CN109881015A - A kind of method of arsenic sulfide slag processing co-production elemental arsenic - Google Patents
A kind of method of arsenic sulfide slag processing co-production elemental arsenic Download PDFInfo
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- CN109881015A CN109881015A CN201910320272.2A CN201910320272A CN109881015A CN 109881015 A CN109881015 A CN 109881015A CN 201910320272 A CN201910320272 A CN 201910320272A CN 109881015 A CN109881015 A CN 109881015A
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Abstract
The invention belongs to harmful field of solid waste disposal; a kind of method for specifically disclosing arsenic sulfide slag processing co-production elemental arsenic; by arsenic sulfide slag, silicon mixture protective atmosphere, not less than 550 at a temperature of react, by reaction product through vacuum distillation, the elemental arsenic is made；The granularity of the silicon is less than or equal to 300 mesh；Reaction time is not less than 90min.Present invention research has been surprisingly found that, displacement reaction is carried out under the conditions of the temperature by arsenic sulfide slag, elementary silicon, cooperation is to silicon grain diameter, reaction time and subsequent vacuum distillation, the yield and purity of elemental arsenic can be unexpectedly obviously improved, silicon disulfide obtained can be used as the raw material of production hydrogen sulfide gas simultaneously, and hydrogen sulfide gas can handle industrial " waste acid " waste water as vulcanizing agent again.
Description
Technical field
The present invention relates to arsenide processing to utilize field, and in particular to a kind of reacting from arsenones using arsenones and silicon
The method of elemental arsenic is recycled in slag.
Background technique
Arsenic is resource indispensable in the national economic development, is had in fields such as agricultural, electronics, medicine, metallurgy, chemical industry
Special purposes.It often is applied to Insecticides (tech) & Herbicides (tech) and timber preservative, decolorising agent, non-ferrous alloy, ceramics etc., especially
Its in a semiconductor material using more and more.Arsenic is widely present among various ores, Chang Yuqian, copper, zinc, tin, tungsten,
The metalliferous minerals association such as antimony, gold, in the processing smelting process of these ores, significant component of arsenic enters diluted acid waste water
In.Currently, the processing of this diluted acid waste water mostly uses greatly vulcanization, to generate a large amount of arsenic sulfide slag.Due to these vulcanizations
Arsenic Slag treatment disposition difficulty is larger, and many smelteries all take the modes such as directly stacking, stabilisation landfill to dispose.And arsenones contain
There is severe toxicity, such disposal options, which exist, generates the hidden danger seriously endangered to soil environment and human health.Therefore, from sulphur
Change recycling arsenic resource in arsenic slag to be not only environmental protection, the needs of human health and resource and make full use of, national economy is lasting
The needs of development.
It is directed to arsenic sulfide slag at present, main treatment process has pyrogenic process and wet process two major classes.Arsenic sulfide slag passes through in pyrogenic process
Oxidizing roasting, arsenones therein are converted to arsenic trioxide and are directly volatized into flue gas, and then arsenic trioxide is realized in condensation
Recycling.The shortcomings that this method is poor product quality, and the sulfur dioxide flue gas of association is high containing arsenic, it is difficult to handle, secondary pollution is serious.
Wet process mainly takes acidleach, alkali leaching or salt to be impregnated into capable processing, and first arsenic is separated from slag, and then further recycling arsenic produces
Product carry out harmless treatment.But the universal production procedure of wet-treating is complicated, processing cost is higher.
Patent CN106756113A discloses a kind of method that arsenic sulfide slag reduction sulphur fixing roast directly produces metallic arsenic, with
Arsenic sulfide slag is raw material, and copper oxide and reducing agent is added, and restores sulphur fixing roast after mixing at high temperature, product of roasting is through vacuum point
From obtaining elemental arsenic.Although the method process is simple, used oxidation copper processing is more expensive, obtains unit mass elemental arsenic product
Consumption oxidation copper mass is larger, and obtained elemental arsenic purity is not high, and the rate of recovery is lower.In addition to this, which is using raw material
Untreated arsenic sulfide slag does not only result in copper oxide and contacts poor, target with arsenones containing a large amount of other metal sulfides
Reaction efficiency is low, while increasing energy consumption, reduces equipment service efficiency.
Patent CN103922294A discloses a kind of method that arsenic is recycled from arsenic sulfide slag, using arsenic sulfide slag as raw material,
The very high arsenones of purity are obtained with the method processing arsenic sulfide slag of staged vacuum distillation first, it is then mixed with iron powder and arsenones
Conjunction is reacted at high temperature, and reaction product obtains elemental arsenic through vacuum separation.The method process is simple, the purified processing of arsenic sulfide slag
Afterwards, it can better contact with and react with iron powder.But side reaction easily occurs with iron and generates arsenic iron compound, drop for the elemental arsenic that the method generates
Also the rate of recovery of arsenic is seriously reduced while the utilization rate of low iron powder.
Summary of the invention
For the limitation of the processing method of existing arsenic sulfide slag, the object of the present invention is to provide a kind of simplicity, cost
It is cheap, the rate of recovery is high, in the slave arsenic sulfide slag of safety and environmental protection recycle elemental arsenic method.
A kind of method of arsenic sulfide slag processing co-production elemental arsenic, by arsenic sulfide slag, silicon mixture in protective atmosphere, no
Reaction (displacement reaction), by reaction product through vacuum distillation, is made the elemental arsenic at a temperature of lower than 550；
The granularity of the silicon is less than or equal to 300 mesh；
Reaction time is not less than 90min.
Present invention research has been surprisingly found that, carries out displacement reaction under the conditions of the temperature by arsenic sulfide slag, elementary silicon,
Cooperation to silicon grain diameter, reaction time and subsequent vacuum distillation, can unexpectedly be obviously improved elemental arsenic yield and
Purity, while silicon disulfide obtained can be used as the raw material of production hydrogen sulfide gas, hydrogen sulfide gas can be used as vulcanizing agent again
Handle industrial " waste acid " waste water.
Preferably, the arsenic sulfide slag is before mixing in advance through vacuum distillation purification processes.The study found that its into
Row vacuum distillation purification processes, the more conducively preparation of elemental arsenic.
Preferably, the temperature of vacuum distillation purification processes process is 400-600 DEG C, pressure 10-400Pa.
Preferably, the vacuum distillation purification processes time is not less than 1h.
In the present invention, the granularity of the silicon is less than or equal to 300 mesh；Preferably 300~1250 mesh.Present invention research hair
It is existing, under the preparating mechanism that the present invention innovates, using small silicon, facilitate the purity for unexpectedly promoting elemental arsenic obtained
And the rate of recovery.
Preferably, the silicon is not less than the theoretical molar amount for reacting the arsenones in arsenic sulfide slag completely.
Preferably, the silicon is 1~2 times of the theoretical molar amount for reacting the arsenones in arsenic sulfide slag completely.
In the present invention, to be further conducive to arsenic sulfide slag being converted to elemental arsenic, need to control the temperature at 550 DEG C
Or more.
Preferably, reaction temperature is 550-600 DEG C.
Reaction process preferably carries out under protective atmosphere, and the protective atmosphere is, for example, nitrogen or inert gas.
Preferably, the reaction time is 90-120min.
In the present invention, it is preferred to use the method for vacuum distillation recycles elemental arsenic from the reaction product.
Preferably, the pressure of vacuum distillation process is 15-25Pa；Temperature is 500-600 DEG C.
Preferably, the vacuum distillation time is not less than 60min；Further preferably 60-90min.
The present invention is a kind of to extract the method that pure arsenones and pasc reaction prepare elemental arsenic from arsenic sulfide slag, it includes following
Step:
(1) by arsenones and excessive silicon powder mixed grinding, in inert gas atmosphere, normal pressure reacts at 550-600 DEG C；
Reaction time is preferably 90-120min.
(2) by reaction product obtained in (1) step in pressure 15-25Pa, temperature is steamed under conditions of being 500-600 DEG C
It evaporates, obtains the condensate of elemental arsenic；Distillation time is preferably 60-90min.
Under reaction temperature of the invention, the present invention prepares elemental arsenic process, the reaction mainly occurred such as following formula (1),
As2S3+ 3/2Si=2As+3/2SiS2 (1)
Arsenic sulfide slag is handled using the mechanism that the present invention innovates, can efficiently realize the arsenic conversion of arsenic sulfide slag, and is not easy
By-product is generated, the rate of recovery of arsenic is higher.
Beneficial effects of the present invention
The method of the present invention, for the purity of elemental arsenic obtained up to 99% or more, the rate of recovery of arsenic reaches 95% or more.We
Method process flow is short, and operating condition is easy to control, whole process safety and environmental protection, and the metallic arsenic product of acquisition can directly carry out industry and answer
With or further Refining is high purity arsenic for semi-conductor industry.And the raw material silicon powder for being used for reduction-sulfurization arsenic is high-efficient,
It is cheap, greatly reduce the cost of arsenic recycling.In general, the present invention is preferably realized by arsenones to elemental arsenic
Transformation, and then be arsenones waste residue resource using a new technical solution is provided, substantially reduce stockpiling hazard waste, tool
There are significant economic benefit and environmental benefit, is worthy of popularization.
Detailed description of the invention
Fig. 1 is EDS (Method of Energy-Dispersive X-Ray Fluorescence Spectrometer instrument) detection for the steaming thing that the embodiment of the present invention 1 obtains
Result figure.
As can be seen from the figure resulting elemental arsenic mass percent reaches 99.51%.
Specific embodiment
The main component of the arsenic sulfide slag (dry slag) of this experiment is (wt.%): As 35.6, S 36.12, Pb 1.15, Ca
9.29.The arsenic sulfide slag distills at 10-100Pa and 450 DEG C after removing a small amount of sulphur and arsenic oxide arsenoxide, so that it may pure required for obtaining
Arsenones experimental raw.
Following embodiment is intended to illustrate invention rather than limitation of the invention further.
Embodiment 1
1.00g arsenones are weighed, 1.00g silicon powder (300 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 90min at 550 DEG C.System is evacuated to after reaction
25Pa persistently distills 60min at 500 DEG C, and collection obtains condensate elemental arsenic 0.587g, and the arsenic rate of recovery is 96.39%；Through EDS
It characterizes purity and is greater than 99%.
Embodiment 2
1.00g arsenones are weighed, 1.00g silicon powder (300 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 90min at 600 DEG C.System is evacuated to after reaction
25Pa, 90min is persistently distilled at 500 DEG C, and collection obtains condensate elemental arsenic 0.580g, the arsenic rate of recovery 95.24%；Through EDS table
It levies purity and is greater than 99%.
Embodiment 3
2.00g arsenones are weighed, 2.00g silicon powder (300 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 120min at 550 DEG C.System is evacuated to after reaction
25Pa, 90min is persistently distilled at 500 DEG C, and collection obtains condensate elemental arsenic 1.165g, the arsenic rate of recovery 95.65%；Through EDS table
It levies purity and is greater than 99%.
Embodiment 4
Compared with Example 1, the main distinction is, uses mesh number for the silicon of 1250 mesh ultra-fine grain diameters.
Test discovery, the arsenic rate of recovery 97.1%；It is greater than 99% through EDS characterization purity.
Embodiment 5
Compared with Example 1, the main distinction is, the temperature of vacuum distillation process is lower, specific as follows:
1.00g arsenones are weighed, 1.00g silicon powder (300 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 90min at 550 DEG C.System is evacuated to after reaction
25Pa, 60min is persistently distilled at 350 DEG C, and collection obtains condensate elemental arsenic 0.366g, the arsenic rate of recovery 60.90%；Through EDS table
It levies purity and is greater than 99%.It compares, can react arsenones conversion Efficient Conversion into elemental arsenic, but subsequent negative pressure with embodiment 1
The temperature of distillation process is lower, and elemental arsenic does not recycle completely, and the rate of recovery is caused to decline.
Embodiment 6
Compared with Example 1, the main distinction is, the time of vacuum distillation process is lower, specific as follows:
1.00g arsenones are weighed, 1.00g silicon powder (300 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 90min at 550 DEG C.System is evacuated to after reaction
25Pa, 15min is persistently distilled at 500 DEG C, and collection obtains condensate elemental arsenic 0.254g, the arsenic rate of recovery 42.26%；Through EDS table
It levies purity and is greater than 99%.
It compares, can react arsenones conversion Efficient Conversion into elemental arsenic, but subsequent vacuum distillation process with embodiment 1
Time it is shorter, elemental arsenic does not recycle completely, and the rate of recovery is caused to decline.
Comparative example 1 (compares) with embodiment 1
1.00g arsenones are weighed, 1.00g silicon powder (300 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 90min at 475 DEG C.System is evacuated to after reaction
25Pa persistently distills 60min at 500 DEG C, and collection obtains condensate 0.911g, is determined as the complete sulphur of unreacted through EDS characterization
Change the mixture of arsenic and elemental arsenic, simple substance arsenic content is considerably less, is 8.58%.
Comparative example 2 (compares) with embodiment 1
1.00g arsenones are weighed, 1.00g silicon powder (300 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 30min at 550 DEG C.System is evacuated to after reaction
25Pa persistently distills 60min at 500 DEG C, and collection obtains condensate 0.641g, is determined as the complete sulphur of unreacted through EDS characterization
Change the mixture of arsenic and elemental arsenic, simple substance arsenic content is 54.17%.
Comparative example 3
Compared with Example 1, the main distinction is, silicon mesh number is lower, and partial size is larger:
1.00g arsenones are weighed, 1.00g silicon powder (100 mesh) is added in corundum crucible after being sufficiently mixed grinding.It will dress
Good corundum crucible is put into furnace, and normal pressure argon atmosphere is protected, reacts 90min at 550 DEG C.System is evacuated to after reaction
25Pa persistently distills 90min at 500 DEG C, and collection obtains condensate 0.855g, essentially all unreacted arsenones.
Claims (10)
1. a kind of method of arsenic sulfide slag processing co-production elemental arsenic, which is characterized in that protecting the mixture of arsenic sulfide slag, silicon
Shield atmosphere, not less than 550 at a temperature of react, by reaction product through vacuum distillation, the elemental arsenic is made；
The granularity of the silicon is less than or equal to 300 mesh；
Reaction time is not less than 90min.
2. the method for arsenic sulfide slag processing co-production elemental arsenic as described in claim 1, which is characterized in that the arsenones
Slag is before mixing in advance through vacuum distillation purification processes.
3. the method for arsenic sulfide slag processing co-production elemental arsenic as claimed in claim 2, which is characterized in that vacuum distillation purification
The temperature for the treatment of process is 400-600 DEG C, pressure 10-400Pa.
4. the method for arsenic sulfide slag processing co-production elemental arsenic as claimed in claim 3, which is characterized in that vacuum distillation purification
The time is handled not less than 1h.
5. such as the method for the described in any item arsenic sulfide slag processing co-production elemental arsenics of Claims 1 to 4, which is characterized in that institute
The silicon stated is not less than the theoretical molar amount for reacting the arsenones in arsenic sulfide slag completely.
6. the method for arsenic sulfide slag processing co-production elemental arsenic as claimed in claim 5, which is characterized in that the silicon is will
1~2 times of the theoretical molar amount that arsenones in arsenic sulfide slag react completely.
7. the method for arsenic sulfide slag as described in claim 1 processing co-production elemental arsenic, which is characterized in that reaction temperature is
550-600℃。
8. the method for arsenic sulfide slag as described in claim 1 processing co-production elemental arsenic, which is characterized in that the reaction time is
90-120min。
9. the method for arsenic sulfide slag processing co-production elemental arsenic as described in claim 1, which is characterized in that vacuum distillation process
Pressure be 15-25Pa；Temperature is 500-600 DEG C.
10. the method for arsenic sulfide slag processing co-production elemental arsenic as claimed in claim 9, which is characterized in that when vacuum distillation
Between be not less than 60min；Preferably 60-90min.
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| CN201910320272.2A CN109881015B (en) | 2019-04-19 | 2019-04-19 | Method for treating arsenic sulfide slag and co-producing elemental arsenic |
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| CN201910320272.2A CN109881015B (en) | 2019-04-19 | 2019-04-19 | Method for treating arsenic sulfide slag and co-producing elemental arsenic |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5353575A (en) * | 1976-10-26 | 1978-05-16 | Nippon Mining Co Ltd | Treating method for arsenic sulfide and apparatus thereof |
| CN103922294A (en) * | 2014-04-05 | 2014-07-16 | 中南大学 | Methods for recovering arsenic sulfide and metallic arsenic from arsenic sulfide waste residues |
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2019
- 2019-04-19 CN CN201910320272.2A patent/CN109881015B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5353575A (en) * | 1976-10-26 | 1978-05-16 | Nippon Mining Co Ltd | Treating method for arsenic sulfide and apparatus thereof |
| CN103922294A (en) * | 2014-04-05 | 2014-07-16 | 中南大学 | Methods for recovering arsenic sulfide and metallic arsenic from arsenic sulfide waste residues |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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