CN101096726A - Production method for high-purity arsenic and its equipment - Google Patents
Production method for high-purity arsenic and its equipment Download PDFInfo
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- CN101096726A CN101096726A CNA2006100881495A CN200610088149A CN101096726A CN 101096726 A CN101096726 A CN 101096726A CN A2006100881495 A CNA2006100881495 A CN A2006100881495A CN 200610088149 A CN200610088149 A CN 200610088149A CN 101096726 A CN101096726 A CN 101096726A
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Abstract
The invention discloses a manufacturing method and specific equipment of semiconductor basic material hyperhigh-purity alpha-typed arsenic with purify at 99.99999% through once vacuum sublimation and twice hydrogen sublimations, which consists of vacuum sublimator and hydrogen sublimator, wherein the vacuum sublimator contains heater A, heater B, vacuum tank, water jacket, copple, obstruct board, conical titanium condenser, low-boiling collecting board and vacuum pump; the hydrogen sublimator includes hydrogen input device, argon input device, casing, quartz tube A, quartz tube B, quartz tube C, heater, scrubbing device and spray device.
Description
Technical field
The present invention relates to a kind of purification production method and equipment of non-metallic material, relate in particular to the production method and the specific equipment thereof of the ultra-pure α type of a kind of semiconductor foundation material arsenic.
Background technology
High-purity α type arsenic is preparation photoelectron, microelectronics gallium arsenide; Infrared optical fiber, Infrared Lens As
2Se
3, As
2Te
3In infrared perspective glass; The indispensable material of sensitization eardrum As-Se alloy, material purity is got over the intrinsic property that Gao Yueneng demonstrates material, can bring into play the using value of material more, make the speed increase of the demand of high purity arsenic with annual 25%-30% with civilian the popularizing of high-purity α type arsenic be base mateiral gallium arsenide, infrared perspective glass and used in electronic industry arsenic-containing alloy.
At present, the production method of the whole world high-purity α type arsenic is mainly based on the chlorination rectification method, and next has arsenical lead nitrogen atmosphere subliming method, plumbous molten bath subliming method, hydrogen arsenide cracking process to carry out small serial production, and its relative merits are respectively arranged.
Chlorination rectifying reduction method: be to produce the general classic methods of high purity arsenic.Its advantage: 1. be fed to the product discharging and all in pipeline, finish technology from raw material, not tight to the cleaning condition requirement of production plant, only need guarantee out that the regional area air ambient of product reaches ultra-clean; 2. the 6N quality product is more stable.Its shortcoming: 1. arsenic trichloride is the deep-etching strong oxidizer, the material of making the arsenic trichloride rectifying tower has only the corrosion of the anti-arsenic trichloride of silica glass energy, the rectifying tower investment of setting up 20 tons of cover annual outputs in the world is no less than 2,500 ten thousand dollars (only has Germany can process such quartz towers, Furukawa Electronic produces 20 tons rectifying tower Germany manufacturing per year, invest 2,500 ten thousand dollars), domestic because quartzy level of processing restriction, all produce house and all use φ 10 wall thickness 5mm left and right sides trourelles, production capacity is low, tower damages easily, product comprehensive cost height, unstable product quality; 2. domestic quartzy rectifying tower can not be made into whole tower, connecting partly, easy leakage of arsenic chloride gas pollutes, and the high component arsenic trichloride of a large amount of reactors waste material is arranged, the tail gas that reduces simultaneously has a large amount of salt acid vapours, handles bad very easily to environment generation damaging influence or loss of life and personal injury; Easy generation was jumped and is boiled when 3. the arsenic trichloride impurity concentration was high in the reactor, made rectifying tower produce vibrations, caused the damage of quartzy body of the tower destructiveness, and operator safety and environment are brought damaging influence.
Arsenical lead nitrogen atmosphere subliming method is with arsenic and the plumbous alloy that forms, utilize impurity and the plumbous alloy that forms and the difference of arsenic vapour pressure progressively to isolate highly purified arsenic again, its advantage is that technological process is based on physical process, does not produce hazardous compound, steady quality, cost is low; Its shortcoming be arsenic with the plumbous tailing that forms in contain 15% the arsenic of having an appointment, sell though this tailing can be made product, this method labour intensity in process of production is big, action required personnel are many.
Plumbous molten bath method: this method is in nineteen sixty-five Shanghai Institute of Metallurgical Technology proposition and develop 6N arsenic, and its method is that arsenic distils in the lead of melting.Its advantage: technological process is a physical process, and technology is finished technology in the negative-pressure vacuum system, and the discharging charging is solid, has thoroughly solved the pollution problem that high purity arsenic is produced, and is the production method of safety non-pollution.Its shortcoming: plumbous proportion is 2 times of proportion of arsenic, arsenic is floating fast to plumbous molten surface when lead melts, and is not obvious to the impurity refining effect in the arsenic, is that the test mass of 100～200g scope is fine at arsenic, the foreign matter content of arsenic＞200g does not reach specification of quality, can not be used for industrialization production.
