A catalyst for the alcoholysis of Methyl Carbamate (MC) to produce dimethyl carbonate (DMC), said catalyst characterized by:
(1) the catalyst is composite metal oxide, and the active metal elements comprise transition metal elements and rare earth metal elements;
(2) the catalyst precursor is of a layered structure, after high-temperature roasting, the layered structure is partially collapsed, and more acidic and alkaline active sites are exposed on the surface of the composite metal oxide catalyst.
2. The catalyst according to claim 1, wherein the transition metal element in the feature (1) can be Zn or Fe.
3. The catalyst according to claim 1, wherein the rare earth metal element in the feature (1) may be La.
4. The catalyst according to claim 1, wherein in the feature (2), the composite metal oxide is prepared by oxidizing a layered composite metal hydroxide under high-temperature calcination conditions, and the degree of collapse of the layered plate structure can be controlled by adjusting the calcination temperature and the calcination time.
5. The method for preparing the catalyst according to claim 4, which mainly comprises the steps of:
(1) dissolving metal nitrate in deionized water, performing ultrasonic treatment to form a mixed solution, adding the mixed solution of the nitrate into a urea solution, stirring and refluxing the mixed solution at a certain temperature, aging at room temperature, performing suction filtration, washing and drying to obtain a catalyst precursor;
(2) grinding the catalyst precursor into powder, and then placing the powder into a muffle furnace to be roasted at a high temperature for a certain time to finally obtain the catalyst.
6. The method according to claim 5, wherein in the step (1), the molar ratio of the rare earth metal to the transition metal element is 0 to 5.
7. The method according to claim 5, wherein in the step (2), the calcination temperature is 100-800 ℃ and the calcination time is 2-10 h.
8. Use of a catalyst according to claim 1 for the MC alcoholysis synthesis of DMC, wherein the ratio of the molar ratio of the reactants methanol to MC of the catalytic reaction is between 0 and 40.
9. The use of the catalyst of claim 1 in the synthesis of DMC by MC alcoholysis, wherein the reaction temperature of the catalytic reaction is 100 ℃ and 240 ℃ and the reaction time is 1-24 h.
10. Use of a catalyst according to claim 1 in the synthesis of DMC by means of MC alcoholysis, wherein the catalyst is used in an amount of 0.1 to 10 wt.%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115124710A (en) * | 2022-07-25 | 2022-09-30 | 万华化学集团股份有限公司 | High-activity double-metal cyanide catalyst and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124710A (en) * | 2022-07-25 | 2022-09-30 | 万华化学集团股份有限公司 | High-activity double-metal cyanide catalyst and preparation method and application thereof |
| CN115124710B (en) * | 2022-07-25 | 2023-05-26 | 万华化学集团股份有限公司 | High-activity double-metal cyanide catalyst and preparation method and application thereof |
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