CN101054168A - Method for producing high-purity arsenic - Google Patents
Method for producing high-purity arsenic Download PDFInfo
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- CN101054168A CN101054168A CN 200610039541 CN200610039541A CN101054168A CN 101054168 A CN101054168 A CN 101054168A CN 200610039541 CN200610039541 CN 200610039541 CN 200610039541 A CN200610039541 A CN 200610039541A CN 101054168 A CN101054168 A CN 101054168A
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 159
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 161
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 229910000967 As alloy Inorganic materials 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 49
- 239000000377 silicon dioxide Substances 0.000 claims description 44
- 239000012535 impurity Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000010433 feldspar Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 27
- 238000005660 chlorination reaction Methods 0.000 abstract description 14
- 238000000859 sublimation Methods 0.000 abstract description 9
- 230000008022 sublimation Effects 0.000 abstract description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 6
- 239000010453 quartz Substances 0.000 abstract description 6
- 229910052745 lead Inorganic materials 0.000 abstract description 4
- 229910000978 Pb alloy Inorganic materials 0.000 abstract 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 16
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 12
- 238000009835 boiling Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HUEBVZADHUOMHL-UHFFFAOYSA-N [As].[Pb] Chemical compound [As].[Pb] HUEBVZADHUOMHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 210000003454 tympanic membrane Anatomy 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a method for producing high-purity As and relates to a method for producing a semi-conductive super-high pure alpha-As. The invention adopts the following steps. First, Pb/As alloy is formed with the ratio of 1:1.5-1:4 between As and Pb. Then, the Pb/As alloy is separated by heating in the vacuum environment to obtain As with the purity of 99.999% and Pb/As alloy. At last, the above As is sublimated to produce As with the purity of 99.99999% in hydrogen phenomenon. The present invention integrates the virtues of Pb fused base method and chlorination rectification and reduction method while overcoming the shortcomings thereof. The invention first put forward the theory that Pb/As alloy is formed first and then As is sublimated and separated from the alloy and the separated As with the purity of 7N is then sublimated in hydrogen phenomenon. The matched apparatuses with the production method in the present invention including specified crucible for synthesis, vacuum pot, tapered canister and quartz sublimation pipe with hydrogen phenomenon are of low cost and small investment, which guarantee small investment, high yield, low cost and high quality of the present invention in the industrialization production.
Description
Technical field
The present invention relates to a kind of purification production method of non-metallic material, relate in particular to the production method 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 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.
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, product purity height, the production method of the high purity arsenic that tooling cost is low.
Technical scheme of the present invention is: adopt following steps:
1), the part by weight according to 1 to 1.5～4 heats raw material arsenic and raw material lead in crucible, Heating temperature is 330～550 ℃, to fully synthetic, makes lead arsenic alloy after the cooling;
2), connect a conically shaped at the above-mentioned crucible oral area that alloy is housed, it is inserted vacuum tank, adjust jar internal pressure to a 5～500Pa, to the vacuum tank heating, the corresponding crucible of vacuum tank position Heating temperature is 320～500 ℃, and the corresponding conically shaped of vacuum tank position Heating temperature is 250～350 ℃, continue about 7.5 ~ 10 hours, arsenic condenses on the sidewall on a top, makes purity and be 99.999% arsenic, makes lead arsenic alloy in crucible;
3), above-mentioned arsenic is taken out, insert a container, this container is established inlet, outlet, toward inlet mouth input argon gas, get rid of the air in the container, container is heated to 610～650 ℃, form arsenic steam and trace impurity steam, be that 0.04～0.05Mpa, flow are the hydrogen of 0.5L/S by the inlet mouth input pressure again, form mixed gas, the air outlet of container connects a feldspar English reacting pipe A;
4), above-mentioned mixed gas enters feldspar English reaction tubes A, it is 750～1100 ℃ that pipeline A is heated to temperature, gas enters a silica tube B who is connected with crystal reaction tube A by crystal reaction tube A;
5), silica tube B is heated to temperature is 350～400 ℃, is 99.99999% α type arsenic in the silica tube B inwall purity of condensing, and connects silica tube C behind silica tube B;
6), silica tube C do not heat, the gas in the silica tube B continues by silica tube C, arsenic steam remaining in the above-mentioned gas condenses at silica tube C inwall, forms β, γ type arsenic;
7), connect a vapor pipe, discharge tail gas behind the silica tube C;
8), at last, tail gas feeds molten alkali, handles discharging.
