CN103613616B - The production equipment of a kind of PMIDA and production method - Google Patents
The production equipment of a kind of PMIDA and production method Download PDFInfo
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- CN103613616B CN103613616B CN201310681943.0A CN201310681943A CN103613616B CN 103613616 B CN103613616 B CN 103613616B CN 201310681943 A CN201310681943 A CN 201310681943A CN 103613616 B CN103613616 B CN 103613616B
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Abstract
The invention provides the production equipment of a kind of PMIDA and production method, phosphorous acid, the suspension of iminodiacetic acid, formaldehyde through described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater, are entered pipeline mixer respectively with hydrochloric acid and mixes, sequentially pass through pipeline reactor again and reactor carries out condensation reaction, obtain PMIDA.Compared with prior art, pipeline reactor and reactor are cascaded by the present invention, by control reaction mass preheated after once enter pipeline mixer, pipeline reactor carries out fast reaction, slow reaction is carried out subsequently into reactor, avoid reaction mass and stop generation side reaction at relatively high temperatures for a long time, and in a kettle., reacting material concentration is relatively low, response speed is slow, in its available pipeline reactor, after reaction, self heat reacts, effectively extend material retention time, improve reaction efficiency.
Description
Technical field
The invention belongs to technical field of fine, particularly relate to production equipment and the production method of a kind of PMIDA.
Background technology
N-phosphonomethylglycine (glyphosate, PMG), it it is a kind of efficient wide spectrum steriland herbicide, because it has good Uptake and translocation performance, the preventing and treating of multiple deep root malignant weed is highly effective, and sales volume progressively increases in recent years, along with the popularization gradually of glyphosate tolerant acid genetically modified crops, its range of application expands further, has now become the herbicide that sales volume in the world is maximum and growth rate is the fastest.
Now industrialized glyphosate production technology mainly has two, the IDA route being initiation material with hydrocyanic acid or diethanolamine that a Tiao Shi About Monsanto Chemicals adopts；The dialkyl phosphite route being initiation material with glycine that another Tiao Shi China is commonly used.
A kind of common precursor N-phosphonomethyl iminodiacetic acid (abbreviation PMIDA) of synthesizing glyphosate, it is to be prepared under strongly acidic conditions with iminodiacetic acid (IDA) or its salt, phosphorous acid, formaldehyde, and synthetic reaction equation is as follows:
In above-mentioned raw materials, diaminourea oxalic acid (IDA) can be hydrolyzed by Iminodiacetonitrile 1,1'-Imidodiacetonitrile or Diethanolamine Dehydrogenation is prepared, and it is used for synthesizing PMIDA can adopt IDA sterling or hydrolysis liquid；Phosphorous acid can use solid or liquid.Iminodiacetic acid, phosphorous acid and formaldehyde react when strong acid, and reaction carries out in a kettle., i.e. autoclave intermittent reaction, and after reaction terminates, crystallization obtains product PMIDA.
But adopt autoclave intermittent reaction to have the disadvantage in that
1, equipment investment is big, if after consersion unit damage, the cycle of operation affecting process units is longer；
2, complex operation, operating environment is poor, and operator are many；
3, technology controlling and process and unstable product quality.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is in that to provide the production equipment of a kind of PMIDA and production method, and this production method efficiency is higher.
The invention provides the production equipment of a kind of PMIDA, including: duct type preheater, pipeline mixer, pipeline reactor and reactor；Described duct type preheater is connected with pipeline reactor by pipeline mixer；Described pipeline reactor is connected with reactor；Described duct type preheater includes the first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater.
Present invention also offers the production method of a kind of PMIDA, including:
PMIDA is provided to produce equipment, including: duct type preheater, pipeline mixer, pipeline reactor and reactor；Described duct type preheater is connected with pipeline reactor by pipeline mixer；Described pipeline reactor is connected with reactor；Described duct type preheater includes the first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater；
Phosphorous acid, the suspension of iminodiacetic acid, formaldehyde through described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater, are entered pipeline mixer respectively with hydrochloric acid and mixes, sequentially pass through pipeline reactor again and reactor carries out condensation reaction, obtain PMIDA.
