CN106367602B - A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony - Google Patents
A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony Download PDFInfo
- Publication number
- CN106367602B CN106367602B CN201610819292.0A CN201610819292A CN106367602B CN 106367602 B CN106367602 B CN 106367602B CN 201610819292 A CN201610819292 A CN 201610819292A CN 106367602 B CN106367602 B CN 106367602B
- Authority
- CN
- China
- Prior art keywords
- arsenic
- antimony
- flue dust
- dust
- vulcanization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to a kind of methods high-arsenic antimony flue dust vulcanization separation arsenic and recycle antimony, belong to resource comprehensive utilization utilization and environmental technology field.The method that the high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony; it will be uniformly mixed after high-arsenic antimony flue dust, vulcanizing agent grinding, sulfidation roasting volatilization arsenic removal under inert gas protection obtains arsenic-containing smoke dust, continues rising temperature reclamation antimony after the completion of arsenic removal; to this, the stage, flue gas gathered dust, and completed the recycling of antimony.It is different volatile that this method makes full use of arsenic, antimony thiophilicity matter and sulfide to have the characteristics that from oxide, solves the problems, such as high-arsenic antimony flue dust As and Sb separation.
Description
Technical field
The present invention relates to a kind of methods high-arsenic antimony flue dust vulcanization separation arsenic and recycle antimony, belong to resource comprehensive utilization profit
With and environmental technology field.
Background technology
Under the premise of material science and technology is constantly progressive, antimony application range constantly expands, and antimony is classified as the crucial original of 14 classes by European Union
One of material, antimony demand are growing day by day.So antimony yield in China's is on a declining curve in recent years, according to mining industry consulting firm of Britain
2010 annual report China can not develop 10 years or more antimony deposits continuously, and US Geological Survey's statistical data is also shown,
If following do not find that important antimony deposit, world's antimonial resources will be exhausted within the more than ten years again, new antimony resource and right is found
It, which carries out recycling treatment, has own strategic significance.China's antimony resource loss situation is serious simultaneously, non-ferrous metal metallurgy technique
Middle antimony resource flow vector accounts for about 27%, is volatilized to enter into flue dust in the form of sb oxide substantially, reinforces to its recycling treatment
It is essential, it forms that arsenic content in flue dust containing antimony is higher, must carry out before antimony recycling efficiently separating with arsenic.
High-arsenic antimony flue dust handled by the present invention is about 28.72% containing antimony, it is necessary to realize that the separation of arsenic antimony could be recycled with business
The antimony of value.
There are mainly two types of the methods of As and Sb flue dust separation：
First, pyrogenic process, basic ideas are all to evaporate the arsenic in material in the form of its trivalent, antimony
It is retained in material in the form of high oxide, then to the further reduction treatment of antimony in flue dust, reaches solid material point
From the purpose recycled with valuable metal antimony.
Second, wet method, basic ideas are the heterogeneitys using As, Sb compound, by controlling the physical chemistry such as pH
Condition further recycles its product to realize the separation of arsenic, antimony.
The present invention is handled high-arsenic antimony flue dust using sulfiding volatilization method, by the arsenic in flue dust with arsenones and arsenic oxide arsenoxide
Form volatilize system, and it is recycled, further heats up generated antimony trisulfide object phase of volatilizing, must realize time of antimony
It receives.On the one hand obtained the stibium trioxide with commercial application value, on the other hand solve traditional As and Sb separation technological process it is long,
It is the problems such as inferior separating effect, significant to the high-efficiency comprehensive utilization of high-arsenic antimony flue dust.
Invention content
The problem of existing for the above-mentioned prior art and deficiency, the present invention provide a kind of high-arsenic antimony flue dust vulcanization separation arsenic
And the method for recycling antimony.This method makes full use of arsenic, antimony thiophilicity matter and sulfide to have different volatile spies from oxide
Point solves the problems, such as high-arsenic antimony flue dust As and Sb separation, and the invention is realized by the following technical scheme.
A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony will mix after high-arsenic antimony flue dust, vulcanizing agent grinding
It closes uniformly, sulfidation roasting volatilization arsenic removal under inert gas protection obtains arsenic-containing smoke dust, continues rising temperature reclamation antimony after the completion of arsenic removal,
To this, the stage, flue gas gathered dust, and completed the recycling of antimony.
The vulcanizing agent is one or more of sulphur, pyrite, sulfate arbitrary proportion mixture, and vulcanizing agent adds
Enter 10~120% that amount is high-arsenic antimony flue dust quality.
The inert gas is nitrogen or argon gas.
The sulfidation roasting temperature is 250~450 DEG C of 30~150min of roasting.
The temperature that is continuously heating to is 600~1100 DEG C of 30~100min of volatilization.
Above-mentioned sulphur, pyrite, sulfate are material purchased in market.
By above steps, high-arsenic antimony flue dust As and Sb separation is more thorough.Key reaction is as follows：
2As2O3=As4O6(g)↑ (1)；
As2O3+S=As2S3↑+SO2↑ (2)；
Sb2O3+S=Sb2S3+SO2↑ (3)。
The present invention makes full use of arsenic oxide and the volatile feature of sulfide, real by high-arsenic antimony flue dust through sulfiding volatilization
Existing As and Sb separation.
The beneficial effects of the invention are as follows：
（1）Using high-arsenic antimony flue dust through sulfiding volatilization dearsenification, recycling antimony, additive is cheap and process control is relatively easy；
（2）Using high-arsenic antimony flue dust through sulfiding volatilization dearsenification, recycling antimony, the oxidizing roasting separating effect relative to pyrogenic process
Good, simple relative to wet processing flow, additive amount is few.
Description of the drawings
Fig. 1 is present invention process flow chart.
Specific implementation mode
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Figure 1, the method that the high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony, is as follows：
（1）First by high-arsenic antimony flue dust（Wherein As mass percentage contents are that 34.86%, Sb mass percentage contents are
28.72%）, vulcanizing agent（Sulphur, the addition of sulphur are the 20% of high-arsenic antimony flue dust quality）It is that 75um mixing is equal to be ground to granularity
It is even, in the case where being passed through the nitrogen inert gas shielding that gas flow is 0.4L/min, sulfidation roasting under the conditions of temperature is 350 DEG C
90min, volatilization arsenic removal obtain arsenic-containing smoke dust, and arsenic-containing smoke dust is absorbed using the NaOH of a concentration of 40g/L；
（2）It is 700 DEG C of volatilization 60min that temperature is continuously heating to after the completion of arsenic removal, recycles antimony, stage, flue gas was received to this
Dirt completes the recycling of antimony
It is detected through analysis, the present embodiment step（1）The volatility 90% of middle arsenic, the volatility 8% of antimony；Through step（2）Antimony afterwards
Resource overall recovery is up to 88%.
Embodiment 2
As shown in Figure 1, the method that the high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony, is as follows：
（1）First by high-arsenic antimony flue dust（Wherein As mass percentage contents are that 34.86%, Sb mass percentage contents are
28.72%）, vulcanizing agent（Sulphur, the addition of sulphur are the 30% of high-arsenic antimony flue dust quality）It is that 75um mixing is equal to be ground to granularity
It is even, in the case where being passed through the nitrogen inert gas shielding that gas flow is 0.4L/min, sulfidation roasting under the conditions of temperature is 400 DEG C
60min, volatilization arsenic removal obtain arsenic-containing smoke dust, and arsenic-containing smoke dust is absorbed using the NaOH of a concentration of 40g/L；
（2）It is 800 DEG C of volatilization 80min that temperature is continuously heating to after the completion of arsenic removal, recycles antimony, stage, flue gas was received to this
Dirt completes the recycling of antimony
It is detected through analysis, the present embodiment step（1）The volatility 92% of middle arsenic, the volatility 4% of antimony；Through step（2）Antimony afterwards
Resource overall recovery is up to 91%.
Embodiment 3
As shown in Figure 1, the method that the high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony, is as follows：
（1）First by high-arsenic antimony flue dust（Wherein As mass percentage contents are that 34.86%, Sb mass percentage contents are
28.72%）, vulcanizing agent（Sulphur, the addition of sulphur are the 110% of high-arsenic antimony flue dust quality）It is that 75um mixing is equal to be ground to granularity
It is even, in the case where being passed through the nitrogen inert gas shielding that gas flow is 0.4l/min, sulfidation roasting under the conditions of temperature is 400 DEG C
150min, volatilization arsenic removal obtain arsenic-containing smoke dust, and arsenic-containing smoke dust is absorbed using the NaOH of a concentration of 40g/L；
（2）It is 900 DEG C of volatilization 100min that temperature is continuously heating to after the completion of arsenic removal, recycles antimony, and to this, stage flue gas carries out
It gathers dust, completes the recycling of antimony
It is detected through analysis, the present embodiment step（1）The volatility 90% of middle arsenic, the volatility 6% of antimony；Through step（2）Antimony afterwards
Resource overall recovery is up to 89%.
Embodiment 4
As shown in Figure 1, the method that the high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony, is as follows：
（1）First by high-arsenic antimony flue dust（Wherein As mass percentage contents are that 34.86%, Sb mass percentage contents are
28.72%）, vulcanizing agent（Pyrite, the addition of sulphur are the 120% of high-arsenic antimony flue dust quality）Granularity is ground to mix for 75um
Uniformly, in the case where being passed through the argon inert gas protection that gas flow is 0.4L/min, sulfidation roasting under the conditions of temperature is 450 DEG C
30min, volatilization arsenic removal obtain arsenic-containing smoke dust, and arsenic-containing smoke dust is absorbed using the NaOH of a concentration of 40g/L；
（2）It is 1100 DEG C of volatilization 30min that temperature is continuously heating to after the completion of arsenic removal, recycles antimony, and to this, stage flue gas carries out
It gathers dust, completes the recycling of antimony
It is detected through analysis, the present embodiment step（1）The volatility 87% of middle arsenic, the volatility 3% of antimony；Through step（2）Antimony afterwards
Resource overall recovery is up to 91%.
Embodiment 5
As shown in Figure 1, the method that the high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony, is as follows：
（1）First by high-arsenic antimony flue dust（Wherein As mass percentage contents are that 34.86%, Sb mass percentage contents are
28.72%）, vulcanizing agent（Vulcanizing agent is that mass ratio is 1:The addition of 1 sulphur and sulfuric acid iron mixture, vulcanizing agent is high-arsenic antimony
The 10% of flue dust quality）It is ground to granularity to be uniformly mixed for 75um, is being passed through the argon inert gas that gas flow is 0.4l/min
Under protection, sulfidation roasting 140min under the conditions of temperature is 250 DEG C, volatilization arsenic removal obtains arsenic-containing smoke dust, and arsenic-containing smoke dust is using dense
Degree is that the NaOH of 40g/L is absorbed；
（2）It is 600 DEG C of volatilization 90min that temperature is continuously heating to after the completion of arsenic removal, recycles antimony, stage, flue gas was received to this
Dirt completes the recycling of antimony
It is detected through analysis, the present embodiment step（1）The volatility 83% of middle arsenic, the volatility 7% of antimony；Through step（2）Antimony afterwards
Resource overall recovery is up to 90%.
The specific implementation mode of the present invention is explained in detail above in association with attached drawing, but the present invention is not limited to above-mentioned
Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept
Put that various changes can be made.
Claims (2)
1. a kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony, it is characterised in that：By high-arsenic antimony flue dust, vulcanizing agent
It is uniformly mixed after grinding, sulfidation roasting volatilization arsenic removal under inert gas protection obtains arsenic-containing smoke dust, after of continuing rising after the completion of arsenic removal
Temperature recycling antimony, to this, the stage, flue gas gathered dust, and completed the recycling of antimony；The inert gas is nitrogen or argon gas；The vulcanization
Calcination temperature is 250~450 DEG C of 30~150min of roasting；It is described be continuously heating to temperature be 600~1100 DEG C volatilization 30~
100min。
2. the method that high-arsenic antimony flue dust vulcanization according to claim 1 detaches arsenic and recycles antimony, it is characterised in that：It is described
Vulcanizing agent is one or more of sulphur, pyrite, sulfate arbitrary proportion mixture, and the addition of vulcanizing agent is high-arsenic antimony
The 10~120% of flue dust quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610819292.0A CN106367602B (en) | 2016-09-13 | 2016-09-13 | A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610819292.0A CN106367602B (en) | 2016-09-13 | 2016-09-13 | A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106367602A CN106367602A (en) | 2017-02-01 |
| CN106367602B true CN106367602B (en) | 2018-07-24 |
Family
ID=57896757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610819292.0A Active CN106367602B (en) | 2016-09-13 | 2016-09-13 | A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106367602B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107858519B (en) * | 2017-10-30 | 2019-08-02 | 河南中原黄金冶炼厂有限责任公司 | A kind of comprehensive processing technique of Copper making flue dust and arsenic sulfide slag |
| CN107904417B (en) * | 2017-11-07 | 2021-01-08 | 中国恩菲工程技术有限公司 | Method for enriching antimony from antimony oxide ore |
| CN108998657B (en) * | 2018-08-17 | 2020-10-27 | 无锡市华易环境科技有限公司 | Method for removing arsenic from arsenic-containing smoke dust and recovering valuable metals |
| CN109136576B (en) * | 2018-09-19 | 2021-08-24 | 昆明理工大学 | Method for removing arsenic from arsenic-containing smoke dust |
| CN109402379A (en) * | 2018-10-17 | 2019-03-01 | 崇义章源钨业股份有限公司 | The method of tungstenic solid arsenic removal |
| CN109321755B (en) * | 2018-11-27 | 2020-09-01 | 中南大学 | Method for removing arsenic from copper smelting smoke dust |
| CN109762996A (en) * | 2019-03-07 | 2019-05-17 | 昆明理工大学 | A kind of method that high-antimony low arsenic soot oxidation-vulcanization fixation separates arsenic and recycles antimony |
| CN112080646A (en) * | 2020-08-26 | 2020-12-15 | 昆明理工大学 | Method for removing arsenic and antimony in crude stannous sulfide of tin refining sulfur slag product treated by vacuum distillation |
| CN113955799A (en) * | 2021-10-20 | 2022-01-21 | 山东恒邦冶炼股份有限公司 | Method for purifying antimony-containing arsenic trioxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB189911894A (en) * | 1899-06-07 | 1900-06-02 | William Smethurst | Improvements in and relating to Furnaces for the Treatment of Refractory and other Ores and Minerals, Animal and Vegetable Refuse or similar Material, and the Recovery therefrom of Bye-products. |
| JPS6487727A (en) * | 1987-09-30 | 1989-03-31 | Sumitomo Metal Mining Co | Removing method for arsenic and antimony involved in copper precipitate |
| CN1377979A (en) * | 2002-01-16 | 2002-11-06 | 史汉祥 | Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material |
| CN1403603A (en) * | 2001-09-08 | 2003-03-19 | 贵研铂业股份有限公司 | Dearsenifying process for anode mud with high As and Pb content |
| CN105112668A (en) * | 2015-09-02 | 2015-12-02 | 中南大学 | Method for separating and enriching valuable metals from copper anode mud |
-
2016
- 2016-09-13 CN CN201610819292.0A patent/CN106367602B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB189911894A (en) * | 1899-06-07 | 1900-06-02 | William Smethurst | Improvements in and relating to Furnaces for the Treatment of Refractory and other Ores and Minerals, Animal and Vegetable Refuse or similar Material, and the Recovery therefrom of Bye-products. |
| JPS6487727A (en) * | 1987-09-30 | 1989-03-31 | Sumitomo Metal Mining Co | Removing method for arsenic and antimony involved in copper precipitate |
| CN1403603A (en) * | 2001-09-08 | 2003-03-19 | 贵研铂业股份有限公司 | Dearsenifying process for anode mud with high As and Pb content |
| CN1377979A (en) * | 2002-01-16 | 2002-11-06 | 史汉祥 | Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material |
| CN105112668A (en) * | 2015-09-02 | 2015-12-02 | 中南大学 | Method for separating and enriching valuable metals from copper anode mud |
Non-Patent Citations (1)
| Title |
|---|
| 关于从有色冶金工艺中除砷问题的新进展;田占欣;《有色矿冶》;19930331;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106367602A (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106367602B (en) | A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony | |
| CN107828967A (en) | A kind of copper anode mud reduction organic sulfide method separation arsenic and the method for reclaiming antimony, tin | |
| CN106381396B (en) | A kind of method that solid oxidizer roasting high-arsenic antimony flue dust detaches arsenic, antimony and recycling wherein antimony | |
| CN106702170B (en) | A kind of method that high-arsenic antimony soot oxidation-fixation separates arsenic and recycles arsenic, antimony | |
| CN103993182B (en) | The comprehensive recovering process of secondary resource in a kind of iron vitriol slag | |
| CN102517439B (en) | Method for selectively roasting and separating tin, zinc and arsenic in compound iron ore containing tin, zinc and arsenic | |
| CN103937989B (en) | Arsenic-bearing gold concentrate treatment technology | |
| CN106222398A (en) | Method for roasting arsenic-containing material to deeply remove arsenic | |
| CN104862440A (en) | Low-grade iron ore direct reduction method | |
| CN105734308A (en) | Vanadium leaching method for high-chrome vanadium residues | |
| CN103088180A (en) | Method for preparing qualified steel-producing raw material and recovering tin by directly reducing high-iron low-tin concentrate | |
| CN109762996A (en) | A kind of method that high-antimony low arsenic soot oxidation-vulcanization fixation separates arsenic and recycles antimony | |
| CN104962762A (en) | Processing method of fine bastnaesite | |
| CN104843770A (en) | Method of resource utilization of tin sludge | |
| JP2013139618A (en) | Treatment method for smoke ash | |
| CN106119557B (en) | A kind of method of zinc, iron, carbon synthetical recovery in blast furnace gas mud | |
| CN104152671B (en) | A kind of method of being prepared ironmaking iron ore concentrate by Iron Ore Containing Tin | |
| CN105950865A (en) | Method for separating and extracting vanadium and chromium from high-chromium vanadium leaching liquid | |
| CN104451126A (en) | Method for intensifying selective decomposition of zinc ferrite | |
| CN107082428B (en) | A method of cementite is prepared using more metal sulfate slags | |
| CN102703716B (en) | Method for extracting rhenium from rhenium-containing smoke tail gas | |
| CN107460328A (en) | A kind of method that lead and zinc are refined from the tutty of steel-making dust recovery | |
| JP7151404B2 (en) | Method for producing zinc oxide ore | |
| CN106676278B (en) | The method of platinum is recycled from barium sulfate base waste platinum catalyst | |
| CN104445401A (en) | Vanadium trioxide for vanadium alloy smelting and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |