阅读说明：本技术 一种甘氨酸二乙酸衍生物螯合剂的生产方法及生产装置 (Production method and production device of glycine diacetic acid derivative chelating agent ) 是由 曹清清 于 2019-12-31 设计创作，主要内容包括：本发明属螯合剂技术领域,尤其涉及一种甘氨酸二乙酸衍生物螯合剂的生产方法包括如下步骤：步骤1,将原料A与水混合,再向混合液中加入卤代乙酸和/或卤代乙酸盐、碱,并搅拌均匀；步骤2,调节pH值在6-13,在加热条件下,搅拌6-48h,即可得到产品混合液。有益效果在于,采用已广泛工业化大生产的工业原料为主要原料,原料简单易得,生产成本低；一步合成,合成工艺简单；反应条件温和,易于工业化生产；以水为溶剂,无有机溶剂的使用、处理和排放。反应产品结构单一,无副产物或副产物少。反应装置简单,无高压及过高温度,材质要求低,装置成本低。(The invention belongs to the technical field of chelating agents, and particularly relates to a production method of a glycine diacetic acid derivative chelating agent, which comprises the following steps: step 1, mixing the raw material A with water, adding halogenated acetic acid and/or halogenated acetate and alkali into the mixed solution, and uniformly stirring; and 2, adjusting the pH value to 6-13, and stirring for 6-48h under a heating condition to obtain a product mixed solution. The method has the advantages that industrial raw materials which are widely industrialized and produced in large scale are adopted as main raw materials, the raw materials are simple and easy to obtain, and the production cost is low; one-step synthesis and simple synthesis process; the reaction condition is mild, and the industrial production is easy to realize; water is used as a solvent, and no organic solvent is used, treated and discharged. The reaction product has a single structure and no or few byproducts. The reaction device is simple, has no high pressure or over high temperature, and has low material requirement and low device cost.)

1. A method for producing a glycine diacetic acid derivative chelating agent, comprising the steps of:

step 1, mixing the raw material A with water, adding halogenated acetic acid and/or halogenated acetate and alkali into the mixed solution, and uniformly stirring;

and 2, adjusting the pH value to 6-13, and stirring for 6-48h under a heating condition to obtain a product mixed solution.

2. A process for the production of glycine diacetic acid derivative chelating agent as claimed in claim 1, further comprising the following purification steps:

step 3, evaporating, concentrating and separating sodium halide from the product mixed solution to obtain the diacetic acid-based phosphorus-free chelating agent with low sodium halide content;

and 4) carrying out nanofiltration on the product treated in the step 3) to prepare the high-purity diacetic acid-based phosphorus-free chelating agent.

3. Process for the production of glycine diacetic acid derivative chelating agent according to claim 1, characterized in that the starting material a is a compound of general formula (I):

wherein:

R₁selected from: H. methyl, ethyl, formate, acetate

And all possible isomers of the above compounds, or hydrates of the above compounds and all possible isomers thereof; wherein: m may be H⁺、NH₄ ⁺、Na⁺、K⁺、Ca²⁺、Zn²⁺、Mg²⁺、Cu²⁺、Mn²⁺、Fe³⁺One or more of them.

4. The process for producing glycine diacetic acid derivative chelating agent according to claim 1, wherein the base is at least one of an oxide of an alkali metal, a hydroxide of an alkali metal, an oxide of an alkaline earth metal, and a hydroxide of an alkaline earth metal.

5. The process for the production of glycine diacetic acid derivative chelating agent as claimed in claim 1, wherein the salt of haloacetic acid is sodium chloroacetate.

6. The process for producing a glycine diacetic acid derivative chelating agent according to claim 1, wherein in step 1, the alkali is first added to the mixture of the raw material a and water, and after stirring the mixture to be uniform, the haloacetic acid and/or the haloacetate is added.

7. The process for the production of glycine diacetic acid derivative chelating agent as claimed in claim 1, wherein the amount of water added in step 1) is 30-70% wt of the total reaction system; according to the mass ratio, the adding amount of the raw material A is 1 standard part, and the adding amount of the haloacetic acid and/or the haloacetate is 0.9-1.3 parts; the heating temperature is from 55 ℃ to boiling reflux temperature.

8. The production device of the glycine diacetic acid derivative chelating agent is characterized by comprising a reaction device (1), a temperature regulating device (2), a detection device (3) and a liquid feeding device (4);

the reaction device (1) comprises a reactor (11) and a stirrer (12), wherein a solid feeding hole (111), a liquid feeding hole (112) and a discharging hole (113) are formed in the reactor (11), the solid feeding hole (111) is formed in the upper portion of the reactor (11), the liquid feeding hole (112) is formed in the upper portion of the reactor (11), and the discharging hole (113) is formed in the lower portion of the reactor (11); the stirrer (12) is arranged on the reactor (11) and used for promoting the materials in the reactor (11) to be uniformly mixed;

the temperature adjusting device (2) is arranged on the reactor (11), the temperature adjusting device (2) adopts at least one of a jacket, a coil and an electric heating device, the jacket and the coil exchange heat with materials in the reactor (11) through an internal heating medium, and the heat exchange comprises heating and/or cooling;

the detection device (3) comprises a thermometer (31), the thermometer (31) is arranged on the reactor (11) and is used for measuring the internal temperature of the reactor (11);

the liquid feed device (4) comprises a liquid storage tank (41); the outlet of the liquid storage tank (41) is connected with the liquid feeding hole (112).

9. The apparatus for the production of glycine diacetic acid derivative chelating agent according to claim 7, wherein the reaction apparatus (1) employs at least one of a tubular reactor, a tank reactor.

10. Glycine diacetic acid derivative chelating agent production plant according to claim 7, characterized in that the detection means (3) further comprise a level gauge (33), the level gauge (33) being arranged on the liquid storage tank (41) for measuring the liquid level inside the liquid storage tank (41).

11. Glycine diacetic acid derivative chelant production plant according to claim 9, characterized in that the level gauge (33) is interlocked with the valve opening at the liquid feed opening (112);

the thermometer (31) is connected and locked with the switch of the temperature adjusting device (2);

when the temperature adjusting device (2) adopts a jacket and/or a coil, the thermometer (31) is connected and locked with the opening of the outlet and/or inlet valve of the temperature adjusting device (2), and the temperature is automatically controlled by automatically adjusting the opening of the valve;

when the temperature adjusting device (2) adopts an electric heating device, the temperature measuring device is connected with the heat exchange device in a current locking way, and the temperature is automatically controlled by automatically adjusting the current.

Technical Field

The invention belongs to the technical field of chelating agents, and particularly relates to a production method and a production device of a glycine diacetic acid derivative chelating agent.

Background

Chelating agents currently have a wide range of applications. Wherein, the glycine diacetic acid and the derivatives thereof as the novel chelating agent have the characteristics of small toxic and side effects, easy degradation and the like. As such, the series of chelating agents are widely used in the fields of agriculture, printing and dyeing, washing, and the like.

The existing production methods all produce a series of isomer by-products and are difficult to purify. This causes an increase in production cost, which hinders the use of the series of chelating agents.

Based on the method, the invention provides a new synthesis method, which can obtain a product in one step under the mild condition of normal pressure, and the product has high selectivity and no isomer by-product.

Disclosure of Invention

The invention aims to solve the technical problem of providing a novel production method and a production device of a chelating agent, and aims to solve the problems of manual operation and multi-step reaction in the prior art.

The invention discloses a production method of glycine diacetic acid derivative chelating agent, comprising the following steps:

step 1, mixing the raw material A with water, adding halogenated acetic acid and/or halogenated acetate and alkali into the mixed solution, and uniformly stirring;

and 2, adjusting the pH value to 6-13, and stirring for 6-48h under a heating condition to obtain a product mixed solution.

Further, the method also comprises the following purification steps:

step 3, evaporating, concentrating and separating sodium halide from the product mixed solution to obtain the diacetic acid-based phosphorus-free chelating agent with low sodium halide content;

and 4) carrying out nanofiltration on the product treated in the step 3) to prepare the high-purity diacetic acid-based phosphorus-free chelating agent.

Further, the raw material A is a compound shown in a general formula (I):

wherein:

R₁selected from: H. methyl, ethyl, formate, acetate

And all possible isomers of the above compounds, or hydrates of the above compounds and all possible isomers thereof; wherein: m may be H⁺、NH₄ ⁺、Na⁺、K⁺、Ca²⁺、Zn²⁺、Mg²⁺、Cu²⁺、Mn²⁺、Fe³⁺One or more of them.

Further, the base is at least one of an oxide of an alkali metal, a hydroxide of an alkali metal, an oxide of an alkaline earth metal, and a hydroxide of an alkaline earth metal.

Further, sodium chloroacetate is adopted as the haloacetate.

Further, in step 1, firstly, adding alkali into the mixture of the raw material A and water, uniformly stirring, and then adding the haloacetic acid and/or the haloacetate. The aim is to prevent the thiourea group from decomposing under excessively high alkaline conditions.

Further, the adding amount of water in the step 1) is 30-70 wt% of the total reaction system; according to the mass ratio, the adding amount of the raw material A is 1 standard part, and the adding amount of the haloacetic acid and/or the haloacetate is 0.9-1.3 parts; the heating temperature is from 55 ℃ to boiling reflux temperature.

Furthermore, the invention also discloses a production device of the glycine diacetic acid derivative chelating agent, which comprises a reaction device, a temperature regulating device, a detection device and a liquid feeding device;

the reaction device comprises a reactor and a stirrer, wherein a solid feeding hole, a liquid feeding hole and a discharging hole are formed in the reactor, the solid feeding hole is formed in the upper portion of the reactor, the liquid feeding hole is formed in the upper portion of the reactor, and the discharging hole is formed in the lower portion of the reactor; the stirrer is arranged on the reactor and used for promoting the materials in the reactor to be uniformly mixed;

the temperature adjusting device is arranged on the reactor and adopts at least one of a jacket, a coil and an electric heating device, the jacket and the coil exchange heat with materials in the reactor through internal heating media, and the heat exchange comprises heating and/or cooling;

the detection device comprises a thermometer, and the thermometer is arranged on the reactor and used for measuring the internal temperature of the reactor;

the liquid feed device comprises a liquid storage tank; and the outlet of the liquid storage tank is connected with the liquid feeding hole.

Further, the detection device also comprises a pH meter which is arranged on the reactor and used for measuring the pH value inside the reactor.

Further, the reaction device adopts at least one of a tubular reactor and a kettle type reactor.

Further, detection device still includes the level gauge, the level gauge sets up on the liquid storage tank for measure the inside liquid level of liquid storage tank.

Further, the liquid level meter is connected with the opening degree of a valve at the liquid feed inlet;

the thermometer is connected with the temperature adjusting device switch;

when the temperature adjusting device adopts a jacket and/or a coil, the thermometer is connected with the opening of the outlet and/or inlet valve of the temperature adjusting device, and the temperature is automatically controlled by automatically adjusting the opening of the valve;

when the temperature adjusting device adopts an electric heating device, the temperature measuring device is connected with the heat exchange device in a current locking way, and the temperature is automatically controlled by automatically adjusting the current.

Further, the production device of the glycine diacetic acid derivative chelating agent further comprises a solid feeding device, wherein the solid feeding device comprises a solid storage tank and a solid feeder; the inlet of the solid feeder is connected with the outlet of the solid storage tank, and the outlet of the solid feeder is connected with the solid feeding hole.

Further, the bottom of the solid storage tank is conical, and the outlet of the solid storage tank is arranged at the bottommost part of the conical shape.

Further, the solid feeder adopts at least one of a conveyor belt and a screw feeder.

Further, the glycine diacetic acid derivative chelating agent production device further comprises an alarm, the alarm is connected with the detection device, and when the numerical value of the detection device exceeds a preset value, the alarm gives an alarm. When the liquid level of the liquid level meter exceeds the highest preset value and/or the lowest preset value, the alarm gives an alarm; and when the thermometer exceeds a preset value, the alarm gives an alarm.

Further, the production device of the glycine diacetic acid derivative chelating agent further comprises a filtering device, and the filtering device is connected with the discharge hole. The filtering device is used for filtering solid impurity particles in the product, and the filtrate is the product which can be directly canned for sale.

Particularly, in the production method, the reaction raw materials and the product are free of gas, the reaction can be carried out under normal pressure without high-pressure equipment, and the reaction system is carried out under a water phase.

The invention has the beneficial effects that:

1. the industrial raw materials which are widely industrialized and produced in large scale are adopted as the main raw materials, the raw materials are simple and easy to obtain, and the production cost is low; one-step synthesis and simple synthesis process; the reaction condition is mild, and the industrial production is easy to realize; water is used as a solvent, and no organic solvent is used, treated and discharged.

2. The reaction product has a single structure and no or few byproducts.

3. The reaction device is simple, has no high pressure or over high temperature, and has low material requirement and low device cost.

Drawings

FIG. 1 is a schematic view of a connection structure according to the present invention;

FIG. 2 is a schematic view of a reaction apparatus according to the present invention;

FIG. 3 is a schematic view of the structure of the solid feeding device of the present invention.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.