CN103172538A - Method for synthesis of carbamate under mild conditions - Google Patents
Method for synthesis of carbamate under mild conditions Download PDFInfo
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- CN103172538A CN103172538A CN2011104422070A CN201110442207A CN103172538A CN 103172538 A CN103172538 A CN 103172538A CN 2011104422070 A CN2011104422070 A CN 2011104422070A CN 201110442207 A CN201110442207 A CN 201110442207A CN 103172538 A CN103172538 A CN 103172538A
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Abstract
The invention discloses a method for synthesis of carbamate under mild conditions. Urea and methanol are used as raw materials, and in the presence of a solid oxide catalyst, a sweeping gas is continuously introduced during the reaction process, so that methyl carbamate is synthesized under mild conditions. Under the optimized reaction conditions, the conversion rate of urea is more than 90%, the selectivity of methyl carbamate is more than 99.9%, and the decomposition rate of urea is less than 1%. The method has advantages of simple preparation method of the catalyst, mild reaction conditions, high selectivity of methyl carbamate, less urea decomposition, no deterioration during the reaction process, easy separation of the catalyst, good catalyst repeatability and the like.
Description
Technical field
The present invention relates to a kind ofly under catalyzer exists, react the method for synthesis of carbamates by urea and methyl alcohol under mild conditions.
Background technology
Urethylane (MC) is a kind of chemical with extensive use, can be used as agricultural chemicals, medicine, improvement agent for synthesis resin and organic synthesis intermediate etc.During as organic synthesis intermediate, can react with polyamine compounds, generate multiple-amino ester formate, then through non-phosgene route pyrolysis method synthesizing isocyanate; MC and polyvalent alcohol carry out transesterification reaction, obtain the polyvalent alcohol amino formate compounds, then further carry out crosslinking reaction with aldehyde and generate the nontoxic polyurethane that does not contain residual poisonous isocyanate group reunion amino ester structure, are widely used as coating, tackiness agent etc.; MC has the advantages such as volatility is moderate, tasteless, toxicity is lower as the clothing anti-moth agent.MC can also be for the synthesis of the derivative of the different purposes such as triazolone, heterocycle pyrroles, quinazolinone and triazine.
Patent CN101570499 discloses a kind of synthetic method of Urethylane, urea and methyl alcohol is synthetic MC under high boiling solvent exists, the synthetic thick product of MC of reaction, thick product distills to get work in-process, again through the 2600-2800Pa underpressure distillation, collect the cut of 70-80 ℃, can obtain content is the MC sterling of 99.4-99.8%.The shortcoming of the method is to add high boiling solvent.
Patent CN1683326 discloses a kind of synthesis technique of Urethylane, it is 100～180 ℃ in temperature of reaction, under reaction pressure 0.1～1.5MPa condition, reacted 0.5～10 hour, to isolate reaction system after condenser condenses by the resultant ammonia that the methyl alcohol of one of reactant is taken out of through rectifying tower in reaction process, and enter the ammoniacal liquor generation system and generate ammoniacal liquor.The shortcoming of this technique is that methyl alcohol constantly taken out of reaction system, and raw material consumption and energy consumption are larger.
Patent CN101518729A before the applicant discloses a kind of for the synthetic catalyzer of alkyl carbamate, reaction is carried out at 160 ℃, easily form as by products such as DMC, methylated MC in process, unreacted urea is partially denaturing due to temperature drift, be not suitable for reclaiming and use, thereby cause the waste discharge amount to increase.Lower than 160 ℃ of whens reaction, catalytic activity is lower, cause yield on the low side low, the time is long.Purity requirement as agriculture medicine intermediate MC is generally higher.Usually, temperature of reaction surpasses 160 ℃, easily forms by product, adds to the difficulties for the quality raising of follow-up separation and purification and target product MC.Simultaneously, higher temperature will cause reaction pressure to rise violently rapidly, thereby cause the difficult risk that hinders conversion, increase reactor cost and the safety in production of raw material urea of discharging of ammonia.
