CN101755831A - Production method of glyphosate solution - Google Patents
Production method of glyphosate solution Download PDFInfo
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Abstract
The invention relates to a production method of a glyphosate solution, which comprises the following reaction processes of: generating iminodiacetic acid calcium salt through the reaction of ammonia water, chloroactic acid and lime, then changing into iminodiacetic acid hydrochloride by adding hydrochloric acid, then adding orthophosphorous acid and formaldehyde to produce N-(phosphonomethyl) iminodiacetic acid, oxidizing the N-(phosphonomethyl) iminodiacetic acid through concentrated sulphuric acid to obtain a glyphosate mixed liquid, adding a glyphosate primary drug or glyphosate wet crystals and introducing liquid ammonia/the ammonia water to prepare a 30-percent glyphosate ammonium salt solution. The production method has simple reaction processes, and no other chemical substances harmful to crops are added, thus the obtained glyphosate is nontoxic and harmless, also contains a phosphate fertilizer and a nitrogenous fertilizer, has very good control effect when applied to several common weeds with universal growth and serious harm, and can also promote the normal growth of plants.
Description
Technical field
The present invention relates to a kind of production method of weed killer herbicide, particularly glyphosate production method.
Background technology
Glyphosate (Glyphosate) is that U.S.'s Monsanto Chemical Company in 1971 is developed the wide spectrum that is with historically new significance go out natural disposition, inner sucting conduction type weed killer herbicide in world agriculture, and it is lasting over more than 30 year to come out.Glyphosate is widely used in orchard, plantation, uncultivated area, the no-tillage ground, become pesticide species most widely used in the world, that output is maximum, its year, sales value occupied first of the agricultural chemicals always, and along with the development of transgenosis glyphosate resistant crops, and the usage amount in glyphosate every year is also increasing.
Chemical name: N-phosphonic acids methylglycine, the physicochemical property of glyphosate: pure product are white, tasteless solid, and 230 ℃ of fusing points also decompose, and the solvability during 25 ℃ of glyphosates in water is 1.2g/100g, solvability is low in the water, is insoluble in organic solvents such as absolute ethyl alcohol, ether, benzene.Pure product pH value of water solution is about 2, and the sodium salt of glyphosate, ammonium salt, trimethyl sulfonium salt are soluble in water.
The toxicity of glyphosate: the main mode of action of glyphosate is the activity of 5-enol acetone shikimic acid-3 phosphonic acids capable of blocking (EPSP) salt synzyme.This synzyme is present in the aromatic amino acid biosynthesis, and only could produce in green plants.Therefore glyphosate is all very malicious to all green plantss, and beneficial organisms such as mammal, fish, earthworm, honeybee are all had no adverse effects.Easily by microbial decomposition, its main metabolites is nontoxic aminomethyl phosphonic acids to glyphosate, does not put aside in environment in soil, is a kind of tight security weed killer herbicide.
The synthetic method of glyphosate, the production technology of open source literature report synthesizing glyphosate reaches kind more than 10 both at home and abroad at present, the production technology that China produces glyphosate mainly contains following three kinds: (1) chloromethyl phosphoric acid method, this method process conditions harshness, equipment corrosion is serious, poor stability is not suitable for China's national situation, is eliminated very soon; (2) alkyl esterification method.This route has the yield height, the three wastes are few, and product purity is higher, and manufacturing technique requirent is advantages of higher not.(3) Iminodiacetate hydrochlorate method (IDA method), iminodiacetic acid (salt) acid system are advanced in the world at present process for synthesizing glyphosate, and the whole world 75% above glyphosate adopts this technology synthetic.Our country was from 1980, also have a lot of enterprises to adopt this method, as raw material, the method for oxidation PMIDA (PMIDA) makes glyphosate to this method with iminodiacetic acid (IDA), this route has that cost is low, process conditions relax, raw material is easy to get, and is fit to bigger device, high-efficiency operation, the product yield height, good in economic efficiency, less demanding to equipment, advantages such as remarkable in economical benefits, and product forms is quite popular with users.Shortcoming is that the product effective ingredient is lower, and quantity of three wastes is big and be difficult to handle.
Some open source literatures have been reported some glyphosate process conditions in recent years, for example: the Guo Jianmin of Zhejiang Polytechnical University, come tiger to admire, Ding Chengrong etc. are at " Zhejiang Polytechnical University's journal " .2009,37 (3) .-276-278 have delivered the article of the new technique for synthesizing research of glyphosate, with the PMIDA is initiation material, through hydrogen peroxide oxidation, catalysis synthetic herbicide glyphosate, when synthesizing glyphosate, adopt ferrous sulfate and the common catalysis synthesizing glyphosate of salt A reaction result ideal. pass through process optimization, 67 ℃ of reaction temperatures, hydrogen peroxide drips time 2h, n (PMIDA) and n (hydrogen peroxide)=1: 1.4, temperature retention time 1-2h, overall yield of reaction reaches 85.9% under the preferred process conditions such as 64 ℃ of holding temperatures, content 94.0%, it is simple that this hydrogen peroxide catalytic oxidation method synthesizing glyphosate has post processing, the advantage that yield is high.
The Shao Zhen prestige Qin David of Zhejiang Xinan Chemical Industry Group Co.Ltd is old waits quietly at " Hangzhou chemical industry " 2007,37 (2) .-34-37 have studied this process using ammonia replacement liquid caustic soda recovery triethylamine of technology that ammonia method glyphosate mother solution is handled, not only reduced cost, increased drug effect, also solve the situation that 10% aqua in the past causes soil compaction, had good benefits in environment and a social benefit.The triethylamine rate of recovery is about 92%.
In above-mentioned correlation retrieval, we see, the improvement that has the technology of glyphosate production, the research that has the selection of different catalysts, it is not advanced that but a lot of technologies yet exist, as process route long (yield is not high), the impure height of product (purification step is many), accessory substance and the many shortcomings such as (environmental protection pressure are big) of the three wastes.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can overcome the deficiencies in the prior art, produce that to have a process route short, the production method of yield height, glyphosate that herbicidal effect is good.
