CN108126704B - Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof - Google Patents

Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN108126704B
CN108126704B CN201711379596.0A CN201711379596A CN108126704B CN 108126704 B CN108126704 B CN 108126704B CN 201711379596 A CN201711379596 A CN 201711379596A CN 108126704 B CN108126704 B CN 108126704B
Authority
CN
China
Prior art keywords
catalyst
cerium
zirconium
iron
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711379596.0A
Other languages
Chinese (zh)
Other versions
CN108126704A (en
Inventor
肖福魁
赵宁
李爱雪
蒲彦锋
雒京
宣铿
王太英
杨金海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Institute of Coal Chemistry of CAS
Original Assignee
Shanxi Institute of Coal Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi Institute of Coal Chemistry of CAS filed Critical Shanxi Institute of Coal Chemistry of CAS
Priority to CN201711379596.0A priority Critical patent/CN108126704B/en
Publication of CN108126704A publication Critical patent/CN108126704A/en
Application granted granted Critical
Publication of CN108126704B publication Critical patent/CN108126704B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A cerium-iron-zirconium composite oxide catalyst is a solid solution catalyst consisting of cerium oxide, iron oxide and zirconium oxide, wherein the molar ratio of various metals is as follows: ce: Fe: Zr =1-30:30-70: 30-70%. The invention has the advantages of high catalytic activity, high selectivity, low cost and no pollution.