Preferably, the suspension of described iminodiacetic acid reactant liquor after iminodiacetic acid water slurry, Iminodiacetate acid suspension, the diethyl acid amide dehydrogenation acidifying and one or more in Iminodiacetonitrile 1,1'-Imidodiacetonitrile basic hydrolysis acidification reaction liquid.
Preferably, the mol ratio of described iminodiacetic acid, phosphorous acid, hydrochloric acid and formaldehyde is 1:(1～1.5): (1～1.45): (1～1.4).
Preferably, the temperature of described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater is each independently 70 DEG C～140 DEG C, and pressure is each independently 0.3～1.5Mpa.
Preferably, the temperature of described pipeline mixer is 70 DEG C～140 DEG C, and pressure is 0.3～1.5Mpa.
Preferably, the temperature of described pipeline reactor is 70 DEG C～140 DEG C, and pressure is 0.3～1.7Mpa.
Preferably, the temperature of described reactor is 100 DEG C～120 DEG C.
Preferably, the time of described condensation reaction is 1～8h.
Preferably, also include crystallization and centrifugation after described condensation reaction, obtain PMIDA.
The invention provides the production equipment of a kind of PMIDA and production method, it is provided that PMIDA produces equipment, including: duct type preheater, pipeline mixer, pipeline reactor and reactor；Described duct type preheater is connected with pipeline reactor by pipeline mixer；Described pipeline reactor is connected with reactor；Described duct type preheater includes the first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater；Phosphorous acid, the suspension of iminodiacetic acid, formaldehyde through described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater, are entered pipeline mixer respectively with hydrochloric acid and mixes, sequentially pass through pipeline reactor again and reactor carries out condensation reaction, obtain PMIDA.Compared with prior art, pipeline reactor and reactor are cascaded by the present invention, by control reaction mass preheated after once enter pipeline mixer, pipeline reactor carries out fast reaction, slow reaction is carried out subsequently into reactor, avoid reaction mass and stop generation side reaction at relatively high temperatures for a long time, and in a kettle., reacting material concentration is relatively low, response speed is slow, in its available pipeline reactor, after reaction, self heat reacts, effectively extend material retention time, improve reaction efficiency.
The results show, PMIDA purity prepared by the present invention is all more than 98%, and yield is all more than 89%.
Detailed description of the invention
The invention provides the production equipment of a kind of PMIDA, including: duct type preheater, pipeline mixer, pipeline reactor and reactor；Described duct type preheater is connected with pipeline reactor by pipeline mixer；Described pipeline reactor is connected with reactor；Described duct type preheater includes the first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater.
According to the present invention, described reactor preferably also receives tank with finished product and is connected；Agitator preferably it is additionally provided with in described reactor.
It is less that PMIDA provided by the invention produces apparatus, the costs such as artificial, equipment, raw material and the energy are saved, improve working environment, Automated condtrol can be realized easily, ensure that the safety in production operability of whole technique and the seriality of production, harmony and stability well, thus ensure that the stability of product quality, improve purity and the yield of product.
Present invention also offers a kind of the said equipment of applying and produce the production method of PMIDA, including:
PMIDA is provided to produce equipment, including: duct type preheater, pipeline mixer, pipeline reactor and reactor；Described duct type preheater is connected with pipeline reactor by pipeline mixer；Described pipeline reactor is connected with reactor；Described duct type preheater includes the first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater；
Phosphorous acid, the suspension of iminodiacetic acid, formaldehyde through described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater, are entered pipeline mixer respectively with hydrochloric acid and mixes, sequentially pass through pipeline reactor again and reactor carries out condensation reaction, obtain PMIDA.
It is same as above identical that described PMIDA produces equipment, does not repeat them here.The restriction that the present invention is not special to the source of all raw materials, for commercially available.
