CN105217667B - During a kind of phosphine oxamate produces, sodium terachloroaluminate recycles technique - Google Patents
During a kind of phosphine oxamate produces, sodium terachloroaluminate recycles technique Download PDFInfo
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Abstract
The invention discloses sodium terachloroaluminate during a kind of phosphine oxamate produces and recycle technique.The step of this technique is as follows: 1) solution joins precipitation；2) solid filters；3) cooling separates out；4) again with: 5) recycle；6) aluminium polychlorid is prepared.Sodium terachloroaluminate solid waste is turned waste into wealth by the present invention, the aluminum chloride obtained after being joined by its solution recycles, not only solve the problem that sodium terachloroaluminate solid waste processes, reduce the pollution to environment, realize three-waste free discharge, and improve the large-scale production of the Atom economy of reaction, beneficially phosphine oxamate；Solution ingredients used by technique, poor solvent, low price, it is easy to get, whole technological operation is easy, is particularly suitable for industrialized production；The polymerization aluminum chloride prepared further can be widely used as water purification agent, is particularly well-suited to the sewage disposal in chemical plant.
Description
Technical field
The present invention relates to the treatment technology of a kind of solid waste, particularly relate to solid during a kind of phosphine oxamate produces
The process technique of garbage.
Background technology
Phosphine oxamate (Glufosinafe) is efficient, the low toxicity, non-selection developed at first by Hoechest company
Property herbicide, trade name Basta, its molecular formula is: C5H12NO4P, its structure is:
Wherein methylisothiouronium methylphosphite diethylester (Formula II) is the key intermediate producing phosphine oxamate.The most industrial
The route preparing methylisothiouronium methylphosphite diethylester mainly has two: route 1, Hoechest are former grinds patent EP
Disclosing Phosphorous chloride. in 0391329 and chloro diethyl phosphite is prepared in NSC 5284 reaction, chloro is sub-
Diethyl phosphate and the reaction of grignard reagent first class magnesium bromide, prepare methylisothiouronium methylphosphite diethylester, and process route is such as
Shown in lower:
Route 2, patent US3840576 disclose with aluminum chloride, chloromethanes, Phosphorous chloride. as raw material
Preparing coordination compound, coordination compound prepares dichloromethylphosphine (MDP) through decomplexing reduction, then becomes ester with ethanol,
Obtaining methylisothiouronium methylphosphite diethylester, process route is as follows:
Wherein route 1 uses grignard reagent, and grignard reagent is expensive, and production cost is significantly greatly increased, unfavorable
Industrialization in product produces, and needs in addition to expend a large amount of solvent, is unfavorable for energy-saving and emission-reduction；Route 2 uses
The technique that MDP becomes ester, although the shortcoming avoiding route 1, but the production process of MDP can produce big
Amount sodium terachloroaluminate solid waste, owing to sodium terachloroaluminate is soluble in water, directly emits after general dissolving,
On the one hand cause waste greatly, on the other hand will also result in water pollution, the most rationally process solid waste
Thing is phosphine oxamate industrialization problem demanding prompt solution.
Summary of the invention
In order to overcome the defect of prior art, it is an object of the invention to provide tetrachloro aluminum during a kind of phosphine oxamate produces
Acid sodium recycles technique, solves the problem that sodium terachloroaluminate solid waste processes, and reduces the dirt to environment
Dye, it is achieved three-waste free discharge.
For achieving the above object, the present invention takes techniques below scheme:
1) solution joins precipitation: adds in sodium terachloroaluminate and solves ingredients, be heated to 40-120 DEG C, generates three
Aluminum chloride and sodium chloride, aluminum chloride is dissolved in solution ingredients, and sodium chloride separates out；
2) solid filters: by step 1) mixed solution that obtains filters while hot, removes solid sodium chloride,
Obtain aluminum trichloride solution；
3) cooling separates out: aluminum trichloride solution is down to room temperature, filters, dry, and obtains white aluminum chloride
Solid, the aluminum chloride obtained meets material condition；
4) again with: by step 3) aluminum chloride that obtains as the raw material of phosphine oxamate, with chloromethanes,
Phosphorous chloride. reaction prepares coordination compound, and coordination compound prepares dichloromethylphosphine, then and ethanol through decomplexing reduction
Become ester, again obtain sodium terachloroaluminate solid:
5) recycle: repeat the above steps 1)-4), after repeatedly circulation, aluminum chloride and chloromethanes,
The complexing power of Phosphorous chloride. declines, and reaction titer reduces, and is carried out at next step by the aluminum chloride of this batch
Reason；
6) aluminium polychlorid is prepared: to step 5) aluminum chloride of gained adds sodium hydroxide solution, instead
Answer temperature to control between 20-100 DEG C, react 1-10h, quickly stir, reach the basicity of requirement
45%-65%, then dries, and obtains product aluminium polychlorid.
Preferably, described step 1) in sodium terachloroaluminate with solve ingredients mass ratio be 1:1-10.
Preferably, described step 1) in the mixture that solution ingredients is alcohol and ether, wherein both volume ratios are
1:1-10.
Preferably, one or more during described alcohol is methanol, ethanol and isopropanol.
Preferably, described ether be methyl tertiary butyl ether(MTBE), tertbutyl ether, ether one or more.
Preferably, described step 6) in pH≤4.5 of reaction solution, Optimal Control is between 2.5-3.5.
Preferably, described step 6) in dry temperature be 100-250 DEG C.
Compared with prior art, the invention has the beneficial effects as follows:
1), sodium terachloroaluminate solid waste is turned waste into wealth, its solution the aluminum chloride circulation obtained after joining
Use, not only solve the problem that sodium terachloroaluminate solid waste processes, reduce the pollution to environment, real
Existing three-waste free discharge, and improve the large-scale production of the Atom economy of reaction, beneficially phosphine oxamate；
2) the solution ingredients, used by technique, poor solvent, low price, it is easy to get, whole technological operation is easy,
It is particularly suitable for industrialized production；
3) polymerization aluminum chloride prepared, further can be widely used as water purification agent, is particularly well-suited to
The sewage disposal in chemical plant.
Detailed description of the invention
In order to be better understood from the present invention, further illustrate the present invention below in conjunction with embodiment, but be not to this
The restriction of invention.
Embodiment 1
1) sodium terachloroaluminate solution is joined and aluminum chloride reclaims
In 200g sodium terachloroaluminate, add methanol 300ml, methyl tertiary butyl ether(MTBE) 300ml, be heated to 80 DEG C,
Filtered while hot, filter cake is sodium chloride, and filtrate is the methanol solution of aluminum chloride, slow cooling, stirring
Overnight, separate out a large amount of white aluminum chloride solid, filter, dry and obtain aluminum chloride 133.2g yield 95%；
2) aluminum chloride recycles
In the autoclave of 1L add 1) prepared by aluminum chloride 100.0g (0.75mol), Phosphorous chloride.
134.0g (0.97mol), sym.-tetrachloroethane 500ml, logical chloromethanes, to 1Mpa, is warming up to 80 DEG C,
After reaction 4h, lower the temperature, filter, dry, obtain white sand shape solid 228.3g, yield 95%；
| Cycle-index | 1 | 2 | 3 | 4 |
| Part yield (%) | 95 | 90 | 85 | 60 |
3) aluminium polychlorid is prepared
It is slowly added dropwise saturated sodium hydroxide solution to circulating in the aluminum chloride after three times, is 2.5 left sides to pH
The right side, it is heated to 85 DEG C, reacts 3-4h, quickly stir, obtain liquid aluminium polychloride, after 170 DEG C dry,
Obtain white aluminium polychlorid solid.
