CN105820187B - A kind of preparation method of glyphosate - Google Patents
A kind of preparation method of glyphosate Download PDFInfo
- Publication number
- CN105820187B CN105820187B CN201610316285.9A CN201610316285A CN105820187B CN 105820187 B CN105820187 B CN 105820187B CN 201610316285 A CN201610316285 A CN 201610316285A CN 105820187 B CN105820187 B CN 105820187B
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- titanium dioxide
- preparation
- pmida
- reaction
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Abstract
The present invention relates to a kind of preparation methods of glyphosate, belong to chemical technology field, specifically include the synthesis of iminodiacetic acid, the preparation of pmida, the preparation of glyphosate and are separated by solid-liquid separation four steps.First carried noble metal is silver-colored on the titanium dioxide by the present invention, influences the surface nature of titanium dioxide, changes electronics distribution, improve catalytic activity, then the titanium dioxide of load silver is loaded in activated carbon again, using ultraviolet source irradiation, substantially increases the selectivity of glyphosate, shorten the process of pmida oxidation, the yield of glyphosate is increased to 96.3%, and product purity can reach 97.6%, and the content of formaldehyde is low, the generation for reducing by-product meets the requirement of Environmental close friend.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of preparation method of glyphosate.
Background technology
Glyphosate is steriland herbicide after a kind of bud of high-efficiency low-toxicity, is the maximum product of current domestic herbicide yield
Kind.The mechanisms of glyphosate are by uptake and translocation effect by weeds killer, thus nontoxic to humans and animals.Separately
Outside, be easily degraded by microorganisms after glyphosate buries, will not contaminated soil and underground water, therefore glyphosate be it is a kind of efficiently, wide spectrum,
Less toxic and environmental-friendly steriland herbicide.Based on the above many merits, glyphosate is just widely popularized once coming out
Using the especially large area plantation of genetically modified crops, more so that demand of the whole world to glyphosate constantly increases.
There are mainly two types of the industrialized preparing process of glyphosate is current：When glycine method, second is that iminodiacetic acid
(IDA) method.The basic process of glycine route is first the then glycine with the Material synthesis glycine such as monoxone or hydrogen cyanide
Again synthesizing glyphosate is reacted with other raw materials.Iminodiacetic acid route is first to synthesize IDA, then IDA and formaldehyde, phosphorous acid
Reactions such as (or replacing phosphorous acid with phosphorus trichloride) generate pmida, and pmida is oxidized again to obtain glyphosate.Currently, glycine
Method is the domestic mainstream way for preparing glyphosate, but glycine method is somebody's turn to do using glycine as the reacted obtained glyphosate of raw material
Process equipment is more complex, and energy consumption is also high, and by-product and mother liquor are more intractable.IDA method preparation methods, raw material is easy to get, is easy to operate,
Process conditions mitigate, not high to equipment requirement, product yield is high, good in economic efficiency, are suitble to China's actual conditions and domestic market demand.
Invention content
The purpose of the present invention is to provide a kind of quick oxidation pmida and high income, product purity it is high glyphosate preparation
Method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of glyphosate, specifically includes following steps：
(1) synthesis of iminodiacetic acid：Under the effect of the catalyst by hydrogen cyanide, formaldehyde and four ammonium of hexa-methylene, instead
It is 30~50 DEG C to answer 5~12h, temperature, and iminodiacetonitrile is made, and Asia then is made through hydrolyzing and being acidified in iminodiacetonitrile
Aminodiacetic acid；
(2) preparation of pmida：By iminodiacetic acid, formaldehyde and phosphorus trichloride under the conditions of 35~55 DEG C, reaction 0.5
Pmida is made in~3h；
(3) preparation of glyphosate：Pmida prepared by step (2) is added in reaction kettle, and oxygen stream is led into reaction kettle,
And absorbent charcoal loading titanium dioxide catalyst and water is added, setting visible light source irradiates in reaction kettle, is gradually heated up reaction kettle extremely
It 80 DEG C, stirs, reaction pressure is 0.2~0.4MPa in kettle；
Wherein, the mass ratio of pmida, absorbent charcoal loading titanium dioxide catalyst and water is (25~30)：(1.2~
2.7)：(60~100)；In absorbent charcoal loading titanium dioxide catalyst, silver metal, titanium dioxide and silver gold are loaded on titanium dioxide
The weight ratio of category is (10~30)：(1~0.05)；
(4) it is separated by solid-liquid separation：Step (3) after reaction, is separated by solid-liquid separation, obtains the filter cake containing glyphosate crystals and mother liquor,
Filter cake is placed in glyphosate saturated solution and is reheated, glyphosate solution is isolated, is finally obtained through supercooling, recrystallization careless sweet
Phosphine finished product.
Further, the preparation method of load silver metal is on titanium dioxide：First by titanium dioxide at 300~360 DEG C
Under the conditions of calcine 10~15h, then titanium dioxide after silver nitrate, water and calcining is added in quartz reactor, stirring 2~
3h, finally by washing, filtering and drying.
Preferably, catalyst described in step (1) is oxygen or air.
Preferably, the reaction time of step (3) is 2~5h.
Preferably, the flow of oxygen stream is 1.2~2.3L/min in step (3).
Preferably, the specific surface area of original activity charcoal is 1000~1400m2/g。
The beneficial effects of the invention are as follows：
First carried noble metal is silver-colored on the titanium dioxide by the present invention, influences the surface nature of titanium dioxide, changes electronics distribution,
Improve catalytic activity, then the titanium dioxide of load silver is loaded in activated carbon again, using ultraviolet source irradiation, is greatly improved
The selectivity of glyphosate shortens the process of pmida oxidation, and the yield of glyphosate is increased to 94.3% or more, product purity
95.6% or more is can reach, and the content of formaldehyde is low, reduce the generation of by-product, meets wanting for Environmental close friend
It asks.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of preparation method of glyphosate, includes the following steps：
(1) synthesis of iminodiacetic acid：By hydrogen cyanide, formaldehyde and four ammonium of hexa-methylene under the action of oxygen, reaction
10h, temperature are 40 DEG C, iminodiacetonitrile are made, then by iminodiacetonitrile through hydrolyzing and being acidified obtained iminodiacetic acid (salt)
Acid；
(2) preparation of pmida：By iminodiacetic acid, formaldehyde and phosphorus trichloride under the conditions of 50 DEG C, 2h is reacted, is made
Pmida；
(3) preparation of glyphosate：Pmida prepared by step (2) is added in reaction kettle, and oxygen stream is led into reaction kettle,
Flow is 2L/min, and absorbent charcoal loading titanium dioxide catalyst and water is added, and setting visible light source irradiates in reaction kettle, gradually
Reaction kettle is heated to 80 DEG C, is stirred, reaction pressure is 0.2~0.4MPa in kettle, reacts 3h；
Wherein, the specific surface area of original activity charcoal is 1000~1100m2/g；Pmida, absorbent charcoal loading titanium dioxide are urged
The mass ratio of agent and water is 25：1.5：80；In absorbent charcoal loading titanium dioxide catalyst, silver metal is loaded on titanium dioxide,
The weight ratio of titanium dioxide and silver metal is 20：0.2；The preparation method of load silver metal is on titanium dioxide：First by dioxy
Change titanium and calcine 12h under the conditions of 320 DEG C, then the titanium dioxide after silver nitrate, water and calcining is added in quartz reactor, stirs
2~3h is mixed, finally by washing, filtering and drying.
(4) it is separated by solid-liquid separation：Step (3) after reaction, is separated by solid-liquid separation, obtains the filter cake containing glyphosate crystals and mother liquor,
Filter cake is placed in glyphosate saturated solution and is reheated, glyphosate solution is isolated, is finally obtained through supercooling, recrystallization careless sweet
Phosphine finished product.
It can be obtained through overtesting, the yield of glyphosate is 94.3%, and product purity can reach 97.6%.
Embodiment 2
A kind of preparation method of glyphosate, includes the following steps：
(1) synthesis of iminodiacetic acid：By hydrogen cyanide, formaldehyde and four ammonium of hexa-methylene under the action of oxygen, reaction
12h, temperature are 45 DEG C, iminodiacetonitrile are made, then by iminodiacetonitrile through hydrolyzing and being acidified obtained iminodiacetic acid (salt)
Acid；
(2) preparation of pmida：By iminodiacetic acid, formaldehyde and phosphorus trichloride under the conditions of 55 DEG C, 3h is reacted, is made
Pmida；
(3) preparation of glyphosate：Pmida prepared by step (2) is added in reaction kettle, and oxygen stream is led into reaction kettle,
Flow is 1.8L/min, and absorbent charcoal loading titanium dioxide catalyst and water is added, and setting visible light source irradiates in reaction kettle, by
Gradually heating reaction kettle is to 80 DEG C, stirring, and reaction pressure is 0.2~0.4MPa in kettle, reacts 3h；
Wherein, the specific surface area of original activity charcoal is 1200~1300m2/g；Pmida, absorbent charcoal loading titanium dioxide are urged
The mass ratio of agent and water is 30：2：:75；In absorbent charcoal loading titanium dioxide catalyst, silver metal is loaded on titanium dioxide, two
The weight ratio of titanium oxide and silver metal is 15：0.5；The preparation method of load silver metal is on titanium dioxide：First by titanium dioxide
Titanium calcines 15h under the conditions of 360 DEG C, and then the titanium dioxide after silver nitrate, water and calcining is added in quartz reactor, stirring
3h, finally by washing, filtering and drying.
(4) it is separated by solid-liquid separation：Step (3) after reaction, is separated by solid-liquid separation, obtains the filter cake containing glyphosate crystals and mother liquor,
Filter cake is placed in glyphosate saturated solution and is reheated, glyphosate solution is isolated, is finally obtained through supercooling, recrystallization careless sweet
Phosphine finished product.
It can be obtained through overtesting, the yield of glyphosate is 96.3%, and product purity can reach 98.6%.
Embodiment 3
A kind of preparation method of glyphosate, includes the following steps：
(1) synthesis of iminodiacetic acid：By hydrogen cyanide, formaldehyde and four ammonium of hexa-methylene under the action of air, reaction
8h, temperature are 50 DEG C, iminodiacetonitrile are made, then by iminodiacetonitrile through hydrolyzing and being acidified obtained iminodiacetic acid (salt)
Acid；
(2) preparation of pmida：By iminodiacetic acid, formaldehyde and phosphorus trichloride under the conditions of 45 DEG C, 2h is reacted, is made
Pmida；
(3) preparation of glyphosate：Pmida prepared by step (2) is added in reaction kettle, and oxygen stream is led into reaction kettle,
Flow is 2.3L/min, and absorbent charcoal loading titanium dioxide catalyst and water is added, and setting visible light source irradiates in reaction kettle, by
Gradually heating reaction kettle is to 80 DEG C, stirring, and reaction pressure is 0.2~0.4MPa in kettle, reacts 4h；
Wherein, the specific surface area of original activity charcoal is 1300~1400m2/g；Pmida, absorbent charcoal loading titanium dioxide are urged
The mass ratio of agent and water is 28：2.5：100；In absorbent charcoal loading titanium dioxide catalyst, silver metal is loaded on titanium dioxide,
The weight ratio of titanium dioxide and silver metal is 28：0.08；The preparation method of load silver metal is on titanium dioxide：First by dioxy
Change titanium and calcine 13h under the conditions of 350 DEG C, then the titanium dioxide after silver nitrate, water and calcining is added in quartz reactor, stirs
3h is mixed, finally by washing, filtering and drying.
(4) it is separated by solid-liquid separation：Step (3) after reaction, is separated by solid-liquid separation, obtains the filter cake containing glyphosate crystals and mother liquor,
Filter cake is placed in glyphosate saturated solution and is reheated, glyphosate solution is isolated, is finally obtained through supercooling, recrystallization careless sweet
Phosphine finished product.
It can be obtained through overtesting, the yield of glyphosate is 95.8%, and product purity can reach 97.9%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (6)
1. a kind of preparation method of glyphosate, which is characterized in that specifically include following steps：
(1) synthesis of iminodiacetic acid：Under the effect of the catalyst by hydrogen cyanide, formaldehyde and hexa, reaction 5~
12h, temperature are 30~50 DEG C, iminodiacetonitrile are made, then by iminodiacetonitrile through hydrolyzing and being acidified obtained imino group
Oxalic acid；
(2) preparation of pmida：By iminodiacetic acid, formaldehyde and phosphorus trichloride under the conditions of 35~55 DEG C, reaction 0.5~
Pmida is made in 3h；
(3) preparation of glyphosate：Pmida prepared by step (2) is added in reaction kettle, oxygen stream is led into reaction kettle, and add
Enter absorbent charcoal loading titanium dioxide catalyst and water, ultraviolet source irradiation be set in reaction kettle, is gradually heated up reaction kettle to 80 DEG C,
It stirs, reaction pressure is 0.2~0.4MPa in kettle；
Wherein, the mass ratio of pmida, absorbent charcoal loading titanium dioxide catalyst and water is (25~30)：(1.2~2.7)：(60
~100)；In absorbent charcoal loading titanium dioxide catalyst, silver metal, the weight of titanium dioxide and silver metal are loaded on titanium dioxide
Than for (10~30)：(1~0.05)；
(4) it is separated by solid-liquid separation：Step (3) after reaction, is separated by solid-liquid separation, obtains the filter cake containing glyphosate crystals and mother liquor, will filter
Cake is placed in glyphosate saturated solution and reheats, and isolates glyphosate solution, finally through supercooling, recrystallization obtain glyphosate at
Product.
2. a kind of preparation method of glyphosate according to claim 1, which is characterized in that load silver metal on titanium dioxide
Preparation method be：Titanium dioxide is calcined to 10~15h under the conditions of 300~360 DEG C first, then by silver nitrate, water and is forged
In titanium dioxide addition quartz reactor after burning, 2~3h is stirred, finally by washing, filtering and drying.
3. a kind of preparation method of glyphosate according to claim 1, which is characterized in that catalyst described in step (1)
For oxygen or air.
4. a kind of preparation method of glyphosate according to claim 1, which is characterized in that the reaction time of step (3) is 2
~5h.
5. a kind of preparation method of glyphosate according to claim 1, which is characterized in that the stream of oxygen stream in step (3)
Amount is 1.2~2.3L/min.
6. a kind of preparation method of glyphosate according to claim 1, which is characterized in that the specific surface area of original activity charcoal
For 1000~1400m2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610316285.9A CN105820187B (en) | 2016-05-11 | 2016-05-11 | A kind of preparation method of glyphosate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610316285.9A CN105820187B (en) | 2016-05-11 | 2016-05-11 | A kind of preparation method of glyphosate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105820187A CN105820187A (en) | 2016-08-03 |
| CN105820187B true CN105820187B (en) | 2018-09-14 |
Family
ID=56529429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610316285.9A Active CN105820187B (en) | 2016-05-11 | 2016-05-11 | A kind of preparation method of glyphosate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105820187B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522738A (en) * | 2017-07-13 | 2017-12-29 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate |
| CN110200023A (en) * | 2019-06-05 | 2019-09-06 | 广西天浩农业发展有限公司 | A kind of sugar-cane herbicide |
| CN110150314A (en) * | 2019-06-05 | 2019-08-23 | 广西天浩农业发展有限公司 | A kind of herbicide |
| CN110756043B (en) * | 2019-10-31 | 2022-04-12 | 江苏清荷材料科技有限公司 | Automobile ceiling capable of purifying VOC in automobile and preparation method thereof |
| CN112473710A (en) * | 2020-11-11 | 2021-03-12 | 陕西浦士达环保科技有限公司 | Activated carbon for synthesizing glyphosate by catalytic oxidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862665A (en) * | 2010-06-24 | 2010-10-20 | 钱仰东 | Preparation of metal carbide on carriers and use of metal carbide as N-(Phosphonomethyl) iminodiacetic acid oxidation catalyst |
| CN102229621A (en) * | 2011-05-07 | 2011-11-02 | 安徽国星生物化学有限公司 | Method for preparing glyphosate by catalyzing and oxidizing glyphosine in the presence of ultraviolet light source |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386627A (en) * | 2008-10-15 | 2009-03-18 | 安徽华星化工股份有限公司 | Process for preparing glyphosate by catalytic oxidation of N-phosphonomethyliminodiacetic acid |
| CN105330688B (en) * | 2015-11-26 | 2017-08-22 | 浙江工业大学 | Utilize the method for visible light catalytic oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid |
-
2016
- 2016-05-11 CN CN201610316285.9A patent/CN105820187B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862665A (en) * | 2010-06-24 | 2010-10-20 | 钱仰东 | Preparation of metal carbide on carriers and use of metal carbide as N-(Phosphonomethyl) iminodiacetic acid oxidation catalyst |
| CN102229621A (en) * | 2011-05-07 | 2011-11-02 | 安徽国星生物化学有限公司 | Method for preparing glyphosate by catalyzing and oxidizing glyphosine in the presence of ultraviolet light source |
Non-Patent Citations (1)
| Title |
|---|
| "草甘膦合成工艺研究进展";陈丹 等;《化工进展》;20130705;第32卷(第7期);第1638页左栏第1.2.2节，第1637页右栏第1.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105820187A (en) | 2016-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105820187B (en) | A kind of preparation method of glyphosate | |
| CN104262393B (en) | Energy-saving clean production method and device of glyphosate | |
| CN101830580B (en) | Method for treating glyphosate mother solution by using oxidization method | |
| CN106348420A (en) | Method for treating glyphosate waste water through wet catalytic oxidation | |
| CN111389450B (en) | Phosphorus-doped carbon nitride material and preparation method and application thereof | |
| CN111333519A (en) | Comprehensive treatment and resource recycling method for glyphosate mother liquor | |
| CN101531676A (en) | Preparation method of N-(phosphonomethyl)iminodiacetic acid | |
| WO2016127890A1 (en) | Glyphosate pesticide active combination and method for preparing same | |
| CN107417368A (en) | A kind of production method of the water soluble fertilizer containing amino acid | |
| CN100417609C (en) | Process for treating wastewater from preparation of N-(phosphonomethyl) iminodiacetic acid as synthetic intermediate of glyphosate | |
| CN102229621B (en) | Method for preparing glyphosate by catalyzing and oxidizing glyphosine in the presence of ultraviolet light source | |
| CN105524107A (en) | New process for clean production of pmida and cyclic utilization of byproducts | |
| CN105330688A (en) | Method for preparing glyphosate by utilizing visible light to catalyze and oxidize phosphonomethyl iminodiacetic acid | |
| CN104326455A (en) | Production method for preparing monopotassium phosphate and by-product special fertilizer for Taxus chinensis | |
| CN100389116C (en) | Method for producing glyphosate monovalent salt using glyphosate bivalent, trivalent salt | |
| CN107163077A (en) | A kind of dimethylphosphite method of purification | |
| CN102068976B (en) | Catalyst for synthesizing glyphosate and method for synthesizing glyphosate by using same | |
| CN108017671A (en) | The method of phosphorous acid glycine synthesizing glyphosate | |
| CN104402535A (en) | Concentrated nitrogen-phosphorous fertilizer and preparation method thereof | |
| CN106747871A (en) | A kind of fertilizer preparation method of chelating amino acids manganese | |
| CN106631846A (en) | Preparation method of N-phosphonomethyl aminodiacetic acid intermediate | |
| CN104310344A (en) | Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for plums as byproduct | |
| CN104326462A (en) | Production method for preparing monocalcium phosphate and by-product special fertilizer for red bean | |
| CN106747869A (en) | A kind of preparation method of fertilizer copper amino acid chelate | |
| CN102286022A (en) | Method for preparing monovalent salt of glyphosate by utilizing bivalent and trivalent salts of glyphosate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of glyphosate Effective date of registration: 20210819 Granted publication date: 20180914 Pledgee: Shucheng Jinlong financing Company limited by guarantee Pledgor: ANHUI YINONG CHEMICAL Co.,Ltd. Registration number: Y2021980007950 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220921 Granted publication date: 20180914 Pledgee: Shucheng Jinlong financing Company limited by guarantee Pledgor: ANHUI YINONG CHEMICAL Co.,Ltd. Registration number: Y2021980007950 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |