CN101307002A - Recovery method of triethylamine in glyphosate mother liquid - Google Patents
Recovery method of triethylamine in glyphosate mother liquid Download PDFInfo
- Publication number
- CN101307002A CN101307002A CNA2008100168929A CN200810016892A CN101307002A CN 101307002 A CN101307002 A CN 101307002A CN A2008100168929 A CNA2008100168929 A CN A2008100168929A CN 200810016892 A CN200810016892 A CN 200810016892A CN 101307002 A CN101307002 A CN 101307002A
- Authority
- CN
- China
- Prior art keywords
- triethylamine
- glyphosate
- mother solution
- glyphosate mother
- recovery method
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 51
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 15
- 230000001172 regenerating effect Effects 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 239000010413 mother solution Substances 0.000 claims description 27
- 238000000605 extraction Methods 0.000 claims description 19
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- -1 2-ethylhexyl Chemical group 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 abstract 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 244000037671 genetically modified crops Species 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 244000144980 herd Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Abstract
The invention relates to a novel method for reclaiming triethylamine in glyphosate mother liquid produced by a method of dialkyl phosphite. The reclaiming method is realized by the following steps that: (1) in the process for preparing the glyphosate by the method of dialkyl phosphite, liquid caustic soda is added into the crystallized mother liquid to make the triethylamine layered, the lower layer is the glyphosate mother liquid; (2) an extracting agent prepared by an organic solvent and an acid phosphorus oxide extracting agent is added into the glyphosate mother liquid, the mixture is stirred and is kept stand to layer and separate; (3) the glyphosate waste water in the lower layer is concentrated to prepare glyphosate; the organic phase in the upper layer is added with hydrochloric acid to generate triethylamine hydrochloride and is kept stand to layer; a regenerating extracting agent in the upper layer returns to the production process and is used to extract continuously; and the triethylamine hydrochloride in the lower layer is added with liquid caustic soda and is adjusted to be basic so that the triethylamine hydrochloride is converted into the triethylamine which is layered and is used to synthesize after dewatered. The novel method effectively improves the coefficient of reclaiming of the triethylamine and has simple process, easy operation and high economical benefits.
Description
(1) technical field
The present invention relates to a kind of recovery method of triethylamine in glyphosate mother liquid, particularly a kind of novel method that reclaims the triethylamine in glyphosate mother liquid of dialkyl phosphite method production.
(2) technical background
Glyphosate is as the organic phosphine post-emergence herbicide of a kind of efficient, wide spectrum, low toxicity, safety, control to perennial dark root malignant weed is very effective, farming, woods, herd, all there is important purposes aspect such as gardening, it is one of weedicide that is most widely used at present, its application approach is constantly widened by the means such as genetically modified crops kind of cultivating various resistance glyphosates, glyphosate kept higher use rate of increase always in recent years, had become at present the weedicide of consumption maximum in the world.
The glyphosate mother solution treatment process of dialkyl phosphite method generation at present mainly is: crystalline mother solution is added liquid caustic soda, the triethylamine layering in the mother liquor is come out, change synthetic the use after the dehydration over to; The separation mother liquor is squeezed into rectifying tower and is carried out rectifying, steams triethylamine and recycles, and the mother liquor after the rectifying concentrates, the gyphosate solution of preparation 10%.
Domestic literature is also introduced the glyphosate crystalline mother solution by adding the alkali neutralization, controls the pH layering, and the upper strata is continued to add alkali and reclaimed triethylamine, and lower floor reclaims the technology of glyphosate.But this technology triethylamine loss is bigger.
We have found a kind of method of easy, economic processing glyphosate mother solution when the problem of research glyphosate.
(3) summary of the invention
The invention provides a kind of recovery method that is different from the triethylamine in glyphosate mother liquid of prior art, this method triethylamine rate of recovery height, and need not rectifying, technology is simple, and stronger economic worth is arranged.
