CN1096058A

CN1096058A - The smelting process of special metallic arsenic

Info

Publication number: CN1096058A
Application number: CN 93115598
Authority: CN
Inventors: 曹玲琦
Original assignee: Chemical Reagent Branch Of Shuikoushan No2 Factory Labour Service Co Hengyang
Current assignee: Chemical Reagent Branch Of Shuikoushan No2 Factory Labour Service Co Hengyang
Priority date: 1993-12-02
Filing date: 1993-12-02
Publication date: 1994-12-07
Anticipated expiration: 2013-12-02
Also published as: CN1030842C

Abstract

A kind of is raw material with the Potassium oxide, smelts the method for low assorted metallic arsenic or high pure metal arsenic.It adopts the vacuum-sublimation method to remove impurities in raw materials earlier, particularly remove Sb and Bi, vacuum tightness is 0.093～0.1013MPa in its subliming furnace, temperature is 300～400 ℃, prepare low assorted white arsenic or high-purity arsenic trioxide, lower assorted metallic arsenic of reduction with carbon or chlorination-hydro-reduction production or high pure metal arsenic.This method is simpler than chlorination-distillation method impurity removal process, and cost is low, the production capacity height, and environmental pollution is little, and can produce has the different special metallic arsenics that require to foreign matter content.

Description

The smelting process of special metallic arsenic

The present invention relates to the white arsenic is the method that raw material is smelted special metallic arsenic.

As everyone knows,, especially smelt special metallic arsenic at metal smelting arsenic, such as: in the process of the high pure metal arsenic of semiconductor industry, the removal of the impurity that metallic impurity, particularly Sb, Bi etc. are close with arsenic character is a problem that difficulty is bigger.At present, domestic is raw material with the white arsenic, and the metallic arsenic that the reduction with carbon method is produced contains As and reaches 99%, contains sb0.4%, and Bi is 0.1%.SUMITOMO CHEMICAL metal mine company (SMM) adopts Wet-process metallurgy method to produce high-purity arsenic trioxide earlier for producing high pure metal arsenic, and product contains As ₂O ₃Reach 99.9%, containing sb still is 0.011%.Therefore, with above-mentioned metallic arsenic or trisenox produce low assorted or high pure metal arsenic before, all also must be with impurity such as the removal of chlorination-distillation (repeatedly) method Sb, Bi.According to the U.S.'s academic annual meeting data report of international arsenic in 1988, SUMITOMO CHEMICAL metal mine company adopts following method: with As with the 7N level metallic arsenic of the high-purity arsenic trioxide production semiconductor industry of above-mentioned wet production ₂O ₃With the HCl dissolving, be converted into AsCl ₃; Remove the muriate of heavy metal, alkali and impurity such as alkaline-earth metal and silicon by successive distillation, fractionation and rectifying, realize AsCl ₃Purification because SbCl ₃With AsCl ₃Vapour pressure very approaching, only could be separated in stage of rectification; AsCl after the purification ₃The hydrogen reducing that purifies with the palladium film becomes metallic arsenic; The metallic arsenic resublime further removes matter matter such as carbon elimination, thereby obtain high pure metal arsenic (" mountain, mouth of a river science and technology " the 2nd～3 phase in 1993 of 7N level, " metallurgical basis of arsenic and application " selects special edition, and 75-81 page or leaf, original text are deposited the Zhongnan Polytechnic Univ Library, money item number 197187) chlorination-distillation method is separated arsenic and impurity such as Sb, Bi, although can obtain good impurity-eliminating effect, there is complex process, the production cost height, problems such as throughput is low, and the environmental improvement difficulty is big.

The objective of the invention is in order to overcome the weak point of above-mentioned chlorination-distillation method removal of impurities, provide that a kind of technology is simple, cost is low, environmental improvement is easy, pollute little, and output height, and make arsenic and the fine separation processes of impurity such as Sb, Bi, thereby provide a kind of production low assorted metallic arsenic, until the new process of high pure metal arsenic.

For achieving the above object, the present invention adopts the vacuum-sublimation method to remove impurity, particularly Sb and Bi in the white arsenic, prepares high-purity arsenic trioxide, and reduction with carbon method is again produced low assorted metallic arsenic, or produces high pure metal arsenic with chlorination-hydrogen reduction method again.

Principle of the present invention is utilize the sublimation temperature of various metal oxides and vapour pressure different, temperature and vacuum tightness by the control subliming furnace, make the white arsenic distillation, other metal chloride then remains in the end slag, and reaches arsenic and the isolating purpose of other metallic impurity.

Vacuum-sublimation method of the present invention, vacuum degree control is in 0.0933～0.1013MPa(MPa), sublimation temperature is 300～400 ℃.

Technological process of the present invention is that the raw material white arsenic is added in the distillation electric furnace of control automatically, give earlier and heating, treat to vacuumize again after water evaporates in the material is done, make in the subliming furnace vacuum tightness reach 0.0933～0.1013MPa(700～760mmHg), temperature is controlled at 300～400 ℃, allows As ₂O ₃Slowly distillation.For improving arsenic and the isolating effect of other metallic impurity, generally adopt controlled repeatedly vacuum-sublimation, and successively the last time is distilled after the As that condensation obtains ₂O ₃, distil again, up to the As that obtains next time ₂O ₃Middle foreign matter content reaches the requirement of producing special metallic arsenic.With the low assorted As that obtains after the vacuum-sublimation ₂O ₃Send in the line frequency furnace that adopts carbon reduction method metal smelting arsenic, can produce the low special metallic arsenics of impurity such as containing Sb, Bi, such as the metallic arsenic that contains sb＜50PPM(0.005%), Bi＜40PPM(0.004%).High-purity As with the back acquisition that repeatedly distils ₂O ₃With getting AsCl behind hydrogen chloride gas chlorination, the separatory ₃, use hydrogen reducing AsCl then ₃, promptly adopt chlorination-hydrogen reduction method can produce 19 kinds of total impurities＜1 * 10 such as containing Sb, Bi, S, Pb, Cu, Zn, K, Na, Ca, Fe ^-6High pure metal arsenic, wherein: Sb＜5 * 10-7, Bi＜5 * 10 ^-9, S＜7 * 10 ^-8, and the high pure metal arsenic of producing with the inventive method carbon containing not basically, be particularly conducive to semi-conductor industry and use.

The technical qualification and the index of embodiments of the invention are listed in table 1, and wherein embodiment 1～3, are the low assorted As that produces with the inventive method ₂O ₃Be raw material, the reduction with carbon method is produced low assorted metallic arsenic, and embodiment 4～5th, with high-purity As of the inventive method production ₂O ₃Be raw material, produce high pure metal arsenic with chlorination-hydrogen reduction method.

The present invention adopts metallic impurity, particularly Sb and the Bi in the vacuum-sublimation method separate arsenic trioxide, and technology is simple, cost is low, the production capacity height, and environmental pollution is little, and operation control flexibly, can satisfy and produce the needs that foreign matter content had the different special metallic arsenics that require.

The technical qualification of the embodiment of the invention and index table one

Embodiment condition and index	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
						1, raw material
As ₂O ₃%	96.75	97.84	97.15	97.5	97.4
						Sb%	0.18	0.16	0.25	0.20	0.19
Bi%	0.1	0.09	0.12	0.09	0.1
						2, vacuum-sublimation technical qualification
Temperature ℃	310	400	350	315	300
						Vacuum tightness MPa	0.0933	0.100	0.0987	0.1007	0.1013
3, the As after the distillation ₂O ₃Technical indicator
						As ₂O ₃%	99.96	99.95	99.95	99.9999	99.9999
Sb%	0.0045	0.0038	0.0047	4×10 ^-5	5×10 ^-5
						Bi%	0.0039	0.0035	0.004	5×10 ^-7	4.5×10 ^-7
4, special metallic arsenic technical indicator
						As%	99.90	99.91	99.90	99.9999	99.9999
Sb%	0.0048	0.0042	0.0048	4×10 ^-5	5×10 ^-5
						Bi%	0.0041	0.0039	0.0041	6×10 ^-7	5×10 ^-7
* 19 kinds of total impurities %				＜1×10 ^－4	＜1×10 ^－4

＊Sb、Bi、S、Mn、Fe、Al、Ca、Zn、Pb、Cr、Cu、Cd、Ag、Co、Ni、Te、Se、K、Na

Claims

1, a kind of with impure height, particularly containing the high white arsenic of Sb, Bi is raw material, the reduction with carbon method is produced low assorted metallic arsenic, or with the method that chlorination-hydrogen reduction method is produced high pure metal arsenic, it is characterized in that adopting the vacuum-sublimation method to remove impurities in raw materials earlier, particularly remove Sb and Bi, prepare low assorted or high-purity arsenic trioxide, reduction with carbon again, or the low assorted metallic arsenic of chlorination one hydrogen reduction method production, or high pure metal arsenic.

2, the low assorted metallic arsenic of production according to claim 1, or the method for high pure metal arsenic, the vacuum tightness when it is characterized in that vacuum-sublimation three oxidations two periodicals is 0.0933～0.1013MPa, sublimation temperature is 300～400 ℃.

3, the low foreign metal arsenic of production according to claim 1, or the method for high pure metal arsenic, after it is characterized in that white arsenic put into the distillation electric furnace, Ying Xianyu heats, treat that water evaporates is done in the material after, vacuumize beginning vacuum-sublimation operation again.