CN111892515A - A kind of production method and production device of urea-based chelating agent - Google Patents

Abstract

The invention belongs to the technical field of chelating agents, and particularly relates to a production method and a production device of a carbamido 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 heating condition to obtain the product ureido 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.

Description

A kind of production method and production device of urea-based chelating agent

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 urea-based chelating agent.

Background technique

Calcium, magnesium, zinc, manganese, iron, copper and other elements are trace elements necessary for plant growth. Although these elements are not lacking in nature, they are generally less available for direct absorption and utilization by plants. The reason is that these elements are easily deposited as insoluble salts in the soil environment, or are adsorbed by soil colloids and cannot move , resulting in the inability to be absorbed and utilized by plants.

In addition, a large amount of element phosphorus required for plant growth is generally applied with fertilizers such as ammonium phosphate and potassium dihydrogen phosphate, and the existence of phosphate radicals can easily form phosphate precipitates with calcium, magnesium, zinc, manganese, iron, copper, etc. As a result, not only plants cannot absorb trace elements, but also affect the absorption and utilization of phosphorus.

In order to activate the trace elements in the soil and fertilizer, and at the same time inhibit the influence of phosphate radicals on their precipitation, a chelating agent can be added to the fertilizer to generate chelated micro-fertilizer, which can promote the absorption and utilization of plants without affecting the absorption of phosphorus by plants. Utilization, improve fertilizer efficiency, and play significant economic and social value.

At present, the main agricultural chelating agent is EDTA (ethylenediaminetetraacetic acid and its various salts). However, due to its non-biodegradability, non-absorption and utilization by plants, potential carcinogenicity, and large-scale use will cause environmental pollution and other disadvantages, domestic Some industries are beginning to restrict and ban their use. For example, in '5.1.1 of "Textile Products HJ 2546-2016", it is clearly prohibited to use: ethylenediaminetetraacetate (EDTA) and diethyltriaminepentaacetate (DTPA)'; "cultural paper HJT 410 -2007", 'In 5.1.3, the use of ethylenediaminetetraacetic acid (EDTA) is prohibited'. In addition, it has been used in agriculture for many years, and there are many residues in the soil, and its yield increasing effect is decreasing year by year. At present, a new type of easily degradable chelating agent is urgently needed to meet the market demand.

Although there are new types of easily degradable chelating agents (such as IDS, iminodisuccinic acid and its salts) on the market currently used as fertilizer synergists, but they are biodegraded into water, carbon dioxide, etc., and then increase the amount of carbon emissions in the atmosphere. At the same time, raw materials are wasted.

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

At present, such sulfur-reducing chelating agents have not been seen on the market, and thiourea-based polycarboxyl chelating agents can just meet the requirements.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a chelating agent containing sulfur and capable of activating calcium element and a production method thereof, so as to solve the problem of soil compaction caused by adding ammonium sulfate to fertilizers in the prior art.

The invention discloses a production method of urea-based chelating agent, comprising the following steps:

Step 1, mix raw material A and water, then add raw material B and alkali to the mixed solution, and stir evenly;

Step 2, adjust the pH value at 6-13, and stir for 6-48h under heating condition, and then the product urea-based chelating agent can be obtained.

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

in:

R ₁ , R ₂ are selected from:

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

Wherein: M can be one or more of H ⁺ , NH ₄ ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Cu ²⁺ , Mn ²⁺ , Fe ³⁺ .

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

(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.

Wherein: M can be one or more of H ⁺ , NH ₄ ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Cu ²⁺ , Mn ²⁺ , Fe ³⁺ .

Further, further, the raw material A can be produced by hydrolysis, alkali hydrolysis and acid hydrolysis

A compound of any of the groups.

Preferably, the raw material A adopts:

And any one or a mixture of any proportion of the acid anhydrides, salts and esters of the above compounds.

The raw material B is capable of producing urea (carbon amide) by hydrolysis, alkali hydrolysis and acid hydrolysis, or a compound represented by general formula (IV) and its ester, amide and salt, which can be produced by hydrolysis, alkali hydrolysis and acid hydrolysis,

wherein _R is selected from:

any one of the groups;

Wherein: M can be one or more of H ⁺ , NH ₄ ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Cu ²⁺ , Mn ²⁺ , Fe ³⁺ .

Further, the alkali adopts any one or a mixture of any one or more of the oxides, hydroxides, carbonates, bicarbonates and ammonia (and derivatives) of alkali metals and alkaline earth metals in any proportion.

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

Further, in step 1, alkali is firstly added to the mixture of raw material A and water, and then the raw material B is added after stirring uniformly. The purpose is to prevent the decomposition of the urea group under too high alkaline conditions.

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

Further, in the production method, according to the amount of the material, the amount of the raw material A added is 1 standard part, and when the raw material B is urea (carbamide), the added amount is 0.4-0.6 part.

Preferably, in the production method, according to the amount of substances, the addition amount of the raw material A is 1 standard part, and when the raw material B is urea (carbamide), the addition amount is 0.5 part.

Further, in the production method, according to the amount of the material, the amount of the raw material A added is 1 standard part, and the raw material B is when the compound represented by the general formula (IV) and its ester, amide, and salt are used. , the addition amount is 0.9-1.3 parts.

Preferably, in the production method, according to the amount of the material, the amount of the raw material A added is 1 standard part, and the raw material B is when the compound represented by the general formula (IV) and its ester, amide, and salt are used. , the addition amount is 1 part. .

Further, in the production method, the heating temperature is from 55°C to the boiling reflux temperature.

Preferably, in the production method, the heating temperature is 95°C-100°C.

Further, the present invention also discloses a production device for the urea-based chelating agent, including a reaction device, a temperature adjustment device, a detection device, and a liquid feeding device;

The reaction device includes a reactor and a stirrer, the reactor is provided with a solid feed port, a liquid feed port, and a discharge port, the solid feed port is arranged on the upper part of the reactor, and the liquid feed The material outlet is arranged at the upper part of the reactor, and the material outlet is arranged at the lower part of the reactor; the agitator is arranged on the reactor to promote uniform mixing of the materials inside the reactor;

The temperature adjustment device is arranged on the reactor, and the temperature adjustment device adopts at least one of a jacket, a coil, and an electric heating device. The jacket and the coil communicate with the reactor through the internal heat medium. The internal material is subjected to heat exchange, and the heat exchange includes heating and cooling;

The detection device includes a thermometer, which is arranged on the reactor and is used to measure the internal temperature of the reactor;

The liquid feeding device includes a liquid storage tank; the outlet of the liquid storage tank is connected with the liquid feeding port.

Further, the detection device further includes a pH meter, which is arranged on the reactor and is used to measure the pH value inside the reactor.

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

Further, the detection device further includes a liquid level gauge, which is arranged on the liquid storage tank and is used to measure the liquid level inside the liquid storage tank.

Further, the liquid level gauge is interlocked with the valve opening at the liquid feed port;

The thermometer is interlocked with the switch of the temperature regulating device;

When the temperature adjusting device adopts a jacket and a coil, the thermometer is interlocked with the opening of the outlet and the 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 current of the heat exchange device, and the temperature is automatically controlled by automatically adjusting the magnitude of the current.

Further, the production device of the thiourea-based chelating agent also includes a solid feeding device, and the solid feeding device includes a solid storage tank and a solid feeder; the inlet of the solid feeder and the outlet of the solid storage tank connected, the solid feeder outlet is connected with the solid feed port.

Further, the bottom of the solid storage tank is conical, and the outlet of the solid storage tank is arranged at the bottom of the cone.

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 includes an alarm device, which is linked with the detection device. When the value of the detection device exceeds a preset value, the alarm device generates an alarm. When the liquid level of the liquid level gauge exceeds the highest preset value and the lowest preset value, the alarm device generates an alarm; when the thermometer exceeds the preset value, the alarm device generates an alarm.

Further, the production device of the thiourea-based chelating agent further includes a filter device, and the filter device is connected with the discharge port. 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.

It should be noted that, in the production method of the present invention, the reaction raw materials and products are gas-free, the reaction can be carried out under normal pressure, no high-pressure equipment is required, and the reaction system is carried out in the aqueous phase.

The beneficial effects of the present invention are:

1. The industrial raw materials that have been widely industrialized and produced are used as the main raw materials, the raw materials are simple and easy to obtain, and the production cost is low; one-step synthesis, the synthesis process is simple; the reaction conditions are mild, and it is easy to industrialize production; water is used as a solvent, and there is no use of organic solvents, disposal and discharge.

2. The reaction product has a single structure, no by-products or few by-products.

3. The reaction device is simple, without high pressure and excessive temperature, low material requirements, and low device cost.

Description of drawings

Fig. 1 is the connection structure schematic diagram of the present invention;

Fig. 2 is the structural formula diagram of the reaction device of the present invention;

Figure 3 is a schematic diagram of the structure of the solid feeding device according to the present invention.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

The invention discloses a production method of urea-based chelating agent, comprising the following steps:

Raw material A uses

Raw material B is used;

Sodium hydroxide is used as the base.

Step 1, mix 10 mol of raw material A with water, add 10 mol of sodium hydroxide to mix and stir evenly, then add 10 mol of raw material B and stir evenly;

In step 2, the pH value is adjusted to 9.5, and the product is stirred at 95° C. for 32 hours to obtain the product chelating agent, trisodium ureidodisuccinate.

The invention also discloses a production device for the urea-based chelating agent, comprising a reaction device 1, a temperature adjustment device 2, a detection device 3, and a liquid feeding device 4;

The reaction device 1 includes a reactor 11 and a stirrer 12. The reactor 11 is provided with a solid feed port 111, a liquid feed port 112, and a discharge port 113. The solid feed port 111 is provided in the In the upper part of the reactor 11, the liquid feed port 112 is arranged in the upper part of the reactor 11, and the outlet port 113 is arranged in the lower part of the reactor 11; the agitator 12 is arranged on the reactor 11 for To promote the uniform mixing of materials in the reactor 11;

The temperature adjustment device 2 is arranged on the reactor 11, and the temperature adjustment device 2 adopts at least one of a jacket, a coil, and an electric heating device. The materials in the reactor 11 are subjected to heat exchange, and the heat exchange includes heating and cooling;

The detection device 3 includes a thermometer 31, and the thermometer 31 is arranged on the reactor 11 for measuring the internal temperature of the reactor 11;

The liquid feeding device 4 includes a liquid storage tank 41 ; the outlet of the liquid storage tank 41 is connected to the liquid feeding port 112 .

In this embodiment, the detection device further includes a pH meter 32 , and the pH meter 32 is arranged on the reactor 11 for measuring the pH value inside the reactor 11 .

As described in this embodiment, the reaction device 1 adopts at least one of a tubular reactor and a tank reactor.

In this embodiment, the detection device 3 further includes a liquid level gauge 33 . The liquid level gauge 33 is disposed on the liquid storage tank 41 and is used to measure the liquid level inside the liquid storage tank 41 .

In this embodiment, the liquid level gauge 33 is interlocked with the valve opening at the liquid feed port 112;

The thermometer 31 is interlocked with the switch of the temperature adjusting device 2;

When the temperature regulating device 2 adopts a jacket and a coil, the thermometer 31 is interlocked with the opening of the outlet and inlet valves of the temperature regulating device 2, and the temperature is automatically controlled by automatically adjusting the valve opening;

When the temperature adjusting device 2 adopts an electric heating device, the temperature measuring device is connected with the current of the heat exchanging device, and the temperature is automatically controlled by automatically adjusting the magnitude of the current.

As described in this embodiment, the production device for the urea-based chelating agent further includes a solid feeding device 5, and the solid feeding device 5 includes a solid storage tank 51 and a solid feeder 52; the solid feeder 52 The inlet is connected to the outlet of the solid storage tank 51 , and the outlet of the solid feeder 52 is connected to the solid feeding port 111 .

In this embodiment, the bottom of the solid storage tank 51 is conical, and the outlet of the solid storage tank 51 is arranged at the bottom of the cone.

In this embodiment, the solid feeder 52 adopts at least one of a conveyor belt and a screw feeder.

As described in this embodiment, the production device for the urea-based chelating agent further includes an alarm 6, which is linked with the detection device 3. When the value of the detection device 3 exceeds a preset value, the The alarm device 6 generates an alarm. When the liquid level of the liquid level gauge 33 exceeds the highest preset value and the lowest preset value, the alarm device 6 generates an alarm; when the thermometer 31 exceeds the preset value, the alarm device 6 generates an alarm.

As described in this embodiment, the production device for the urea-based chelating agent further includes a filter device 7 , and the filter device 7 is connected to the discharge port 113 . The filtering device 7 is used to filter solid impurity particles in the product, and the filtrate is the product that can be directly canned for sale.

Examples 2-6

Embodiment 2-6 still adopts the used method of embodiment 1, just changes the selection of raw material and the selection of reaction conditions, and concrete scheme is shown in table 1-4.

Examples 1-6,

Table 1 embodiment 1-6 raw material selection table

Table 2 embodiment 1-6 reaction condition table

Table 3 Examples 1-6 product urea-based chelating agent structural formula list

Remarks: For polycarboxyl compounds, their carboxylate and carboxyl groups coexist, the above compound structural formula is only to represent the structure of the obtained product, not all of its actual substances. For example, in reaction 7, only disodium ureidosuccinate is used to represent the main product N7 at pH=6.8, but in fact the solution is monosodium, disodium, and trisodium ureidosuccinate (and their hydrates). ) coexist, and ureidosuccinic acid and tetrasodium ureidosuccinate (and its hydrate) may also exist in trace amounts.

Table 4 embodiment 1-6 product urea-based chelating agent output and yield table

Example Yield (mol) 1 8 2 8.3 3 7.5 4 7.9 5 8.5 6 7.7 7 9.1 8 8.8

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (12)

1. A method for producing a urea-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, adjusting the pH value to 6-13, and stirring for 6-48h under a heating condition to obtain the carbamido chelating agent product.

2. The method for producing a urea-based chelating agent according to claim 1, wherein the urea-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 for the production of urea-based chelants according to claim 2, wherein the preferred structure of the urea-based chelants is:

(1)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

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

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

4. The method for producing a urea-based chelating agent according to claim 1, wherein the raw material A is a raw material capable of being produced by hydrolysis, alkaline hydrolysis or acid hydrolysis

A compound of any one of the groups;

the raw material B can generate urea (carbamide) through hydrolysis, alkaline hydrolysis and acid hydrolysis or generate a compound shown by a general formula (II) through hydrolysis, alkaline hydrolysis and acid hydrolysis, and ester, amide and salt thereof,

wherein R is₃Selected from:

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 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.

5. The method for the production of a urea-based chelant according to claim 1 wherein feedstock a is selected from the group consisting of: one or more of maleic acid (and salts), maleic anhydride, fumaric acid (and salts), glutaconic acid (and salts); the raw material B is selected from: urea (carbamide), ureido succinic acid (and salts), ureido glutaric acid (and salts).

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

7. The method for producing a carbamido chelating agent according to claim 1, wherein the water is added in an amount of 30-70 wt% of the total reaction system; according to the material quantity ratio, when the raw material A is added in 2 standard parts and the raw material B can generate urea (carbamide) through hydrolysis, alkaline hydrolysis and acidolysis, the adding quantity is 0.8-1.2 parts; the heating temperature is from 55 ℃ to boiling reflux temperature.

8. The method for producing a carbamido chelating agent according to claim 1, wherein the water is added in an amount of 30-70 wt% of the total reaction system; according to the quantity proportion of substances, when the raw material A is added in 1 standard part and the raw material B can generate the compound shown by the general formula (II) and the ester, amide and salt thereof through hydrolysis, alkaline hydrolysis and acid hydrolysis, the adding quantity is 0.8-1.2 parts; the heating temperature is from 55 ℃ to boiling reflux temperature.

9. The production device of the carbamido chelating agent is characterized by comprising a reaction device (1), a temperature adjusting 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 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).

10. The apparatus for producing a urea-based chelant according to claim 7 wherein the reaction apparatus (1) employs at least one of a tubular reactor and a tank reactor.

11. The apparatus for the production of urea-based chelant according to claim 7, wherein the detection device (3) further comprises a level gauge (33), the level gauge (33) being arranged on the liquid tank (41) for measuring the level inside the liquid tank (41).

12. The apparatus for producing a urea-based chelant according to claim 9, wherein the level gauge (33) is linked to the valve opening at the liquid feed inlet (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 a coil, the thermometer (31) is connected with the opening of an outlet and an inlet valve of the temperature adjusting device (2) and automatically controls the temperature 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.

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