CN113426440A - Pretreatment method and application of catalyst for cyclic carbonate synthesis - Google Patents

Pretreatment method and application of catalyst for cyclic carbonate synthesis Download PDF

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CN113426440A
CN113426440A CN202110791335.XA CN202110791335A CN113426440A CN 113426440 A CN113426440 A CN 113426440A CN 202110791335 A CN202110791335 A CN 202110791335A CN 113426440 A CN113426440 A CN 113426440A
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cyclic carbonate
oxide
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mixed gas
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CN113426440B (en
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李德宝
郭荷芹
陈从标
贾丽涛
侯博
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Shanxi Institute of Coal Chemistry of CAS
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    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
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    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

The invention provides a pretreatment method of a catalyst for cyclic carbonate synthesis and application thereof, wherein a metal oxide base is catalyzedTreating the mixture for 4-10 h under the conditions of pressure of 0.5-2.0 MPa and temperature of 400-600 ℃ under the condition of off-line agent and nitrogen or argon atmosphere. After the treatment, the temperature is adjusted to 130-300 ℃, and the temperature is switched to 5-100 v% CO2CO of2A nitrogen/argon mixed gas, and pretreating the catalyst for 2-60 hours under the pressure of 1.0-4.0 MPa. The invention realizes the control of the structure and the surface acidity and alkalinity of the catalyst by pretreating the metal oxide based catalyst2The method has the advantages that the yield of the cyclic carbonate is improved by synergistic activation, and meanwhile, the catalyst is pretreated by an off-line scheme, so that the cost of cycloaddition reaction equipment can be obviously reduced, and the process economy is improved.

Description

Pretreatment method and application of catalyst for cyclic carbonate synthesis
Technical Field
The invention belongs to the field of heterogeneous catalysis, and particularly relates to a pretreatment method and application of a catalyst for cyclic carbonate synthesis.
Background
Carbon dioxide (CO)2) Is the most important greenhouse gas causing global warming, the annual emission amount of the whole world reaches hundreds of billions of tons, and the recovery, fixation and resource utilization of the greenhouse gas become a problem of close attention of all countries in the world. From the standpoint of recycling, CO2Is the most abundant and cheap carbon-resource in the world, and therefore, CO is vigorously developed2The green utilization technology develops a green and high-tech fine chemical industry chain, improves the added value of products, and has important economic and environmental significance.
The cyclic carbonate is an important organic chemical product and a high-boiling-point polar solvent with excellent performance, and is mainly used for synthesizing dimethyl carbonate, beta-hydroxylamine and derivatives thereof, vinylene carbonate, ethylene glycol, phenol ester and derivatives thereof and the like. With epoxide and CO2The preparation of cyclic carbonates by cycloaddition as starting material is an environmentally friendly and atom-economical process route (gas. Sci. technol.,2011,1: 142-. The catalysts currently used in industry for cycloaddition reaction are mainly homogeneous catalysts such as polyethylene glycol/potassium iodide system and quaternary ammonium salt system, and there are main problems: the halogen remaining in the cyclic carbonate degrades the product quality, limiting its application as a high-quality raw material. In order to solve the above problems, heterogeneous catalysts are receiving wide attention, and the catalysts reported at present mainly include supported ionic liquid catalysts, high molecular catalysts, metal oxide catalysts, molecular sieves and clay catalysts thereof (catal.sci.technol,2014,4, 1513; curr.org.chem.2015,19,681; j.catal).2016,37,826). The reaction performance of the supported organic base catalyst, the supported ionic liquid catalyst and the high molecular catalyst is good, but the active components continuously run off into the product in the reaction process, and the problem of product quality cannot be essentially solved. In contrast, metal oxide based catalysts have both acidic and basic sites, enabling the control of epoxide and CO2The synthesis of the cyclic carbonate is promoted by the synergistic activation of the components; the catalyst has good heat resistance and is especially suitable for cycloaddition reaction with large heat release; more importantly, the catalyst can essentially solve the intrinsic problem of cycloaddition products (CN 202010944228.1; CN 202010638230.6). However, the yield of cyclic carbonate on the metal oxide catalyst needs to be further improved, and the important ways to improve the yield of cyclic carbonate are as follows: promoting activated epoxide and CO2In time, perform insertion-ring closure reaction to inhibit self-polymerization of epoxide and inhibit epoxide and CO2The alternating copolymerization reaction of (a) occurs. The above purpose is achieved by two ways: 1) constructing bifunctional catalyst with matched strength and microscopic distance of acid center and alkaline center to realize epoxide and CO2Synergistic activation of (1); 2) the surface of the catalyst is pretreated, and the acidity and the alkalinity of the surface of the catalyst are adjusted, so that the acid-base center can achieve better synergistic matching.
