阅读说明：本技术 一种用黄磷生产红磷的新工艺 (New process for producing red phosphorus by using yellow phosphorus ) 是由 徐先海 彭治华 于 2019-12-16 设计创作，主要内容包括：本发明涉及红磷生产技术领域,公开了一种用黄磷生产红磷的新工艺。本发明通过S1.熔融、S2.粉碎、S3.转化、S4.老化、S5.碱煮、S6.漂洗和S7.分离七步工序,成功将黄磷制成了粉末状的红磷。本发明具有以下优点和效果：1、工艺更加先进,本发明使用了流化剂生产出粉末状红磷,生产中途不用进行人工分选、凿取、转移等复杂的操作,可以实现自动化生产。2、安全更有保障,仅S1和S7两个步骤需要工人接触磷,其他工序中都不接触到磷,生产安全性得到极大提高。3、效率明显提高,本发明工艺改变,需要的工人数大幅减少,降低人工成本；生产周期缩短,产品产量提高；未反应黄磷量少,产品质量提高。4、更加节能环保,水和副产品都能循环利用,减少废物排放。(The invention relates to the technical field of red phosphorus production, and discloses a novel process for producing red phosphorus by using yellow phosphorus. The invention successfully prepares the yellow phosphorus into the powdery red phosphorus through seven steps of S1 melting, S2 crushing, S3 converting, S4 aging, S5 alkali boiling, S6 rinsing and S7 separating. The invention has the following advantages and effects: 1. the process is more advanced, the fluidizing agent is used for producing the powdery red phosphorus, the complex operations such as manual sorting, chiseling, transferring and the like are not needed in the production process, and the automatic production can be realized. 2. Safety is guaranteed, workers are required to contact phosphorus in only two steps S1 and S7, phosphorus is not contacted in other processes, and production safety is greatly improved. 3. The efficiency is obviously improved, the process of the invention is changed, the number of required workers is greatly reduced, and the labor cost is reduced; the production cycle is shortened, and the product yield is improved; the amount of unreacted yellow phosphorus is less, and the product quality is improved. 4. The energy is saved, the environment is protected, water and byproducts can be recycled, and the waste discharge is reduced.)

1. A new process for producing red phosphorus by using yellow phosphorus is characterized by comprising the following steps:

s1, melting: putting yellow phosphorus into a melting tank, and heating to a molten state;

s2, dispersing: adding warm water into the high-pressure reaction kettle, adding the yellow phosphorus in the molten state in the S1 and the fluidizing agent into the high-pressure reaction kettle, and starting a stirring paddle to stir and disperse;

s3, transformation: keeping the stirring paddle running, raising the temperature of the reaction kettle to the conversion temperature, and preserving the heat for 35-40 hours;

s4, aging: evaporating water by using waste heat, sending the water into a pure water tank, leaving unstable red phosphorus, raising the temperature of the reaction kettle to an aging temperature without stopping the operation of a stirring paddle, and aging for a period of time;

s5, alkaline cooking: introducing cooling water into a jacket of the reaction kettle, cooling to below 100 ℃, adding pure water, uniformly stirring, and feeding into an alkaline cooking tank for alkaline cooking for a period of time;

s6, rinsing: s5, feeding wet red phosphorus subjected to alkali cooking in the alkali cooking step into a rinsing pool for rinsing;

s7, separation: and S6, feeding the rinsed red phosphorus in rinsing into multistage hydrocyclones for separation, wherein the separation particle size of each stage of hydrocyclones is reduced in sequence, and the wet red phosphorus separated from each hydrocyclone is dried independently to obtain the red phosphorus with various particle sizes, wherein the red phosphorus separated from the first stage needs to be sieved by a 200-mesh sieve after being dried, cannot be ground by the 200-mesh sieve and then is sieved until the red phosphorus can be sieved by the 200-mesh sieve, and the wet red phosphorus separated from the last stage is not dried and is directly used for producing the flame retardant.

2. The process of claim 1, wherein the process comprises the steps of: s1, in melting, the temperature of the melting tank for melting yellow phosphorus is set to be 45-55 ℃.

3. The process of claim 1, wherein the process comprises the steps of: in the step S2, the fluidizing agent comprises the following components in parts by mass:

sodium aluminate: 10-15 parts;

polyethylene glycol: 6-8 parts;

polyvinylpyrrolidone: 5-8 parts;

7-10 parts of oxalic acid.

4. The process of claim 2, wherein the process comprises the steps of: the adding amount of the fluidizing agent is that 6-8 parts of warm water is added into each 1000 parts of the warm water in parts by mass, the adding method comprises the steps of adding polyethylene glycol, oxalic acid and polyvinylpyrrolidone into a high-pressure reaction kettle, stirring and dissolving, adding melted yellow phosphorus, stirring and dispersing the yellow phosphorus for 2-4 minutes, and then adding sodium aluminate.

5. The process of claim 1, wherein the process comprises the steps of: in the steps S2, S3 and S4, the rotating speed of the stirring paddle is set to be 80-120 r/min.

6. The process of claim 1, wherein the process comprises the steps of: in the step S3, the conversion temperature is 270-290 ℃.

7. The process of claim 1, wherein the process comprises the steps of: in the S4, the aging temperature is set to 290 ℃ and 300 ℃.

8. The process of claim 1, wherein the process comprises the steps of: in the step S4, the aging time is 10-12 hours.

9. The process of claim 1, wherein the process comprises the steps of: in step S5, the hydrocyclone is at least three-stage.

Technical Field

The invention belongs to the technical field of red phosphorus production, and particularly relates to a novel process for producing red phosphorus by using yellow phosphorus.

Background

At present, the technological process for producing red phosphorus comprises the following steps: yellow phosphorus → melting in a pot → high temperature conversion → ball milling → alkali boiling → cleaning → centrifugal dehydration → vacuum drying → packaging and warehousing. The transformation principle is as follows: the yellow phosphorus is heated for a long time at about 295-300 ℃ under the condition of air isolation, and can be converted into red phosphorus, and after the grinding material and the alkali boiling reaction, the finished product red phosphorus is obtained after cleaning, dehydration and drying.

Patent publication No. CN108640094A provides an industrial process for producing red phosphorus, which comprises preparing yellow phosphorus by electric furnace method, grinding yellow phosphorus, heating under inert gas protection for three-stage heating to convert into red phosphorus, grinding, and decocting with alkali to obtain red phosphorus powder. The method firstly needs to transfer the yellow phosphorus for many times, so that the method has great harm to the life health of workers, and meanwhile, the yellow phosphorus has lower safety when being exposed in the air, and simultaneously, a great deal of manpower is consumed.

Patent publication No. CN108726493A provides a method for preparing red phosphorus under high pressure, which comprises melting yellow phosphorus, heating the molten yellow phosphorus in a high-pressure closed kettle to 280 plus 285 deg.C, taking out the red phosphorus block from the kettle, grinding, alkali washing, rinsing and drying to obtain red phosphorus powder. The method has the defects that the red phosphorus blocks are actually tightly combined with the kettle wall in the high-pressure closed kettle, workers are required to chisel and take the red phosphorus blocks when the red phosphorus blocks are taken out, time and labor are wasted, the health safety of the workers is threatened, and the temperature of the reaction kettle needs to be reduced to be low enough for the workers to contact the reaction kettle, so that energy is wasted.

Disclosure of Invention

The invention aims to provide a new process for producing red phosphorus by using yellow phosphorus, which has the effects of reducing pollution and waste.

The technical purpose of the invention is realized by the following technical scheme:

a new process for producing red phosphorus by using yellow phosphorus comprises the following steps:

s1, melting: putting yellow phosphorus into a melting tank, and heating to a molten state;

s2, dispersing: adding warm water into the high-pressure reaction kettle, adding the yellow phosphorus in the molten state in the S1 and the fluidizing agent into the high-pressure reaction kettle, and starting a stirring paddle to stir and disperse;

s3, transformation: keeping the stirring paddle running, raising the temperature of the reaction kettle to the conversion temperature, and preserving the heat for 35-40 hours;

s4, aging: evaporating water by using waste heat, sending the water into a pure water tank, leaving unstable red phosphorus, raising the temperature of the reaction kettle to an aging temperature without stopping the operation of a stirring paddle, and aging for a period of time;

s5, alkaline cooking: introducing cooling water into a jacket of the reaction kettle, cooling to below 100 ℃, adding pure water, uniformly stirring, and feeding into an alkaline cooking tank for alkaline cooking for a period of time;

s6, rinsing: s5, feeding wet red phosphorus subjected to alkali cooking in the alkali cooking step into a rinsing pool for rinsing;

s7, separation: and S6, feeding the rinsed red phosphorus in rinsing into multistage hydrocyclones for separation, wherein the separation particle size of each stage of hydrocyclones is reduced in sequence, and the wet red phosphorus separated from each hydrocyclone is dried independently to obtain the red phosphorus with various particle sizes, wherein the red phosphorus separated from the first stage needs to be sieved by a 200-mesh sieve after being dried, cannot be ground by the 200-mesh sieve and then is sieved until the red phosphorus can be sieved by the 200-mesh sieve, and the wet red phosphorus separated from the last stage is not dried and is directly used for producing the flame retardant.

As a further improvement of the invention: s1, in melting, the temperature of the melting tank for melting yellow phosphorus is set to be 45-55 ℃.

By adopting the technology, the yellow phosphorus has a good melting effect at 45-55 ℃, cannot be dissolved at too low temperature, and has a risk of deflagration at too high temperature.

As a further improvement of the invention: in the step S2, the fluidizing agent comprises the following components in parts by mass:

sodium aluminate: 10-15 parts;

polyethylene glycol: 6-8 parts;

polyvinylpyrrolidone: 5-8 parts;

7-10 parts of oxalic acid.

As a further improvement of the invention: the adding amount of the fluidizing agent is that 6-8 parts of warm water is added into each 1000 parts of the warm water in parts by mass, the adding method comprises the steps of adding polyethylene glycol, oxalic acid and polyvinylpyrrolidone into a high-pressure reaction kettle, stirring and dissolving, adding melted yellow phosphorus, stirring and dispersing the yellow phosphorus for 2-4 minutes, and then adding sodium aluminate.

By adopting the technology, polyethylene glycol, polyvinylpyrrolidone and oxalic acid are firstly dissolved in water to form a high molecular system, then yellow phosphorus is added and stirred, the polyvinylpyrrolidone has a certain surfactant effect and can separate the yellow phosphorus from the water, the reaction of the yellow phosphorus and dissolved oxygen in the water in a temperature rise period is avoided, and meanwhile, the polyvinylpyrrolidone has a certain reducibility and can consume the dissolved oxygen in the water in the temperature rise process; after adding sodium aluminate, starting hydrolysis under the action of oxalic acid, and forming aluminum hydroxide particles under the action of polyethylene glycol and polyvinylpyrrolidone; in the later stage of temperature rise, the polyethylene glycol, the polyvinylpyrrolidone and the sodium oxalate are gradually decomposed and separated from the aluminum hydroxide particles to form porous aluminum hydroxide particles, compared with the kettle wall, the aluminum hydroxide particles have huge surface area, so that yellow phosphorus molecules can be adsorbed to react on the aluminum hydroxide particles, and powdery red phosphorus is finally formed instead of red phosphorus agglomerated on the kettle wall; the decomposition products of polyethylene glycol and polyvinylpyrrolidone and aluminium hydroxide particles can be completely removed in the alkaline boiling process, and the by-product sodium aluminate can be continuously used as the raw material of the fluidizing agent after being refined.

As a further improvement of the invention: in the steps S2, S3 and S4, the rotating speed of the stirring paddle is set to be 80-120 r/min.

As a further improvement of the invention: in the step S3, the conversion temperature is 270-290 ℃.

As a further improvement of the invention: in the S4, the aging temperature is set to 290 ℃ and 300 ℃.

As a further improvement of the invention: in the step S4, the aging time is 10-12 hours.

By adopting the technology, the red phosphorus is unstable when the conversion is completed, the aging process needs to be carried out for one end time, and the solvent needs to be discharged before the aging process, so that only the emptying valve on the high-pressure reaction kettle needs to be opened to generate steam by utilizing waste heat and lead the steam into the pure water tank, and the condensed water can be used for secondary production.

As a further improvement of the invention: in step S5, the hydrocyclone is at least three-stage.

Compared with the prior art, the invention has the beneficial effects that:

1. the process is more advanced. The invention further improves the type, quality and parts of the fluidizing agent, does not need to start a reaction kettle to carry out complicated operations such as manual sorting, chiseling, transferring and the like during production, and can realize automatic production.

2. The safety is more guaranteed. In the invention, workers are only required to contact phosphorus in the charging and final separation of the melting tank, and the workers do not contact phosphorus in other processes, thereby greatly reducing the poisoning probability. The temperature can be automatically controlled, and the production safety is greatly improved.

3. The efficiency is obviously improved. The process is changed, the number of required workers is greatly reduced, the labor cost is reduced, and the production efficiency is improved; the production cycle is shortened, and the product yield is improved; the amount of unreacted yellow phosphorus is small, and the product quality is improved; the production efficiency and the economic benefit are both obviously improved.

4. The energy is saved and the environment is protected. And water and byproducts can be recycled, so that waste discharge is reduced. The whole production process is finished at one step, and the energy consumption is reduced.

Detailed Description

The technical solutions in the examples will be clearly and completely described below.