CN105251496A - Catalyst and method preparing dimethyl carbonate by using catalyst - Google Patents
Catalyst and method preparing dimethyl carbonate by using catalyst Download PDFInfo
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- CN105251496A CN105251496A CN201510593678.XA CN201510593678A CN105251496A CN 105251496 A CN105251496 A CN 105251496A CN 201510593678 A CN201510593678 A CN 201510593678A CN 105251496 A CN105251496 A CN 105251496A
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Abstract
The invention discloses a catalyst and a method preparing dimethyl carbonate by using the catalyst. The method comprises two steps: step 1, with urea and aliphatic dihydric alcohol as raw materials, reacting urea with aliphatic dihydric alcohol under the action of the catalyst to synthesize ethylene carbonate or propylene carbonate, wherein reaction conditions are that reaction temperature is 100 to 200 DEG C and 0.5 to 5 mL of nitrogen is introduced into a reaction system per minute; and step 2, subjecting ethylene carbonate or propylene carbonate and methanol to ester interchange so as to synthesize dimethyl carbonate, wherein a reaction condition is that reaction temperature is 60 to 170 DEG C, and the catalyst is a supported catalyst prepared by preparing a solution with a certain concentration from a metal salt or metal oxide and then impregnating a same-volume carrier with the solution. The technical characteristics of the invention are that reaction conditions are mild; reaction is carried out at normal pressure; and the catalyst is easy to separate and recycle, can be repeatedly used and poses no corrosion to equipment and no environmental pollution.
Description
Technical field
The present invention relates to the technique of alcoholysis of urea Synthesis of dimethyl carbonate and the preparation method of catalyst thereof, being specifically related to a kind of take aliphatic dihydroxy alcohol as the technique of alcoholysis of urea Synthesis of dimethyl carbonate and the preparation method of catalyst thereof of circulation agent.Be related specifically to the preparation method of the various salts substances loaded catalyst of alcoholysis of urea Synthesis of dimethyl carbonate metal used.
Technical background
Dimethyl carbonate (DMC) has nontoxic, that evaporation rate is fast feature, and has good intermiscibility with other solvent.West Europe is classified as it as non-malicious chemicals, Devoting Major Efforts To Developing it as the application of solvent aspect, as sticked with glue agent, medical production solvent etc. as paint, the solvent of coating, high-energy battery solvent, glue water, also can be used as spray.Be raw material production downstream product with it, accessory substance can be recycled, and meets cleaner Production in Chemical Industry requirement.Owing to containing methyl in DMC molecular structure, the multiple functional group such as carbonyl, thus has very high chemical reactivity.In recent years, breakthrough is achieved to the research and development that its derivative carries out, make the application of DMC constantly expand and successively permeate.On the one hand, the chemical reactions such as DMC is mainly used in substituting has the phosgene that highly endangers and the chemical raw material such as dimethyl suflfate to carry out carbonylation to health and environment, methylate, esterification and ester exchange.On the other hand, be that raw material can prepare the high fine chemicals of multiple added value with DMC, this obtains extensive use in fields such as medicine, agricultural chemicals, chemical reagent, dyestuff, foodstuff flavouring agent, electronic chemical products, has now developed into the cleaner Production in Chemical Industry new technology that a class take DMC as raw material.In addition, DMC is also stepping in practical production as solvent and gasoline additive.DMC is also the environment-friendly chemical products being subject to domestic and international extensive concern in recent years.Within 1992, it have passed the registration of non-malicious chemicals (Nontoxicsubstance) in Europe, is called as green chemical.
In recent years, due to DMC downstream product---Merlon, polyurethane, paint solvent, gasoline additive, electrolyte solution of high-energy battery market development rapidly, have driven the high of DMC market demand.The main application of its product is: the maximum purposes of DMC makes green solvent, for coating and paint.Also can be used as polycarbonate synthesis main intermediate.Another potential huge purposes of DMC is that alternative MTBE makes vapour/diesel fuel additives.From economy, they are suitable reasonable.The U.S. has proposed progressively to substitute MTBE as gasoline additive with DMC, and DMC is listed in 50 fine chemical product scopes of country's 95 focus developments by China.So DMC is described as one " new matrix " of 21 century organic synthesis, its development plays huge impetus to the Coal Chemical Industry of China, methanol chemistry, C1 chemical industry.
