CN1962611A - Process for preparing glycine using hydroxy-acetonitrile method - Google Patents
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Abstract
The invention discloses a glycine preparing method, which comprises the following steps: 1) blending hydroxy acetonitrile solution or composition to produce hydroxy acetonitrile with ammonia composition to obtain ammonization reacting liquid; 2) blending the ammonization reacting liquid and inorganic alkaline to obtain the alkaline hydrolytic solution; 3) neutralizing the alkaline hydrolytic solution through inorganic acid to obtain the neutralized liquid; 4) disposing the neutralized liquid to obtain the glycine.
Description
Technical field
The preparation method who the present invention relates to that the direct ammonia of a kind of hydroxyacetonitrile is separated, alkaline hydrolysis, neutralization, purifying obtains glycine, characteristics are to be starting raw material with the hydroxyacetonitrile, replace the aminating reaction liquid that obtains to contain aminoacetonitriles, the easy method for preparing glycine by ammonia.
Background technology
Glycine is the important source material of industry such as chemical industry, medicine, agricultural chemicals, has purposes widely.At present, have several different methods to produce glycine, wherein, the alpha-halogen acid system is domestic main industrialized preparing process, and it is to be raw material with Mono Chloro Acetic Acid, ammonia, reacts in solvent phase in the presence of catalyzer urotropine (vulkacit H).Adopt the alpha-halogen acid system, solvent phase can be a water, but this water method is produced the method for glycine many defectives are arranged, for example exist catalyzer not reclaim, consumption is big, catalytic efficiency is low, the intact raw material of unreacted can not reuse, and owing to reasons such as system alkalescence are strong and moisture, easily generates the hydrolyzate oxyacetic acid, cause waste, contaminate environment; Inorganic salt separation difficulty such as the ammonium chloride that produces in the reaction, post-processing difficulty is big, building-up reactions endpoint difficulty or the like.In addition, reported also in the document that solvent is the method for preparing glycine of pure phase, but it still exists the reaction times longer, and reacts bad control, and catalyst efficiency is lower, detect (see figure 1) through NMR, there are two kinds of by products of 5%-7% to generate, thus still there is the lower defective of yield, and difficult solvent recovery, defectives such as solvent consumption is big are not suitable for the big production of industry.
There is bibliographical information to adopt hydroxyacetonitrile, amide and carbon dioxide reaction to prepare the method for glycine in recent years successively.This method can roughly be divided into following three classes again:
1) method that adopts alkali lye to carry out aftertreatment is referring to for example JP-A-06-065168, JP-A-05-320106, JP-A-53-031616, US5225592A, JP-A-02-250854, WO92/06069, JP-A-53-028115, CN1107139A.These patent documentations disclose employing alkali lye and have carried out aftertreatment, many employing acid neutralizations in subsequent operations, but have by-product object height in the product, inorganic salt are carried secretly seriously, and finished color is darker; Do not have optimized process conditions, so quality product is difficult to reach customer requirements.
2) method that adopts acid solution to carry out aftertreatment, for example JP-A-2-286651, JP-A-04-066559, JP-A-02-306946, JP-A-53-028116, US2384816A.When adopting mineral acid or organic acid derivatives to be hydrolyzed, the general basic metal aqueous solution such as sodium hydroxide or potassium hydroxide of adopting of neutralization neutralizes, exist product purity low equally, inorganic salt are carried secretly, the three wastes are handled difficult problem, and the product color that obtains is darker.
3) method that adopts the highly basic resin cation (R.C.) to carry out aftertreatment, for example JP-A-03-190851.The purity of this method reaction yield and glycine is undesirable.Aforesaid method adopts ammonia to react, need under the condition of High Temperature High Pressure, carry out, and severe reaction conditions, facility investment is big, and the separation problem of inorganic salt is effectively solved as yet.
Therefore, explore the easy operational path that the direct ammonia of hydroxyacetonitrile is separated, the alkaline hydrolysis legal system is equipped with glycine, find the recovery set usefulness of inorganic salt and the yield of raising glycine, it is valuable suppressing the generation of iminodiethanoic acid and easier separation and purification and clean preparation method.
At the deficiencies in the prior art, the present inventor has carried out deep research, invented and directly carried out intermittence or continuous reaction with hydroxyacetonitrile and excess of ammonia, high yield, highly selective obtains the commercial run of aminoacetonitriles, the ammonia of gained is separated liquid can high conversion under the determined processing condition of the present invention, highly selective obtains glycine, can well solve by different recycled flow processs and to reduce cost, reduce the material consumption energy consumption, cleaner production, three wastes resource utilization, the yield and the quality of raising product.This processing method can well solve the pyrolysis polymerization of aminoacetonitriles, the recycling of ammonia, and the recycling of ammonia and inorganic salt, glycine can reach about 95% the converted in-situ rate of hydroxyacetonitrile.The growing amount of wherein by product oxyacetic acid, iminodiethanoic acid and nitrilotriacetic acid seldom is more suitable for suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who aminoacetonitriles or the direct alkaline hydrolysis of interior uride mixture, neutralization is obtained glycine.
Preferably, the invention provides a kind of mixture and ammoniac compounds that adopts hydroxyacetonitrile maybe can produce hydroxyacetonitrile is initial feed, through ammonification, and alkaline hydrolysis, neutralization procedure, prepares the method for glycine to high purity at high yield.
Specifically, the invention provides a kind of method for preparing glycine, this method comprises the steps:
1), obtains containing the alkali solution liquid of glycinate with aminoacetonitriles and mineral alkali reaction;
2) above-mentioned alkali solution liquid is neutralized with mineral acid, obtain neutralizer (mainly containing glycine and inorganic salt);
3) the aftertreatment neutralizer obtains glycine product.
The inventive method can adopt for example following specific embodiments:
1) aminoacetonitriles, mineral alkali are mixed, the mol ratio of reaction mass is an aminoacetonitriles: mineral alkali=1: 0.7-3.0 is preferably 1: 1.0-1.5, temperature of reaction control is no more than 100 ℃, be preferably 20-80 ℃, reacted 1-8 hour, obtain containing the alkali solution liquid of glycinate; Mineral alkali can be the mixture of sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium hydroxide and sodium sulfate (potassium) or yellow soda ash (potassium), and preferred alkali is the mixture of sodium hydroxide or calcium hydroxide and sodium sulfate.
2) behind the alkali solution liquid deamination that step 1) is obtained with mineral acid neutralization, the consumption of mineral acid be in and the consumption of mineral alkali, for example, the mol ratio that adopts during reaction is a glycinate: mineral acid=1: 0.7-3.0 is preferably 1: 1.0-1.5 obtains neutralizer; Mineral acid is sulfuric acid, hydrochloric acid, nitric acid, carbonic acid (or feeding carbonic acid gas), phosphoric acid, Lewis acid etc., is preferably sulfuric acid, hydrochloric acid, carbonic acid gas.
3) pre-treatment step 2) neutralizer that obtains, decolouring, desalination, dehydration, crystallization, oven dry obtains white glycine solid.
In the aforesaid method, the aminoacetonitriles employing prepares aminating reaction liquid with the method that hydroxyacetonitrile maybe can produce the mixture ammonification of hydroxyacetonitrile, directly carries out alkaline hydrolysis.
Therefore, mixture and ammoniac compounds that the inventive method preferably adopts hydroxyacetonitrile maybe can produce hydroxyacetonitrile are initial feed, through ammonification, and alkaline hydrolysis, neutralization procedure prepares glycine, and described method comprises the steps:
1) mixture that hydroxyacetonitrile solution maybe can be produced hydroxyacetonitrile mixes with ammoniac compounds, obtains containing the aminating reaction liquid of aminoacetonitriles;
2) the aminating reaction liquid that step 1) is obtained mixes with mineral alkali, obtains containing the alkali solution liquid of glycinate;
3) above-mentioned alkali solution liquid is neutralized with mineral acid, obtain neutralizer;
4) post-processing step 3) neutralizer that obtains, obtain glycine.
When implementing above-mentioned preferred method, in step 1), hydroxyacetonitrile solution maybe can produce the mixture of hydroxyacetonitrile and the reaction control temperature of ammoniac compounds is not higher than 100 ℃, for example, 0-90 ℃, reacts 0.2-3 hour; The mol ratio that adopts during reaction is a hydroxyacetonitrile: ammoniac compounds=1: 0.5-12.0 is preferably 1: 1.0-8.5.
In step 2) in, the mol ratio that adopts during reaction is an aminoacetonitriles: mineral alkali=1: 0.7-3.0, be preferably 1: 1.0-1.5, control reaction temperature is no more than 100 ℃, for example under 20-80 ℃, reacted 1-8 hour, mineral alkali can be the mixture of sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium hydroxide and sodium sulfate (potassium) or yellow soda ash (potassium), and preferred alkali is the mixture of sodium hydroxide or calcium hydroxide and sodium sulfate.
In step 3), the mol ratio that adopts during reaction is a glycinate: mineral acid=1: 0.7-3.0, be preferably 1: 1.0-1.5, mineral acid is sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, carbonic acid gas, phosphoric acid, Lewis acid etc., is preferably sulfuric acid, hydrochloric acid, carbonic acid.
The preferred process of the present invention can adopt for example following specific embodiments:
1) at-10 ℃ under 100 ℃, for example under 0-90 ℃, the mixture and the ammoniac compounds that hydroxyacetonitrile solution maybe can be produced hydroxyacetonitrile mix, reacted 0.2-3 hour, the mol ratio of reaction mass is a hydroxyacetonitrile: ammoniac compounds=1: 1.0-8.5, preferred 1: 1.2-5.5 obtains containing the aminating reaction liquid of aminoacetonitriles;
2) above-mentioned aminating reaction liquid, mineral alkali are mixed, the mol ratio of reaction mass is an aminoacetonitriles: mineral alkali=1: 0.7-3 is preferably 1: 1.0-1.5, and control reaction temperature is no more than 100 ℃, for example under 20-80 ℃, reacts 1-8 hour, obtains glycinate; Mineral alkali can be the mixture of sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium hydroxide and sodium sulfate (potassium) or yellow soda ash (potassium), and preferred alkali is the mixture of sodium hydroxide or calcium hydroxide and sodium sulfate.
3) with step 2) neutralize with mineral acid behind the alkali solution liquid deamination that obtains, the consumption of mineral acid be in and the consumption of mineral alkali, for example, the mol ratio that adopts during reaction is a glycinate: mineral acid=1: 0.7-3.0, be preferably 1: 1.0-1.5, obtain neutralizer, mineral acid is sulfuric acid, hydrochloric acid, nitric acid, carbonic acid (or feeding carbonic acid gas), phosphoric acid, Lewis acid etc., is preferably sulfuric acid, hydrochloric acid, carbonic acid gas.
4) post-processing step 3) neutralizer that obtains, decolouring, desalination, dehydration, crystallization, oven dry obtain white glycine solid.
In the present invention, described hydroxyacetonitrile solution maybe can produce the mixture of hydroxyacetonitrile, and for example the latter can be the mixture of mixture, ammonium cyanide and formaldehyde of mixed solution, alkaline-earth metal prussiate and the formaldehyde of prussic acid and formaldehyde, preferably hydroxyacetonitrile.The molar weight of the hydroxyacetonitrile that adopts in the reaction is when only adopting hydroxyacetonitrile, in the molar weight of hydroxyacetonitrile, when adopting mixture, in the molar weight of formaldehyde in the mixture.
In the present invention, described ammoniac compounds is meant that ammonia maybe can produce the compound of ammonia, for example can be ammonia, ammoniacal liquor, inorganic ammonium salts such as ammonium nitrate, bicarbonate of ammonia, volatile salt etc., preferably ammonia and volatile salt.The molar weight of the ammoniac compounds that adopts in the reaction is when only adopting ammonia, in the molar weight of ammonia, when employing can produce the compound of ammonia, can produce the molar equivalent of ammonia in the compound.
In the present invention, described mineral alkali can be the mixture of sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium hydroxide and sodium sulfate (potassium) or yellow soda ash (potassium), and preferred alkali is the mixture of sodium hydroxide or calcium hydroxide and sodium sulfate.Adopt the molar weight of alkali in the reaction, when adopting sodium hydroxide, in the molar weight of sodium hydroxide, when adopting mixture, in the molar equivalent of hydroxide ion in the mixture.
In the present invention, described mineral acid can be sulfuric acid, hydrochloric acid, nitric acid, carbonic acid (or feeding carbonic acid gas), phosphoric acid, Lewis acid etc.Preferably sulfuric acid, hydrochloric acid, carbonic acid gas.
Adopt above-mentioned reaction method effectively to control reaction by control reaction raw materials, reaction conditions, highly selective obtains glycine.
The inventive method has following advantage:
One when adopting hydroxyacetonitrile class and Ammonia to be the method for starting raw material, can effectively reduce the generation of glycolylurea and peptide, is easier to the hydrolysis of product intermediate.
Its two, be in the method for starting raw material adopting hydroxyacetonitrile class and Ammonia, can directly the aminating reaction liquid caustic soda be separated, both can guarantee that hydrolysis is thorough, avoided the side reaction of ammonification liquid in the deamination process again.
They are three years old, neutralization procedure uses more cheap mineral acid to be raw material, can effectively reduce production costs, because the optimization processing condition that provided make the selectivity of glycine and transformation efficiency improve greatly, this technology has utilized glycine can effectively separate with the dissolubility difference of inorganic salt cleverly in addition, and obtains high yield, high-quality glycine.
The 4th, adopt the inventive method except can the refining glycine of preparing product purity＞99%, can also contain the crude product glycine of certain inorganic salt according to the disposable preparation with high yield of customer demand.In addition, the inventive method entire reaction mild condition, control easily, aftertreatment is simple, improves selectivity, yield and the quality of reaction well.The NMR process detects and shows that this processing method can make the generation of by product oxyacetic acid, iminodiethanoic acid and nitrilotriacetic acid(NTA) be effectively suppressed, thereby is more suitable for carrying out suitability for industrialized production.
Specific embodiment
The present invention can be further described with indefiniteness embodiment hereinafter.
The preparation of embodiment 1 glycine
At room temperature in reactor, add 400 grams, 50% hydroxyacetonitrile solution, feed 237 gram ammoniacal liquor, react after 30 minutes, in aminating reaction liquid, add the 526g32% sodium hydroxide solution again, obtain the ammonia solution of glycine sodium salt in 40-60 ℃ of insulation 4-5h, deamination obtains the Sodium glycocollate salts solution, adds the mixing solutions that obtains glycine and inorganic salt sodium sulfate in the 210g98% sulfuric acid with acidifying subsequently.Add 20g activated carbon decolorizing postcooling to 10 ℃, crystallization, the centrifugal sodium sulfate crystal of removing, filtrate crystallization purifying according to a conventional method can get glycine solid 235～250g, and purity can reach more than 98.5%, rolls over hundred yields 90～95%.
The preparation of embodiment 2 glycine
At room temperature in reactor, add 400 grams, 50% hydroxyacetonitrile solution, feed 237 gram ammoniacal liquor, react after 30 minutes, in aminating reaction liquid, add 299gNa again
2SO
4And 156gCa (OH)
2The mixing solutions of forming obtains the ammonia solution of glycinate in 40-60 ℃ of insulation 4-5h, and deamination obtains glycinate solution.Add subsequently in the 210g98% sulfuric acid and acidifying obtains the mixing solutions of glycine and inorganic salt sodium sulfate, calcium sulfate.After removing by filter calcium sulfate precipitation, add 20g activated carbon decolorizing postcooling to 10 ℃, crystallization, the centrifugal sodium sulfate crystal of removing is reduced to room temperature after the filtrate heating concentrates and is separated out the glycine crystal, the 220g that weighs after the drying, purity 98.5%, yield 82.35%.
The preparation of embodiment 3 glycine
At room temperature in reactor, add 400 grams, 50% hydroxyacetonitrile solution, feed 237 gram ammoniacal liquor, react after 30 minutes, in aminating reaction liquid, add the 526g32% sodium hydroxide solution again, obtain the ammonia solution of glycine sodium salt in 40-60 ℃ of insulation 4-5h, deamination obtains the Sodium glycocollate salts solution, adds in the 426.6g36% hydrochloric acid subsequently and acidifying, obtains the mixing solutions of glycine and inorganic salt sodium-chlor.After adding the 20g activated carbon decolorizing, be warming up to 90 ℃, be evaporated to crystal and separate out, filtered while hot is removed inorganic salt sodium-chlor, filtrate crystallization purifying according to a conventional method can obtain glycine solid 230～250g, and purity 98.5～99.5% is rolled over hundred yields 85～95%.
The preparation of embodiment 4 glycine
At room temperature in reactor, add 400 grams, 50% hydroxyacetonitrile solution, feed 237 gram ammoniacal liquor, react after 30 minutes, in aminating reaction liquid, add the 526g32% sodium hydroxide solution again, obtain the ammonia solution of glycine sodium salt in 40-60 ℃ of insulation 4-5h, deamination obtains the Sodium glycocollate salts solution, reduce to 10 ℃ after in the feed liquid logical CO
2Gas, after a large amount of solid precipitations occurring, the centrifugal sodium bicarbonate salt of removing, filtrate crystallization purifying according to a conventional method can obtain glycine solid 220～240g, and purity 99% is rolled over hundred yield 83-91%.
Claims (4)
1, a kind of new process for preparing glycine, this method comprises the steps:
1) hydroxyacetonitrile is mixed with excess of ammonia water, reaction obtains containing the ammonification liquid of aminoacetonitriles and ammoniacal liquor under the certain temperature condition;
2) in the above-mentioned ammonification liquid that obtains, directly add alkali, under suitable temperature and time condition, carry out the ammonia soln that alkaline hydrolysis obtains Sodium glycocollate;
3) post-processing step 2) ammonia soln of the Sodium glycocollate that obtains is by deamination, and acidifying obtains glycine and inorganic salt mixt;
4) utilize the difference in solubility of glycine and inorganic salt again,, can obtain saliniferous glycine and high purity glycine respectively by fractional crystallization and recrystallization, and the by-product inorganic salt.
2, according to the method for claim 1, it comprises the steps:
1) hydroxyacetonitrile, ammoniacal liquor are mixed, the mol ratio of reaction feed liquid is a hydroxyacetonitrile: ammonia=1: 2～10, the proportioning of optimizing is a hydroxyacetonitrile: ammonia=1: 3～6 control reaction temperature are between 20-60 ℃, the temperature of reaction of optimizing is 30-60 ℃, reaction times is 0.5-8 hour, can obtain the ammonia soln of aminoacetonitriles; Used ammoniacal liquor can be step 2) ammoniacal liquor that reclaims.
2) to step 1) aminoacetonitriles, mineral alkali are mixed, the mol ratio of reaction mass is an aminoacetonitriles: mineral alkali=1: 0.7-3.0 is preferably 1: 1.0-1.5, temperature of reaction control is no more than 100 ℃, be preferably 20-80 ℃, reacted 1-8 hour, obtain containing the alkali solution liquid of glycinate; Mineral alkali can be the mixture of sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium hydroxide and sodium sulfate (potassium) or yellow soda ash (potassium), and preferred alkali is the mixture of sodium hydroxide or calcium hydroxide and sodium sulfate
3) post-processing step 2) behind the alkali solution liquid deamination that obtains with the mineral acid neutralization, the consumption of mineral acid be in and the consumption of mineral alkali, for example, the mol ratio that adopts during reaction is a glycinate: mineral acid=1: 0.7-3.0 is preferably 1: 1.0-1.5 obtains neutralizer; Mineral acid is sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, carbonic acid gas, phosphoric acid, Lewis acid etc., is preferably sulfuric acid, hydrochloric acid, carbonic acid.Add activated carbon decolorizing subsequently, destainer can obtain qualified glycine and inorganic salt through concentrated fractional crystallization, recrystallization; Described acid can be sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, carbonic acid gas, phosphoric acid, Lewis acid etc., and preferred acid is sulfuric acid, hydrochloric acid, carbonic acid.
3, according to the method for claim 1, difference according to glycine and inorganic salt solubleness, can or concentrate by cooling, the method of cocrystallization and fractional crystallization, recrystallization obtains the glycine and the inorganic salt of different industrial requirements, for most preferably, wherein can apply mechanically among the claim 2-2 by sodium sulfate with sodium sulfate and sodium-chlor for separable inorganic salt.
4, according to the method for claim 1, described glycine neutralizer and thick product also can carry out purifying by electrodialysis except that recrystallization method is purified.
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| CN102432478A (en) * | 2011-11-09 | 2012-05-02 | 重庆紫光化工股份有限公司 | Preparation process of glycine |
| CN102633663A (en) * | 2012-03-20 | 2012-08-15 | 石家庄杰克化工有限公司 | Clean technique for producing nitrilotriacetic acid |
| CN101747218B (en) * | 2008-12-16 | 2013-02-13 | 北京紫光英力化工技术有限公司 | Method for removing impurities in glycine synthetic process |
| CN104744279A (en) * | 2015-04-03 | 2015-07-01 | 重庆紫光化工股份有限公司 | Method for removing impurities in glycine crystallization mother liquor |
| CN104892440A (en) * | 2015-04-16 | 2015-09-09 | 重庆紫光化工股份有限公司 | Clean production method of glycine and derivatives thereof |
| CN107325015A (en) * | 2017-08-15 | 2017-11-07 | 阳泉煤业（集团）有限责任公司 | A kind of method that hydroxyacetonitrile serialization prepares glycine |
| CN109879786A (en) * | 2019-04-02 | 2019-06-14 | 禄丰天宝磷化工有限公司 | A kind of technique of the continuous rapid synthesis methionine of cyanalcohol method |
| CN111484426A (en) * | 2020-05-18 | 2020-08-04 | 营口德瑞化工有限公司 | Method for synthesizing aminoacetonitrile hydrochloride from hydrocyanic acid |
| CN114507150A (en) * | 2022-02-22 | 2022-05-17 | 天宝动物营养科技股份有限公司 | Hydantoin precursor liquid and method for preparing glycine by using hydantoin precursor liquid |
| CN114524738A (en) * | 2022-02-22 | 2022-05-24 | 天宝动物营养科技股份有限公司 | Glycine preparation method for reducing iminodiacetic acid content |
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| CN101747218B (en) * | 2008-12-16 | 2013-02-13 | 北京紫光英力化工技术有限公司 | Method for removing impurities in glycine synthetic process |
| CN102432478A (en) * | 2011-11-09 | 2012-05-02 | 重庆紫光化工股份有限公司 | Preparation process of glycine |
| CN102432478B (en) * | 2011-11-09 | 2013-11-13 | 重庆紫光化工股份有限公司 | Preparation process of glycine |
| CN102633663A (en) * | 2012-03-20 | 2012-08-15 | 石家庄杰克化工有限公司 | Clean technique for producing nitrilotriacetic acid |
| CN104744279A (en) * | 2015-04-03 | 2015-07-01 | 重庆紫光化工股份有限公司 | Method for removing impurities in glycine crystallization mother liquor |
| CN104892440A (en) * | 2015-04-16 | 2015-09-09 | 重庆紫光化工股份有限公司 | Clean production method of glycine and derivatives thereof |
| CN107325015A (en) * | 2017-08-15 | 2017-11-07 | 阳泉煤业（集团）有限责任公司 | A kind of method that hydroxyacetonitrile serialization prepares glycine |
| CN107325015B (en) * | 2017-08-15 | 2020-03-17 | 阳泉煤业（集团）有限责任公司 | Method for continuously preparing glycine from hydroxyacetonitrile |
| CN109879786A (en) * | 2019-04-02 | 2019-06-14 | 禄丰天宝磷化工有限公司 | A kind of technique of the continuous rapid synthesis methionine of cyanalcohol method |
| CN111484426A (en) * | 2020-05-18 | 2020-08-04 | 营口德瑞化工有限公司 | Method for synthesizing aminoacetonitrile hydrochloride from hydrocyanic acid |
| CN114507150A (en) * | 2022-02-22 | 2022-05-17 | 天宝动物营养科技股份有限公司 | Hydantoin precursor liquid and method for preparing glycine by using hydantoin precursor liquid |
| CN114524738A (en) * | 2022-02-22 | 2022-05-24 | 天宝动物营养科技股份有限公司 | Glycine preparation method for reducing iminodiacetic acid content |
| CN115611758A (en) * | 2022-10-25 | 2023-01-17 | 安徽泰格生物科技有限公司 | Production method of sarcosine |
| CN115611758B (en) * | 2022-10-25 | 2024-05-07 | 安徽泰格生物科技有限公司 | Method for producing sarcosine |
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Addressee: Chongqing Sanxia Yingli Chemical Co., Ltd Document name: Notification of Termination of Patent Right |
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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100929 Termination date: 20131111 |