CN113861055A - Material washing method of industrial grade glycine crude product - Google Patents

Material washing method of industrial grade glycine crude product Download PDF

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CN113861055A
CN113861055A CN202111198059.2A CN202111198059A CN113861055A CN 113861055 A CN113861055 A CN 113861055A CN 202111198059 A CN202111198059 A CN 202111198059A CN 113861055 A CN113861055 A CN 113861055A
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washing
glycine
industrial grade
crude product
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姚红
田义群
彭春雪
刘三六
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Hubei Taisheng Chemical Co Ltd
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Hubei Taisheng Chemical Co Ltd
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    • 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

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Abstract

The invention relates to a washing method of an industrial grade glycine crude product, which aims at the glycine crude product (the main content of the glycine is 93-96%, the ammonium chloride is 2-5% and other impurities are 1-2%) produced by a novel process technology of glycine in a non-aqueous phase, and obtains a glycine product which meets the synthesis of glyphosate and reaches the national standard (the main content is more than or equal to 98.5% and the chloride radical is less than or equal to 0.4%) by two-step washing of a prepared mixed solvent (low-chain alcohol and inorganic base or organic base) and a low-chain alcohol solution.

Description

Material washing method of industrial grade glycine crude product
Technical Field
The invention discloses a material washing method for an industrial grade glycine crude product, belongs to the technical field of chemical production, and particularly relates to a novel method for producing a qualified glycine product in a non-aqueous solvent.
Background
Glycine, is an important chemical intermediate, and is pesticide, food, feed, medicine and the like in various fields according to the consumption ratio from high to low, and about 80% of glycine in China is used for producing herbicide glyphosate. At present, the traditional chloroacetic acid ammonolysis method using water as a solvent is still adopted by domestic glycine enterprises, and the method is continuously optimized in nearly 40 years, and still has the following problems: (1) the production cost is high. The urotropin catalyst cannot be recovered; 1 ton glycine requires about 6-7 tons of steam to be consumed; the method has high requirements on equipment and pipelines and high maintenance frequency when recovering the ammonium chloride with low added valueEquipment operation and maintenance costs are high. (2) The yield is low and is difficult to break through 85 percent. The alkalinity of a water phase system is strong, the conversion rate of chloroacetic acid into glycine is low, and about 15 percent of chloroacetic acid is hydrolyzed to generate glycolic acid; iminodiacetic acid (NH (CH) is easily generated when high-temperature ammonia is insufficient2COOH)2]And nitrilotriacetic acid [ N (CH)2COOH)3]And the like. (3) The environmental risk cannot be completely eliminated. The problems of decomposition of ammonium chloride and a catalyst urotropine at high temperature, complex chemical reaction caused by high temperature and the like can generate evaporation condensate water with high ammonia nitrogen and high COD and red filtrate. In addition, hazardous waste (ammonium dichloroacetate, ammonium trichloroacetate, urotropin, etc.) is present in low purity ammonium chloride products, and the current disposal methods may present legal risks.
The traditional chloroacetic acid ammonolysis method has a plurality of defects and can not completely meet the requirements of national policy or era development, so that the exploration of a new synthesis method from the source has strong practical significance for glycine production enterprises. In recent years, glycine enterprises compete to develop a new process technology for producing glycine in a non-aqueous solvent so as to greatly reduce the production cost and realize cleaner production. Currently, new glycine process technologies are continuously developed, but most of the new glycine process technologies are in a small test or a pilot test stage, only a crude glycine product (with a main content of 93-96%, 2-4% of ammonium chloride and 1% of other impurities) can be obtained, and qualified glycine products can be produced only through aftertreatment.
The invention patents with publication numbers of CN 102030669B and CN 103570568A mainly use urotropine or paraformaldehyde as a catalyst, use organic amine as an acid-binding agent to realize the separation of glycine and ammonium chloride, and use ammonia to recover triethylamine. However, the ammonia introduction amount, the reaction end point and the triethylamine are difficult to control, the ammonium chloride content in the glycine is high, and the glycine product which meets the national standard (the main content is more than or equal to 98.5 percent, and the chlorine content is less than or equal to 0.4 percent) and is suitable for the production of the glyphosate cannot be obtained. The method is disclosed as CN109836344, firstly mixing one or more of ethylene glycol, propylene glycol, dimethylacetamide, methanol and ethanol to prepare an organic solvent, then adding the organic solvent, urotropine, chloroacetic acid and ammonia in a glycine synthesis kettle to synthesize glycine, obtaining a byproduct ammonium chloride by adding ammonium chloride and chloroacetic acid or ammonium chloroacetate into the organic solvent under different temperature conditions, and obtaining the byproduct ammonium chloride by freezing and cooling. However, this method can only obtain crude glycine (main content is about 98%).
Disclosure of Invention
The invention aims to provide a washing method of an industrial grade glycine crude product, aiming at the glycine crude product (the main content of the glycine is 93-96%, the ammonium chloride is 2-5% and other impurities are 1-2%) produced by a novel process technology of glycine in a non-aqueous phase, the glycine product which meets the synthesis of glyphosate and reaches the national standard (the main content is more than or equal to 98.5% and the chloride radical is less than or equal to 0.4%) is obtained by simply washing the material, no waste water is generated, and clean production can be realized.
The invention is realized by the following steps and methods:
step (1), preparing a mixed solvent: preparing a mixed solution of more than 99% (mass fraction, the same below) of low-chain alcohol and inorganic base (or organic base) according to a weight ratio of 2: 1-10: 1 for later use.
Step (2), washing materials for the first time: the mixed solution is adopted to be washed for 2 times (the total volume is preferably 400-800L for 2 times) at the temperature of 20-40 ℃, the washing speed of a centrifuge is 200-500 rpm/min, the spin-drying speed is 500-850 rpm/min, and the washing liquid is circularly washed in a storage tank and the centrifuge for about 10 minutes.
And (3) washing the materials for the second time: washing with 50-400L of over 99% low-chain alcohol at a washing speed of 200-500 rpm/min and a spin-drying speed of 500-850 rpm/min, and feeding a washing solvent into the washing tank. The washing liquid can be repeatedly used, and after the accumulation reaches a certain amount, the washing liquid is recovered by rectification.
More preferably, the low-chain alcohol comprises one or more of methanol, ethanol, n-propanol, isopropanol, butanol and the like.
It is further preferred that the inorganic base comprises one or a combination of several of hydroxides of alkali metals of the first main group (lithium, sodium, potassium, rubidium, cesium).
More preferably, the organic base includes an alkoxide compound in which a hydrogen atom of an alcoholic hydroxyl group such as methanol or ethanol is substituted with an atom such as lithium, sodium, potassium, rubidium or cesium, and also includes an organic base compound such as a primary, secondary or tertiary amine in which a hydrogen atom in ammonia gas is substituted with another alkane.
The technical scheme of the invention has the following beneficial effects:
1) and washing the crude glycine product by using a mixed solvent, alcohol and other solvents in sequence to obtain a glycine product which has the main content of more than or equal to 98.5 percent and the chlorine content of less than or equal to 0.4 percent and is suitable for synthesizing glyphosate.
2) In recent years, the domestic glycine manufacturers still explore the new glycine process in a laboratory or a pilot-scale stage, and the method can be completely matched with a new process industrial production device.
3) At present, the yield of the new glycine process by the alcohol phase method generally reaches more than 95%, the total yield of the glycine is not influenced after the glycine is treated by the method, and the industrial production of the new process is guaranteed.
4) In recent years, the glycine new process explored by domestic glycine manufacturers mainly carries out laboratory small tests and industrial pilot-scale tests of different degrees around a mixed solvent method, an organic amine method, an electrodialysis method, a novel halogen preparation method and the like, but the qualified glycine products cannot be directly obtained by the methods. The method utilizes the chemical reaction between ammonium chloride and mixed solvent to process the crude glycine product produced by the new process into the glycine product meeting the national standard.
Drawings
FIG. 1 is a process diagram of crude glycine washing.
Detailed Description
Example 1
The industrial grade glycine washing centrifuge adopts a flat plate type automatic bag-pulling scraper discharging centrifuge of model L (P) of the manufacturing company L (P) of Jiangsu Saideli pharmaceutical machinery. The glycine crude product produced by any new glycine process technology enters a centrifuge, and is subjected to conventional feeding and centrifuging operations (solid materials are uniformly distributed on filter cloth of the centrifuge and have no material collapse, 400kg, and the main content of glycine is 96.9-9%8.1 percent and 0.9 to 2.5 percent of chloride ion content), and the method is adopted for washing materials: (1) firstly, 500L of ethanol with the mass fraction of 99 percent (the same below) and 100L of triethylamine with the content of 99 percent are prepared into a first mixed solution, a special material washing tank is used for storing the first mixed solution, and a pump is used for connecting a feed inlet of a centrifuge and a filtrate outlet with the material washing tank to form a circulating material washing loop. (2) Washing materials for the first time: adjusting the washing speed of the centrifuge to 200rpm/min, starting the centrifuge, starting the mixed liquid circulating pump, and circularly washing materials at 20 ℃ for 10 minutes; and then gradually increasing the rotating speed of the centrifuge to 850rpm/min for high-speed spin-drying for 5 min. (3) And (3) washing materials for the second time: readjusting the speed of the centrifuge to 200rpm/min, washing with 99% ethanol 200L for 1 time, and gradually increasing the rotation speed of the centrifuge to 850rpm/min for high-speed spin-drying for 5 min. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. Repeating the above operation for 5 times, and washing to obtain dry weight, product quality and yield (m)Before washing the material×ωPrincipal content×100/mAfter washing the material×ωPrincipal content) See table 1 below.
Figure BDA0003303849000000041
Example 2
The method and the steps are the same as the example 1, and only the step (1) is as follows: 500L of ethanol with the mass fraction of 99 percent and 150L of dimethylamine with the content of 99 percent are prepared into a first mixed solution, a special material washing tank is used for storing the first mixed solution, and a pump is used for connecting a feed inlet of a centrifuge and a filtrate outlet with the material washing tank to form a circulating material washing loop. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight, product quality and yield after washing (the same applies hereinafter) are shown in Table 2 below.
Figure BDA0003303849000000042
Figure BDA0003303849000000051
Example 3
The method and the steps are the same as the example 1, and only the step (1) is as follows: 500L of ethanol with the mass fraction of 99 percent and 10kg of caustic soda flakes are prepared into a first mixed solution, a special material washing tank is used for storing the first mixed solution, and a feed inlet and a filtrate outlet of a centrifuge are connected with the material washing tank by a pump to form a circulating material washing loop. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 3 below.
Figure BDA0003303849000000052
Example 4
The method and the steps are the same as the example 1, and only the step (1) is as follows: 500L of ethanol with the mass fraction of 99 percent and 10kg of sodium methoxide are prepared into a first mixed solution, a special material washing tank is used for storing the first mixed solution, and a feed inlet and a filtrate outlet of a centrifuge are connected with the material washing tank by a pump to form a circulating material washing loop. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 4 below.
Figure BDA0003303849000000053
Figure BDA0003303849000000061
Example 5
The method and the steps are the same as the example 1, and only the step (1) is as follows: firstly, preparing 500L of methanol with the mass fraction of 99% and 10kg of sodium methoxide into a first mixed solution, storing the first mixed solution by using a special material washing tank, and simultaneously connecting a feed inlet of a centrifuge and a filtrate outlet with the material washing tank by using a pump to form a circulating material washing loop. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 5 below.
Figure BDA0003303849000000062
Example 6
The method and the steps are the same as the example 1, and only the step (1) is as follows: 500L of 99 percent of glycol and 10kg of cesium hydroxide. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 6 below.
Figure BDA0003303849000000063
Example 7
The method and the steps are the same as the example 1, and only the step (1) is as follows: 500L of isopropanol and 10kg of sodium ethoxide with the mass fraction of 99 percent.
After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 7 below.
Figure BDA0003303849000000071
Example 8
The method and the steps are the same as the example 1, and only the step (1) is as follows: 99% mass fraction of methanol 500L. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 8 below.
Figure BDA0003303849000000072
Example 9
The method and the steps are the same as the example 1, and the material washing temperature in the step (2) is 50 ℃. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 9 below.
Figure BDA0003303849000000073
Figure BDA0003303849000000081
Example 10
The method and the steps are the same as the example 1, and the material washing temperature in the step (2) is 15 ℃. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 10 below.
Figure BDA0003303849000000082
Example 11
The method and steps are the same as example 1, only the centrifuge washing speed in step (2) is adjusted to 100 rpm/min. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 11 below.
Figure BDA0003303849000000083
Example 12
The method and steps are the same as example 1, only the centrifuge washing speed in step (2) is adjusted to 600 rpm/min. After glycine wet part is dried by a disc type dryer at 90 ℃, the particles are better. The above operations were repeated 5 times, and the dry weight after washing, the product quality and the yield (the same applies hereinafter) are shown in Table 12 below.
Figure BDA0003303849000000091

Claims (7)

1. A method for washing industrial grade glycine crude products is characterized by comprising the following steps:
step (1), preparing a mixed solvent: preparing a mixed solution of low-chain alcohol with the mass fraction of 99% and alkali for later use;
step (2), adding the mixed solvent prepared in the step (1) into industrial glycine for washing, and centrifuging after washing to obtain a material;
and (3) washing the material obtained in the step (2) again by using low-chain alcohol with the mass fraction of more than 99%, and centrifuging after washing to obtain a pure glycine product.
2. The method for washing the industrial-grade crude glycine as claimed in claim 1, wherein the weight ratio of the low-chain alcohol with the mass fraction of 99% to the alkali is 2: 1-10: 1.
3. The method as claimed in claim 1, wherein the low-chain alcohol comprises one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, and butanol.
4. The method as claimed in claim 1, wherein the base comprises inorganic base or organic base, wherein the inorganic base comprises any one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide;
the organic base comprises amine compounds of trimethylamine, triethylamine and guanidine, or alkoxy metal compounds of which the hydrogen atoms of the alcoholic hydroxyl groups of pyridine, methanol and ethanol are replaced by lithium, sodium, potassium, rubidium and cesium atoms, or organic base compounds of primary, secondary and tertiary amines of which the hydrogen atoms in ammonia gas are replaced by other alkanes.
5. The method for washing the industrial grade glycine crude product as claimed in claim 1, wherein the physical and chemical properties of the industrial grade glycine in the step (2) are that the main glycine content of the glycine is 93-96%, the ammonium chloride is 2-5%, and other impurities are 1-2%.
6. The method for washing the industrial grade glycine crude product as claimed in claim 1, wherein the washing is carried out at 20-40 ℃ for 8-15min, the rotation speed in the washing process is 200-500 rpm/min, and the spin-drying rotation speed in the centrifugation process is 600-850 rpm/min.
7. The method for washing the industrial grade glycine crude product as claimed in claim 1, wherein the washing in the step (3) is carried out at 20-40 ℃ for 8-15min, the rotation speed in the washing process is 200-500 rpm/min, and the spin-drying rotation speed in the centrifugation process is 600-850 rpm/min.
CN202111198059.2A 2021-10-14 2021-10-14 Material washing method of industrial grade glycine crude product Pending CN113861055A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470502A (en) * 2002-07-25 2004-01-28 北京清华紫光英力化工技术有限责任公 Method for purifying amino acetic acid by electrodialytic separation
CN105859571A (en) * 2015-01-19 2016-08-17 刘长飞 Method for producing glycine by mixed solvent method
CN109836344A (en) * 2017-11-26 2019-06-04 刘长飞 A kind of method of organic solvent production glycine
CN110305028A (en) * 2019-06-21 2019-10-08 湖北泰盛化工有限公司 A kind of device and technique of alcohol phase method washing glycine crude product
CN210656752U (en) * 2019-06-21 2020-06-02 湖北泰盛化工有限公司 Device for washing glycine crude product by alcohol phase method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470502A (en) * 2002-07-25 2004-01-28 北京清华紫光英力化工技术有限责任公 Method for purifying amino acetic acid by electrodialytic separation
CN105859571A (en) * 2015-01-19 2016-08-17 刘长飞 Method for producing glycine by mixed solvent method
CN109836344A (en) * 2017-11-26 2019-06-04 刘长飞 A kind of method of organic solvent production glycine
CN110305028A (en) * 2019-06-21 2019-10-08 湖北泰盛化工有限公司 A kind of device and technique of alcohol phase method washing glycine crude product
CN210656752U (en) * 2019-06-21 2020-06-02 湖北泰盛化工有限公司 Device for washing glycine crude product by alcohol phase method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
彭春雪等: "以三乙胺为缚酸剂合成甘氨酸的实验研究" *

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Application publication date: 20211231