CN1958594A - Method for preparing solid of glyphosate isopropyl amine salt - Google Patents
Method for preparing solid of glyphosate isopropyl amine salt Download PDFInfo
- Publication number
- CN1958594A CN1958594A CN 200610154750 CN200610154750A CN1958594A CN 1958594 A CN1958594 A CN 1958594A CN 200610154750 CN200610154750 CN 200610154750 CN 200610154750 A CN200610154750 A CN 200610154750A CN 1958594 A CN1958594 A CN 1958594A
- Authority
- CN
- China
- Prior art keywords
- reaction
- glyphosate
- isopropyl amine
- amine salt
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
This invention provides a method for preparing solid isopropyl ammonium glyphosate. The method comprises: adding water-soluble salt and appropriate amount of water into a conventional reactor, stirring to completely dissolve the salt and obtain salt solution, adding glyphosate, uniformly dispersing, controlling the temperature, adding isopropylamine, reacting to obtain white crystals of isopropyl ammonium glyphosate, and filtering to obtain isopropyl ammonium glyphosate solid. The method can recycle the mother liquor to reduce water and water-soluble salt usage amounts and maximize precipitated solid amount.
Description
Technical field
The present invention relates to a kind of agricultural that is applied to, and other needs the weedicide solid preparation in the place of management of weeds or other plant.Specifically, the isopropyl amine salt solid preparation method who relates to herbicidal active component N-phosphonomethyl glycine (glyphosate).
Background technology
Glyphosate is a kind of wide spectrum steriland herbicide, but because glyphosate solubleness in water is very low, in actual use, normally glyphosate is mixed with water miscible salt.Present most popular soluble glyphosate salt is mainly isopropyl amine salt, ammonium salt, sylvite and sodium salt etc.Wherein glyphosate isopropyl amine salt be in the soluble glyphosate salt effect best also be one of the widest kind of global use range.
Glyphosate isopropyl amine salt generally is meant single isopropyl amine salt of glyphosate.Its chemical formula is as follows:
At present, the glyphosate formulation is still based on aqua, thereby because aqua comprises a large amount of aqueous solvent and brings many-sided inconveniences such as packing, transportation and storage, increased cost simultaneously.Along with the development and the demand in market, the technical need for preparing high-load glyphosate formulation is more and more urgent.What the former medicine of common at present employing glyphosate salt was prepared into the solid preparation product is ammonium glyphosate.
Chinese patent 96196134.1 discloses a kind of with Dilute Ammonia Solution and glyphosphonic acid is counter removes, and it is not high that energy consumption height and moisture content are removed efficient.Because hot air dries causes the oxidation of glyphosphonic acid for a long time, can generate the nitrosamine that needs controlled contents, reaction process also need be added the antioxidant S-WAT.
Chinese patent 02141788.1 by the applicant's application discloses a kind of glyphosate and water of adding earlier, and then feeding ammonia gas react, generate the glyphosphonic acid aqueous ammonium after reacting completely, utilizing organic solvent that ammonium glyphosate is extracted acquisition ammonium glyphosate solid then.This method speed of response is fast, simple to operate, has increased cost but introduced organic solvent, has increased unsafe factor simultaneously.
Foregoing invention all provides the method for the exsiccant ammonium glyphosate that can be used to prepare the soluble solids preparation, but all exists deficiencies such as expensive height of energy consumption or complex process, we can say that prior art does not reach gratifying effect as yet.In addition, glyphosate isopropyl amine salt at present still the former capital be aqua product, still find no solid of glyphosate isopropyl amine salt preparation method's bibliographical information so far.And since the different in kind of raw materials for production and product according to the production method of above-mentioned preparation ammonium salt raw powder, can not obtain the former medicine of isopropyl amine salt or can not obtain the former medicine of high-quality isopropyl amine salt.For example, because isopropyl amine salt solubleness in water is bigger, therefore be difficult to find a kind of organic solvent of routine that it is therefrom extracted at present, need the present invention to solve in the prior art open question still, and reach the demand that foregoing invention or known technology fail to realize.
Summary of the invention
At above deficiency, the invention provides a kind of method for preparing the former medicine of glyphosate isopropyl amine salt of suitable suitability for industrialized production.
For reaching the technical scheme that goal of the invention adopts be: in the popular response device, add the certain soluble salt and the water of suitable amount, fully stir and make salt dissolving becoming salts solution, add glyphosphonic acid again and stir and make it to be uniformly dispersed, control reaction temperature, in agitation condition downhill reaction device, add Isopropylamine, make it and the glyphosphonic acid reaction, after reacting completely, there are a large amount of glyphosate isopropyl amine salt white crystals to form, filter and obtain solid of glyphosate isopropyl amine salt.Mother liquor is used for recycled, to reduce the consumption of water and salt, increases the amount of solid precipitate.
The present invention crystallizes out reaction product and obtains solid of glyphosate isopropyl amine salt by add certain density soluble salt in system from the aqueous solution.Thereby provide a kind of succinct industrialized method that is used to prepare solid of glyphosate isopropyl amine salt that presses for that realizes easily.
Glyphosphonic acid and Isopropylamine add-on mol ratio are controlled at 1 among the present invention: 1-1.25.
The acid group of soluble salt of the present invention is SO
4 2-, Cl
-, NO
3 -, OH
-, positively charged ion is Mg
2+, Na
+, K
+, NH
4 +Deng.Comprise ammonium sulfate, sodium sulfate, sal epsom, sodium-chlor, ammonium chloride, potassium hydroxide, sodium hydroxide etc., preferably adopt ammonium sulfate, sodium-chlor and ammonium chloride.
Soluble salt of the present invention can be in the above-mentioned salt any one, also can be two or more mixing salt wherein.
The structural formula of glyphosate:
The structural formula of its isopropyl amine salt:
Because glyphosate is a kind of amino acid derivatives, its isopropyl amine salt also is a kind of amino acid derivative, the present invention adopts the method that adds soluble salt in system that glyphosate isopropyl amine salt is separated out from system when obtaining solid product, needs hierarchy of control pH value to separate out the amount of solid maximum with assurance near the iso-electric point of glyphosate isopropyl amine salt.Consider that in conjunction with aspects such as precipitate stability the method for the invention is controlled the pH value in 3.5～6.0 scope in reaction process, preferably between 4.0～5.0.
Temperature of reaction is divided into two processes among the present invention: one is that glyphosate and the Isopropylamine temperature when reacting in salts solution is controlled at 40 ℃～80 ℃ higher range, more preferably 45 ℃～55 ℃; It two leaves standstill that temperature should be controlled at room temperature and following in the process after finishing for reaction, more preferably below 0 ℃.
After the reaction of glyphosate and Isopropylamine finishes, leave standstill for some time, and no longer stirred, be beneficial to solid of glyphosate isopropyl amine salt and separate out and grow up; It is easily that time of repose was controlled at about half an hour, should keep lesser temps to be beneficial to solid simultaneously and separate out.
Reaction solution obtains solid of glyphosate isopropyl amine salt after filtration, and the residue mother liquor carries out recycled.After promptly adopting mother liquor to add an amount of water and salt, add the reaction of glyphosate technicals and Isopropylamine again, control reaction temperature has a large amount of white crystals to form in suitable scope after reaction finishes, filtration obtains the wet product of solid of glyphosate isopropyl amine salt, obtains the former medicine of glyphosate isopropyl amine salt after the oven dry.
Determining of soluble salt consumption: consider that from the best effect of saltouing the salt that is added reaches capacity with salts solution and is the best; But because heat release in the reaction process of glyphosate and Isopropylamine will cause the part of salts solution moisture to be scattered and disappeared, reaching capacity as salt concn to have part salt to separate out simultaneously when then isopropyl amine salt is separated out, thereby will influence the quality of isopropyl amine salt.Because the different solubility of different salting-out agent, so the highest amount ranges is also different, but the salting-out agent amount ranges is in the practical application: under the service temperature in the solution salt concn be 0.1% to saturated.
The invention provides a kind of succinct method for preparing the former medicine of glyphosate isopropyl amine salt, reduced the oven dry thermal load, reduced the generation of nitrosamine, entire reaction course does not need to add antioxidant, also avoid the intervention of organic solvent in addition, reduce and pollute, reduced cost.
Embodiment
Embodiment
Following examples are not to limit the scope of the invention only in order to illustrative purposes, and these embodiment will make you better understand the present invention, understand the variation of its advantage and some skills.
Embodiment 1:
Wherein add entry 100g and ammonium sulfate 30g (industrial goods) in the reaction that has stirring and refrigerating unit, stirring makes ammonium sulfate dissolve the formation ammoniumsulphate soln fully, to add glyphosate technicals (content 95%) 50g in the solution again, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 75 ℃ gradually by 20 ℃, and reaction system changes water white solution into by the suspension system of white gradually simultaneously.Dropwise postcooling, separate out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 44.8g of glyphosate isopropyl amine salt, mother liquor 153.4g.Get the former medicine 41.2g of glyphosate isopropyl amine salt after the oven dry, content is 96.3% (in glyphosate isopropyl amine salt) by analysis, and yield is 61.9%.
Embodiment 2:
Wherein add entry 100g and sodium-chlor 20g (industrial goods) in the reaction that has stirring and refrigerating unit, stirring makes sodium-chlor dissolve the formation sodium chloride solution fully, to add glyphosate technicals (content 95%) 50g in the solution again, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 75 ℃ gradually by 20 ℃, and reaction system changes water white solution into by the suspension system of white gradually simultaneously.Dropwise postcooling, separate out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 48.8g of glyphosate isopropyl amine salt, mother liquor 139.4g.Get the former medicine 46.2g of glyphosate isopropyl amine salt after the oven dry, content is 97.1% (in glyphosate isopropyl amine salt) by analysis, and yield is 70.0%.。
Embodiment 3:
Wherein add entry 100g and ammonium chloride 30g (industrial goods) in the reaction that has stirring and refrigerating unit, stirring makes ammonium chloride dissolve the formation ammonium chloride solution fully, to add glyphosate technicals (content 95%) 50g in the solution again, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 65 ℃ gradually by 20 ℃, and reaction system changes water white solution into by the suspension system of white gradually simultaneously.Dropwise postcooling, separate out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 38.8g of glyphosate isopropyl amine salt, mother liquor 159.4g.Get the former medicine 36.9g of glyphosate isopropyl amine salt after the oven dry, content is 98.1% (in glyphosate isopropyl amine salt) by analysis, and yield is 56.5%.。
Embodiment 4:
Wherein add entry 100g and sodium sulfate 15g (industrial goods) in the reaction that has stirring and refrigerating unit, stirring makes sodium sulfate dissolve the formation metabisulfite solution fully, to add glyphosate technicals (content 95%) 50g in the solution again, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 70 ℃ gradually by 20 ℃, and reaction system changes water white solution into by the suspension system of white gradually simultaneously.Dropwise postcooling, separate out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 47.8g of glyphosate isopropyl amine salt, mother liquor 135.4g.Get the former medicine 44.0g of glyphosate isopropyl amine salt after the oven dry, content is 95.7% (in glyphosate isopropyl amine salt) by analysis, and yield is 65.7%.。
Embodiment 5:
Wherein add embodiment 1 mother liquid obtained 100g and ammonium sulfate 5g (industrial goods) in the reaction that has stirring and refrigerating unit, add water 10g, stirring makes ammonium sulfate dissolve formation solution fully, glyphosate technicals (content 95%) 50g will be added again in the solution, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 75 ℃ gradually by 20 ℃, and reaction system changes translucent solution into by the suspension system of white gradually simultaneously.Dropwise postcooling, separate out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 71.1g of glyphosate isopropyl amine salt, mother liquor 112.1g.Get the former medicine 64.7g of glyphosate isopropyl amine salt after the oven dry, content is 96.9% (in glyphosate isopropyl amine salt) by analysis, and yield is 97.8%.
Embodiment 6:
Wherein add embodiment 5 mother liquid obtained 112.1g and ammonium sulfate 5g (industrial goods) in the reaction that has stirring and refrigerating unit, add water 10g, stirring makes ammonium sulfate dissolve formation solution fully, glyphosate technicals (content 95%) 50g will be added again in the solution, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 75 ℃ gradually by 20 ℃, and reaction system is thin out gradually by the suspension system of white gradually simultaneously.Dropwise postcooling, separate out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 72.8g of glyphosate isopropyl amine salt, mother liquor 122.5g.Get the former medicine 65.2g of glyphosate isopropyl amine salt after the oven dry, content is 97.2% (in glyphosate isopropyl amine salt) by analysis, and yield is 98.9%.
Embodiment 7:
Wherein add embodiment 2 mother liquid obtained 139.4g and sodium-chlor 5g (industrial goods) in the reaction that has stirring and refrigerating unit, add water 10g, stirring makes sodium-chlor dissolve formation solution fully, glyphosate technicals (content 95%) 50g will be added again in the solution, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 75 ℃ gradually by 20 ℃, and reaction system changes translucent solution into by the suspension system of white gradually simultaneously.Dropwise to concentrate and remove 20g water, cooling is separated out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 73.1g of glyphosate isopropyl amine salt, mother liquor 149.5g.Get the former medicine 65.0g of glyphosate isopropyl amine salt after the oven dry, content is 97.5% (in glyphosate isopropyl amine salt) by analysis, and yield is 98.9%.
