阅读说明：本技术 一种去除黄磷中混合杂质的方法 (Method for removing mixed impurities in yellow phosphorus ) 是由 何建军 吴展平 于 2020-08-21 设计创作，主要内容包括：本发明涉及一种去除黄磷中混合杂质的方法,其特征在于：所述方法具体为：在高纯石英管内注入熔融的黄磷,待黄磷全部凝固后,对高纯石英管内的黄磷再次进行加热,加热由环形加热器与加热棒同时从外围与中心进行,加热采用先自上而下依次分段进行再自下而上依次分段相结合的方式,加热的同时加热端上方或下方区域进行冷却,实现分区熔融定向去除杂质。本发明优点是：热转化率高,使得环形加热器的移动速度可达到12mm/min以上；黄磷二次熔融层的高度更加一致,提纯效果好,能够减少区域熔融定向的次数,提纯效率高。(The invention relates to a method for removing mixed impurities in yellow phosphorus, which is characterized by comprising the following steps: the method specifically comprises the following steps: injecting molten yellow phosphorus into the high-purity quartz tube, heating the yellow phosphorus in the high-purity quartz tube again after the yellow phosphorus is completely solidified, wherein the heating is carried out by the annular heater and the heating rod from the periphery and the center at the same time, the heating adopts a mode of sequentially segmenting from top to bottom and sequentially segmenting from bottom to top, and the heating is carried out while cooling the region above or below the heating end, so that the impurities are directionally removed by zone melting. The invention has the advantages that: the heat conversion rate is high, so that the moving speed of the annular heater can reach more than 12 mm/min; the height of the yellow phosphorus secondary melting layer is more consistent, the purification effect is good, the number of times of regional melting orientation can be reduced, and the purification efficiency is high.)

1. A method for removing mixed impurities in yellow phosphorus is characterized in that: the method specifically comprises the following steps:

s0: preparing a regional melting device, wherein the regional melting device comprises a high-purity quartz tube, an annular heat exchanger group, a heating rod and an axial driver, the high-purity quartz tube is a cylindrical tube body with the inner diameter of 50-70 mm and the height of 1100mm and is vertically arranged, the upper end and the lower end of the tube body are respectively sealed by an upper sealing head plate and a lower sealing head plate to form a sealed inner cavity, a feed inlet and a water sealing opening are formed in the upper sealing head plate, and a discharge outlet and an impurity outlet are formed in the lower sealing head plate; the annular heat exchanger group is sleeved outside the high-purity quartz tube and comprises an annular heater, an upper annular cooler and a lower annular cooler which are coaxially arranged above and below the annular heater, and the annular heat exchanger group is driven by an axial driver to reciprocate along the axial direction of the high-purity quartz tube; the heating rod is vertically inserted into the high-purity quartz tube and is superposed with the axis of the high-purity quartz tube, and the heating rod consists of a plurality of heating bodies which are arranged in the quartz sleeve along the axial direction;

s1: filling pure water into the high-purity quartz tube, introducing the molten yellow phosphorus into the inner cavity of the high-purity quartz tube to be replaced with the pure water, controlling the amount of the yellow phosphorus to enable the yellow phosphorus to be 100-200 mm away from the upper end tube opening of the high-purity quartz tube, and isolating the yellow phosphorus from air by using the residual pure water as a water seal;

s2: after the yellow phosphorus is completely solidified, heating the yellow phosphorus in the high-purity quartz tube again:

the annular heat exchanger group moves from top to bottom from the upper end of the high-purity quartz tube at a constant speed of 12-16 mm/min, the annular heater heats yellow phosphorus from the periphery of the high-purity quartz tube, meanwhile, the heating rod selects a heating body with a corresponding height to work to heat the yellow phosphorus from the center of the high-purity quartz tube, and then solid yellow phosphorus is melted near the current height to form a yellow phosphorus secondary melting layer;

starting an upper annular cooler in an annular heat exchanger group while heating the yellow phosphorus, cooling an area above a current secondary melting layer of the yellow phosphorus, cooling and solidifying the yellow phosphorus which is not solidified above the current secondary melting layer of the yellow phosphorus, and making impurities with a melting point lower than that of the yellow phosphorus gradually move downwards in the process of solidifying the yellow phosphorus by utilizing the difference of the melting points of the impurities in the yellow phosphorus and the yellow phosphorus;

s3: repeating the step S2-13-17 times, heating all yellow phosphorus in the high-purity quartz tube to a molten state through a heating rod, and re-purifying part of yellow phosphorus at the height of 1/3-2/3 in the yellow phosphorus;

s4: after the yellow phosphorus purified for the second time is completely solidified, the yellow phosphorus in the high-purity quartz tube is heated again:

the annular heat exchanger group moves from the lower end of the high-purity quartz tube to the upper end at a constant speed of 12-16 mm/min, the yellow phosphorus is heated from the periphery of the high-purity quartz tube by the annular heater, meanwhile, the heating rod selects a heating body with a corresponding height to work to heat the yellow phosphorus from the center of the high-purity quartz tube, and then the solid yellow phosphorus is melted near the current height to form a yellow phosphorus secondary melting layer;

starting a lower annular cooler in an annular heat exchanger group while heating the yellow phosphorus, cooling a lower area of a current secondary melting layer of the yellow phosphorus, cooling and solidifying the yellow phosphorus which is not solidified above the current secondary melting layer of the yellow phosphorus, and making impurities with melting points higher than that of the yellow phosphorus move upwards gradually in the process of solidifying the yellow phosphorus by utilizing the difference between the melting points of the impurities in the yellow phosphorus and the melting points of the impurities in the yellow phosphorus;

s5: and (5) repeating the step (S4) to 12-15 times, heating all the yellow phosphorus in the high-purity quartz tube to a molten state by using a heating rod, wherein the yellow phosphorus with the height of less than 2/3 in the yellow phosphorus is the purified finished product high-purity yellow phosphorus.

2. The method for removing mixed impurities in yellow phosphorus according to claim 1, wherein: in the steps S2 and S4, the temperature of the annular heater is controlled to be 80-105 ℃, so that the temperature of yellow phosphorus close to the inner wall part of the high-purity quartz tube is 60-75 ℃; the temperature of the heating block is controlled to be 60-75 ℃, and is 2-3 ℃ lower than the temperature of yellow phosphorus close to the inner wall of the high-purity quartz tube; the temperature of the annular cooler is controlled to be 2-10 ℃.

Technical Field

The invention relates to a production process of yellow phosphorus, in particular to a method for removing mixed impurities in the yellow phosphorus.

Background

Yellow phosphorus is widely used in the fields of electronics, food, petrochemicals, automobile manufacturing and the like, and the purity requirement of yellow phosphorus in the fields is high.

In yellow phosphorus purification processes of different routes, a secondary refining route is carried out on the regional melting method compared with industrial-grade yellow phosphorus obtained by an electric furnace method, the energy consumption is low, and no environmental pollution is caused, so that the method is widely valued by production enterprises.

The zone melting method is characterized in that an annular heater is sleeved on a columnar industrial yellow phosphorus, the annular heater is used for locally melting the yellow phosphorus, the annular heater is controlled to axially move on the columnar industrial yellow phosphorus, so that a melting zone of the yellow phosphorus moves along with the annular heater, and impurities in the yellow phosphorus move below or above the yellow phosphorus relative to the yellow phosphorus by utilizing that the diffusion of molecules in a melting state is far larger than that in a solid state.

The process route for purifying the yellow phosphorus by adopting the zone melting method has lower energy consumption and higher yellow phosphorus recovery rate. However, the current zone melting method has certain limitations: because the yellow phosphorus is melted by the annular heater, the heat transfer of the yellow phosphorus is performed in an outside-in mode, the heating efficiency is low, when the periphery of the columnar yellow phosphorus opposite to the annular heater is melted, the central yellow phosphorus is still partially unmelted, the moving speed of the heater is generally required to be controlled below 5mm/min, and the heating efficiency is low;

in addition, under this heating method, this melting region is a disc form that reduces from outside to inside thickness along the radial of cylindricality yellow phosphorus all the time, and is not ideal to the impurity purification effect in cylindricality yellow phosphorus central zone, if reach higher purity, then need whole repetitious repetition regional melting many times, reciprocal one-way number of times is 18 ~ 25 usually, and is inefficient, the energy consumption is high.

Disclosure of Invention

The invention aims to provide a method for removing mixed impurities in yellow phosphorus with high efficiency and low energy consumption.

In order to solve the technical problems, the technical scheme of the invention is as follows: the method for removing the mixed impurities in the yellow phosphorus has the innovation points that: the method specifically comprises the following steps:

s0: preparing a regional melting device, wherein the regional melting device comprises a high-purity quartz tube, an annular heat exchanger group, a heating rod and an axial driver, the high-purity quartz tube is a cylindrical tube body with the inner diameter of 50-70 mm and the height of 1100mm and is vertically arranged, the upper end and the lower end of the tube body are respectively sealed by an upper sealing head plate and a lower sealing head plate to form a sealed inner cavity, a feed inlet and a water sealing opening are formed in the upper sealing head plate, and a discharge outlet and an impurity outlet are formed in the lower sealing head plate; the annular heat exchanger group is sleeved outside the high-purity quartz tube and comprises an annular heater, an upper annular cooler and a lower annular cooler which are coaxially arranged above and below the annular heater, and the annular heat exchanger group is driven by an axial driver to reciprocate along the axial direction of the high-purity quartz tube; the heating rod is vertically inserted into the high-purity quartz tube and is superposed with the axis of the high-purity quartz tube, and the heating rod consists of a plurality of heating bodies which are arranged in the quartz sleeve along the axial direction;

s1: filling pure water into the high-purity quartz tube, introducing the molten yellow phosphorus into the inner cavity of the high-purity quartz tube to be replaced with the pure water, controlling the amount of the yellow phosphorus to enable the yellow phosphorus to be 100-200 mm away from the upper end tube opening of the high-purity quartz tube, and isolating the yellow phosphorus from air by using the residual pure water as a water seal;

s2: after the yellow phosphorus is completely solidified, heating the yellow phosphorus in the high-purity quartz tube again:

the annular heat exchanger group moves from top to bottom from the upper end of the high-purity quartz tube at a constant speed of 12-16 mm/min, the annular heater heats yellow phosphorus from the periphery of the high-purity quartz tube, meanwhile, the heating rod selects a heating body with a corresponding height to work to heat the yellow phosphorus from the center of the high-purity quartz tube, and then solid yellow phosphorus is melted near the current height to form a yellow phosphorus secondary melting layer;

starting an upper annular cooler in an annular heat exchanger group while heating the yellow phosphorus, cooling an area above a current secondary melting layer of the yellow phosphorus, cooling and solidifying the yellow phosphorus which is not solidified above the current secondary melting layer of the yellow phosphorus, and making impurities with a melting point lower than that of the yellow phosphorus gradually move downwards in the process of solidifying the yellow phosphorus by utilizing the difference of the melting points of the impurities in the yellow phosphorus and the yellow phosphorus;

s3: repeating the step S2-13-17 times, heating all yellow phosphorus in the high-purity quartz tube to a molten state through a heating rod, and re-purifying part of yellow phosphorus at the height of 1/3-2/3 in the yellow phosphorus;

s4: after the yellow phosphorus purified for the second time is completely solidified, the yellow phosphorus in the high-purity quartz tube is heated again:

the annular heat exchanger group moves from the lower end of the high-purity quartz tube to the upper end at a constant speed of 12-16 mm/min, the yellow phosphorus is heated from the periphery of the high-purity quartz tube by the annular heater, meanwhile, the heating rod selects a heating body with a corresponding height to work to heat the yellow phosphorus from the center of the high-purity quartz tube, and then the solid yellow phosphorus is melted near the current height to form a yellow phosphorus secondary melting layer;

starting a lower annular cooler in an annular heat exchanger group while heating the yellow phosphorus, cooling a lower area of a current secondary melting layer of the yellow phosphorus, cooling and solidifying the yellow phosphorus which is not solidified above the current secondary melting layer of the yellow phosphorus, and making impurities with melting points higher than that of the yellow phosphorus move upwards gradually in the process of solidifying the yellow phosphorus by utilizing the difference between the melting points of the impurities in the yellow phosphorus and the melting points of the impurities in the yellow phosphorus;

s5: and (5) repeating the step (S4) to 12-15 times, heating all the yellow phosphorus in the high-purity quartz tube to a molten state by using a heating rod, wherein the yellow phosphorus with the height of less than 2/3 in the yellow phosphorus is the purified finished product high-purity yellow phosphorus.

Preferably, in the steps S2 and S4, the temperature of the annular heater is controlled to be 80-105 ℃, so that the temperature of yellow phosphorus close to the inner wall part of the high-purity quartz tube is 60-75 ℃; the temperature of the heating block is controlled to be 60-75 ℃, and is 2-3 ℃ lower than the temperature of yellow phosphorus close to the inner wall of the high-purity quartz tube; the temperature of the annular cooler is controlled to be 2-10 ℃.

The invention has the advantages that: the mode of internal and external synchronous heating is adopted, the heat conversion rate is high, and the moving speed of the annular heater can reach more than 12 mm/min; more importantly, the purification effect is good by combining temperature difference control, the number of times of regional melting orientation can be reduced, and the purification efficiency is high.

Drawings

FIG. 1 is a schematic view of a zone melting apparatus according to the present invention.

FIG. 2 is a partial cross-sectional view of a heating rod in the zone melting apparatus of the present invention.

Detailed Description

The route of the method for removing the mixed impurities in the yellow phosphorus is as follows:

s0: preparing a regional melting device, wherein the regional melting device is shown in figure 1 and comprises a high-purity quartz tube, an annular heat exchanger group, a heating rod 3 and an axial driver, the high-purity quartz tube is a cylindrical tube body 11 with the inner diameter of 50-70 mm and the height of 1100mm, the cylindrical tube body is vertically arranged, the upper end and the lower end of the tube body 11 are respectively sealed by an upper sealing head plate 12 and a lower sealing head plate 13 to form a sealed inner cavity, a feed port and a water sealing port are formed in the upper sealing head plate 12, and a discharge port and an impurity outlet are formed in the lower sealing head plate 13; the annular heat exchanger group is sleeved outside the high-purity quartz tube 11 and comprises an annular heater 21, an upper annular cooler 22 and a lower annular cooler 23 which are coaxially arranged above and below the annular heater 21, the annular heat exchanger group is driven by an axial driver (not shown in the figure) to reciprocate along the axial direction of the high-purity quartz tube, and in the embodiment, the axial driver adopts a screw-nut pair driven by a servo motor to meet the precision requirement; the heating rod 3 is vertically inserted into the high-purity quartz tube and is overlapped with the axis of the high-purity quartz tube, as shown in fig. 2, the heating rod 3 is composed of a quartz sleeve 31 and a plurality of heating bodies 32 which are distributed along the axial direction, the heating bodies 32 are annular body structures which are tightly attached to the inner wall of the quartz sleeve 31, a ceramic heat insulation ring is arranged between the adjacent heating bodies 32, and the height of each heating body 32 is the same as that of the annular heater 21.

S1: filling pure water into the high-purity quartz tube, introducing the molten yellow phosphorus into the inner cavity of the high-purity quartz tube to be replaced with the pure water, controlling the amount of the yellow phosphorus to enable the yellow phosphorus to be 100-200 mm away from the upper end tube opening of the high-purity quartz tube, and isolating the yellow phosphorus from air by using the residual pure water as a water seal;

s2: after the yellow phosphorus is completely solidified, heating the yellow phosphorus in the high-purity quartz tube again:

the annular heat exchanger group moves from top to bottom from the upper end of the high-purity quartz tube at a constant speed of 12-16 mm/min, the annular heater heats yellow phosphorus from the periphery of the high-purity quartz tube, meanwhile, the heating rod selects a heating body with a corresponding height to work to heat the yellow phosphorus from the center of the high-purity quartz tube, and then solid yellow phosphorus is melted near the current height to form a yellow phosphorus secondary melting layer;

when the yellow phosphorus is heated, an upper annular cooler in an annular heat exchanger group is started, a lower annular cooler does not work, the upper area of the current secondary melting layer of the yellow phosphorus is cooled, the yellow phosphorus which is not solidified above the current secondary melting layer of the yellow phosphorus is cooled and solidified, and impurities with the melting points lower than that of the yellow phosphorus gradually move downwards in the process of solidifying the yellow phosphorus by utilizing the difference between the melting points of the impurities in the yellow phosphorus and the melting points of the impurities in the yellow phosphorus;

s3: repeating the step S2-13-17 times, heating all yellow phosphorus in the high-purity quartz tube to a molten state through a heating rod, and re-purifying part of yellow phosphorus at the height of 1/3-2/3 in the yellow phosphorus;

s4: after the yellow phosphorus purified for the second time is completely solidified, the yellow phosphorus in the high-purity quartz tube is heated again:

the annular heat exchanger group moves from the lower end of the high-purity quartz tube to the upper end at a constant speed of 12-16 mm/min, the yellow phosphorus is heated from the periphery of the high-purity quartz tube by the annular heater, meanwhile, the heating rod selects a heating body with a corresponding height to work to heat the yellow phosphorus from the center of the high-purity quartz tube, and then the solid yellow phosphorus is melted near the current height to form a yellow phosphorus secondary melting layer;

starting a lower annular cooler in the annular heat exchanger group while heating the yellow phosphorus, wherein the upper annular cooler does not work, cooling the lower area of the current secondary melting layer of the yellow phosphorus, cooling and solidifying the yellow phosphorus which is not solidified above the current secondary melting layer of the yellow phosphorus, and making impurities with melting points higher than that of the yellow phosphorus gradually move upwards in the process of solidifying the yellow phosphorus by utilizing the difference of the melting points of the impurities in the yellow phosphorus and the yellow phosphorus;

s5: and (5) repeating the step (S4) to 12-15 times, heating all the yellow phosphorus in the high-purity quartz tube to a molten state by using a heating rod, wherein the yellow phosphorus with the height of less than 2/3 in the yellow phosphorus is the purified finished product high-purity yellow phosphorus.

In the steps S2 and S4, the temperature of the annular heater is controlled to be 80-105 ℃, so that the temperature of yellow phosphorus close to the inner wall part of the high-purity quartz tube is 60-75 ℃; the temperature of the heating block is controlled to be 60-75 ℃, and is 2-3 ℃ lower than the temperature of yellow phosphorus close to the inner wall of the high-purity quartz tube; the temperature of the annular cooler is controlled to be 2-10 ℃.