Domestic existing dimethyl carbonate production technology mainly contains four kinds: four kinds of techniques such as ester-interchange method, methanol solution oxidative carbonylation method, alcoholysis of urea (or claiming urea one-step method) and urea two step method.Take expoxy propane as the ester-interchange method of raw material, raw material expoxy propane price is too high, accessory substance propanediol is seriously superfluous, price is at a low tide, and the market demand of propane diols is limited, therefore, a lot of enterprise is not because propane diols is sold or price inversion phenomenon is serious, cause device deficiency in economic performance or loss, enterprise have to stop production.Methanol solution oxidative carbonylation method is due to reasons such as catalytic erosion are large, dimethyl carbonate production cost is high, and the method development is limited.
At present, although alcoholysis of urea technique has had 16 years at the search time of China, the technique of advanced person is less, and the catalyst used mainly homogeneous catalyst and fine catalyst.MasaharuDayaSu in 1993, the reaction of people's carbonate synthesis alkene esters such as wei-yang improves, and propose at reduced pressure conditions in patent EP0581131A2, with the metal dust of zinc, magnesium, lead, calcium or compound for catalyst carbonate synthesis alkene ester, being that the yield of carbonic acid alkene ester has had significant raising, is 80 ~ 92% paper with the yield of the carbonic acid alkene ester of ureometer.But in course of reaction, decompression operation is consumes energy not only, and wayward, be unfavorable for normally carrying out of reaction.The common shortcoming of two technique is homogeneous phase and powder catalyst and product separation recycling difficulty.
US5534649 reports and adopts alkali metal compound (as CsOH, Cs
2cO
3, K
2cO
3, Na
2cO
3, CHO
3na) and quaternary ammonium tire out compound and make catalyst, but product yield is very low.Under alkali metal compound catalyst action, dimethyl carbonate yield is less than 2%.JP10-109960 have employed a series of alkali metal monoesters and compound catalyst, and the dimethyl carbonate yield wherein under LiH effect, is up to 36.4%, but this reaction need be carried out in the two ends reactor being furnished with distillation column, complex process, operating difficulties.
Employing take aliphatic dihydroxy alcohol as the urea two step synthetic method DMC technology of circulation agent, namely with in urea and traditional ester-interchange method DMC technique accessory substance---propane diols is for raw material, first synthetic intermediate---propene carbonate, propene carbonate synthesizes DMC with methyl alcohol ester exchange reaction again, and the propane diols of by-product returns to and continues synthesizing acrylic ester with urea.The real raw material of synthesis DMC is urea and methyl alcohol in fact.The amount in urea and methyl alcohol market is at home sufficient, and cost advantage is obvious.Therefore, efficient, non-environmental-pollution, support type the catalyst of exploitation is the industrialized key of alcoholysis of urea process for synthesizing methyl carbonate.
Summary of the invention
The object of the invention is, on synthesis under normal pressure device, utilize the O composite metallic oxide catalyst of the high-efficiency catalytic activity of support type, easily recycle, and non-environmental-pollution, take aliphatic dihydroxy alcohol as the technique of the alcoholysis of urea Synthesis of dimethyl carbonate of circulation agent.
Technical problem solved by the invention is: provide a kind of catalyst and utilize the method for this catalyst preparing dimethyl carbonate; This loaded catalyst is easily separated with reactant liquor; And after regeneration, can repeated multiple timesly use.Concrete technical scheme is:
A kind of loaded catalyst, is by the nitrate of the metal of one or more solubilities, sulfate, acetate, stearate, hydrochloride, subcarbonate, is mixed with solution, and incipient impregnation is on carrier, and preparation draws in loaded catalyst.What its preparation method adopted infusion process to prepare is loaded catalyst, and step is as follows:
(1) take in the nitrate of the metal of solubility, sulfate, acetate, hydrochloride, subcarbonate, stearate one or more, dissolve with distilled water or alcohol, be mixed with the solution of 0.1-1.5mol/L;
(2) solution prepared and isopyknic carrier are flooded: the solution prepared slowly is added drop-wise in carrier, after dripping, leave standstill 10-30h;
(3) by the loaded article that above-mentioned dipping is good, be placed in 100-110 DEG C of drying box and dry;
(4) loaded article of oven dry is placed in high temperature Muffle furnace, roasting 2-10h at 200-900 DEG C, after cooling, takes out and obtain catalyst.
Described carrier is silica gel, molecular sieve, zeolite.
In step (4), sintering temperature is 550-750 DEG C; Best roasting time is 2-5h.
Described catalyst can be passed through high-temperature activation, regeneration process after using, repeated multiple times use, is specially: at 550-750 DEG C of roasting 2-5h and renewable.
Utilize a method for above-mentioned catalyst preparing dimethyl carbonate, it is characterized in that: the method comprises the following steps:
(1) with urea and aliphatic dihydroxy alcohol ethylene glycol or 1,2-propane diols is raw material, Reactive Synthesis ethylene carbonate or propene carbonate under the effect of catalyst, its reaction condition is reaction temperature is 100-200 DEG C, and reaction system introduces the nitrogen of 0.5-5mL/min;
(2) ethylene carbonate or propene carbonate and methyl alcohol, ester exchange Synthesis of dimethyl carbonate, reaction condition: reaction temperature is 60-170 DEG C;
Described catalyst amount is the 0.5%-12% of reactant feed weight.
Be compared with the prior art, the present invention has following advantages:
A) be that preparation method's technique of the technique of alcoholysis of urea Synthesis of dimethyl carbonate of circulation agent and catalyst thereof is flexible with aliphatic dihydroxy alcohol, process conditions are gentle, react under normal pressure.Be a kind of process route of cleaner production, the ammonia produced in the reaction can be recycled.Whole production technology does not have harmful substance externally to discharge, the raw material producing reaction is mainly the bulk product of modern chemical industry, and wherein more expensive raw material achieves and recycles, therefore this technique meets the one " zero-emission " of modern chemical industry developing direction and the process for cleanly preparing of economy.
B) method for preparing catalyst is simple.Catalyst preparation process, without particular/special requirement, can prepare a series of composite metal oxide loaded catalyst, and without the need to special auxiliary equipment.
C) catalyst easily and separation and recovery.Homogeneous catalyst and fine catalyst exist with separation of products, are recovered in and utilize difficulty.
D) composite metal oxide loaded catalyst, active high, the yield of first step reaction propene carbonate can reach 90%-93.5%, the yield 39.5%-48.1% of second step reaction dimethyl carbonate.
E) catalyst stability is good, easily regenerates.Composite metal oxide loaded catalyst, can rush and repeatedly use.After active reduction, only need carry out simply after high-temperature roasting, getting final product activity recovery.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
embodiment 1
Getting ferric nitrate 9.696g and zinc nitrate 28.559g is dissolved in 200mL distilled water, be made into the metal salt solution containing zinc, iron, solution is slowly added drop-wise in isopyknic silica gel, after dripping, leave standstill 24h, in the drying box of about 100 DEG C, carry out drying, then in 600 DEG C of-700 DEG C of high temperature Muffle furnaces, carry out roasting 4h, make zinc, iron Compound Negative supported catalyst.
In 250mL four-hole bottle, add 9g urea, 46g1,2-propane diols, the above-mentioned catalyst of 5.5g, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 170 DEG C-180 DEG C, reaction 3.5h, and product composition gas-chromatography is carried out analysis and detected.The yield of propene carbonate is 93.5%.
Choose and state zinc, iron Compound Negative supported catalyst as the catalyst of Synthesis of dimethyl carbonate.The ratio being 4:1 in the mol ratio of methyl alcohol and propene carbonate in 250mL four-hole bottle adds methyl alcohol and propene carbonate, and 5.5g zinc, iron Compound Negative supported catalyst, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 100 DEG C-150 DEG C, reaction 2h, and product composition gas-chromatography is carried out analysis and detected.The yield 47.5% of dimethyl carbonate.
embodiment 2
Getting magnesium nitrate 7.77g and zinc nitrate 36.00g is dissolved in 200mL distilled water, be made into the metal salt solution containing zinc, magnesium, solution is slowly added drop-wise in isopyknic silica gel, after dripping, leave standstill 24h, in the drying box of about 100 DEG C, carry out drying, then in 600 DEG C of-700 DEG C of high temperature Muffle furnaces, carry out roasting 4h, make zinc, magnesium Compound Negative supported catalyst.
In 250mL four-hole bottle, add 9g urea, 46g1,2-propane diols, the above-mentioned catalyst of 5.5g, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 170 DEG C-180 DEG C, reaction 3.5h, and product composition gas-chromatography is carried out analysis and detected.The yield of propene carbonate is 93%.
Choose and state multiple zinc, magnesium Compound Negative supported catalyst as the catalyst of Synthesis of dimethyl carbonate.The ratio being 4:1 in the mol ratio of methyl alcohol and propene carbonate in 250mL four-hole bottle adds methyl alcohol and propene carbonate, and 5.5g zinc, magnesium Compound Negative supported catalyst, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 100 DEG C-150 DEG C, reaction 2h, and product composition gas-chromatography is carried out analysis and detected.The yield 48% of dimethyl carbonate.
embodiment 3
Getting magnesium nitrate 25.64g and aluminum nitrate 37.513gg is dissolved in 200mL distilled water, be made into the metal salt solution containing magnesium, aluminium, solution is slowly added drop-wise in isopyknic silica gel, after dripping, leave standstill 24h, in the drying box of about 100 DEG C, carry out drying, then in 600 DEG C of-700 DEG C of high temperature Muffle furnaces, carry out roasting 4h, make magnesium, aluminium Compound Negative supported catalyst.
In 250mL four-hole bottle, add 9g urea, 46g1,2-propane diols, the above-mentioned catalyst of 5.5g, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 170 DEG C-180 DEG C, reaction 3.5h, and product composition gas-chromatography is carried out analysis and detected.The yield of propene carbonate is 92.5%.
Choose and state magnesium, aluminium Compound Negative supported catalyst as the catalyst of Synthesis of dimethyl carbonate.The ratio being 4:1 in the mol ratio of methyl alcohol and propene carbonate in 250mL four-hole bottle adds methyl alcohol and propene carbonate, and 5.5g magnesium, aluminium Compound Negative supported catalyst, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 100 DEG C-150 DEG C, reaction 2h, and product composition gas-chromatography is carried out analysis and detected.The yield 41.5% of dimethyl carbonate.
embodiment 4
Getting calcium acetate 26.43g and magnesium acetate 38.46g is dissolved in 200mL distilled water, be made into the metal salt solution of calcic, magnesium, solution is slowly added drop-wise in isopyknic silica gel, after dripping, leave standstill 24h, in the drying box of about 100 DEG C, carry out drying, then in 600 DEG C of-700 DEG C of high temperature Muffle furnaces, carry out roasting 4h, make calcium, magnesium Compound Negative supported catalyst.
In 250mL four-hole bottle, add 9g urea, 46g1,2-propane diols, the above-mentioned catalyst of 5.5g, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 170 DEG C-180 DEG C, reaction 3.5h, and product composition gas-chromatography is carried out analysis and detected.The yield of propene carbonate is 93.5%
Choose and state calcium, magnesium Compound Negative supported catalyst as the catalyst of Synthesis of dimethyl carbonate.The ratio being 4:1 in the mol ratio of methyl alcohol and propene carbonate in 250mL four-hole bottle adds methyl alcohol and propene carbonate, and 5.5g calcium, magnesium Compound Negative supported catalyst, four-hole bottle is equipped with thermometer, reflux condenser, agitator and nitrogen inlet.Add hot reflux to react, reaction temperature controls at 100 DEG C-150 DEG C, reaction 2h, and product composition gas-chromatography is carried out analysis and detected.The yield 44.5% of dimethyl carbonate.
Claims (7)
1. a catalyst, it is characterized in that, this catalyst is loaded catalyst, by the nitrate of the metal of one or more solubilities, sulfate, acetate, stearate, hydrochloride, subcarbonate, be mixed with solution, incipient impregnation, on carrier, is prepared in loaded catalyst.
2. catalyst according to claim 1, is characterized in that: the preparation method of this catalyst adopt infusion process to prepare in loaded catalyst, its step is as follows:
(1) take in the nitrate of the metal of solubility, sulfate, acetate, hydrochloride, subcarbonate, stearate one or more, dissolve with distilled water or alcohol, be mixed with the solution of 0.1-1.5mol/L;
(2) solution prepared and isopyknic carrier are flooded: the solution prepared slowly is added drop-wise in carrier, after dripping, leave standstill 10-30h;
(3) by the loaded article that above-mentioned dipping is good, be placed in 100-110 DEG C of drying box and dry;
(4) loaded article of oven dry is placed in high temperature Muffle furnace, roasting 2-10h at 200-900 DEG C, after cooling, takes out and obtain catalyst.
3. catalyst according to claim 2, is characterized in that: described carrier is silica gel, molecular sieve, zeolite.
4. catalyst according to claim 2, is characterized in that: in step (4), sintering temperature is 550-750 DEG C; Roasting time is 2-5h.
5. catalyst according to claim 1, is characterized in that, this catalyst can be passed through high-temperature activation, regeneration process after using, repeated multiple times use, is specially: at 550-750 DEG C of roasting 2-5h and renewable.
6. utilize a method for catalyst preparing dimethyl carbonate as described in claim 1-4 any one, it is characterized in that: the method comprises the following steps:
With urea and aliphatic dihydroxy alcohol ethylene glycol or 1,2-PD for raw material, Reactive Synthesis ethylene carbonate or propene carbonate under the effect of catalyst, its reaction condition is reaction temperature is 100-200 DEG C, and reaction system introduces the nitrogen of 0.5-5mL/min;
Ethylene carbonate or propene carbonate and methyl alcohol ester exchange Synthesis of dimethyl carbonate, reaction condition: reaction temperature is 60-170 DEG C.
7. be the preparation method of dimethyl carbonate according to claim 6, it is characterized in that: by the weighing scale of reactant feed, described catalyst amount is the 0.5%-12% of reactant feed weight.
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| CN105664953A (en) * | 2016-03-04 | 2016-06-15 | 陕西煤业化工技术研究院有限责任公司 | Composite catalyst for synthesizing ethylene carbonate by urea alcoholysis and preparation process and application thereof |
| CN107353207A (en) * | 2017-08-21 | 2017-11-17 | 中石化上海工程有限公司 | A kind of method and its system of urea two-step method production dimethyl carbonate |
| CN107915574A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | Method for Synthesis of dimethyl carbonate |
| CN110156742A (en) * | 2019-07-02 | 2019-08-23 | 中国科学院过程工程研究所 | A kind of method of ionic liquid-catalyzed urea and dihydric alcohol synthesizing annular carbonate |
| CN110204444A (en) * | 2019-07-02 | 2019-09-06 | 滕州京腾鑫汇新材料科技有限公司 | Synthesis method of dimethyl carbonate |
| CN114210273A (en) * | 2021-12-24 | 2022-03-22 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
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| CN105664953A (en) * | 2016-03-04 | 2016-06-15 | 陕西煤业化工技术研究院有限责任公司 | Composite catalyst for synthesizing ethylene carbonate by urea alcoholysis and preparation process and application thereof |
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| CN110156742A (en) * | 2019-07-02 | 2019-08-23 | 中国科学院过程工程研究所 | A kind of method of ionic liquid-catalyzed urea and dihydric alcohol synthesizing annular carbonate |
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| CN110156742B (en) * | 2019-07-02 | 2020-12-04 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by catalyzing urea and dihydric alcohol with ionic liquid |
| CN110204444B (en) * | 2019-07-02 | 2022-04-22 | 滕州京腾鑫汇新材料科技有限公司 | Synthesis method of dimethyl carbonate |
| CN114210273A (en) * | 2021-12-24 | 2022-03-22 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
| CN114210273B (en) * | 2021-12-24 | 2023-09-05 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
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Application publication date: 20160120 |
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| WD01 | Invention patent application deemed withdrawn after publication |