CN116173999A - Catalyst for decarbonylation reaction and its preparation method and use - Google Patents

Catalyst for decarbonylation reaction and its preparation method and use Download PDF

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CN116173999A
CN116173999A CN202111422862.XA CN202111422862A CN116173999A CN 116173999 A CN116173999 A CN 116173999A CN 202111422862 A CN202111422862 A CN 202111422862A CN 116173999 A CN116173999 A CN 116173999A
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catalyst
carbonate
butyl
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nitrogen
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修轶鲲
刘俊
汪婧妍
张龙
徐鑫
董晶晶
钱俊
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High Chemical Shaanxi Management Co ltd
East China Engineering Science and Technology Co Ltd
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East China Engineering Science and Technology Co Ltd
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Abstract

The invention relates to a catalyst for decarbonylation reaction, a preparation method and application thereof, which are used for decarbonylating dialkyl oxalate to prepare dialkyl carbonate. The catalyst comprises two or more of an alkali metal, an alkaline earth metal, and phosphorus, wherein the support is a nitrogen-modified carbon-based material.

Description

Catalyst for decarbonylation reaction and its preparation method and use
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a catalyst for decarbonylation reaction, a preparation method and application thereof.
Background
With the rapid development of the polycarbonate industry and the increasing development of new Li batteries in recent years, the demand for dimethyl carbonate (DMC) has to be increased gradually. The DMC can be prepared by conventional phosgene method, transesterification method, and methanol oxidative carbonylation method. In these processes dimethyl oxalate is directly decarbonylated to dimethyl carbonate and gaseous by-product CO in the presence of a catalyst. The process has the advantages of low toxicity, cheap raw materials, no three wastes, high yield, low corrosion and CO byproduct, which is also an important chemical product. The process route has the advantages of green environmental protection, high economic efficiency and the like, meets the requirements of modern green chemical development, and is widely focused by people.
Original Tian Shengzheng, et al (CN 1179414A), from Yuzheng, invented a catalyst composed of an organophosphorus compound or a mixture of an organophosphorus compound and a halogen atom-containing compound containing a trivalent or pentavalent phosphorus atom and at least one carbon-phosphorus bond, which was effective for decarbonylation reaction, i.e., for releasing CO from a compound containing a-CO-O-moiety in its molecular structure.
China Shanghai institute of petrochemistry Chen Liangfeng (CN 110857272A) and the like invented a material prepared by using polystyrene resin and quaternary phosphonium salt as raw materials for decarbonylating oxalate to prepare carbonate. When the catalyst is prepared, acetonitrile, benzonitrile, toluene, xylene and other organic reagents are required to be used, and the solvents have toxic effects on the environment and human bodies, do not meet the development requirements of green chemistry, and limit the industrialized application to a certain extent.
Zhang Wei et al in CN113181894a disclose a catalytic system for the decarbonylation of dimethyl oxalate directly to dimethyl carbonate. The preparation method of the catalyst comprises the steps of dispersing catalyst components in a surfactant solvent to obtain dispersion liquid, soaking a carrier in the dispersion liquid, drying, and calcining at 700-1000 ℃ for 2-5h to obtain the catalyst. However, the invention has the defects of complex preparation process, low selectivity of target products, high cost of MOF as a carrier and the like, and simultaneously, the process dissolves dimethyl oxalate in a solvent for decarbonylation reaction, thereby increasing the subsequent separation cost.
Xu Jie et al in CN106076387a disclose a heterogeneous catalyst for the transesterification of cyclic carbonates with alcohols to synthesize linear carbonates and a process for its preparation. The catalyst uses graphite phase carbon nitride as carrier, uses alkaline earth metal nitrate (Mg (NO) 3 ) 2 Or Ba (NO) 3 ) 2 ) MgO or BaO obtained after decomposition is used as an active component. However, when the catalyst is used, the conversion of the cyclic carbonate and the yield of the linear carbonate are low.
Zhang Haoyang (research of using solid base catalyst in dimethyl oxalate decarbonylation to dimethyl carbonate) from Shanghai university (2016's Shuoshi treatise) uses alkali carbonate as active component and activated carbon as carrier, and uses isovolumetric impregnation method to prepare a series of carbon-based catalysts with 5% Rb 2 CO 3 Carbon CMK-3 activity was better and 98% of DMO was decarbonylated to give DMC. However, the conversion is significantly reduced after four repeated uses of the catalyst.
Tianjin university Ma Xinbin et al (chemical reagent, 2004, 26 (4): 197-200) studied Zn (OAc) 2 .2H 2 O catalyzes the reaction of synthesizing diphenyl carbonate (DPC) by decarbonylating diphenyl oxalate (DPO), and examines the technological parameters of reaction temperature, reaction time and the like, and establishes the optimal reaction condition that the reaction temperature is 260 ℃ and the reaction time is 3h, wherein the mass ratio of DPO to catalyst is 100:1.5, and the DPC yield and DPO conversion rate reach the maximum values of 18.9% and 40.5%, respectively.