Description

Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof
Technical Field
The invention relates to a cerium-iron-zirconium composite oxide catalyst, a preparation method thereof and application of the catalyst in direct synthesis of dimethyl carbonate from carbon dioxide and methanol.
Background
Dimethyl carbonate (DMC) is an important environmental-friendly green chemical product, can be widely applied to organic synthesis reactions such as carbonylation, methylation, methoxylation, carbonylation and the like, and can also be used as a methylation reagent or a carbonylation reagent instead of virulent phosgene, methyl chloroformate, dimethyl sulfate and the like. In addition, DMC has high oxygen content and high octane number, can greatly increase the gasoline oxygen content value and can be used as a petroleum additive. DMC is also an excellent green solvent, and has wide application prospect in the fields of paint, adhesive, coating and the like. DMC has excellent solubility in lithium salts and low viscosity, and thus, DMC can be used as an electrolyte for lithium batteries.
At present, DMC synthesis methods mainly comprise a phosgene method, a methanol oxidation carbonylation method, an ester exchange method, a urea alcoholysis method and the like. The phosgene process is gradually eliminated due to the extreme toxicity of the raw materials and the corrosiveness of chloride ions. The raw material of methanol oxidation carbonylation contains CO and O simultaneously2There is a potential explosion hazard. Recent research efforts have focused primarily on the transesterification process and the urea alcoholysis process, but both of these processes have certain limitations. The ester exchange method has the prominent weaknesses of two-step reaction, complex separation process, large reactant circulation amount and high operation cost. The reaction conditions of the urea alcoholysis method are harsh and the subsequent separation procedure is complex.
Compared with the traditional synthesis method, the direct synthesis of dimethyl carbonate from carbon dioxide and methanol is a green synthesis method. CO 22Is nontoxic, cheap and rich in CO2The raw materials not only reduce the production cost, but also reduce the greenhouse gas CO2The reaction by-product is only water, so the method has good application prospect. However, the reaction is limited by thermodynamics, so the key to the process is to develop a high efficiency catalyst on the one hand and to add a suitable coupling agent to shift the thermodynamic equilibrium and drive the reaction to the right on the other hand. The catalysts currently under investigation are alkoxylates, basic compounds, supported metal catalysts and metal oxide catalysts. Alkoxy compounds belong to homogeneous catalysts, are easily decomposed and deactivated by generated water in the using process, and tin with high activity easily pollutes the environment. The basic compound needs to be added with an equivalent amount of an alkylating reagent methyl iodide, but the methyl iodide has higher cost and is corrosive. Supported metal catalysts require reduction of the metal and are carried out in a fixed bed reactor. The metal oxide catalyst is mainly ZrO2Mainly, the acid-base group simultaneously existing on the surface of the zirconia can simultaneously activate methanol and CO2However, the surface acidity and alkalinity of the catalyst cannot meet the requirements of the reaction, and the catalyst needs to be modified to improve the catalytic activity.
Disclosure of Invention
The invention aims to provide a cerium-iron-zirconium composite oxide catalyst which has high catalytic activity, high selectivity, low cost and no pollution, and a preparation method and application thereof.
The catalyst of the invention is a solid solution catalyst composed of cerium oxide, iron oxide and zirconium oxide, wherein the molar ratio of various metals is as follows: ce, Fe, Zr 1-30:30-70: 30-70%.
The preparation method of the invention comprises the following steps:
preparing a cerium iron zirconium solid solution catalyst by adopting a sol-gel method: according to the catalyst composition, the preparation concentration is 0.1-1.0 mol.L-1Mixing ferric salt (ferric nitrate or ferric chloride), zirconium salt (zirconium nitrate or zirconium oxychloride or zirconium oxynitrate) and cerium salt (cerium nitrate or cerium sulfate) in ethanol to obtain a mixed solution with a concentration of 0.1-1.0 mol.L-1The citric acid ethanol solution is dripped into the salt solution, wherein the salt ethanol mixed solution: the volume ratio of the citric acid ethanol solution to the citric acid ethanol solution is 1:2-2:1, the mixed solution is stirred at room temperature, the solvent is evaporated to obtain dry gel of cerium, iron and zirconium, the dry gel is dried at 50-120 ℃ to obtain a catalyst precursor, and finally the catalyst precursor is roasted at the temperature of 300-900 ℃ in the air to obtain the cerium, iron and zirconium composite oxide catalyst.