The sealing when heating of described crucible, and rotate.
The material of described container is quartzy.
Quartzy dividing plate is crisscross arranged in the described crystal reaction tube A.
The present invention combines the advantage of plumbous molten bath method and chlorination rectifying reduction method, and has overcome their shortcoming.Propose to form earlier arsenical lead, and sum up in test arsenic and plumbous best proportioning, the arsenic lead ratio is 1 to 1.5～4, from arsenical lead, the arsenic sublimation separation is come out again, isolated arsenic distils in nitrogen atmosphere and obtains purity is 7N arsenic, and with the supporting synthetic crucible of special use, vacuum tank, conically shaped, the quartzy sublimation pipe of nitrogen atmosphere of production method of the present invention, cost is low, less investment, its performance have guaranteed the present invention, and investment is little in industrialization is produced, production capacity is high, cost is low, quality is good.The present invention has also solved the big problem of high purity arsenic production scale of investment, uses investment seldom just can realize industrialization.
Arsenic and lead can form alloy in the stove of 360 ° of rotations uniformly, guaranteed that impurity fully forms alloy with lead in the arsenic, thereby changed the rerum natura of impurity in the arsenic, improved the thermograde of principal element arsenic and impurity, make the arsenic impurities concentration removal of impurity lead of separating reach the same level of chlorination rectification method outward, remove impurity lead in the arsenic through nitrogen atmosphere distillation, make in the arsenic impurity such as Determination of Trace Sulfur, tellurium, oxygen of remnants when synthetic remove totallyer simultaneously, obtain the ultra-pure arsenic of 7N, the present invention will produce following positively effect.
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 oxygen atmosphere distillation, synthetic and separating device all is reusable special metal material manufacturing, do not re-use the silica glass of rapid wear piece, 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, and the present invention is owing to reduce quartzy loss in a large number, and the tailing after separating simultaneously can be done product and sell, and production cost is 250,000 yuan/ton, reduces by 55% than chlorination rectifying 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%.
Chlorination rectifying and quality examination 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 |
| The present invention | 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 |
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/kilogram | 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 | |
| Production method of the present invention | 3,500,000 yuan | 40 | 600 cubic metres | 50 yuan/kilogram | 16 tons | 250,000 yuan | There is the lead arsenic alloy that contains arsenic 15% to make product for 46 tons and sells no chemical pollution |
Description of drawings
Fig. 1 is vapour pressure, the temperature contrast figure of principal element arsenic and other elements among the present invention
Fig. 2 is principal element arsenic and lead selenide among the present invention, the vapour pressure of lead sulfide, temperature contrast figure
Embodiment
Embodiment 1
At first, raw material arsenic and raw material lead are prepared according to 1 to 1.5 part by weight, arsenic wherein is the particulate state of 1～2cm, both are inserted crucible, and sealed crucible heats crucible, Heating temperature is 330 ℃, in heat-processed, the material in the crucible is stirred or crucible is rotated,, make lead arsenic alloy after the cooling to fully synthetic; Crucible is inserted in the rotating electric furnace, and two outer side walls at electric furnace middle part are provided with rotating shaft, the axis horizontal of this rotating shaft, and perpendicular to the axis of electric furnace.The sublimation temperature of arsenic is 613 ℃, and plumbous melting temperature is 327.4 ℃.If plumbous arsenic total mass is 10Kg, when Heating temperature was 330 ℃, generated time was about 8 ~ 10 hours.Make lead arsenic alloy.
Then, connect a cone-shaped metal tube at the above-mentioned crucible oral area that alloy is housed, this shape is up big and down small, fuses with crucible, insert a vacuum tank, vacuumize, and to the vacuum tank heating, when pressure is 5Pa, corresponding crucible position Heating temperature is 320 ℃, corresponding conically shaped position Heating temperature is 250 ℃, by thermal radiation, material is heated.According to quality of material, choose different heat-up times, when material was 10Kg, about 7.5 ~ 10 hours of heat-up time, arsenic condensed on the sidewall on a top, made purity and be 99.999% arsenic.In crucible, make lead arsenic alloy.At this moment, the impurity in the 5N arsenic is mainly based on Pb, and the arsenic steam forms bubble separation and comes out in fused lead, minimum plumbous particulate is arranged with the arsenic condensation, and the Pb concentration in the arsenic is 0.5PPm.
Lead arsenic alloy separates purification arsenic, the vapour pressure that depends on alloy constituent element under the certain temperature, Fig. 1 is the vapour pressure of principal element arsenic and other elements, temperature contrast figure, as can be seen from Figure 200～400 ℃ of temperature, during pressure 10～300Pa, immediate with principal element arsenic is S and Se, other impurity are as Zn, Mg, Sb, Te, Ca, Pb etc. have bigger gradient with the vapour pressure and the temperature of principal element arsenic, the synthetic purpose is exactly to make the S very approaching with the vapour pressure of arsenic, Se and the plumbous compound Pb S that forms, the vapour pressure of the vapour pressure of PbSe and temperature and principal element forms bigger gradient, abandons the most difficult impurity S that removes thereby reach to remove, the purpose of Se.
Fig. 2 is the temperature relation contrast figure of the vapour pressure of principal element arsenic and PbS, PbSe, the fusing point of PbSe is 1065 ℃, there is not related data that the boiling point and relevant vapour pressure of PbSe are provided, in experiment, temperature is made as 600 ℃ during vapour pressure 10Pa, do not see in the product arsenic that Se exceeds standard, the volatilization temperature that PbSe when pressure is 10Pa is described is greater than 600 ℃.
Other are examined impurity A g, Al, Ca, Cu, Fe, Mg, Ni, Zn, Cr, Sb, C, form very big gradient once the temperature and the vapour pressure itself that are its element with principal element arsenic; The 2nd, with the synthetic high boiling intermetallic compound of lead, all stay in the fused lead, thereby reach the purpose of purification principal element arsenic.
Above-mentioned arsenic is taken out, insert a quartz container, volume is no more than 2/3 of container volume; This container is established air inlet/outlet, toward inlet mouth input argon gas, gets rid of the air in the container earlier,, blasts when feeding hydrogen and heating to prevent residual air.Container is heated to 610 ℃, and input pressure is that 0.04MPa, flow are the hydrogen of 0.5L/S in the container, and the air outlet of container connects a long reacting pipe; When temperature was 610 ℃, purity was that the arsenic of 5N can form steam, enters next reacting pipe jointly with hydrogen.Simultaneously, Determination of Trace Sulfur residual in 5N arsenic forms steam simultaneously, and the boiling point of sulphur is that 445 ℃ and arsenic steam, hydrogen enter next pipeline together.Lead, selenium and other metallic elements residual in the 5N arsenic can not gasify, and remain in this container.
Behind this container, connect a crystal reaction tube A, in this pipeline A, be staggeredly equipped with dividing plate, make and form S shape flowing lumen in the pipeline A; In the present embodiment, pipeline A is the coaxial three layers of silica tube that are provided with, and both ends of the surface are established end cap, and an end of innermost layer silica tube is established inlet mouth, open semicircle shape hole on the other end mouth of pipe place tube wall; The middle layer the other end is opened same hole; The outermost the other end is communicated with next pipeline.Temperature is heated to 750 ℃ in the crystal reaction tube A, and hydrogen energy and reaction of Salmon-Saxl under this temperature generate hydrogen sulfide, and this temperature is higher than the sublimation temperature of arsenic, and arsenic can not condense in this reaction tubes.
Above-mentioned gas enters a silica tube B from crystal reaction tube A outlet; Temperature is heated to be 350 ℃ in the silica tube B, and under this temperature, the arsenic in the gas condenses in the silica tube inwall, makes purity and be 99.99999% α type arsenic.At this moment, discharge in the gas of this pipeline B and be mainly hydrogen, be entrained with the hydrogen sulfide and the arsenic steam of trace.
Behind silica tube B, connect another silica tube C; The temperature that places of pipeline C does not heat less than 40 ℃ air, and residual arsenic in the above-mentioned gas is condensed into β, γ type arsenic on this grade duct wall.β, γ type arsenic can be used as the raw material of the inventive method.
Behind above-mentioned another silica tube C, connect a vapor pipe, discharge tail gas; Main component is a hydrogen in the tail gas, also is entrained with β, γ arsenic particles, the hydrogen sulfide of trace.
At last, above-mentioned tail gas is fed molten alkali, in the alkali lye energy and the hydrogen sulfide in the tail gas, β, γ arsenic particles form sodium arseniate by alkali lye the time, stay in the alkali lye.By the alkali lye expellant gas is hydrogen, feeds atmosphere.
Embodiment 2
At first, raw material arsenic and raw material lead are prepared according to 1 to 2.75 part by weight, arsenic wherein is the particulate state of 1～2CM, both are inserted crucible, and sealed crucible heats crucible, Heating temperature is 440 ℃, in heat-processed, the material in the crucible is stirred or crucible is rotated,, make lead arsenic alloy after the cooling to fully synthetic; Crucible is inserted in the rotating electric furnace, and two outer side walls at electric furnace middle part are provided with rotating shaft, the axis horizontal of this rotating shaft, and perpendicular to the axis of electric furnace.The sublimation temperature of arsenic is 613 ℃, and plumbous melting temperature is 321 ℃.If plumbous arsenic total mass is 10Kg, when Heating temperature was 440 ℃, generated time was about 5 ~ 6 hours.Make lead arsenic alloy.
Then, connect a cone-shaped metal tube at the above-mentioned crucible oral area that alloy is housed, this shape is up big and down small, fuses with crucible, insert a vacuum tank, vacuumize, and to the vacuum tank heating, when pressure is 260Pa, corresponding crucible position Heating temperature is 410 ℃, corresponding conically shaped position Heating temperature is 275 ℃, by thermal radiation, material is heated.According to quality of material, choose different heat-up times, when material was 10Kg, about 7.5 ~ 10 hours of heat-up time, arsenic condensed on the sidewall on a top, made purity and be 99.999% arsenic.In crucible, make lead arsenic alloy.At this moment, the impurity in the 5N arsenic is mainly based on Pb, and the arsenic steam forms bubble separation and comes out in fused lead, minimum plumbous particulate is arranged with the arsenic condensation, and the Pb concentration in the arsenic is 0.5PPm.
Lead arsenic alloy separates purification arsenic, the vapour pressure that depends on alloy constituent element under the certain temperature, Fig. 1 is the vapour pressure of principal element arsenic and other elements, temperature contrast figure, as can be seen from Figure 200～400 ℃ of temperature, during pressure 10～300Pa, immediate with principal element arsenic is S and Se, other impurity are as Zn, Mg, Sb, Te, Ca, Pb etc. have bigger gradient with the vapour pressure and the temperature of principal element arsenic, the synthetic purpose is exactly to make the S very approaching with the vapour pressure of arsenic, Se and the plumbous compound Pb S that forms, the vapour pressure of the vapour pressure of PbSe and temperature and principal element forms bigger gradient, abandons the most difficult impurity S that removes thereby reach to remove, the purpose of Se.
Fig. 2 is the temperature relation contrast figure of the vapour pressure of principal element arsenic and PbS, PbSe, the fusing point of PbSe is 1065 ℃, there is not related data that the boiling point and relevant vapour pressure of PbSe are provided, in experiment, temperature is made as 600 ℃ during vapour pressure 10Pa, do not see in the product arsenic that Se exceeds standard, the volatilization temperature that PbSe when pressure is 10Pa is described is greater than 600 ℃.
Other are examined impurity A g, Al, Ca, Cu, Fe, Mg, Ni, Zn, Cr, Sb, C, form very big gradient once the temperature and the vapour pressure itself that are its element with principal element arsenic; The 2nd, with the synthetic high boiling intermetallic compound of lead, all stay in the fused lead, thereby reach the purpose of purification principal element arsenic.
Above-mentioned arsenic is taken out, insert a quartz container, volume is no more than 2/3 of container volume; This container is established air inlet/outlet, toward inlet mouth input argon gas, gets rid of the air in the container earlier,, blasts when feeding hydrogen and heating to prevent residual air.Container is heated to 630 ℃, and input pressure is that 0.045MPa, flow are the hydrogen of 0.5L/S in the container, and the air outlet of container connects a long reacting pipe; When temperature was 630 ℃, purity was that the arsenic of 5N can form steam, enters next reacting pipe jointly with hydrogen.Simultaneously, Determination of Trace Sulfur residual in 5N arsenic forms steam simultaneously, and the boiling point of sulphur is that 445 ℃ and arsenic steam, hydrogen enter next pipeline together.Lead, selenium and other metallic elements residual in the 5N arsenic can not gasify, and remain in this container.
Behind this container, connect a crystal reaction tube A, in this pipeline A, be staggeredly equipped with dividing plate, make and form S shape flowing lumen in the pipeline A; In the present embodiment, pipeline A is the coaxial three layers of silica tube that are provided with, and both ends of the surface are established end cap, and an end of innermost layer silica tube is established inlet mouth, open semicircle shape hole on the other end mouth of pipe place tube wall; The middle layer the other end is opened same hole; The outermost the other end is communicated with next pipeline.Temperature is heated to 925 ℃ in the crystal reaction tube A, and hydrogen energy and reaction of Salmon-Saxl under this temperature generate hydrogen sulfide, and this temperature is higher than the sublimation temperature of arsenic, and arsenic can not condense in this reaction tubes.
Above-mentioned gas enters a silica tube B from crystal reaction tube A outlet; Temperature is heated to be 375 ℃ in the silica tube B, and under this temperature, the arsenic in the gas condenses in the silica tube inwall, makes purity and be 99.99999% α type arsenic.At this moment, discharge in the gas of this pipeline B and be mainly hydrogen, be entrained with the hydrogen sulfide and the arsenic steam of trace.
Behind silica tube B, connect another silica tube C; The temperature that places of pipeline C does not heat less than 40 ℃ air, and residual arsenic in the above-mentioned gas is condensed into β, γ type arsenic on this grade duct wall.β, γ type arsenic can be used as the raw material of the inventive method.
Behind above-mentioned another silica tube C, connect a vapor pipe, discharge tail gas; Main component is a hydrogen in the tail gas, also is entrained with β, γ arsenic particles, the hydrogen sulfide of trace.
At last, above-mentioned tail gas is fed molten alkali, in the alkali lye energy and the hydrogen sulfide in the tail gas, β, γ arsenic particles form sodium arseniate by alkali lye the time, stay in the alkali lye.By the alkali lye expellant gas is hydrogen, feeds atmosphere.
Embodiment 3
At first, raw material arsenic and raw material lead are prepared according to 1 to 4 part by weight, arsenic wherein is the particulate state of 1～2cm, both are inserted crucible, and sealed crucible heats crucible, Heating temperature is 550 ℃, in heat-processed, the material in the crucible is stirred or crucible is rotated,, make lead arsenic alloy after the cooling to fully synthetic; Crucible is inserted in the rotating electric furnace, and two outer side walls at electric furnace middle part are provided with rotating shaft, the axis horizontal of this rotating shaft, and perpendicular to the axis of electric furnace.The sublimation temperature of arsenic is 613 ℃, and plumbous melting temperature is 321 ℃.If plumbous arsenic total mass is 10Kg, when Heating temperature was 550 ℃, generated time was about 3 ~ 4 hours.Make lead arsenic alloy.
Then, connect a cone-shaped metal tube at the above-mentioned crucible oral area that alloy is housed, this shape is up big and down small, fuses with crucible, insert a vacuum tank, vacuumize, and to the vacuum tank heating, when pressure is 500Pa, corresponding crucible position Heating temperature is 500 ℃, corresponding conically shaped position Heating temperature is 350 ℃, by thermal radiation, material is heated.According to quality of material, choose different heat-up times, when material was 10Kg, about 7.5 ~ 10 hours of heat-up time, arsenic condensed on the sidewall on a top, made purity and be 99.999% arsenic.In crucible, make lead arsenic alloy.At this moment, the impurity in the 5N arsenic is mainly based on Pb, and the arsenic steam forms bubble separation and comes out in fused lead, minimum plumbous particulate is arranged with the arsenic condensation, and the Pb concentration in the arsenic is 0.5PPm.
Lead arsenic alloy separates purification arsenic, the vapour pressure that depends on alloy constituent element under the certain temperature, Fig. 1 is the vapour pressure of principal element arsenic and other elements, temperature contrast figure, as can be seen from Figure 200～400 ℃ of temperature, during pressure 10～300Pa, immediate with principal element arsenic is S and Se, other impurity are as Zn, Mg, Sb, Te, Ca, Pb etc. have bigger gradient with the vapour pressure and the temperature of principal element arsenic, the synthetic purpose is exactly to make the S very approaching with the vapour pressure of arsenic, Se and the plumbous compound Pb S that forms, the vapour pressure of the vapour pressure of PbSe and temperature and principal element forms bigger gradient, abandons the most difficult impurity S that removes thereby reach to remove, the purpose of Se.
Fig. 2 is the temperature relation contrast figure of the vapour pressure of principal element arsenic and PbS, PbSe, the fusing point of PbSe is 1065 ℃, there is not related data that the boiling point and relevant vapour pressure of PbSe are provided, in experiment, temperature is made as 600 ℃ during vapour pressure 10Pa, do not see in the product arsenic that Se exceeds standard, the volatilization temperature that PbSe when pressure is 10Pa is described is greater than 600 ℃.
Other are examined impurity A g, Al, Ca, Cu, Fe, Mg, Ni, Zn, Cr, Sb, C, form very big gradient once the temperature and the vapour pressure itself that are its element with principal element arsenic; The 2nd, with the synthetic high boiling intermetallic compound of lead, all stay in the fused lead, thereby reach the purpose of purification principal element arsenic.
Above-mentioned arsenic is taken out, insert a quartz container, volume is no more than 2/3 of container volume; This container is established air inlet/outlet, toward inlet mouth input argon gas, gets rid of the air in the container earlier,, blasts when feeding hydrogen and heating to prevent residual air.Container is heated to 650 ℃, and input pressure is that 0.05Mpa, flow are the hydrogen of 0.5L/S in the container, and the air outlet of container connects a long reacting pipe; When temperature was 650 ℃, purity was that the arsenic of 5N can form steam, enters next reacting pipe jointly with hydrogen.Simultaneously, Determination of Trace Sulfur residual in 5N arsenic forms steam simultaneously, and the boiling point of sulphur is that 445 ℃ and arsenic steam, hydrogen enter next pipeline together.Lead, selenium and other metallic elements residual in the 5N arsenic can not gasify, and remain in this container.
Behind this container, connect a crystal reaction tube A, in this pipeline A, be staggeredly equipped with dividing plate, make and form S shape flowing lumen in the pipeline A; In the present embodiment, pipeline A is the coaxial three layers of silica tube that are provided with, and both ends of the surface are established end cap, and an end of innermost layer silica tube is established inlet mouth, open semicircle shape hole on the other end mouth of pipe place tube wall; The middle layer the other end is opened same hole; The outermost the other end is communicated with next pipeline.Temperature is heated to 1100 ℃ in the crystal reaction tube A, and hydrogen energy and reaction of Salmon-Saxl under this temperature generate hydrogen sulfide, and this temperature is higher than the sublimation temperature of arsenic, and arsenic can not condense in this reaction tubes.
Above-mentioned gas enters a silica tube B from crystal reaction tube A outlet; Temperature is heated to be 400 ℃ in the silica tube B, and under this temperature, the arsenic in the gas condenses in the silica tube inwall, makes purity and be 99.99999% α type arsenic.At this moment, discharge in the gas of this pipeline B and be mainly hydrogen, be entrained with the hydrogen sulfide and the arsenic steam of trace.
Behind silica tube B, connect another silica tube C; The temperature that places of pipeline C does not heat less than 40 ℃ air, and residual arsenic in the above-mentioned gas is condensed into β, γ type arsenic on this grade duct wall.β, γ type arsenic can be used as the raw material of the inventive method.
Behind above-mentioned another silica tube C, connect a vapor pipe, discharge tail gas; Main component is a hydrogen in the tail gas, also is entrained with β, γ arsenic particles, the hydrogen sulfide of trace.
At last, above-mentioned tail gas is fed molten alkali, in the alkali lye energy and the hydrogen sulfide in the tail gas, β, γ arsenic particles form sodium arseniate by alkali lye the time, stay in the alkali lye.By the alkali lye expellant gas is hydrogen, feeds atmosphere.
Claims (4)
1, a kind of production method of high purity arsenic is characterized in that, adopts following steps:
1), the part by weight according to 1 to 1.5～4 heats raw material arsenic and raw material lead in crucible, Heating temperature is 330～550 ℃, to fully synthetic, makes lead arsenic alloy after the cooling;
2), connect a conically shaped at the above-mentioned crucible oral area that alloy is housed, it is inserted vacuum tank, adjust jar internal pressure to a 5～500Pa, to the vacuum tank heating, the corresponding crucible of vacuum tank position Heating temperature is 320～500 ℃, and the corresponding conically shaped of vacuum tank position Heating temperature is 250～350 ℃, continue about 7.5 ~ 10 hours, arsenic condenses on the sidewall on a top, makes purity and be 99.999% arsenic, makes lead arsenic alloy in crucible;
3), above-mentioned arsenic is taken out, insert a container, this container is established inlet, outlet, toward inlet mouth input argon gas, get rid of the air in the container, container is heated to 610～650 ℃, form arsenic steam and trace impurity steam, be that 0.04～0.05Mpa, flow are the hydrogen of 0.5L/S by the inlet mouth input pressure again, form mixed gas, the air outlet of container connects a feldspar English reacting pipe A;
4), above-mentioned mixed gas enters feldspar English reaction tubes A, it is 750～1100 ℃ that pipeline A is heated to temperature, gas enters a silica tube B who is connected with crystal reaction tube A by crystal reaction tube A;
5), silica tube B is heated to temperature is 350～400 ℃, is 99.99999% α type arsenic in the silica tube B inwall purity of condensing, and connects silica tube C behind silica tube B;
6), silica tube C do not heat, the gas in the silica tube B continues by silica tube C, arsenic steam remaining in the above-mentioned gas condenses at silica tube C inwall, forms β, γ type arsenic;
7), connect a vapor pipe, discharge tail gas behind the silica tube C;
8), at last, tail gas feeds molten alkali, handles discharging.
2, the production method of a kind of high purity arsenic according to claim 1 is characterized in that, the sealing when heating of described crucible, and rotate.
3, the production method of a kind of high purity arsenic according to claim 1 is characterized in that, the material of described container is quartzy.
4, the production method of a kind of high purity arsenic according to claim 1 is characterized in that, quartzy dividing plate is crisscross arranged in the described crystal reaction tube A.
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| CN101798636A (en) * | 2010-04-20 | 2010-08-11 | 南昌大学 | Process for purifying coarse arsenic |
| CN101935767A (en) * | 2010-09-26 | 2011-01-05 | 山西龙港高纯材料有限公司 | Method for preparing high-purity arsenic |
| CN102072833A (en) * | 2010-12-17 | 2011-05-25 | 扬州高能新材料有限公司 | Sample preparation method for measuring impurity element in high-purity arsenic by ICP-MS method |
| CN102321813A (en) * | 2011-09-30 | 2012-01-18 | 昆明理工大学 | Method for preparing raw arsenic by vacuum carbon thermal reduction of arsenic trioxide |
| CN103290237A (en) * | 2013-05-23 | 2013-09-11 | 扬州高能新材料有限公司 | Arsenic lead alloy synthesis and sublimation integral furnace used for producing high-purity arsenic |
| WO2015180210A1 (en) * | 2014-05-28 | 2015-12-03 | 深圳市华星光电技术有限公司 | Evaporation source heating device |
| CN105506311A (en) * | 2015-12-28 | 2016-04-20 | 中南大学 | Method for preparing metal arsenic block |
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| CN110923457A (en) * | 2019-12-27 | 2020-03-27 | 中国科学院电工研究所 | Preparation method of high-purity arsenic crystal |
| CN114107698A (en) * | 2021-12-02 | 2022-03-01 | 扬州中天利新材料股份有限公司 | Production method of high-stability high-purity arsenic |
| WO2022110811A1 (en) * | 2020-11-24 | 2022-06-02 | 中国电子科技集团公司第十三研究所 | Purification apparatus and purification method for non-metal semiconductor material |
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| CN101798636A (en) * | 2010-04-20 | 2010-08-11 | 南昌大学 | Process for purifying coarse arsenic |
| CN101798636B (en) * | 2010-04-20 | 2012-07-04 | 南昌大学 | Process for purifying coarse arsenic |
| CN101935767A (en) * | 2010-09-26 | 2011-01-05 | 山西龙港高纯材料有限公司 | Method for preparing high-purity arsenic |
| CN102072833A (en) * | 2010-12-17 | 2011-05-25 | 扬州高能新材料有限公司 | Sample preparation method for measuring impurity element in high-purity arsenic by ICP-MS method |
| CN102072833B (en) * | 2010-12-17 | 2012-07-25 | 扬州高能新材料有限公司 | Sample preparation method for measuring impurity element in high-purity arsenic by ICP-MS method |
| CN102321813A (en) * | 2011-09-30 | 2012-01-18 | 昆明理工大学 | Method for preparing raw arsenic by vacuum carbon thermal reduction of arsenic trioxide |
| CN103290237A (en) * | 2013-05-23 | 2013-09-11 | 扬州高能新材料有限公司 | Arsenic lead alloy synthesis and sublimation integral furnace used for producing high-purity arsenic |
| WO2015180210A1 (en) * | 2014-05-28 | 2015-12-03 | 深圳市华星光电技术有限公司 | Evaporation source heating device |
| CN105506311A (en) * | 2015-12-28 | 2016-04-20 | 中南大学 | Method for preparing metal arsenic block |
| CN107881351A (en) * | 2017-11-30 | 2018-04-06 | 广东先导先进材料股份有限公司 | The device for deoxidizing and method of high purity arsenic |
| CN110923457A (en) * | 2019-12-27 | 2020-03-27 | 中国科学院电工研究所 | Preparation method of high-purity arsenic crystal |
| WO2022110811A1 (en) * | 2020-11-24 | 2022-06-02 | 中国电子科技集团公司第十三研究所 | Purification apparatus and purification method for non-metal semiconductor material |
| CN114107698A (en) * | 2021-12-02 | 2022-03-01 | 扬州中天利新材料股份有限公司 | Production method of high-stability high-purity arsenic |
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