Traditional Activated Carbon (AC) supported catalysts are increasingly difficult to meet the needs of modern industrial production due to some of the following drawbacks: firstly, the microporous structure of the activated carbon greatly limits mass transfer of substrate molecules during the reaction process; second, micropores smaller than 2nm greatly limit the attachment sites of the active metal, resulting in a large amount of metal outside the pores of the catalyst, and further resulting in loss and agglomeration of the active metal during the reaction.
The development of nitrogen-modified porous carbon materials (CN) brings a life to the solution of the above-described problems. The introduction of nitrogen atoms can cause the change of the acid-base properties of the carbon skeleton and the surface thereof, improve the electron transfer efficiency of the catalyst skeleton, enhance the interaction of metal nano particles and carriers in a supported catalyst system, and the like, so that the catalyst is widely applied to heterogeneous catalytic reactions as a nano metal carrier for preparing metal-nitrogen modified carbon composite materials.
Disclosure of Invention
The existing catalyst for preparing carbonic ester by decarbonylation of oxalic ester has the defects of large pollution, low activity and easy deactivation of the catalyst in the preparation process. In view of the above-mentioned prior art, the present inventors have conducted extensive and intensive studies on a catalyst for the decarbonylation of dialkyl carbonate from dialkyl oxalate in order to find a catalyst for the decarbonylation of dialkyl oxalate to prepare dialkyl carbonate, which can overcome the above-mentioned drawbacks of the prior art, and which has a higher conversion rate of dialkyl oxalate and selectivity of dialkyl carbonate, and a prolonged catalyst lifetime and rapid decarbonylation performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
1. a supported catalyst comprising two or more of an alkali metal, an alkaline earth metal and phosphorus, wherein the support is a nitrogen-modified carbon-based material, preferably an amorphous nitrogen-modified carbon-based material.
2. The catalyst according to scheme 1, wherein the specific surface area of the catalyst is 200m or more 2 Per gram, preferably 300-800m 2 /g, more preferably 400-700m 2 /g, and/or pore volume of 0.1-2.5cm 3 Preferably 0.2-2.0 cm/g 3 Preferably 0.4-1.5 cm/g 3 And/or a pore size of from 0.5 to 60nm, preferably from 1 to 30nm, more preferably from 1.2 to 10nm, and/or a nitrogen content in the catalyst of from 0.5 to 30% by weight, preferably from 1 to 25% by weight, more preferably from 2 to 20% by weight, and/or a sum of the weights of alkali metal, alkaline earth metal and/or phosphorus of from 10 to 40% by weight, preferably from 12 to 35% by weight, more preferably from 15 to 30% by weight, based in each case on the total weight of the catalyst.
3. The catalyst according to scheme 1 or 2, wherein the weight ratio of alkali metal to alkaline earth metal to phosphorus to nitrogen modified carbon based material is (0-1.5): (0-2.5): (0-0.1): (2.1-4.5), preferably (0.1-1): (0.01-2.4): (0-0.09): (2.2-4.0), more preferably (0.1-0.8): (0.01-2.2): (0-0.08): (2.3-2.8).
4. A method of preparing the catalyst of any one of schemes 1-3, comprising the steps of:
(1): mixing two or more of an alkali metal source, an alkaline earth metal source, and a quaternary phosphonium salt with water to obtain a slurry;
(2): adding a precursor of a nitrogen-modified carbon-based material into the slurry obtained in the step (1), stirring to obtain a mixture, and drying the mixture;
(3): roasting the sample obtained in the step (2) to obtain the catalyst for decarbonylation reaction.
5. The method of scheme 4, wherein the alkali metal source is one or more of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, potassium sulfate, sodium oleate, and potassium oleate.
6. The method of either of schemes 4 or 5, wherein the alkaline earth metal source is one or more of calcium hydroxide, magnesium hydroxide, calcium oxide, strontium oxide, barium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, magnesium nitrate, and calcium nitrate.
7. The method of any one of schemes 4-6, wherein the quaternary phosphonium salt is tetraphenyl chloride
Figure BDA0003378060300000041
Benzyl triethyl chloride->
Figure BDA0003378060300000042
And tetrabutyl chloride->
Figure BDA0003378060300000043
One or more of the following. />
8. The method of any one of schemes 4-7, wherein the precursor of the nitrogen-modified carbon-based material is one or more of chitosan, N-acetyl-D-glucose, glucosamine hydrochloride, D-glucosamine sulfate, D-glucosamine acid, sodium glucosamine sulfate, melamine monoamide, and dicyandiamide.
9. A process for the preparation of dialkyl carbonate from dialkyl oxalate decarbonylation comprising decarbonylating dialkyl oxalate in the presence of the catalyst according to any one of schemes 1 to 3 or the catalyst prepared according to the process of any one of schemes 4 to 8 to obtain dialkyl carbonate, wherein the alkyl group is a linear or branched alkyl group of carbon number 1 to 6, preferably a linear or branched alkyl group of carbon number 1 to 4, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, most preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl.
10. Use of the catalyst according to any one of schemes 1 to 3 or the catalyst prepared according to the method of any one of schemes 4 to 8 for decarbonylating a dialkyl oxalate to prepare a dialkyl carbonate, wherein the alkyl group is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, most preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl.
Compared with the currently reported catalyst for preparing the dimethyl carbonate by decarbonylating the dimethyl oxalate, the catalyst for preparing the dialkyl carbonate by decarbonylating the dialkyl oxalate provided by the invention has the following advantages:
(1) The composite active component is inlaid in the nitrogen modified carbon-based material by a one-step method, so that the interaction between the active component and a carrier in a sample system is enhanced, the electron transfer efficiency of an active catalyst framework is accelerated, the removal of carbonyl is facilitated, and excellent catalytic activity is shown;
(2) The material prepared by the invention has rich pore canal structure, and expands the application in the catalysis or adsorption field;
(3) The nitrogen modified carbon-based material anchors the active component, effectively inhibits the loss of the active component in the reaction process, and prolongs the service life of the catalyst.
Drawings
Fig. 1 shows an X-ray diffraction (XRD) pattern of the catalyst support in example 1.
Detailed Description
According to one aspect of the present invention, there is provided a supported catalyst comprising two or more of an alkali metal, an alkaline earth metal and phosphorus, wherein the support is a nitrogen-modified carbon-based material.
According to one embodiment of the invention, the catalyst has a specific surface area of 200m or more 2 Per gram, preferably 300-800m 2 /g, more preferably 400-700m 2 /g。
According to one embodiment of the invention, the catalyst has a pore volume of 0.1-2.5cm 3 Preferably 0.2-2.0 cm/g 3 Preferably 0.4-1.5 cm/g 3 /g。
According to one embodiment of the invention, the pore size of the catalyst is from 0.5 to 60nm, preferably from 1 to 30nm, more preferably from 1.2 to 10nm.
According to one embodiment of the invention, the support in the catalyst is preferably an amorphous nitrogen-modified carbon-based material.
According to one embodiment of the invention, the nitrogen content of the catalyst is from 0.5 to 30% by weight, preferably from 1 to 25% by weight, more preferably from 2 to 20% by weight, based on the total weight of the catalyst.
According to one embodiment of the invention, the sum of the weights of alkali metal, alkaline earth metal and/or phosphorus in the catalyst is from 10 to 40% by weight, preferably from 12 to 35% by weight, more preferably from 15 to 30% by weight, based on the total weight of the catalyst.
According to one embodiment of the invention, the weight ratio of alkali metal to alkaline earth metal to phosphorus to nitrogen modified carbon based material in the catalyst is (0-1.5): (0-2.5): (0-0.1): (2.1-4.5), preferably (0.1-1): (0.01-2.4): (0-0.09): (2.2-4.0), more preferably (0.1-0.8): (0.01-2.2): (0-0.08): (2.3-2.8).
According to another aspect of the present invention there is provided a process for preparing the catalyst of the present invention, the process comprising the steps of:
(1): mixing two or more of an alkali metal source, an alkaline earth metal source, and a quaternary phosphonium salt with water to obtain a slurry;
(2): adding a precursor of a nitrogen-modified carbon-based material into the slurry obtained in the step (1), stirring to obtain a mixture, and drying the mixture;
(3): roasting the sample obtained in the step (2) to obtain the catalyst for decarbonylation reaction.
In step (1) of the method of the present invention, the alkali metal source is not particularly limited, and may be selected according to actual needs. For example, the alkali metal source is one or more of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, potassium sulfate, sodium oleate, and potassium oleate.
In step (1) of the method of the present invention, the source of the alkaline earth metal is not particularly limited, and may be selected according to actual needs. For example, the alkaline earth metal source is one or more of calcium hydroxide, magnesium hydroxide, calcium oxide, strontium oxide, barium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, magnesium nitrate, and calcium nitrate.
In step (1) of the method of the present invention, the quaternary phosphonium salt is not particularly limited and may be selected according to actual needs. For example, the quaternary phosphonium salt is tetraphenyl chloride
Figure BDA0003378060300000061
Benzyl triethyl chloride->
Figure BDA0003378060300000062
And tetrabutyl chloride->
Figure BDA0003378060300000063
One or more of the following.
In the step (1) of the method of the present invention, the amount of water to be used is not particularly limited, and may be selected according to actual needs.
In step (1) of the process of the invention, the mixing may be carried out with stirring, for example at a temperature of from 10 to 80 ℃, preferably from 20 to 60 ℃, more preferably from 25 to 40 ℃. The stirring time is not particularly limited, and may be selected according to actual needs. For example, the stirring time may be 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 1.5 to 6 hours. The stirring speed is not particularly limited, and may be selected according to actual needs. For example, the stirring speed may be 400 to 1000rpm, preferably 500 to 900rpm, more preferably 600 to 850rpm.
In step (2) of the method of the present invention, the precursor of the nitrogen-modified carbon-based material is not particularly limited, and may be selected according to actual needs. For example, the precursor of the nitrogen-modified carbon-based material is one or more of chitosan, N-acetyl-D-glucose, glucosamine hydrochloride, D-glucosamine sulfate, D-glucosamine acid, sodium glucosamine sulfate, melamine monoamide, and dicyandiamide.
In step (2) of the method of the present invention, the stirring temperature is not particularly limited, and may be selected according to actual needs. For example, at a temperature of 40-100 ℃, preferably 50-90 ℃, more preferably 60-85 ℃. The stirring time is not particularly limited, and may be selected according to actual needs. For example, the stirring time may be 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 1.5 to 6 hours. The stirring speed is not particularly limited, and may be selected according to actual needs. For example, the stirring speed may be 400 to 1000rpm, preferably 500 to 900rpm, more preferably 600 to 850rpm.
In step (2) of the method of the present invention, the drying temperature is not particularly limited, and may be selected according to actual needs. For example, the mixture is dried at 80-150 ℃, preferably 90-120 ℃, more preferably 95-110 ℃. The drying time is not particularly limited and may be selected according to actual needs. For example, the drying time may be 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 1.5 to 6 hours.
In step (3) of the method of the present invention, the firing temperature is not particularly limited, and may be selected according to actual needs. For example, the sample obtained in step (2) is calcined at 300 to 900 ℃, preferably 320 to 750 ℃, more preferably 350 to 600 ℃. The firing time is not particularly limited and may be selected according to actual needs. For example, the calcination time may be 0.5 to 12 hours, preferably 1 to 8 hours, more preferably 1.5 to 6 hours. The calcination may be performed under an inert gas atmosphere, for example, a gas atmosphere of nitrogen, argon or the like.
According to a further aspect of the present invention there is provided a process for the preparation of a dialkyl carbonate from a dialkyl oxalate decarbonylation comprising decarbonylating a dialkyl oxalate in the presence of a catalyst of the present invention or a catalyst prepared according to the process of the present invention to give a dialkyl carbonate.
In the process for producing a dialkyl carbonate according to the present invention, the alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, most preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl. The dialkyl carbonate is preferably selected from the group consisting of dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-n-butyl carbonate and di-n-pentyl carbonate.
According to the method for preparing dialkyl carbonate of the present invention, preferably, the dialkyl oxalate raw material is dialkyl oxalate and/or dialkyl oxalate solution.
Preferably, the solvent in the dialkyl oxalate solution is selected from at least one of methanol, ethanol and dialkyl carbonate. Preferably, the dialkyl carbonate as solvent is the same substance as the target product dialkyl carbonate.
In a preferred embodiment, the dialkyl carbonate is dimethyl carbonate.
In another preferred embodiment, the conditions for the decarbonylation reaction of the dialkyl carbonate include: the reaction temperature is 160-280 ℃, preferably 180-260 ℃, more preferably 200-240 ℃; and/or the reaction time is from 0.5 to 12 hours, preferably from 1 to 8 hours, more preferably from 1.5 to 6 hours; and/or the stirring speed is 600-1000rpm, preferably 700-900rpm, more preferably 750-850rpm.
The process for preparing dialkyl carbonates according to the invention can be carried out in any reactor capable of achieving the above-mentioned reaction conditions, for example in a fixed bed reactor, a fluidized bed reactor or a slurry bed reactor, preferably in a slurry bed reactor.
According to a final aspect of the present invention there is provided the use of the catalyst of the present invention or the catalyst prepared according to the process of the present invention for decarbonylating a dialkyl oxalate to prepare a dialkyl carbonate.
The invention is illustrated below in connection with specific examples which are provided for the purpose of illustration only and are not to be construed as limiting the scope of the invention.
Examples
Materials:
purchased from national pharmaceutical group chemical reagent limited, used without purification.
The testing method comprises the following steps:
specific surface area, pore volume, pore size were measured by ASAP2460 model instrument from microphone company.
The nitrogen content was measured by a FlashSmart model elemental analyzer from sammer.
The liquid phase product was analyzed by a model 456C gas chromatograph from warrior.
X-ray diffraction (XRD) analysis was performed using Cu K.alpha.radiation on XRD-7000S manufactured by Shimadzu corporation.
Example 1:
1. preparation of the catalyst:
step 1: respectively weighing 0.5g Rb 2 CO 3 And 1.5g CaCO 3 Mixing with 50.0g of water, and stirring at 50deg.C for 2 hr to obtain slurry;
step 2: adding 2.5g of dicyandiamide into the slurry obtained in the step 1, stirring for 3 hours at the temperature of 80 ℃, and then placing the semi-finished product at the temperature of 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 3 hours in a nitrogen atmosphere at 550 ℃, and cooling to obtain a finished product, which is named as a sample A.
Sample A having a specific surface area of 610m by BET detection 2 Per g, pore volume of 0.5cm 3 And/g, pore diameter of 1.5nm, and N content of 20 wt.% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample a was placed in a slurry bed reactor for dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on test sample a was 98.6% and the selectivity to dimethyl carbonate was 98.4%. Table 1 shows the repeated use of the catalyst, and it can be seen from the table that the yield of dimethyl carbonate can be maintained at 83.4% after 10 repeated use of the catalyst.
Table 1: sample A was decarbonylated to dimethyl oxalate for a number of applications to prepare dimethyl carbonate
Conversion of dimethyl oxalate% Selectivity of dimethyl carbonate,% Yield of dimethyl carbonate%
First time apply mechanically 98.6 98.4 97.0
Second time apply 97.6 98.2 95.8
For a third time apply 96.8 97.8 94.7
Fourth time apply mechanically 94.9 96.9 92.0
Fifth time apply 95.1 97.2 92.4
Sixth application 94.4 95.1 89.8
Seventh time apply mechanically 93.8 94.8 88.9
Eighth time apply mechanically 93.1 91.3 85.0
Ninth time apply mechanically 91.6 92.8 85.0
Tenth time apply mechanically 90.5 92.1 83.4
Example 2:
1. preparation of the catalyst:
step 1: weigh 1.0. 1.0g K separately 2 CO 3 And 0.2g CaCO 3 Mixing with 30.0g of water, and stirring at 40deg.C for 2 hr to obtain slurry;
step 2: adding 4.0g of glucosamine hydrochloride into the slurry obtained in the step 1, stirring for 3 hours at the temperature of 70 ℃, and then placing the semi-finished product at the temperature of 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 4 hours in a nitrogen atmosphere at 450 ℃, and cooling to obtain a finished product, which is named as a sample B.
Sample B having a specific surface area of 532m by BET detection 2 Per g, pore volume of 0.62cm 3 And/g, pore diameter of 2.1nm, and N content of 9 wt.% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample B was placed in a slurry bed reactor for dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on test sample B was 94.1% and the selectivity to dimethyl carbonate was 97.4%.
Example 3:
1. preparation of the catalyst:
step 1: 1.0g Rb are weighed respectively 2 CO 3 And 2.0g of Mg (NO) 3 ) 2 Mixing with 20.0g of water, and stirring at 30deg.C for 2 hr to obtain slurry;
step 2: adding 2.0g of melamine into the slurry obtained in the step 1, stirring for 3 hours at the temperature of 80 ℃, and then placing the semi-finished product at the temperature of 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 5 hours in a nitrogen atmosphere at 550 ℃, and cooling to obtain a finished product, which is named as a sample C.
Sample C obtained by BET detection had a specific surface area of 460m 2 Per g, pore volume of 0.81cm 3 And/g, pore diameter of 3.6nm, and N content of 17 wt% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample C was placed in a slurry bed reactor and used for the decarbonylation of dimethyl oxalate to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on test sample C was 97.7% and the selectivity to dimethyl carbonate was 98.1%.
Example 4:
1. preparation of the catalyst:
step 1: 1.0g of tetraphenyl chloride was weighed out separately
Figure BDA0003378060300000101
Mixing 2.5g CaO with 40.0g water, and stirring at 30 ℃ for 2 hours to obtain slurry;
step 2: adding 5.0g of glucosamine hydrochloride into the slurry obtained in the step 1, stirring for 3 hours at the temperature of 80 ℃, and then placing the semi-finished product at the temperature of 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 6 hours in a nitrogen atmosphere at 350 ℃, and cooling to obtain a finished product, which is named as a sample D.
Sample D obtained by BET detection had a specific surface area of 480m 2 Per g, pore volume of 0.73cm 3 And/g, pore diameter of 1.2nm, and N content of 2 wt.% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample D was placed in a slurry bed reactor for dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on test sample D was 94.6% and the selectivity to dimethyl carbonate was 96.2%.
Example 5:
1. preparation of the catalyst:
step 1: 1.4g of lithium carbonate and 2.5g of BaO are respectively weighed and mixed with 40.0g of water, and stirred for 2 hours at the temperature of 30 ℃ to obtain slurry;
step 2: adding 7.0g of glucosamine hydrochloride into the slurry obtained in the step 1, stirring for 3 hours at the temperature of 80 ℃, and then placing the semi-finished product at the temperature of 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 3 hours in a nitrogen atmosphere at 460 ℃, and cooling to obtain a finished product, which is named as a sample E.
Sample E having a specific surface area of 534m by BET detection 2 Per g, pore volume of 0.72cm 3 And/g, pore diameter of 1.9nm, and N content of 6.8 wt.% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample E was placed in a slurry bed reactor and used for the dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on test sample E was 96.6% and the selectivity to dimethyl carbonate was 95.4%.
Example 6:
1. preparation of the catalyst:
step 1: 1.4g of rubidium carbonate and 2.5g of BaO are respectively weighed and mixed with 40.0g of water, and stirred for 2 hours at the temperature of 30 ℃ to obtain slurry;
step 2: adding 10.0g N-acetyl-D-glucose into the slurry obtained in the step 1, stirring at 80 ℃ for 3 hours, and then placing the semi-finished product at 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 5 hours in a nitrogen atmosphere at 500 ℃, and cooling to obtain a finished product, which is named as a sample F.
The specific surface area of sample F obtained by BET detection was 454m 2 Per g, pore volume of 0.9cm 3 And/g, pore diameter of 3.8nm, and N content of 7 wt.% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample F was placed in a slurry bed reactor for dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on test sample F was 98.6% and the selectivity to dimethyl carbonate was 96.4%.
Example 7:
1. preparation of the catalyst:
step 1: 2.4g of potassium oleate and 2.5g of CaO are respectively weighed and mixed with 40.0g of water, and stirred for 2 hours at the temperature of 30 ℃ to obtain slurry;
step 2: adding 10.0g N-acetyl-D-glucose into the slurry obtained in the step 1, stirring at 80 ℃ for 3 hours, and then placing the semi-finished product at 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 5 hours in a nitrogen atmosphere at 500 ℃, and cooling to obtain a finished product, which is named as a sample G.
Sample G obtained by BET detection had a specific surface area of 487m 2 Per g, pore volume of 0.67cm 3 And/g, pore diameter of 1.5nm, and N content of 5.8 wt.% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample G was placed in a slurry bed reactor for dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on the test sample G was 94.3% and the selectivity to dimethyl carbonate was 93.4%.
Example 8:
1. preparation of the catalyst:
step 1: respectively weighing 0.5g of cesium carbonate and 1.0g of BaO, mixing with 80.0g of water, and stirring at 30 ℃ for 2 hours to obtain slurry;
step 2: adding 3.0g of melamine monoamide into the slurry obtained in the step 1, stirring for 3 hours at the temperature of 80 ℃, and then placing the semi-finished product at the temperature of 100 ℃ for 4 hours;
step 3: and (3) roasting the semi-finished product obtained in the step (2) for 4 hours in a nitrogen atmosphere at 550 ℃, and cooling to obtain a finished product, which is named as a sample H.
Sample H having a specific surface area of 567m by BET detection 2 Per g, pore volume of 0.78cm 3 And/g, pore diameter of 1.8nm, and N content of 7.5 wt.% measured by an elemental analyzer.
2. Evaluation of the catalyst:
sample H was placed in a slurry bed reactor and used for the dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of dimethyl oxalate on sample H was 95.5% and the selectivity to dimethyl carbonate was 94.2%.
Example 9:
1. preparation of the catalyst:
sample a was prepared as in example 1.
2. Evaluation of the catalyst:
sample A was placed in a slurry bed reactor and used for diethyl oxalate decarbonylation to prepare diethyl carbonate. The reaction conditions are as follows: 100g of diethyl oxalate, 220 ℃ of bed temperature, 1.0g of catalyst sample addition amount, 4h of reaction time and 800rpm of stirring speed. The conversion of diethyl oxalate on this sample was tested to be 97.8% and the selectivity to diethyl carbonate was 98.2%.
Example 10:
1. preparation of the catalyst:
sample a was prepared as in example 1.
2. Evaluation of the catalyst:
sample A was placed in a slurry bed reactor and used for the di-n-propyl oxalate decarbonylation to prepare di-n-propyl carbonate. The reaction conditions are as follows: 100g of di-n-propyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of di-n-propyl oxalate on this sample was tested to be 98.6% and the selectivity to di-n-propyl carbonate was 97.8%.
Example 11:
1. preparation of the catalyst:
sample a was prepared as in example 1.
2. Evaluation of the catalyst:
sample A was placed in a slurry bed reactor and used for the di-n-butyl carbonate decarbonylation of di-n-butyl oxalate. The reaction conditions are as follows: 100g of di-n-butyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The conversion of di-n-butyl oxalate on this sample was tested to be 96.9% and the selectivity to di-n-butyl carbonate was tested to be 96.9%.
Comparative example 1:
1. preparation of the catalyst:
according to the method disclosed in CN106076387A, mgO/g-C was prepared 3 N 4 Catalyst, in particular, 20 parts by mass of Mg (NO 3 ) 2 And 40 parts by mass of dicyandiamide in ethanol, then heating the mixture in an open manner until the solid is dried, placing the solid in a muffle furnace, and roasting the solid in a closed crucible at 550 ℃ to obtain the catalyst.
2. Evaluation of the catalyst:
and placing the prepared catalyst in a slurry bed reactor for the reaction of preparing dimethyl carbonate by decarbonylation of dimethyl oxalate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The product was analyzed by gas chromatography, and the conversion of dimethyl oxalate was 52.8% and the selectivity of dimethyl carbonate was 92.8%.
Comparative example 2:
1. preparation of the catalyst:
the preparation procedure as described in example 3 is followed, except that only Mg (NO 3 ) 2 Rather than Rb 2 CO 3 And Mg (NO) 3 ) 2 A single component MgO-supported nitrogen-modified carbon material was prepared.
2. Evaluation of the catalyst:
and placing the prepared catalyst in a slurry bed reactor for the reaction of preparing dimethyl carbonate by decarbonylation of dimethyl oxalate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. The product was analyzed by gas chromatography, and the conversion of dimethyl oxalate was 62.6% and the selectivity of dimethyl carbonate was 93.4%.
Comparative example 3:
1. preparation of the catalyst:
in order to compare the catalytic performance of the sample prepared by the impregnation method and the sample prepared by the invention on the decarbonylation of dimethyl oxalate to prepare dimethyl carbonate, a comparative sample 3 was prepared by the impregnation method, and the life of the comparative sample 3 on the decarbonylation of dimethyl oxalate to prepare dimethyl carbonate was examined.
Comparative sample 3 was prepared in a sample ratio similar to example 1, as follows:
respectively weighing 0.5g Rb 2 CO 3 、1.5g CaCO 3 And 2.5g of activated carbon are mixed with 50.0g of water, stirred for 2 hours at the temperature of 30 ℃ to obtain slurry, kept stand for 1 night, kept at 100 ℃ for 4 hours, and the obtained semi-finished product is baked for 3 hours in a nitrogen atmosphere at 550 ℃ and cooled to obtain a finished product which is named as a comparative sample 3.
2. Evaluation of the catalyst:
comparative sample 3 was placed in a slurry bed reactor for the dimethyl oxalate decarbonylation to prepare dimethyl carbonate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. Table 2 shows the catalyst reuse cases of comparative sample 3.
Table 2: comparative sample 3 life in dimethyl oxalate decarbonylation to dimethyl carbonate
Conversion of dimethyl oxalate% Selectivity of dimethyl carbonate,% Yield of dimethyl carbonate%
First time apply mechanically 91.5 95.0 86.9
Second time apply 84.3 91.8 77.4
For a third time apply 80.9 78.9 63.8
Comparative example 4:
1. preparation of the catalyst:
to further verify the effect of the present invention, a comparative sample 4Rb was prepared according to the preparation protocol disclosed in Shanghai university Zhang Haoyang (research of the university of Shuoshi in 2016, solid base catalyst for decarbonylation of dimethyl oxalate into dimethyl carbonate) 2 CO 3 Carbon CMK-3.
2. Evaluation of the catalyst:
and placing the prepared sample in a slurry bed reactor for the reaction of preparing the dimethyl carbonate by decarbonylating the dimethyl oxalate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. Table 3 shows the catalyst reuse cases of comparative sample 4.
Table 3: comparative sample 4 life of dimethyl oxalate decarbonylation to dimethyl carbonate
Conversion of dimethyl oxalate% Selectivity of dimethyl carbonate,% Yield of dimethyl carbonate%
First time apply mechanically 93.0 94.1 87.5
Second time apply 90.1 93.0 83.8
For a third time apply 82.1 93.4 76.7
Comparative example 5:
1. preparation of the catalyst:
to further examine the effect of the present invention, a comparative sample 5Rb-Ca/C was prepared according to the preparation protocol disclosed in CN113181894A, in which 0.5g Rb was used 2 CO 3 、1.5g CaCO 3 And 2g CTAB in 500mL deionized water/ethanol (volume ratio 5:1) followed by stirring, and then a specific surface area of 500m 2 Soaking/g of active carbon to adsorb ethyl orthogermanate for 3 hours, taking out, pyrolyzing at high temperature under argon to obtain active carbon coated with germanium dioxide layer, dispersing 5g of active carbon coated with the germanium dioxide layer in Rb-Ca slurry, drying, and calcining the obtained solid at 800 ℃ for 3 hours to prepare the Rb-Ca/C catalyst.
