CN105907945A - Method for reduction, self vulcanization and dearsenification of refractory high-arsenic high-sulphur gold ore - Google Patents
Method for reduction, self vulcanization and dearsenification of refractory high-arsenic high-sulphur gold ore Download PDFInfo
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- CN105907945A CN105907945A CN201610279308.3A CN201610279308A CN105907945A CN 105907945 A CN105907945 A CN 105907945A CN 201610279308 A CN201610279308 A CN 201610279308A CN 105907945 A CN105907945 A CN 105907945A
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- dearsenification
- arsenic
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- 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
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- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
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Abstract
The invention discloses a method for reduction, self vulcanization and dearsenification of refractory high-arsenic high-sulphur gold ore. The method includes the steps that the high-arsenic high-sulphur gold ore is roasted on the condition of the medium and low temperature in the presence of a reduction agent; and the obtained roasted ore is isolated from air cooling, so that the gold ore product with arsenic removed is obtained. By means of the method, arsenic and sulphur in the high-arsenic high-sulphur gold ore are volatilized and removed as arsenic sulfide; since the arsenic sulfide is low in toxicity, and no external sulphur source or other additives is needed in the roasting process, compared with an existing oxidation roasting method, the method has the advantages of being economical and environmentally friendly. Besides, the technical process is short, practicability is high, and the method can be applied and popularized advantageously.
Description
Technical field
The present invention relates to a kind of remove the method for arsenic in difficult high-As and high-S gold mine, particularly to one by also
The method that the former pozzuolite solvate forms making self-contained arsenic and sulphur in high-As and high-S gold mine removes；Belong to gold smelting
Technical field.
Technical background
Development along with gold industry, it is easy to the gold ore resource of extracting directly is the most exhausted, containing pozzuolite difficulty
Reason gold mine has become the important source material of golden production.Arsenic-containing gold ore is due to composition complexity, and the embedding cloth of gold is typically thin
The micro-shape of grain or micro-and Asia is contaminated in pyrite, magnetic iron ore and mispickel, and the arsenic contained and sulphur are to carrying
Gold produces and adversely affects so that under the conditions of Cyanide Leaching, gold recovery is the lowest, only 50%～70%.Research
Show to pre-process is to solve the key technology that gold recovery rate is low.
At present, the method containing pozzuolite gold ore pretreatment dearsenification is a lot, mainly include oxidizing roasting, chloridising roasting,
The methods such as Chemical Leaching and bacterial oxidation leaching.Wherein two-stage oxidizing roasting method is most widely used, i.e. in oxidation
By the arsenic in gold mine mainly with As under property atmosphere2O3Form volatilization removing.This method has low cost and gold extracts
The advantage that rate is high, but in roasting process, generation containing As2O3SO2Flue gas not only cannot be used for relieving haperacidity, and
Hypertoxicity As2O3Gas can cause serious environmental pollution.In order to solve this problem, it is thus proposed that in vacuum
Or under inert gas shielding, carry out roasting, make arsenic in mispickel react generation with the Lattice Oxygen of gangue oxide
As2O3And separation of volatilizing, the desulfurization in oxidizing atmosphere again of the sample after dearsenification, although this technology solves SO2
And As2O3The problem that gas difficulty separates, but arsenic is still with hypertoxicity As2O3Form is volatilized, and effect on environment is big.
Additionally, also there are some researches show, under inert gas shielding, arsenic can be with avirulent simple substance and the form of sulfide
Volatilization removing, the major defect that the method exists the most only is passed through protective gas can increase intractability and cost,
And the elemental arsenic generated easy reoxidized one-tenth As in dust collecting system2O3Gas.Therefore, a kind of warp of exploitation
The dearsenic technique of Ji environmental protection is the technical bottleneck efficiently utilizing difficult high-As and high-S gold mine.
Summary of the invention
Hypertoxicity As can be produced for during existing oxidizing roasting dearsenification2O3Gas and bring environmental problem,
It is an object of the invention to provide a kind of arsenic making full use of high-As and high-S gold mine self and sulphur composition, at reducing agent
In the presence of, it is achieved high-As and high-S gold mine degree of depth dearsenification and the method for sulphur, the method is without the SO of environmental pollution2
And As2O3Produce, and technological process is short, simple to operate, low cost, current non-ferrous metals industry is walked cleaning
Change production line and provide reliable technical support and valuable application reference value.
In order to realize above-mentioned technical purpose, the invention provides a kind of difficult high-As and high-S gold mine reduction autovulcanization
The method of dearsenification, the method is: high-As and high-S gold mine in the presence of a reducing agent, at a temperature of 600 DEG C～900 DEG C
Roasting；The isolation air cooling of gained calcining, obtains dearsenification gold mine product.
Preferably scheme, sintering temperature is 700 DEG C～800 DEG C.
More preferably scheme, roasting time is 1h～3h.
Preferably scheme, reducing agent includes carbon solid reducing agent, and/or carbon monoxide and/or hydrogen gas are also
Former dose.Carbon solid reducing agent is of a great variety, typically uses cheap coal as reducing agent.
More preferably scheme, carbon solid reducing agent addition is the 2%～20% of high-As and high-S gold mine quality.
More preferably scheme, carbon monoxide and/or hydrogen gas reducing agent volumetric concentration in calcination atmosphere are
5%～70%.
Preferably scheme, calcining puts in water, quickly cools down completely cutting off air, or described calcining is put
In protective atmosphere, cool down completely cutting off air.
The general principle of technical solution of the present invention, and the advantage that hinge structure is brought:
The general principle of technical solution of the present invention: (mainly by adding carbon or other reduction under reductive condition
Agent realizes), roasting under the middle cryogenic conditions of the present invention, make full use of pyrite heating in high-As and high-S gold mine
Decompose the S generated2Reacting generation pozzuolite compound and removing of volatilizing with arsenic, and the sulfide of various arsenic is the most non-toxic,
Therefore severe toxicity during technical scheme can be prevented effectively from high-As and high-S gold mine oxidizing roasting dearsenification
As2O3And sulfur dioxide pollution problem.The high-As and high-S gold mine of the present invention is main under the reductive condition of the present invention
Shown in reaction to be occurred such as equation (1)～(4).
FeAsS=FeS+As (1)
2FeS2=2FeS+S2(g) (2)
4As+3S2(g)=2As2S3(g) (3)
4As+2S2(g)=As4S4(g) (4)
The relation of Fig. 1 gibbs free energy change value with temperature for reacting (1)～(4), as shown in Figure 1,
In the range of 600～900, the Gibbs free energy of above-mentioned each reaction is negative, these reactions is described thermodynamically
Can occur.
The reduction roasting of the present invention can also make the arsenic oxide in gold mine be converted into pozzuolite compound, it is achieved degree of depth sulphur
Change, shown in the key reaction such as formula (5)～(9) that arsenic oxide vulcanizes under reductive condition, reduce with carbon
Illustrate as a example by agent.
2As2O3+3S2(g)+3C=2As2S3(g)+3CO2(g) (5)
2As2O3+2S2(g)+3C=As4S4(g)+3CO2(g) (6)
2As2O5+2S2(g)+5C=As4S4(g)+5CO2(g) (7)
2As2O5+3S2(g)+5C=2As2S3(g)+5CO2(g) (8)
4FeAsO4+2S2(g)+6C=4FeO+As4S4(g)+6CO2(g) (9)
The relation of Fig. 2 gibbs free energy change value with temperature for reacting (5)～(9), as seen from the figure,
Under reductive condition, the vulcanization reaction of arsenic trioxide, diarsenic pentoxide and ferric arsenate is easier to occur, respectively
The standard Gibbs free energy changing value of reaction is the most negative, shows that reduction roasting can not only be by the pozzuolite in mispickel
Change, but also arsenic oxide arsenoxide and arsenate thing can be vulcanized mutually, thus can reach the mesh of degree of depth sulfuration dearsenification
's.It should be noted that the S in above reaction equation2It is mainly derived from pyritous pyrolysis process；C is only
It is a kind of representative of reducing agent, CO and H2Reducing agent use is can also serve as Deng reducibility gas.
Hinge structure, the technical advantage that technical solution of the present invention is brought:
1, there is no hypertoxicity As during the roasting for arsenic removal of the present invention2O3Gas and contaminative SO2Gas produces,
Arsenic and sulphur volatilize with the form of non-toxic sulfide, beneficially environmental protection；
2, only a small amount of reducing agent need to be added during the sulfidation roasting of the present invention, it is not necessary to additional vulcanizing agent or help
Agent etc., the arsenic and the sulphur that make full use of self react, and make process simplification, cost reduce；
3, the method for the high-As and high-S gold mine reduction autovulcanization dearsenification of the present invention is simple to operate, technological process is short,
Practical, be conducive to promoting industrial production application；
4, the method for the present invention is to high-As and high-S gold mine dearsenification effect clearly, arsenic content in calcining after dearsenification
Can take off to less than 1%, dearsenification efficiency is more than 90%.
Accompanying drawing explanation
[Fig. 1] is the relation of reaction (1)～(4) standard Gibbs free energy change with temperature；
[Fig. 2] is the relation of the standard Gibbs free energy change of reaction (5)-(9) with temperature.
Detailed description of the invention
Below in conjunction with instantiation, present invention is further illustrated, but protect without limitation on the claims in the present invention
Protect scope.
Embodiment 1:
With Hunan high-As and high-S gold mine as raw material, this gold mine containing As 8.26%, Fe 16.16%, S 10.76%,
Si 18.92%, Al, 6.64%, Ca 5.13% and O 32.90%.After the coal of this gold mine and 8% is mixed,
In revolution roasting in kilns at 800 DEG C, it is direct that residence time of material controls hot calcine after about 2h, dearsenification
Shrend.Result shows: the burn tinctuer of material is about 23.31%, and the removal efficiency of arsenic is 95.94%, in volatile matter
Arsenic is mainly based on arsenones, and after burning, sample arsenic content only remains 0.48%.
Embodiment 2:
With Yunnan high-As and high-S gold mine as raw material, this gold mine contains As 6.72%, Fe 17.28%, S 11.05.
In the CO gas of 18%, at 700 DEG C after electricity kiln roasting 1.5h, stop heating, cold under nitrogen protection
But to after room temperature, take out sample, weigh, and sample analysis.Result shows: the burn tinctuer of sample is about 21.08%,
The removal efficiency of arsenic is 93.66%, and in volatile matter, arsenic is mainly based on arsenones, and after burning, sample arsenic content is the most surplus
0.54%.
Embodiment 3:
With Guangxi high-As and high-S gold mine as raw material, this gold mine contains As 15.88%, Fe 22.22%, S 21.32.
In the CO gas of 68%, at 850 DEG C after electricity kiln roasting 2.5h, stop heating, cold under nitrogen protection
But to after room temperature, take out sample, weigh, and sample analysis.Result shows: the burn tinctuer of sample is about 31.11%,
The removal efficiency of arsenic is 96.4%, and in volatile matter, arsenic is mainly based on arsenones, and after burning, sample arsenic content is the most surplus
0.83%.
Claims (6)
1. the method for a difficult high-As and high-S gold mine reduction autovulcanization dearsenification, it is characterised in that: high-As and high-S gold
Ore deposit in the presence of a reducing agent, in 600 DEG C～900 DEG C of roasting temperatures；The isolation air cooling of gained calcining, to obtain final product
Dearsenification gold mine product.
The method of difficult high-As and high-S gold mine the most according to claim 1 reduction autovulcanization dearsenification, its feature
It is: sintering temperature is 700 DEG C～800 DEG C.
The method of difficult high-As and high-S gold mine the most according to claim 2 reduction autovulcanization dearsenification, its feature
It is: roasting time is 1h～3h.
4. according to the method for the difficult high-As and high-S gold mine reduction autovulcanization dearsenification described in any one of claims 1 to 3,
It is characterized in that: described reducing agent includes carbon solid reducing agent, and/or carbon monoxide and/or hydrogen gas
Reducing agent.
The method of difficult high-As and high-S gold mine the most according to claim 4 reduction autovulcanization dearsenification, its feature
It is:
Described carbon solid reducing agent addition is high-As and high-S gold mine quality 2%～20%；
Described carbon monoxide and/or hydrogen gas reducing agent volumetric concentration in calcination atmosphere are 5%～70%.
The method of difficult high-As and high-S gold mine the most according to claim 1 reduction autovulcanization dearsenification, its feature
It is: described calcining puts in water, quickly cools down completely cutting off air, or described calcining is placed in guarantor
Protect in atmosphere, cool down completely cutting off air.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106636678A (en) * | 2016-11-14 | 2017-05-10 | 中南大学 | Method for preparing arsenic by direct reduction and roasting of arsenic-containing material |
| CN106756112A (en) * | 2016-12-29 | 2017-05-31 | 湖南工业大学 | A kind of method that heavy arsenic slag reduction sulphur fixing roast is directly produced metallic arsenic |
| CN107904395A (en) * | 2017-11-03 | 2018-04-13 | 江苏省冶金设计院有限公司 | A kind of arsenic removing method of iron ore |
| CN108103322A (en) * | 2017-12-19 | 2018-06-01 | 东北大学 | Thiocarbamide and the technique for carrying gold from difficult-treating gold mine is prepared in situ |
| CN110283990A (en) * | 2019-07-31 | 2019-09-27 | 尚明东 | A kind of the arsenic removal desulfurizer and method of arsenic-containing sulphur-containing refractory gold ore |
| CN113528846A (en) * | 2021-06-18 | 2021-10-22 | 广西壮族自治区环境保护科学研究院 | Treatment method for resource utilization of arsenic-containing waste residues |
| CN113789437A (en) * | 2021-07-30 | 2021-12-14 | 烟台市金奥环保科技有限公司 | Process method for recovering gold and silver by desulfurization and dearsenification of high-arsenic gold concentrate |
| CN115178575A (en) * | 2022-07-08 | 2022-10-14 | 山东恒邦冶炼股份有限公司 | Method for volatilizing arsenic from arsenic-containing cyanidation tailings |
| CN115354146A (en) * | 2022-08-11 | 2022-11-18 | 红河砷业有限责任公司 | Triple process superposition reinforced white smoke arsenic removal method and white smoke arsenic removal equipment |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106636678A (en) * | 2016-11-14 | 2017-05-10 | 中南大学 | Method for preparing arsenic by direct reduction and roasting of arsenic-containing material |
| CN106636678B (en) * | 2016-11-14 | 2018-10-19 | 中南大学 | A kind of method that arsenic-containing material direct-reduction roasting prepares arsenic |
| CN106756112A (en) * | 2016-12-29 | 2017-05-31 | 湖南工业大学 | A kind of method that heavy arsenic slag reduction sulphur fixing roast is directly produced metallic arsenic |
| CN107904395A (en) * | 2017-11-03 | 2018-04-13 | 江苏省冶金设计院有限公司 | A kind of arsenic removing method of iron ore |
| CN108103322A (en) * | 2017-12-19 | 2018-06-01 | 东北大学 | Thiocarbamide and the technique for carrying gold from difficult-treating gold mine is prepared in situ |
| CN108103322B (en) * | 2017-12-19 | 2019-10-25 | 东北大学 | Thiocarbamide and the technique for mentioning gold from difficult-treating gold mine is prepared in situ |
| CN110283990A (en) * | 2019-07-31 | 2019-09-27 | 尚明东 | A kind of the arsenic removal desulfurizer and method of arsenic-containing sulphur-containing refractory gold ore |
| CN113528846A (en) * | 2021-06-18 | 2021-10-22 | 广西壮族自治区环境保护科学研究院 | Treatment method for resource utilization of arsenic-containing waste residues |
| CN113789437A (en) * | 2021-07-30 | 2021-12-14 | 烟台市金奥环保科技有限公司 | Process method for recovering gold and silver by desulfurization and dearsenification of high-arsenic gold concentrate |
| CN115178575A (en) * | 2022-07-08 | 2022-10-14 | 山东恒邦冶炼股份有限公司 | Method for volatilizing arsenic from arsenic-containing cyanidation tailings |
| CN115354146A (en) * | 2022-08-11 | 2022-11-18 | 红河砷业有限责任公司 | Triple process superposition reinforced white smoke arsenic removal method and white smoke arsenic removal equipment |
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Application publication date: 20160831 |