Disclosure of Invention
The invention aims to provide a pretreatment method of a catalyst for cyclic carbonate synthesis and application thereof, so as to improve the yield of cyclic carbonate on the existing metal oxide based catalyst.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides a pretreatment method of a catalyst for synthesizing cyclic carbonate, which comprises the following steps: placing a metal oxide-based catalyst in a tubular furnace, and carrying out primary pretreatment on the catalyst in a nitrogen or argon atmosphere; then in the presence of CO2The catalyst is subjected to a second pretreatment under the mixed gas of (1).
Further, the metal oxide-based catalyst is a hydrotalcite-like-graphene oxide catalyst or a metal oxide anda composite catalyst of carbon nitride. The catalyst has both acid center and basic center, and can realize the reaction of epoxide and CO2The synthesis of the cyclic carbonate is promoted by the synergistic activation of (A) and (B).
Further, the temperature in the first pretreatment process is 400-600 ℃, the pressure is 0.5-2.0 MPa, and the time is 4-10 h; in the second pretreatment process, the temperature is 130-300 ℃, the pressure is 1.0-4.0 MPa, and the time is 2-60 h. So as to realize the regulation and control of the acidity and the alkalinity of the surface of the catalyst.
Further, the carbon monoxide-containing gas contains CO2Removing CO from the mixed gas2In addition, nitrogen or argon is also available.
Further, the carbon monoxide-containing gas contains CO2CO in the mixed gas2The content of (A) is 5-100 v%; the protective gas and the gas containing CO2The mixed gas is dehydrated by adopting a dehydrating agent, wherein the dehydrating agent is silica gel, a 5A molecular sieve or calcium oxide. In the second pretreatment process of the invention, CO in the pretreatment atmosphere2Content and H in the pretreatment atmosphere2The content of O has important influence on the acidity and alkalinity of the surface of the catalyst, and CO in the pretreatment atmosphere is controlled2And H2The O content is used for realizing the precise regulation and control of the acidity and the alkalinity of the surface of the catalyst.
The invention also provides the method for preparing the metal oxide based catalyst in CO after the pretreatment by adopting the pretreatment method2And an epoxide cycloaddition reaction, wherein the cycloaddition reaction comprises the following specific steps:
in the presence of CO2Under the protection of the mixed gas, the pretreated catalyst is cooled to room temperature, and is filled into a fixed bed reactor, and epoxide and CO are introduced2Controlling the reaction pressure to be 4.0-8.0 MPa, the temperature to be 100-180 ℃, and the epoxide liquid-air LHSV to be 0.1-1.0 h-1，CO2And (3) performing cycloaddition reaction at a space velocity GHSV of 500-1000 ml/gcat.h to obtain the cyclic carbonate.
Further, the cyclic carbonate is ethylene carbonate, propylene carbonate or cyclohexene oxide, preferably ethylene carbonate, propylene carbonate.
Further, the epoxide is one of ethylene oxide, propylene oxide, epichlorohydrin and cyclohexene oxide, preferably ethylene oxide and propylene oxide. The catalyst used in the invention has better catalytic effect on cycloaddition reaction of small molecular weight epoxide such as propylene oxide and ethylene oxide, and has slightly poor effect on cycloaddition reaction of large molecular weight epoxide such as ethylene glycol diglycidyl ether.