2. Evaluation of the catalyst:
and placing the prepared sample in a slurry bed reactor for the reaction of preparing the dimethyl carbonate by decarbonylating the dimethyl oxalate. The reaction conditions are as follows: 100g of dimethyl oxalate, the bed temperature is 220 ℃, the catalyst sample addition amount is 1.0g, the reaction time is 4h, and the stirring speed is 800rpm. Table 4 shows comparative sample 5 catalyst reuse.
Table 4: service life of comparative sample 5 in preparation of dimethyl carbonate by decarbonylation of dimethyl oxalate
Conversion of dimethyl oxalate% Selectivity of dimethyl carbonate,% Yield of dimethyl carbonate%
First time apply mechanically 85.1 91.2 77.6
Second time apply 72.8 90.6 65.9
By comparing the data with the comparative samples of the comparative examples, it can be seen that the samples of the examples of the present invention have better decarbonylation properties and stability.

Claims (10)

1. A supported catalyst comprising two or more of an alkali metal, an alkaline earth metal and phosphorus, wherein the support is a nitrogen-modified carbon-based material, preferably an amorphous nitrogen-modified carbon-based material.
2. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 200m or more 2 Per gram, preferably 300-800m 2 /g, more preferably 400-700m 2 /g, and/or pore volume of 0.1-2.5cm 3 Preferably 0.2-2.0 cm/g 3 Preferably 0.4-1.5 cm/g 3 And/or a pore size of from 0.5 to 60nm, preferably from 1 to 30nm, more preferably from 1.2 to 10nm, and/or a nitrogen content in the catalyst of from 0.5 to 30% by weight, preferably from 1 to 25% by weight, more preferably from 2 to 20% by weight, and/or a sum of the weights of alkali metal, alkaline earth metal and/or phosphorus of from 10 to 40% by weight, preferably from 12 to 35% by weight, more preferably from 15 to 30% by weight, based in each case on the total weight of the catalyst.
3. The catalyst according to claim 1 or 2, wherein the weight ratio of alkali metal to alkaline earth metal to phosphorus to nitrogen modified carbon based material is (0-1.5): (0-2.5): (0-0.1): (2.1-4.5), preferably (0.1-1): (0.01-2.4): (0-0.09): (2.2-4.0), more preferably (0.1-0.8): (0.01-2.2): (0-0.08): (2.3-2.8).
4. A process for preparing a catalyst according to any one of claims 1 to 3, comprising the steps of:
(1): mixing two or more of an alkali metal source, an alkaline earth metal source, and a quaternary phosphonium salt with water to obtain a slurry;
(2): adding a precursor of a nitrogen-modified carbon-based material into the slurry obtained in the step (1), stirring to obtain a mixture, and drying the mixture;
(3): roasting the sample obtained in the step (2) to obtain the catalyst for decarbonylation reaction.
5. The method of claim 4, wherein the alkali metal source is one or more of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, potassium sulfate, sodium oleate, and potassium oleate.
6. The method of claim 4 or 5, wherein the alkaline earth metal source is one or more of calcium hydroxide, magnesium hydroxide, calcium oxide, strontium oxide, barium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, magnesium nitrate, and calcium nitrate.
7. The method of any one of claims 4-6, wherein the quaternary phosphonium salt is tetraphenyl chloride
Figure FDA0003378060290000013
Benzyl triethyl chloride->
Figure FDA0003378060290000012
And tetrabutyl chloride->
Figure FDA0003378060290000014
One or more of the following.
8. The method of any one of claims 4-7, wherein the precursor of the nitrogen-modified carbon-based material is one or more of chitosan, N-acetyl-D-glucose, glucosamine hydrochloride, D-glucosamine sulfate, D-glucosamine acid, sodium glucosamine sulfate, melamine monoamide, and dicyandiamide.
9. A process for the preparation of dialkyl carbonates from the decarbonylation of dialkyl oxalates, comprising decarbonylation of an alkyl oxalate in the presence of a catalyst according to any one of claims 1 to 3 or a catalyst prepared according to any one of claims 4 to 8 to obtain an alkyl carbonate, wherein the alkyl group is an alkyl group of 1 to 6 carbon atoms, preferably an alkyl group of 1 to 4 carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, most preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl.
10. Use of the catalyst according to any one of claims 1-3 or the catalyst prepared according to any one of claims 4-8 for decarbonylating a dialkyl oxalate to prepare a dialkyl carbonate, wherein the alkyl is a c 1-6 alkyl, preferably c 1-4 alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, most preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl.
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