CN103288666B - Method for continuous gas phase synthesis of oxamide - Google Patents
Method for continuous gas phase synthesis of oxamide Download PDFInfo
- Publication number
- CN103288666B CN103288666B CN201310197093.7A CN201310197093A CN103288666B CN 103288666 B CN103288666 B CN 103288666B CN 201310197093 A CN201310197093 A CN 201310197093A CN 103288666 B CN103288666 B CN 103288666B
- Authority
- CN
- China
- Prior art keywords
- oxamide
- ammonia
- reaction
- gas
- fatty alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for continuous gas phase synthesis of oxamide. In a gas phase reactor, gas phase oxalic acid dialkyl ester and ammonia gas perform ammonolysis reaction under high temperature to generate oxamide product and corresponding fatty alcohol secondary product, and the oxamide product is collected by a cyclone separator. The method uses the gas phase continuous synthesis technology, and solves the defects of long reaction time and poor capacity of intermittent reaction in the existing oxamide preparation technology; by adopting the method, the reaction time is reduced remarkably, the reaction is continuous and steady, the oxalic ester aminolysis conversion rate is high, the quality of the obtained oxamide is high, and continuous steady industrial production of the oxamide is realized.
Description
Technical field
The present invention relates to a kind of method of synthesizing oxamide, particularly a kind of method of continuous vapor-phase synthesis oxamide, belongs to oxamide preparing technical field.
Background technology
Be a kind of nontoxic and stable colourless crystallization or powder under oxamide room temperature, as a kind of urea aldehydes slow-release fertilizer with more wide application prospect, its nitrogen content is 31.8%, solubleness in water is 0.016%, nonhygroscopic in atmosphere, nontoxic, be easy to storage, in hydrolysis or biological decomposition process, progressively release ammonia-state nitrogen and carbonic acid gas, meet crop whole breeding time to the demand of nitrogen, decrease the loss caused by the leaching loss of nitrogen, volatilization and denitrification, improve chemical fertilizer utilization ratio, decrease fertilizer application frequency, save manpower and time.Its advantage being used as slow release fertilizer is proven in agricultural practice abroad, within 1969 to 1970, Japanese agriculture technical institute carries out paddy rice and wheat class manurial experiment to oxamide, synthesis measuring and comparative result, made the evaluation of certainty to the advantage of oxamide nitrogenous fertilizer.Hoechst AG of West Germany also carried out field experiment in 1974, and prove that oxamide is in crop whole vegetative period, stably can provide the nutrient required for suitable crop, it is a kind of excellent Slowly release nitrogen fertilizer certainly.In addition, oxamide is also used as the stablizer of nitrocotton goods, is used as reduction of speed agent in propelling agent, is used as chain viscosity increaser, in gas generator propellant, is used as foaming agent and cooling agent etc. in liners formulation.
The preparation technology of prior art medium-height grass acid amides mainly contains following three kinds:
(1) with prussic acid (HCN) for raw material preparation method (US3989753), HCN first generates cyanogen (CN) through oxidation
2, then through being hydrolyzed obtained oxamide.This method can be divided into Degussa method, phase modulus method, Asahi Chemical Industry's method and Hoechat method, and the difference of four kinds of methods is that oxygenant, catalyzer and technique are different, and the shortcoming of this preparation method is that prussic acid toxicity is large, cost is high, also reports there are no industrialization;
(2) pyrolysis method, namely adopt ammonium oxalate or oxalic acid urea to carry out pyrolysis and obtain oxamide, but the method cost is high, does not have practical value, research is less at present.
(3) dialkyl oxalate ammonolysis process (US6348626, US5393319, CN102267921A), the method be dialkyl oxalate under the dissolving of corresponding fatty alcohol with ammonia generation ammonolysis reaction, generate oxamide and corresponding fatty alcohol, the method is generally liquid phase rhythmic reaction, cannot realize continuous and steady operation.
Other preparation method of oxamide, as utilized hafnium complexes directly from nitrogen and carbon monoxide preparation (NatureChemistry, 2, pp.30-35,2010), is still in conceptual phase.
In the production method of above-mentioned listed oxamide, the ammonolysis process of dialkyl oxalate is the comparatively economically viable preparation method of oxamide comparatively speaking, particularly carbon monoxide coupling method synthesizing dimethyl oxalate route successfully realizes suitability for industrialized production in recent years, for the large-scale industrial production of oxamide is laid a good foundation.But above-mentioned dialkyl oxalate ammonolysis process is prepared in the preparation technology of oxamide, have that temperature of reaction is low, the problem such as long reaction time and reaction cannot be carried out continuously, because needs fatty alcohol dissolves dialkyl oxalate, therefore temperature of reaction is general lower, simultaneous reactions is liquid phase contact reacts, and the reaction times is generally 20 hours, and reaction need be carried out in batch reactor, can not continuous and steady operation, thus the requirement of suitability for industrialized production cannot be reached.
Summary of the invention
The object of the invention is to overcome defect of the prior art, provide a kind of method of continuous vapor-phase synthesis oxamide, the synthetic method of described oxamide has reaction continous-stable, the reaction times is short, oxalic acid ester aminolysis transformation efficiency is high, oxamide quality high.
The present invention is achieved by the following technical programs.
A kind of method of continuous vapor-phase synthesis oxamide, step is as follows: (1) enters Gas-phase reactor from Gas-phase reactor top after being gasified by dialkyl oxalate heater via, liquefied ammonia is entered gas distributor after vaporizer, surge tank gasification, then Gas-phase reactor is entered by bottom Gas-phase reactor, ammonolysis reaction is there is in the two in Gas-phase reactor, ammonia is excessive, and temperature of reaction is 165-185 DEG C, reaction pressure is 1-1.5MPa, residence time 5-30min; (2) in the powdery oxamide generated by ammonolysis reaction, reaction, part excess of ammonia gas and by-product fatty alcohol steam realize being separated of gas-solid phase through cyclonic separator with recycle gas strainer, and powdery oxamide is collected from whirlwind separator bottom; (3) the isolated part excessive ammonia of institute in step (2) and by-product fatty alcohol steam and the part ammonia of discharging through dust filter unit from Gas-phase reactor top and the merging of fatty alcohol steam are cooled through recycle gas water cooler again, and then realize being separated of ammonia and liquid phase fatty alcohol through gas-liquid separator gas-liquid separation, ammonia still residual in liquid phase fatty alcohol generates aluminum hydroxide precipitation and ammonium sulfate removing by adding appropriate alum reaction, and then obtains fatty alcohol byproduct through rectification process; Ammonolysis reaction liberated heat is removed in the process of refrigerated separation ammonia and fatty alcohol steam; (4) the isolated ammonia of institute in step (3) is returned through circulating air compressor together with fresh ammonia participate in reacting to Gas-phase reactor.
The method of above-mentioned a kind of continuous vapor-phase synthesis oxamide, wherein, described dialkyl oxalate is dimethyl oxalate or oxalic acid diethyl ester.
The method of above-mentioned a kind of continuous vapor-phase synthesis oxamide, wherein, described Gas-phase reactor is fluidized-bed reactor, and gas-phase reaction temperature is 170-185 DEG C, reaction pressure is 1.3MPa, residence time 15min.
The method of above-mentioned a kind of continuous vapor-phase synthesis oxamide, wherein, in described ammonolysis reaction, the mol ratio of ammonia and dialkyl oxalate is 2.1-2.5 ︰ 1.
The method of above-mentioned a kind of continuous vapor-phase synthesis oxamide, wherein, the mol ratio of described alum and ammonia is 1.1-1.5 ︰ 3.
The method of above-mentioned a kind of continuous vapor-phase synthesis oxamide, wherein, the transformation efficiency of described ammonolysis reaction mesoxalic acid dialkyl is greater than 99%, and the purity of oxamide product is greater than 98.5%.
The reaction equation that dialkyl oxalate ammonia solution prepares oxamide is as follows:
The method of a kind of continuous vapor-phase synthesis oxamide of the present invention, at high temperature ammonolysis reaction is there is by gas phase dialkyl oxalate and ammonia in Gas-phase reactor, generate oxamide product and corresponding fatty alcohol byproduct, obtain oxamide product by cyclone collection.Present method significantly shorten the reaction times, and reaction continous-stable, oxalic acid ester aminolysis transformation efficiency are high, and the oxamide quality obtained is high, achieves the continous-stable suitability for industrialized production of oxamide.
The present invention has following features:
(1) the present invention adopts gas phase continuous synthesis technique, solves the long reaction time of current oxamide preparation technology discontinuous reaction existence, the defect of production capacity deficiency;
(2) present invention process temperature of reaction is higher, and the transformation efficiency of ammonolysis reaction mesoxalic acid dialkyl is high, can reach more than 99%, and the purity of oxamide product is greater than 98.5%.