The invention discloses a kind of recovery method of triethylamine in glyphosate mother liquid, realize by following steps:
The invention discloses a kind of recovery method of triethylamine in glyphosate mother liquid, it is characterized in that adopting following steps:
(1) adopt the dialkyl phosphite legal system to be equipped with in the glyphosate technology, crystalline mother solution is added liquid caustic soda, the triethylamine layering is come out, lower floor gets glyphosate mother solution;
(2) add the extraction agent that is mixed with by organic solvent and acid phosphorus oxygen kind of extractants in the glyphosate mother solution, stir standing demix, separatory;
(3) glyphosate waste water of lower floor concentrates, the preparation glyphosate; The organic phase on upper strata adds hydrochloric acid and generates triethylamine hydrochloride, standing demix; The regenerating extracting agent on upper strata is returned to produce and is continued the extraction use; The triethylamine hydrochloride of lower floor adds liquid caustic soda and transfers to alkalescence, makes triethylamine hydrochloride change into the triethylamine layering and comes out, and changes synthetic the use after the dehydration over to.
In the recovery method of the invention described above, described organic solvent is preferably the benzene class, and described acid phosphorus oxygen kind of extractants is preferably di(2-ethylhexyl)phosphate (2-ethylhexyl) ester (P-204) or 2-ethylhexyl phosphonic acid-2-ethylhexyl (P507).
In the recovery method of the invention described above, the add-on of described organic solvent is the 8-80% of glyphosate mother solution quality, is preferably 40-80%; The add-on of described acid phosphorus oxygen kind of extractants is the 2-20% of glyphosate mother solution quality, is preferably 10-20%.
In the recovery method of the invention described above, the concentration of described hydrochloric acid is 10-36.5%wt; The concentration of described liquid caustic soda is 10-50%wt.
The principal character of this process: react with acid phosphorus oxygen compounds as extraction agent (1); (2) reaction is a main raw material with the glyphosate mother solution; (3) in the reaction process with organic solvent as solvent.
Add in the aqueous solution behind the adjusting PH with base and contain a spot of triethylamine, can return and continue extraction.
The present invention effectively raises the rate of recovery of triethylamine, and technology is simple, and is easy to operate, has high economic benefit.
(4) embodiment
Below be that example illustrates embodiments of the present invention with the glyphosate mother solution after separating, dimethylbenzene (or toluene) with di(2-ethylhexyl)phosphate (2-ethylhexyl) ester (or 2-ethylhexyl phosphonic acid-2-ethylhexyl).
Embodiment 1
Adopt the dialkyl phosphite legal system to be equipped with glyphosate, the crystalline mother solution that produces in this technological process adds liquid caustic soda, layering, the upper strata is a triethylamine, lower floor is for handling back glyphosate mother solution 100g, and the extraction agent (containing 20gP-204 and 80g dimethylbenzene) for preparing with 100g joins in the four-hole boiling flask, starts to stir, stir 0.5-2h, make and handle back glyphosate mother solution and extraction agent thorough mixing.Mixed solution is poured in the separating funnel, left standstill 0.5-1h, layering, separatory, lower floor is a glyphosate waste water, concentrates the gyphosate solution of preparation 10%; The upper strata be organic phase, (about 10 grams) hydrochloric acid generates triethylamine hydrochloride, standing demix to wherein adding 30%; The upper strata be regenerating extracting agent, return and produce to continue extraction and use.The triethylamine hydrochloride of lower floor adds 30% liquid caustic soda and transfers to alkalescence (pH value 12), makes triethylamine hydrochloride change into the triethylamine layering and comes out, and changes synthetic the use after the dehydration over to, and the triethylamine rate of recovery is 98%.
Embodiment 2
Extraction agent is recycled, and all the other steps are with embodiment 1.The extraction agent that obtains can recycled for multiple times, and the rate of recovery of triethylamine is still higher.(for the first time: 95%; For the second time: 93%; For the third time 60%; The 4th time: 55%).
Embodiment 3
Utilize the regenerating extracting agent of embodiment 1 to extract, step is with embodiment 1.Extraction agent after obtaining regenerating is little with normal extraction agent effect of extracting difference, and the rate of recovery of triethylamine is 95%.
Embodiment 4
Regenerating extracting agent is recycled, and all the other steps are with embodiment 1.Obtaining regenerating extracting agent can utilize twice, the twice back triethylamine rate of recovery to descend (for the first time: 95%; For the second time: 60%; For the third time 30%).
Embodiment 5
Adopt the dialkyl phosphite legal system to be equipped with glyphosate, the crystalline mother solution that produces in this technological process adds liquid caustic soda, layering, the upper strata is a triethylamine, lower floor is for handling back glyphosate mother solution 100g, and the extraction agent (containing 5g P-204 and 45g toluene) for preparing with 50g joins in the four-hole boiling flask, starts to stir, stir 0.5-2h, make and handle back glyphosate mother solution and extraction agent thorough mixing.Mixed solution is poured in the separating funnel, left standstill 0.5-1h, layering, separatory, lower floor is a glyphosate waste water, concentrates the gyphosate solution of preparation 10%; The upper strata be organic phase, (about 10 grams) hydrochloric acid generates triethylamine hydrochloride, standing demix to wherein adding 30%; The upper strata be regenerating extracting agent, return and produce to continue extraction and use.The triethylamine hydrochloride of lower floor adds 30% liquid caustic soda and transfers to alkalescence (pH value 10), makes triethylamine hydrochloride change into the triethylamine layering and comes out, and changes synthetic the use after the dehydration over to, and the triethylamine rate of recovery is 92%.
Embodiment 6
Adopt the dialkyl phosphite legal system to be equipped with glyphosate, the crystalline mother solution that produces in this technological process adds liquid caustic soda, layering, the upper strata is a triethylamine, lower floor is for handling back glyphosate mother solution 100g, and the extraction agent (containing 15g2-ethylhexyl phosphonic acids-2-ethylhexyl (P507) and 20g toluene) for preparing with 35g joins in the four-hole boiling flask, starts to stir, stir 0.5-2h, make and handle back glyphosate mother solution and extraction agent thorough mixing.Mixed solution is poured in the separating funnel, left standstill 0.5-1h, layering, separatory, lower floor is a glyphosate waste water, concentrates the gyphosate solution of preparation 10%; The upper strata be organic phase, (about 10 grams) hydrochloric acid generates triethylamine hydrochloride, standing demix to wherein adding 30%; The upper strata be regenerating extracting agent, return and produce to continue extraction and use.The triethylamine hydrochloride of lower floor adds 30% liquid caustic soda and transfers to alkalescence (pH value 14), makes triethylamine hydrochloride change into the triethylamine layering and comes out, and changes synthetic the use after the dehydration over to, and the triethylamine rate of recovery is 86%.
Claims (5)
1, a kind of recovery method of triethylamine in glyphosate mother liquid is characterized in that adopting following steps:
(1) adopt the dialkyl phosphite legal system to be equipped with in the glyphosate technology, crystalline mother solution is added liquid caustic soda, the triethylamine layering is come out, lower floor gets glyphosate mother solution;
(2) add the extraction agent that is mixed with by organic solvent and acid phosphorus oxygen kind of extractants in the glyphosate mother solution, stir standing demix, separatory;
(3) glyphosate waste water of lower floor concentrates, the preparation glyphosate; The organic phase on upper strata adds hydrochloric acid and generates triethylamine hydrochloride, standing demix; The regenerating extracting agent on upper strata is returned to produce and is continued the extraction use; The triethylamine hydrochloride of lower floor adds liquid caustic soda and transfers to alkalescence, makes triethylamine hydrochloride change into the triethylamine layering and comes out, and changes synthetic the use after the dehydration over to.
2, according to the recovery method of claim 1, it is characterized in that: described organic solvent is the benzene class, and described acid phosphorus oxygen kind of extractants is di(2-ethylhexyl)phosphate (2-ethylhexyl) ester or 2-ethylhexyl phosphonic acid-2-ethylhexyl.
3, recovery method according to claim 1 and 2 is characterized in that: the add-on of described organic solvent is the 8-80% of glyphosate mother solution quality; The add-on of described acid phosphorus oxygen kind of extractants is the 2-20% of glyphosate mother solution quality.
4, recovery method according to claim 3 is characterized in that: the add-on of described organic solvent is the 40-80% of glyphosate mother solution quality; The add-on of described acid phosphorus oxygen kind of extractants is the 10-20% of glyphosate mother solution quality.
5, recovery method according to claim 1 and 2 is characterized in that: the concentration of described hydrochloric acid is 10-36.5wt%; The concentration of described liquid caustic soda is 10-50wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100168929A CN101307002B (en) | 2008-06-24 | 2008-06-24 | Recovery method of triethylamine in glyphosate mother liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100168929A CN101307002B (en) | 2008-06-24 | 2008-06-24 | Recovery method of triethylamine in glyphosate mother liquid |
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| CN101307002A true CN101307002A (en) | 2008-11-19 |
| CN101307002B CN101307002B (en) | 2011-04-13 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875612A (en) * | 2009-04-28 | 2010-11-03 | 苏州佳辉化工有限公司 | Method for continuously drying triethylamine in glyphosate production |
| CN102079712A (en) * | 2010-12-31 | 2011-06-01 | 大连联化化学有限公司 | Method for recycling anhydrous organic amine from organic amine salt |
| CN101503425B (en) * | 2009-03-06 | 2011-06-08 | 山东潍坊润丰化工有限公司 | Process for recovering triethylamine from glyphosate mother liquor |
| CN101905941B (en) * | 2009-06-08 | 2012-08-08 | 正大能源材料(大连)有限公司 | Treatment method of triethylamine-containing sewage |
| CN103115922A (en) * | 2013-03-04 | 2013-05-22 | 重庆紫光国际化工有限责任公司 | Method for determining content of triethylamine salt |
| CN108129328A (en) * | 2017-12-28 | 2018-06-08 | 浙江新安化工集团股份有限公司 | A kind of preparation method of methyl triethyl ammonium chloride |
| CN109573953A (en) * | 2018-12-25 | 2019-04-05 | 武汉工程大学 | A kind of preparation method of hydroxide |
| CN116715586A (en) * | 2023-02-21 | 2023-09-08 | 福建紫金选矿药剂有限公司 | Recovery method of acid binding agent triethylamine in preparation process of 5-nonylsalicylaldehyde |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165540C (en) * | 2000-08-31 | 2004-09-08 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN101190926A (en) * | 2006-11-29 | 2008-06-04 | 浙江新安化工集团股份有限公司 | Method for treating glyphosate mother liquid |
-
2008
- 2008-06-24 CN CN2008100168929A patent/CN101307002B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503425B (en) * | 2009-03-06 | 2011-06-08 | 山东潍坊润丰化工有限公司 | Process for recovering triethylamine from glyphosate mother liquor |
| CN101875612A (en) * | 2009-04-28 | 2010-11-03 | 苏州佳辉化工有限公司 | Method for continuously drying triethylamine in glyphosate production |
| CN101875612B (en) * | 2009-04-28 | 2013-07-10 | 苏州佳辉化工有限公司 | Method for continuously drying triethylamine in glyphosate production |
| CN101905941B (en) * | 2009-06-08 | 2012-08-08 | 正大能源材料(大连)有限公司 | Treatment method of triethylamine-containing sewage |
| CN102079712A (en) * | 2010-12-31 | 2011-06-01 | 大连联化化学有限公司 | Method for recycling anhydrous organic amine from organic amine salt |
| CN103115922A (en) * | 2013-03-04 | 2013-05-22 | 重庆紫光国际化工有限责任公司 | Method for determining content of triethylamine salt |
| CN103115922B (en) * | 2013-03-04 | 2015-07-01 | 重庆紫光国际化工有限责任公司 | Method for determining content of triethylamine salt |
| CN108129328A (en) * | 2017-12-28 | 2018-06-08 | 浙江新安化工集团股份有限公司 | A kind of preparation method of methyl triethyl ammonium chloride |
| CN109573953A (en) * | 2018-12-25 | 2019-04-05 | 武汉工程大学 | A kind of preparation method of hydroxide |
| CN116715586A (en) * | 2023-02-21 | 2023-09-08 | 福建紫金选矿药剂有限公司 | Recovery method of acid binding agent triethylamine in preparation process of 5-nonylsalicylaldehyde |
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