CN104549208A - Catalyst for synthesizing dimethyl carbonate, preparation method and application of catalyst - Google Patents
Catalyst for synthesizing dimethyl carbonate, preparation method and application of catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a supported catalyst for preparing dimethyl carbonate from urea and methanol. The preparation method comprises the following steps: (1) adding metal salt or metallic oxide to distilled water, and uniformly stirring; (2) adding an alcohol solvent and a silicon-containing precursor into the solution obtained in the step (1), uniformly stirring the solution, and regulating the pH value of the solution to be 2-5; (3) stirring the solution obtained in the step (2) at constant temperature until converting the solution to gel, and ageing the gel at the room temperature; (4) drying the gel obtained in the step (3) to constant weight, and grinding, so as to obtain the final supported catalyst for preparing dimethyl carbonate from urea and methanol. The catalyst prepared by the method overcomes the defects that the equilibrium conversion rate in the existing dimethyl carbonate preparing technology from urea and methanol is low, and the homogeneous catalyst is difficult to separate out; the catalyst is high in activity stability.
Description
Technical field
The present invention relates to Catalysts and its preparation method and the application of a kind of Synthesis of dimethyl carbonate Catalysts and its preparation method and application, particularly urea and Methanol 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 suflfate, chloromethane and methylchloroformate as carbonylation, methylate, the reagent of esterification and ester exchange, and is a kind of good green solvent and gasoline additive.
Methyl alcohol and alcoholysis of urea catalytic synthesizing dimethyl carbonate (DMC) are novel artistic routes of alternative phosgene production DMC.Alcoholysis of urea makes base stock with wide material sources, cheap urea and methyl alcohol, the advantage such as have that raw material is cheap and easy to get, ammonia that the simple and reaction of technique produces can be recycled, and the anhydrous generation of course of reaction, avoid the separation problem of methyl alcohol-DMC-water complex system, later separation is purified simplify, reduce investment outlay, especially attractive to existing chemical fertilizer factory exploitation downstream product.
Patent WO9517369 adopts Dibutyltin oxide, dimethoxide base tin, dibutyl methoxyl group NCO tin as catalyst, react with methyl carbamate or urea and methyl alcohol, steam dimethyl carbonate continuously simultaneously, although such catalyst can obtain higher product yield, also can the decomposition of catalytic amino methyl formate.US5902894 adopts higher boiling electron donor oxycompound to do solvent and co-catalyst, effectively inhibits the generation of the decomposition of methyl carbamate and the side reaction that methylates.Its methyl carbamate conversion ratio can reach 98.3%, and dimethyl carbonate is selective simultaneously reaches 98.2%.Although organo-tin compound has good catalytic effect, their toxicity is large, price is high, homogeneous catalyst separation and recovery from product is very difficult.
Patent CN1569809 proposes a kind of method by methyl alcohol and Synthesis of Dimethyl Carbonate from Urea.In autoclave reactor, at 130-180 DEG C, adopt amine salt type ionic liquid as catalyst, one-step synthesis dimethyl carbonate, its productive rate is 25-30%, and selective is 100%.Although this catalyst effect is better, but still the problem of existence and product separation difficulty.
Therefore, exploitation heterogeneous catalysis that is efficient, non-environmental-pollution is that Synthesis of Dimethyl Carbonate from Urea technique realizes industrialized key.
Summary of the invention
For deficiencies such as in existing urea and Methanol dimethyl carbonate technology, equilibrium conversion are low, homogeneous catalyst is not easily separated, the invention provides a kind of Catalysts and its preparation method for urea and Methanol dimethyl carbonate and application.
The urea of support type and a preparation method for Methanol catalyst, comprise following content:
(1) in distilled water, add metallic salt or metal oxide, and stir;
(2) in step (1) solution, add alcoholic solvent and containing silicon precursor, after being stirred by solution, regulate solution pH value to be 2 ~ 5;
(3) step (2) solution constant temperature is stirred to is converted into gel, aged at room temperature;
(4) by the gel drying that obtains in step (3) to constant weight, grinding, obtain urea and the Methanol catalyst of final support type.
Metallic salt described in the inventive method step (1) is one or more in zinc nitrate, zinc acetate, cerous nitrate or cerous nitrate, preferred zinc nitrate/or cerous nitrate; Metal oxide be zinc oxide, cupric oxide, cerium oxide or be oxidized in sub-cerium one or more, be preferably oxidized sub-cerium.Its load capacity counts 3% ~ 20% with active metal simple substance, is preferably 5% ~ 15%.
Alcoholic solvent described in the inventive method step (2) is one or more in absolute ethyl alcohol, n-butanol, isopropyl alcohol, preferred n-butanol.Described is ethyl orthosilicate containing silicon precursor.In solution, water is 1 ~ 20 with the mol ratio of ethyl orthosilicate added, preferably 5 ~ 15; N-butanol and ethyl orthosilicate mol ratio are 0.1 ~ 5, preferably 0.5 ~ 3.
Thermostat temperature described in the inventive method step (3) is 60 ~ 120 DEG C, and be preferably 70 ~ 100 DEG C, constant temperature time is 1 ~ 5h, preferably 2 ~ 4h; Ageing time is 1 ~ 30h, is preferably 5 ~ 26h.
In the inventive method step (3), aged at room temperature is carried out under the effect of phosphoric acid.The described amount adding phosphoric acid is 10% ~ 50% of active metal simple substance molal quantity, is preferably 20% ~ 40%.Phosphoric acid add same gel rubber system acting in conjunction, substantially increase the stability of catalyst and the yield of dimethyl carbonate.
Baking temperature described in the inventive method step (4) is 60 ~ 250 DEG C, preferably 70 ~ 230 DEG C, and drying time is 6 ~ 28h, is preferably 8 ~ 15h.
The support type urea adopting above method to prepare and a Methanol catalyst, by the weight content of catalyst, contain in the active metal of simple substance 3% ~ 20%, all the other are carrier S iO
2, preferably contain the active metal of 5% ~ 15%.
The application of above-mentioned loaded catalyst in urea and Methanol dimethyl carbonate, with urea and methyl alcohol for raw material, urea and methanol molar ratio are 1:5 ~ 1:20, catalyst amount is 5% ~ 20% of reactant quality, and reaction temperature is 100-250 DEG C, preferably two sections of temperature reactions, at one section of reaction temperature 120 ~ 160 DEG C, reaction 1 ~ 8h, at second-stage reaction temperature 180 ~ 220 DEG C, reaction 2 ~ 10h.
The metallic salt that the present invention adopts sol-gal process to prepare or metal oxide catalyst, solve that equilibrium conversion in urea 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, be easy to reclaim and be separated, improve product quality.
Detailed description of the invention
Functions and effects of the present invention are further illustrated below in conjunction with embodiment.
Example 1
(1) get 38g zinc nitrate, be dissolved in 42ml distilled water, uniform stirring dissolves completely to zinc nitrate;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol added and ethyl orthosilicate mol ratio are 2.1; In solution, water is 10 with the mol ratio of the ethyl orthosilicate added, and continues to stir, in solution, instills nitric acid, and the pH value regulating solution is 3;
(3) step (2) solution 90 DEG C of constant temperature being stirred 3h to solution transforms is gel, then aged at room temperature 12h.
(4) the gel dry 10h at 100 DEG C of temperature will obtained in step (3), grinding, obtains final loaded catalyst.Wherein the amount of active metal zinc be 15%, all the other are SiO
2.
Autoclave reactor is adopted to carry out evaluating catalyst, with urea and methyl alcohol for raw material, wherein urea 15g, methyl alcohol 136g, catalyst quality 27 grams, one section of reaction temperature 150 DEG C, reaction 6h, second-stage reaction temperature 215 DEG C, reaction 5h, dimethyl carbonate yield reaches 20.3%, after catalyst recovery, use three times, dimethyl carbonate yield is 16.9%.
Example 2
(1) get 30g cerous nitrate, be dissolved in 45ml distilled water, uniform stirring dissolves completely to cerous nitrate;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol added and ethyl orthosilicate mol ratio are 3; In solution, water is 14 with the mol ratio of the ethyl orthosilicate added, and continues to stir, in solution, instills nitric acid, and the pH value regulating solution is 4;
(3) step (2) solution 80 DEG C of constant temperature being stirred 2h solution transforms is gel, then aged at room temperature 24h.
(4) the gel dry 12h at 100 DEG C of temperature will obtained in step (3), grinding, obtains final loaded catalyst.Wherein the amount of active metal cerium be 11%, all the other are SiO
2.
