CN100581997C - Method for producing ultra-pure yellow phosphorus - Google Patents
Method for producing ultra-pure yellow phosphorus Download PDFInfo
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Abstract
Disclosed is a production method of ultra-pure yellow phosphorus, which uses the material of industrial yellow phosphorus, and the industrial yellow phosphorus is prepared to be the ultra-pure yellow phosphorus via extracting, zone melting, pressurizing or depressurizing micro-filtration sequentially. Extracting agent is at least one of di-(2-ethylhexyl) phosphoric acid, tributyl phosphate or calixarene, diluting agent is kerosene or paraffin oil or chloroform or carbon tetrachloride, and extraction technological parameter is that the volume ratio of organic phase and the industrial yellow phosphorus is 1:2-1:3. Apparatus for zone melting comprises a zone molten pool, a ring heater, an annular chiller and a driving device, wherein the ring heater and the annular chiller are assembled around the zone molten pool, and are arranged at intervals along the axial direction of the zone molten pool, the pressurizing or depressurizing micro-filtration utilizes a pressurizing or depressurizing filter with grade of 0.1 um-0.5 um. Utilizing the invention of the method to purify the industrial yellow phosphorus, the purity of yellow phosphorus products can reach 99.99%-99.9999%, and the yield coefficient can reach 73.2%-88.4%.
Description
Technical field
The invention belongs to the production method of ultra-pure yellow phosphorus, particularly a kind of is the method for raw material production ultra-pure yellow phosphorus with the industrial yellow phosphorus.
Background technology
Industrial yellow phosphorus is that Rock Phosphate (72Min BPL) is used SiO in electric furnace
2Carry out high temperature reduction reaction with coke and obtain, purity is generally about 99.8%, contains following impurity:
Metallic element: Ca, Fe, Al, Mg, Sr, Mn, Na, K, Ti, V, Cr, Ni, Ga, Cd, Cu, Sb, Pb, Zn, Sn, U.
Semimetallic elements: Se, Si, C, B, As, Bi.
Organism: phenol, anthracene, tar and polyatom polycyclic aromatic hydrocarbons, about more than 30 kinds.The color of yellow phosphorus and organic impurity, Qi Shi perylene of You is relevant with anthanthrene etc.What occupy machine total impurities about 70% in the yellow phosphorus is following material: carbazole, pyrene, anthracene, phenanthrene etc.Benzo (a) pyrene, benzo (g, h, i) pyrene, benzo (k) fluoranthene, acridine, perylene, dibenzothiophen, dibenzofuran, dibenzo (a, c) anthracene, anthanthrene, coronene etc. account for 10% of total amount of organic, other as naphthalene, biphenyl, acenaphthene, fluorenes, fluoranthene, Ku, benzo (a) anthracene, 7,12-dimethylbenzanthracene, benzo (e) pyrene etc. account for 10%～15%.
In the above-mentioned impurity, most importantly arsenic (As) and organism (being commonly called as oil content, mainly is polynuclear aromatic hydrocarbons) are Fe, Ni, Cu, Pb, Zn secondly.Other total impurities is 10
-9On the order of magnitude.
Owing to contain above-mentioned impurity in the industrial yellow phosphorus, have a strong impact on its range of application.In order to satisfy the demand of industrial sectors such as food, medicine, electronics, petrochemical industry, automobile making to ultra-pure yellow phosphorus, people constantly explore and study preparation (or production) method of ultra-pure yellow phosphorus.
Publication number is the production method that the patent application of CN 1532140A discloses a kind of high-purity yellow phosphorus, has adopted following processing step: (1) tentatively removes mechanical impurity to the industrial yellow phosphorus underpressure distillation; (2) under the secluding air situation,, remove remaining sulfuric acid with distilled water wash again with vitriol oil stirring reaction; (3) with nitric acid and oxidation toughener stirring reaction, wash yellow phosphorus with hydrogen peroxide solution then, use distilled water wash again; (4) strainer with 2 μ m～5 μ m filters, and obtains purity and be 99.99%～99.99999% yellow phosphorus.From above-mentioned steps as can be seen, mechanical impurity in the industrial yellow phosphorus adopts distillation (physics method) to remove, topmost impurity arsenic and organism take chemical process to remove in the industrial yellow phosphorus, the shortcoming that exists mainly contains: (1) is with the vitriol oil and industrial yellow phosphorus stirring reaction, then with industrial yellow phosphorus and nitric acid and oxidation toughener stirring reaction.The vitriol oil and the security of industrial yellow phosphorus stirring reaction are extremely low, and report was once arranged both at home and abroad, and this method once set off an explosion; With treated yellow phosphorus and nitric acid and oxidation toughener hybrid reaction, a lot of data prove all that the effect that removes arsenic is limited and (see " high purity phosphorus production process initial probe ", Yang Luhua, Ma Xinliang, 2004 36 the 2nd phases of volume of inorganic chemicals industry; " the aqueous phase oxidation method removes the experimental study of arsenic in the yellow phosphorus ", appoint Yongsheng, Zhang Zhen, 2007 39 the 5th phases of volume of inorganic chemicals industry), the contriver of present patent application has carried out test of many times, and test-results also shows the Yellow phosphorus arsenic removing effect relatively poor, decreasing ratio is low, only 90%, if will reach high arsenic-removing rate, then the phosphorus loss is very big.(2) nitric acid, sulfuric acid belong to strongly-acid, strong corrosive material, because this method consumption is big, thereby recycling is inconvenient, if directly neutralization discharging then causes environmental pollution, increase the purification cost.
Publication number is that the Chinese patent application of CN 1962419A discloses a kind of " utilizing the method for regional melt molecule diffusion method purifying industrial yellow phosphorus ", used equipment comprises melting appartus, device for casting, purification system and recovery system in this method, purification system mainly comprises the excellent shell of well heater, electro-motor and carrying phosphorus, well heater is an annular electro torrid zone well heater, is sleeved on the excellent shell that carries phosphorus and with electro-motor to be connected.During purification operations, all apparatus systems all place cooling trough.Operation steps is: a, solid-state industrial yellow phosphorus raw material is fused into liquid state, extracts by the pump in the device for casting, pour into liquid phosphor through flowrate control valve in excellent shell housing again, will cool off afterwards and become solid-state phosphorus; B, starter motor, annular electro torrid zone well heater moves at excellent shell outside surface vertically with the motor constant speed, the melt region of formation also along excellent columella to moving; Cutting unit in c, the recovery system is after purifying, by the higher part excision of arsenic content in the yellow phosphorus rod that takes out in the excellent shell; Pumping unit in d, the recovery system is after purifying, and is molten again for liquid finished product phosphorus is filled in the storage vessel, finally obtains highly purified yellow phosphorus.Mainly there is following problem in this kind method and apparatus: 1, the heat part that produces of well heater be used for tank water heating heat all contribution give fusing system, cause the waste of the energy; 2, along with the growth of operating time, water temperature raises gradually, and cooling performance descends; 3, the recovery method of finished phosphorus has increased facility investment; 4, be difficult to realize suitability for industrialized production.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of production method of ultra-pure yellow phosphorus is provided, adopt this kind method that industrial yellow phosphorus is purified, not only product purity height, and safe operation process, blowdown is few, is easy to realize suitability for industrialized production.
Technical scheme of the present invention: high and many according to the industrial yellow phosphorus foreign matter content, topmost impurity is arsenic (As) and organic characteristics, to reach total impurities decreasing ratio height, phosphorus yield height, operational safety, blowdown is the target design technical process less, and industrial yellow phosphorus is prepared into ultra-pure yellow phosphorus by extraction, zone melting, pressurization or decompression micro-filtration successively.
Extraction is carried out under nitrogen protection; the percent by volume of extraction agent is 10%～35% in the organic phase; the percent by volume of thinner is 65%～90%; extraction agent is at least a kind of in di-(2-ethylhexyl)phosphoric acid (being commonly called as P204), tributyl phosphate, the calixarene; thinner is kerosene or paraffin oil or trichloromethane or tetracol phenixin; the extraction process parameter: the volume ratio of organic phase and industrial yellow phosphorus is 1: 2～1: 3; 60 ℃～80 ℃ of temperature; stir linear velocity 200r/min～800r/min, churning time 20min～45min.Test shows: when extraction agent is a di-(2-ethylhexyl)phosphoric acid or/and during tributyl phosphate, thinner is kerosene or paraffin oil better effects if; When extraction agent was calixarene, thinner was trichloromethane or tetracol phenixin or kerosene better effects if.If extraction agent is the mixture of di-(2-ethylhexyl)phosphoric acid and tributyl phosphate, preferred version be di-(2-ethylhexyl)phosphoric acid and tributyl phosphate volume ratio be 1: 1; If extraction agent is the mixture of di-(2-ethylhexyl)phosphoric acid and calixarene, preferred version is that the volume ratio of di-(2-ethylhexyl)phosphoric acid and calixarene is 1: 1.
Equipment and operation steps that zone melting is used are as follows:
1. zone melting equipment comprises molten bath, district, ring heater, annular water cooler, combination cover and drive unit; Molten bath, described district is the cylindrical barrel body of closed at both ends, is installed on the bearing; Described ring heater is at least one group, and the quantity of annular water cooler is identical with the quantity of ring heater, and ring heater and annular water cooler are installed around the molten bath, district, and along the axial phase of distinguishing the molten bath alternately across a certain distance; Described combination cover is sleeved on ring heater and the annular water cooler, forms integral structure with ring heater and annular water cooler; Drive unit is connected with the combination cover by transom;
In aforesaid device, one group of ring heater is 0.04～0.06 of district's molten bath total length along the axial length of distinguishing the molten bath, one group of annular water cooler is one group of ring heater 1～3 times along the axial length of distinguishing the molten bath along the axial length of distinguishing the molten bath, and the spacing d between ring heater and the annular water cooler is 2mm～5mm.
2. the zone melting method is followed successively by following steps
A, will distinguish and fill 60 ℃～80 ℃ hot water in the inner chamber of molten bath;
B, will be through the liquid phosphor of extraction by pressing the phosphorus groove be pressed into district's molten bath inner chamber, meanwhile, the hot water in district's molten bath inner chamber is discharged from, and after district's molten bath inner chamber is full of liquid phosphor, closes yellow phosphorus inlet and water port;
C, the liquid phosphor that will distinguish in the inner chamber of molten bath solidify;
D, ring heater and annular water cooler are adjusted to state with thermal source and low-temperature receiver conducting, open drive unit then, drive ring heater and annular water cooler axially moving back and forth along the molten bath, district, make the fusing of solid yellow phosphorus subregion, produce along axially movable melting zone, molten bath, district, transport each melting zone like this to next ring heater, repeat such circulation, impurity in the industrial yellow phosphorus is along with the melting zone moves, the two ends of transferring to the molten bath, district gradually, after reaching the removal of impurities requirement, close drive unit;
E, the fusing of at first that foreign matter content is high yellow phosphorus are emitted by row's phosphorus mouth in molten bath, district, cut off annular water cooler low-temperature receiver then, will make with extra care with ring heater and emit after the yellow phosphorus fusing and with hot water cleaning area molten bath.
Test shows, during zone melting, by following processing parameter operation, then can satisfy the removal of impurities requirement, makes the arsenic decreasing ratio reach 99.99%: 60 ℃～80 ℃ of Heating temperatures, 5 ℃～20 ℃ of cooling temperatures; Ring heater and annular water cooler axially move back and forth in the process along the molten bath, district, the molten speed 0.2mm/min～3mm/min in district, and retum speed is at least 100mm/min; Ring heater and annular water cooler axially move back and forth number of times and are at least (concrete mobile number of times is determined according to district's pool size and raw material impurity content) 20 times along the molten bath, district.If ring heater and annular water cooler axially move back and forth along the molten bath, district priority by two kinds of molten speed operations in district, promptly at first by the molten speed 0.2mm/min in district～1mm/min operation, the number of times that moves back and forth is at least 10 times, then by the molten speed 1mm/min in district～3mm/min operation, the number of times that moves back and forth is at least 5 times, and impurity-eliminating effect is better like this.Need to prove: when calculating " moving back and forth number of times ", will " ring heater and annular water cooler by the molten speed in the district that determines from the end in molten bath, district to the other end miles of relative movement D (axial length of one group of ring heater of D=+between them spacing d) along the axial length+one group annular water cooler in molten bath, district along the molten bath, district, turn back to initiating terminal with the retum speed of determining again " be defined as " 1 time ";
In the aforementioned region fusion apparatus, the molten bath, district can be cylindrical tube or the cylindroid cylindrical shell or the prismatic cylindrical shell of closed at both ends, and the wall thickness in molten bath, district is 2mm～5mm; The quadrangular cylindrical shell of district's preferred closed at both ends in molten bath, the high h of quadrangular cylinder lumen and the ratio of wide b preferred 2～10; Ring heater is heating medium circulation tube group or electrical induction heating coil, and annular water cooler is a heat-eliminating medium circulation tube group.
Pressurization or decompression micro-filtration filter with the pressurization or the vacuum filter of 0.1 μ m～0.5 μ m level.
The present invention has following beneficial effect:
1, adopt the method for the invention that industrial yellow phosphorus is purified, the purity of the yellow phosphorus product that obtains can reach 99.99%～99.99999%, and yield can reach 73.2%～88.4%.
The operational safety of 2, extraction, zone melting, pressurization or each operation of decompression micro-filtration.
3, zone melting, pressurization or decompression micro-filtration all belong to physics method, environmentally safe; The extraction process blowdown is few, and extraction agent is renewable, can be recycled after the regeneration, can not pollute environment.
4, in the zone melting step, the yellow phosphorus that foreign matter content is high adopts fractional melting to discharge with refining yellow phosphorus and realizes separating, can save recovery system of the prior art, help reducing investment.
5, be easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the process flow sheet of the production method of ultra-pure yellow phosphorus of the present invention;
Fig. 2 is a kind of structural representation of Zone melting purifying device for industrial yellow phosphorus of the present invention, and ring heater is a heating medium circulation tube group, and annular water cooler is a heat-eliminating medium circulation tube group, is set with the combination cover on ring heater and the annular water cooler;
Fig. 3 is another structural representation of Zone melting purifying device for industrial yellow phosphorus of the present invention, and ring heater is the electrical induction heating coil, and annular water cooler is a heat-eliminating medium circulation tube group, is set with the combination cover on ring heater and the annular water cooler;
Fig. 4 is the B-B sectional view of Fig. 2;
Fig. 5 is that the A of Fig. 2 is to view;
Fig. 6 is installation, the arrangement schematic perspective view of heating medium circulation tube group and heat-eliminating medium circulation tube group;
The scheme of installation of syringe when Fig. 7 is the thief hole that is provided with of district's molten bath end face and sampling;
When Fig. 8 is to use Zone melting purifying device for industrial yellow phosphorus of the present invention to purify, the state graph of impurity in the yellow phosphorus.
Among the figure, 1-advances the phosphorus pipe, the 2-flow control valve, 3-heating medium inlet, the 4-hydraulic pipe, 5-heating medium circulation tube group, molten bath, 6-district, the outlet of 7-heating medium, the 8-bearing, 9-heat-eliminating medium inlet, 10-heat-eliminating medium circulation tube group, the 11-swivel nut, the 12-screw mandrel, the 13-transom, the 14-speed reduction unit, the 15-motor, the outlet of 16-heat-eliminating medium, 17-row phosphorus pipe, the 18-base, the 19-thief hole, 20-makes up cover, the 21-syringe, the 22-thermopair, the 23-pad, the 24-cap, the 25-compressing rubber, the solid-state district of 26-, the 27-melting zone, 28-electrical induction heating coil.
Embodiment
Below the raw material of each embodiment identical, described raw material---the composition such as the table 1 of impurity in the industrial yellow phosphorus.
Table 1 industrial yellow phosphorus foreign matter content (mg/kg of unit)
Annotate: total amount of organic (in C) metric measurement; Polynuclear aromatic hydrocarbons high-efficient liquid phase color spectrometry; As, Zn, Pb, Fe, Cu, Ni measure with inductively coupled plasma atomic emission spectrum (ICP-AES).
The technical process of present embodiment as shown in Figure 1, processing step is followed successively by extraction, zone melting, decompression micro-filtration.
1, extraction
Extraction agent is a di-(2-ethylhexyl)phosphoric acid, and thinner is a kerosene, and in the organic phase, the percent by volume of extraction agent is 15%, thinner percent by volume be 85%.The volume ratio of organic phase and industrial yellow phosphorus is 1: 3.
Extraction reactor is the simple glass jacketed reactor; in the chuck 70 ℃ of circulating hot waters; add organic phase then; and in reactor, feed nitrogen; after the air in the reactor is discharged fully, industrial yellow phosphorus by pressing the phosphorus groove to be pressed into reactor, is extracted under nitrogen protection; the stirring linear velocity is 200r/min, churning time 45min.Stop to stir the back and discharge organic phase,, then yellow phosphorus is put into first product storage phosphorus groove with hot wash yellow phosphorus twice.Foreign matter content in the extraction post analysis yellow phosphorus is as shown in table 2:
Table 2 extraction back yellow phosphorus impurity content (mg/kg of unit)
2, zone melting
The structure of zone melting equipment comprises molten bath 6, district, ring heater, annular water cooler, drive unit, bearing 8, base 18 and combination cover 20 as shown in Figure 2.
District's molten bath 6 usefulness stainless steels are made, and are the quadrangular cylindrical shell of closed at both ends, and its lateral wall thickness is 2mm, and the wall thickness at two ends is 5mm; The length overall L of described quadrangular cylindrical shell is 400mm (do not comprise the two ends wall thickness, the two ends wall thickness is for embedding the bearing part), and the high h of quadrangular cylinder lumen was 4 (the high 60mm of being, wide is 15mm) (as shown in Figure 4) with the ratio of wide b; The bottom, two ends of quadrangular cylindrical shell is provided with row's phosphorus mouth 17, described row's phosphorus mouth and row's phosphorus pipe 17 combinations phosphorus passage in a row; One end top of quadrangular cylindrical shell is provided with into phosphorus mouth and water inlet/water port, describedly advances the phosphorus mouth and advances phosphorus pipe 1 and be combined into into phosphorus passage, and described water inlet/water port and hydraulic pipe 4 are combined into into water/drainage channel; The both ends of the surface of quadrangular cylindrical shell are provided with thief hole 19, are plugged with compressing rubber 25 in the thief hole, and thief hole covers with cap 24, adopt syringe 21 samplings, as shown in Figure 7; Want the caution area molten bath to advance/arrange the sealing problem at phosphorus mouth, water inlet/water port, thief hole place especially during making, the yellow phosphorus of guaranteeing to distinguish in the molten bath and being adorned does not have leakage.
Ring heater is 9 groups, the quantity of annular water cooler is identical with the quantity of ring heater, one group of ring heater is along 0.04 (16mm) of the axial length of distinguishing molten bath 6 for district's molten bath total length, one group of bad shape water cooler is similarly 0.04 (16mm) that distinguishes the molten bath total length along the axial length of distinguishing molten bath 6, and the spacing d between ring heater and the annular water cooler is 3mm; Ring heater is a heating medium circulation tube group 5, and each is organized heating medium circulation tube group and is connected in series, and is provided with 3 and heating medium outlets 7 of a heating medium inlet; The annular water cooler is a heat-eliminating medium circulation tube group 10, and each is organized heat-eliminating medium circulation tube group and is connected in series, and is provided with 9 and heat-eliminating medium outlets 16 of a heat-eliminating medium inlet; The pipe of forming heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 can be pipe or rectangular pipe, the preferred rectangle copper pipe of present embodiment, and its physical dimension is 4 * 3mm; Heating medium is 75 ℃ a water, the water that heat-eliminating medium is 10 ℃.
Drive unit comprises motor 15, speed reduction unit 14, drive lead screw 12 and swivel nut 11, and the power input shaft of speed reduction unit is connected with the power output shaft of motor, and the power output shaft of speed reduction unit is connected with drive lead screw, and drive lead screw and swivel nut are formed transmission pair.
The assembling mode of each parts: bearing 8 is two, and (described spacing and the length L coupling of distinguishing the molten bath) is installed on the table top of base 18 mutually across a certain distance; The two ends in molten bath 6, district are installed on the bearing 8, and its axis and horizontal angle theta are 5 degree; Each heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 are installed around molten bath 6, district, and axially are separated by spacing d alternately along the molten bath, district; Drive unit is installed on the base 18; Combination cover 20 is sleeved on heating medium circulation tube group 5 and the heat-eliminating medium circulation tube group 10, forms integral structure with heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10, and the swivel nut 11 in the drive unit is connected with combination cover 20 by transom 13.
The zone melting method is followed successively by following steps:
A, inject about 70 ℃ hot water by hydraulic pipe 4 to district's molten bath 6 inner chambers, till district's molten bath 6 inner chambers are full of hot water;
B, by the liquid industrial yellow phosphorus after advancing phosphorus pipe 1 and will extracting by pressing the phosphorus groove to be pressed into district's molten bath inner chamber, meanwhile, the hot water in district's molten bath inner chamber is discharged by hydraulic pipe 4, after district's molten bath inner chamber is full of liquid industrial yellow phosphorus, closes yellow phosphorus inlet and water port;
C, the liquid industrial yellow phosphorus in district's molten bath inner chamber is solidified by naturally cooling;
D, (the heating medium temperature is 75 ℃ at first heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 to be adjusted to state with heating medium and heat-eliminating medium conducting, heat-eliminating medium is 10 ℃), open drive unit then, drive heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 axially moving back and forth 20 times along the molten bath, district, the molten speed in preceding 15 districts is 0.5mm/min, retum speed is 100mm/min, and the molten speed in back 5 districts is 1.5mm/min, and retum speed is 100mm/min; During zone melting, the state of impurity as shown in Figure 8 in the yellow phosphorus; After moving back and forth end, close drive unit;
E, at first that foreign matter content is high yellow phosphorus melt, emit by row's phosphorus pipe 17, cut off the heat-eliminating medium of heat-eliminating medium circulation tube group 10 then, will make with extra care yellow phosphorus and emit by row's phosphorus pipe 17 with heating medium circulation tube group 5 fusing backs, deposit with refining yellow phosphorus storage phosphorus groove, and with hot water cleaning area molten bath.As shown in table 3 through the foreign matter content in this step back yellow phosphorus:
Yellow phosphorus impurity content after table 3 zone melting (mg/kg of unit)
3, decompression micro-filtration
A, vacuum filter is vacuumized vacuum tightness 0.09Mpa;
B, with temperature hot water injection's filter membrane (filter membrane adopt aperture be the poly tetrafluoroethylene of 0.3 μ m) of 60 ℃;
C, the liquid phosphor after the zone melting purification is filtered by pressing the phosphorus groove to be pressed into vacuum filter.
Industrial production can adopt inlet outlet pressure differential not to be higher than the large-scale microfiltration equipment (commercial goods is arranged) of 0.2Mpa, as the efficient Microfilter of WL type PE.
The yield that present embodiment obtains the yellow phosphorus product is 88.4%, and the analytical results of impurities sees Table 4.
Table 4 foreign matter content analytical results (mg/kg of unit)
Embodiment 2
The technical process of present embodiment as shown in Figure 1, processing step is followed successively by extraction, zone melting, decompression micro-filtration.
1, extraction
Extraction agent is a tributyl phosphate, and thinner is a paraffin oil, and in the organic phase, the percent by volume of extraction agent is 30%, thinner percent by volume be 70%.The volume ratio of organic phase and industrial yellow phosphorus is 1: 3.
Extraction reactor is the simple glass jacketed reactor; in the chuck 70 ℃ of circulating hot waters; add organic phase then; and in reactor, feed nitrogen; after the air in the reactor is discharged fully, industrial yellow phosphorus by pressing the phosphorus groove to be pressed into reactor, is extracted under nitrogen protection; the stirring linear velocity is 600r/min, churning time 35min.Stop to stir the back and discharge organic phase,, then yellow phosphorus is put into first product storage phosphorus groove with hot wash yellow phosphorus twice.
2, zone melting
The structure of zone melting equipment as shown in Figure 2, and is identical with embodiment 1.
The zone melting method is followed successively by following steps:
A, inject about 70 ℃ hot water by hydraulic pipe 4 to district's molten bath 6 inner chambers, till district's molten bath 6 inner chambers are full of hot water;
B, by the liquid industrial yellow phosphorus after advancing phosphorus pipe 1 and will extracting by pressing the phosphorus groove to be pressed into district's molten bath inner chamber, meanwhile, the hot water in district's molten bath inner chamber is discharged by hydraulic pipe 4, after district's molten bath inner chamber is full of liquid industrial yellow phosphorus, closes yellow phosphorus inlet and water port;
C, the liquid industrial yellow phosphorus in district's molten bath inner chamber is solidified by naturally cooling;
D, (the heating medium temperature is 70 ℃ at first heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 to be adjusted to state with heating medium and heat-eliminating medium conducting, heat-eliminating medium is 15 ℃), open drive unit then, drive heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 axially moving back and forth 20 times along the molten bath, district, the molten speed in preceding 10 districts is 0.6mm/min, retum speed is 120mm/min, and the molten speed in back 10 districts is 1.2mm/min, and retum speed is 120mm/min; During zone melting, the state of impurity as shown in Figure 8 in the yellow phosphorus; After moving back and forth end, close drive unit;
E, at first that foreign matter content is high yellow phosphorus melt, emit by row's phosphorus pipe 17, cut off the heat-eliminating medium of heat-eliminating medium circulation tube group 10 then, will make with extra care yellow phosphorus and emit by row's phosphorus pipe 17 with heating medium circulation tube group 5 fusing backs, deposit with refining yellow phosphorus storage phosphorus groove, and with hot water cleaning area molten bath.
3, decompression micro-filtration
The device that uses is identical with embodiment 1 with operation.
The yield that present embodiment obtains the yellow phosphorus product is 81.2%, and the analytical results of impurities sees Table 5.
Table 5 foreign matter content analytical results (mg/kg of unit)
The technical process of present embodiment as shown in Figure 1, processing step is followed successively by extraction, zone melting, decompression micro-filtration.
1, extraction
Extraction agent is di-(2-ethylhexyl)phosphoric acid and tributyl phosphate, the volume ratio of di-(2-ethylhexyl)phosphoric acid and tributyl phosphate is 1: 1, and thinner is a paraffin oil, in the organic phase, the percent by volume of extraction agent is 20%, and the percent by volume of thinner is 80%.The volume ratio of organic phase and industrial yellow phosphorus is 1: 2.
Extraction reactor is the simple glass jacketed reactor; in the chuck 70 ℃ of circulating hot waters; add organic phase then; and in reactor, feed nitrogen; after the air in the reactor is discharged fully, industrial yellow phosphorus by pressing the phosphorus groove to be pressed into reactor, is extracted under nitrogen protection; the stirring linear velocity is 800r/min, churning time 25min.Stop to stir the back and discharge organic phase,, then yellow phosphorus is put into first product storage phosphorus groove with hot wash yellow phosphorus twice.
2, zone melting
The structure of zone melting equipment as shown in Figure 2, and is identical with embodiment 1.
The zone melting method is followed successively by following steps:
A, inject about 70 ℃ hot water by hydraulic pipe 4 to district's molten bath 6 inner chambers, till district's molten bath 6 inner chambers are full of hot water;
B, by the liquid industrial yellow phosphorus after advancing phosphorus pipe 1 and will extracting by pressing the phosphorus groove to be pressed into district's molten bath inner chamber, meanwhile, the hot water in district's molten bath inner chamber is discharged by hydraulic pipe 4, after district's molten bath inner chamber is full of liquid industrial yellow phosphorus, closes yellow phosphorus inlet and water port;
C, the liquid industrial yellow phosphorus in district's molten bath inner chamber is solidified by naturally cooling;
D, (the heating medium temperature is 70 ℃ at first heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 to be adjusted to state with heating medium and heat-eliminating medium conducting, heat-eliminating medium is 15 ℃), open drive unit then, drive heating medium circulation tube group 5 and heat-eliminating medium circulation tube group 10 axially moving back and forth 25 times along the molten bath, district, the molten speed in preceding 10 times district is 0.5mm/min, retum speed is 140mm/min, and the molten speed in back 15 times district is 2mm/min, and retum speed is 140mm/min; During zone melting, the state of impurity as shown in Figure 8 in the yellow phosphorus; After moving back and forth end, close drive unit;
E, at first that foreign matter content is high yellow phosphorus melt, emit by row's phosphorus pipe 17, cut off the heat-eliminating medium of heat-eliminating medium circulation tube group 10 then, will make with extra care yellow phosphorus and emit by row's phosphorus pipe 17 with heating medium circulation tube group 5 fusing backs, deposit with refining yellow phosphorus storage phosphorus groove, and with hot water cleaning area molten bath.
3, decompression micro-filtration
The device that uses is identical with embodiment 1 with operation.
The yield that present embodiment obtains the yellow phosphorus product is 73.2%, and the analytical results of impurities sees Table 6.
Table 6 foreign matter content analytical results (mg/kg of unit)
Embodiment 4
The technical process of present embodiment as shown in Figure 1, processing step is followed successively by extraction, zone melting, decompression micro-filtration.
1, extraction
Extraction agent is di-(2-ethylhexyl)phosphoric acid and calixarene, and the volume ratio of di-(2-ethylhexyl)phosphoric acid and calixarene is 1: 1, and thinner is a kerosene, and in the organic phase, the percent by volume of extraction agent is 30%, thinner percent by volume be 70%.The volume ratio of organic phase and industrial yellow phosphorus is 1: 2.
Extraction reactor is the simple glass jacketed reactor; in the chuck 70 ℃ of circulating hot waters; add organic phase then; and in reactor, feed nitrogen; after the air in the reactor is discharged fully, industrial yellow phosphorus by pressing the phosphorus groove to be pressed into reactor, is extracted under nitrogen protection; the stirring linear velocity is 600r/min, churning time 40min.Stop to stir the back and discharge organic phase,, then yellow phosphorus is put into first product storage phosphorus groove with hot wash yellow phosphorus twice.
2, zone melting
The structure of zone melting equipment as shown in Figure 3, difference from Example 1 is: 1, ring heater is an electrical induction heating coil 28; 2, the length overall L in quadrangular barrel molten bath 6 is 400mm (do not comprise the two ends wall thickness, the two ends wall thickness is for embedding the bearing part), and the high h of quadrangular cylinder lumen is 2 (the high 40mm of being, wide is 20mm) with the ratio of wide b; 3, ring heater is 5 groups, the quantity of annular water cooler is identical with the quantity of ring heater, one group of ring heater is along 0.04 (16mm) of the axial length of distinguishing molten bath 6 for district's molten bath total length, one group of annular water cooler is along 0.10 (40mm) of the axial length of distinguishing molten bath 6 for district's molten bath total length, and the spacing d between ring heater and the annular water cooler is 4mm; 4, the table top of base 18 and horizontal angle theta are 13 degree;
The zone melting method is followed successively by following steps:
A, inject about 70 ℃ hot water by hydraulic pipe 4 to district's molten bath 6 inner chambers, till district's molten bath 6 inner chambers are full of hot water;
B, by the liquid industrial yellow phosphorus after advancing phosphorus pipe 1 and will extracting by pressing the phosphorus groove to be pressed into district's molten bath inner chamber, meanwhile, the hot water in district's molten bath inner chamber is discharged by hydraulic pipe 4, after district's molten bath inner chamber is full of liquid industrial yellow phosphorus, closes yellow phosphorus inlet and water port;
C, the liquid industrial yellow phosphorus in district's molten bath inner chamber is solidified by naturally cooling;
D, at first electrical induction heating coil 28 and heat-eliminating medium circulation tube group 10 are adjusted to (Heating temperature is 80 ℃ with the state that heats thermal source and heat-eliminating medium conducting, heat-eliminating medium is 5 ℃), open drive unit then, drive electrical induction heating coil 28 and heat-eliminating medium circulation tube group 10 axially moving back and forth 40 times along the molten bath, district, the molten speed in preceding 20 times district is 0.3mm/min, retum speed is 150mm/min, and the molten speed in back 20 times district is 1.5mm/min, and retum speed is 150mm/min; During zone melting, in the yellow phosphorus state of impurity as shown in Figure 8, move back and forth end after, close drive unit;
E, at first that foreign matter content is high yellow phosphorus melt, emit by row's phosphorus pipe 17, cut off the heat-eliminating medium of heat-eliminating medium circulation tube group 10 then, will make with extra care yellow phosphorus electricity consumption load coil 28 fusing backs and emit by row's phosphorus pipe 17, deposit with refining yellow phosphorus storage phosphorus groove, and with hot water cleaning area molten bath.
3, decompression micro-filtration
The device that uses is identical with embodiment 1 with operation.
The yield that present embodiment obtains the ultra-pure yellow phosphorus product is 78.3%, and the analytical results of impurities sees Table 7.
Table 7 foreign matter content analytical results (mg/kg of unit)
Claims (5)
1, a kind of production method of ultra-pure yellow phosphorus is characterized in that with the industrial yellow phosphorus being raw material, and industrial yellow phosphorus is prepared into ultra-pure yellow phosphorus by extraction, zone melting, pressurization or decompression micro-filtration successively;
Equipment and operation steps that described zone melting is used are as follows:
1. zone melting equipment comprises molten bath (6), district, ring heater, annular water cooler, combination cover (20) and drive unit; Molten bath, described district (6) is the cylindrical barrel body of closed at both ends, is installed on the bearing (8); Described ring heater is at least one group, and the quantity of annular water cooler is identical with the quantity of ring heater, and ring heater and annular water cooler are installed around district molten bath (6), and along the axial phase of distinguishing the molten bath alternately across a certain distance; Described combination cover (20) is sleeved on ring heater and the annular water cooler, forms integral structure with ring heater and annular water cooler, and drive unit is connected with combination cover (20) by transom (13);
2. the zone melting method is carried out according to the following steps
A, will distinguish in the inner chamber of molten bath (6) and fill 60 ℃～80 ℃ hot water;
B, will be through the liquid phosphor of extraction by pressing the phosphorus groove be pressed into district's molten bath (6) inner chamber, meanwhile, the hot water in district's molten bath (6) inner chamber is discharged from, and after district's molten bath (6) inner chamber is full of liquid phosphor, closes yellow phosphorus inlet and water port;
C, the liquid phosphor that will distinguish in the inner chamber of molten bath solidify;
D, ring heater and annular water cooler are adjusted to state with thermal source and low-temperature receiver conducting, open drive unit then, drive ring heater and annular water cooler axially moving back and forth along the molten bath, district, make the fusing of solid yellow phosphorus subregion, produce along axially movable melting zone, molten bath, district, after reaching the removal of impurities requirement, close drive unit;
E, the fusing of at first that foreign matter content is high yellow phosphorus are emitted by row's phosphorus mouth of district molten bath (6), cut off annular water cooler low-temperature receiver then, will make with extra care with ring heater and emit after the yellow phosphorus fusing and with hot water cleaning area molten bath.
2, the production method of ultra-pure yellow phosphorus according to claim 1, when it is characterized in that zone melting, 60 ℃～80 ℃ of Heating temperatures, 5 ℃～20 ℃ of cooling temperatures; Ring heater and annular water cooler axially move back and forth in the process along the molten bath, district, the molten speed 0.2mm/min～3mm/min in district, and retum speed is at least 100mm/min; Ring heater and annular water cooler axially move back and forth number of times along the molten bath, district and are at least 20 times.
3, the production method of ultra-pure yellow phosphorus according to claim 2, it is characterized in that ring heater and annular water cooler are along the molten bath, district when axially moving back and forth, successively by two kinds of molten speed operations in district, promptly at first by the molten speed 0.2mm/min in district～1mm/min operation, the number of times that moves back and forth is at least 10 times, by the molten speed 1mm/min in district～3mm/min operation, the number of times that moves back and forth is at least 5 times then.
4, the production method of ultra-pure yellow phosphorus according to claim 1 is characterized in that ring heater is heating medium circulation tube group (5) or electrical induction heating coil (28), and annular water cooler is a heat-eliminating medium circulation tube group (10).
5, the production method of ultra-pure yellow phosphorus according to claim 4, the micro-filtration that it is characterized in that pressurizeing or reduce pressure filters with the pressurization or the vacuum filter of 0.1 μ m～0.5 μ m level.
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| CN101650301B (en) * | 2009-08-10 | 2010-12-08 | 四川大学 | Atomic absorption spectrometry of content of Fe and Zn impurities in yellow phosphorus |
| WO2011097961A1 (en) * | 2010-02-12 | 2011-08-18 | Dongying Jieda Chemical Technology Co., Ltd. | Method for production of ultrapure phosphorus by zone melting and apparatus thereof |
| CN103641087A (en) * | 2013-11-18 | 2014-03-19 | 瓮福（集团）有限责任公司 | Apparatus and method for purifying yellow phosphorus |
| CN103641089A (en) * | 2013-11-18 | 2014-03-19 | 瓮福（集团）有限责任公司 | Apparatus and method for purifying yellow phosphorus |
| CN103641085B (en) * | 2013-11-18 | 2015-04-01 | 瓮福（集团）有限责任公司 | Apparatus and method for purifying yellow phosphorus |
| CN103641091B (en) * | 2013-11-18 | 2015-04-01 | 瓮福（集团）有限责任公司 | Apparatus and method for producing high-purity yellow phosphorus |
| CN103641084A (en) * | 2013-11-18 | 2014-03-19 | 瓮福（集团）有限责任公司 | Apparatus and method for purifying yellow phosphorus |
| CN104211132B (en) * | 2014-09-05 | 2016-02-03 | 广东溢达纺织有限公司 | A kind of method of extraction agent and process reactive dyed wastewater |
| CN109592657B (en) * | 2019-01-21 | 2020-04-03 | 江山市艺康化学有限公司 | Yellow phosphorus cutting reaction device |
| CN111204724B (en) * | 2020-02-24 | 2021-04-06 | 江苏秦烯新材料有限公司 | Method for removing trace sulfur in yellow phosphorus |
| CN111517296A (en) * | 2020-05-22 | 2020-08-11 | 四川君和环保股份有限公司 | Method for recovering yellow phosphorus from phosphorus-containing sludge by utilizing trichloromethane |
| CN111704163A (en) * | 2020-06-24 | 2020-09-25 | 湖南锐异资环科技有限公司 | Arsenic trioxide purification system and purification method |
| CN111892029B (en) * | 2020-08-21 | 2021-12-24 | 江苏秦烯新材料有限公司 | Method for removing mixed impurities in yellow phosphorus |
| CN113896176B (en) * | 2021-11-10 | 2023-09-26 | 贵州威顿晶磷电子材料股份有限公司 | Preparation process of ultralow-sulfur high-purity red phosphorus |
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