CN100415712C - Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction - Google Patents
Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction Download PDFInfo
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- CN100415712C CN100415712C CNB2005100424851A CN200510042485A CN100415712C CN 100415712 C CN100415712 C CN 100415712C CN B2005100424851 A CNB2005100424851 A CN B2005100424851A CN 200510042485 A CN200510042485 A CN 200510042485A CN 100415712 C CN100415712 C CN 100415712C
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- urea
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Abstract
The present invention relates to an industrial production method for producing fine chemicals, medicines, and intermediate methyl carbamate of the medicines and pesticides, which belongs to the technical field of production and synthesis of fine chemical industry. The present invention has the technical scheme that urea and methanol are used as raw materials, and the urea and the methanol are mixed according to the weight ratio of 1 to 20: 1; the concentration of the mixed urea methanol solution is 0.01 to 10 mol/L, and the solution reacts for 0.5 to 10 hours at the reaction temperature of 100 to 180 DEG C under the reaction pressure of 0.1 to 1.5Mpa; in the process of reaction, the take-off rate of released mixed steam of ammonium and the methanol is identical to the rate of the replenished urea methanol solution by replenishing the urea methanol solution; after the reaction is finished, a reaction product is purified. The mixed steam of the ammonium and the methanol, which is released in the process of reaction, is rectified to separate ammonia and the methanol; the methanol is recovered after cooled, the pressure of NH3 is reduced by a jet pump, and then, the NH3 is absorbed by water through an ammonia forming system to prepare a finished product of industrial ammonia. The present invention has the advantages of fully enclosed reaction system, basically no discharge of waste water, waste gas and waste residues, low production cost, obvious economic benefit and low equipment investment; compared with the prior art, the equipment investment of the present invention is reduced by 30 to 40%.
Description
One, technical field
The present invention relates to a kind of production fine chemicals and medicine and medicine, pesticide intermediate Urethylane industrial process, belong to fine chemistry industry and produce synthetic field.
Two, background technology
Urethylane (Methyl Cabamate is called for short MC), another name urethylan (Ureaghylane) is a kind of important organic synthesis intermediate.Be mainly used in the synthetic of medicine, agricultural chemicals, its derivative obtains application more and more widely as weedicide, sterilant, rubber antioxygen, thermo-stabilizer etc. at agricultural, rubber industry.Carbamate chemicals for agriculture, since it with the agricultural chemicals of other kind lamp compare people and other Mammals have low toxicity, poisoning specificity by force, easily by multiple factor degrade, residual low, to characteristics such as the side effect of environment are little, develop novel pesticide, weedicide and kill mosquito faster, fly agent so become countries in the world in recent years, and its Application Areas is expanded very fast.
The present existing MC synthetic production method in home and abroad mainly contains methyl-chloroformate method, alcoholysis of urea, isocyanide acid system, electrolysis methane amide method etc.The methyl-chloroformate method has the yield height, product is easy to advantages such as purification, but the methyl-chloroformate method is the phosgene product, and it is all poisonous to produce raw materials used and solvent, and has limited its application.The isocyanide acid system is huge to equipment requirements height, investment, and isocyanic acid is also poisonous, and synthetic cost is very high.Electrolysis methane amide method is produced the electric energy that needs consume significant.Aforesaid method all exists equipment complexity, cost than problems such as height.The conversion rate of urea of existing alcoholysis of urea manufacturer is too low.At present, the method for urea and methyl alcohol system MC roughly has three types both at home and abroad, and the one, the normal temperature and pressure catalysis synthesis method, this method is introduced inorganic acid as catalyst, and the reaction times reaches 35h, and yield has only 40% (with ureometer), and there is heavy corrosion in equipment, and product such as is difficult to make with extra care at problem; The 2nd, though the time of this class reaction shortens greatly, there is not the equipment corrosion problem in high temperature and high pressure synthesis yet, and temperature of reaction is very high, and reaction pressure reaches tens Mpa, yield less than 40%, and a large amount of urea lose because of decomposition.This class is reflected at external 20th century five, sixties employing (domestic alcoholysis of urea promptly adopts this method at present); The 3rd, the medium temperature and medium pressure catalysis synthesis process, this is the novel method of external 20th century the seventies exploitation, and temperature of reaction, pressure and reaction times are all moderate, and yield is not low yet, but the catalyzer that reaction is used is oxide compound or the salt and the H of transition metal
2SO
4, HNO
3, H
3PO
4And the mixture of mineral acid such as polyphosphoric acid, still there is etching problem to equipment.At the beginning of 21 century, the research worker who has has tested spent ion exchange resin and has added the method for micro-zinc oxide as the synthetic MC of catalyzer, about 140 ℃ of temperature, pressure is about 2.0Mpa, though gained MC yield is higher, but still has two problems, the one, complex phase catalysis, the equipment complexity, the 2nd, catalyst system therefor is short work-ing life, is difficult to regeneration.
Three, summary of the invention
The purpose of this invention is to provide a kind of is raw material with urea and methyl alcohol, and catalyst-free participates in, and equipment is simple, and the reaction times is short, the method for the producing methyl carbamate by low pressure solvation homogeneous phase reaction that cost is low.
The technical scheme that adopts is: with urea and methyl alcohol is raw material, and by urea: the ratio of the weight of methyl alcohol is 1～20: 1 mixing; Under the condition of 100～180 ℃ of temperature of reaction, reaction pressure 0.1～1.5Mpa, reacted 0.5～10 hour, pass through to replenish the urea methanol solution in the reaction process, make the speed of the ammonia-methanol mixed steam elution speed of release and additional urea methanol solution suitable, after reaction finishes resultant of reaction is carried out product and purify.The ammonia that discharges in the reaction process-methanol mixed steam goes out ammonia gas and methyl alcohol by rectifying separation, and methyl alcohol reclaims after cooling off, NH
3Adopt squirt pump decompression ammoniacal liquor to form system water and absorb, make the industrial ammonia finished product.In the Methanol Recovery process, isolate ammonia gas and after cooling, isolate methyl alcohol once more, and reclaim methyl alcohol.Material dissolution is realized by the pre-mixing still; Reaction is synthetic to be to carry out in the totally enclosed reactor that has an agitator; It is to carry out in by separating still under pressure 0.01～0.1Mpa pressure condition that product is purified; Methanol Recovery realizes by essence slide tower, water cooler.In reaction is synthetic,, reach balance, under 140-180 ℃ of low pressure condition, impel molecular balance to move to generating the Urethylane direction at 100-140 ℃ of synthesis under normal pressure by the burst size of control ammonia gas and the additional speed of urea methanol solution.
Compared with the prior art the present invention has following characteristics:
(1) technological line of the present invention's employing is totally-enclosed reaction system, can reach basic three-waste free discharge, the significant technical indicator of environmental benefit.
(2) reaction raw materials is easy to get, and the reaction times is short, and reaction conversion ratio and selectivity are all higher, and by product all can utilize again.Production cost is low, remarkable in economical benefits.
(3) this production technology does not need catalyzer, adopts reactant to make solvent, only needs reaction conditions control just can realize excellent reactivity worth, is easy to carry out scale operation.
(4) facility investment is low, than similar technique investment low 30～40%.
Four, description of drawings:
Do not have.
Five, embodiment
Embodiment 1:
With 1T urea and 3m
3Methyl alcohol joins 5m
3In the reactor, 140 ℃ of reacting by heating temperature, rectifying tower was started working when pressure reached 1.2Mpa, simultaneously with 0.2m
3/ h speed is replenished the urea methanol solution of 1mol/L, reaction times 4h.The Urethylane productive rate is 86%.While by-product 30% ammoniacal liquor 0.85T.
Embodiment 2:
With 0.8T urea and 3.2m
3Methyl alcohol joins 5m
3In the reactor, 150 ℃ of reacting by heating temperature, rectifying tower was started working when pressure reached 1.5Mpa, simultaneously with 0.2m
3/ h speed is replenished the urea methanol solution of 1.5mol/L, reaction times 4h.The Urethylane productive rate is 88%, simultaneously by-product 30% ammoniacal liquor 0.86T.
Embodiment 3:
With 1T urea and 3.5m
3Methyl alcohol joins 5m
3In the reactor, 160 ℃ of reacting by heating temperature, rectifying tower was started working when pressure reached 1.4Mpa, simultaneously with 1.0m
3/ h speed is replenished the urea methanol solution of 1.2mol/L, reaction times 3h.The Urethylane productive rate is 91%.While by-product 30% ammoniacal liquor 0.88T.
Embodiment 4:
With 1.2T urea and 3m
3Methyl alcohol joins 5m
3In the reactor, heating, 170 ℃ of temperature of reaction, rectifying tower was started working when pressure reached 1.5Mpa, simultaneously with 0.05m
3/ h speed is replenished the urea methanol solution of 1mol/L, reaction times 2h.The Urethylane productive rate is 89%.While by-product 30% ammoniacal liquor 0.87T.
Claims (5)
1. the method for a producing methyl carbamate by low pressure solvation homogeneous phase reaction, it is characterized in that: with urea and methyl alcohol is raw material, and by urea: the ratio of the weight of methyl alcohol is to mix at 1～20: 1; Under the condition of 100～180 ℃ of temperature of reaction, reaction pressure 0.1～1.5Mpa, reacted 0.5～10 hour, pass through to replenish the urea methanol solution in the reaction process, make the speed of the ammonia-methanol mixed steam elution speed of release and additional urea methanol solution suitable, after reaction finishes resultant of reaction is carried out product and purify.
2. the method for producing methyl carbamate by low pressure solvation homogeneous phase reaction according to claim 1, it is characterized in that: the ammonia that discharges in the reaction process-methanol mixed steam goes out ammonia gas and methyl alcohol by rectifying separation, and methyl alcohol reclaims after cooling off, NH
3Adopt and spray the absorption of decompression ammoniacal liquor formation system water, make the industrial ammonia finished product.
3. the method for producing methyl carbamate by low pressure solvation homogeneous phase reaction according to claim 2 is characterized in that: isolate ammonia gas and isolate methyl alcohol once more in the Methanol Recovery process after cooling, and reclaim methyl alcohol.
4. the method for producing methyl carbamate by low pressure solvation homogeneous phase reaction according to claim 2, it is characterized in that: material dissolution is realized by the pre-mixing still; Reaction is synthetic to be to carry out in the totally enclosed reactor that has an agitator; It is to carry out in by separating still under pressure 0.01～0.1Mpa pressure condition that product is purified; Methanol Recovery realizes by essence slide tower, water cooler.
5. the method for producing methyl carbamate by low pressure solvation homogeneous phase reaction according to claim 1, it is characterized in that: in reaction is synthetic, pass through the burst size of control ammonia gas and the additional speed of urea methanol solution, reach balance at 100-140 ℃ of synthesis under normal pressure, under 140-180 ℃ of low pressure condition, impel molecular balance to move to generating the Urethylane direction.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100424851A CN100415712C (en) | 2005-02-21 | 2005-02-21 | Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction |
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| CNB2005100424851A CN100415712C (en) | 2005-02-21 | 2005-02-21 | Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction |
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| CN1693302A CN1693302A (en) | 2005-11-09 |
| CN100415712C true CN100415712C (en) | 2008-09-03 |
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| CNB2005100424851A Expired - Fee Related CN100415712C (en) | 2005-02-21 | 2005-02-21 | Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570499A (en) * | 2009-03-07 | 2009-11-04 | 垦利三合新材料科技有限责任公司 | Method for preparing methyl carhamate |
| 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 |
| CN113651751B (en) * | 2021-09-28 | 2023-04-11 | 大连九信精细化工有限公司 | Preparation method of N-methoxycarbonyl-3-trifluoromethylpyridine-2-sulfonamide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534649A (en) * | 1994-10-21 | 1996-07-09 | Tama Chemicals Co., Ltd. | Process for preparing dialkyl carbonates |
| CN1475481A (en) * | 2003-07-11 | 2004-02-18 | 中国科学院山西煤炭化学研究所 | Method of synthesizing methyl carbamate |
-
2005
- 2005-02-21 CN CNB2005100424851A patent/CN100415712C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534649A (en) * | 1994-10-21 | 1996-07-09 | Tama Chemicals Co., Ltd. | Process for preparing dialkyl carbonates |
| CN1475481A (en) * | 2003-07-11 | 2004-02-18 | 中国科学院山西煤炭化学研究所 | Method of synthesizing methyl carbamate |
Non-Patent Citations (4)
| Title |
|---|
| 尿素和甲醇制氨基甲酸甲酯体系热力学分析. 郑卓群等.天然气化工，第5期. 2004 |
| 尿素和甲醇制氨基甲酸甲酯体系热力学分析. 郑卓群等.天然气化工，第5期. 2004 * |
| 尿素醇解法合成氨基甲酸甲酯的研究. 茆福林等.浙江师范大学学报，第28卷第1期. 2005 |
| 尿素醇解法合成氨基甲酸甲酯的研究. 茆福林等.浙江师范大学学报，第28卷第1期. 2005 * |
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