The hydrogen arsenide cracking process: this method advantage is that quality is all better than the high purity arsenic quality of other any method production, and cost is suitable with chlorination rectifying.Its shortcoming is that hydrogen arsenide is the violent poison gas of colorless and odorless, in case take place to leak direct labor and environment is brought great potential safety hazard.Only abroad be used at present producing high-purity α type arsenic among a small circle, do not realize industrialization.
Summary of the invention
The present invention is directed to above problem, provide a kind of can be not influential to operator and environment, facility investment is little, the product purity height, tooling cost is low, labour intensity is low, the technology stroke short, simple and safe easy to operate, but industrialization production purity is the production method and the equipment thereof of 99.99999% high purity arsenic.
Production method of the present invention has following steps:
1), raw material arsenic is inserted in the crucible, the tube end of a conically shaped, be connected with crucible, is provided with the baffler that has some apertures at crucible and conically shaped connecting portion, establishes a low collecting board that boils that has a macropore in the upper end of conically shaped;
2), the crucible with coupling together, conically shaped, baffler, the low collecting board that boils insert vacuum tank, the corresponding conically shaped of vacuum tank upper end is provided with water jacket, adjusting a jar internal pressure is 10
-1～2*10
1Pa feeds the recirculated water of normal temperature in the water jacket of vacuum tank; Heated in the conically shaped position, to 250～350 ℃, insulation; Then, heated in the crucible position, to 280～400 ℃, insulation; Continue about 7.5～10 hours, condensing on the inwall of crucible upper taper tube has arsenic, makes purity and be 99.99% arsenic;
3), above-mentioned arsenic is taken out, insert a silica tube A, A inserts a sleeve pipe with this silica tube, dock silica tube B with silica tube A in the sleeve pipe, docks silica tube C with silica tube B again, and air inlet/outlet is established at the sleeve pipe two ends, imports argon gas, the air in the purger by inlet mouth; By inlet mouth input hydrogen, silica tube A is heated to 550～650 ℃ again, silica tube B is heated to 400～500 ℃, with silica tube C heating and remain on 250～350 ℃; At this moment, the material in the silica tube A forms arsenic steam and trace impurity steam, and boiling point is higher than the impurity of A pipe temperature to be stayed in the A pipe, and arsenic steam and trace impurity steam enter silica tube B; Selenium in silica tube B in the impurity steam and H-H reaction form Selenium hydride, and sulphur and H-H reaction form hydrogen sulfide; Arsenic steam, Selenium hydride, hydrogen sulfide continue to enter silica tube C, and to get purity be 99.9999% arsenic in condensation on the inwall of silica tube C; Selenium hydride, hydrogen sulfide and the impurity steam that contains Determination of Trace Sulfur are discharged from the air outlet, are entered in the sodium hydroxide solution in the air-washer by the escape pipe on the air outlet, carry out neutralization reaction; Air-washer connects elution device, and the β arsenic that remains in the tail gas is precipitated in elution device, and clean hydrogen is discharged in the air outlet of elution device;
4) process, above-mentioned arsenic is taken out, set by step 3) reprocess one time, and except that silica tube A Heating temperature was constant, silica tube B was heated to 700～900 ℃, and silica tube C heats also and remains on 300～400 ℃.
Production unit of the present invention, according to the high purity arsenic procedure of processing, form by vacuum-sublimation device and nitrogen atmosphere sublimer two portions, described vacuum-sublimation device comprises well heater A, well heater B, vacuum tank, water jacket, crucible, baffler, the taper titanium condenser, the low collecting board that boils, vacuum pump, the tube end of taper titanium condenser, be connected with crucible, establish a baffler that has some apertures at crucible and taper titanium condenser connecting portion, establish a low collecting board that boils that has a macropore in the upper end of taper titanium condenser, the taper titanium condenser, crucible, baffler, the low collecting board that boils is arranged on vacuum tank inside, establish well heater A at the outside corresponding crucible of vacuum tank position, well heater B is established at corresponding taper titanium condenser position, and water jacket is located at vacuum tank top; Described nitrogen atmosphere sublimer comprises the hydrogen input unit, the argon gas input unit, sleeve pipe, silica tube A, silica tube B, silica tube C, well heater, air-washer, spray equipment, silica tube A, silica tube B, silica tube C is serially connected in the sleeve pipe, the outer corresponding silica tube A of sleeve pipe, silica tube B, silica tube C is respectively equipped with well heater, sleeve pipe is established air inlet/outlet, the inlet mouth of hydrogen input unit and argon gas input unit sleeved, air-washer comprises jar, intubate, plug, the telescopic air outlet connects the air inlet intubate of air-washer, the intubate of giving vent to anger of air-washer connects elution device, be provided with shower in the elution device, settling bath, the air outlet of elution device connects atmosphere.
Production method of the present invention and supporting vacuum-sublimation device, the quartzy sublimer of nitrogen atmosphere, cost is low, and less investment, its performance have guaranteed the present invention investment are little in industrialization is produced, production capacity is high, cost is low, quality is good.Solve the big problem of high purity arsenic production scale of investment, used investment seldom just can realize industrialization.Remove impurity in the arsenic through nitrogen atmosphere distillation, obtain the ultra-pure arsenic of 7N, and environmentally safe.The positively effect that the present invention produces is:
At first, the present invention is mainly physical process, does not produce poisonous and hazardous intermediate compound, has thoroughly solved pollution problem and potential safety hazard, has realized green non-pollution production high purity arsenic.
Secondly, the present invention uses the quartz except that the nitrogen atmosphere distillation, vacuum-sublimation equipment is reusable special metal material manufacturing, do not re-use flimsy silica glass, investment is reduced greatly, and producing 20 tons of 7N high purity arsenic production lines per year with investment is example, and the only domestic producing apparatus of chlorination rectifying will be invested about 2,000 ten thousand, and the present invention only needs about 5,000,000, and output investment ratio chlorination rectification method saves 75%.
Then, about 550,000 yuan/ton of comprehensive cost is produced in chlorination rectifying, 250,000 yuan/ton of arsenical lead nitrogen atmosphere subliming methods, the present invention is because the quartzy loss of a large amount of minimizings, and synthetic alloy and isolating operation have been reduced than arsenical lead nitrogen atmosphere subliming method, electric energy, facility investment and personnel labor intensity have been saved greatly, production cost is reduced to 200,000 yuan/ton, reduce by 63.5% than chlorination rectifying cost, reduce cost 25% than lead arsenic alloy nitrogen atmosphere subliming method, and reduced operator, saved labor cost.
At last, chlorination rectifying does not have the proprietary technology of 7N product, in the product rule of thumb the middle part 1/3 be 7N, be 6N end to end, 7N product instability appears easily, the present invention is a 7N product special process, to go out product all be the 7N product, added value of product raising 30%.
Produce the investment of 10 tons of 7N high purity arsenics, raw materials consumption, ton cost per year and pollute comparison sheet:
| Method | Investment | Plumbous | Hydrogen | Chlorine | Quartzy | Raw material arsenic | The ton cost | Tailing and pollution |
| Chlorination rectifying reduction method | 1,200 ten thousand yuan | 5600 cubic metres | 700 cubic metres | 250 yuan/ |
12 tons | 550,000 yuan | There are arsenic trichloride waste liquid, a large amount of hydrochloric acid tail gas, chlorine and arsenic trichloride to leak | |
| Lead arsenic alloy nitrogen atmosphere subliming method | 3,500,000 yuan | 40 tons | 600 cubic metres | 50 yuan/kilogram | 39.6 ton | 250,000 yuan | No chemical pollution | |
| The present invention | 3,000,000 yuan | 600 cubic metres | 50 yuan/kilogram | 10.5 ton | 200,000 yuan | No chemical pollution |
Chlorination rectifying, arsenical lead nitrogen atmosphere subliming method and quality comparison sheet of the present invention
Unit: PPm
| Impurity | ||||||||||||||
| Ag | ?Al | ?Ga | ?Cu | ?Fe | ?Mg | ?Ni | ?Pb | ?Zn | ?Se | ?Cr | ?Sb | ?S | ?C | |
| Chlorination rectifying | 0.001 | ?0.005 | ?0.01 | ?0.005 | ?0.01 | ?0.005 | ?0.005 | ?0.005 | ?0.02 | ?0.01 | ?0.001 | ?0.002 | ?0.005 | ?0.02 |
| Plumbous arsenic hydrogen method | 0.001 | ?0.001 | ?0.001 | ?0.001 | ?0.005 | ?0.001 | ?0.002 | ?0.005 | ?0.005 | ?0.005 | ?0.005 | ?0.002 | ?0.001 | ?0.005 |
| The present invention | 0.001 | ?0.001 | ?0.001 | ?0.001 | ?0.005 | ?0.001 | ?0.003 | ?0.005 | ?0.005 | ?0.005 | ?0.005 | ?0.002 | ?0.001 | ?0.005 |
Description of drawings
Fig. 1 is the structural representation of the vacuum-sublimation device in the production unit of the present invention
1 is vacuum tank among the figure, the 2nd, and well heater A, the 3rd, well heater B, the 4th, water jacket, the 5th, water jacket water-in, the 6th, water jacket water outlet, the 7th, the low collecting board that boils, the 8th, vacuum pump, the 9th, condensed arsenic, the 10th, taper titanium condenser, the 11st, baffler, the 12nd, sorbing material, the 13rd, raw material arsenic, the 14th, crucible;
Fig. 2 is the vertical view of the low collecting board 7 that boils among Fig. 1
Fig. 3 is the vertical view of the baffler 11 among Fig. 1
Fig. 4 is the structural representation of nitrogen atmosphere sublimer
15 is inlet mouths of nitrogen atmosphere sublimer among the figure, the 16th, and silica tube A, the 17th, 4N arsenic, the 18th, sleeve pipe, the 19th, silica tube B, the 20th, silica tube C, the 21st, high purity arsenic, the 22nd, telescopic escape pipe, the 23rd, the escape pipe of air-washer;
Fig. 5 is the structural representation of spray equipment among the present invention
24 is tanks among the figure, the 25th, and inlet pipe, the 26th, spray nozzle, the 27th, spray nozzle, the 28th, spray colunm, the 29th, air outlet, the 30th, water pump.
Embodiment
Embodiment 1
At first with primary industry 1
#Arsenic 13 (purity is 99%) is put into a crucible 14, again crucible 14 is inserted in the vacuum tank 1, then, connect the obstructing instrument 11 that 2 layers of stainless steel sheet of a usefulness are made at crucible 14 oral areas, the aperture that is covered with Φ 2mm on the obstructing instrument 11, in the interlayer of obstructing instrument 11, can fill the sorbing material 12 of some high temperature resistant pollution-free band micropores, as activated carbon etc., the top of obstructing instrument 11 connects a taper condensation tube 10, taper condensation tube 10 is made of titanium, and there is the roughness requirement on the surface, and the osculum place, upper end of taper condensation tube 10 is provided with the low collecting board 7 that boils that a size is coincide, the low collecting board 7 that boils is made for metallic substance, and the hole of 3 Φ 30mm is laid on the surface.Vacuum tank 1 oral area outer ring is provided with refrigeration cycle water jacket 4; also be provided with watercooling jacket covering of vacuum tank 1; water coolant enters water jacket from the water-in 5 of tank body water jacket; discharge from the water outlet 6 of cover water jacket; a cold zone is formed at the top at vacuum tank 1; collect the condensation low-boiling-point substance, can protect the sealing-ring of vacuum tank 1 simultaneously.
Start vacuum pump 8, the pressure of adjusting in the vacuum tank 1 is 10
-1Pa; Start water coolant, making in the water jacket 4 has recirculated water; Start well heater B3, the temperature that makes condenser 10 positions is 350 ℃, insulation; Start well heater A2, making the temperature at crucible 14 and obstructing instrument 11 positions is 400 ℃, insulation.Amount according to material 13 in the crucible 14 is chosen different heating, soaking time, accept 3 hours speed of thermal radiation with per 5 kilograms of materials and determine heating and soaking time, reach set heating, soaking time after, condensation has arsenic 9 on the inwall of conically shaped 10, makes purity and be 99.99% arsenic 9.
Long silica tube 18 horizontal positioned that one two ends had quartzy frosted cap, the quartzy frosted cap at two ends is respectively equipped with inlet mouth 15 and air outlet 22, place silica tube A16, silica tube B19, the silica tube C20 of three diameter unanimities in the long silica tube 18, the end face of the mouth of pipe requires and axis normal, guarantee that the connection between the mouth of pipe is closely reliable, do not have and leak; With the purity that makes on the taper condenser 10 is that 99.99% arsenic takes out, and is placed in the silica tube A16; Air outlet 22 connects jar, sodium hydroxide solution is housed in the jar, air outlet 22 expellant gas stretch into sodium hydroxide solution by a vapor pipe, the empty vapor pipe 23 of inserting in jar top, this vapor pipe 23 connects the inlet pipe 25 of drip washing post 28, spray colunm 28 is by being tubbiness, tank 24 is established in the bottom, water pump 30 is established in the bottom of tank 24, and water pump 30 also connects the additional mouth of a river, establishes shower 27 on spray colunm 28 tops, establish plurality of nozzles 26 on the shower 27, set out gas port 29 on the top of spray colunm 28, the β arsenic that remains in the tail gas is precipitated in drip washing post 28, and clean hydrogen is discharged in air outlet 29.
Feed argon gas by inlet mouth 15 in the nitrogen atmosphere sublimer, the air in the purger prevents from feeding hydrogen, and blasts during heating; After waiting to drain air, in the nitrogen atmosphere sublimer, feed hydrogen by inlet mouth 15, the hydrogen pressure that feeds is 0.4Mpa, flow is 0.5L/S, simultaneously silica tube A16, silica tube B19, silica tube C20 are heated respectively, the order of pressing product condensation segment, interlude, raw material section successively heats up, and silica tube C20 is heated to 250 ℃, insulation; Again silica tube B19 is heated to 400 ℃, insulation; At last silica tube A16 is heated to 550 ℃, material 17 distillations in the silica tube A16, insulation; At this moment, the material in the silica tube A16 forms arsenic steam and trace impurity steam, and enters silica tube B19, and boiling point is higher than the impurity of temperature in this pipe and stays in the pipe; Selenium in silica tube B19 in the impurity steam and H-H reaction form Selenium hydride, sulphur and H-H reaction form hydrogen sulfide, arsenic steam, Selenium hydride, hydrogen sulfide continue to enter silica tube C20, to get purity be 99.9999% arsenic in condensation on the inwall of silica tube C20, Selenium hydride, hydrogen sulfide and the impurity steam that contains Determination of Trace Sulfur are discharged from the air outlet, enter sodium hydroxide solution in the filter flask by air outlet 22, after the neutralization, discharge fully.Treat that material 17 distillations finish, switch to feed argon gas, close each well heater, lower the temperature in proper order by material section, intermediate reaction section, product section.Because therefore the decomposition temperature of hydrogen sulfide, has Determination of Trace Sulfur and remains in the product that makes near reactor temperature.
Arsenic with 99.9999% takes out and inserts the nitrogen atmosphere sublimer again, repeats step, and different is that silica tube C20 is heated to 300 ℃, insulation; Silica tube B19 is heated to 700 ℃, insulation; Sulphur and hydrogen residual in the material form hydrogen sulfide, discharge reactor; What make is that purity is 99.99999% arsenic 21.
At first with primary industry 1
#Arsenic 13 (purity is 99%) is put into a crucible 14, again crucible 14 is inserted in the vacuum tank 1, then, connect the obstructing instrument 11 that 2 layers of stainless steel sheet of a usefulness are made at crucible 14 oral areas, the aperture that is covered with Φ 3mm on the obstructing instrument 11, in the interlayer of obstructing instrument 11, can fill the sorbing material 12 of some high temperature resistant pollution-free band micropores, as activated carbon etc., the top of obstructing instrument 11 connects a taper condensation tube 10, taper condensation tube 10 is made of titanium, and there is the roughness requirement on the surface, and the osculum place, upper end of taper condensation tube 10 is provided with the low collecting board 7 that boils that a size is coincide, the low collecting board 7 that boils is made for metallic substance, and the hole of 3 Φ 25mm is laid on the surface.Vacuum tank 1 oral area outer ring is provided with refrigeration cycle water jacket 4; also be provided with watercooling jacket covering of vacuum tank 1; water coolant enters water jacket from the water-in 5 of tank body water jacket; discharge from the water outlet 6 of cover water jacket; a cold zone is formed at the top at vacuum tank 1; collect the condensation low-boiling-point substance, can protect the sealing-ring of vacuum tank 1 simultaneously.
Start vacuum pump 8, the pressure of adjusting in the vacuum tank 1 is 10Pa; Start water coolant, making in the water jacket 4 has recirculated water; Start well heater B3, the temperature that makes condenser 10 positions is 300 ℃, insulation; Start well heater A2, making the temperature at crucible 14 and obstructing instrument 11 positions is 340 ℃, insulation.Amount according to material 13 in the crucible 14 is chosen different heating, soaking time, accept 3 hours speed of thermal radiation with per 5 kilograms of materials and determine heating and soaking time, reach set heating, soaking time after, condensation has arsenic 9 on the inwall of conically shaped 10, makes purity and be 99.99% arsenic 9.Long silica tube 18 horizontal positioned that one two ends had quartzy frosted cap, the quartzy frosted cap at two ends is respectively equipped with inlet mouth 15 and air outlet 22, place silica tube A16, silica tube B19, the silica tube C20 of three diameter unanimities in the long silica tube 18, the end face of the mouth of pipe requires and axis normal, guarantee that the connection between the mouth of pipe is closely reliable, do not have and leak; With the purity that makes on the taper condenser 10 is that 99.99% arsenic takes out, and is placed in the silica tube A16; Air outlet 22 connects jar, sodium hydroxide solution is housed in the jar, air outlet 22 expellant gas stretch into sodium hydroxide solution by a vapor pipe, the empty vapor pipe 23 of inserting in jar top, this vapor pipe 23 connects the inlet pipe 25 of drip washing post 28, spray colunm 28 is by being tubbiness, tank 24 is established in the bottom, water pump 30 is established in the bottom of tank 24, and water pump 30 also connects the additional mouth of a river, establishes shower 27 on spray colunm 28 tops, establish plurality of nozzles 26 on the shower 27, set out gas port 29 on the top of spray colunm 28, the β arsenic that remains in the tail gas is precipitated in drip washing post 28, and clean hydrogen is discharged in air outlet 29.
Feed argon gas by inlet mouth 15 in the nitrogen atmosphere sublimer, the air in the purger prevents from feeding hydrogen, and blasts during heating; After waiting to drain air, in the nitrogen atmosphere sublimer, feed hydrogen by inlet mouth 15, the hydrogen pressure that feeds is 0.4Mpa, flow is 0.5L/S, simultaneously silica tube A16, silica tube B19, silica tube C20 are heated respectively, the order of pressing product condensation segment, interlude, raw material section successively heats up, and silica tube C20 is heated to 300 ℃, insulation; Again silica tube B19 is heated to 450 ℃, insulation; At last silica tube A16 is heated to 600 ℃, material 17 distillations in the silica tube A16, insulation; At this moment, the material in the silica tube A16 forms arsenic steam and trace impurity steam, and enters silica tube B19, and boiling point is higher than the impurity of temperature in this pipe and stays in the pipe; Selenium in silica tube B19 in the impurity steam and H-H reaction form Selenium hydride, sulphur and H-H reaction form hydrogen sulfide, arsenic steam, Selenium hydride, hydrogen sulfide continue to enter silica tube C20, to get purity be 99.9999% arsenic in condensation on the inwall of silica tube C20, Selenium hydride, hydrogen sulfide and the impurity steam that contains Determination of Trace Sulfur are discharged from the air outlet, enter sodium hydroxide solution in the filter flask by air outlet 22, after the neutralization, discharge fully.Treat that material 17 distillations finish, switch to feed argon gas, close each well heater, lower the temperature in proper order by material section, intermediate reaction section, product section.Because therefore the decomposition temperature of hydrogen sulfide, has Determination of Trace Sulfur and remains in the product that makes near reactor temperature.
Arsenic with 99.9999% takes out and inserts the nitrogen atmosphere sublimer again, repeats step, and different is that silica tube C20 is heated to 350 ℃, insulation; Silica tube B19 is heated to 800 ℃, insulation; Sulphur and hydrogen residual in the material form hydrogen sulfide, discharge reactor; What make is that purity is 99.99999% arsenic 21.
At first with primary industry 1
#Arsenic 13 (purity is 99%) is put into a crucible 14, again crucible 14 is inserted in the vacuum tank 1, then, connect the obstructing instrument 11 that 2 layers of stainless steel sheet of a usefulness are made at crucible 14 oral areas, the aperture that is covered with Φ 4mm on the obstructing instrument 11, in the interlayer of obstructing instrument 11, can fill the sorbing material 12 of some high temperature resistant pollution-free band micropores, as activated carbon etc., the top of obstructing instrument 11 connects a taper condensation tube 10, taper condensation tube 10 is made of titanium, and there is the roughness requirement on the surface, and the osculum place, upper end of taper condensation tube 10 is provided with the low collecting board 7 that boils that a size is coincide, the low collecting board 7 that boils is made for metallic substance, and the hole of 3 Φ 20mm is laid on the surface.Vacuum tank 1 oral area outer ring is provided with refrigeration cycle water jacket 4; also be provided with watercooling jacket covering of vacuum tank 1; water coolant enters water jacket from the water-in 5 of tank body water jacket; discharge from the water outlet 6 of cover water jacket; a cold zone is formed at the top at vacuum tank 1; collect the condensation low-boiling-point substance, can protect the sealing-ring of vacuum tank 1 simultaneously.
Start vacuum pump 8, the pressure of adjusting in the vacuum tank 1 is 2*10
1Pa; Start water coolant, making in the water jacket 4 has recirculated water; Start well heater B3, the temperature that makes condenser 10 positions is 250 ℃, insulation; Start well heater A2, making the temperature at crucible 14 and obstructing instrument 11 positions is 280 ℃, insulation.Amount according to material 13 in the crucible 14 is chosen different heating, soaking time, accept 3 hours speed of thermal radiation with per 5 kilograms of materials and determine heating and soaking time, reach set heating, soaking time after, condensation has arsenic 9 on the inwall of conically shaped 10, makes purity and be 99.99% arsenic 9.
Long silica tube 18 horizontal positioned that one two ends had quartzy frosted cap, the quartzy frosted cap at two ends is respectively equipped with inlet mouth 15 and air outlet 22, place silica tube A16, silica tube B19, the silica tube C20 of three diameter unanimities in the long silica tube 18, the end face of the mouth of pipe requires and axis normal, guarantee that the connection between the mouth of pipe is closely reliable, do not have and leak; With the purity that makes on the taper condenser 10 is that 99.99% arsenic takes out, and is placed in the silica tube A16; Air outlet 22 connects jar, sodium hydroxide solution is housed in the jar, air outlet 22 expellant gas stretch into sodium hydroxide solution by a vapor pipe, the empty vapor pipe 23 of inserting in jar top, this vapor pipe 23 connects the inlet pipe 25 of drip washing post 28, spray colunm 28 is by being tubbiness, tank 24 is established in the bottom, water pump 30 is established in the bottom of tank 24, and water pump 30 also connects the additional mouth of a river, establishes shower 27 on spray colunm 28 tops, establish plurality of nozzles 26 on the shower 27, set out gas port 29 on the top of spray colunm 28, the β arsenic that remains in the tail gas is precipitated in drip washing post 28, and clean hydrogen is discharged in air outlet 29.
Feed argon gas by inlet mouth 15 in the nitrogen atmosphere sublimer, the air in the purger prevents from feeding hydrogen, and blasts during heating; After waiting to drain air, in the nitrogen atmosphere sublimer, feed hydrogen by inlet mouth 15, the hydrogen pressure that feeds is 0.4Mpa, flow is 0.5L/S, simultaneously silica tube A16, silica tube B19, silica tube C20 are heated respectively, the order of pressing product condensation segment, interlude, raw material section successively heats up, and silica tube C20 is heated to 350 ℃, insulation; Again silica tube B19 is heated to 500 ℃, insulation; At last silica tube A16 is heated to 650 ℃, material 17 distillations in the silica tube A16, insulation; At this moment, the material in the silica tube A16 forms arsenic steam and trace impurity steam, and enters silica tube B19, and boiling point is higher than the impurity of temperature in this pipe and stays in the pipe; Selenium in silica tube B19 in the impurity steam and H-H reaction form Selenium hydride, sulphur and H-H reaction form hydrogen sulfide, arsenic steam, Selenium hydride, hydrogen sulfide continue to enter silica tube C20, to get purity be 99.9999% arsenic in condensation on the inwall of silica tube C20, Selenium hydride, hydrogen sulfide and the impurity steam that contains Determination of Trace Sulfur are discharged from the air outlet, enter sodium hydroxide solution in the filter flask by air outlet 22, after the neutralization, discharge fully.Treat that material 17 distillations finish, switch to feed argon gas, close each well heater, lower the temperature in proper order by material section, intermediate reaction section, product section.Because therefore the decomposition temperature of hydrogen sulfide, has Determination of Trace Sulfur and remains in the product that makes near reactor temperature.
Arsenic with 99.9999% takes out and inserts the nitrogen atmosphere sublimer again, repeats step, and different is that silica tube C20 is heated to 400 ℃, insulation; Silica tube B19 is heated to 900 ℃, insulation; Sulphur and hydrogen residual in the material form hydrogen sulfide, discharge reactor; What make is that purity is 99.99999% arsenic 21.
Principle of the present invention is to utilize the characteristic of arsenic gas, solid binary states, in conjunction with different pressures down with the difference of impurity element volatilization ability, realize separate impurities by the mass transfer between solid phase and gas phase.When vapour pressure 10
-1～2*10
1During Pa, control equilibrium temperature and rate of sublimation, in condenser, can obtain the arsenic of 4N.This technological process can be isolated elements such as impurity A g, Mg in the raw material arsenic, Zn, Ca, Cu, Fe, Ni, Pb, Cr, Sb, C effectively.
The most unmanageable in vacuum-sublimation processing is selenium and sulphur, therefore the present invention has also adopted the nitrogen atmosphere subliming method, in the nitrogen atmosphere sublimer, trace selenium in the 4N arsenic and sulphur and hydrogen reaction, form hydrogen sulfide and Selenium hydride, the temperature of reaction that forms hydrogen sulfide and Selenium hydride is respectively 300 ~ 400 ℃, 250 ~ 500 ℃, but the temperature of the decomposition temperature of hydrogen sulfide product zone during near first set reaction, have Determination of Trace Sulfur and continue to remain in the arsenic, can isolate the selenium in the material in this step.When reacting for the second time, reduce the temperature of product zone, avoided the decomposition of hydrogen sulfide, made hydrogen sulfide discharge reactor, made the arsenic that purity is 7N.For effectively protecting environment, the invention allows for processing scheme for tail gas, by the two-stage exhaust gas processing device is set, make trace hydrogen sulfide, selenium sulfide steam and β arsenic particles in the tail gas obtain fully handling.Throw out after the processing, a small amount of vacuum-sublimation tailing are canned, provide the ground secondary recovery to handle for raw material.
Claims (2)
1, a kind of production method of high purity arsenic is characterized in that, following steps are arranged:
1), raw material arsenic is inserted in the crucible, the tube end of a conically shaped, be connected with crucible, is provided with the baffler that has some apertures at crucible and conically shaped connecting portion, establishes a low collecting board that boils that has a macropore in the upper end of conically shaped;
2), the crucible with coupling together, conically shaped, baffler, the low collecting board that boils insert vacuum tank, the corresponding conically shaped of vacuum tank upper end is provided with water jacket, adjusting a jar internal pressure is 10
-1～2*10
1Pa feeds the recirculated water of normal temperature in the water jacket of vacuum tank; Heated in the conically shaped position, to 250～350 ℃, insulation; Then, heated in the crucible position, to 280～400 ℃, insulation; Continue about 7.5～10 hours, condensing on the inwall of crucible upper taper tube has arsenic, makes purity and be 99.99% arsenic;
3), above-mentioned arsenic is taken out, insert a silica tube A, A inserts a sleeve pipe with this silica tube, dock silica tube B with silica tube A in the sleeve pipe, docks silica tube C with silica tube B again, and air inlet/outlet is established at the sleeve pipe two ends, imports argon gas, the air in the purger by inlet mouth; By inlet mouth input hydrogen, silica tube A is heated to 550～650 ℃ again, silica tube B is heated to 400～500 ℃, with silica tube C heating and remain on 250～350 ℃; At this moment, the material in the silica tube A forms arsenic steam and trace impurity steam, and boiling point is higher than the impurity of A pipe temperature to be stayed in the A pipe, and arsenic steam and trace impurity steam enter silica tube B; Selenium in silica tube B in the impurity steam and H-H reaction form Selenium hydride, and sulphur and H-H reaction form hydrogen sulfide; Arsenic steam, Selenium hydride, hydrogen sulfide continue to enter silica tube C, and to get purity be 99.9999% arsenic in condensation on the inwall of silica tube C; Selenium hydride, hydrogen sulfide and the impurity steam that contains Determination of Trace Sulfur are discharged from the air outlet, are entered in the sodium hydroxide solution in the air-washer by the escape pipe on the air outlet, carry out neutralization reaction; Air-washer connects elution device, and the β arsenic that remains in the tail gas is precipitated in elution device, and clean hydrogen is discharged in the air outlet of elution device;
4) process, above-mentioned arsenic is taken out, set by step 3) reprocess one time, and except that silica tube A Heating temperature was constant, silica tube B was heated to 700～900 ℃, and silica tube C heats also and remains on 300～400 ℃.
2, a kind of production unit of high purity arsenic, it is characterized in that, according to the high purity arsenic procedure of processing, form by vacuum-sublimation device and nitrogen atmosphere sublimer two portions, described vacuum-sublimation device comprises well heater A, well heater B, vacuum tank, water jacket, crucible, baffler, the taper titanium condenser, the low collecting board that boils, vacuum pump, the tube end of taper titanium condenser, be connected with crucible, establish a baffler that has some apertures at crucible and taper titanium condenser connecting portion, establish a low collecting board that boils that has a macropore in the upper end of taper titanium condenser, the taper titanium condenser, crucible, baffler, the low collecting board that boils is arranged on vacuum tank inside, establish well heater A at the outside corresponding crucible of vacuum tank position, well heater B is established at corresponding taper titanium condenser position, and water jacket is located at vacuum tank top; Described nitrogen atmosphere sublimer comprises the hydrogen input unit, the argon gas input unit, sleeve pipe, silica tube A, silica tube B, silica tube C, well heater, air-washer, spray equipment, silica tube A, silica tube B, silica tube C is serially connected in the sleeve pipe, the outer corresponding silica tube A of sleeve pipe, silica tube B, silica tube C is respectively equipped with well heater, sleeve pipe is established air inlet/outlet, the inlet mouth of hydrogen input unit and argon gas input unit sleeved, air-washer comprises jar, intubate, plug, the telescopic air outlet connects the air inlet intubate of air-washer, the intubate of giving vent to anger of air-washer connects elution device, be provided with shower in the elution device, settling bath, the air outlet of elution device connects atmosphere.
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