CN104447860A - Technological method for producing glyphosate and co-producing ammonium sulfate with glycine method - Google Patents
Technological method for producing glyphosate and co-producing ammonium sulfate with glycine method Download PDFInfo
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- CN104447860A CN104447860A CN201410706674.3A CN201410706674A CN104447860A CN 104447860 A CN104447860 A CN 104447860A CN 201410706674 A CN201410706674 A CN 201410706674A CN 104447860 A CN104447860 A CN 104447860A
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Abstract
The invention provides a technological method for producing glyphosate and co-producing ammonium sulfate with a glycine method. The method comprises steps as follows: ammonium hydroxide obtained after catalytic wet oxidation and ammonia concentration of a glyphosate mother solution and dilute sulphuric acid obtained after purification and dehydration of methyl chloride are mixed and enter a reaction kettle, ammonia gas is rapidly introduced into the reaction kettle for reaction, an obtained ammonium sulfate solution is filtered, evaporated, crystallized and dried to obtain a finished product of ammonium sulfate; and ammonia-introduced blow-out gas enters a biochemical pool for treatment after catalytic wet oxidation. According to the technological method, dilute sulphuric acid dried by methyl chloride is treated, ammonia after catalytic wet oxidation is effectively utilized, and ammonium sulfate required by glyphosate preparation production is obtained through co-production, so that the environmental protection pressure is reduced, and the purpose of resource utilization of diluted acid and ammonia is achieved.
Description
Technical field
The present invention relates to glyphosate production technical field, be specifically related to a kind of processing method of producing glyphosate by using glycine coproduction of ammonia sulfate.
Background technology
Glyphosate synthesis mainly contains glycine method and IDA method two kinds, wherein produce methyl chloride in process of producing glyphosate by using glycine, it is main for being formed containing methyl chloride, and contain the hydrolysis tail gas of the organism such as a certain amount of methyl alcohol, methylal and hydrogenchloride and water, in order to obtain methyl chloride finished product, must purify methyl chloride, first carry out washing organics removal, the acidic substance such as hydrogenchloride are removed in alkali cleaning, finally dewater with the vitriol oil.Dilute sulphuric acid is obtained after dehydration, content is generally between 65% to 75%, color is yellowish brown, the impurity carried secretly due to methyl chloride is more, containing more organism, such as: formaldehyde, methyl alcohol, methylal etc., though there are the processes such as washing, still have organism to bring in sulfuric acid, dilute sulphuric acid plays oxygenizement in dehydration part, partial organic substances is carbonization even, partial organic substances and sulfuric acid reaction, partial organic substances is dissolved in dilute sulphuric acid, causes dilute sulphuric acid inferior quality, deal with very inconvenient, more there is no suitable comprehensive utilization means.If be directly used in production of compound fertilizer, because condensation puffs away containing formaldehyde, COD is high, cannot carry out biochemical treatment, can bring secondary pollution, is difficult to realize industrial application.And for glyphosate mother solution obtain after evaporation concentration desalination containing ammonia condensing liquid, prior art does not also make full use of effectively.
Often there is the glyphosate formulation such as gyphosate solution and granule in glyphosate production producer on the other hand, all needs to use ammonium sulfate as synergistic agent, and the dilute sulphuric acid purifying treatment therefore produced workshop produces ammonium sulfate also again for the production of there being great economic implications.
Summary of the invention
Object of the present invention is just to provide one can overcome above-mentioned defect, by by-product dilute sulphuric acid, ammonia, accomplishes that comprehensive resource utilizes simultaneously, and solves the method for dilute sulphuric acid blow-out gas secondary pollution.
The processing method of a kind of producing glyphosate by using glycine coproduction of ammonia sulfate that the present invention proposes, it is characterized in that, after glyphosate mother solution Catalytic Wet Oxidation, through ammonia concentrate the ammoniacal liquor that obtains with from carry out purifying to methyl chloride dewater after the dilute sulphuric acid that obtains be mixed in reactor, thin up sulfuric acid concentration to 18% ~ 32%, then ammonia is passed into gas distributor and enter reactor fast with tangential way, controlling temperature of reaction is 120 ~ 132 DEG C, and pH is 4.3 ~ 4.5; The ammoniumsulphate soln that reaction terminates to obtain removes mechanical impurity through high-temperature resistant filter, then obtains ammonium sulfate wet product through multiple-effect evaporation, obtains ammonium sulfate finished product finally by centrifugal crystallization, air stream drying; Enter after logical ammonia blow-out gas condensation to be oxidized in the titania-based ruthenium rhodium Catalytic Wet Oxidation tower that is catalyzer, then enter biochemistry pool process.
For the glyphosate contained in glyphosate mother solution, increase sweet phosphine etc. containing amine organism, after catalytic wet catalyzed oxidation, organism is degraded, amine is oxidized to nitrogen and ammonia, ammonia enters in oxidation solution, after oxidation solution reclaims phosphor resource, through evaporation concentration desalination, obtain the phlegma containing ammonia, phlegma carries out that ammonia is concentrated obtains ammoniacal liquor.Described ammonia is concentrated comprises ammonia aeration technique or ammonia rectifying tower rectification process, belongs to common process.
Above-mentioned comprise the methyl chloride dehydration produced for glyphosate and raw material dimethylphosphite with the vitriol oil from the dilute sulphuric acid that obtains after methyl chloride being carried out to purify dehydration after the dilute sulphuric acid that obtains.
The preferred multiple-effect evaporation of the present invention is: by the ammoniumsulphate soln after removing impurity through MVR(steam mechanical recompression) evaporate, steam most of moisture, obtain ammonium sulfate wet product.
Further, the present invention preferably operational path comprises: the heat needed for liquid ammonia gasification is by reacting the confession of blow-out gas condensation Posterior circle water extraction, and liquefied ammonia is vaporized and reduces circulating water temperature simultaneously, improves circulating water efficiency, conserve energy, reduces cooling area.
The present invention is in ammonia and sulfuric acid reaction, and liquefied ammonia, after gasifier gasification, enters gas distributor in a kettle. and enters reactor with tangential way, the organism blowout that can will dissolve in diluted acid.Drive the mixing of dilute sulphuric acid in gas ammonia uphill process, accomplish to exempt from mechanical stirring, play energy-conserving action.
The invention solves the dilute sulphuric acid that obtains after methyl chloride is carried out purifying dehydration and to glyphosate mother solution obtain after evaporation concentration desalination containing ammonia condensing liquid process problem, achieve the resource comprehensive recycling of by-product dilute sulphuric acid, ammonia in glyphosate production.Blow-out gas in dilute sulphuric acid carries out Catalytic Wet Oxidation process, avoids secondary pollution and pollution transportation.Utilize the comprehensive treating process of two kinds of glyphosate by-products, and the Catalytic Wet Oxidation to blow-out gas, be not reported.
The present invention had both processed the dilute sulphuric acid of methyl chloride drying, and the ammonia obtained after make use of Catalytic Wet Oxidation, alleviates environmental protection pressure, and coproduction obtains producing the ammonium sulfate needed for glyphosate formulation again, reaches diluted acid, ammonia recycling object.Simultaneously, because in the organism of blowout, COD is very high, and contain by the formaldehyde etc. of sulfuric acid oxidation, can not directly enter in biochemistry pool, blow gas, after overcooling, enters Catalytic Wet Oxidation operation, Catalytic Wet Oxidation is carried out to blowout liquid, by air compressing, at high temperature, ruthenium rhodium catalyst, under effect, the COD substance oxidations such as formaldehyde are become CO
2and H
2o, can reach the requirement entering biochemistry pool process, and the difficult biochemical substances of blow-out gas is dealt carefully with.
Accompanying drawing explanation
Fig. 1 is present invention process general flow chart.
Wherein: dotted line is energy exchange comprehensive utilization process.
Embodiment
Embodiment one,
The ammoniacal liquor obtained after dilute sulphuric acid after dehydration and Catalytic Wet Oxidation is mixed in reactor, add water and sulfuric acid concentration is diluted to 32%, pass into ammonia, temperature of reaction rises to 132 DEG C, control pH4.5 reacts end, and reacting liquor while hot is filtered and entered MVR evaporator evaporation, centrifugal crystallization, air stream drying obtains ammonium sulfate, and in detection ammonium sulfate, nitrogen content 21.0%(is in butt).Meet GB535 " ammonium sulfate " requirement.The logical ammonia Catalytic Wet Oxidation tower (with metallic coating multistage catalytic pole plate form) entered with titania-based ruthenium rhodium catalyst that puffs away is oxidized, and passes into air, oxidizing temperature 150 DEG C, pressure 4Mpa.COD content 400mg/l after oxidation, enters biochemistry pool process.
Embodiment two,
Dilute sulphuric acid after dehydration is mixed with the weak ammonia obtained after Catalytic Wet Oxidation, dilute sulphuric acid concentration to 28% in reactor, pass into ammonia, temperature of reaction rises to 128 DEG C, and control pH4.7 reacts end, filtered while hot, crystallisation by cooling, obtain ammonium sulfate, dry, in ammonium sulfate, nitrogen content 21.0%(is in butt).Meet GB535 " ammonium sulfate " requirement.Add in glyphosate granule and make synergistic agent, meet GB 20686 " glyphosate soluble powder (grain) agent " standard-required.Logical ammonia puffs away and enters the oxidation of Catalytic Wet Oxidation tower, oxidizing temperature 180 DEG C, pressure 6Mpa..COD content 350mg/l after oxidation, enters biochemistry pool process.
Embodiment three,
Dilute sulphuric acid after dehydration is mixed with the weak ammonia obtained after Catalytic Wet Oxidation, dilute sulphuric acid concentration to 22% in reactor, pass into ammonia, temperature of reaction rises to 125 DEG C, and control pH4.3 reacts end, filtered while hot, crystallisation by cooling, obtain ammonium sulfate, dry, in ammonium sulfate, nitrogen content 21.1%(is in butt).Meet GB535 " ammonium sulfate " requirement.Add in gyphosate solution and make synergistic agent, meet GB 20684 " gyphosate solution " standard-required.Logical ammonia puffs away and enters the oxidation of Catalytic Wet Oxidation tower, oxidizing temperature 200 DEG C, pressure 8Mpa..COD content 320mg/l after oxidation, enters biochemistry pool process.
Embodiment four,
Dilute sulphuric acid after dehydration is mixed with the weak ammonia obtained after Catalytic Wet Oxidation, dilute sulphuric acid concentration to 18% in reactor, pass into ammonia, temperature of reaction rises to 120 DEG C, and control pH4.5 reacts end, filtered while hot, crystallisation by cooling, obtain ammonium sulfate, dry, in ammonium sulfate, nitrogen content 21.0%(is in butt).Meet GB535 " ammonium sulfate " requirement.Logical ammonia puffs away and enters the oxidation of Catalytic Wet Oxidation tower, oxidizing temperature 220 DEG C, pressure 12Mpa..COD content 300mg/l after oxidation, enters biochemistry pool process.
Claims (4)
1. the processing method of a producing glyphosate by using glycine coproduction of ammonia sulfate, it is characterized in that, after glyphosate mother solution Catalytic Wet Oxidation, through ammonia concentrate the ammoniacal liquor that obtains with from carry out purifying to methyl chloride dewater after the dilute sulphuric acid that obtains be mixed in reactor, thin up sulfuric acid concentration to 18% ~ 32%, then ammonia is passed into gas distributor and enter reactor fast with tangential way, controlling temperature of reaction is 120 ~ 132 DEG C, and pH is 4.3 ~ 4.5; The ammoniumsulphate soln that reaction terminates to obtain removes mechanical impurity through high-temperature resistant filter, then obtains ammonium sulfate wet product through multiple-effect evaporation, obtains ammonium sulfate finished product finally by centrifugal crystallization, air stream drying; Enter after logical ammonia blow-out gas condensation to be oxidized in the titania-based ruthenium rhodium Catalytic Wet Oxidation tower that is catalyzer, then enter biochemistry pool process.
2. the processing method of producing glyphosate by using glycine coproduction of ammonia sulfate as claimed in claim 1, is characterized in that: described multiple-effect evaporation be by removing impurity after ammoniumsulphate soln evaporate through MVR.
3. the processing method of producing glyphosate by using glycine coproduction of ammonia sulfate as claimed in claim 1 or 2, is characterized in that: the heat needed for liquid ammonia gasification supplies by reacting blow-out gas condensation Posterior circle water extraction.
4. the processing method of producing glyphosate by using glycine coproduction of ammonia sulfate as claimed in claim 1 or 2, it is characterized in that: the oxidizing temperature carrying out in Catalytic Wet Oxidation tower being oxidized is 150 ~ 220 DEG C, pressure is 4 ~ 12Mpa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316780A (en) * | 2016-08-13 | 2017-01-11 | 安徽东至广信农化有限公司 | Acid pickling and recycling method of methyl chloride in glyphosate production |
| CN106395860A (en) * | 2016-08-30 | 2017-02-15 | 爱森（中国）絮凝剂有限公司 | Ammonia gas water washing evaporative crystallization recovery system |
| CN106431821A (en) * | 2016-08-25 | 2017-02-22 | 江西金龙化工有限公司 | Method for comprehensively utilizing dehydrated dilute sulphuric acid and byproduct sodium chloride and producing byproduct sodium hydrogen sulfate |
| CN108483462A (en) * | 2018-03-12 | 2018-09-04 | 江西金龙化工有限公司 | A kind of technique recycling ammonium sulfate from glyphosate mother solution |
| CN108689392A (en) * | 2018-07-09 | 2018-10-23 | 江西金龙化工有限公司 | A kind of glyphosate three wastes integrated conduct method |
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| CN101328182A (en) * | 2008-07-17 | 2008-12-24 | 湖北励创科技开发有限公司 | Method for producing urotropine and gyphosate solution by using glyphosate waste water |
| CN102728350A (en) * | 2012-07-10 | 2012-10-17 | 北京纬纶华业环保科技股份有限公司 | Catalyst for treating industrial waste water by catalytic wet air oxidation (CWAO) |
| CN103663667A (en) * | 2012-09-19 | 2014-03-26 | 中国中化股份有限公司 | Catalytic wet oxidation pretreatment method of glyphosate production wastewater |
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| CN101328182A (en) * | 2008-07-17 | 2008-12-24 | 湖北励创科技开发有限公司 | Method for producing urotropine and gyphosate solution by using glyphosate waste water |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316780A (en) * | 2016-08-13 | 2017-01-11 | 安徽东至广信农化有限公司 | Acid pickling and recycling method of methyl chloride in glyphosate production |
| CN106431821A (en) * | 2016-08-25 | 2017-02-22 | 江西金龙化工有限公司 | Method for comprehensively utilizing dehydrated dilute sulphuric acid and byproduct sodium chloride and producing byproduct sodium hydrogen sulfate |
| CN106431821B (en) * | 2016-08-25 | 2019-03-05 | 江西金龙化工有限公司 | The method for being dehydrated the comprehensive utilization and by-product sodium bisulfate of dilute sulfuric acid and byproduct sodium chloride |
| CN106395860A (en) * | 2016-08-30 | 2017-02-15 | 爱森（中国）絮凝剂有限公司 | Ammonia gas water washing evaporative crystallization recovery system |
| CN108483462A (en) * | 2018-03-12 | 2018-09-04 | 江西金龙化工有限公司 | A kind of technique recycling ammonium sulfate from glyphosate mother solution |
| CN108689392A (en) * | 2018-07-09 | 2018-10-23 | 江西金龙化工有限公司 | A kind of glyphosate three wastes integrated conduct method |
| CN108689392B (en) * | 2018-07-09 | 2019-10-25 | 江西金龙化工有限公司 | A kind of glyphosate three wastes integrated conduct method |
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