According to the present invention, institute's phosphorous acid is the phosphorous acid that art technology is known, and it can be solid phosphorous acid, liquid phosphorous acid or Phosphorous chloride. hydrolyzed solution, there is no special restriction；Described phosphorous acid preferably employs the phosphorous acid that mass fraction is 50%～60%；The suspension of described iminodiacetic acid is preferably selected from the reactant liquor after iminodiacetic acid water slurry, Iminodiacetate acid suspension, diethyl acid amide dehydrogenation acidifying and one or more in Iminodiacetonitrile 1,1'-Imidodiacetonitrile basic hydrolysis acidification reaction liquid；The mass fraction of the suspension of described iminodiacetic acid is preferably 30%～50%, more preferably 35%～45%；Described formaldehyde is preferably formalin, more preferably mass fraction is the formalin of 20%～40%；Described hydrochloric acid is preferably the hydrochloric acid that mass fraction is 20%～37%.
Phosphorous acid, the suspension of iminodiacetic acid, formaldehyde are entered in pipeline mixer through described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater respectively with hydrochloric acid and mixes.Wherein, the mol ratio of described iminodiacetic acid, phosphorous acid, hydrochloric acid and formaldehyde is preferably 1:(1～1.5): (1～1.45): (1～1.4)；The temperature of described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater is preferably 70 DEG C～140 DEG C independently of one another, more preferably 70 DEG C～110 DEG C, be further preferably 70 DEG C～90 DEG C；Pressure is each independently 0.3～1.5Mpa, more preferably 0.7～1.5Mpa, is further preferably 0.7～1.2Mpa.
After iminodiacetic acid, phosphorous acid, hydrochloric acid and formaldehyde preheat in duct type preheater, then can in pipeline mixer moment mixing, moment reaction, compared with adopting autoclave batch production process with prior art, present invention, avoiding at relatively high temperatures, raw material stops generation side reaction for a long time.Wherein, the temperature of described pipeline mixer is preferably 70 DEG C～140 DEG C, more preferably 100 DEG C～120 DEG C；Described pressure is preferably 0.3～1.5Mpa, more preferably 0.5～1.5Mpa, is further preferably 1.0～1.2Mpa.
In pipeline mixer after mixing, enter reaction in pipeline reactor.The temperature of described pipeline reactor is preferably 70 DEG C～140 DEG C, more preferably 100 DEG C～120 DEG C；Described pressure is preferably 0.3～1.5Mpa, more preferably 0.5～1.5Mpa, is further preferably 1.0～1.2Mpa.
After raw material reacts in pipeline reactor, enter in reactor and proceed condensation reaction.The temperature of described reactor is preferably 100 DEG C～120 DEG C.When reaction raw materials enters the reaction of reactor internal condensation, material concentration is relatively low, and response speed is relatively slow, and the heat of self after reaction can also be utilized in pipeline reactor to react, and effectively extends material retention time；Simultaneously as be additionally provided with agitator in reactor, its reaction carries out under complete mixing flow state, and reaction is more thorough, is that reaction-ure conversion-age is further enhanced, reduces supplies consumption.
According to the present invention, described condensation reaction total time is preferably 1～8, more preferably 2～8h, is further preferably 4～6h.
In order to improve the purity of product, also include crystallization and centrifugation after described condensation reaction, finally obtain PMIDA.
Pipeline reactor and reactor are cascaded by the present invention, by control reaction mass preheated after once enter pipeline mixer, pipeline reactor carries out fast reaction, slow reaction is carried out subsequently into reactor, avoid reaction mass and stop generation side reaction at relatively high temperatures for a long time, and in a kettle., reacting material concentration is relatively low, response speed is slow, in its available pipeline reactor, after reaction, self heat reacts, effectively extend material retention time, improve reaction efficiency.
The present invention is according to production scale, pipeline reactor may be designed as multi-form and specification the pipeline reactor composition in series or in parallel of many groups, reactor is also designed to the reactor composition in series or in parallel of multiple different size, so can meet different production capacity, substantially increase the automaticity of production, and the production of serialization also substantially reduces the original production cycle, improve production capacity and utilization rate of equipment and installations.
The results show, PMIDA purity prepared by the present invention is all more than 98%, and yield is all more than 89%.
In order to further illustrate the present invention, it is described in detail below in conjunction with the embodiment production equipment to a kind of PMIDA provided by the invention and production method.
Reagent used in following example is commercially available.
PMIDA is provided to produce equipment, including: duct type preheater, pipeline mixer, pipeline reactor and reactor；Described duct type preheater is connected with pipeline reactor by pipeline mixer；Described pipeline reactor is connected with reactor；Described duct type preheater includes the first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater.
By the iminodiacetic acid suspension described in table 1, phosphorous acid, hydrochloric acid and formalin are respectively through delivery pump, effusion meter is to duct type preheater, with pipeline mixer carries out preheat and mix, its flow-control, preheating temperature and pressure is in Table 2, pipeline mixer material out continuously enters pipeline reactor, pipeline reactor material out enters and continues reaction in reactor, the temperature and pressure of pipeline reactor and reactor controls in Table 3, material is transferred to crystallisation by cooling still after reacting 3～5h in reactor, it is cooled to less than 10 DEG C, centrifugal, dry, the product appearance obtained, content and yield are in Table 4.
The parameter of each raw material used by table 1
The various process parameters of raw material described in table 2
The each technical parameter of table 3
Table 4 PMIDA and yield
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. the production method of a PMIDA, it is characterised in that including:
PMIDA is provided to produce equipment, including: duct type preheater, pipeline mixer, pipeline reactor and reactor；Described duct type preheater is connected with pipeline reactor by pipeline mixer；Described pipeline reactor is connected with reactor；Described duct type preheater includes the first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater；
Phosphorous acid, the suspension of iminodiacetic acid, formaldehyde through described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater, are entered pipeline mixer respectively with hydrochloric acid and mixes, sequentially pass through pipeline reactor again and reactor carries out condensation reaction, obtain PMIDA.
2. production method according to claim 1, it is characterized in that, the suspension of described iminodiacetic acid reactant liquor after iminodiacetic acid water slurry, Iminodiacetate acid suspension, the diethyl acid amide dehydrogenation acidifying and one or more in Iminodiacetonitrile 1,1'-Imidodiacetonitrile basic hydrolysis acidification reaction liquid.
3. production method according to claim 1, it is characterised in that the mol ratio of described iminodiacetic acid, phosphorous acid, hydrochloric acid and formaldehyde is 1:(1～1.5): (1～1.45): (1～1.4).
4. production method according to claim 1, it is characterized in that, the temperature of described first duct type preheater, second pipe formula preheater, the 3rd duct type preheater and the 4th duct type preheater is each independently 70 DEG C～140 DEG C, and pressure is each independently 0.3～1.5Mpa.
5. production method according to claim 1, it is characterised in that the temperature of described pipeline mixer is 70 DEG C～140 DEG C, and pressure is 0.3～1.5Mpa.
6. production method according to claim 1, it is characterised in that the temperature of described pipeline reactor is 70 DEG C～140 DEG C, and pressure is 0.3～1.7Mpa.
7. production method according to claim 1, it is characterised in that the temperature of described reactor is 100 DEG C～120 DEG C.
8. production method according to claim 1, it is characterised in that the time of described condensation reaction is 1～8h.
9. production method according to claim 1, it is characterised in that also include crystallization and centrifugation after described condensation reaction, obtain PMIDA.
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| CN201310681943.0A CN103613616B (en) | 2013-12-12 | 2013-12-12 | The production equipment of a kind of PMIDA and production method |
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| CN103613616B true CN103613616B (en) | 2016-06-29 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514170A (en) * | 2009-04-03 | 2009-08-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinonitrile |
| CN101747369A (en) * | 2010-01-05 | 2010-06-23 | 淄博万昌科技股份有限公司 | Environmental-friendly new method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514170A (en) * | 2009-04-03 | 2009-08-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinonitrile |
| CN101747369A (en) * | 2010-01-05 | 2010-06-23 | 淄博万昌科技股份有限公司 | Environmental-friendly new method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid |
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