In sum, development has highly active MC catalyzer under cold condition, when realizing energy-saving and emission-reduction, can obtain the synthetic method of high-quality MC, has important Research Significance and using value.
Summary of the invention
The object of the present invention is to provide the synthetic method of carbamate under a kind of mild conditions.
We have selected a kind of soild oxide catalyzer, and are used for urea and methyl alcohol reaction preparation Urethylane, conversion rate of urea＞90% wherein, and product Urethylane yield＞90% separates rear Urethylane purity＞99.9%.The soda acid double function characteristic of the catalyzer that we use itself may be the source of high activity of catalyst.Be the formation of the acidic site promotion HNCO of catalyzer, basic sites can activate methyl alcohol at low temperatures simultaneously, forms CH
3O
-Species are conducive to the carbon atom in nucleophilic attack HNCO, thereby can realize effective synthesis of carbamates under mild conditions.
The synthetic method of carbamate under a kind of mild conditions, it is characterized in that adopting urea and methyl alcohol is raw material, under the existence of soild oxide catalyzer, in reaction process by passing into continuously sweeping gas, synthesizing amino methyl-formiate under mild conditions; The active ingredient of described catalyzer is the mixture of a kind or 2 kinds metal oxide in iron, zinc, magnesium, aluminium, yttrium, lanthanum or cerium, and wherein in 2 kinds of composite oxide of metal, the metallic element mol ratio is 0.1～5.
The present invention's sweeping gas in reaction process is nitrogen or carbonic acid gas, and its flow rates is 20～200L/kg urea hour.
Method of the present invention, temperature of reaction are 120～150 ℃.
Method of the present invention, the reaction times is 1～10 hour.
Method of the present invention, the mol ratio of methyl alcohol and urea are 3-10.
Method of the present invention, catalyst levels are 1～10wt% of amount of urea.
The soild oxide catalyzer that the present invention is used, by the precipitator method or coprecipitation method preparation, catalyst precursor is nitrate, carbonate, acetate, halogenide, vitriol or phosphoric acid salt, 200～600 ℃ of the maturing temperatures of catalyst precursor.
Method of the present invention, preferred soild oxide catalyzer Zn
aY represents, wherein the span of a is 0.1～5.
Implementation process of the present invention is: add oxide catalyst urea and methyl alcohol in autoclave, then use air in the nitrogen purging reactor, the flow of regulating sweep gas nitrogen or carbonic acid gas is 20～200L/kg urea hour, is warming up to 120～150 ℃, reaction 1～10h.Reaction finishes, and after question response liquid cooling but, reclaims catalyzer by sedimentation or filtering separation, and the gained catalyzer is after ethanol or the simple cleaning-drying of acetone, and is namely reusable.The reaction after product carries out qualitative and quantitative analysis through gas-chromatography (GC), gas chromatography mass spectrometry (GC-MS).20～50 ℃ of underpressure distillation separation of methanol.80-115 ℃ of decompression steams the Urethylane product, purity＞99.9%.
The advantage that the present invention compares with traditional carbamate production method:
Catalyst levels is only 1～10wt% based on amount of urea.
Reaction is carried out at 120～150 ℃, and catalytic activity is high, and reaction 1～10h gets final product the synthetic of effective catalytic amino methyl-formiate, yield＞90%.
Adopt the method for low-temp reaction, can reduce energy consumption on the one hand, guarantee that on the other hand raw material urea never degenerates in reaction process, and can obtain the Urethylane product of high purity (＞99.9%).
Analysis condition:
The reaction after product adopts Agilent Technologies 6820 gas chromatography system quantitative analyses.Chromatographic condition is: the kapillary of chromatographic column 30m * 0.25mm * 0.33 μ m, hydrogen flameionization (FID) detector.Qualitative analysis utilizes HP 6890/5973GC-MS to complete, and this HP 6890/5973GC-MS has the kapillary of 30m * 0.25mm * 0.33 μ m and with the chem workstation of NIST spectra database.
Embodiment
In order to understand better the present invention, further set forth below in conjunction with embodiment, but these embodiment should not be construed as any limitation of the invention.
The catalyzer preparation:
Zinc nitrate and Yttrium trinitrate, 1mol/L sodium hydroxide precipitation agent is titrated to pH=9-11, and throw out is in 70 ℃ of aging 12h, and the gained precipitation is repeatedly washed to neutrality through distilled water, 120 ℃ of dryings, 300～600 ℃ of roastings get pulverulent solids, are labeled as Zn
aY, wherein the span of a is 0.1～5.
Embodiment 1
186g technical grade urea, the above-mentioned Zn of 9.3g
aThe Y catalyzer, 1000ml methyl alcohol adds the 2L stainless steel cauldron, closed reactor after nitrogen purging, is pressurized to 1.4MPa, nitrogen flow rate 20L/h is warming up to 140 ℃ of reaction 8h, after question response liquid cooling but, catalyzer passes through filtered and recycled, products therefrom adds internal standard substance Isosorbide-5-Nitrae-dioxane, through the inner mark method ration analysis, the transformation efficiency of gained urea＞90%, Urethylane selectivity＞99.9%.
Embodiment 2
186g technical grade urea, the above-mentioned Zn of 9.3g
aThe Y catalyzer, 1000ml methyl alcohol adds the 2L stainless steel cauldron, closed reactor after nitrogen purging, is pressurized to 1.4MPa, nitrogen flow rate 20L/h is warming up to 120 ℃ of reaction 8h, after question response liquid cooling but, catalyzer passes through filtered and recycled, products therefrom adds internal standard substance Isosorbide-5-Nitrae-dioxane, through the inner mark method ration analysis, the transformation efficiency 33% of gained urea, Urethylane selectivity＞99.9%.
Embodiment 3
186g technical grade urea, the above-mentioned Zn of 9.3g
aThe Y catalyzer, 1000ml methyl alcohol adds the 2L stainless steel cauldron, closed reactor after nitrogen purging, is pressurized to 1.4MPa, nitrogen flow rate 20L/h is warming up to 130 ℃ of reaction 8h, after question response liquid cooling but, catalyzer passes through filtered and recycled, products therefrom adds internal standard substance Isosorbide-5-Nitrae-dioxane, through the inner mark method ration analysis, the transformation efficiency 75% of gained urea, Urethylane selectivity＞99.9%.
Embodiment 4
186g technical grade urea, 9.3g uses the Zn of 5 times
aThe Y catalyzer, 1000ml methyl alcohol adds the 2L stainless steel cauldron, closed reactor after nitrogen purging, is pressurized to 1.4MPa, nitrogen flow rate 20L/h is warming up to 140 ℃ of reaction 8h, after question response liquid cooling but, catalyzer passes through filtered and recycled, products therefrom adds internal standard substance Isosorbide-5-Nitrae-dioxane, through the inner mark method ration analysis, the transformation efficiency of gained urea＞90%, Urethylane selectivity＞99.9%.
Embodiment 5
After finishing as the reaction process in embodiment 1, the recycling step of subsequent product is: after question response liquid cooling but, catalyzer is by filtered and recycled, and 20～50 ℃ of Rotary Evaporators reclaim unnecessary methyl alcohol, and 80-115 ℃ of decompression steamed and got MC, and remaining solid is insoluble urea.The white solid that distills out is MC, purity＞99.9%.Separate the urea obtain after reaction and continue to use, but still highly selective obtains Urethylane, prove that urea is rotten in the low-temp reaction process, show with the infrared result contrast of raw material urea yet, the rear urea of reaction does not go bad.
Claims (7)
1. the synthetic method of carbamate under a mild conditions, it is characterized in that adopting urea and methyl alcohol is raw material, under the existence of soild oxide catalyzer, in reaction process by passing into continuously sweeping gas, synthesizing amino methyl-formiate under mild conditions; The active ingredient of described catalyzer is the mixture of a kind or 2 kinds metal oxide in iron, zinc, magnesium, aluminium, yttrium, lanthanum or cerium, and wherein in 2 kinds of composite oxide of metal, the metallic element mol ratio is 0.1～5.