Further, the carbon monoxide-containing gas contains CO2The mixed gas is dehydrated by adopting a dehydrating agent, wherein the dehydrating agent is silica gel, a 5A molecular sieve or calcium oxide. To CO2Gas is subjected to H removal2O treatment for suppressing CO2H contained in2And the O and the epoxide are competitively adsorbed on the surface of the catalyst to promote the cycloaddition reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention realizes the control of the structure and the surface acidity and alkalinity of the catalyst by pretreating the metal oxide based catalyst2The synergistic activation of the two components promotes the cycloaddition reaction and improves the yield of the cyclic carbonate.
(2) The method adopts an off-line scheme to pretreat the catalyst, so that the cost of cycloaddition reaction equipment can be obviously reduced, and the process economy is improved.
Detailed Description
The following examples are given in the detailed description and the specific operation on the premise of the technical solutions of the present invention, but do not limit the protection scope of the patent of the present invention, and all technical solutions obtained by using equivalent alternatives or equivalent variations should fall within the protection scope of the present invention.
Example 1
With urea, Mg (NO)3)2.6H2O、Al(NO3)3.9H2O, 50 wt% manganese nitrate solution, NaOH and Na2CO3The cycloaddition catalyst is prepared by adopting a catalyst preparation method in patent CN202010944228.1 as a raw material, and the obtained catalyst comprises the following components: magnesium aluminum manganese oxygen in catalystThe mass ratio of the carbide to the carbon nitride is 100:3, and the magnesium-aluminum-manganese oxide comprises the following components: al (Al)2O3: the MnO molar ratio is 100: 20: 3.
treating the cycloaddition reaction catalyst with 5A molecular sieve dehydrated nitrogen gas under the conditions of 1.0MPa of pressure and 500 ℃ for 4 h. After the treatment, the temperature was adjusted to 200 ℃ and the mixture was switched to a mixture containing 10% by volume of CO and dehydrated by 5A molecular sieves2CO of2The catalyst was pretreated with nitrogen mixed gas at a pressure of 2.0MPa for 10 h.
The pretreated catalyst was placed in the above-described reactor containing 10% by volume of CO2Cooling to room temperature in nitrogen atmosphere, charging into fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel2The reaction pressure is controlled to be 6.0MPa, and the temperature is controlled to be 130 ℃, and the liquid-air volume of the epoxy ethane is controlled to be 0.1h-1，CO2Space velocity GHSV of 800ml/gcatH, cycloaddition reaction was carried out with an ethylene oxide conversion of 99.5% and an ethylene carbonate yield of 96.2%.
Example 2
With melamine, Zn (NO)3)2.6H2O、Al(NO3)3.9H2O、La(NO3)3.6H2O, NaOH and K2CO3The cycloaddition catalyst is prepared by adopting a catalyst preparation method in patent CN202010944228.1 as a raw material, and the obtained catalyst comprises the following components: the mass ratio of the zinc-aluminum-lanthanum oxide to the carbon nitride in the catalyst is 100:5, and the zinc-aluminum-lanthanum oxide comprises the following components: al (Al)2O3：La2O3The molar ratio is 100: 30: 3.
treating the cycloaddition reaction catalyst with 5A molecular sieve dehydrated nitrogen for 5h under the conditions that the pressure is 2.0MPa and the temperature is 550 ℃. After the treatment, the temperature was adjusted to 300 ℃ and the mixture was switched to 50% by volume CO dehydrated by 5A molecular sieves2CO of2The catalyst was pretreated with argon gas mixture at a pressure of 4.0MPa for 2.0 h.
The pretreated catalyst was placed in the above-described apparatus containing 50% by volume of CO2In an argon atmosphereCooling to room temperature, loading into a fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel2The reaction pressure is controlled to be 7.0MPa, the temperature is controlled to be 140 ℃, and the liquid air of the ethylene oxide is controlled to be 0.2h-1，CO2Space velocity GHSV of 800ml/gcatH, cycloaddition reaction was carried out with ethylene oxide conversion of 99.8% and ethylene carbonate yield of 95.9%.
Example 3
With dicyandiamide, Mg (NO)3)2.6H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O, KOH and K2CO3The cycloaddition catalyst is prepared by adopting a catalyst preparation method in patent CN202010944228.1 as a raw material, and the obtained catalyst comprises the following components: the mass ratio of the zinc-magnesium-aluminum oxide to the carbon nitride in the catalyst is 100:4, and the zinc-magnesium-aluminum oxide comprises the following components: MgO: al (Al)2O3The molar ratio is 100: 10: 30.
treating the cycloaddition reaction catalyst with 5A molecular sieve dehydrated nitrogen gas at the pressure of 1.0MPa and the temperature of 600 ℃ for 5 h. After the treatment, the temperature was adjusted to 200 ℃ and the mixture was switched to 90% by volume CO dehydrated by 5A molecular sieves2CO of2The catalyst was pretreated with argon gas mixture at a pressure of 2.0MPa for 40 h.
The pretreated catalyst was placed in the above-described 90 v% CO-containing reactor2Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, and introducing propylene oxide and CO dehydrated by silica gel2The reaction pressure is controlled to be 7.0MPa, the temperature is controlled to be 170 ℃, and the liquid air of the propylene oxide is controlled to be 0.8h-1，CO2Space velocity GHSV of 1000ml/gcatH, cycloaddition reaction is carried out, the conversion rate of the propylene oxide is 99.4 percent, and the yield of the propylene carbonate is 94.5 percent.
Example 4
Graphene oxide and Mg (NO)3)2.6H2O、Al(NO3)3.9H2O, NaOH and Na2CO3Prepared by adopting the catalyst preparation method in patent CN202010638230.6 as raw materialThe content of graphene oxide in the obtained catalyst is 10 wt%, and the content of Mg in the obtained catalyst is 10 wt%2+/Al3+The molar ratio was 3.0.
Treating the cycloaddition reaction catalyst with silica gel dehydrated nitrogen gas at 400 deg.C under 2.0MPa for 8 hr. After the treatment, the temperature was adjusted to 130 ℃ and the reaction was switched to 100 v% CO-containing dehydrated on silica gel2Gas, the catalyst was pretreated for 24h at a pressure of 2.0 MPa.
The pretreated catalyst was placed in the above-described reactor containing 100% by volume of CO2Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, and introducing propylene oxide and CO dehydrated by silica gel2The reaction pressure is controlled to be 6.5MPa, the temperature is controlled to be 140 ℃, and the liquid air of the propylene oxide is controlled to be 0.2h-1，CO2Space velocity GHSV of 500ml/gcatH, cycloaddition reaction is carried out, the conversion rate of the propylene oxide is 99.6 percent, and the yield of the propylene carbonate is 93.8 percent.
Example 5
Graphene oxide and Ca (NO)3)2.4H2O、Al(NO3)3.9H2O, NaOH and Na2CO3The catalyst is prepared by adopting the catalyst preparation method in patent CN202010638230.6 as a raw material, the content of graphene oxide in the obtained catalyst is 30 wt%, and Ca is2+/Al3+The molar ratio was 4.0.
The cycloaddition reaction catalyst is treated for 6 hours by nitrogen dehydrated by silica gel under the conditions that the pressure is 1.5MPa and the temperature is 550 ℃. After the treatment, the temperature was adjusted to 250 ℃ and the reaction was switched to 80 v% CO-containing by silica gel dehydration2Gas, the catalyst was pretreated for 40h at a pressure of 1.0 MPa.
The pretreated catalyst was treated as described above with 80 v% CO2Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel2The reaction pressure is controlled to be 6.5MPa, the temperature is controlled to be 150 ℃, and the liquid air of the ethylene oxide is controlled to be 0.1h-1，CO2Space velocity GHSV of 500ml/gcatH, performing cycloaddition reaction to convert propylene oxide into propylene oxideThe conversion rate was 99.9%, and the yield of propylene carbonate was 96.5%.
Example 6
With urea, Mg (NO)3)2.6H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O, KOH and K2CO3The cycloaddition catalyst is prepared by adopting a catalyst preparation method in patent CN202010944228.1 as a raw material, and the obtained catalyst comprises the following components: the mass ratio of the zinc-magnesium-aluminum oxide to the carbon nitride in the catalyst is 100:4, and the zinc-magnesium-aluminum oxide comprises the following components: MgO: al (Al)2O3The molar ratio is 100: 20: 30.
treating the cycloaddition reaction catalyst with 5A molecular sieve dehydrated nitrogen gas at the pressure of 1.0MPa and the temperature of 500 ℃ for 6 h. After the treatment, the temperature was adjusted to 180 ℃ and the mixture was switched to 100 v% CO by dehydration over a 5A molecular sieve2CO of2The catalyst was pretreated with argon gas mixture at a pressure of 1.0MPa for 40 h.
The pretreated catalyst was placed in the above-described reactor containing 100% by volume of CO2Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel2The reaction pressure is controlled to be 6.8MPa, the temperature is controlled to be 155 ℃, and the liquid air of the propylene oxide is controlled to be 0.2h-1，CO2Space velocity GHSV of 900ml/gcatH, cycloaddition reaction is carried out, the conversion rate of the propylene oxide is 98.9 percent, and the yield of the propylene carbonate is 95.6 percent.

Claims (10)

1. A pretreatment method of a catalyst for cyclic carbonate synthesis is characterized by comprising the following steps: placing a metal oxide-based catalyst in a tubular furnace, and carrying out primary pretreatment on the catalyst in a nitrogen or argon atmosphere; then in the presence of CO2The catalyst is subjected to a second pretreatment under the mixed gas of (1).
2. The method for pretreating a catalyst for synthesizing cyclic carbonate according to claim 1, wherein the metal oxide-based catalyst is a hydrotalcite-like-graphene oxide catalyst or a composite catalyst of a metal oxide and carbon nitride.
3. The method for pretreating a catalyst for synthesizing cyclic carbonate according to claim 1, wherein the temperature in the first pretreatment process is 400 to 600 ℃, the pressure is 0.5 to 2.0MPa, and the time is 4 to 10 hours; in the second pretreatment process, the temperature is 130-300 ℃, the pressure is 1.0-4.0 MPa, and the time is 2-60 h.
4. The method for pretreating a catalyst for synthesizing a cyclic carbonate according to claim 1, wherein said catalyst comprises CO2Removing CO from the mixed gas2In addition, nitrogen or argon is also available.
5. The method for pretreating a catalyst for synthesizing a cyclic carbonate according to claim 1, wherein said catalyst comprises CO2CO in the mixed gas2The content of (b) is 5 to 100 v%.
6. The method for pretreating a catalyst for synthesizing a cyclic carbonate according to claim 1, wherein said protective gas comprises CO2The mixed gas is dehydrated by adopting a dehydrating agent, wherein the dehydrating agent is silica gel, a 5A molecular sieve or calcium oxide.
7. Use of a catalyst for cyclic carbonate synthesis, characterized in that the catalyst for cyclic carbonate synthesis according to any one of claims 1 to 7 is used for CO treatment of a metal oxide based catalyst by a pretreatment method2And epoxide cycloaddition reaction, the specific steps are as follows:
in the presence of CO2Under the protection of the mixed gas, the pretreated catalyst is cooled to room temperature, and is filled into a fixed bed reactor, and epoxide and CO are introduced2The reaction pressure is controlled to be 4.0-8.0 MPa, the temperature is controlled to be 100-180 ℃, and epoxidation is carried outLHSV of liquid and liquid is 0.1-1.0 h-1，CO2And (3) performing cycloaddition reaction at a space velocity GHSV of 500-1000 ml/gcat.h to obtain the cyclic carbonate.
8. The use of the catalyst for the synthesis of a cyclic carbonate according to claim 7, wherein the cyclic carbonate is ethylene carbonate, propylene carbonate or cyclohexene oxide.
9. The use of the catalyst for the synthesis of cyclic carbonate according to claim 7, wherein the epoxide is one of ethylene oxide, propylene oxide, epichlorohydrin and cyclohexene oxide.
10. The use of the catalyst for cyclic carbonate synthesis according to claim 7, wherein the catalyst contains CO2The mixed gas is dehydrated by adopting a dehydrating agent, wherein the dehydrating agent is silica gel, a 5A molecular sieve or calcium oxide.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116272948A (en) * 2021-12-20 2023-06-23 中国科学院过程工程研究所 Stable cerium-containing catalyst and preparation method and application thereof

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