The application of the invention is as follows:
putting the catalyst into a high-pressure reaction kettle, adding methanol and a dehydrating agent, introducing carbon dioxide, heating to a temperature required by the reaction under the condition of stirring to perform a synthetic reaction, and separating the dehydrating agent and the catalyst from a reaction product after the reaction is finished to obtain dimethyl carbonate; wherein the reaction pressure PCO21-15MPa, the reaction temperature is 40-150 ℃, the dosage of the catalyst is 0.5-10 wt% of the methanol, the dosage of the dehydrating agent is 5-200 wt% of the methanol, and the reaction time is 1-24 h.
The dehydrating agent as described above is a physical dehydrating agent or a chemical dehydrating agent.
The physical dehydrating agent is CaCl2Molecular sieves or SiO2(ii) a The chemical dehydrating agent is 2, 2-Dimethoxypropane (DMP), 2-cyanopyridine, Dicyclohexylcarbodiimide (DCC) or acetonitrile.
Compared with the prior art, the invention has the following advantages:
1) the catalyst has simple preparation method, convenient preparation and cheap and easily obtained raw materials.
2) The catalyst has adjustable quantity of medium-strength acid sites and basic sites on the surface, and can be used for CO2In the synthesis of dimethyl carbonate directly by using methanol, the catalytic activity is high (the DMC yield is 0.21-6.4 mmol. gcat)-1)。
3) The catalyst is not lost in the using process, is easy to separate from products, is easy to regenerate and reuse, and has small environmental pollution.
Detailed Description
The preparation and use of the catalysts proposed by the invention are further described below by way of examples.
Example 1
1.20mmol of Fe (NO)3)3·9H2O、2.76mmol ZrOCl2·8H2O、0.4mmol Ce(NO3)3·6H2O was dissolved in 200mL of ethanol, and 10.00mmol of citric acid was dissolved in 100mL of ethanol. An ethanol solution of citric acid was added dropwise to the above salt solution (the volume ratio of the two solutions was 2: 1). Stirring the mixed solution at room temperature, evaporating the solvent to obtain a dry gel of cerium, iron and zirconium, drying at 55 ℃ to obtain a catalyst precursor, and finally roasting the catalyst precursor in the air at 300 ℃ to obtain the 1% Ce-30% Fe-69% Zr solid solution catalyst.
Methanol and dehydrating agent SiO are used as raw materials2Adding into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: methanol content 12g, SiO20.6g, catalyst amount 0.06g, PCO2Reaction at 2MPa and 40 deg.c for 1 hr. Methanol conversion 0.12%, DMC yield 0.23 mmol. gcat-1。
Example 2
Mixing 3.30 mmoleFe (NO)3)3·9H2O、6.40mmolZrOCl2·8H2O、0.30mmolCe2(SO4)3·8H2O was dissolved in 100mL of ethanol, and 40.00mmol of citric acid was dissolved in 200mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 1: 2). And stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 70 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in the air at 400 ℃ to obtain the 3% Ce-33% Fe-64% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: 12g of methanol, 1.2g of molecular sieve, 0.12g of catalyst and PCO2Reaction at 4MPa and 60 deg.c for 4 hr. Methanol conversion 0.23% and DMC yield 0.44 mmol. gcat-1。
Example 3
Mixing 16.20mmol Fe (NO)3)3·9H2O、26.55mmolZr(NO3)4·5H2O、2.25mmolCe2(SO4)3·8H2O was dissolved in 150mL of ethanol, and 15.00mmol of citric acid was dissolved in 150mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 1: 1). Stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 80 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in the air at 500 ℃ to obtain the 5% Ce-36% Fe-59% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: the amount of methanol is 12g, CaCl22.4g for catalystAmount 0.36g, PCO26MPa, T80 ℃, and 8 h. Methanol conversion 0.45%, DMC yield 0.84 mmol. gcat-1。
Example 4
21.28mmol Fe (NO)3)3·9H2O、28.20mmolZr(NO3)4·5H2O、3.72mmolCe(NO3)3·6H2O was dissolved in 133mL of ethanol, and 33.40mmol of citric acid was dissolved in 167mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 4: 5). The mixed solution is stirred at room temperature, the solvent is evaporated to obtain dry gel of cerium, iron and zirconium, and the dry gel is dried at 90 ℃ to obtain a catalyst precursor. And finally, roasting the catalyst precursor in the air at 600 ℃ to obtain the 7% Ce-40% Fe-53% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: methanol amount of 12g, DMP3.6g, catalyst amount of 0.60g, PCO2Reaction at 8MPa and 100 deg.c for 12 hr. Methanol conversion 0.67%, DMC yield 1.25 mmol. gcat-1。
Example 5
Mixing 38.70 mmoleFe (NO)3)3·9H2O、42.30mmolZrO(NO3)2、9.00mmolCe(NO3)3·6H2O was dissolved in 180mL of ethanol, and 36.00mmol of citric acid was dissolved in 120mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 3: 2). And stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 100 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in the air at 800 ℃ to obtain the 10% Ce-43% Fe-47% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out the synthetic reaction, and after the reaction is finished, carrying out dehydrating agent and catalyst from the reaction productSeparating to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: methanol amount of 12g, 2-cyanopyridine of 8.4g, catalyst amount of 0.96g, PCO2Reaction at 12MPa and 130 deg.c for 20 hr. Methanol conversion 0.86% and DMC yield 1.61 mmol. gcat-1。
Example 6
45.09 mmoleFe (NO)3)3·9H2O、42.08mmolZrO(NO3)2、13.03mmolCe2(SO4)3·8H2O was dissolved in 167mL of ethanol, and 66.50mmol of citric acid was dissolved in 133mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 5: 4). And stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 110 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in the air at 900 ℃ to obtain the 13% Ce-45% Fe-42% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: 12g of methanol, 24.0g of DCC24.0g of catalyst and 1.20g of PCO2Reaction at 14MPa and 150 deg.c for 24 hr. The methanol conversion was 1.17% and the DMC yield was 2.19 mmol. gcat-1。
Example 7
66.85mmol of FeCl3、46.85mmolZrOCl2·8H2O、20.06mmolCe2(SO4)3·8H2O was dissolved in 191mL of ethanol, and 87.20mmol of citric acid was dissolved in 109mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 7: 4). Stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 120 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in air at 500 ℃ to obtain the 15% Ce-50% Fe-35% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Under stirring conditionsHeating to the temperature required by the reaction for synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: methanol amount of 12g, 2-cyanopyridine of 20.8g, catalyst amount of 0.06g, PCO2Reaction at 10MPa and 110 deg.c for 16 hr. The methanol conversion was 2.88% and the DMC yield was 5.40 mmol. gcat-1。
Example 8
63.60mmol of FeCl3、36.00mmolZrOCl2·8H2O、20.40mmolCe(NO3)3·6H2O was dissolved in 150mL of ethanol, and 20.40mmol of citric acid was dissolved in 150mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 1: 1). And stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 60 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in the air at 300 ℃ to obtain the 17% Ce-53% Fe-30% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: 12g of methanol, 2.4g of molecular sieve, 0.10g of catalyst and PCO2Reaction at 5MPa and 80 deg.c for 10 hr. Methanol conversion 0.36%, DMC yield 0.19 mmol. gcat-1。
Example 9
32.40mmol of FeCl3、54.00mmolZr(NO3)4·5H2O、21.60mmolCe(NO3)3·6H2O was dissolved in 120mL of ethanol, and 162.00mmol of citric acid was dissolved in 180mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 2: 3). And stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 75 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in the air at 400 ℃ to obtain the 20% Ce-30% Fe-50% Zr solid solution catalyst. Will be provided withAdding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: 12g of methanol, 6.0g of DCC, 0.08g of catalyst and PCO2Reaction at 8MPa and 90 deg.c for 8 hr. Methanol conversion 0.49% and DMC yield 0.92 mmol. gcat-1。
Example 10
49.05mmol FeCl3、32.70mmolZr(NO3)2·5H2O、27.25mmolCe2(SO4)3·8H2O was dissolved in 109mL of ethanol, and 115.00mmol of citric acid was dissolved in 191mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 4: 7). And stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 100 ℃ to obtain the catalyst precursor. And finally, roasting the catalyst precursor in the air at 500 ℃ to obtain the 25% Ce-45% Fe-30% Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: methanol amount 12g, acetonitrile 8.4g, catalyst amount 0.5g, PCO2Reaction at 12MPa and 130 deg.c for 16 hr. Methanol conversion 0.70%, DMC yield 1.31 mmol. gcat-1。
Example 11
Adding 7.40mmol of FeCl3、6.80mmolZrO(NO3)2、5.80mmolCe(NO3)3·6H2O was dissolved in 200mL of ethanol, and 100mmol of citric acid was dissolved in 100mL of ethanol. The citric acid ethanol solution is added into the salt solution dropwise (the volume ratio of the two solutions is 2: 1). And stirring the mixed solution at room temperature, evaporating the solvent to obtain dry gel of cerium, iron and zirconium, and drying at 110 ℃ to obtain the catalyst precursor. Finally the catalyst is put in front ofAnd roasting the precursor at 900 ℃ in the air to obtain the 29 percent Ce-37 percent Fe-34 percent Zr solid solution catalyst. Adding the raw materials and a dehydrating agent into a batch type reaction kettle, and filling CO2Heating to the temperature required by the reaction under the condition of stirring to carry out synthesis reaction, and separating the dehydrating agent and the catalyst from the reaction product after the reaction is finished to obtain the dimethyl carbonate. Methanol and CO2Conditions for direct synthesis of DMC were: methanol content 12g, SiO21.2g, catalyst amount 1.00g, PCO2Reaction at 10MPa and 110 deg.c for 20 hr. Methanol conversion 0.15%, DMC yield 0.29 mmol. gcat-1。

Claims (7)

1. The cerium-iron-zirconium composite oxide catalyst is characterized in that the catalyst is a solid solution catalyst consisting of cerium oxide, iron oxide and zirconium oxide, wherein the molar ratio of various metals is as follows: ce: Fe: Zr =1-30:30-70: 30-70%.
2. The method of claim 1, wherein the method comprises the steps of:
preparing a cerium iron zirconium solid solution catalyst by adopting a sol-gel method: according to the catalyst composition, the preparation concentration is 0.1-1.0 mol.L-1The mixed solution of ferric salt, zirconium salt and cerium salt is prepared by mixing the solution with concentration of 0.1-1.0 mol.L-1The citric acid ethanol solution is dripped into the salt ethanol mixed solution, wherein the salt ethanol mixed solution: the volume ratio of the citric acid ethanol solution is 1:2-2:1, the mixed solution is stirred at room temperature, the solvent is evaporated to obtain dry gel of cerium, iron and zirconium, the dry gel is dried at 50-120 ℃ to obtain a catalyst precursor, and finally the catalyst precursor is roasted at the temperature of 300-900 ℃ in the air to obtain the cerium, iron and zirconium composite oxide catalyst.
3. The method of claim 2, wherein the iron salt is ferric nitrate or ferric chloride, the zirconium salt is zirconium nitrate, zirconium oxychloride or zirconium oxynitrate, and the cerium salt is cerium nitrate or cerium sulfate.
4. The use of a cerium-iron-zirconium composite oxide catalyst according to claim 1, comprising the steps of:
putting the catalyst into a high-pressure reaction kettle, adding methanol and a dehydrating agent, introducing carbon dioxide, heating to a temperature required by the reaction under the condition of stirring to perform a synthetic reaction, and separating the dehydrating agent and the catalyst from a reaction product after the reaction is finished to obtain dimethyl carbonate; wherein the reaction pressure PCO21-15MPa, the reaction temperature is 40-150 ℃, the dosage of the catalyst is 0.5-10 wt% of the methanol, the dosage of the dehydrating agent is 5-200 wt% of the methanol, and the reaction time is 1-24 h.
5. The use of the cerium-iron-zirconium composite oxide catalyst according to claim 4, wherein the dehydrating agent is a physical dehydrating agent or a chemical dehydrating agent.
6. The use of a cerium-iron-zirconium composite oxide catalyst as claimed in claim 5, wherein the physical dehydrating agent is CaCl2Molecular sieves or SiO2。
7. The use of a cerium-iron-zirconium mixed oxide catalyst as claimed in claim 5, wherein the chemical dehydrating agent is 2, 2-dimethoxypropane, 2-cyanopyridine, dicyclohexylcarbodiimide or acetonitrile.
CN201711379596.0A 2017-12-20 2017-12-20 Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof Active CN108126704B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711379596.0A CN108126704B (en) 2017-12-20 2017-12-20 Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711379596.0A CN108126704B (en) 2017-12-20 2017-12-20 Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108126704A CN108126704A (en) 2018-06-08
CN108126704B true CN108126704B (en) 2021-04-02

Family

ID=62390801

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711379596.0A Active CN108126704B (en) 2017-12-20 2017-12-20 Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108126704B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108689850A (en) * 2018-07-01 2018-10-23 北京化工大学 A kind of method of cerium zirconium oxide/molecular sieve catalytic synthesizing diethyl carbonate
US20220009873A1 (en) * 2018-12-07 2022-01-13 Mitsubishi Gas Chemical Company, Inc. Dialkyl carbonate production method
CN110563585B (en) * 2019-10-11 2021-02-09 山东德普化工科技有限公司 Preparation method of dimethyl carbonate
CN112844393B (en) * 2019-11-27 2022-05-06 中国科学院大连化学物理研究所 Cerium-iron-zirconium solid solution oxide catalyst and preparation and application thereof
CN111905752B (en) * 2020-08-12 2022-12-27 陕西科技大学 Method for synthesizing dimethyl carbonate by using superfine cobalt-cerium bimetallic nano catalyst as catalyst
CN113620806B (en) * 2021-07-02 2023-07-25 湘南学院 Preparation method of dimethyl carbonate
CN113578331B (en) * 2021-08-05 2023-10-24 大连海事大学 Cobalt cerium zirconium composite oxide catalyst and preparation method thereof
CN115322097B (en) * 2022-09-21 2023-06-23 胜华新材料集团股份有限公司 Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1768927A (en) * 2005-10-12 2006-05-10 中国科学院山西煤炭化学研究所 A kind of catalyst for multi-phase catalytic synthesis of methyl carbonate and method for making thereof and application
CN102423707A (en) * 2011-12-28 2012-04-25 河北联合大学 Preparation method and application method of iron-zirconium composite oxide catalyst
CN103709040A (en) * 2013-12-02 2014-04-09 唐雅蓉 Dimethyl carbonate preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1768927A (en) * 2005-10-12 2006-05-10 中国科学院山西煤炭化学研究所 A kind of catalyst for multi-phase catalytic synthesis of methyl carbonate and method for making thereof and application
CN102423707A (en) * 2011-12-28 2012-04-25 河北联合大学 Preparation method and application method of iron-zirconium composite oxide catalyst
CN103709040A (en) * 2013-12-02 2014-04-09 唐雅蓉 Dimethyl carbonate preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"CexZr(1-x)O2(0≤x≤1)催化CO2和CH3OH直接合成碳酸二甲酯研究";张增庆;《中国优秀硕士学位论文全文数据库工程科技I辑》;20140915;B016-26 *
"Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over transition metal oxide/Ce0.6Zr0.4O2 catalysts: Effect of acidity and basicity of the catalysts";Hye Jin Lee et al.;《Korean Journal of Chemical Engineering》;20111114;第29卷(第3期);第317-322页 *
The proportion of Ce4+ in surface of CexZr1-xO2 catalysts: The key parameter for direct carboxylation of methanol to dimethyl carbonate;Hui Liu et al.;《Journal of CO2 Utilization》;20161122;第17卷;第43-49页 *

Also Published As

Publication number Publication date
CN108126704A (en) 2018-06-08

Similar Documents

Publication Publication Date Title
CN108126704B (en) Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof
CN101507917B (en) Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof
Wang et al. Two-step synthesis of dimethyl carbonate from urea, ethylene glycol and methanol using acid–base bifunctional zinc-yttrium oxides
CN103896811B (en) The method of hexa-methylene diamino-methyl formate is prepared in a kind of heterogeneous catalysis
CN110368933B (en) Ruthenium-based ammonia synthesis catalyst with Ce-Ti composite oxide as carrier and preparation method thereof
Wang et al. Zn/Fe mixed oxide: Heterogeneous catalyst for the synthesis of dimethyl carbonate from methyl carbamate and methanol
CN105251496A (en) Catalyst and method preparing dimethyl carbonate by using catalyst
CN112138708B (en) Solid acid catalyst and preparation method and application thereof
CN107739444B (en) Based on amino functionalization of YbIIIMetal organic framework material with hexanuclear molecular structural unit and preparation method and application thereof
CN110152733B (en) Catalyst, preparation method thereof and application of catalyst in catalyzing reaction of glycerol and urea
CN105879892A (en) Solid base catalyst for synthesizing dimethyl carbonate through transesterification method and preparation method and application
CN103551154B (en) Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst
CN104072376B (en) A kind of by CO 2with the method for methanol-fueled CLC methylcarbonate
CN104069858B (en) A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof
CN102964248B (en) Method for producing nitric oxide and synthesizing dimethyl oxalate through carbonylation
Li et al. Incorporation of CO2 into carbonates through carboxylation/hydration reaction
CN106944050A (en) A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application
CN103694141A (en) A method of synthesizing phenylcarbamate
KR20150085676A (en) Method of preparation of glycerol carbonate by using the zirconium containing metal organic frameworks as catalysts
CN113828359B (en) Zr-based MOFs composite material with organic alkali immobilized by 'shipbuilding in bottle' method and application thereof
CN101602014B (en) Load type carbon nano-fiber catalyst and application thereof
CN101306386A (en) Palladium catalyst for synthesizing oxalate using liquid phase coupling method and use thereof
CN108586193A (en) A method of preparing 1,3-PD using 3- methoxy methyl propionates
CN102964254B (en) Method for preparing dimethyl carbonate
CN111672493A (en) Alkaline mesoporous catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant