CN112028785B - Preparation method of green chelating agent glutamic acid diacetic acid sodium salt - Google Patents
Preparation method of green chelating agent glutamic acid diacetic acid sodium salt Download PDFInfo
- Publication number
- CN112028785B CN112028785B CN202010902845.5A CN202010902845A CN112028785B CN 112028785 B CN112028785 B CN 112028785B CN 202010902845 A CN202010902845 A CN 202010902845A CN 112028785 B CN112028785 B CN 112028785B
- Authority
- CN
- China
- Prior art keywords
- acid
- chelating agent
- sodium salt
- sodium glutamate
- preparation
- 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.)
- Active
Links
- -1 glutamic acid diacetic acid sodium salt Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 title claims description 19
- 235000013922 glutamic acid Nutrition 0.000 title claims description 19
- 239000004220 glutamic acid Substances 0.000 title claims description 19
- 239000002738 chelating agent Substances 0.000 title claims description 14
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 66
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 62
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000019253 formic acid Nutrition 0.000 claims abstract description 31
- 235000013923 monosodium glutamate Nutrition 0.000 claims abstract description 23
- 229940073490 sodium glutamate Drugs 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 claims abstract description 9
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims abstract 6
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000004321 preservation Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 abstract description 4
- 229940106681 chloroacetic acid Drugs 0.000 abstract description 4
- 231100000614 poison Toxicity 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 239000003440 toxic substance Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000000243 solution Substances 0.000 description 21
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 238000007599 discharging Methods 0.000 description 6
- GJBHGUUFMNITCI-QTNFYWBSSA-M sodium;(2s)-2-aminopentanedioate;hydron;hydrate Chemical compound O.[Na+].OC(=O)[C@@H](N)CCC([O-])=O GJBHGUUFMNITCI-QTNFYWBSSA-M 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 230000009919 sequestration Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004223 monosodium glutamate Substances 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- NDSNRTJGRWAWQD-UHFFFAOYSA-M ClCC(=O)[O-].[Na+].C(C)(=O)O Chemical compound ClCC(=O)[O-].[Na+].C(C)(=O)O NDSNRTJGRWAWQD-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017454 sodium diacetate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940061605 tetrasodium glutamate diacetate Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of glutamic diacetic acid sodium salt, belonging to the technical field of organic synthesis. The preparation method takes sodium glutamate, glyoxylic acid and formic acid as raw materials, and after the glyoxylic acid and the sodium glutamate fully react at a certain temperature, sodium glutamate diacetate saline solution is generated under the action of the formic acid. Sodium glutamate, glyoxylic acid and formic acid used in the method are all easily available raw materials, byproducts are mainly water and carbon dioxide, highly toxic substances such as cyanide and the like are abandoned, and a large amount of wastewater and toxic byproducts are not generated; chloroacetic acid is also abandoned as a raw material, so that the influence of chloride ions in the product on certain use scenes is prevented, and the method is green, economical, environment-friendly and easy for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and provides a preparation method for synthesizing a green chelating agent glutamic acid diacetic acid sodium salt by taking sodium glutamate and glyoxylic acid as raw materials.
Background
Glutamic acid diacetic acid sodium salt (GLDA) is a green chelating agent widely used in the market at present. The glutamic diacetic acid sodium salt has strong metal chelating capacity, and has similar performance to nitrilotriacetic acid (NTA), ethylene Diamine Tetraacetic Acid (EDTA), sodium tripolyphosphate (STTP) and the like. Among them, NTA is a suspicious carcinogen which has been prohibited by Europe and America, EDTA is not easily biodegradable, STTP contains phosphorus, and is easy to cause eutrophication of rivers and lakes, and the three substances all cause harm to the environment and human body. GLDA is undoubtedly the best choice, given the requirement of phosphorus-free, and considering the negative effects of EDTA and NTA on the environment and human body. The glutamic diacetic acid sodium salt has good biodegradability, the biodegradation rate in 28 days in OECD test exceeds 80%, and the glutamic diacetic acid sodium salt belongs to a harmless product in the latest classification of GHS. Sodium glutamate (monosodium glutamate) is used as a main raw material, more than half of carbon atoms are derived from natural carbon atoms, and the sodium glutamate (monosodium glutamate) is a sustainable development product.
Japanese patent JP1987039554A mentions a method for producing alkyl amino acids using sodium cyanide; european patent EP0913461A1 mentions the use of sodium glutamate diacetate and its related chelating agents, primarily for use in detergents; european patent EP1004571 discloses a method for preparing high-purity glutamic acid diacetic acid sodium salt, which improves the use value of the product; chinese patent CN101784513B proposes a method for preparing glutamic acid diacetic acid sodium salt by using sodium glutamate, hydrocyanic acid and formaldehyde, but the use of highly toxic substances such as cyanide and the like is still not avoided, and the generated toxic wastewater is difficult to treat; chinese patent CN109369427A proposes a method for preparing glutamic acid diacetic acid sodium salt by using sodium glutamate and chloroacetic acid as raw materials, but the product contains a large amount of chloride ions, which not only affects the product quality, but also causes damage to some use equipment.
Disclosure of Invention
The invention aims to provide a green method for preparing glutamic acid diacetic acid sodium salt, which takes sodium glutamate, glyoxylic acid and formic acid as raw materials, and generates a glutamic acid diacetic acid sodium salt aqueous solution under the action of formic acid after the glyoxylic acid and the sodium glutamate fully react at a certain temperature. Sodium glutamate, glyoxylic acid and formic acid used in the method are all easily available raw materials, byproducts are mainly water and carbon dioxide, highly toxic substances such as cyanide and the like are eliminated, and a large amount of wastewater and toxic byproducts are not generated; chloroacetic acid is also abandoned as a raw material, so that the influence of chloride ions in the product on certain use scenes is prevented, and the method is green, economical, environment-friendly and easy for large-scale industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a green chelating agent glutamic acid diacetic acid sodium salt comprises the following steps:
(1) Adding the metered sodium glutamate and deionized water into a reaction kettle, stirring and mixing uniformly at room temperature;
(2) Respectively filling glyoxylic acid, formic acid and liquid alkali into a dripping device for later use;
(3) Heating the reaction kettle in the step (1) to a specified temperature, starting to dropwise add glyoxylic acid, and continuing to keep the temperature for a period of time after dropwise addition is finished;
(4) After the heat preservation is finished, formic acid is dripped, negative pressure concentration is kept after the dripping is finished, and reflux heat preservation is carried out;
(5) Adding liquid alkali to adjust the pH value;
(6) Cooling to 40-60 ℃ to obtain the finished product of the sodium glutamate diacetate aqueous solution.
Further, the mass ratio of the sodium glutamate to the deionized water in the step (1) is 1. Furthermore, the mass ratio of the sodium glutamate to the deionized water in the step (1) is 1.
Further, the molar ratio of the sodium glutamate to the glyoxylic acid and the formic acid in the step (2) is 1.5-5.0. Furthermore, the molar ratio of the sodium glutamate to the glyoxylic acid and the formic acid in the step (2) is 1.5-3.0.
Further, the mass fraction of the glyoxylic acid is 40-50%, and the mass fraction of the formic acid is 80-90%.
Further, the specified temperature in the step (3) is 50-95 ℃, the dripping time of the glyoxylic acid is 0.5-8 hours, and the heat preservation time is 0.5-5 hours.
Further, the dripping temperature in the step (4) is 50-95 ℃, the dripping time of the formic acid is 0.5-8 hours, the negative pressure range is 0-minus 0.01Mpa, and the reflux heat preservation time is 2-12 hours.
Further, the mass fraction of the liquid caustic soda in the step (5) is 30-40%, and the pH value is adjusted to be 4-12.
The invention uses sodium glutamate, glyoxylic acid and formic acid as raw materials, uses glyoxylic acid to replace cyanide, chloroacetonitrile and chloroacetic acid in the traditional method, and obtains a green chelating agent, namely glutamic acid diacetic acid sodium salt through condensation reduction, wherein the specific reaction is as follows:
compared with the prior art, the invention has the beneficial effects that:
1. sodium glutamate, glyoxylic acid and formic acid are used as raw materials, so that the use of highly toxic substances is avoided, the product quality is improved, toxic by-products and chloride ions are not contained in the product, and the atom utilization rate is greatly improved.
2. Vacuum concentration is added, the reaction concentration is kept in the reaction process, the reaction efficiency is improved, and the effective content is increased.
3. The effective content in the product is greatly improved to more than 45 percent while the by-products are reduced.
4. The reaction condition is simple and mild, green, safe and environment-friendly, and is easy for industrial mass production.
Detailed Description
The present invention is described in detail below by way of examples, which should be construed as being merely illustrative, and not limitative of the remainder of the disclosure.
Example 1
936g of monosodium glutamate monohydrate and 702g of deionized water are added into a reaction kettle, stirred and mixed evenly at room temperature, and 1727g of glyoxylic acid (mass fraction is 45%), 530g of formic acid (mass fraction is 88%) and 980g of sodium hydroxide solution (mass fraction is 32%) are respectively filled into a dropping device for standby. Heating the reaction system to 90 ℃, starting to dropwise add glyoxylic acid, controlling the dropwise adding speed to keep the reaction temperature at 90 ℃, finishing dropwise adding within 1.5 hours, and preserving heat for 1 hour after dropwise adding. After the heat preservation, the reaction system is heated to 95 ℃, formic acid is dripped, the dripping speed is controlled to keep the reaction temperature at 95 ℃, the dripping is finished within 2 hours, after the dripping is finished, the heat preservation is carried out for 2 hours under the negative pressure condition of-0.01 Mpa, and the excess water in the reaction is removed. And (3) beginning to dropwise add liquid caustic soda, controlling the temperature to be less than 95 ℃, adjusting the pH to 9, cooling and discharging. 3850g of yellow transparent sodium glutamate diacetate solution is obtained, the effective content is 43 percent, and the product yield is 94 percent.
Example 2
936g of monosodium glutamate monohydrate and 936g of deionized water are added into a reaction kettle, stirred and mixed uniformly at room temperature, and 2056g of glyoxylic acid (with the mass fraction of 45%), 445g of formic acid (with the mass fraction of 88%) and 1080g of sodium hydroxide solution (with the mass fraction of 32%) are respectively filled into a dropping device for standby. Heating the reaction system to 60 ℃, starting to dropwise add glyoxylic acid, controlling the dropwise adding speed to keep the reaction temperature at 60 ℃, finishing dropwise adding within 2 hours, and keeping the temperature for 1 hour after dropwise adding. After the heat preservation, the reaction system is heated to 75 ℃, formic acid is dripped, the dripping speed is controlled, the reaction temperature is kept at 75 ℃, the dripping is finished within 2 hours, after the dripping is finished, the heat preservation is carried out for 3 hours under the negative pressure condition of-0.01 Mpa, and the excess water in the reaction is removed. And (3) beginning to dropwise add liquid caustic soda, controlling the temperature to be less than 75 ℃, adjusting the pH to 9, cooling and discharging. 4034g of yellow transparent sodium glutamate diacetate solution is obtained, the effective content is 38 percent, and the product yield is 87 percent.
Example 3
936g of monosodium glutamate monohydrate and 1158g of deionized water are added into a reaction kettle, stirred and mixed evenly at room temperature, and 1727g of glyoxylic acid (mass fraction is 45%), 530g of formic acid (mass fraction is 88%) and 1030g of sodium hydroxide solution (mass fraction is 32%) are respectively filled into a dropping device for standby. Heating the reaction system to 65 ℃, starting to dropwise add glyoxylic acid, controlling the dropwise adding speed to keep the reaction temperature at 65 ℃, finishing dropwise adding after 4 hours, and keeping the temperature for 1 hour after the dropwise adding is finished. After the heat preservation, the reaction system is heated to 95 ℃, formic acid is dripped, the dripping speed is controlled to keep the reaction temperature at 95 ℃, the dripping is finished within 3 hours, after the dripping is finished, the heat preservation is carried out for 4 hours under the negative pressure condition of-0.01 Mpa, and the excess water in the reaction is removed. Dropping liquid alkali, controlling the temperature to be less than 50 ℃, adjusting the pH value to 10, cooling and discharging. 4164g of yellow transparent glutamic acid disodium diacetate solution with an effective content of 43 percent and a product yield of 93 percent are obtained.
Example 4
936g of monosodium glutamate monohydrate and 1872g of deionized water are added into a reaction kettle, stirred and mixed uniformly at room temperature, and 1891g of glyoxylic acid (mass fraction of 45%), 630g of formic acid (mass fraction of 88%) and 1130g of sodium hydroxide solution (mass fraction of 32%) are respectively filled into a dripping device for standby. Heating the reaction system to 50 ℃, starting to dropwise add glyoxylic acid, controlling the dropwise adding speed to keep the reaction temperature at 50 ℃, finishing dropwise adding within 5 hours, and keeping the temperature for 1 hour after dropwise adding. After the heat preservation, the reaction system is heated to 75 ℃, formic acid is dripped, the dripping speed is controlled, the reaction temperature is kept at 75 ℃, the dripping is finished within 2 hours, after the dripping is finished, the heat preservation is carried out for 5 hours under the negative pressure condition of-0.01 Mpa, and the excess water in the reaction is removed. And (3) beginning to dropwise add liquid caustic soda, controlling the temperature to be less than 55 ℃, adjusting the pH to 11, cooling and discharging. 4337g of yellow transparent glutamic acid disodium diacetate solution is obtained, the effective content is 45 percent, and the product yield is 96 percent.
The product of this example was subjected to nuclear magnetic testing, and the resulting nuclear magnetic data: 1 H NMR(400MHz,D 2 O)(ppm)δ3.18-2.93(m,5H),2.17-1.97(m,2H),1.78-1.62(m，2H)。
example 5
936g of monosodium glutamate monohydrate and 1200g of deionized water are added into a reaction kettle, stirred and mixed uniformly at room temperature, and 1727g of glyoxylic acid (mass fraction of 45%), 730g of formic acid (mass fraction of 88%) and 1565g of sodium hydroxide solution (mass fraction of 32%) are respectively filled into a dripping device for standby. Heating the reaction system to 85 ℃, starting to dropwise add glyoxylic acid, controlling the dropwise adding speed to keep the reaction temperature at 85 ℃, finishing dropwise adding within 2.5 hours, and preserving the temperature for 2 hours after dropwise adding. And (3) dropwise adding formic acid after the heat preservation is finished, controlling the dropwise adding speed to keep the reaction temperature at 85 ℃, finishing dropwise adding within 1.5 hours, preserving the heat for 5 hours under the negative pressure condition of-0.01 Mpa after the dropwise adding is finished, and removing the excessive water in the reaction. And (3) beginning to dropwise add liquid caustic soda, controlling the temperature to be less than 50 ℃, adjusting the pH to 11, cooling and discharging. 4253g of yellow transparent glutamic acid sodium diacetate solution is obtained, the effective content is 44 percent, and the product yield is 95 percent.
Example 6
936g of monosodium glutamate monohydrate and 500g of deionized water are added into a reaction kettle, stirred and mixed uniformly at room temperature, and 2200g of glyoxylic acid (with the mass fraction of 45%), 730g of formic acid (with the mass fraction of 88%) and 1875g of sodium hydroxide solution (with the mass fraction of 32%) are respectively filled into a dripping device for standby. Heating the reaction system to 70 ℃, starting to dropwise add glyoxylic acid, controlling the dropwise adding speed to keep the reaction temperature at 70 ℃, finishing dropwise adding within 4.5 hours, and preserving the temperature for 1 hour after dropwise adding. After the heat preservation, the reaction system is heated to 85 ℃, formic acid is dripped, the dripping speed is controlled, the reaction temperature is kept at 85 ℃, the dripping is finished within 1.5 hours, after the dripping is finished, the heat preservation is carried out for 5 hours under the negative pressure condition of-0.01 Mpa, and the excess water in the reaction is removed. And (3) beginning to dropwise add liquid caustic soda, controlling the temperature to be less than 55 ℃, adjusting the pH to 11, cooling and discharging. 4550g of yellow transparent glutamic acid disodium diacetate solution is obtained, the effective content is 46 percent, and the product yield is 97 percent.
Example 7
The calcium sequestering performance of the samples of examples 1-6 was determined:
the experiments were carried out according to the method for determining the calcium sequestration value provided in GB/T26324-2010 hydroxyethylidenediphosphonic acid. The experimental conditions are as follows: about 1.5g of the sample (to the nearest 0.01 g) was weighed into a 250ml beaker and 100ml of deionized water was added. The beaker is placed on an electromagnetic stirrer, a stirrer is placed in the beaker, and stirring is started. The samples were mixed well and 10ml of sodium carbonate solution was added. The electrode was inserted into the solution, sodium hydroxide solution was added dropwise to a pH of 11, and water was added to 150ml. Titrating with calcium standard solution, and simultaneously dropwise adding sodium hydroxide solution to maintain the pH value at 11. The end point is that turbidity does not disappear when the solution appears.
Calcium sequestration value (as CaCO) 3 In ω) and values in mg/g: ω = ρ V (M) 1 /M 2 )/m
[ remarks: ρ, the value of the actual solution of the calcium standard solution in milligrams per milliliter (mg/ml); v, number of volumes of calcium standard solution consumed in titration, in milliliters (ml); m 1 The molar mass of calcium carbonate is given in grams per mole (g/mol) (M) 1 ＝100.09)；M 2 The value of the molar mass of calcium is given in grams per mole (g/mol) (M) 2 = 40.08); m, the numerical value of the mass of the sample, in grams (g).
The test results are shown in table 1.
Table 1 comparative results of calcium chelating properties of samples of examples
| Numbering | Effective content% | Calcium sequestration value (CaCO) 3 ,mg/g) |
| Example 1 | 43 | 229 |
| Example 2 | 38 | 215 |
| Example 3 | 43 | 231 |
| Example 4 | 45 | 245 |
| Example 5 | 44 | 240 |
| Example 6 | 46 | 247 |
| Outsourcing sample | 40 | 219 |
The test results in table 1 show that the sodium glutamate diacetate product prepared by the method has higher effective content, and the calcium chelating performance is superior to or equivalent to that of an outsourcing sample.
Note: the method for measuring the effective content of the sample comprises the following steps:
weighing about 0.5g of sample (accurate to 0.2 mg), placing the sample in a 250ml beaker, adding 50ml of chloroacetic acid-sodium acetate buffer solution with the pH value of 10ml and approximately equal to 3, adding 2 drops of 2 percent (mass percent) of titanium indicator, placing the beaker containing the sample on an electromagnetic stirrer, stirring uniformly, and titrating to bright green by using 0.1mol/L ferric trichloride standard titration solution while stirring, thus obtaining the end point.
Effective content in w 1 In% and w is calculated according to the formula 1 ＝V·C·M/1000m×100％
[ remarks: v, the value of the volume of ferric trichloride standard solution consumed in milliliters (ml); c, an accurate value of the actual concentration of the ferric trichloride standard titration solution, wherein the unit is mole per liter (ml/L); m, the number of molar masses of tetrasodium glutamate diacetate in grams per mole (g/mol) (M = 351); m, the numerical value of the mass of the sample, in grams (g).
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A preparation method of glutamic diacetic acid sodium salt as a green chelating agent is characterized by comprising the following steps:
(1) Adding the metered sodium glutamate and deionized water into a reaction kettle, stirring and mixing uniformly at room temperature;
(2) Respectively filling glyoxylic acid, formic acid and liquid alkali into a dripping device for later use;
(3) Heating the reaction kettle in the step (1) to a specified temperature, starting to dropwise add glyoxylic acid, and continuing to keep the temperature for a period of time after dropwise addition is finished;
(4) Dripping formic acid after the heat preservation is finished, keeping negative pressure concentration after the dripping is finished, and performing reflux heat preservation;
(5) Adding liquid alkali to adjust the pH value;
(6) And cooling to 40-60 ℃ to obtain the sodium glutamate diacetate aqueous solution.
2. The method for preparing glutamic diacetic acid sodium salt as a green chelating agent of claim 1, wherein the mass ratio of sodium glutamate to deionized water in the step (1) is 1.
3. The method for preparing glutamic acid diacetic acid sodium salt as a green chelating agent according to claim 1, wherein the molar ratio of sodium glutamate to glyoxylic acid and formic acid in the step (2) is 1.5 to 5.0.
4. The preparation method of the green chelating agent glutamic acid diacetic acid sodium salt according to claim 1, wherein the mass fraction of the glyoxylic acid is 40 to 50 percent, and the mass fraction of the formic acid is 80 to 90 percent.
5. The method for preparing the green chelating agent sodium glutamate diacetate according to the claim 1, wherein the temperature specified in the step (3) is 50 to 95 ℃, the dripping time of glyoxylic acid is 0.5 to 8 hours, and the holding time is 0.5 to 5 hours.
6. The preparation method of the green chelating agent glutamic acid diacetic acid sodium salt as the claim 1, wherein the dropping temperature in the step (4) is 50 to 95 ℃, the dropping time of formic acid is 0.5 to 8 hours, the negative pressure range is 0 to-0.01 MPa, and the reflux insulation time is 2 to 12 hours.
7. The preparation method of the green chelating agent glutamic acid diacetic acid sodium salt according to claim 1, wherein the mass fraction of the liquid alkali in the step (5) is 30 to 40%, and the pH value is adjusted to be 4 to 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010902845.5A CN112028785B (en) | 2020-09-01 | 2020-09-01 | Preparation method of green chelating agent glutamic acid diacetic acid sodium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010902845.5A CN112028785B (en) | 2020-09-01 | 2020-09-01 | Preparation method of green chelating agent glutamic acid diacetic acid sodium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112028785A CN112028785A (en) | 2020-12-04 |
| CN112028785B true CN112028785B (en) | 2023-01-31 |
Family
ID=73590419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010902845.5A Active CN112028785B (en) | 2020-09-01 | 2020-09-01 | Preparation method of green chelating agent glutamic acid diacetic acid sodium salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112028785B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920069A (en) * | 2021-02-01 | 2021-06-08 | 合肥艾普拉斯环保科技有限公司 | Biodegradable chelating agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009024519A1 (en) * | 2007-08-17 | 2009-02-26 | Akzo Nobel N.V. | Glutamic acid n,n-diacetic amide, glutamic acid n-acetic amide n-acetonitrile, alkali metal salts thereof, process to prepare them and their use |
| WO2011113822A1 (en) * | 2010-03-18 | 2011-09-22 | Basf Se | Method for producing aminocarboxylates low in by-product |
| CN105924365A (en) * | 2016-05-19 | 2016-09-07 | 河北诚信有限责任公司 | Method for continuously synthesizing tetrasodium glutamate diacetate through tubular reactor |
-
2020
- 2020-09-01 CN CN202010902845.5A patent/CN112028785B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009024519A1 (en) * | 2007-08-17 | 2009-02-26 | Akzo Nobel N.V. | Glutamic acid n,n-diacetic amide, glutamic acid n-acetic amide n-acetonitrile, alkali metal salts thereof, process to prepare them and their use |
| WO2011113822A1 (en) * | 2010-03-18 | 2011-09-22 | Basf Se | Method for producing aminocarboxylates low in by-product |
| CN105924365A (en) * | 2016-05-19 | 2016-09-07 | 河北诚信有限责任公司 | Method for continuously synthesizing tetrasodium glutamate diacetate through tubular reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112028785A (en) | 2020-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093296B (en) | Synthesis method of imidazoline compound | |
| US2855428A (en) | Preparation of amino nitriles | |
| CN103420497B (en) | Non-phosphorous corrosion and scale inhibitor containing lignosulfonate and application thereof | |
| CN112028785B (en) | Preparation method of green chelating agent glutamic acid diacetic acid sodium salt | |
| CN114162980B (en) | Reverse osmosis membrane scale inhibitor and preparation method thereof | |
| CN109369427A (en) | A kind of preparation method of four sodium of green chelating agent glutamic acid diacetic acid | |
| CN110980971B (en) | Non-phosphorus scale and corrosion inhibitor for industrial circulating water and preparation method thereof | |
| CN107814734A (en) | The preparation method of the green sodium of chelating agent aspartic acid oxalic acid four | |
| CN112919650A (en) | Scale and corrosion inhibitor, composition for scale and corrosion inhibitor, preparation method and application thereof | |
| US9403853B2 (en) | Trimethylolpropane core, phosphonic acid terminated dendrimer and its preparation method | |
| CN109503402B (en) | Preparation method of green chelating agent | |
| CN111020599A (en) | Corrosion inhibitor for soft water circulating heating/cooling system and preparation method thereof | |
| CN109400492B (en) | Preparation method of tetrasodium aspartate diacetate | |
| CN110563596B (en) | Preparation method of dicarboxymethylamino acid salt | |
| CN113477096A (en) | Alkaline low-phosphorus reverse osmosis membrane scale inhibitor and preparation method and application thereof | |
| CN109437415B (en) | Non-phosphorus reverse osmosis scale inhibitor PER-PAMAM and preparation method thereof | |
| CN112010769A (en) | Preparation method of green chelating agent methylglycine diacetic acid sodium salt | |
| CN114456277A (en) | Preparation method of ternary scale and corrosion inhibitor | |
| CN115678530A (en) | Shielding agent suitable for high-salinity water quality, guanidine gum fracturing fluid system and preparation method | |
| US4086146A (en) | Water treating process | |
| CN106396144A (en) | A water stabilizing agent for middle- and low-pressure steam boilers | |
| CN118221538A (en) | Preparation method of biodegradable chelating agent methyl glycine diacetic acid trisodium salt | |
| CN119119361B (en) | Terpolymer, terpolymer scale inhibitor and preparation method and application thereof | |
| CN107513158B (en) | Refining process of polyoxypropylene ether | |
| CN116693072B (en) | water treatment agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |