CN105618126A - High-activity catalyst for synthesizing dimethyl carbonate, and preparation method and application thereof - Google Patents
High-activity catalyst for synthesizing dimethyl carbonate, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a supported catalyst for preparing dimethyl carbonate with urea and methanol. The catalyst is prepared from the following components by weight: 40%-75% of an alkaline earth metal modified MFI molecular sieve, 15%-30% of active metal oxide, and 10%-20% of phosphorus pentoxide; in the alkaline earth metal modified MFI molecular sieve, the weight of an alkaline earth metal accounts for 0.3-2% of the weight of the MFI molecular sieve; the MFI molecular sieve is a ZSM-5 molecular sieve preferably; the alkaline earth metal comprises beryllium, magnesium, calcium, strontium, barium or radium, and preferably magnesium or calcium; the active metal oxide is zinc oxide and/or cerium oxide. The catalyst can overcome the defects in the prior art that the equilibrium conversion rate is low and a homogeneous catalyst is not easy to separate in the technology of adopting urea and methanol to prepare dimethyl carbonate; the yield of dimethyl carbonate is high.
Description
Technical field
The present invention relates to the Catalysts and its preparation method of a kind of Synthesis of dimethyl carbonate and application, especially for Catalysts and its preparation method and the application of carbamide and methanol preparing dimethyl carbonate.
Background technology
Dimethyl carbonate (DMC) is the environment-friendly type Organic Chemicals that one meets that the modern times " cleaning procedure " require, is one of green chemical products of unanimously assert of international community. It can not only replace phosgene, dimethyl sulfate, chloromethane and methylchloroformate as carbonylation, methylate, is esterified and the reagent of ester exchange, and is a kind of good green solvent and gasoline additive.
Methanol and alcoholysis of urea catalytic synthesizing dimethyl carbonate (DMC) are the novel artistic routes substituting phosgene production DMC. Alcoholysis of urea makes base stock with wide material sources, cheap carbamide and methanol, there is the ammonia that raw material is cheap and easy to get, technique simple and reaction produces and the advantage such as can recycle, and the anhydrous generation of course of reaction, avoid the separation problem of methanol-DMC-water complex system, make later separation purify to simplify, reduce investment outlay, especially existing chemical fertilizer factory is developed downstream product attractive.
Patent WO9517369 adopts Dibutyltin oxide, dimethoxide base stannum, dibutyl methoxyl group NCO stannum as catalyst, react with methanol with methyl carbamate or carbamide, steam dimethyl carbonate continuously simultaneously, although such catalyst can obtain higher product yield, but also can the decomposition of catalytic amino methyl formate. US5902894 adopts high boiling point electron donor's oxycompound to do solvent and co-catalyst, effectively inhibits the decomposition of methyl carbamate and the generation of the side reaction that methylates. Its methyl carbamate conversion ratio is up to 98.3%, and dimethyl carbonate selectivity reaches 98.2% simultaneously. Although organo-tin compound has good catalytic effect, but their toxicity is big, price is high, homogeneous catalyst separates and recovers extremely difficult from product.
Patent CN1569809 proposes a kind of by the method for methanol and Synthesis of Dimethyl Carbonate from Urea. In autoclave reactor, at 130-180 DEG C, adopting amine salt type ionic liquid as catalyst, one-step synthesis dimethyl carbonate, its productivity is 25-30%, and selectivity is 100%. Although this catalyst effect is better, but still the problem of existence and product separation difficulty.
Therefore, exploitation heterogeneous catalysis efficient, non-environmental-pollution is that Synthesis of Dimethyl Carbonate from Urea technique realizes industrialized key.
Summary of the invention
For the deficiencies such as equilibrium conversion is low, homogeneous catalyst is not readily separated in existing urea and methanol preparing dimethyl carbonate technology, the present invention provides a kind of Catalysts and its preparation method for carbamide and methanol preparing dimethyl carbonate and application.
The carbamide of support type of the present invention and methanol catalyst for preparing dimethyl carbonate, content meter by weight, containing the alkali-earth metal modified MFI molecular sieve of 40% ~ 75%, the reactive metal oxides of 15% ~ 30%, and the phosphorus pentoxide of 10% ~ 20%; In described alkali-earth metal modified MFI molecular sieve, alkaline-earth metal accounts for the 0.3% ~ 2% of MFI molecular sieve, MFI molecular sieve is preferably ZSM-5 molecular sieve, described alkaline-earth metal includes beryllium, magnesium, calcium, strontium, barium or radium, preferably magnesium or calcium, described reactive metal oxides is zinc oxide and/or cerium oxide.
The carbamide of above-mentioned support type and the preparation method of methanol catalyst for preparing dimethyl carbonate, including following content:
(1) select or prepare ZSM-5 molecular sieve;
(2) ZSM-5 molecular sieve in step (1) is modified preparing alkali-earth metal modified ZSM-5 molecular sieve, adopts infusion process, with the nitrate solution of alkaline-earth metal, ZSM-5 is impregnated, then to the dry materials after dipping, roasting;
(3) suitable binding agent is selected, the material making beating appropriate active metal precursor solution, phosphorus pentoxide, binding agent and step (2) prepared, is made into suspension, then dries, extruded moulding, obtains carbamide and methanol catalyst for preparing dimethyl carbonate after roasting.
Wherein in step (1), ZSM-5 molecular sieve adopts hydrothermal synthesis method to prepare, and Si/Al mol ratio is 10 ~ 150, it is preferred to 20 ~ 100. Silicon source is the one in metso, waterglass, Ludox or metasilicate; Aluminum source is the one in aluminium salt or aluminate; Template is the one in n-butylamine, triethylamine, 4-propyl bromide or ethylenediamine. Take the desired amount of silicon source and aluminum source, dissolve with distilled water respectively and make solution, after two kinds of solution mixing, strong stirring, it is simultaneously introduced required template, adopts rare acid for adjusting pH value in 9��11 scopes, obtain white gels and stop stirring. Gel is moved to autoclave, crystallization 20��80 hours at 50��300 DEG C of temperature, obtain ZSM-5 molecular sieve after products therefrom washing, filtration.
Modifiying described in step (2), adopts the nitrate solution dipping ZSM-5 molecular sieve of alkaline-earth metal, and the nitrate solution of alkaline-earth metal is magnesium nitrate or calcium nitrate solution, it is preferred to magnesium nitrate solution, and dip time is 1��15 hour, it is preferable that 2��10 hours; At 70��350 DEG C of temperature dry, and 250��650 DEG C of roasting temperatures 2��20 hours, it is preferable that dry at 80��300 DEG C of temperature, and 300��600 DEG C of roasting temperatures 2��10 hours. Ammonium exchange can also be entered before modification process, obtain Hydrogen ZSM-5 molecular sieve.
Addition is catalyst quality 10% ~ 17% of phosphorus pentoxide described in step (3). Phosphorus pentoxide can effectively absorption reaction produce ammonia, promote molecular balance to carry out to positive direction, thus improving the yield of dimethyl carbonate.
Binding agent described in step (3) is selected from Ludox or Al2O3In one, it is preferable that Al2O3. Binder dosage is the 10%��50% of catalyst quality, it is preferred to the 20%��40% of catalyst quality.
Active metal presoma described in step (3) is one or both in zinc salt or cerium salt, and wherein zinc salt is zinc nitrate, zinc acetate or zinc chloride, and cerium salt is cerous nitrate, cerous nitrate or cerous chlorate. (3) amount is modified ZSM-5 15%��35% of the active metal presoma described in.
Containing also having 1,3,5-appropriate trimesic acid in active metal precursor solution described in step (3), content is the 5% ~ 25% of active metal presoma quality, it is preferred to 10% ~ 20%. The introducing to interact with the molecular sieve after alkali-earth metal modified of 1,3,5-trimesic acid significantly improves the yield of dimethyl carbonate.
In step (3), article shaped obtains carbamide and methanol catalyst for preparing dimethyl carbonate for 2��8 hours through 300��550 DEG C of roasting temperatures.
The application in carbamide and methanol preparing dimethyl carbonate of the above-mentioned loaded catalyst, with carbamide and methanol for raw material, carbamide and methanol molar ratio are 1:5��1:20, catalyst amount is the 7%��20% of reactant gross mass, and reaction temperature is 90-210 DEG C, it is preferred to use two-stage nitration temperature reaction, at one section of reaction temperature 100��150 DEG C, reaction 2��6h, at second-stage reaction temperature 170��200 DEG C, reacts 2��8h.
The carbamide of the present invention and methanol catalyst for preparing dimethyl carbonate, solving that equilibrium conversion in carbamide and methanol-fueled CLC dimethyl carbonate technology is low, homogeneous catalyst is difficult to the problems such as separation and recovery, this method for preparing catalyst is simple, it is easy to reclaims and separates, improve product quality, good stability.
Detailed description of the invention
The functions and effects of the present invention are further illustrated below in conjunction with embodiment.
Example 1
(1) ZSM-5 molecular sieve is prepared. The preparation aqueous solution 100ml containing 90 grams of waterglass, is added thereto to the aqueous solution 30ml containing 13 grams of aluminum sulfate, strong stirring. Being simultaneously introduced 16 grams of 4-propyl bromides as template, regulating pH value with dilute sulfuric acid is 10. Continue stirring, until obtaining jelly, gained jelly being moved in autoclave, at 140 DEG C, being incubated 40 hours. After crystallization terminates, products therefrom washs, and obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 50 after filtration, obtains the ZSM-5 molecular sieve of Hydrogen after ammonium exchange.
(2) Hydrogen ZSM-5 is modified, adopts Mg (NO3)2Aqueous solution is modified to ZSM-5 dipping. Take 8gMg (NO3)2It is made into 60ml aqueous solution, and is added thereto to 65 grams of ZSM-5, stir, after impregnating 6 hours, drying at room temperature, 100 DEG C of drying, obtain the Mg modified ZSM-5 of Hydrogen after 500 DEG C of roastings, Mg content is 0.5wt%.
(3) 12g zinc nitrate and 2.4g phosphorus pentoxide are dissolved in 40ml distilled water, adopt Al2O3For binding agent, the mixing of ZSM-550g modified for Mg, binding agent 20g and zinc nitrate solution being made into suspension, dried extruded moulding, at 500 DEG C, roasting 6h obtains catalyst.
Autoclave reactor is adopted to carry out evaluating catalyst, with carbamide and methanol for raw material, wherein carbamide 20g, methanol 70g, catalyst quality 10 grams, one section of reaction temperature 120 DEG C, react 4h, second-stage reaction temperature 190 DEG C, reacts 4h, and dimethyl carbonate yield reaches 20.5%.
Example 2
(1) ZSM-5 molecular sieve is prepared. The preparation aqueous solution 120ml containing 95 grams of waterglass, is added thereto to the aqueous solution 30ml containing 12 grams of aluminum sulfate, strong stirring. Being simultaneously introduced 18 grams of 4-propyl bromides as template, regulating pH value with dilute sulfuric acid is 11. Continue stirring, until obtaining jelly, gained jelly being moved in autoclave, at 150 DEG C, being incubated 30 hours. After crystallization terminates, products therefrom washs, and obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 80 after filtration, obtains the ZSM-5 molecular sieve of Hydrogen after ammonium exchange.
(2) Hydrogen ZSM-5 is modified, adopts Mg (NO3)2Aqueous solution is modified to ZSM-5 dipping. Take 20gMg (NO3)2It is made into 110ml aqueous solution, and is added thereto to 85 grams of ZSM-5, stir, after impregnating 6 hours, drying at room temperature, 130 DEG C of drying, obtain the Mg modified ZSM-5 of Hydrogen after 500 DEG C of roastings, Mg content is 1.3wt%.
(3) 20g zinc nitrate and 2.4g phosphorus pentoxide are dissolved in 40ml distilled water, adopt Al2O3For binding agent, the mixing of ZSM-586g modified for Mg, binding agent 35g and zinc nitrate solution being made into suspension, dried extruded moulding, at 400 DEG C, roasting 5h obtains catalyst.
Autoclave reactor is adopted to carry out evaluating catalyst, with carbamide and methanol for raw material, wherein carbamide 15g, methanol 100g, catalyst quality 23g, one section of reaction temperature 120 DEG C, react 4h, second-stage reaction temperature 180 DEG C, reacts 5h, and dimethyl carbonate yield reaches 23.4%.
Example 3
(1) ZSM-5 molecular sieve is prepared. The preparation aqueous solution 90ml containing 75 grams of waterglass, is added thereto to the aqueous solution 50ml containing 23 grams of aluminum sulfate, strong stirring. Being simultaneously introduced 16 grams of 4-propyl bromides as template, regulating pH value with dilute sulfuric acid is 11. Continue stirring, until obtaining jelly, gained jelly being moved in autoclave, at 150 DEG C, being incubated 25 hours. After crystallization terminates, products therefrom washs, and obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 30 after filtration, obtains the ZSM-5 molecular sieve of Hydrogen after ammonium exchange.
(2) Hydrogen ZSM-5 is modified, adopts Mg (NO3)2Aqueous solution is modified to ZSM-5 dipping. Take 13gMg (NO3)2It is made into 90ml aqueous solution, and is added thereto to 65 grams of ZSM-5, stir, after impregnating 5 hours, drying at room temperature, 130 DEG C of drying, obtain the Mg modified ZSM-5 of Hydrogen after 450 DEG C of roastings, Mg content is 1.0wt%.
(3) 18g cerous nitrate and 2.4g phosphorus pentoxide are dissolved in 40ml distilled water, adopt Al2O3For binding agent, the mixing of ZSM-570g modified for Mg, binding agent 42g and cerium nitrate solution being made into suspension, dried extruded moulding, at lower 450 DEG C of nitrogen protection, roasting 4h obtains catalyst.
Autoclave reactor is adopted to carry out evaluating catalyst, with carbamide and methanol for raw material, wherein carbamide 12g, methanol 130g, catalyst quality 12g, one section of reaction temperature 130 DEG C, react 5h, second-stage reaction temperature 180 DEG C, reacts 5h, and dimethyl carbonate yield reaches 24.7%.
Example 4
(1) ZSM-5 molecular sieve is prepared. The preparation aqueous solution 80ml containing 65 grams of waterglass, is added thereto to the aqueous solution 20ml containing 8 grams of aluminum sulfate, strong stirring. Being simultaneously introduced 10 grams of 4-propyl bromides as template, regulating pH value with dilute sulfuric acid is 11. Continue stirring, until obtaining jelly, gained jelly being moved in autoclave, at 180 DEG C, being incubated 20 hours. After crystallization terminates, products therefrom washs, and obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 70 after filtration, obtains the ZSM-5 molecular sieve of Hydrogen after ammonium exchange.
(2) Hydrogen ZSM-5 is modified, adopts Mg (NO3)2Aqueous solution is modified to ZSM-5 dipping. Take 21gMg (NO3)2It is made into 90ml aqueous solution, and is added thereto to 68 grams of ZSM-5, stir, after impregnating 5 hours, drying at room temperature, 150 DEG C of drying, obtain the Mg modified ZSM-5 of Hydrogen after 500 DEG C of roastings, Mg content is 1.8wt%.
(3) by 22g zinc nitrate, the equal benzene of 1.8g1,3,5-Tricarboxylic acidIt is dissolved in 45ml distilled water with 1.8g phosphorus pentoxide, adopts Al2O3For binding agent, the mixing of ZSM-575g modified for Mg, binding agent 53g and zinc nitrate solution being made into suspension, dried extruded moulding, at 600 DEG C, roasting 7h obtains catalyst.
Autoclave reactor is adopted to carry out evaluating catalyst, with carbamide and methanol for raw material, wherein carbamide 12g, methanol 108g, catalyst quality 19 grams, one section of reaction temperature 140 DEG C, react 5h, second-stage reaction temperature 160 DEG C, reacts 6h, and dimethyl carbonate yield reaches 26.3%.
Example 5
(1) ZSM-5 molecular sieve is prepared. The preparation aqueous solution 110ml containing 90 grams of waterglass, is added thereto to the aqueous solution 25ml containing 10 grams of aluminum sulfate, strong stirring. Being simultaneously introduced 13 grams of 4-propyl bromides as template, regulating pH value with dilute sulfuric acid is 10. Continue stirring, until obtaining jelly, gained jelly being moved in autoclave, at 150 DEG C, being incubated 35 hours. After crystallization terminates, products therefrom washs, and obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 90 after filtration, obtains the ZSM-5 molecular sieve of Hydrogen after ammonium exchange.
(2) Hydrogen ZSM-5 is modified, adopts Mg (NO3)2Aqueous solution is modified to ZSM-5 dipping. Take 15gMg (NO3)2It is made into 80ml aqueous solution, and is added thereto to 60 grams of ZSM-5, stir, after impregnating 6 hours, drying at room temperature, 130 DEG C of drying, obtain the Mg modified ZSM-5 of Hydrogen after 500 DEG C of roastings, Mg content is 1.5wt%.
(3) 15g cerous nitrate, 2.5g1,3,5-trimesic acids and 1.7g phosphorus pentoxide are dissolved in 35ml distilled water, adopt Al2O3For binding agent, the mixing of ZSM-560g modified for Mg, binding agent 45g and cerium nitrate solution being made into suspension, dried extruded moulding, the lower 550 DEG C of roasting 5h of nitrogen protection obtain catalyst.
Autoclave reactor is adopted to carry out evaluating catalyst, with carbamide and methanol for raw material, wherein carbamide 18g, methanol 130g, catalyst quality 20 grams, one section of reaction temperature 110 DEG C, react 6h, second-stage reaction temperature 170 DEG C, reacts 5h, and dimethyl carbonate yield reaches 29.6%.
Embodiment 6
Preparation evaluation procedure, with embodiment 4, is simply added without 1,3,5-trimesic acid, and dimethyl carbonate yield reaches 22.1%.
Embodiment 7
Preparation evaluation procedure, with embodiment 5, is simply added without 1,3,5-trimesic acid, and dimethyl carbonate yield reaches 23.7%.
Comparative example 1
With embodiment 4, simply molecular sieve does not carry out alkaline earth and modifiies, and adopts autoclave reactor to carry out evaluating catalyst, and appreciation condition is identical with embodiment 4, and dimethyl carbonate yield reaches 14.6%.
Comparative example 2
With embodiment 4, being simply added without phosphorus pentoxide, adopt autoclave reactor to carry out evaluating catalyst, appreciation condition is identical with embodiment 4, and dimethyl carbonate yield reaches 20.5%.
Comparative example 3
With embodiment 5, being simply added without phosphorus pentoxide, adopt autoclave reactor to carry out evaluating catalyst, appreciation condition is identical with embodiment 4, and dimethyl carbonate yield reaches 23.2%.
Claims (13)
1. the carbamide of a support type and methanol catalyst for preparing dimethyl carbonate, it is characterised in that: content meter by weight, containing 40%~75The alkali-earth metal modified MFI molecular sieve of %, the reactive metal oxides of 15% ~ 30%, and 10% ~ 20%Phosphorus pentoxide; In described alkali-earth metal modified MFI molecular sieve, alkaline-earth metal accounts for the 0.3% ~ 2% of MFI molecular sieve, and described alkaline-earth metal includes beryllium, magnesium, calcium, strontium, barium or radium, and described reactive metal oxides is zinc oxide and/or cerium oxide.
2. catalyst according to claim 1, it is characterised in that: MFI molecular sieve is preferably ZSM-5 molecular sieve, and described alkaline-earth metal is magnesium or calcium.
3. the preparation method of the catalyst described in claim 1, it is characterised in that:
(1) select or prepare ZSM-5 molecular sieve;
(2) ZSM-5 molecular sieve in step (1) is modified preparing alkali-earth metal modified ZSM-5 molecular sieve, adopts infusion process, with the nitrate solution of alkaline-earth metal, ZSM-5 is impregnated, then to the dry materials after dipping, roasting;
(3) select suitable binding agent, by appropriate active metal precursor solution,Phosphorus pentoxide, the material making beating for preparing of binding agent and step (2), be made into suspension, then dry, extruded moulding, obtain carbamide and methanol catalyst for preparing dimethyl carbonate after roasting.
4. method according to claim 3, it is characterised in that: in step (1), ZSM-5 molecular sieve adopts hydrothermal synthesis method to prepare, and Si/Al mol ratio is 10 ~ 150, it is preferred to 20 ~ 100; Silicon source is the one in metso, waterglass, Ludox or metasilicate; Aluminum source is the one in aluminium salt or aluminate; Template is the one in n-butylamine, triethylamine, 4-propyl bromide or ethylenediamine; Take the desired amount of silicon source and aluminum source, dissolve with distilled water respectively and make solution, after two kinds of solution mixing, strong stirring, it is simultaneously introduced required template, adopts rare acid for adjusting pH value in 9��11 scopes, obtain white gels and stop stirring; Gel is moved to autoclave, crystallization 20��80 hours at 50��300 DEG C of temperature, obtain ZSM-5 molecular sieve after products therefrom washing, filtration.
5. method according to claim 3, it is characterized in that: modifiying described in step (2), adopt the nitrate solution dipping ZSM-5 molecular sieve of alkaline-earth metal, the nitrate solution of alkaline-earth metal is magnesium nitrate or calcium nitrate solution, it is preferably magnesium nitrate solution, dip time is 1��15 hour, it is preferable that 2��10 hours; At 70��350 DEG C of temperature dry, and 250��650 DEG C of roasting temperatures 2��20 hours, it is preferable that dry at 80��300 DEG C of temperature, and 300��600 DEG C of roasting temperatures 2��10 hours.
6. method according to claim 3, it is characterised in that: step (2) processes in alkali-earth metal modified advance ammonium exchange, obtains Hydrogen ZSM-5 molecular sieve.
7. method according to claim 3, it is characterised in that: the addition of the phosphorus pentoxide described in step (3) is catalyst quality10%~17%��
8. method according to claim 3, it is characterised in that: the binding agent described in step (3) is selected from Ludox or Al2O3In one, binder dosage is the 10%��50% of catalyst quality.
9. method according to claim 3, it is characterized in that: the active metal presoma described in step (3) is one or both in zinc salt or cerium salt, wherein zinc salt is zinc nitrate, zinc acetate or zinc chloride, and cerium salt is cerous nitrate, cerous nitrate or cerous chlorate.
10. method according to claim 3, it is characterised in that: containing also having 1,3,5-appropriate trimesic acid in the active metal precursor solution described in step (3), content is the 5% ~ 25% of active metal presoma quality, it is preferred to 10% ~ 20%.
11. method according to claim 3, it is characterised in that: in step (3), article shaped obtains carbamide and methanol catalyst for preparing dimethyl carbonate for 2��8 hours through 300��550 DEG C of roasting temperatures.
12. the application that catalyst described in claim 1 is in carbamide and methanol preparing dimethyl carbonate, it is characterized in that: with carbamide and methanol for raw material, carbamide and methanol molar ratio are 1:5��1:20, and catalyst amount is the 7%��20% of reactant gross mass, and reaction temperature is 90-210 DEG C.
13. method according to claim 12, it is characterised in that: adopt two-stage nitration temperature reaction, at one section of reaction temperature 100��150 DEG C, react 2��6h, at second-stage reaction temperature 170��200 DEG C, react 2��8h.
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| CN108114741A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of catalyst of preparing dimethyl carbonate and its preparation method and application |
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| CN113499766A (en) * | 2021-06-30 | 2021-10-15 | 南京工业大学 | Preparation method of mesoporous bimetal solid base catalyst for synthesizing DMC |
| CN115124423A (en) * | 2022-07-14 | 2022-09-30 | 山东德普新材料科技有限公司 | Process for preparing dimethyl carbonate by urea alcoholysis method |
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| CN108114741A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of catalyst of preparing dimethyl carbonate and its preparation method and application |
| CN109647497A (en) * | 2018-11-30 | 2019-04-19 | 中国科学院山西煤炭化学研究所 | For epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate and preparation method and application |
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| CN110252274B (en) * | 2019-06-14 | 2022-09-02 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Preparation method of catalyst for synthesizing diphenyl carbonate by ester exchange |
| CN113499766A (en) * | 2021-06-30 | 2021-10-15 | 南京工业大学 | Preparation method of mesoporous bimetal solid base catalyst for synthesizing DMC |
| CN115124423A (en) * | 2022-07-14 | 2022-09-30 | 山东德普新材料科技有限公司 | Process for preparing dimethyl carbonate by urea alcoholysis method |
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