Embodiment 8:
Wherein add embodiment 4 mother liquid obtained 135.4g and sodium sulfate 5g (industrial goods) in the reaction that has stirring and refrigerating unit, stirring makes sodium sulfate dissolve formation solution fully, glyphosate technicals (content 95%) 50g will be added again in the solution, stirring makes it to be uniformly dispersed, and forms the suspension that contains glyphosate; The 18.2g Isopropylamine is added drop-wise under stirring state gradually makes its reaction in the glyphosate suspension, produce a large amount of heat in the reaction process, the reaction mixture temperature rises to 75 ℃ gradually by 20 ℃, and reaction system changes translucent solution into by the suspension system of white gradually simultaneously.Dropwise to concentrate and remove 20g water, cooling is separated out by crystal gradually.To be cooled when the room temperature filtering separation, obtain the wet product 77.5g of glyphosate isopropyl amine salt, mother liquor 131.1g.Get the former medicine 70.4g of glyphosate isopropyl amine salt after the oven dry, content is 97.3% (in glyphosate isopropyl amine salt) by analysis, and yield is 106.9%.(with embodiment 4 average yield be 86.3%)
Claims (13)
1, a kind of preparation glyphosphonic acid isopropyl amine salt solid method, be included in and add glyphosphonic acid, water and Isopropylamine in the popular response device, reaction obtains the glyphosphonic acid isopropyl amine salt, it is characterized in that in system, adding soluble salt, the glyphosphonic acid isopropyl amine salt is crystallized out from system, obtain the solid glyphosate isopropyl amine salt after filtration.
2, the method for claim 1, the acid group that it is characterized in that described soluble salt is SO
4 2-, Cl
-, NO
3 -, OH
-, positively charged ion is Mg
2+, Na
+, NH
4 +, Ka
+
3, method as claimed in claim 2 is characterized in that described soluble salt is ammonium sulfate, sodium-chlor and ammonium chloride.
4, the method for claim 1 is characterized in that described glyphosphonic acid and Isopropylamine add-on mol ratio are controlled at 1: 1-1.25.
5, the method for claim 1 is characterized in that control pH value is in 3.5～6.0 scope in the reaction process.
6, method as claimed in claim 5 is characterized in that control pH value is 4.0～5.0 in the reaction process.
7, the method for claim 1 is characterized in that temperature of reaction is controlled at 40 ℃～80 ℃, and reaction is left standstill after finishing, and temperature should be controlled at room temperature and following.
8, method as claimed in claim 7 is characterized in that temperature of reaction is controlled at 45 ℃～55 ℃, and reaction is left standstill after finishing, and temperature should be controlled at below 0 ℃.
9, the method for claim 1 is characterized in that controlling the amount that adds soluble salt and makes its concentration greater than 0.1%, even saturated.
10, the method for claim 1, it is characterized in that described reactant glyphosphonic acid be weight content the dry powder more than 90% or not the water ratio of drying be the wet-milling of 5-20%.
11, the method for claim 1 is characterized in that the Recycling Mother Solution cover that will isolate solid of glyphosate isopropyl amine salt is used for reaction process.
12, the method for claim 1, it is characterized in that soluble salt can add before reaction also can finish the back in reaction and join in the system solid is separated out.
13, the method for claim 1, it is characterized in that adding earlier in the popular response device the certain soluble salt and the water of suitable amount, and then adding glyphosphonic acid and Isopropylamine reaction, after reacting completely, there are a large amount of glyphosate isopropyl amine salt white crystals to form, filter and obtain solid of glyphosate isopropyl amine salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610154750XA CN1958594B (en) | 2006-11-17 | 2006-11-17 | Method for preparing solid of glyphosate isopropyl amine salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610154750XA CN1958594B (en) | 2006-11-17 | 2006-11-17 | Method for preparing solid of glyphosate isopropyl amine salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1958594A true CN1958594A (en) | 2007-05-09 |
| CN1958594B CN1958594B (en) | 2011-08-10 |
Family
ID=38070459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610154750XA Active CN1958594B (en) | 2006-11-17 | 2006-11-17 | Method for preparing solid of glyphosate isopropyl amine salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1958594B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723973B (en) * | 2009-12-09 | 2012-09-26 | 浙江新安化工集团股份有限公司 | Method for preparing glyphosate dimethylamine salt solid |
| CN102939991A (en) * | 2012-11-05 | 2013-02-27 | 沙隆达集团公司 | Preparation technology of isopropylamine salt of n-glycine with mass percentage of 41% |
| CN104961769A (en) * | 2015-06-29 | 2015-10-07 | 湖北沙隆达股份有限公司 | Preparation method and device for glyphosate isopropylamine mother liquor |
| CN111820235A (en) * | 2020-08-13 | 2020-10-27 | 陕西标正作物科学有限公司 | Trivalent glyphosate salt containing isopropylamine, preparation method thereof, herbicide and weeding method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266553A (en) * | 1991-10-21 | 1993-11-30 | Riverdale Chemical Company | Method of manufacturing a dry water-soluble herbicidal salt composition |
| US5633397A (en) * | 1995-06-07 | 1997-05-27 | Monsanto Company | Preparation of ammonium glyphosate via a gas-solid reaction system |
| CN1235479C (en) * | 2002-11-28 | 2006-01-11 | 四川贝尔实业有限责任公司 | Glyphosate isopropyl amine salt solution preparation method and its composition as herbicide |
-
2006
- 2006-11-17 CN CN200610154750XA patent/CN1958594B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723973B (en) * | 2009-12-09 | 2012-09-26 | 浙江新安化工集团股份有限公司 | Method for preparing glyphosate dimethylamine salt solid |
| US9221853B2 (en) | 2009-12-09 | 2015-12-29 | Zhejiang Wynca Chemical Industry Group Co., Ltd. | Glyphosate dimethylamine salt crystal, preparation method and use thereof |
| CN102939991A (en) * | 2012-11-05 | 2013-02-27 | 沙隆达集团公司 | Preparation technology of isopropylamine salt of n-glycine with mass percentage of 41% |
| CN104961769A (en) * | 2015-06-29 | 2015-10-07 | 湖北沙隆达股份有限公司 | Preparation method and device for glyphosate isopropylamine mother liquor |
| CN111820235A (en) * | 2020-08-13 | 2020-10-27 | 陕西标正作物科学有限公司 | Trivalent glyphosate salt containing isopropylamine, preparation method thereof, herbicide and weeding method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1958594B (en) | 2011-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3029762A1 (en) | Method for synthesizing nano-lithium iron phosphate without water of crystallization in aqueous phase at normal pressure | |
| US10125262B2 (en) | Method for producing stabilized amorphous calcium carbonate | |
| CN1958594A (en) | Method for preparing solid of glyphosate isopropyl amine salt | |
| CN103723761A (en) | Preparing method for nano micron lead sulfate with electrochemical activity and method adopting lead sulfate to prepare lead-acid cell | |
| CN108456331A (en) | A kind of metal-organic framework materials are the preparation method of the vulcanizing activator of carrier | |
| CN102070535A (en) | Preparing method for synthesizing sanmate from calcium cyanamide | |
| CN101074103A (en) | Production of lithium fluoride | |
| CN102249281A (en) | Lensing spherical vaterite calcium carbonate crystal with high purity and preparation method thereof | |
| US9586894B2 (en) | Preparation method of solid acrylamidealkyl sulfonate | |
| US8779188B2 (en) | Process for the production of L-carnitine tartrate | |
| CN110330439A (en) | A kind of zinc-glycine complex and preparation method thereof not introducing foreign ion | |
| CN1302992C (en) | Method for making potassium nitrate using magnesium hydroxide circular reaction method | |
| CN107324375A (en) | A kind of preparation method of basic zinc chloride | |
| CN107032409B (en) | Preparation method of basic manganese chloride | |
| CN101702433B (en) | Method for preparing battery-grade lithium dihydrogen phosphate | |
| CN102442925B (en) | Preparation method of oxalic acid amide esters and salts thereof | |
| CN103497133B (en) | Method for preparing N-methylol group-D,L-calcium methionine microelement chelates by means of saponification liquid produced through D,L- methionine | |
| CN101759553A (en) | Method for preparing alpha-calcium picrolonate | |
| CN1114579C (en) | Method for preparing ferrous ammonium sulfate by using waste water from sulfuric acid method prodn. of titanium dioxide | |
| CN101979313A (en) | Simple synthesis method of spherical-like iron phosphate | |
| CN115819209B (en) | Preparation method of lithium squarate | |
| CN103467331A (en) | Iron glycine chelate crystal growth method | |
| JPH0928310A (en) | Feed additive | |
| CN106542987B (en) | A method of preparing cobalt laurate | |
| CN1216035C (en) | Method for preparing amantadine sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |