CN113426440B - 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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CN113426440B
CN113426440B CN202110791335.XA CN202110791335A CN113426440B CN 113426440 B CN113426440 B CN 113426440B CN 202110791335 A CN202110791335 A CN 202110791335A CN 113426440 B CN113426440 B CN 113426440B
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cyclic carbonate
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pretreatment
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CN113426440A (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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    • C07D317/32—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 synthesizing cyclic carbonate and application thereof, wherein a metal oxide based catalyst is treated for 4-10 hours under the conditions of pressure of 0.5-2.0 MPa and temperature of 400-600 ℃ under the condition of off-line in a nitrogen or argon atmosphere. After the treatment, the temperature is adjusted to 130 to 300 ℃ and the content is switched to 5 to 100v% 2 CO of 2 -mixed gas of nitrogen/argon, the catalyst is pretreated for 2 to 60 hours under the pressure of 1.0 to 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 catalyst 2 The method has the advantages that the yield of the cyclic carbonate is improved by the 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 synthesizing cyclic carbonate.
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, CO 2 Is the most abundant and cheap carbon-resource in the world, and therefore, CO is vigorously developed 2 The 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 CO 2 The preparation of cyclic carbonates by cycloaddition as starting material is an environmentally friendly and atom-economical process route (gas.sci.technol., 2011, 1. 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 reduces the product quality, limiting its application as a high-quality raw material. In order to solve the above problems, heterogeneous catalysts are receiving much attention, and the catalysts reported at present mainly include supported ionic liquid catalysts, high molecular catalysts, metal oxide catalysts, molecular sieves and clay-based catalysts thereof (catal. Sci. Technol,2014,4,1513, curr. Org. Chem.2015,19,681, j.catal.2016,37, 826. The supported organic base catalyst, the supported ionic liquid catalyst and the high molecular catalyst have good reaction performance, but active components continuously run off into products in the reaction process, so that 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 CO 2 Synergistic activation of (A) to promote cyclic carbonic acidSynthesizing an ester; 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 essential 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 CO 2 In time, perform insertion-ring closure reaction to inhibit self-polymerization of epoxide and inhibit epoxide and CO 2 The 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 CO 2 Synergistic activation of (2); 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 CO 2 The catalyst is subjected to a second pretreatment under the mixed gas of (2).
Further, the metal oxide-based catalyst is a hydrotalcite-like-graphene oxide catalyst or a composite catalyst of a metal oxide and carbon nitride. The catalyst has both acid center and basic center, and can realize the reaction of epoxide and CO 2 The 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; the temperature in the second pretreatment process 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 alkalinity of the surface of the catalyst.
Further, the carbon monoxide-containing gas contains CO 2 Removing CO from the mixed gas 2 In addition, nitrogen or argon gas is also included.
Further, the carbon monoxide-containing gas contains CO 2 CO in the mixed gas 2 The content of (A) is 5-100 v%; the protective gas and the CO-containing gas 2 The 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 atmosphere 2 Content and H in the pretreatment atmosphere 2 The content of O has important influence on the acidity and alkalinity of the surface of the catalyst, and CO in the pretreatment atmosphere is controlled 2 And H 2 The 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 a method for preparing the metal oxide based catalyst in CO after the pretreatment by adopting the pretreatment method 2 And an epoxide cycloaddition reaction, wherein the cycloaddition reaction comprises the following specific steps:
in the presence of CO 2 Under the protection of mixed gas, the pretreated catalyst is cooled to room temperature, is loaded into a fixed bed reactor, and epoxide and CO are introduced 2 Controlling the reaction pressure to be 4.0-8.0 MPa, the temperature to be 100-180 ℃, and the epoxide liquid-air LHSV = 0.1-1.0 h -1 ，CO 2 And 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 CO 2 The mixed gas is dehydrated by adopting a dehydrating agent, wherein the dehydrating agent is silica gel, a 5A molecular sieve or calcium oxide. To CO 2 Gas is subjected to H removal 2 O treatment for suppressing CO 2 In (b) H 2 And 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 catalyst 2 The 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 carried out on the premise of the technical solutions of the present invention, and detailed embodiments and specific operation procedures are given, but the protection scope of the present invention is not limited, 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 .6H 2 O、Al(NO 3 ) 3 .9H 2 O, 50wt% manganese nitrate solution, naOH and Na 2 CO 3 The cycloaddition catalyst is prepared by 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 magnesium-aluminum-manganese oxide to the carbon nitride in the catalyst is 100, and the magnesium-aluminum-manganese oxide comprises the following components in percentage by mass: al (Al) 2 O 3 : the MnO molar ratio is 100:20:3.
treating the cycloaddition catalyst with 5A molecular sieve dehydrated nitrogen gas under the conditions of 1.0MPa of pressure and 500 ℃ for 4h. After the treatment, the temperature is adjusted to 200 ℃, and the process is switched to 5AMolecular sieve dehydrated content of 10v% CO 2 CO of 2 Nitrogen mixed gas, and the catalyst is pretreated for 10 hours under the pressure of 2.0 MPa.
The pretreated catalyst contained 10v% CO in the above 2 Cooling to room temperature in nitrogen atmosphere, charging into fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel 2 The 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 ，CO 2 Space velocity GHSV =800ml/g cat H, 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 .6H 2 O、Al(NO 3 ) 3 .9H 2 O、La(NO 3 ) 3 .6H 2 O, naOH and K 2 CO 3 Adopts the catalyst preparation method in the patent CN202010944228.1 as the raw material to prepare the cycloaddition reaction catalyst, 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: al (Al) 2 O 3 ：La 2 O 3 The molar ratio is 100:30:3.
treating the cycloaddition catalyst with 5A molecular sieve dehydrated nitrogen at 550 deg.C under 2.0MPa for 5h. Adjusting the temperature to 300 deg.C after the treatment, switching to 5A molecular sieve dehydration containing 50v% of CO 2 CO of 2 The catalyst was pretreated with argon gas mixture at a pressure of 4.0MPa for 2.0 h.
The pretreated catalyst contained 50v% CO as described above 2 Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel 2 The 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 ，CO 2 Space velocity GHSV =800ml/g cat H, 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 .6H 2 O、Zn(NO 3 ) 2 .6H 2 O、Al(NO 3 ) 3 .9H 2 O, KOH and K 2 CO 3 Adopts the catalyst preparation method in the patent CN202010944228.1 as the raw material to prepare the cycloaddition reaction catalyst, 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, wherein the zinc-magnesium-aluminum oxide comprises the following components: mgO: al (Al) 2 O 3 The molar ratio is 100:10:30.
treating the cycloaddition reaction catalyst with 5A molecular sieve dehydrated nitrogen for 5h under the conditions that the pressure is 1.0MPa and the temperature is 600 ℃. Adjusting the temperature to 200 ℃ after the completion of the treatment, switching to 90v% CO dehydrated by 5A molecular sieves 2 CO of 2 The catalyst was pretreated with argon gas mixture at a pressure of 2.0MPa for 40 h.
The pretreated catalyst contained 90v% CO as described above 2 Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, and introducing propylene oxide and CO dehydrated by silica gel 2 The 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 ，CO 2 Space velocity GHSV =1000ml/g cat H, performing cycloaddition reaction, wherein 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 .6H 2 O、Al(NO 3 ) 3 .9H 2 O, naOH and Na 2 CO 3 The catalyst is prepared by adopting the catalyst preparation method in the patent CN202010638230.6 as a raw material, the content of graphene oxide in the obtained catalyst is 10wt%, and Mg 2+ /Al 3+ The molar ratio was 3.0.
Treating the cycloaddition reaction catalyst with silica gel dehydrated nitrogen under the conditions of pressure of 2.0MPa and temperature of 400 ℃ for 8h. After the treatment, the temperature was adjusted to 130 ℃ and the content was changed to 100v% CO by silica gel dehydration 2 Gas, the catalyst was pretreated for 24h at a pressure of 2.0 MPa.
The pretreated catalyst contained 100v% CO as described above 2 Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, and introducing propylene oxide and CO dehydrated by silica gel 2 The 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 ，CO 2 Space velocity GHSV =500ml/g cat H, 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 .4H 2 O、Al(NO 3 ) 3 .9H 2 O, naOH and Na 2 CO 3 The catalyst is prepared by the catalyst preparation method in patent CN202010638230.6, the content of graphene oxide in the obtained catalyst is 30wt%, and Ca is added 2+ /Al 3+ 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 ℃. Adjusting the temperature to 250 ℃ after the completion of the treatment, switching to the 80v% CO content by silica gel dehydration 2 Gas, the catalyst was pretreated for 40h at a pressure of 1.0 MPa.
