阅读说明：本技术 一种硫脲基螯合剂的生产方法及生产装置 (Production method and production device of thiourea-based chelating agent ) 是由 常领山 张杰纯 朱洪波 于 2019-12-29 设计创作，主要内容包括：本发明属螯合剂技术领域,尤其涉及一种硫脲基螯合剂的生产方法及生产装置。将原料A、与水混合,再向混合液中加入原料B及碱,并搅拌均匀；调节pH值在6-13,在加热条件下,搅拌6-48h,即可得到产品硫脲基螯合剂。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 and a production device of a thiourea-based chelating agent. Mixing the raw material A with water, adding the raw material B and alkali into the mixed solution, and uniformly stirring; adjusting the pH value to 6-13, and stirring for 6-48h under the heating condition to obtain the thiourea-based chelating agent. 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 thiourea-based chelating agent, comprising the steps of:

step 1, mixing a raw material A with water, adding a raw material B and alkali into the mixed solution, and uniformly stirring;

and 2, regulating the pH value to 6-13, and stirring for 6-48h under a heating condition to obtain the thiourea-based chelating agent.

2. The method of claim 1, wherein the thiourea-based chelating agent is a compound represented by the general formula (I):

wherein:

R₁、R₂selected from:

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.

3. The method of claim 2, wherein the preferred structure of the thiourea-based chelating agent is:

(1)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

and all possible isomers of the above compounds, or hydrates of the above compounds and all possible isomers thereof.

4. The method of claim 1, wherein the raw material a is a compound capable of producing urea (carbamide) by hydrolysis, alkaline hydrolysis, acid hydrolysis or a compound represented by the general formula (II) and esters, amides, salts thereof:

wherein R is₃Selected from:

H、

any one of the groups; wherein: m may be H⁺、NH₄ ⁺、Na⁺、K⁺、Ca²⁺、Zn²⁺、Mg²⁺、Cu²⁺、Mn²⁺、Fe³⁺One or more of them.

The raw material B can be generated by hydrolysis, alkaline hydrolysis and acidolysis

A compound of any one of the groups;

the alkali is any one or mixture of more of alkali metal, alkaline earth metal oxide, hydroxide, carbonate, bicarbonate and ammonia derivatives in any proportion.

5. The method for producing a thiourea-based chelating agent as claimed in claim 1, wherein in the step 1, the alkali is added to the mixture of the raw material a and water, and after stirring uniformly, the raw material B is added.

6. The method of claim 1, wherein water is added in an amount of 30 to 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 raw material B is 0.9-1.3 parts; the heating temperature is from 55 ℃ to boiling reflux temperature.

7. The production device of the thiourea-based 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).

8. The apparatus for producing a thiourea-based chelating agent as defined in claim 7, wherein said reaction unit (1) employs at least one of a tubular reactor and a tank reactor.

9. The apparatus for producing a thiourea-based chelating agent as defined in claim 7, wherein said detecting means (3) further comprises a liquid level meter (33), said liquid level meter (33) being disposed on said liquid tank (41) for measuring a liquid level inside said liquid tank (41).

10. The apparatus for producing a thiourea-based chelating agent as defined in claim 9, wherein said level gauge (33) is interlocked with a valve opening at said liquid feed port (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 thiourea-based chelating agent.

Background

Among the 16 medium nutrient elements necessary for plant growth, calcium and sulfur are used as medium elements to play a remarkable role. Wherein, calcium can stabilize the structure of the biological membrane and keep the integrity of cells, and plays an important role in the aspects of selective absorption of plant ions, growth, aging, information transmission and plant stress resistance.

Sulfur is an indispensable component constituting proteins and enzymes. Cystine, cysteine and methionine in plants are three sulfur-containing amino acids, essential for the synthesis of proteins, and thus sulfur is a constitutional element of protoplasm; the synthesis of amino acid, fat and carbohydrate is participated in coenzyme A, and the coenzyme A, thiamine, biotin and other vitamins contain sulfur; sulfur is also a component of thioredoxin, iron-sulfur protein and nitrogenase, and plays an important role in reactions such as photosynthesis, nitrogen fixation and the like. When the plants lack sulphur, the leaves of the whole plants are faded and are light green or yellow green; the leaves are uniformly faded, the young leaves are obvious compared with the old leaves, the leaves are small and thin, and the falling is early; stem growth is hindered, the plant is short, stiff and suberized; delayed growth period, etc.

At present, common sulfur supplement is mainly performed by ammonium sulfate, and although the sulfur supplement has the advantage of low price, the sulfur supplement is easy to react with sulfate radicals due to the fact that soil contains abundant calcium (ions), calcium sulfate precipitates are generated, so that the plants can be seriously inhibited from absorbing and utilizing calcium and sulfur, and the generated calcium sulfate can cause soil hardening and inhibit the respiration of plant roots.

At present, a sulfur-containing chelating agent is urgently needed in agriculture, which not only can supplement sulfur for plants, but also can activate calcium ions in soil and supplement chelated calcium for the plants. And the production process is simple and is easy for large-scale industrial production.

No sulphur-reducing chelating agent exists in the current market, and the thiourea-based polycarboxyl chelating agent can just meet the requirement.

Disclosure of Invention

The invention aims to solve the technical problem of providing a chelating agent containing sulfur and capable of activating calcium element and a production method thereof, so as to solve the problem of soil hardening caused by adding ammonium sulfate in the fertilizer in the prior art.

The invention discloses a production method of a thiourea-based chelating agent, which comprises the following steps:

step 1, mixing a raw material A with water, adding a raw material B and alkali into the mixed solution, and uniformly stirring;

and 2, regulating the pH value to 6-13, and stirring for 6-48h under a heating condition to obtain the thiourea-based chelating agent.

Further, the thiourea-based chelating agent is a compound represented by the general formula (I):

wherein:

R₁、R₂selected from:

and all possible isomers of the above compounds, or hydrates of the above compounds and all possible isomers thereof.

Further, the present invention discloses a preferred structure of the thiourea-based chelating agent:

and all possible isomers of the above compounds, or hydrates of the above compounds and all possible isomers thereof.

Further, the raw material a is a compound capable of producing urea (carbamide) by hydrolysis, alkaline hydrolysis, acid hydrolysis or a compound represented by the general formula (II) and esters, amides thereof by hydrolysis, alkaline hydrolysis, acid hydrolysis:

wherein R is₃Selected from:

H、

any one of the groups;

wherein: m may be H⁺、NH₄ ⁺、Na⁺、K⁺、Ca²⁺、Zn²⁺、Mg²⁺、Cu²⁺、Mn²⁺、Fe³⁺One or more of them.

Further, the raw material B can be generated by hydrolysis, alkaline hydrolysis and acidolysis

A compound of any one of the groups.

Preferably, the raw material B adopts:

and any one or a mixture of more of anhydride, salt and ester of the compound in any proportion.

Further, the alkali is any one or a mixture of several of alkali metal, alkaline earth metal oxide, hydroxide, carbonate, bicarbonate and ammonia (and derivatives) in any proportion.

Preferably, the alkali is at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate.

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

Further, in the production method, the adding amount of water is 30-70 wt% of the total reaction system.

Further, in the production method, according to the mass ratio, the adding amount of the raw material A is 1 standard part, and the adding amount of the raw material B is 0.9-1.3 parts.

Preferably, in the production method, the adding amount of the raw material A is 1 standard part and the adding amount of the raw material B is 1 part according to the mass ratio.

Further, in the production method, the heating temperature is 55 ℃ to the boiling reflux temperature.

Preferably, in the production method, the heating temperature is 85 ℃.

Furthermore, the invention also discloses a production device of the thiourea-based 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 thiourea-based chelating agent also 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 production device of the thiourea-based chelating agent 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 thiourea-based chelating agent also 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.