CN104844432A - Process method and device for producing glycine-method glyphosate raw material by using formaldehyde solution as raw material - Google Patents
Process method and device for producing glycine-method glyphosate raw material by using formaldehyde solution as raw material Download PDFInfo
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- CN104844432A CN104844432A CN201510291250.XA CN201510291250A CN104844432A CN 104844432 A CN104844432 A CN 104844432A CN 201510291250 A CN201510291250 A CN 201510291250A CN 104844432 A CN104844432 A CN 104844432A
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
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Abstract
The invention discloses a process method and a device for producing a glycine-method glyphosate raw material by using formaldehyde solution as a raw material. The process method comprises the following steps: by using cheap 37-50% formaldehyde solution as a basic raw material, transforming the formaldehyde solution into a water-insoluble organic phase with an adjuvant, reducing the organic phase into a formaldehyde gas by dehydrating and then depolymerising, thereby obtaining the methanol solution of formaldehyde in a raw material device through rectification and methanol absorption, and compounding with glycine to obtain a reaction raw material, and producing glyphosate by a glycine method. According to the process method and the device disclosed by the invention, the problems of long depolymerization time of paraformaldehyde, large floor area of equipment, high cost of the raw material, and the like are overcome; relative to common formaldehyde solution, the yield is higher, the wastewater treatment amount is low, and the energy consumption is low.
Description
Technical field
The invention belongs to derived energy chemical technical field, particularly relate to production equipment and the processing method of glyphosate.
Background technology
Glyphosate, chemical name is N-((phosphonomethyl)) glycine, is current widely used a kind of weedicide.Since eighties of last century 70 mid-nineties 90 commercialization, due to the herbicidal performance of its brilliance, range of application constantly expands.
The method bibliographical information of synthesizing glyphosate has multiple, as iminodiacetic acid (salt) acid system, phosphonous acid dialkyl group ester process, chloromethyl phosphonic acid method, phosphorous test etc., but really realizes industrialized method mainly iminodiacetic acid (salt) acid system and dialkyl phosphite method at present.
Glycine method adopts paraformaldehyde as raw material, but paraformaldehyde itself is without chemically reactive, mainly utilize paraformaldehyde depolymerization city monomer formaldehyde could be used for reaction, with paraformaldehyde do raw material mainly paraformaldehyde be pressed powder, be convenient to storage and transport, do not adopt formaldehyde solution too high as moisture content in raw material mainly formaldehyde solution, unfavorable to reaction, and wastewater treatment capacity in system can be caused to increase, and energy expenditure is high.
Therefore be prepared by raw material with paraformaldehyde, mainly there is following problem: 1) the formaldehyde depolymerization time is long, the depolymerization of paraformaldehyde needs 2 ~ 3 days aborning; 2) due to the needs of formaldehyde depolymerization, the mode that formaldehyde depolymerization adopts multi-stage stirred tank to connect usually, floor space is large, and facility investment is large, and power consumption is large; 3) paraformaldehyde is raw material, and the price of paraformaldehyde is high relative to formaldehyde solution, and raw materials cost is high.
Summary of the invention
Goal of the invention: for above-mentioned existing Problems existing and deficiency, the object of this invention is to provide processing method and device that a kind of formaldehyde solution is raw material production glyphosate by using glycine raw material, formaldehyde solution with more cheap 37 ~ 50% is basic raw material, and the depolymerization time overcoming paraformaldehyde is long, the problems such as occupation area of equipment is large, raw materials cost is high; Relative to general formaldehyde solution, have higher yield, and wastewater treatment capacity is little, ability consumes low.
Technical scheme: in order to solve the problems of the technologies described above, the present invention by the following technical solutions: a kind of formaldehyde solution is the processing method of raw material production glyphosate by using glycine raw material, and it comprises the following steps:
(1) the depickling process of formaldehyde solution, carries out depickling with filling gel or macroporous weakly basic anion exchange resin PARA FORMALDEHYDE PRILLS(91,95) solution, to make in formaldehyde solution acid content at below 10ppm, and is preheated to 60 ~ 100 DEG C;
(2) Reaction Separation of formaldehyde solution, by the formaldehyde solution after waste heat and the abundant hybrid reaction of auxiliary, obtains water-fast organic phase, and through leaving standstill, obtains the organic phase on upper strata; Described auxiliary to be carbonatoms be 8 ~ 11 saturated alcohol monohydroxy-alcohol, dibasic alcohol, ether or phenol, and preferred one or more mixture in diisopropyl ether, dimethyl formamide, ethylene glycol, isopropylcarbinol, 4-methyl-2-amylalcohol or hexalin;
(3) organic phase is sent in dehydration tower, under negative-pressure vacuum condition, remove moisture further from dehydration column overhead, and bottom dehydration tower, obtain the organic phase after dewatering;
(4) organic phase after dehydration is sent in raw material device, at 140 ~ 200 DEG C, there is depolymerization obtain formaldehyde gas and auxiliary liquid, the methanol solution that carrying out with methyl alcohol in formaldehyde gas uphill process refluxes absorbs and obtain formaldehyde as the raw material of glycine legal system glyphosate; Meanwhile, resolve separation to obtain auxiliary and be recycled in step (2) and recycle;
(5) methanol solution of the formaldehyde obtained with step (4) and glycine, for raw material, under triethylamine is catalytic condition, are obtained by reacting the triethylamine salt of hydroxymethylglycinate; Obtain the triethylamine salt of glyphosphonic acid dialkyl again with dialkyl phosphite through condensation reaction, eventually pass hydrochloric acid hydrolysis and obtain glyphosate.
When in step (1), formaldehyde solution carries out depickling, reaction velocity is 1 ~ 5h
-1, enter the speed of deacidifying device according to 0.001 ~ 0.2m/s.
In step (2), the temperature of reaction of formaldehyde solution and auxiliary is 80 ~ 100 DEG C, and reaction time is 1 ~ 5h.
Step (3) dehydration tower working pressure is 20 ~ 100KPa, and temperature is 60 ~ 100 DEG C.
Step (4) formaldehyde gas is 40 ~ 80 DEG C by temperature during methanol absorption.
Present invention also offers a kind of process unit of the production glyphosate by using glycine raw material based on above-mentioned processing method, comprise formaldehyde deacidifying device, preheater, reaction unit, dehydration tower and reactive distillation column, described formaldehyde deacidifying device is provided with formaldehyde solution entrance, and be connected with preheater and reaction unit successively, described reaction unit is provided with auxiliary entrance, and top is connected with dehydration tower entrance by pipeline; The top of described dehydration tower is provided with the outlet of rare formaldehyde, and bottom is connected with reactive distillation column by pipeline.
Further improvement, described reactive distillation column comprises the stripping section of bottom and the absorber portion on top, and absorber portion is also provided with methyl alcohol spray inlet.
As preferably, described reaction unit is the storage tank that stirs of band or tower.
Beneficial effect: compared with prior art, the present invention to overcome depolymerization time of paraformaldehyde long, the problems such as occupation area of equipment is large, raw materials cost is high; Relative to general formaldehyde solution, have higher yield, and wastewater treatment capacity is little, energy expenditure is low.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of producing glyphosate by using glycine of the present invention.
Wherein, deacidifying device 1, preheater 2, reaction unit 3, dehydration tower 4, reactive distillation column 5.
Embodiment
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
Of the present invention take formaldehyde solution as the process unit of raw material production glyphosate by using glycine raw material, comprise formaldehyde deacidifying device, preheater, reaction unit, dehydration tower and reactive distillation column, described formaldehyde deacidifying device is provided with formaldehyde solution entrance, and be connected with preheater and reaction unit successively, described reaction unit is provided with auxiliary entrance, and top is connected with dehydration tower entrance by pipeline; The top of described dehydration tower is provided with the outlet of rare formaldehyde, and bottom is connected with reactive distillation column by pipeline.Concrete technology method is as follows:
37 ~ 50% formaldehyde solutions market bought or produces, carry out depickling process through the fixed-bed reactor of filling sorbent material, after depickling process, solution acid content is 1 ~ 10ppm; Sorbent material is mainly silica gel or macropore weak basic anion exchange resin etc., controls reaction velocity 1 ~ 5h
-1, enter the speed of deacidifying device according to 0.001 ~ 0.2m/s.Concrete structure is fixed-bed reactor, filling gel or macropore weak basic anion exchange resin etc. in reactor, and weighting agent adopts water cap as grid, in case stopping leak dew.
Formaldehyde solution after depickling process is by after being preheating to 60 ~ 100 DEG C, enter reaction unit and auxiliary etc. again and carry out abundant hybrid reaction, reacted component due to density ratio water little, after leaving standstill, reaction unit upper strata light liquid is through Liquid transfer to dehydration tower, and due to the thermolysis effect of reaction product, dehydration tower controls vacuum operating, moisture is deviate from by dewatering unit top, is sent in reactive distillation column bottom dewatering unit by liquid organic phase e Foerderanlage.Reaction unit can be the storage tank of the band whipping appts of plural serial stage, also can be tower, and tower must ensure that top is with relatively large liquid phase separation space.For preventing carrying oxymethylene polymerization blocking secretly in dehydration overhead water, be rectifying bottom dehydration tower, top is for absorbing; Water is that light constituent directly enters absorber portion by rectifying section top, and absorber portion can adopt the rare formaldehyde solution bottom reaction unit.Auxiliary can be the monohydroxy-alcohol of 8 to 11 for carbonatoms, dibasic alcohol, (auxiliary of 8 to 11 carbon atoms can be polymerized with formaldehyde and obtains transient intermediate phenols, be insoluble in water, and there is depolymerization reduction at about 160 DEG C, carbonatoms is too high makes the too high balance affecting depolymerization reaction of de-polymerization temperature), it can be preferably diisopropyl ether, dimethyl formamide, ethylene glycol, isopropylcarbinol, one or more mixture in 4-methyl-2-amylalcohol or hexalin, wherein especially with diisopropyl ether and ethylene glycol, thus make the depolymerization time at 140 ~ 200 degrees Celsius, depolymerization is more thorough, yield is higher.Alkylphenol is may also be through overtesting.
Reaction unit is mainly reactive distillation column, the region residence time long Reaction Separation being beneficial to formaldehyde and auxiliary system of major control tower reactor section 140 ~ 200 DEG C, thus formaldehyde can depart from by reaction system, and the transformation efficiency that formaldehyde departs from is high, because the formaldehyde gas detached 100 ~ 120 DEG C time is easily polymerized in tower, therefore adopt methanol eddy to absorb formaldehyde, thus top obtains the methanol solution of formaldehyde, as the raw material of glyphosate by using glycine, thus the depolymehzation process of paraformaldehyde can be avoided.Then with the methanol solution of formaldehyde and glycine for raw material, and prepare the methanol solvate of reaction two, under triethylamine is catalytic condition, be obtained by reacting the triethylamine salt of hydroxymethylglycinate; Obtain the triethylamine salt of glyphosphonic acid dialkyl again with dialkyl phosphite through condensation reaction, eventually pass hydrochloric acid hydrolysis and obtain glyphosate.The technique of follow-up preparing glyphosate by glycin method is prior art.
Above production method mainly includes deacidifying device, reaction unit, dewatering unit, reactive distillation column.In major control index charging formaldehyde, acid content can not more than 1000ppm, reaction controlling temperature of reaction 80 ~ 100 DEG C, reaction time 1 ~ 5h, dehydration tower red-tape operati pressure 20 ~ 100KPa (A), service temperature controls 60 ~ 100 DEG C, raw material tower controls pressure-fired, and tower top service temperature controls 40 ~ 80 DEG C.
Claims (9)
1. formaldehyde solution is a processing method for raw material production glyphosate by using glycine raw material, and it comprises the following steps:
(1) the depickling process of formaldehyde solution, carries out depickling with filling gel or macroporous weakly basic anion exchange resin PARA FORMALDEHYDE PRILLS(91,95) solution, to make in formaldehyde solution acid content at below 10ppm, and is preheated to 60 ~ 100 DEG C;
(2) Reaction Separation of formaldehyde solution, by the formaldehyde solution after waste heat and the abundant hybrid reaction of auxiliary, obtains water-fast organic phase, and through leaving standstill, obtains the organic phase on upper strata; Described auxiliary is monohydroxy-alcohol, dibasic alcohol or phenols;
(3) organic phase is sent in dehydration tower, under negative-pressure vacuum condition, remove moisture further from dehydration column overhead, and bottom dehydration tower, obtain the organic phase after dewatering;
(4) organic phase after dehydration is sent in raw material device, at 140 ~ 200 DEG C, there is depolymerization obtain formaldehyde gas and auxiliary liquid, the methanol solution that carrying out with methyl alcohol in formaldehyde gas uphill process refluxes absorbs and obtain formaldehyde as the raw material of glycine legal system glyphosate; Meanwhile, resolve separation to obtain auxiliary and be recycled in step (2) and recycle;
(5) methanol solution of the formaldehyde obtained with step (4) and glycine, for raw material, under triethylamine is catalytic condition, are obtained by reacting the triethylamine salt of hydroxymethylglycinate; Obtain the triethylamine salt of glyphosphonic acid dialkyl again with dialkyl phosphite through condensation reaction, eventually pass hydrochloric acid hydrolysis and obtain glyphosate.
2. processing method according to claim 1, is characterized in that: when in step (1), formaldehyde solution carries out depickling, reaction velocity is 1 ~ 5h
-1, enter the speed of deacidifying device according to 0.001 ~ 0.2m/s.
3. processing method according to claim 1, is characterized in that: in step (2), the temperature of reaction of formaldehyde solution and auxiliary is 80 ~ 100 DEG C, and reaction time is 1 ~ 5h.
4. processing method according to claim 1, is characterized in that: described auxiliary is one or more mixture in diisopropyl ether, dimethyl formamide, ethylene glycol, isopropylcarbinol, 4-methyl-2-amylalcohol or hexalin.
5. processing method according to claim 1, it is characterized in that: step (3) dehydration tower working pressure is 20 ~ 100KPa, temperature is 60 ~ 100 DEG C.
6. processing method according to claim 1, is characterized in that: step (4) formaldehyde gas is 40 ~ 80 DEG C by temperature during methanol absorption.
7. one kind will be removed the process unit of the production glyphosate by using glycine raw material of 1 ~ 6 arbitrary described processing method based on right, it is characterized in that: comprise formaldehyde deacidifying device, preheater, reaction unit, dehydration tower and reactive distillation column, described formaldehyde deacidifying device is provided with formaldehyde solution entrance, and be connected with preheater and reaction unit successively, described reaction unit is provided with auxiliary entrance, and top is connected with dehydration tower entrance by pipeline; The top of described dehydration tower is provided with the outlet of rare formaldehyde, and bottom is connected with reactive distillation column by pipeline.
8. process unit according to claim 7, is characterized in that: described reactive distillation column comprises the stripping section of bottom and the absorber portion on top, and absorber portion is also provided with methyl alcohol spray inlet.
9. process unit according to claim 8, is characterized in that: described reaction unit is the storage tank that stirs of band or tower.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510291250.XA CN104844432A (en) | 2015-06-01 | 2015-06-01 | Process method and device for producing glycine-method glyphosate raw material by using formaldehyde solution as raw material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510291250.XA CN104844432A (en) | 2015-06-01 | 2015-06-01 | Process method and device for producing glycine-method glyphosate raw material by using formaldehyde solution as raw material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631735A (en) * | 2016-12-03 | 2017-05-10 | 宜都市多邦化工有限公司 | Polyformaldehyde redepolymerization system and method, and application thereof |
| CN107337600A (en) * | 2017-07-04 | 2017-11-10 | 湖北三里枫香科技有限公司 | A kind of method and process unit of methanol and methyl acetate production methyl methacrylate |
| CN110860194A (en) * | 2018-08-27 | 2020-03-06 | 湖北泰盛化工有限公司 | Device and method for treating paraformaldehyde dust in glyphosate production feeding process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3423368A (en) * | 1965-10-14 | 1969-01-21 | Hary E Cier | Extractive recovery of formaldehyde |
| CN1340507A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN103339095A (en) * | 2010-12-03 | 2013-10-02 | 阿勒根公司 | Alkyne and alkene derivatives as sphingosine 1-phosphate-1 receptor modulators |
-
2015
- 2015-06-01 CN CN201510291250.XA patent/CN104844432A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3423368A (en) * | 1965-10-14 | 1969-01-21 | Hary E Cier | Extractive recovery of formaldehyde |
| CN1340507A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN103339095A (en) * | 2010-12-03 | 2013-10-02 | 阿勒根公司 | Alkyne and alkene derivatives as sphingosine 1-phosphate-1 receptor modulators |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631735A (en) * | 2016-12-03 | 2017-05-10 | 宜都市多邦化工有限公司 | Polyformaldehyde redepolymerization system and method, and application thereof |
| CN106631735B (en) * | 2016-12-03 | 2023-10-20 | 湖北泰盛化工有限公司 | System for depolymerizing paraformaldehyde and method and application thereof |
| CN107337600A (en) * | 2017-07-04 | 2017-11-10 | 湖北三里枫香科技有限公司 | A kind of method and process unit of methanol and methyl acetate production methyl methacrylate |
| CN110860194A (en) * | 2018-08-27 | 2020-03-06 | 湖北泰盛化工有限公司 | Device and method for treating paraformaldehyde dust in glyphosate production feeding process |
| CN110860194B (en) * | 2018-08-27 | 2021-09-07 | 湖北泰盛化工有限公司 | Device and method for treating paraformaldehyde dust in glyphosate production feeding process |
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