The pretreated catalyst contained 80v% CO as described above 2 Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel 2 The 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 ，CO 2 Space velocity GHSV =500ml/g cat H, performing cycloaddition reaction, wherein the conversion rate of the propylene oxide is 99.9 percent, and the yield of the propylene carbonate is 96.5 percent.
Example 6
With urea, mg (NO) 3 ) 2 .6H 2 O、Zn(NO 3 ) 2 .6H 2 O、Al(NO 3 ) 3 .9H 2 O, KOH and K 2 CO 3 As raw material, the method adopts the method disclosed in patent CN202010944228.1The catalyst preparation method of (2) is used for preparing a cycloaddition reaction catalyst, 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, wherein the zinc-magnesium-aluminum oxide comprises the following components: mgO: al (aluminum) 2 O 3 The molar ratio is 100:20:30.
treating the cycloaddition catalyst with 5A molecular sieve dehydrated nitrogen gas at 500 deg.C under 1.0MPa for 6 hr. Adjusting the temperature to 180 ℃ after the treatment, switching to a content of 100v% CO dehydrated with 5A molecular sieves 2 CO of (2) 2 The catalyst was pretreated with argon gas mixture at a pressure of 1.0MPa for 40 h.
The pretreated catalyst contained 100v% CO as described above 2 Cooling to room temperature in argon atmosphere, loading into a fixed bed reactor, introducing ethylene oxide and CO dehydrated by silica gel 2 The 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 ，CO 2 Space velocity GHSV =900ml/g cat H, performing cycloaddition reaction, wherein the conversion rate of the propylene oxide is 98.9 percent, and the yield of the propylene carbonate is 95.6 percent.

Claims (8)

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 CO 2 Under the mixed gas, carrying out secondary pretreatment on the catalyst;
the metal oxide-based catalyst is a hydrotalcite-like-graphene oxide catalyst or a composite catalyst of metal oxide and carbon nitride;
the nitrogen or argon gas and a gas containing CO 2 The mixed gas is dehydrated by adopting a dehydrating agent;
in the first pretreatment process, the temperature is 400-600 ℃, the pressure is 0.5-2.0 MPa, and the time is 4-10 h; the temperature in the second pretreatment process is 130-300 ℃, the pressure is 1.0-4.0 MPa, and the time is 2-60 h.
2. The method for pretreating a catalyst for synthesizing a cyclic carbonate according to claim 1, wherein said catalyst comprises CO 2 Removing CO from the mixed gas 2 In addition, nitrogen or argon is also available.
3. The method for pretreating a catalyst for synthesizing a cyclic carbonate according to claim 1, wherein said catalyst comprises CO 2 CO in the mixed gas 2 The content of (b) is 5 to 100v%.
4. The method for pretreating a catalyst for synthesizing a cyclic carbonate according to claim 1, wherein said nitrogen gas, argon gas and CO are contained 2 The mixed gas is dehydrated by adopting a dehydrating agent, wherein the dehydrating agent is silica gel, a 5A molecular sieve or calcium oxide.
5. Use of a catalyst for cyclic carbonate synthesis characterized in that a metal oxide based catalyst is treated for CO by the pretreatment method of a catalyst for cyclic carbonate synthesis according to any one of claims 1 to 4 2 And epoxide cycloaddition reaction, the specific steps are as follows:
in the presence of CO 2 Under 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 introduced 2 Controlling the reaction pressure to be 4.0-8.0 MPa, the temperature to be 100-180 ℃, and the epoxide liquid-air LHSV = 0.1-1.0 h -1 ，CO 2 Performing cycloaddition reaction at a space velocity GHSV = 500-1000 ml/gcat.h to obtain cyclic carbonate;
said CO-containing 2 The mixed gas of (2) is dehydrated by a dehydrating agent.
6. The use of the catalyst for the synthesis of a cyclic carbonate according to claim 5, wherein the cyclic carbonate is ethylene carbonate, propylene carbonate or cyclohexene oxide.
7. The use of the catalyst for the synthesis of a cyclic carbonate according to claim 5, wherein the epoxide is one of ethylene oxide, propylene oxide, epichlorohydrin and cyclohexene oxide.
8. The use of the catalyst for cyclic carbonate synthesis according to claim 5, wherein the dehydrating agent is silica gel, 5A molecular sieve or calcium oxide.
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