2. the method for claim 1, is characterized in that in reaction process, sweeping gas is nitrogen or carbonic acid gas, and its flow rates is 20～200L/kg urea hour.
3. the method for claim 1, is characterized in that temperature of reaction is 120～150 ℃.
4. the method for claim 1, is characterized in that the reaction times is 1～10 hour.
5. the method for claim 1, the mol ratio that it is characterized in that methyl alcohol and urea is 3-10.
6. the method for claim 1, is characterized in that catalyst levels is 1～10wt% of amount of urea.
7. the method for claim 1, is characterized in that soild oxide catalyzer Zn
aY represents, wherein the span of a is 0.1～5.
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| CN2011104422070A CN103172538A (en) | 2011-12-23 | 2011-12-23 | Method for synthesis of carbamate under mild conditions |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761454A (en) * | 2014-01-07 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Method for direct synthesis of diethyl carbonate and simultaneously by-production of ethyl carbamate through urea alcoholysis |
| CN104892331A (en) * | 2015-05-12 | 2015-09-09 | 中北大学 | Biodegradable organic polymeric nitrogen fertilizer and preparation method therefor |
| WO2015135176A1 (en) * | 2014-03-13 | 2015-09-17 | East China University Of Science And Technology | Catalysts, methods, and systems for preparing carbamates |
| CN105777583A (en) * | 2016-05-07 | 2016-07-20 | 长春工业大学 | Method for preparing methyl carbamate by urea methanolysis method |
| CN106631901A (en) * | 2016-12-14 | 2017-05-10 | 中榆化工科技有限公司 | Method for preparing methyl carbamate by urea alcoholysis method and device thereof |
| CN106669654A (en) * | 2016-12-14 | 2017-05-17 | 中榆化工科技有限公司 | Catalyst for preparing methyl carbamate and preparation method of catalyst |
| CN110526837A (en) * | 2019-09-19 | 2019-12-03 | 重庆化工职业学院 | The method for preparing methyl carbamate as raw material using urea |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761454A (en) * | 2014-01-07 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Method for direct synthesis of diethyl carbonate and simultaneously by-production of ethyl carbamate through urea alcoholysis |
| WO2015135176A1 (en) * | 2014-03-13 | 2015-09-17 | East China University Of Science And Technology | Catalysts, methods, and systems for preparing carbamates |
| US10000448B2 (en) | 2014-03-13 | 2018-06-19 | East China University Of Science And Technology | Catalysts, methods, and systems for preparing carbamates |
| CN104892331A (en) * | 2015-05-12 | 2015-09-09 | 中北大学 | Biodegradable organic polymeric nitrogen fertilizer and preparation method therefor |
| CN104892331B (en) * | 2015-05-12 | 2017-05-17 | 中北大学 | Biodegradable organic polymeric nitrogen fertilizer and preparation method therefor |
| CN105777583A (en) * | 2016-05-07 | 2016-07-20 | 长春工业大学 | Method for preparing methyl carbamate by urea methanolysis method |
| CN106631901A (en) * | 2016-12-14 | 2017-05-10 | 中榆化工科技有限公司 | Method for preparing methyl carbamate by urea alcoholysis method and device thereof |
| CN106669654A (en) * | 2016-12-14 | 2017-05-17 | 中榆化工科技有限公司 | Catalyst for preparing methyl carbamate and preparation method of catalyst |
| CN106631901B (en) * | 2016-12-14 | 2019-02-05 | 中榆化工科技有限公司 | A kind of method and device thereof preparing methyl carbamate using alcoholysis of urea |
| CN110526837A (en) * | 2019-09-19 | 2019-12-03 | 重庆化工职业学院 | The method for preparing methyl carbamate as raw material using urea |
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Application publication date: 20130626 |