Embodiment 2
1) sodium terachloroaluminate solution is joined and aluminum chloride reclaims
In 200g solid waste, add ethanol 300ml, tertbutyl ether 300ml, be heated to 85 DEG C, filtered while hot,
Filter cake is sodium chloride, and filtrate is the methanol solution of aluminum chloride, slow cooling, is stirred overnight, and separates out
A large amount of white aluminum chloride solids, filter, dry and obtain aluminum chloride 126.9g yield 90%；
2) aluminum chloride recycles
In the autoclave of 1L add 1) prepared by aluminum chloride 100.0g (0.75mol), Phosphorous chloride.
134.0g (0.97mol), sym.-tetrachloroethane 500ml, logical chloromethanes, to 1Mpa, is warming up to 80 DEG C,
After reaction 4h, lower the temperature, filter, dry, obtain white sand shape solid 216.3g, yield 90%；
3) aluminium polychlorid is prepared
It is slowly added dropwise saturated sodium hydroxide solution to circulating in the aluminum chloride after three times, is 3.5 left sides to pH
The right side, is heated to 85 DEG C, reacts 3-4h, quickly stirs, obtain liquid aluminium polychloride, after 170 DEG C dry,
Obtain white aluminium polychlorid solid.
Embodiment 3
1) sodium terachloroaluminate solution is joined and aluminum chloride reclaims
In 200g solid waste, add isopropanol 300ml, tertbutyl ether 300ml, be heated to 90 DEG C, mistake while hot
Filter, filter cake is sodium chloride.Filtrate is the methanol solution of aluminum chloride, slow cooling, is stirred overnight,
Separate out a large amount of white aluminum chloride solid, filter, dry and obtain aluminum chloride 119.9g yield 86%.
2) aluminum chloride recycles
In the autoclave of 1L add 1) prepared by aluminum chloride 100.0g (0.75mol), Phosphorous chloride.
134.0g (0.97mol), sym.-tetrachloroethane 500ml, logical chloromethanes, to 1Mpa, is warming up to 80 DEG C,
After reaction 4h, cooling, filter, dry, obtain white sand shape solid 230.3g, yield 96%.
3) aluminium polychlorid is prepared
It is slowly added dropwise saturated sodium hydroxide solution to circulating in the aluminum chloride after three times, is 3.0 left sides to pH
The right side, is heated to 85 DEG C, reacts 3-4h, quickly stirs, obtain liquid aluminium polychloride, after 170 DEG C dry,
Obtain white aluminium polychlorid solid.
Embodiment 4
1) sodium terachloroaluminate solution is joined and aluminum chloride reclaims
In 200g solid waste, add methanol 300ml, first tertiary base ether 600ml, be heated to 90 DEG C, filtered while hot,
Filter cake is sodium chloride, and filtrate is the methanol solution of aluminum chloride, slow cooling, is stirred overnight, and separates out
A large amount of white aluminum chloride solids, filter, dry and obtain aluminum chloride 128.2g yield 92%；
2) aluminum chloride recycles
In the autoclave of 1L add 1) prepared by aluminum chloride 100.0g (0.75mol), Phosphorous chloride.
134.0g (0.97mol), sym.-tetrachloroethane 500ml, logical chloromethanes, to 1Mpa, is warming up to 80 DEG C,
After reaction 4h, cooling, filter, dry, obtain white sand shape solid 218.3g, yield 91%.
3) aluminium polychlorid is prepared
It is slowly added dropwise saturated sodium hydroxide solution to circulating in the aluminum chloride after three times, is 2.5 left sides to pH
The right side, is heated to 85 DEG C, reacts 3-4h, quickly stirs, obtain liquid aluminium polychloride, after 170 DEG C dry,
Obtain white aluminium polychlorid solid.
Embodiment 5
1) sodium terachloroaluminate solution is joined and aluminum chloride reclaims
In 500g solid waste, add methanol 700ml, methyl tertiary butyl ether(MTBE) 800ml, be heated to 90 DEG C, while hot
Filtering, filter cake is sodium chloride, and filtrate is the methanol solution of aluminum chloride, is slowly dropped to room temperature, stirring
Overnight, separate out a large amount of white aluminum chloride solid, filter, dry and obtain aluminum chloride 333.2g yield 96%；
2) aluminum chloride recycles
In the autoclave of 1L add 1) prepared by aluminum chloride 200.0g (1.49mol), Phosphorous chloride.
263.4g (1.93mol), sym.-tetrachloroethane 1L, logical chloromethanes, to 1Mpa, is warming up to 80 DEG C, instead
After answering 4h, cooling, filter, dry, obtain white sand shape solid 433.8g, yield 91%.
3) aluminium polychlorid is prepared
It is slowly added dropwise saturated sodium hydroxide solution to circulating in the aluminum chloride after three times, is 2.5 left sides to pH
The right side, is heated to 85 DEG C, reacts 3-4h, quickly stirs, obtain liquid aluminium polychloride, after 170 DEG C dry,
Obtain white aluminium polychlorid solid.
Claims (9)
1. during a phosphine oxamate produces, sodium terachloroaluminate recycles technique, it is characterised in that according to the following steps
Specifically carry out:
1) solution joins precipitation: adds in sodium terachloroaluminate and solves ingredients, be heated to 40-120 DEG C, generates three
Aluminum chloride and sodium chloride, aluminum chloride is dissolved in solution ingredients, and sodium chloride separates out；
2) solid filters: by step 1) mixed solution that obtains filters while hot, removes solid sodium chloride,
Obtain aluminum trichloride solution；
3) cooling separates out: aluminum trichloride solution is down to room temperature, filters, dry, and obtains white aluminum chloride
Solid, the aluminum chloride obtained meets material condition；
4) again with: by step 3) aluminum chloride that obtains as the raw material of phosphine oxamate, with chloromethanes,
Phosphorous chloride. reaction prepares coordination compound, and coordination compound prepares dichloromethylphosphine, then and ethanol through decomplexing reduction
Become ester, again obtain sodium terachloroaluminate solid:
5) recycle: repeat the above steps 1)-4), after repeatedly circulation, aluminum chloride and chloromethanes,
The complexing power of Phosphorous chloride. declines, and reaction titer reduces, and is carried out at next step by the aluminum chloride of this batch
Reason；
6) aluminium polychlorid is prepared: to step 5) aluminum chloride of gained adds sodium hydroxide solution, instead
Answer temperature to control between 20-100 DEG C, react 1-10h, quickly stir, reach the basicity of requirement
45%～65%, then dry, obtain product aluminium polychlorid；
Wherein above-mentioned steps 1) in the mixture that solution ingredients is alcohol and ether, wherein both volume ratios are 1:
1-10；Above-mentioned steps 6) in pH≤4.5 of reaction solution.
During phosphine oxamate the most according to claim 1 produces, sodium terachloroaluminate recycles technique, its feature
Be, described step 1) in sodium terachloroaluminate with solve ingredients mass ratio be: 1:1-10.
During phosphine oxamate the most according to claim 2 produces, sodium terachloroaluminate recycles technique, its feature
Being, described alcohol is one or more in methanol, ethanol and isopropanol.
During phosphine oxamate the most according to claim 3 produces, sodium terachloroaluminate recycles technique, its feature
Be, described ether be methyl tertiary butyl ether(MTBE), tertbutyl ether, ether one or more.
During phosphine oxamate the most according to claim 4 produces, sodium terachloroaluminate recycles technique, its feature
Be, described step 5) in cycle-index be more than 3 times.
During phosphine oxamate the most according to claim 5 produces, sodium terachloroaluminate recycles technique, its feature
Be, described step 6) in dry temperature be 100-250 DEG C.
During phosphine oxamate the most according to claim 2 produces, sodium terachloroaluminate recycles technique, its feature
Be, described step 1) in sodium terachloroaluminate with solve ingredients mass ratio be: 1:1-6.
During phosphine oxamate the most according to claim 1 produces, sodium terachloroaluminate recycles technique, its feature
Be, described step 1) in the mixture that solution ingredients is alcohol and ether, wherein both volume ratios are 1:1-3.
During phosphine oxamate the most according to claim 1 produces, sodium terachloroaluminate recycles technique, its feature
Be, described step 6) in the pH of reaction solution control between 2.5-3.5.
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| CN106986318A (en) * | 2017-04-11 | 2017-07-28 | 四川福思达生物技术开发有限责任公司 | The method that glufosinate-ammonium by-product waste residue prepares hypo-aluminum orthophosphate |
| CN108238621B (en) * | 2018-03-06 | 2020-09-11 | 洪湖源泰科技有限公司 | Method for producing polyaluminum chloride by using by-product of diethyl methylphosphonite production |
| CN109160502B (en) * | 2018-09-17 | 2020-08-11 | 四川省乐山市华莱利科技有限公司 | Method for synthesizing aluminum tripolyphosphate by using glufosinate-ammonium production byproduct |
| CN109052444B (en) * | 2018-10-17 | 2020-01-10 | 浙江新安化工集团股份有限公司 | Method for preparing polyaluminum chloride by using by-product generated in production of diethyl methylphosphite |
| CN112456462B (en) * | 2019-09-09 | 2022-03-29 | 江苏优士化学有限公司 | Recovery processing method of sodium tetrachloroaluminate catalyst composition |
| CN111921153A (en) * | 2020-04-15 | 2020-11-13 | 浙江安力能源有限公司 | Method for treating sodium tetrachloroaluminate |
| CN111804704B (en) * | 2020-07-15 | 2021-09-24 | 浙江新安化工集团股份有限公司 | Method for treating tetrachloro sodium aluminate solid slag |
| CN112552338B (en) * | 2020-12-10 | 2021-07-27 | 洪湖市一泰科技有限公司 | Comprehensive recycling method of phosphorus-containing composite salt as byproduct in organic phosphine production |
| CN114671447B (en) * | 2022-03-28 | 2023-05-30 | 河北诚信集团有限公司 | Treatment method of sodium tetrachloroaluminate solid waste residue generated in production process of methyl phosphorus dichloride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3840576A (en) * | 1951-08-09 | 1974-10-08 | Mini Of Supply | Preparation of complex aluminum compounds and alkyl phosphorus halides |
| EP0391329A2 (en) * | 1989-04-07 | 1990-10-10 | Hoechst Aktiengesellschaft | Process for preparing alkylphosphonous acids diesters and/or dialkylphosphinous acids esters |
| DE10057483A1 (en) * | 2000-11-20 | 2002-05-23 | Solarworld Ag | Removing aluminum chloride from chlorosilanes comprises contacting gaseous chlorosilanes with a mixture comprising a molten alkali metal tetrachloroaluminate and alkali metal chloride |
| CN102459091A (en) * | 2009-05-18 | 2012-05-16 | 孟山都技术公司 | Recovery of phosphorus values and salt impurities from aqueous waste streams |
| CN103964622A (en) * | 2013-02-05 | 2014-08-06 | 江苏优士化学有限公司 | Comprehensive treatment and resource utilization method for industrial organic phosphorus waste liquid |
-
2015
- 2015-10-22 CN CN201510697507.1A patent/CN105217667B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3840576A (en) * | 1951-08-09 | 1974-10-08 | Mini Of Supply | Preparation of complex aluminum compounds and alkyl phosphorus halides |
| EP0391329A2 (en) * | 1989-04-07 | 1990-10-10 | Hoechst Aktiengesellschaft | Process for preparing alkylphosphonous acids diesters and/or dialkylphosphinous acids esters |
| DE10057483A1 (en) * | 2000-11-20 | 2002-05-23 | Solarworld Ag | Removing aluminum chloride from chlorosilanes comprises contacting gaseous chlorosilanes with a mixture comprising a molten alkali metal tetrachloroaluminate and alkali metal chloride |
| CN102459091A (en) * | 2009-05-18 | 2012-05-16 | 孟山都技术公司 | Recovery of phosphorus values and salt impurities from aqueous waste streams |
| CN103964622A (en) * | 2013-02-05 | 2014-08-06 | 江苏优士化学有限公司 | Comprehensive treatment and resource utilization method for industrial organic phosphorus waste liquid |
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