(3) mode that present invention process generates aluminum hydroxide precipitation and ammonium sulfate by adding appropriate alum and ammonia gas react effectively eliminates the remaining ammonia be dissolved in fatty alcohol, eliminate the harm that ammonia dissipation produces environmental and human health impacts, be conducive to the fatty alcohol byproduct obtaining high-quality simultaneously.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the method for a kind of continuous vapor-phase synthesis oxamide of the present invention.
Embodiment
Below by way of specific embodiment, the specific embodiment of the present invention is described in further detail.
Embodiment 1
A kind of method of continuous vapor-phase synthesis oxamide, step is as follows: dimethyl oxalate is entered Gas-phase reactor from Gas-phase reactor top through tangential direction through steam heater, hotline heater after being heated to 170 DEG C of gasifications by (1), liquefied ammonia is entered gas distributor after vaporizer, surge tank gasification, then Gas-phase reactor is entered by bottom Gas-phase reactor, ammonolysis reaction is there is in the two in Gas-phase reactor, the mol ratio of ammonia and dimethyl oxalate is 2.1 ︰ 1, and temperature of reaction is 165 DEG C, reaction pressure is 1MPa, reaction time is 5min; (2) in the powdery oxamide generated by ammonolysis reaction, reaction, part excess of ammonia gas and by-product methanol steam realize being separated of gas-solid phase through cyclonic separator with recycle gas strainer, powdery oxamide is collected from whirlwind separator bottom, and the purity of liquid-phase chromatographic analysis oxamide product is 98.8%; (3) the isolated part excessive ammonia of institute in step (2) and by-product methanol steam and the part ammonia of discharging through dust filter unit from Gas-phase reactor top and methanol steam merging are cooled through recycle gas water cooler again, and then realize being separated of ammonia and Liquid Phase Methanol through gas-liquid separator gas-liquid separation, ammonia still residual in Liquid Phase Methanol generates aluminum hydroxide precipitation and ammonium sulfate removing by adding alum reaction, the mol ratio of alum and ammonia is 1.1 ︰ 3, and then obtains methyl alcohol byproduct through rectification process; (4) the isolated ammonia of institute in step (3) is returned through circulating air compressor together with fresh ammonia participate in reacting to Gas-phase reactor.
Embodiment 2
A kind of method of continuous vapor-phase synthesis oxamide, step is as follows: dimethyl oxalate is entered Gas-phase reactor from Gas-phase reactor top through tangential direction through steam heater, hotline heater after being heated to 170 DEG C of gasifications by (1), liquefied ammonia is entered gas distributor after vaporizer, surge tank gasification, then Gas-phase reactor is entered by bottom Gas-phase reactor, ammonolysis reaction is there is in the two in Gas-phase reactor, the mol ratio of ammonia and dimethyl oxalate is 2.3 ︰ 1, and temperature of reaction is 175 DEG C, reaction pressure is 1.3MPa, reaction time is 15min; (2) in the powdery oxamide generated by ammonolysis reaction, reaction, part excess of ammonia gas and by-product methanol steam realize being separated of gas-solid phase through cyclonic separator with recycle gas strainer, powdery oxamide is collected from whirlwind separator bottom, and the purity of liquid-phase chromatographic analysis oxamide product is 99.2%; (3) the isolated part excessive ammonia of institute in step (2) and by-product methanol steam and the part ammonia of discharging through dust filter unit from Gas-phase reactor top and methanol steam merging are cooled through recycle gas water cooler again, and then realize being separated of ammonia and Liquid Phase Methanol through gas-liquid separator gas-liquid separation, ammonia still residual in Liquid Phase Methanol generates aluminum hydroxide precipitation and ammonium sulfate removing by adding alum reaction, the mol ratio of alum and ammonia is 1.3 ︰ 3, and then obtains methyl alcohol byproduct through rectification process; (4) the isolated ammonia of institute in step (3) is returned through circulating air compressor together with fresh ammonia participate in reacting to Gas-phase reactor.
Embodiment 3
A kind of method of continuous vapor-phase synthesis oxamide, step is as follows: oxalic acid diethyl ester is entered Gas-phase reactor from Gas-phase reactor top through tangential direction through steam heater, hotline heater after being heated to 185 DEG C of gasifications by (1), liquefied ammonia is entered gas distributor after vaporizer, surge tank gasification, then Gas-phase reactor is entered by bottom Gas-phase reactor, ammonolysis reaction is there is in the two in Gas-phase reactor, the mol ratio of ammonia and oxalic acid diethyl ester is 2.5 ︰ 1, and temperature of reaction is 185 DEG C, reaction pressure is 1.5MPa, reaction time is 30min; (2) in the powdery oxamide generated by ammonolysis reaction, reaction, part excess of ammonia gas and by-product alcohol vapour realize being separated of gas-solid phase through cyclonic separator with recycle gas strainer, powdery oxamide is collected from whirlwind separator bottom, and the purity of liquid-phase chromatographic analysis oxamide product is 99.0%; (3) the isolated part excessive ammonia of institute in step (2) and by-product alcohol vapour and the part ammonia of discharging through dust filter unit from Gas-phase reactor top and alcohol vapour merging are cooled through recycle gas water cooler again, and then realize being separated of ammonia and liquid phase ethanol through gas-liquid separator gas-liquid separation, ammonia still residual in liquid phase ethanol generates aluminum hydroxide precipitation and ammonium sulfate removing by adding alum reaction, the mol ratio of alum and ammonia is 1.5 ︰ 3, and then obtains ethanol byproduct through rectification process; (4) the isolated ammonia of institute in step (3) is returned through circulating air compressor together with fresh ammonia participate in reacting to Gas-phase reactor.
Here description of the invention and application is illustrative, not wants by scope restriction of the present invention in the above-described embodiments, and therefore, the present invention is not by the restriction of the present embodiment, and the technical scheme that any employing equivalence replacement obtains is all in the scope of protection of the invention.
Claims (5)
1. the method for a continuous vapor-phase synthesis oxamide, it is characterized in that, step is as follows: (1) enters fluidized-bed reactor from fluidized-bed reactor top after being gasified by dialkyl oxalate heater via, liquefied ammonia is entered gas distributor after vaporizer, surge tank gasification, then fluidized-bed reactor is entered by bottom fluidized-bed reactor, there is ammonolysis reaction in a fluidized bed reactor in the two, ammonia is excessive, and temperature of reaction is 170-185 DEG C, reaction pressure is 1.3MPa, residence time 15min; (2) in the powdery oxamide generated by ammonolysis reaction, reaction, part excess of ammonia gas and by-product fatty alcohol steam realize being separated of gas-solid phase through cyclonic separator with recycle gas strainer, and powdery oxamide is collected from whirlwind separator bottom; (3) the part ammonia of the isolated part excessive ammonia of institute in step (2) and by-product fatty alcohol steam and self-fluidized type bed bioreactor top being discharged through dust filter unit and the merging of fatty alcohol steam cool through recycle gas water cooler again, and then realize being separated of ammonia and liquid phase fatty alcohol through gas-liquid separator gas-liquid separation, ammonia still residual in liquid phase fatty alcohol generates aluminum hydroxide precipitation and ammonium sulfate removing by adding appropriate alum reaction, and then obtains fatty alcohol byproduct through rectification process; (4) the isolated ammonia of institute in step (3) is returned through circulating air compressor together with fresh ammonia participate in reacting to fluidized-bed reactor.
2. the method for a kind of continuous vapor-phase synthesis oxamide as claimed in claim 1, it is characterized in that, described dialkyl oxalate is dimethyl oxalate or oxalic acid diethyl ester.
3. the method for a kind of continuous vapor-phase synthesis oxamide as claimed in claim 1, it is characterized in that, in described ammonolysis reaction, the mol ratio of ammonia and dialkyl oxalate is 2.1-2.5 ︰ 1.
4. the method for a kind of continuous vapor-phase synthesis oxamide as claimed in claim 1, is characterized in that, the mol ratio of described alum and ammonia is 1.1-1.5 ︰ 3.
5. the method for a kind of continuous vapor-phase synthesis oxamide as claimed in claim 1, is characterized in that, the transformation efficiency of described ammonolysis reaction mesoxalic acid dialkyl is greater than 99%, and the purity of oxamide product is greater than 98.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310197093.7A CN103288666B (en) | 2013-05-21 | 2013-05-21 | Method for continuous gas phase synthesis of oxamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310197093.7A CN103288666B (en) | 2013-05-21 | 2013-05-21 | Method for continuous gas phase synthesis of oxamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103288666A CN103288666A (en) | 2013-09-11 |
| CN103288666B true CN103288666B (en) | 2015-07-15 |
Family
ID=49090268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310197093.7A Active CN103288666B (en) | 2013-05-21 | 2013-05-21 | Method for continuous gas phase synthesis of oxamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103288666B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367439B (en) * | 2015-09-07 | 2017-06-06 | 中国科学院福建物质结构研究所 | A kind of process of ester ammonia exchange process coproduction oxamides and carbamate |
| CN106674013B (en) * | 2016-11-29 | 2019-06-18 | 中国科学院福建物质结构研究所 | A kind of process of co-producing dimethyl carbonate and oxamides |
| CN112010783B (en) * | 2019-05-30 | 2024-01-30 | 浙江新和成股份有限公司 | Ammonolysis reaction system, taurine intermediate sodium taurate and preparation method of taurine |
| CN110862331B (en) * | 2019-12-06 | 2021-05-11 | 东华工程科技股份有限公司 | Method for continuously generating oxamide |
| CN111495312B (en) * | 2020-05-22 | 2023-07-28 | 河南心连心化学工业集团股份有限公司 | Oxamide synthesis device and synthesis method |
| CN113582869B (en) * | 2021-09-06 | 2022-06-10 | 中国科学院福建物质结构研究所 | Process method for producing oxamide and methyl carbamate in series |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393319A (en) * | 1992-07-10 | 1995-02-28 | Ube Industries, Ltd. | Process for producing oxamide granules |
| US6348626B1 (en) * | 1991-03-15 | 2002-02-19 | Ube Industries, Ltd. | Process for producing oxamide |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
-
2013
- 2013-05-21 CN CN201310197093.7A patent/CN103288666B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6348626B1 (en) * | 1991-03-15 | 2002-02-19 | Ube Industries, Ltd. | Process for producing oxamide |
| US5393319A (en) * | 1992-07-10 | 1995-02-28 | Ube Industries, Ltd. | Process for producing oxamide granules |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103288666A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103288666B (en) | Method for continuous gas phase synthesis of oxamide | |
| CN103755608B (en) | Thick hydrocyanic acid is utilized to produce method and the device thereof of D, L-2-2-hydroxy-4-methylthio calcium butyrate continuously | |
| CN103936623B (en) | Process for preparing toluene diisocyanate (TDI) by using toluenediamine and dimethyl carbonate | |
| CN102040400B (en) | Green synthesis process of slow release carbon base nitrogen fertilizer | |
| CN105399768A (en) | Clean production process for preparing N-(N-butyl)thiophosphoric triamide | |
| CN106496231B (en) | A kind of environment-friendly type preparation method for synthesizing folic acid | |
| CN110372545B (en) | Preparation method of high-purity gliclazide intermediate p-toluenesulfonylurea | |
| CN105732350A (en) | Method of producing anhydrous formaldehyde through oxygen-free dehydrogenation | |
| CN101531367A (en) | Process for producing silicane | |
| CN101857556A (en) | System and method for preparing isocyanate by gas-phase themolysis | |
| CN105367439A (en) | Process method of co-production of oxamide and carbamic acid ester through ammonia ester exchange method | |
| CN102250016B (en) | Method for preparing 4,5,6-trichloropyrimidine | |
| CN101367733B (en) | Heat pump distillation apparatus and process for diethyl carbonate | |
| CN209848872U (en) | Production device for synthesizing oxamide | |
| CN101844064B (en) | Reactor and method for preparing isocyanate by gas phase pyrolysis | |
| CN111995592B (en) | Method and device for co-production of urea and melamine | |
| CN212263269U (en) | Synthetic device of oxamide | |
| CN210765084U (en) | Heterogeneous continuous acidolysis device for glyphosate | |
| CN111495312B (en) | Oxamide synthesis device and synthesis method | |
| CN103626664B (en) | Method for synthesizing 2-methyl-1,2-propane diamine | |
| CN102584636A (en) | Synthetic method of kreatine | |
| CN106316933A (en) | Continuous preparation method for 2-fluoro-6-trifluoromethyl pyridine | |
| CN110862331B (en) | Method for continuously generating oxamide | |
| CN202113843U (en) | Device for preparing chloromethane and ammonia | |
| CN106829878B (en) | Dichloride sulphur preparing process and preparation facilities |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |