阅读说明：本技术 电子级黄磷生产方法 (Production method of electronic grade yellow phosphorus ) 是由 杨亚斌 梅毅 何锦林 蒋波 叶林祥 于 2021-02-09 设计创作，主要内容包括：本发明属于磷化工技术领域,特别涉及黄磷除杂质和提纯成电子级黄磷的生产方法。所述方法包括工业黄磷与多聚磷酸在隔绝氧气的条件下混合搅拌、沉降分离得到含量为99.999％-99.99999％的电子级黄磷,其原理是利用多聚磷酸的络合性和螯合性除去黄磷中的金属元素、半金属元素及有机物得到超纯黄磷,多聚磷酸中添加双氧水、硝酸、硫酸等强氧化剂中的一种或多种。本发明所述生产方法得到的黄磷的回收率达94％以上,并且操作安全、流程简单、利于工业化,具有实用性和良好的经济效益。(The invention belongs to the technical field of phosphorus chemical industry, and particularly relates to a production method for removing impurities from yellow phosphorus and purifying the yellow phosphorus into electronic-grade yellow phosphorus. The method comprises the steps of mixing and stirring industrial yellow phosphorus and polyphosphoric acid under the condition of isolating oxygen, settling and separating to obtain electronic grade yellow phosphorus with the content of 99.999% -99.99999%, wherein the principle is that metal elements, semimetal elements and organic matters in the yellow phosphorus are removed by utilizing the complexation and chelation of the polyphosphoric acid to obtain ultrapure yellow phosphorus, and one or more strong oxidants such as hydrogen peroxide, nitric acid and sulfuric acid are added into the polyphosphoric acid. The recovery rate of the yellow phosphorus obtained by the production method of the invention reaches more than 94 percent, and the method has safe operation, simple flow, is beneficial to industrialization, and has practicability and good economic benefit.)

1. A production method of electronic grade yellow phosphorus is characterized in that industrial yellow phosphorus and polyphosphoric acid are mixed and stirred in a reactor under the condition of oxygen isolation, the characteristics of the complexation capacity and the chelation capacity of the polyphosphoric acid on metal elements and organic matters are utilized to complex and chelate the metal elements and the organic matters in the yellow phosphorus, and the density difference of two mediums of the polyphosphoric acid and the yellow phosphorus is utilized to carry out sedimentation separation on the mixture of the industrial yellow phosphorus and the polyphosphoric acid under the condition of oxygen isolation to obtain the electronic grade yellow phosphorus.

2. The method for producing electronic grade yellow phosphorus according to claim 1, wherein an oxidant is further added in the reaction of the industrial yellow phosphorus and the polyphosphoric acid, and the mass of the oxidant is 0-20% of that of the polyphosphoric acid.

3. The method for producing electronic grade yellow phosphorus according to claim 2, wherein the oxidant is one or more of hydrogen peroxide, nitric acid or sulfuric acid.

4. The method for producing electronic grade yellow phosphorus according to claim 2, wherein the mass ratio of the industrial yellow phosphorus to the mixed polyphosphoric acid containing the oxidant is 1: 0.05-0.9.

5. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the polyphosphoric acid is polyphosphoric acid with a phosphoric acid mass concentration of 100-120%.

6. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the reactor for industrial yellow phosphorus and polyphosphoric acid is a closed reactor isolated from air, and comprises a stirring reaction kettle, a tubular reactor and a micro-reactor.

7. The method of claim 1, wherein the isolation of oxygen is performed by filling inert gas such as nitrogen, argon, helium, or a mixture thereof.

8. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the mixing and stirring temperature of the industrial yellow phosphorus and the polyphosphoric acid is 45-80 ℃, and the mixing and stirring time is 0.5-3 h.

9. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the settling separation temperature of industrial yellow phosphorus and polyphosphoric acid is 45-80 ℃ and the settling separation time is 0.5-3 h.

10. The method for producing electronic grade yellow phosphorus according to any one of claims 1 to 9, characterized in that the method can remove more than 99% of metallic elements, semimetallic elements and organic impurities in industrial yellow phosphorus, and the obtained electronic grade yellow phosphorus has a purity of 99.999% -99.99999% and a yield of 94-99%.

Technical Field

The invention belongs to the technical field of phosphorus chemical industry, and particularly relates to a production method for removing impurities from yellow phosphorus and purifying the yellow phosphorus into electronic-grade yellow phosphorus.

Background

Yellow phosphorus, also called white phosphorus, has molecular formula P4, molecular weight 124.08, relative density of 1.82(20 deg.C), melting point of 44.1 deg.C, boiling point of 280 deg.C, and is white to light yellow brittle waxy solid. Yellow phosphorusIs an important basic chemical raw material, industrial yellow phosphorus is produced by an electric furnace method, and the product purity is generally 99.95 percent. The yellow phosphorus contains more metal elements, semimetal elements and organic impurities, so that the application of the yellow phosphorus in the semiconductor industry and the electronic industry is influenced, and the requirement of the production of high-purity electronic grade phosphoric acid on the purity of raw materials cannot be met in the production of the electronic grade phosphoric acid. The yellow phosphorus mainly contains metal elements such as calcium, magnesium, iron, aluminum, potassium, sodium, titanium, vanadium, chromium, cadmium, copper, nickel, lead, tin, zinc, antimony, manganese, cobalt, gallium and the like, semimetal elements mainly contain silicon, sulfur, arsenic, bismuth, boron, carbon and the like, organic substances mainly contain phenols, anthracene, tar, polyatomic polycyclic aromatic hydrocarbon and the like (commonly called oil component), wherein the most impurities are arsenic and organic substances, the next most impurities are iron, nickel, copper, zinc and antimony, and the total content of other impurities is 10^-9An order of magnitude. The high-purity electronic grade yellow phosphorus is mainly obtained by purifying industrial yellow phosphorus, and the purifying method mainly comprises a chemical purifying method and a physical purifying method. The chemical method is generally used for the refining process of low-arsenic yellow phosphorus, the arsenic removal rate is high, but impurity ions brought by chemical reagents are difficult to remove in the refining process, the process for separating the chemical reagents is complex and difficult, and devices for purifying the yellow phosphorus by the chemical method of an aqueous phase oxidation method or an organic solvent extraction method to reach the electronic grade requirement have the defects of more types of the added chemical reagents, more brought impurity ions, more washing times, large treatment capacity of residual liquid, complex separation process of the solvent, long flow, low recovery rate of phosphorus and the like. The electromagnetic method for preparing high-purity yellow phosphorus (electronic-grade yellow phosphorus) purely by adopting a physical method has no industrial device yet.

The high-purity yellow phosphorus refining technology in China is promoted and developed in recent years due to rapid development of the electronic industry, but the yield of the high-purity yellow phosphorus is far from meeting the requirement of the domestic market, the high-purity yellow phosphorus still depends on import, the proportion of industrial yellow phosphorus, intermediate products and final products in developed foreign industries is usually 1:3:5, 1:1.5:0.8 in China, a large-scale production device for the high-purity yellow phosphorus is not provided, the requirement of industrial development in China cannot be met, and the development of the low-cost, short-flow, safe and reliable high-purity yellow phosphorus production technology is the requirement of the phosphorus chemical industry at present.

Polyphosphoric acidThe acid is called PPA for short, also called polyphosphoric acid, and is a mixture of phosphoric acids with different polymerization degrees. The general molecular formula is as follows: h_n+2P_nO_3n+1. The pure anhydrous polyphosphoric acid is colorless, transparent and sticky liquid at normal temperature, is easy to wet, can be mixed with water and hydrolyzed into orthophosphoric acid, and is not crystallized and corrosive. 115% of polyphosphoric acid containing 83.2% of P₂O₅The relative density was 2.09g/cm³The boiling point is 856 ℃. The density of phosphorus pentoxide with a content of 72.46% (100% polyphosphoric acid) was 1.87g/cm³(20 ℃ C.), a phosphorus pentoxide content of 86.96% (120% polyphosphoric acid) and a density of 2.099g/cm³(25℃)。

The polyphosphoric acid is mixed phosphoric acid consisting of orthophosphoric acid, various polymerized phosphoric acids and a small amount of metaphosphoric acid and polymetaphosphoric acid, compared with orthophosphoric acid, the polyphosphoric acid not only has different concentrations, but also has a plurality of special properties, and can be used as a catalyst, a complexing agent, a chelating agent and the like and also has the function of mixing an oxidizing agent. Polyphosphoric acid can complex and chelate metal elements and metal ions in solution, and organic matters form chelate so as to be stably present in acid.

Disclosure of Invention

The invention aims to solve the technical problems of long process, high risk, high investment, high cost, difficult operation and the like in the existing yellow phosphorus purification technology, provides a method for producing high-purity electronic-grade yellow phosphorus by combining physical purification and chemical purification of yellow phosphorus, and provides an electronic-grade yellow phosphorus phosphate raw material with low cost, short process, easy operation and good quality for industrially producing electronic-grade phosphoric acid.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the method is characterized in that industrial yellow phosphorus and polyphosphoric acid are mixed and stirred in a reactor under the condition of oxygen isolation, the characteristics of the complexation capacity and the chelation capacity of the polyphosphoric acid on metal elements and organic matters are utilized to complex and chelate the metal elements and the organic matters in the yellow phosphorus, and the density difference of two mediums of the polyphosphoric acid and the yellow phosphorus is utilized to carry out sedimentation separation on the mixture of the industrial yellow phosphorus and the polyphosphoric acid under the condition of oxygen isolation to obtain the ultra-pure electronic grade yellow phosphorus.

Preferably, the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 72.46-86.96 wt%, namely polyphosphoric acid with corresponding phosphoric acid concentration of 100-120 wt%, namely polyphosphoric acid molecular formula H_n+2P_nO_3n+1Wherein n is 1-14.

Preferably, a strong oxidant is added in the reaction of the industrial yellow phosphorus and the polyphosphoric acid, the mass of the strong oxidant is 0-20% of that of the polyphosphoric acid, and the mass of the strong oxidant is more preferably 1-20% of that of the polyphosphoric acid; more preferably, the strong oxidant is a strong oxidant such as peroxide, strong acid and the like, and more preferably, the strong oxidant is one or more of strong oxidants such as hydrogen peroxide, nitric acid, sulfuric acid and the like, so that the complexing and chelating time can be further shortened.

Preferably, the mass ratio of the industrial yellow phosphorus to the mixed polyphosphoric acid containing the strong oxidant is 1: 0.05-0.9.

Preferably, the reactor for industrial yellow phosphorus and polyphosphoric acid is a closed reactor isolated from air, such as a stirring reaction kettle, a tubular reactor, a micro-reactor and the like; more preferably, the oxygen-insulating condition is not only a closed reactor, but also includes insulating measures such as filling inert gas such as nitrogen, argon, helium and the like or mixed gas thereof, and also includes insulating measures such as vacuum pumping and the like.

Preferably, the mixing and stirring temperature of the industrial yellow phosphorus and the polyphosphoric acid is 45-80 ℃, and the mixing and stirring time is 0.5-3 h.

Preferably, the settling separation temperature of the industrial yellow phosphorus and the polyphosphoric acid is 45-80 ℃, and the settling separation time is 0.5-3 h.

Preferably, the method can remove more than 99% of impurities such as metal elements, semimetal elements, organic matters and the like in the industrial yellow phosphorus, the purity of the obtained electronic-grade yellow phosphorus is 99.999% -99.99999%, and the yield of the yellow phosphorus is 94% -99%.

Preferably, the specific operation of the method comprises the following steps:

(1) if the strong oxidant exists, uniformly mixing the polyphosphoric acid with a certain concentration and the strong oxidant with a certain concentration to obtain mixed polyphosphoric acid;

(2) under the condition of isolating oxygen, putting the mixed industrial yellow phosphorus and the polyphosphoric acid obtained in the step (1) into a reaction kettle according to a certain mass ratio (if the mixed industrial yellow phosphorus and the polyphosphoric acid do not contain a strong oxidant, putting the industrial yellow phosphorus and the polyphosphoric acid with a certain concentration into the reaction kettle according to a certain mass ratio), and stirring for a certain time at a certain temperature to obtain a mixture;

(3) and feeding the mixture into a separator under the condition of isolating oxygen, and settling and separating at a certain temperature for a certain time to obtain the electronic-grade yellow phosphorus.

The yellow phosphorus and the polyphosphoric acid are mutually insoluble, the density of the yellow phosphorus and the polyphosphoric acid is different, the density of the polyphosphoric acid is greater than that of the yellow phosphorus, and the polyphosphoric acid has good natural settling separation performance. Strong oxidants such as hydrogen peroxide, nitric acid, sulfuric acid and the like are added into polyphosphoric acid and do not react, phosphoric acid and oxides produced by the reaction of the oxidants and yellow phosphorus and impurities in the yellow phosphorus are only dissolved in the polyphosphoric acid or are chelated by the polyphosphoric acid, so that the method has better implementation and operability, short production flow, less investment and easy realization of industrialization, and has a promotion effect on the electronic grade yellow phosphorus and electronic grade phosphoric acid industry in China.

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

the invention provides a production method of ultra-pure electronic grade yellow phosphorus, which utilizes the characteristic that polyphosphoric acid can be used as a catalyst, a complexing agent and a chelating agent, and the characteristic that polyphosphoric acid can complex and chelate metal elements, metal ions and organic matters in a solution to form a complex, a chelate and the like so as to stably exist in acid, and utilizes the characteristic that polyphosphoric acid can be mixed with a strengthening agent such as hydrogen peroxide, nitric acid, sulfuric acid and the like without changing the performances of the respective agents to remove impurities such as metal elements, semimetal elements, organic matters and the like in industrial yellow phosphorus. The method utilizes physical characteristics of substances and adopts mild chemical reaction measures, has better implementation and operability, short production flow, low investment cost, easy realization of industrialization, greatly reduces the operation risk, and has promotion effect on the industries of electronic grade yellow phosphorus and electronic grade phosphoric acid in China.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples.

Example 1:

a method for producing electronic grade yellow phosphorus comprises the following steps of mixing and stirring industrial yellow phosphorus and polyphosphoric acid in a reactor under the condition of oxygen isolation, complexing and chelating metal elements and organic matters in the yellow phosphorus by utilizing the characteristics of complexing ability and chelating ability of the polyphosphoric acid to the metal elements and the organic matters, and settling and separating a mixture of the industrial yellow phosphorus and the polyphosphoric acid under the condition of oxygen isolation by utilizing the density difference of two mediums of the polyphosphoric acid and the yellow phosphorus to obtain the ultra-pure electronic grade yellow phosphorus, wherein the specific operation steps are as follows:

(1) and uniformly mixing polyphosphoric acid with the concentration of 120% and hydrogen peroxide with the concentration of 50% in a stirring tank, wherein the mass of the added hydrogen peroxide is 20% of that of the polyphosphoric acid, so as to obtain the mixed polyphosphoric acid containing hydrogen peroxide. Wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 86.96%, namely polyphosphoric acid with corresponding phosphoric acid concentration of 120%, and the mass concentration of the mixed polyphosphoric acid is 100%;

(2) putting industrial yellow phosphorus and mixed polyphosphoric acid containing hydrogen peroxide into a stirring reaction kettle according to the mass ratio of 1:0.9 under the condition of nitrogen protection, and mixing and stirring for 3 hours at the temperature of 45 ℃; wherein, the purity of the industrial yellow phosphorus is 99.95 percent;

(3) after mixing and stirring are finished, conveying a mixture of polyphosphoric acid and yellow phosphorus to a settling separator with nitrogen protection, settling and separating for 3 hours at 60 ℃ under the nitrogen protection, conveying the separated yellow phosphorus to a yellow phosphorus storage tank by using a pump to obtain the ultra-pure electronic grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic grade yellow phosphorus is 99.9994%, and the yield is 97.6%.

Example 2:

a production method of electronic grade yellow phosphorus comprises the following specific operation steps:

(1) uniformly mixing polyphosphoric acid with the concentration of 115% and nitric acid with the concentration of 68% in a stirring tank, wherein the mass of the added nitric acid is 10% of that of the polyphosphoric acid, and obtaining mixed polyphosphoric acid containing nitric acid. Wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 83.32%, namely polyphosphoric acid with corresponding phosphoric acid concentration of 115%, and the mass concentration of the mixed polyphosphoric acid is 104.5%;

(2) putting industrial yellow phosphorus and mixed polyphosphoric acid containing nitric acid into a stirring reaction kettle according to the mass ratio of 1:0.10 under the protection of nitrogen, and mixing and stirring for 2 hours at 60 ℃; wherein, the content of industrial yellow phosphorus is 99.96 percent;

(3) after mixing and stirring are finished, conveying a mixture of polyphosphoric acid and yellow phosphorus to a settling separator with nitrogen protection, settling and separating for 3 hours at 60 ℃ under the nitrogen protection, conveying the separated yellow phosphorus to a yellow phosphorus storage tank by using a pump to obtain the ultra-pure electronic grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic grade yellow phosphorus is 99.99997%, and the yield is 98.4%. .

Example 3:

a production method of electronic grade yellow phosphorus comprises the following specific operation steps:

(1) and uniformly mixing polyphosphoric acid with the concentration of 100% and sulfuric acid with the concentration of 98% in a stirring tank, wherein the mass of the added sulfuric acid is 1% of that of the polyphosphoric acid, and obtaining the mixed polyphosphoric acid containing sulfuric acid. Wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 72.46 percent, namely polyphosphoric acid with corresponding phosphoric acid concentration of 100 percent; the mass concentration of the mixed polyphosphoric acid is 99 percent;

(2) putting industrial yellow phosphorus and mixed polyphosphoric acid containing sulfuric acid into a microreactor according to the mass ratio of 1:0.5 under the protection of nitrogen, and mixing and stirring for 0.5h at 80 ℃; wherein, the content of industrial yellow phosphorus is 99.94%;

(3) after mixing and stirring are finished, conveying a mixture of polyphosphoric acid and yellow phosphorus to a settling separator with nitrogen protection, settling and separating for 0.5h at 80 ℃ under the nitrogen protection, conveying the separated yellow phosphorus to a yellow phosphorus storage tank by using a pump to obtain the ultra-pure electronic grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic grade yellow phosphorus is 99.9995%, and the yield is 94%.

Example 4:

a production method of electronic grade yellow phosphorus comprises the following specific operation steps:

(1) conveying industrial yellow phosphorus and polyphosphoric acid into a microreactor according to a mass ratio of 1:0.6 under the protection of nitrogen, and reacting at 60 ℃; wherein, the content of industrial yellow phosphorus is 99.96 percent; wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 83.32%; i.e. polyphosphoric acid with a corresponding phosphoric acid concentration of 115%;

(2) conveying a mixture of polyphosphoric acid and yellow phosphorus from the microreactor into a settling separator with nitrogen protection, settling and separating for 2 hours at 60 ℃ under the nitrogen protection, conveying the separated yellow phosphorus into a yellow phosphorus storage tank by using a pump to obtain ultra-pure electronic-grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic-grade yellow phosphorus is 99.9999%, and the yield is 98%. .

The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.