Glyphosate production method of the present invention comprises following processing step:
1, iminodiacetic acid is synthetic:
By stoichiometric proportion calcium hydroxide and ammoniacal liquor are dropped into reaction pot, (calcium hydroxide can be used milk of lime, by stoichiometric proportion excessive 10%) stirs, then the solid monoxone is slowly added, reacted 3 hours, 30 ℃～60 ℃ of reaction temperatures obtain the iminodiacetic acid (salt) acid calcium salt, the hydrochloric acid that adds mass fraction 31% after finishing, stirring reaction 2 hours, 70 ℃～90 ℃ of reaction temperatures are cooled to 5 ℃～15 ℃ after reaction is finished, crystallization, suction filtration get the Iminodiacetate hydrochlorate.
(2) preparation of phosphorous acid
Phosphorus trichloride is added the hydrolyzer that band stirs, obtain liquid phosphorous acid.
(3) preparation of PMIDA
Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are thrown into reactor according to the chemical reaction ratio, heat while stirring 90 ℃～100 ℃, slowly add formaldehyde (according to the chemical reaction ratio), 90 ℃～100 ℃ reactions 3 hours, obtain PMIDA, through reflux dewatering, obtain the PMIDA concentrate.
(4) PMIDA prepares the glyphosate mixed liquor through concentrated sulfuric acid oxidation
With the sulfuric acid of the above-mentioned PMIDA concentrate adding mass fraction 95% that makes, 115 ℃～140 ℃ of oxidizing reaction temperatures reacted 2 hours, and the glyphosate mixed liquor that obtains brownish black is finished in reaction.
(5) the ammonium glyphosate aqua of preparation quality mark 30%
With the above-mentioned glyphosate mixed liquor that makes, add the wet crystalline substance of former powder of glyphosate or glyphosate, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
The present invention's 30% glyphosate the required reaction pot of production method have agitator and steam-heated chuck, other equipment adopts common chemical industry equipment.
Giving national detection department after the present invention trial-produces successfully detects, utilize the method for liquid chromatogram and mass spectrum complementation analysis the glyphosate sample to be carried out the analysis of effective ingredient, can prove through experiment and analytic process, in the gyphosate solution sample of being analyzed, contain glyphosate, PMIDA, iminodiacetic acid and unknown compound C
5H
9NO
4These four kinds of compositions, the gyphosate solution herbicidal effect of production is better than the glyphosate of direct pulvis or Dilution for powder, the unknown material C that may obtain with concentrated sulfuric acid oxidation PMIDA
5H
9NO
4Relevant, might play certain booster action to weeding and promotion plant growth.
The obvious improvement of outstanding substantive distinguishing features of the present invention is:
The present invention adopts ammoniacal liquor and monoxone, lime reaction to generate the iminodiacetic acid (salt) acid calcium salt, add hydrochloric acid again and become the Iminodiacetate hydrochlorate, add phosphorous acid, Formaldehyde Production PMIDA then, PMIDA obtains the glyphosate mixed liquor after concentrated sulfuric acid oxidation, it is wet brilliant to add glyphosate technicals or glyphosate, feed liquefied ammonia or ammoniacal liquor, make 30% ammonium glyphosate aqua.Course of reaction is simple, do not have other crops detrimental substance is added, thereby the glyphosate that obtains is nontoxic, also contains phosphate fertilizer and nitrogenous fertilizer, and using not only can weeding, and ammonium, phosphorus also can be used as the fertilizer of plant normal growth.
2, the weeds kind that can prevent and kill off of glyphosate of the present invention is very many, and clear and definite 30% gyphosate solution is general and endanger serious weeds extraordinary preventive effect is arranged to several frequently seen growth.
Description of drawings
Fig. 1 is the process chart of the aqua glyphosate of production 30% of the present invention.
Fig. 2 is the liquid chromatogram of glyphosate stoste sample.
Recognize from Fig. 1, the aqua glyphosate of production 30% of the present invention comprises synthetic, the preparation of phosphorous acid of iminodiacetic acid, the preparation of two sweet phosphorus, the preparation of glyphosate mixed liquor, the processing steps such as preparation of 30% ammonium glyphosate aqua have specifically had detailed description in technical scheme.
The liquid chromatography detecting method of Fig. 2 is with glyphosate stoste (diluting 100 times) sample introduction 100 μ 1, the gained chromatogram is compared the retention time at each peak as shown in Figure 3 with above standard items, can judge that tentatively peak 1 is iminodiacetic acid, peak 3 is a glyphosate, and peak 4 is unknown compound C
5H
9NO
4, peak 2 temporarily can not be judged.
Embodiment
Embodiment 1
The monoxone of solid is added 50 ℃～65 ℃ hot water dissolving, standby; In stoichiometric proportion with ammonia and according to the ratio of chemical reaction suitably excessive 10% calcium hydroxide (milk of lime) drop into reaction pot, stir, chloroacetic acid solution with dissolving under agitation slowly adds then, reacted then 2 hours, 50 ℃～70 ℃ of reaction temperatures, reaction obtains the iminodiacetic acid (salt) acid calcium salt, after reaction is finished the iminodiacetic acid (salt) acid calcium salt is transferred to the acidifying pot, add the concentrated hydrochloric acid of mass fraction 31%, stirring reaction 2 hours, 60 ℃～90 ℃ of reaction temperatures, reaction is cooled to 5 ℃～10 ℃ after finishing, and suction filtration is separated out the Iminodiacetate hydrochlorate of solid, filter standbyly, filtrate decontamination water station is handled.The watery hydrochloric acid of phosphorus trichloride and mass fraction 10%～15% is placed reactor, reacted at normal temperatures 0.5～1 hour, obtain phosphorous acid and concentrated hydrochloric acid.Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are put into reactor according to the chemical reaction ratio, heat while stirring 90 ℃～100 ℃, under agitation slowly add formaldehyde (according to the chemical reaction ratio), 90 ℃～100 ℃ reactions 2～4 hours, obtain PMIDA, through reflux dewatering, obtain the PMIDA concentrate.The concentrated sulfuric acid that the more above-mentioned PMIDA concentrate that makes is added mass fraction 95%～98%, 115 ℃～120 ℃ of oxidizing reaction temperatures, reacted 2～4 hours, the mass fraction of the two sweet phosphorus and the concentrated sulfuric acid is 1: 1, the glyphosate mixed liquor that obtains brownish black is finished in reaction, and the glyphosate weight concentration is approximately 18-20%.With the above-mentioned glyphosate mixed liquor that makes, add the former powder of glyphosate at last, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
The monoxone of solid is added 60 ℃～70 ℃ hot water dissolving, standby; In stoichiometric proportion with ammonia and according to the ratio of chemical reaction suitably excessive 10% calcium hydroxide (milk of lime) drop into reaction pot, stir, chloroacetic acid solution with dissolving under agitation slowly adds then, reacted then 2 hours, 60 ℃～80 ℃ of reaction temperatures, reaction obtains the iminodiacetic acid (salt) acid calcium salt, after reaction is finished the iminodiacetic acid (salt) acid calcium salt is transferred to the acidifying pot, add 31% concentrated hydrochloric acid, stirring reaction 3 hours, 50 ℃～80 ℃ of reaction temperatures, reaction is cooled to 10 ℃～15 ℃ after finishing, and suction filtration is separated out the Iminodiacetate hydrochlorate of solid, filter standbyly, filtrate decontamination water station is handled.The watery hydrochloric acid of phosphorus trichloride and 10%～15% is placed reactor, reacted at normal temperatures 1～2 hour, obtain phosphorous acid and concentrated hydrochloric acid.Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are put into reactor according to the chemical reaction ratio, heat while stirring 70 ℃～90 ℃, under agitation slowly add formaldehyde (according to the chemical reaction ratio), 90 ℃～100 ℃ reactions 3～5 hours, through dehydration, obtain two sweet phosphorus,, obtain the PMIDA concentrate through reflux dewatering.The concentrated sulfuric acid that the more above-mentioned PMIDA concentrate that makes is added mass fraction 95%～98%, 120 ℃～140 ℃ of oxidizing reaction temperatures, reacted 3～5 hours, the mass fraction of the PMIDA and the concentrated sulfuric acid is 1: 1, the glyphosate mixed liquor that obtains brownish black is finished in reaction, and the glyphosate weight concentration is approximately 18-20%.With the above-mentioned glyphosate mixed liquor that makes, add the former powder of glyphosate at last, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
The monoxone of solid is added 50 ℃～70 ℃ hot water dissolving, standby; In stoichiometric proportion with ammonia and according to the ratio of chemical reaction suitably excessive 10% calcium hydroxide (milk of lime) drop into reaction pot, stir, chloroacetic acid solution with dissolving under agitation slowly adds then, reacted then 4～6 hours, 60 ℃～70 ℃ of reaction temperatures, reaction obtains the iminodiacetic acid (salt) acid calcium salt, after reaction is finished the iminodiacetic acid (salt) acid calcium salt is transferred to the acidifying pot, add the concentrated hydrochloric acid of mass fraction 30%～35%, stirring reaction 1～2 hour, 50 ℃～90 ℃ of reaction temperatures, reaction is cooled to 8 ℃～12 ℃ after finishing, and suction filtration is separated out the Iminodiacetate hydrochlorate of solid, filter standbyly, filtrate decontamination water station is handled.The watery hydrochloric acid of phosphorus trichloride and mass fraction 8%～18% is placed reactor, reacted at normal temperatures 0.5～1 hour, obtain phosphorous acid and concentrated hydrochloric acid.Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are put into reactor according to the chemical reaction ratio, heat while stirring 70 ℃～100 ℃, under agitation slowly add formaldehyde (according to the chemical reaction ratio), 90 ℃～100 ℃ reactions 2～5 hours, obtain two sweet phosphorus, through reflux dewatering, obtain the PMIDA concentrate.The concentrated sulfuric acid that the above-mentioned two sweet phosphorus concentrate that makes is added mass fraction 95%～98%, 115 ℃～140 ℃ of oxidizing reaction temperatures, reacted 2～5 hours, the mass fraction of the two sweet phosphorus and the concentrated sulfuric acid is 1: 1, the glyphosate mixed liquor that obtains brownish black is finished in reaction, and the glyphosate mass fraction is approximately 18-20%.With the above-mentioned glyphosate mixed liquor that makes, add the former powder of glyphosate, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
Embodiment 4
The monoxone of solid is added 50 ℃～65 ℃ hot water dissolving, standby; In stoichiometric proportion with ammonia and according to the ratio of chemical reaction suitably excessive 10% calcium hydroxide (milk of lime) drop into reaction pot, stir, chloroacetic acid solution with dissolving under agitation slowly adds then, reacted then 2 hours, 50 ℃～70 ℃ of reaction temperatures, reaction obtains the iminodiacetic acid (salt) acid calcium salt, after reaction is finished the iminodiacetic acid (salt) acid calcium salt is transferred to the acidifying pot, add the concentrated hydrochloric acid of mass fraction 31%, stirring reaction 2 hours, 60 ℃～90 ℃ of reaction temperatures, reaction is cooled to 5 ℃～10 ℃ after finishing, and suction filtration is separated out the Iminodiacetate hydrochlorate of solid, filter standbyly, filtrate decontamination water station is handled.The watery hydrochloric acid of phosphorus trichloride and mass fraction 10%～15% is placed reactor, reacted at normal temperatures 0.5～1 hour, obtain phosphorous acid and concentrated hydrochloric acid.Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are put into reactor according to the chemical reaction ratio, heat while stirring 90 ℃～100 ℃, under agitation slowly add formaldehyde (according to the chemical reaction ratio), 90 ℃～100 ℃ reactions 2～4 hours, obtain PMIDA, through reflux dewatering, obtain the PMIDA concentrate.The concentrated sulfuric acid that the more above-mentioned PMIDA concentrate that makes is added mass fraction 95%～98%, 130 ℃～140 ℃ of oxidizing reaction temperatures, reacted 2～4 hours, the mass fraction of the two sweet phosphorus and the concentrated sulfuric acid is 1: 1, the mixing glyphosate solution that obtains brownish black is finished in reaction, and the glyphosate weight concentration is approximately 18-20%.With the above-mentioned glyphosate mixed liquor that makes, add the wet crystalline substance of glyphosate at last, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
Embodiment 5
The monoxone of solid is added 60 ℃～70 ℃ hot water dissolving, standby; In stoichiometric proportion with ammonia and according to the ratio of chemical reaction suitably excessive 10% calcium hydroxide (milk of lime) drop into reaction pot, stir, chloroacetic acid solution with dissolving under agitation slowly adds then, reacted then 2 hours, 60 ℃～80 ℃ of reaction temperatures, reaction obtains the iminodiacetic acid (salt) acid calcium salt, after reaction is finished the iminodiacetic acid (salt) acid calcium salt is transferred to the acidifying pot, add 31% concentrated hydrochloric acid, stirring reaction 3 hours, 50 ℃～80 ℃ of reaction temperatures, reaction is cooled to 10 ℃～15 ℃ after finishing, and suction filtration is separated out the Iminodiacetate hydrochlorate of solid, filter standbyly, filtrate decontamination water station is handled.The watery hydrochloric acid of phosphorus trichloride and 10%～15% is placed reactor, reacted at normal temperatures 1～2 hour, obtain phosphorous acid and concentrated hydrochloric acid.Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are put into reactor according to the chemical reaction ratio, heat while stirring 70 ℃～90 ℃, under agitation slowly add formaldehyde (according to the chemical reaction ratio), 90 ℃～100 ℃ reactions 3～5 hours, through dehydration, obtain two sweet phosphorus,, obtain the PMIDA concentrate through reflux dewatering.The concentrated sulfuric acid that the more above-mentioned PMIDA concentrate that makes is added mass fraction 95%～98%, 125 ℃～135 ℃ of oxidizing reaction temperatures, reacted 3～5 hours, the mass fraction of the PMIDA and the concentrated sulfuric acid is 1: 1, the glyphosate mixed liquor that obtains brownish black is finished in reaction, and the glyphosate weight concentration is approximately 18-20%.With the above-mentioned glyphosate mixed liquor that makes, add the wet crystalline substance of glyphosate at last, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
Embodiment 6
The monoxone of solid is added 50 ℃～70 ℃ hot water dissolving, standby; In stoichiometric proportion with ammonia and according to the ratio of chemical reaction suitably excessive 10% calcium hydroxide (milk of lime) drop into reaction pot, stir, chloroacetic acid solution with dissolving under agitation slowly adds then, reacted then 4～6 hours, 60 ℃～70 ℃ of reaction temperatures, reaction obtains the iminodiacetic acid (salt) acid calcium salt, after reaction is finished the iminodiacetic acid (salt) acid calcium salt is transferred to the acidifying pot, add the concentrated hydrochloric acid of mass fraction 30%～35%, stirring reaction 1～2 hour, 50 ℃～90 ℃ of reaction temperatures, reaction is cooled to 8 ℃～12 ℃ after finishing, and suction filtration is separated out the Iminodiacetate hydrochlorate of solid, filter standbyly, filtrate decontamination water station is handled.The watery hydrochloric acid of phosphorus trichloride and mass fraction 8%～18% is placed reactor, reacted at normal temperatures 0.5～1 hour, obtain phosphorous acid and concentrated hydrochloric acid.Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are put into reactor according to the chemical reaction ratio, heat while stirring 70 ℃～100 ℃, under agitation slowly add formaldehyde (according to the chemical reaction ratio), 90 ℃～100 ℃ reactions 2～5 hours, obtain two sweet phosphorus, through reflux dewatering, obtain the PMIDA concentrate.The concentrated sulfuric acid that the above-mentioned two sweet phosphorus concentrate that makes is added mass fraction 95%～98%, 125 ℃～140 ℃ of oxidizing reaction temperatures, reacted 2～5 hours, the mass fraction of the two sweet phosphorus and the concentrated sulfuric acid is 1: 1, the glyphosate mixed liquor that obtains brownish black is finished in reaction, and the glyphosate mass fraction is approximately 18-20%.With the above-mentioned glyphosate mixed liquor that makes, add the wet crystalline substance of glyphosate, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
Below be weeding test of the present invention:
One, the test effect of the present invention 30% gyphosate solution management of weeds
The weeds kind that glyphosate can be prevented and kill off is very many, and clear and definite 30% gyphosate solution is general and endanger the preventive effects of serious weeds to several frequently seen growth, provides technical data for it rationally uses.
Reagent agent: the present invention's 30% gyphosate solution, (1#, the autonomous chemical industry in applicant Guangxi Co., Ltd produce), being diluted to concentration is that 10% gyphosate solution is tested, below all with;
The contrast medicament: 10% gyphosate solution (2#, Xinanjiang River Chemical Manufacture), 10% gyphosate solution (3#, pesticide chemical factory of Guangxi University produces), 10% gyphosate solution (4#, chemical industry institute in Guangxi produces), 41% farming reaches aqua (5#, Monsanto Company produces).
Glyphosate is to the preventive effect of cogongrass
Cogongrass (having another name called yellow cogongrass, the thatch lalang grass rhizome) is a kind of perennial dark root malignant weed.Its growth is rapid, the underground rhizome prosperity, and penetration power is strong, absorbs a large amount of soil nutrients with the crop competition, manually prevents and kill off very difficulty, becomes the farmland running to weeds easily, is one of the main weeds in harm dry crop, orchard.By sugarcane field, the evidence of oranges and tangerines field, clear and definite 10% gyphosate solution has excellent effect to preventing and kill off cogongrass, and dosage is at 1.5-2kg/ mu (active ingredient 150-200g/ mu), and preventive effect reaches more than 95% and (sees table 1 for details).That the preventive effect of cogongrass and farming are reached the weed killer herbicide preventive effect is suitable for 10% gyphosate solution produced of the autonomous chemical industry in reagent agent Guangxi Co., Ltd as can be seen from the test results, slightly is better than other contrast medicament, but difference not remarkable (p＞0.05).
Table 1 glyphosate is to the preventive effect of cogongrass
(1) glyphosate is to the preventive effect of Herba panici repentics
Herba panici repentics has another name called floor file broomcorn millet, wind platform grass, big wide grass, horsewhip joint, is a kind of perennial dark root malignant weed, is one of main weeds such as harm orchard, Guangxi, forest land, tea place and sugarcane field.To the preventive effect of Herba panici repentics, we have carried out the field trial that glyphosate is prevented and kill off Herba panici repentics at sugarcane field and oranges and tangerines garden in order to estimate 10% gyphosate solution (production of the autonomous chemical industry in Guangxi Co., Ltd).
Result of the test (seeing table 2 for details) shows: at the growth Herba panici repentics in vigorous period, according to the mu dosage when 100-150 (active ingredient) gram/mu, the effect that glyphosate is prevented and kill off Herba panici repentics reaches more than 94%, but for the Herba panici repentics that is in the maturing stage of setting seeds, its preventive effect obviously descends.As can be seen from the test results, 10% gyphosate solution that the autonomous chemical industry in reagent agent the applicant Guangxi Co., Ltd produces to preventive effect and the 5# farming of Herba panici repentics reach, the 4# weed killer herbicide is suitable, slightly is better than other contrast medicament, but difference not remarkable (p＞0.05).
Table 2 glyphosate is to the preventive effect of Herba panici repentics
(2) glyphosate is to the preventive effect of multiple weeds
For clear and definite 10% gyphosate solution (production of the autonomous chemical industry in Guangxi Co., Ltd) removes effect to bermudagrass herb, Bermuda grass, lady's-grass, the rhizome of nutgrass flatsedge, Ageratum conyzoides, Herba youngiae japonicae, killing of other common weed, we have carried out the field trial that glyphosate is prevented and kill off multiple weeds in sugarcane field and oranges and tangerines garden.
Result of the test (seeing table 3 for details) shows: 10% gyphosate solution according to the mu dosage when 100-150 (active ingredient) gram/mu, the comprehensive preventive effect that glyphosate is prevented and kill off multiple upland weeds reaches 95%-100%, and is better than some other dry land herbicide such as effects such as dalapon, methoxone.As can be seen from the test results, 10% gyphosate solution that reagent agent Guangxi autonomous chemical industry Co., Ltd produces removes effect to killing of bermudagrass herb, Bermuda grass, lady's-grass, the rhizome of nutgrass flatsedge, Ageratum conyzoides, Herba youngiae japonicae, other common weed and contrasts with 5# that the medicament farming reaches, the 4# weed killer herbicide is suitable, slightly be better than other contrast medicament, but difference not significantly (p＞0.05).
Table 3 glyphosate is to the preventive effect of multiple weeds
Two, glyphosate is the influence of gramineous crop and broad leaf crop to succession crop
This test adopts the pot experiment method to investigate the influence of glyphosate to succession crop gramineous crop (corn) and broad leaf crop (soybean).
1. materials and methods
1.1 test material
Reagent agent: 10% gyphosate solution (production of the autonomous chemical industry in the applicant Guangxi Co., Ltd), 10% gyphosate solution (Xinanjiang River production), 10% gyphosate solution (the Guangxi University chemical plant produces), 10% gyphosate solution (production of Guangxi chemical industry institute), 41% farming reaches aqua (Monsanto Company's production).
Test soil is taken from agricultural college of Guangxi University farm.Soil physico-chemical property is: pH value 6.11; Organic 25.8g/kg; Cation exchange capacity 7.9cmol/kg; Soil texture loam.
For studying thing: corn (beautiful beautiful 102), soybean (No. 2, Gui Chun)
1.2 experimental scheme
The soil of pot experiment is taken from the clear area of not dispenser respectively.Test is that (30cm * 16cm), every basin is adorned air dried soil 3.0kg to fluid-tight pottery pot with basin.Add experimental group, will join respectively in the soil by default concentration gradient for the reagent product earlier, fully behind the mixing, in the basin of packing into, make it ultimate density and be respectively 0,1,5,10mg/kg, each is handled and repeats 3 times.After planting investigating emergence rate in the 10d, is the relative emergence rate of 100% each crop of calculating with the check plot emergence rate.The amount of growth minute, crop carries out at 40d after planting.Each is handled every kind of crop and gets 10 young plants at random, measures its plant height, claims its fresh weight.
2. test results and analysis
Result of the test shows: in each of adding the reagent agent glyphosate handled, soybean, emergence of corn rate and the no significant difference of contrast illustrates and use glyphosate to succession crop gramineous crop corn, broad leaf crop soybean not tangible influence of emerging.Two kinds of confessions study thing each that adds the reagent agent glyphosate handle with to biomass indexs such as the plant height that impinges upon 40d after planting, fresh weights, do not have significant difference yet.After this explanation glyphosate enters soil, be easy to by adsorption by soil, and the mineralising that easily is degraded by microorganisms, change into inorganic substances such as carbonic acid gas and water, thereby glyphosate is the gramineous crop corn to succession crop, broad leaf crop soybean safety.
Three, glyphosate of the present invention is to the influence of soil Main physical character
1 materials and methods
1.1 test material
Reagent agent: 10% gyphosate solution is that 30 former medicine dilutions obtain (the autonomous chemical industry in the applicant Guangxi Co., Ltd produces, ammonium salt)
Experimental field click in agricultural college of Guangxi University experiment oranges and tangerines field, base.Varieties of plant is red Jiang Cheng, and planting patterns is a trench, seeding row spacing 3m * 4m.Oranges and tangerines plantation 6 years.The test region physical features is smooth, the rich water quality management unanimity.Soil physico-chemical property is: pH value 6.23; Organic 19.1g/kg; Cation exchange capacity 6.2cmol/kg; Soil texture loam.
1.2 test method
Soil hardness (consolidation) is measured: measure respectively apart from trunk 50cm, 100cm, the soil hardness at 180cm place digs 3 soil profiles in each sample ground, by 5 and 15cm with hardness instrumentation soil compactibility, each section survey 3 times.
The bulk density of soil and porosity determination: measure with core cutter method.Each sample ground adopts 5 samplings of " S " type route, respectively gets a duplicate samples at 2～10cm and 2 soil layers of 10～20cm respectively, and 3 results that repeat in each group get its mean value.Choose in contrast sampling in kind with bare area soil in the zone.
1.3 experimental scheme
The processing garden is that 1000～1500ml converts water and sprays for 50 kilograms with reagent agent with the mu consumption, annual glyphosate 2 times, and the routine method of manually hoeing up weeds, annual weeding 4～6 times are adopted in the contrast garden.Processing garden and contrast garden branch-finishing and pruning, flower and fruit thinning over the years operated by the special messenger, and other management are identical.
2 test results and analysis
2.1 influence to soil hardness
The continuous oranges and tangerines garden mould earth that sprayed 10% gyphosate solution in 4 years and the routine oranges and tangerines garden of handling of manually hoeing up weeds is compared, apart from trunk 50cm, and 100cm, the soil hardness at 180cm place has descended 0.23,0.16 respectively, 0.26kg/cm
2
2.2 glyphosate is to the influence of the bulk density of soil and porosity etc.
After using 10% gyphosate solution weeding year in year out, no matter the plow layer of the topsoil of 2～10cm and 10～20cm, the bulk density of soil all decreases, wherein 2～10cm topsoil unit weight has reduced by 8.18%, 10～20cm plow layer unit weight reduces by 5.1%, thereby has improved the air conditions of soil and protected ability fertile, water conservation.The voidage of using 2～10cm topsoil in oranges and tangerines garden behind the glyphosate year in year out is that the porosity of the plow layer of 61.5%, 10～20cm is 51.8%, has improved 11.4% and 4.1% than artificial weeding respectively.The oranges and tangerines garden uses 10% gyphosate solution weed killer herbicide to improve the physical property and the farming of soil significantly year after year.
Four, glyphosate of the present invention is to the influence of soil pH value and soil nitrification, ammoniation
1 materials and methods
1.1 test material
Reagent agent: 1#10% gyphosate solution (production of the autonomous chemical industry in the applicant Guangxi Co., Ltd), 2#10% gyphosate solution (Xinanjiang River production), 3#10% gyphosate solution (the Guangxi University chemical plant produces), 4#10% gyphosate solution (production of Guangxi chemical industry institute), the 5#41% farming reaches aqua (Monsanto Company's production).
Experimental field click in oranges and tangerines field, agricultural college of Guangxi University farm.Soil physico-chemical property is: pH value 6.23; Organic 19.1g/kg; Cation exchange capacity 6.2cmol/kg; Soil texture loam.
Be taken from oranges and tangerines field, agricultural college of Guangxi University farm for examination soil.
1.2 test method
Soil pH value is measured: is 1000ml with 10% gyphosate solution of different manufacturers with the mu consumption, and 41% farming reaches aqua converts water with 200ml and spray for 40 kilograms, and after the dispenser 0, pH potentiometry determination method is adopted in the 40d sampling.Simultaneously, establish control treatment in identical plot, same procedure is measured.
Soil nitrification, ammoniation: nitrification: claim 50g soil; Ammoniation claims 10g soil.Add 25mg urea nitrogen/100g dry ground during each is handled, and add 0,100 respectively, the reagent agent of 1000mg/kg in the 100ml tool plug ground triangular flask of packing into after fully mixing thoroughly, is regulated moisture to 60% of maximum water-holding capacity, bottle stopper places in 25 ± 2 ℃ of constant incubators and cultivates beyond the Great Wall.Each handles counterpoise multiple twice.After on-test 0,14,, 28d is sampling and measuring NO3-N respectively, the content of NH4-N.
Result and analysis
2.1 glyphosate is to the influence of soil pH value
Result of the test shows that glyphosate is handled soil pH value has been risen between 0.05 and 0.11 unit.After this showed that glyphosate is used in the orchard, face of land pH had had certain variation, has improved the physicochemical character of soil, and it is neutral that soil is tending towards, and neutral loam helps fruit tree growth.Each kind glyphosate to the pH value to influence difference very little, and with the no significant difference of contrast.
Glyphosate is to the influence of soil nitrification, ammoniation
The ammoniation of soil is under the effect of all kinds of putrefactivebacterias in soil, and by decomposing, it is the process of the inorganic nitrogen of form that organic nitrogen is transformed into NH4-N with the organic matter in the soil.Experimental result shows (table 1): at the cultivation initial stage, in each processing of adding glyphosate, the intensity of soil ammoniation all strengthens with the increase of the consumption of glyphosate, when 100mg/kg concentration is handled, the multiple that the intensity of soil ammoniation increases 2.692.86 doubly between.But when cultivating 28d, each influence of handling the ammonifying process of soil disappears substantially.
The nitrification of soil is the NH in the reflection soil
4-N changes into NO
3The process of-N.Usually represent with the inhibiting nitrification rate.Add concentration when being 10mg/kg at glyphosate, the inhibiting nitrification rate in when cultivating 14d and 28d between 18.5%-26.8%, glyphosate add concentration when being 100mg/kg the inhibiting nitrification rate when cultivating 14d and 28d reach about 80%.The glyphosate of different cultivars in identical interpolation level to the ammoniation of soil and digestion difference not significantly (table 1).
From result of the test (table 1) as can be seen, at the glyphosate initial stage in the soil of adding to soil is had in various degree facilitation in ammoniation, this process helps increasing soil fertility, but in the culture experiment later stage, the NH in the soil
4The accumulation of-N is to return to the level close with control group.Soil nitrification there is certain inhibitory action, helps preservation of fertility.
Table 1 glyphosate is to the influence of soil nitrification, ammoniation
Five, glyphosate is to the influence of soil microbial activities
1 materials and methods
1.1 test material
Reagent agent: 1#10% gyphosate solution (production of the autonomous chemical industry in the applicant Guangxi Co., Ltd), 2#10% gyphosate solution (Xinanjiang River production), 3#10% gyphosate solution (production of pesticide chemical factory of Guangxi University), 4#10% gyphosate solution (production of Guangxi chemical industry institute), the 5#41% farming reaches aqua (Monsanto Company's production).
For trying soil: be taken from the dark topsoil of agricultural college of Guangxi University farm oranges and tangerines field 2-15cm.The sample of gathering is divided on vinyon cloth, at room temperature dried in the shade, soil block is crumbed, and chooses except that plant roots, stem, leaf and stone foreign material, crosses 40 mesh sieves, and is standby.
Soil physico-chemical property is: pH value 6.23; Organic 19.1g/kg; Cation exchange capacity 6.2cmol/kg; Soil texture loam.
1.2 test method
The edaphon population quantity influence assay method: in the brown wide-mouth bottle of the 250ml that before the test above-mentioned standby soil packed into, every bottle of 200g, add sterile water adaptability cultivation at room temperature 7d, add a certain amount of reagent agent then respectively, the mass fraction of regulating water in the soil with sterile water is 20%.And abundant mixing, make the glyphosate mass fraction in the soil reach 1mgkg respectively
-1, 10mgkg
-1, 100mgkg
-1Seal with brown paper, lucifuge is cultivated under the room temperature.Not add glyphosate but the soil that adds aqua sterilisa is contrast.Every processing repeats 3 times.Respectively at handling back 2,7,15, the quantity that counting method is observed bacterium, fungi and actinomycetes population in each processing is cultivated in the coating of 30d sampling employing solid plate gradient dilution.
Respiration adopts airtight leaving standstill to survey CO
2Method: take by weighing 50g for trying soil sample in the 100ml beaker, add 2g glucose, mixing, add water 10ml, stir, place airtight specimen bottle, the pre-7d that cultivates adds reagent agent then in 25 ℃ incubator, makes that its concentration in soil is respectively 0,10,100mgkg
-1, soil moisture content is adjusted to 60% of maximum water holding capacity.In closed container, add simultaneously 0.1molL respectively
-1NaOH solution 25.00ml, respectively at cultivate back the 3rd, 9,15,25d takes out these solution, with the remaining NaOH of HCI titration.After each titration is intact, changes to the new small beaker that same NaOH solution is housed simultaneously and continue to cultivate.Test parallel 3 groups, with the CO of 50g dry ground generation
2Amount of substance represent the soil respiration action intensity.
2 test results and analysis
2.1 glyphosate is to the influence of microbial population quantity
2.1.1 glyphosate is to the influence of bacterial population quantity
Result of the test shows that glyphosate shows certain inhibitory action to bacterial population in the experimental concentration scope, and strengthens gradually with the rising of the concentration inhibitory action to bacterium.2d after the dosing is 33.5%-62.1% to the inhibiting rate of bacterium, 7d after the dosing, and inhibiting rate is 11.2%-44.7%, 15d after the dosing, inhibiting rate are 8.8%-37.1%; 30d after the dosing, inhibiting rate are 0%-21.2%.This explanation is along with the prolongation of administration timing of drug, and glyphosate weakens gradually to the inhibitory action of bacterial population.ANOVA showed significant, 1mg/kg and 100mg/kg be to the inhibitory action difference of bacterium not significantly (p＞0.05), and five kinds of reagent agents are added concentration levels to the difference of bacteriostasis not significantly (p＞0.05) at three kinds.
2.1.2 glyphosate is to the influence of fungal population quantity
Result of the test shows that glyphosate shows certain inhibitory action to fungal population in the experimental concentration scope, and strengthens gradually with the rising of the concentration inhibitory action to fungi.When 100mg/kg added concentration, 2d after the dosing was 75.8-100% to eubacterial inhibiting rate, 7d after the dosing, and inhibiting rate is 61.2%-89.7%, 15d after the dosing, inhibiting rate are 55.6%-78.3%; 30d after the dosing, inhibiting rate are 12%-22.2%.This explanation is along with the prolongation of administration timing of drug, and glyphosate weakens gradually to the inhibitory action of fungal population.When 10mg/kg added concentration, 2d after the dosing was 64.8-90.1% to eubacterial inhibiting rate, 7d after the dosing, and inhibiting rate is 51.2%-72.7%, 15d after the dosing, inhibiting rate are 35.6%-48.3%; 30d after the dosing, inhibiting rate are 2.5%-12.2%.When 1mg/kg added concentration, 2d after the dosing was 31.8-64.1% to the inhibiting rate of fungi, 7d after the dosing, and inhibiting rate is 3.2%-12.5%, 15d after the dosing does not have inhibitory action to fungal population, shows certain spread effect on the contrary.Under the normal application conditions in field, glyphosate is little to the influence of soil fungi population, and faint spread effect is arranged.ANOVA showed significant, 1mg/kg and 10mg/kg, 100mg/kg be to the inhibitory action difference of fungi extremely significantly (p＜0.01), and five kinds of reagent agents are added concentration levels to the inhibiting difference of fungi not significantly (p＞0.05) at three kinds.
2.1.3 glyphosate is to the influence of actinomycetes population quantity
Result of the test shows that glyphosate shows certain inhibitory action to the actinomycetes population when concentration 100mg/kg, and with the rising of concentration actinomycetic inhibitory action is strengthened gradually.2d after the dosing is 68.5%-100% to actinomycetic inhibiting rate, 7d after the dosing, and inhibiting rate is 50.3%-89.2%, 15d after the dosing, inhibiting rate are 30.2%-46.4%; 30d after the dosing, inhibiting rate are 2.4%-27.0%.This explanation is along with the prolongation of administration timing of drug, and glyphosate weakens gradually to the inhibitory action of bacterial population.When 1mg/kg and 10mg/kg concentration, remove after the dosing 15, the 30d glyphosate shows outside certain spread effect the actinomycetes population, and remaining result of the test shows that the actinomycetic inhibiting rate of glyphosate is 1.8%-64.3%.ANOVA showed significant, the difference between two kinds of concentration of 1mg/kg and 10mg/kg be remarkable (p＞0.05) not.Difference between they and 100mg/kg reaches utmost point significance level (p＜0.01).Five kinds of reagent agents are added concentration levels to the difference of bacteriostasis not significantly (p＞0.05) at three kinds.
2.1 glyphosate is to the influence of microbial respiratory intensity
Result of the test shows: glyphosate shows faint spread effect to the respiration for the examination edaphon, and each breathing total amount of handling has increased 6.9%-13.41% than control group respectively, and the activity that can promote edaphon of using of glyphosate is described.
Six, glyphosate divides effect of accumulation to the sucrose of sugarcane
Glyphosate as good weed killer herbicide, has the growth regulating effect to crop when low concentration when high concentration.In the screening to the sugarcane ripener, glyphosate is promoted application as the effective ripener of sugarcane.Increase the mechanism research of sugar effect for clear and definite glyphosate accelerates the ripening to sugarcane, carried out glyphosate and sugarcane is accelerated the ripening increased the sugar test, provide the theory and practice foundation for applying in the production.
1. experiment material and method
Experimental cultivar: Guangdong sugar 71/210, No. 11, osmanthus sugar.
Field trial: adopt the split block experiment design, spray 0.3% glyphosate (active ingredient 10% aqua, active ingredient concentration when using is 0.01%) and 0.6% glyphosate (active ingredient 10% aqua, the active ingredient concentration when using is 0.02%) and clear water control treatment.Growth later stage foliage-spray is handled, and every mu of water consumption 100kg adds 20g washing powder and makes surfactant.
Assay method: mid-November and mid-December sugarcane stem sample 5-6 bar is adopted in every processing and carried out sugarcane sucrose and divide and analyze.
2. experimental result and analysis
The result that measure November in the processing that sprays 0.3% glyphosate increases by 0.55% for the sugarcane sugar average specific contrast of sugar cane breed Guangdong sugar 71/210; Sugar No. 11 sugarcane sugar average specific contrasts in osmanthus increase by 0.76%.The result who measures December is that the sugarcane sugar average specific contrast of sugar cane breed Guangdong sugar 71/210 increases by 1.34%; And sugar No. 11 sugarcane sugar average specific contrasts in osmanthus reduce 0.97%.The result who measures January next year is that the sugarcane sugar average specific contrast of sugar cane breed Guangdong sugar 71/210 increases by 0.13%; And sugar No. 11 sugarcane sugar average specific contrasts in osmanthus reduce 0.57%.This explanation glyphosate has certain sugar that increases to act on to different sugar cane breeds in low strength range.So 10-20d before harvesting sugarcane increases the sugar effect better to spray the low dosage glyphosate.
Sum up
Prove by field control effectiveness test: glyphosate is a kind of leaf surface treatment agent, has good Foliage Absorption conduction, broad weed-killing spectrum except that annual narrow leaf and broad leaved weed are had the excellent preventive effect, also has good effect for perennial dark root malignant weed, fern, undershrub; To dark root malignant weed such as cogongrass, Herba panici repentics, Bermuda grass, eleusine indica, can poison underground rhizome with poison especially.In for examination oranges and tangerines garden and sugarcane field weeding test, it is suitable that 30% gyphosate solution that the present invention produces reaches the weed killer herbicide preventive effect to the farming of the preventive effects of 25 kinds of weeds such as cogongrass, Herba panici repentics, Bermuda grass, eleusine indica, the rhizome of nutgrass flatsedge, guayule, bermudagrass herb, lady's-grass, Ageratum conyzoides, Herba youngiae japonicae, non-irrigated barnyard grass, Paspalum conjugatum, water peanut, bidens pilosa and U.S. Monsanto Company production, slightly is better than domestic other similar glyphosate kind.Results of comparison is found after continuous several times is used, and it is long that 30% gyphosate solution that the present invention produces kills the grass cycle, helps reducing labour intensity and saves cost.
30% gyphosate solution of producing by the present invention of recommended dose continuous administration can significantly improve soil physical properties, reduces soil hardness, reduces the bulk density of soil, increases soil porosity, the physical property and the farming that have improved soil.And after continuous several times is used other producer's glyphosate, find to have soil compaction hardening phenomenon in various degree.Because 30% gyphosate solution that Guangxi autonomous chemical industry Co., Ltd produces does not add synergist, other producer all adds the multiple components synergist, and the soil compaction phenomenon estimates that to have synergist to destroy soil physical properties relevant with adding.
30% gyphosate solution of using the production of the applicant Guangxi autonomous chemical industry Co., Ltd by recommended dose helps improving soil pH value, improves soil acidity or alkalinity.As can be seen from the test results, there is in various degree facilitation at the 30% gyphosate solution initial stage of using to the ammoniation of soil, this process helps increasing soil fertility, but in the culture experiment later stage, the accumulation of the NH4-N in the soil is to return to the level close with control group.Soil nitrification there is certain inhibitory action, helps preservation of fertility.
Use the activity that 30% gyphosate solution that the applicant Guangxi autonomous chemical industry Co., Ltd produces can promote edaphon by recommended dose, each breathing total amount of handling has increased 6.9%-13.41% than control group respectively.
The present invention's 30% gyphosate solution can be used for the weeding operation of no-tillage field to succession crop safety such as gramineous crop and broad leaf crops.
10-20d before harvesting sugarcane produces 30% gyphosate solution to spray low dosage the applicant Guangxi autonomous chemical industry Co., Ltd, increases the sugar effect better.
Claims (1)
1. glyphosate production method is characterized in that: comprise following processing step:
(1) iminodiacetic acid is synthetic
By stoichiometric proportion calcium hydroxide and ammoniacal liquor are dropped into reaction pot, stir, then the solid monoxone is slowly added, reacted 3 hours, 30 ℃～60 ℃ of reaction temperatures, obtain the iminodiacetic acid (salt) acid calcium salt, add the hydrochloric acid of mass fraction 31% after finishing, stirring reaction 2 hours, 70 ℃～90 ℃ of reaction temperatures, after finishing, reaction is cooled to 5 ℃～15 ℃, crystallization, and suction filtration gets the Iminodiacetate hydrochlorate;
(2) preparation of phosphorous acid
Phosphorus trichloride is added the hydrolyzer that band stirs, obtain liquid phosphorous acid;
(3) preparation of PMIDA
Above-mentioned Iminodiacetate hydrochlorate that makes and phosphorous acid are thrown into reactor according to the chemical reaction ratio, heat while stirring 90 ℃～100 ℃, slowly add formaldehyde according to the chemical reaction ratio, 90～100 ℃ of reactions 3 hours, obtain PMIDA, through reflux dewatering, obtain the PMIDA concentrate;
(4) PMIDA prepares the glyphosate mixed liquor through concentrated sulfuric acid oxidation
With the sulfuric acid of the above-mentioned PMIDA concentrate adding mass fraction 95% that makes, 115 ℃～140 ℃ of oxidizing reaction temperatures reacted 2 hours, and the glyphosate mixed liquor that obtains brownish black is finished in reaction;
(5) the ammonium glyphosate aqua of preparation quality mark 30%
With the above-mentioned glyphosate mixed liquor that makes, add the wet crystalline substance of former powder of glyphosate or glyphosate, feed liquefied ammonia or ammoniacal liquor, the pH of regulator solution is 5～7, makes 30% ammonium glyphosate aqua, and precipitation is removed impurity, and be up to the standards bottling or barrelling obtain product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102067879A (en) * | 2010-09-27 | 2011-05-25 | 陈运谋 | Method for preparing gyphosate solution from glyphosate raw material |
| CN102702254A (en) * | 2010-10-18 | 2012-10-03 | 浙江拜克开普化工有限公司 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
| CN102850393A (en) * | 2011-07-02 | 2013-01-02 | 李坚 | Method for synthesizing glyphosate original drug or its aqua through one-pot process |
| CN112250235A (en) * | 2020-10-10 | 2021-01-22 | 镇江江南化工有限公司 | Method for resource utilization of white carbon black production waste gas and alcohol-containing wastewater in glyphosate production by gas phase method |
-
2010
- 2010-01-22 CN CN201010045653A patent/CN101755831A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102067879A (en) * | 2010-09-27 | 2011-05-25 | 陈运谋 | Method for preparing gyphosate solution from glyphosate raw material |
| CN102702254A (en) * | 2010-10-18 | 2012-10-03 | 浙江拜克开普化工有限公司 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
| CN102702254B (en) * | 2010-10-18 | 2015-04-15 | 浙江拜克开普化工有限公司 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
| CN102850393A (en) * | 2011-07-02 | 2013-01-02 | 李坚 | Method for synthesizing glyphosate original drug or its aqua through one-pot process |
| CN112250235A (en) * | 2020-10-10 | 2021-01-22 | 镇江江南化工有限公司 | Method for resource utilization of white carbon black production waste gas and alcohol-containing wastewater in glyphosate production by gas phase method |
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