CN117586122A - Method for preparing dialkyl carbonate by heterogeneous catalysis - Google Patents

Method for preparing dialkyl carbonate by heterogeneous catalysis Download PDF

Info

Publication number
CN117586122A
CN117586122A CN202311546783.9A CN202311546783A CN117586122A CN 117586122 A CN117586122 A CN 117586122A CN 202311546783 A CN202311546783 A CN 202311546783A CN 117586122 A CN117586122 A CN 117586122A
Authority
CN
China
Prior art keywords
carbonate
oxide
reaction
dialkyl carbonate
molecular sieve
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.)
Pending
Application number
CN202311546783.9A
Other languages
Chinese (zh)
Inventor
呼延成
孙五群
孙博
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.)
Qingke New Materials Technology Hebei Co ltd
Original Assignee
Qingke New Materials Technology Hebei Co ltd
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 Qingke New Materials Technology Hebei Co ltd filed Critical Qingke New Materials Technology Hebei Co ltd
Priority to CN202311546783.9A priority Critical patent/CN117586122A/en
Publication of CN117586122A publication Critical patent/CN117586122A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

Landscapes

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

Abstract

The invention discloses a method for preparing dialkyl carbonate by heterogeneous catalysis. The invention takes propylene carbonate or ethylene carbonate and alkyl alcohol as raw materials, and prepares dialkyl carbonate through transesterification reaction under the action of heterogeneous catalyst. The catalyst provided by the invention is simple to prepare, can be reused, can reduce the production cost of dialkyl carbonate, improves the economic benefit, and has potential for industrial production.

Description

Method for preparing dialkyl carbonate by heterogeneous catalysis
Technical Field
The invention relates to the technical field of catalytic synthesis, in particular to a method for preparing dialkyl carbonate by heterogeneous catalysis.
Background
Dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and methylethyl carbonate are nontoxic, biodegradable and environmentally friendly bulk chemicals, can be used for preparing various fine special chemicals with high added value, and have wide application in the fields of medicines, pesticides, synthetic materials, dyes, and the like. The dimethyl carbonate can replace hazardous chemical dimethyl sulfate as a methylating agent, can replace highly toxic phosgene as a carbonylation agent, can be used as an environment-friendly additive to improve the octane number of gasoline and enhance shock resistance. In particular, the dialkyl carbonate has good conductivity and is widely applied to the lithium battery industry in the new energy field which is vigorously developed.
Industrially, the principle of the method for producing dialkyl carbonate by transesterification is that carbon dioxide and propylene oxide firstly produce propylene carbonate, and then the propylene carbonate and alkyl alcohol undergo transesterification reaction under the catalysis of alkali to produce dialkyl carbonate and 1, 2-propylene glycol. The catalyst used in the technology is sodium methoxide, but sodium methoxide belongs to a homogeneous catalyst, is difficult to separate and recycle, and is easy to corrode equipment due to strong alkalinity, and can also cause dehydration between propylene glycol molecules to generate byproducts such as dipropylene glycol, tripropylene glycol and the like.
Therefore, it is of great importance to develop a process for the heterogeneously catalyzed preparation of dialkyl carbonates.
Disclosure of Invention
The invention aims to provide a method for preparing dialkyl carbonate by heterogeneous catalysis.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a method for preparing dialkyl carbonate by heterogeneous catalysis, which comprises the following specific steps: propylene carbonate or ethylene carbonate and alkyl alcohol are taken as reaction raw materials, uniformly mixed and then added into a reaction kettle, a supported catalyst is added, the mixture is heated to 50-200 ℃, and the constant temperature reaction is kept for 0.5-36h, so that dialkyl carbonate is prepared;
the molar ratio of propylene carbonate or ethylene carbonate to alkyl alcohol is from 1:10 to 1:30;
the carrier of the supported catalyst is one or a mixture of more of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, niobium oxide, zinc oxide, magnesium oxide, calcium oxide, H-ZSM5 molecular sieve, H-Y molecular sieve and H-Beta molecular sieve; the supported metal active component is one or more of La, co, cu, mo, K, na, ca, ce, mg, al, zn; the mass of the metal active component is 1-80% of the mass of the carrier.
The invention also provides a method for preparing dialkyl carbonate by heterogeneous catalysis, which comprises the following specific steps: propylene carbonate or ethylene carbonate and alkyl alcohol are taken as reaction raw materials, uniformly mixed, a supported catalyst is added into a fixed bed reactor, the raw materials are pumped into a reaction bed layer at a feeding speed of 0.02-4mL/min under the flow of carrier gas, heated to 50-200 ℃, and kept at a constant temperature for reaction for 0.5-36h, so that dialkyl carbonate is prepared;
the molar ratio of propylene carbonate or ethylene carbonate to alkyl alcohol is from 1:10 to 1:30;
the carrier of the supported catalyst is one or a mixture of more of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, niobium oxide, zinc oxide, magnesium oxide, calcium oxide, H-ZSM5 molecular sieve, H-Y molecular sieve and H-Beta molecular sieve; the supported metal active component is one or more of La, co, cu, mo, K, na, ca, ce, mg, al, zn; the mass of the metal active component is 1-80% of the mass of the carrier.
Preferably, the catalyst is selected from K-Na/Al with a metal loading of 5-40% 2 O 3 、K-Na/SiO 2 、K/Al 2 O 3 、Na/Al 2 O 3 One of them.
Preferably, the catalyst is used in an amount of 0.01 to 2 times the mass of the reactant propylene carbonate or ethylene carbonate.
Preferably, the alkyl alcohol is any one of methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol and benzyl alcohol.
Preferably, the molar ratio of propylene carbonate or ethylene carbonate to alkyl alcohol is from 1:10 to 1:30.
Preferably, the reaction temperature is 110-150 ℃ and the reaction time is 2-10h.
Preferably, the reactant feed rate is 0.1-2mL/min when reacting in a fixed bed.
Preferably, in the fixed bed reaction, the carrier gas is inert gas, and the flow rate of the carrier gas is 120mL/min.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the existing homogeneous sodium methoxide catalytic process, the method has no corrosiveness to equipment, can reuse the catalyst, and is suitable for two reaction devices, namely an intermittent reaction kettle and a fixed bed.
2. The developed supported catalyst has the advantages of simple preparation method, cheap raw materials, easy amplification and potential market prospect.
3. The reaction applicability is wide, and a series of dialkyl carbonates can be prepared, including dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The starting materials and catalyst precursors in the examples of the present application were purchased commercially, unless otherwise specified.
The supported catalyst is obtained by an impregnation method, and the specific process is as follows: the metal salt precursor (4.0 g) was placed in a beaker, deionized water (6 mL) was added and stirred at 60℃with heating until completely dissolved. Then, a carrier (6.0 g, siO respectively) was added to the solution 2 、Al 2 O 3 、CeO 2 、TiO 2 The H-Y molecular sieve and the H-Beta molecular sieve), soaking for 12 hours, then slowly heating up to evaporate water, putting the soaked catalyst into a baking oven, drying for 5 hours at 160 ℃, putting into a muffle furnace, and roasting for 6 hours at 700 ℃ to obtain the supported catalyst.
The preparation method of the magnesium aluminum and zinc aluminum supported catalyst comprises the following steps: a nitrate solution was first prepared and to 100mL of deionized water, magnesium nitrate/zinc nitrate (0.093 mol) and aluminum nitrate (0.0465 mol) were added in this order and stirred until dissolved. In another beaker, an alkaline solution was prepared, sodium hydroxide (0.219 mol) and sodium carbonate (0.0565 mol) were added to 100mL of deionized water, and stirred until dissolved. The alkaline solution was slowly added dropwise to the metal nitrate solution with stirring at 70 ℃ until ph=10, at which temperature aging was continued for 20 hours. The precipitate was filtered, washed with deionized water until the filtrate ph=7, dried in an oven at 80 ℃ for 12 hours, and then placed in a muffle furnace for 8 hours at 500 ℃ to obtain a magnesium aluminum and zinc aluminum supported catalyst.
Example 1-example 24
Propylene carbonate (10.0 mmol,1.0 g), methanol (200.0 mmol,6.4 g) and a supported catalyst (0.1 g) were sequentially added to a 35mL pressure-resistant reaction tube, and the mixture was stirred at a certain temperature for 8 hours, cooled to room temperature after the completion of the reaction, tridecane (40 mg) was added as an internal standard, diluted with 10mL ethyl acetate, and 0.5mL of a gas chromatograph was taken out, and compared with a standard dimethyl carbonate, whereby the yield of dimethyl carbonate produced by the reaction was calculated.
TABLE 1 influence of Supported catalyst and temperature on reaction yield
Note that: for the supported catalyst, when a mixture precursor was used, the mass ratio of the two salts was 1:1, each 2.0g.
As can be seen from Table 1, the potassium nitrate, sodium nitrate, potassium carbonate and sodium carbonate are supported on silicon dioxide or aluminum oxide, and can promote transesterification reaction of propylene carbonate and methanol (examples 1-6), wherein the nitrate precursor has better effect, and the gas phase yield of the target product dimethyl carbonate can reach more than 60 percent (examples 5-6). When potassium carbonate and sodium carbonate were used as the mixed precursor, the reaction effect was improved (example 7). In particular, with a mixture of potassium nitrate and sodium nitrate as precursors, alumina or silica as support, the yield of dimethyl carbonate can be increased to 74% and 78%, respectively (examples 8-9). Other mixture precursors, such as potassium bicarbonate and sodium bicarbonate mixtures, can also give good results (example 10), but potassium chloride and sodium chloride mixtures do not give better results (example 11). Other supports, including cerium oxide, titanium oxide, and molecular sieves, all had reduced reaction yields (examples 12-15). The reaction efficiency can be further improved by increasing the temperature, and the yield of the dimethyl carbonate is close to 90% at 130 ℃ (examples 16-18). The catalysts prepared with other metal nitrates showed moderate downward reactivity (examples 19-22). The magnesium aluminum or zinc aluminum supported catalytic activity was relatively low (examples 23, 24). Therefore, potassium nitrate and sodium nitrate are used as mixture precursors, and are loaded on silicon oxide or aluminum oxide, so that the catalytic transesterification reaction effect is optimal.
Example 25
In a 1.5L three port reaction flask, propylene carbonate (1.0 mol,100 g), methanol (20.0 mol,640 g) and supported catalyst K-Na-2/SiO 2 (10.0 g), stirring under reflux at 130℃for 8 hours, cooling to room temperature, removing excess methanol by rotary evaporation at low temperature, and distilling dimethyl carbonate (boiling point: 90 ℃ C.) under normal pressure, 78 g in total, and isolation yield of 87%.
100mg of the obtained product is weighed and dissolved in 1.0mL of deuterated chloroform, 0.5mL of deuterated chloroform is taken out and put into a nuclear magnetic tube, and hydrogen spectrum and carbon spectrum detection are carried out by using Bruker 400MHz nuclear magnetic field. According to chemical displacement and integration, and combining with gas phase mass spectrum, the structure of the target product can be confirmed to be obtained, and specific nuclear magnetic data are as follows: 1 H NMR(400MHz,Chloroform-d)δ3.78(s,6H)； 13 c NMR (100 MHz, chlorine-d). Delta. 158.0,54.8. This characterization data is consistent with the chemical structure of dimethyl carbonate.
Example 26
In a fixed bed reactor, a supported catalyst K-Na-2/SiO is added 2 (0.30 g) in the presence of carrier gas nitrogenA mixed solution of propylene carbonate (0.5 mol,50 g) and methanol (10.0 mol,320 g) is pumped into a reaction bed at a flow rate of 0.05mL/min under the condition of gas (flow rate of 120 mL/min), sampling is started after the reaction is carried out for 4 hours at 140 ℃, sampling is carried out every 1 hour, and the yield of the dimethyl carbonate is kept at about 86 percent, so that the continuous stable operation can be carried out for 60 hours.
Example 27
In a 1.0L three port reaction flask, propylene carbonate (0.5 mol,50 g), ethanol (10.0 mol,460 g) and supported catalyst K-Na-2/SiO 2 (5.0 g), at 130℃under reflux stirring for 8 hours, cooling to room temperature was completed, excess ethanol was removed by rotary evaporation at low temperature, and diethyl carbonate (boiling point 127 ℃) was distilled off under normal pressure, 52 g in total, and the isolation yield was 88%.
100mg of the obtained product is weighed and dissolved in 1.0mL of deuterated chloroform, 0.5mL of deuterated chloroform is taken out and put into a nuclear magnetic tube, and hydrogen spectrum and carbon spectrum detection are carried out by using Bruker 400MHz nuclear magnetic field. According to chemical displacement and integration, and combining with gas phase mass spectrum, the structure of the target product can be confirmed to be obtained, and specific nuclear magnetic data are as follows: 1 H NMR(400MHz,Chloroform-d)δ4.21(q,J＝7.6Hz,4H),1.31(t,J＝7.6Hz,6H)； 13 c NMR (100 MHz, chlorine-d). Delta. 155.4,65.4,14.2. This characterization data is consistent with the chemical structure of diethyl carbonate.
Example 28
In a 1.0L three port reaction flask, propylene carbonate (0.5 mol,50 g), n-butanol (5.0 mol,370 g) and supported catalyst K-Na-2/SiO 2 (5.0 g) was stirred at 130℃under reflux for 8 hours, cooled to room temperature, excess butanol was removed by rotary evaporation, and dibutyl carbonate was distilled off under reduced pressure to give a total of 71 g, and the isolation yield was 82%.
100mg of the obtained product is weighed and dissolved in 1.0mL of deuterated chloroform, 0.5mL of deuterated chloroform is taken out and put into a nuclear magnetic tube, and hydrogen spectrum and carbon spectrum detection are carried out by using Bruker 400MHz nuclear magnetic field. According to chemical displacement and integration, and combining with gas phase mass spectrum, the structure of the target product can be confirmed to be obtained, and specific nuclear magnetic data are as follows: 1 H NMR(400MHz,Chloroform-d)δ4.23(q,J＝7.2Hz,4H),1.57-1.36(m,8H),0.91(t,J＝7.2Hz,6H)； 13 c NMR (100 MHz, chlorine-d). Delta. 154.8,68.8,28.8,18.7,13.9. This characterization data is consistent with the chemical structure of dibutyl carbonate.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.

Claims (9)

1. A method for preparing dialkyl carbonate by heterogeneous catalysis is characterized by comprising the following specific steps: propylene carbonate or ethylene carbonate and alkyl alcohol are taken as reaction raw materials, uniformly mixed and then added into a reaction kettle, a supported catalyst is added, the mixture is heated to 50-200 ℃, and the constant temperature reaction is kept for 0.5-36h, so that dialkyl carbonate is prepared;
the molar ratio of propylene carbonate or ethylene carbonate to alkyl alcohol is from 1:10 to 1:30;
the carrier of the supported catalyst is one or a mixture of more of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, niobium oxide, zinc oxide, magnesium oxide, calcium oxide, H-ZSM5 molecular sieve, H-Y molecular sieve and H-Beta molecular sieve; the supported metal active component is one or more of La, co, cu, mo, K, na, ca, ce, mg, al, zn; the mass of the metal active component is 1-80% of the mass of the carrier.
2. A method for preparing dialkyl carbonate by heterogeneous catalysis is characterized by comprising the following specific steps: propylene carbonate or ethylene carbonate and alkyl alcohol are taken as reaction raw materials, uniformly mixed, a supported catalyst is added into a fixed bed reactor, the raw materials are pumped into a reaction bed layer at a feeding speed of 0.02-4mL/min under the flow of carrier gas, heated to 50-200 ℃, and kept at a constant temperature for reaction for 0.5-36h, so that dialkyl carbonate is prepared;
the molar ratio of propylene carbonate or ethylene carbonate to alkyl alcohol is from 1:10 to 1:30;
the carrier of the supported catalyst is one or a mixture of more of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, niobium oxide, zinc oxide, magnesium oxide, calcium oxide, H-ZSM5 molecular sieve, H-Y molecular sieve and H-Beta molecular sieve; the supported metal active component is one or more of La, co, cu, mo, K, na, ca, ce, mg, al, zn; the mass of the metal active component is 1-80% of the mass of the carrier.
3. A process for the heterogeneously catalysed preparation of a dialkyl carbonate according to claim 1 or 2, characterized in that the preferred catalyst is K-Na/Al with a metal loading of 5% to 40% 2 O 3 、K-Na/SiO 2 、K/Al 2 O 3 、Na/Al 2 O 3 One of them.
4. A method for the heterogeneously catalyzed preparation of a dialkyl carbonate according to claim 1 or 2, characterized in that the catalyst is used in an amount of 0.01-2 times the mass of the reactant propylene carbonate or ethylene carbonate.
5. The method for preparing dialkyl carbonate by heterogeneous catalysis according to claim 1 or 2, wherein the alkyl alcohol is any one of methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol and benzyl alcohol.
6. A method for the heterogeneously catalyzed preparation of a dialkyl carbonate according to claim 1 or 2, characterized in that the molar ratio of propylene carbonate or ethylene carbonate to alkyl alcohol is 1:10-1:30.
7. The process for the heterogeneously catalyzed preparation of dialkyl carbonates according to claim 1 or 2, characterized in that the reaction temperature is 110 to 150℃and the reaction time is 2 to 10h.
8. A process for the heterogeneously catalyzed preparation of a dialkyl carbonate according to claim 2, characterized in that the reactant feed rate is 0.1-2mL/min when reacting in a fixed bed.
9. The method for preparing dialkyl carbonate by heterogeneous catalysis according to claim 2, wherein the carrier gas is inert gas and the flow rate of the carrier gas is 120mL/min when reacting in a fixed bed.
CN202311546783.9A 2023-11-20 2023-11-20 Method for preparing dialkyl carbonate by heterogeneous catalysis Pending CN117586122A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311546783.9A CN117586122A (en) 2023-11-20 2023-11-20 Method for preparing dialkyl carbonate by heterogeneous catalysis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311546783.9A CN117586122A (en) 2023-11-20 2023-11-20 Method for preparing dialkyl carbonate by heterogeneous catalysis

Publications (1)

Publication Number Publication Date
CN117586122A true CN117586122A (en) 2024-02-23

Family

ID=89909300

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311546783.9A Pending CN117586122A (en) 2023-11-20 2023-11-20 Method for preparing dialkyl carbonate by heterogeneous catalysis

Country Status (1)

Country Link
CN (1) CN117586122A (en)

Similar Documents

Publication Publication Date Title
EP3950123B1 (en) Heterogeneous catalyst based on ionic liquid, and preparation method therefor and use thereof
CN101659616B (en) Technology of preparing diethyl carbonate by urea alcoholysis method
CN109821560B (en) Catalyst for synthesizing dimethyl carbonate by ester exchange and application thereof
EP3950660A1 (en) Method for preparing dimethyl carbonate
CN112495431B (en) Method for synthesizing cyclic carbonate by mild catalysis of multi-site ionic liquid
CN109772286B (en) Solid base catalyst and preparation method and application thereof
CN1900047A (en) Process for preparing methyl ethyl carbonate by ester exchanging reaction
CN105294409A (en) Eugenol synthesis method
CN102863335B (en) Preparation method of diethyl succinate
CN110152733B (en) Catalyst, preparation method thereof and application of catalyst in catalyzing reaction of glycerol and urea
CN106478583A (en) The synthetic method of ethylene carbonate
CN108043454A (en) A kind of mesoporous basic catalyst and preparation method and application
CN117586122A (en) Method for preparing dialkyl carbonate by heterogeneous catalysis
CN111777589A (en) Method for continuously preparing dicyclohexyl-18-crown-6-ether and derivative thereof
CN111393402B (en) N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide
CN113398912A (en) Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate
CN102671705B (en) Preparation method and application of catalyst for synthesizing dimethyl carbonate
JP2011236146A (en) Method for producing diaryl carbonate and method for producing polycarbonate
CN104549208A (en) Catalyst for synthesizing dimethyl carbonate, preparation method and application of catalyst
CN115521204B (en) Method for synthesizing carbonic ester by alkaline ionic liquid one-pot catalysis
CN116273185B (en) Immobilized bifunctional catalyst and method for preparing cyclic carbonate in outer loop reaction process
CN104289215B (en) For catalyst of urea and ethanol synthesizing diethyl carbonate and its preparation method and application
CN112439405B (en) Catalyst for preparing dimethyl carbonate from methanol, carbon dioxide and 2-cyanopyridine and preparation method and application thereof
CN110724276B (en) Preparation method of acid-alkali difunctional MOFs material and method for synthesizing 3, 4-dimethylfurazan by using acid-alkali difunctional MOFs material as catalyst
CN117776887A (en) Preparation method of cyclopropyl methyl ketone

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