Autoclave reactor is adopted to carry out evaluating catalyst, with urea and methyl alcohol for raw material, wherein urea 18g, methyl alcohol 116g, catalyst quality 17 grams, one section of reaction temperature 120 DEG C, reaction 7h, second-stage reaction temperature 190 DEG C, reaction 4h, dimethyl carbonate yield reaches 22.8%, after catalyst recovery, use three times, dimethyl carbonate yield is 19.6%.
Example 3
(1) get 32g cerous nitrate, be dissolved in 40ml distilled water, uniform stirring dissolves completely to cerous nitrate;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol added and ethyl orthosilicate mol ratio are 1.0; In solution, water is 9 with the mol ratio of the ethyl orthosilicate added, and continues to stir, in solution, instills nitric acid, and the pH value regulating solution is 4;
(3) step (2) solution 80 DEG C of constant temperature being stirred 2.5h solution transforms is gel, then aged at room temperature 16h.
(4) the gel dry 14h at 70 DEG C of temperature will obtained in step (3), grinding, obtains final loaded catalyst.Wherein the amount of active metal cerium be 8%, all the other are SiO
2.
Autoclave reactor is adopted to carry out evaluating catalyst, with urea and methyl alcohol for raw material, wherein urea 15g, methyl alcohol 95g, catalyst quality 17 grams, one section of reaction temperature 120 DEG C, reaction 4h, second-stage reaction temperature 180 DEG C, reaction 8h, dimethyl carbonate yield reaches 21.7%, after catalyst recovery, use three times, dimethyl carbonate yield is 18.6%.
Example 4
(1) get 33g zinc nitrate, be dissolved in 35ml distilled water, uniform stirring dissolves completely to zinc nitrate;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol added and ethyl orthosilicate mol ratio are 1.8; In solution, water is 12 with the mol ratio of the ethyl orthosilicate added, and continues to stir, in solution, instills nitric acid, and the pH value regulating solution is 5;
(3) step (2) solution 80 DEG C of constant temperature being stirred 2h to solution transforms is gel, after then adding 8g phosphoric acid, and aged at room temperature 20h.
(4) the gel dry 9h at 120 DEG C of temperature will obtained in step (3), grinding, obtains final loaded catalyst.Wherein the amount of active metal zinc be 13%, all the other are SiO
2.
Autoclave reactor is adopted to carry out evaluating catalyst, with urea and methyl alcohol for raw material, wherein urea 12g, methyl alcohol 70g, catalyst quality 6 grams, one section of reaction temperature 140 DEG C, reaction 5h, second-stage reaction temperature 200 DEG C, reaction 7h, dimethyl carbonate yield reaches 28.7%, after catalyst recovery, use three times, dimethyl carbonate yield is 27.2%.
Example 5
(1) get 20g zinc nitrate, be dissolved in 30ml distilled water, uniform stirring dissolves completely to zinc nitrate;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol added and ethyl orthosilicate mol ratio are 0.8; In solution, water is 6 with the mol ratio of the ethyl orthosilicate added, and continues to stir, in solution, instills nitric acid, and the pH value regulating solution is 4;
(3) step (2) solution 70 DEG C of constant temperature being stirred 3.5h to solution transforms is gel, after then adding 6g phosphoric acid, and aged at room temperature 8h.
(4) the gel dry 12h at 70 DEG C of temperature will obtained in step (3), grinding, obtains final loaded catalyst.Wherein the amount of active metal zinc be 11%, all the other are SiO
2.
Autoclave reactor is adopted to carry out evaluating catalyst, with urea and methyl alcohol for raw material, wherein urea 18g, methyl alcohol 135g, catalyst quality 15 grams, one section of reaction temperature 130 DEG C, reaction 3h, second-stage reaction temperature 170 DEG C, reaction 3h, dimethyl carbonate yield reaches 25.6%, after catalyst recovery, use three times, dimethyl carbonate yield is 24.3%.
Example 6
With embodiment 4, just do not add phosphoric acid, dimethyl carbonate yield reaches 22.4%, and after catalyst recovery, use three times, dimethyl carbonate yield is 17.5%.
Example 7
With embodiment 4, just do not add phosphoric acid, dimethyl carbonate yield reaches 21.7%, and after catalyst recovery, use three times, dimethyl carbonate yield is 18.2%.
Comparative example 1
With the SiO after 40 order phosphoric acid modification process
2as carrier, adopt conventional infusion process load zinc nitrate, the load capacity obtaining zinc is the catalyst of 13%, and appreciation condition is with embodiment 1, and obtaining dimethyl carbonate yield is 10.5%, and after catalyst recovery, yield is down to 3.2% again.
Claims (15)
1. the urea of support type and a preparation method for Methanol catalyst, is characterized in that: comprise following content:
(1) in distilled water, add metallic salt or metal oxide, and stir;
(2) in step (1) solution, add alcoholic solvent and containing silicon precursor, after being stirred by solution, regulate solution pH value to be 2 ~ 5;
(3) step (2) solution constant temperature is stirred to is converted into gel, aged at room temperature;
(4) by the gel drying that obtains in step (3) to constant weight, grinding, obtain urea and the Methanol catalyst of final support type.
2. method according to claim 1, is characterized in that: the metallic salt described in step (1) is one or more in zinc nitrate, zinc acetate, cerous nitrate or cerous nitrate; Metal oxide be zinc oxide, cupric oxide, cerium oxide or be oxidized in sub-cerium one or more, its load capacity counts 3% ~ 20% with active metal simple substance.
3. method according to claim 1, is characterized in that: the metallic salt described in step (1) is zinc nitrate/or cerous nitrate; Metal oxide is the sub-cerium of oxidation, and its load capacity counts 5% ~ 15% with active metal simple substance.
4. method according to claim 1, is characterized in that: the alcoholic solvent described in step (2) is one or more in absolute ethyl alcohol, n-butanol, isopropyl alcohol, and described is ethyl orthosilicate containing silicon precursor.
5. method according to claim 1, is characterized in that: in step (2) solution, water is 1 ~ 20 with the mol ratio containing silicon precursor added; Alcoholic solvent and ethyl orthosilicate mol ratio are 0.1 ~ 5, and described alcoholic solvent is n-butanol.
6. method according to claim 5, is characterized in that: in step (2) solution, water is 5 ~ 15 with the mol ratio containing silicon precursor added; Alcoholic solvent and ethyl orthosilicate mol ratio are 0.5 ~ 3.
7. method according to claim 1, is characterized in that: the thermostat temperature described in step (3) is 60 ~ 120 DEG C, and constant temperature time is 1 ~ 5h, and ageing time is 1 ~ 30h.
8. method according to claim 7, is characterized in that: the thermostat temperature described in step (3) is 70 ~ 100 DEG C, and constant temperature time is 2 ~ 4h; Ageing time is 5 ~ 26h.
9. method according to claim 1, is characterized in that: in step (3), aged at room temperature is carried out under the effect of phosphoric acid.
10. method according to claim 9, is characterized in that: described in add phosphoric acid amount be 10% ~ 50% of active metal simple substance molal quantity, be preferably 20% ~ 40%.
11. methods according to claim 1, is characterized in that: the baking temperature described in step (4) is 60 ~ 250 DEG C, and drying time is 6 ~ 28h.
12. methods according to claim 11, is characterized in that: the baking temperature described in step (4) is 70 ~ 230 DEG C, and drying time is 8 ~ 15h.
13. 1 kinds of support type urea and Methanol catalyst adopting claim 1-12 either method to prepare, is characterized in that: by the weight content of catalyst, containing the active metal simple substance of 3% ~ 20%, all the other are carrier S iO
2, preferably contain the active metal of 5% ~ 15%.
The application of loaded catalyst described in 14. claims 13 in urea and Methanol dimethyl carbonate, it is characterized in that: with urea and methyl alcohol for raw material, urea and methanol molar ratio are 1:5 ~ 1:20, and catalyst amount is 5% ~ 20% of reactant quality, and reaction temperature is 100-250 DEG C.
15. application according to claim 14, is characterized in that: adopt two sections of temperature reactions, at one section of reaction temperature 120 ~ 160 DEG C, and reaction 1 ~ 8h, at second-stage reaction temperature 180 ~ 220 DEG C, reaction 2 ~ 10h.
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| CN106622382B (en) * | 2015-11-04 | 2020-05-19 | 中国石油化工股份有限公司 | Catalyst for synthesizing dimethyl carbonate and preparation method and application thereof |
| 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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