CN1079004A - Remove and reclaim the technology of orpiment in the difficult metallurgical ore deposit of self-contained arsenic - Google Patents
Remove and reclaim the technology of orpiment in the difficult metallurgical ore deposit of self-contained arsenic Download PDFInfo
- Publication number
- CN1079004A CN1079004A CN92103508A CN92103508A CN1079004A CN 1079004 A CN1079004 A CN 1079004A CN 92103508 A CN92103508 A CN 92103508A CN 92103508 A CN92103508 A CN 92103508A CN 1079004 A CN1079004 A CN 1079004A
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- China
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- arsenic
- orpiment
- dissolving
- ammonia
- dearsenification
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- 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 invention belongs to metallurgy and chemical field, is a kind of orpiment extracting method.Under normal pressure and 10～80 ℃, with containing 3～8% ammoniacal liquor and containing the dissolving of arsenic ore or material stirring, thereafter gained is contained As
2S
3Ammonia solution pass into steam and distill, the ammonia Recycling that distillates is in the dissolving operation; The vinasse acidifying makes its pH＜4, can obtain As
2S
3Precipitation, purity is higher.
Present method is applicable to the gold mine that contains orpiment, the dearsenification of copper mine, and arsenic-removing rate can reach 97%; Also be applicable to the extraction and the purification of red arsenic material or natural mineral.
Description
The invention belongs to metallurgy and chemical field, is to dissolve arsenones with ammoniacal liquor in the ore deposit or in the arsenic slag, and adopts the ammonia still process method that it is recovered as pure arsenones, can be used for containing the dearsenification of the difficult metallurgical ore deposit of arsenic or copper mine, also can be used for the arsenic slag purification of non-ferrous metals smelting works.
In containing the difficult-treating gold mine of arsenic, arsenic is mainly with mispickel (FeAsS) orpiment (As
2S
3) and realgar (As
2S
2) the mineral existence, cyaniding harmful or the interference gold mine is extracted, so need remove in advance.In gold mine, mispickel is the inclusion enclave of gold normally, and as not making gold fully dissociate out to certain degree its Oxidative demage, then the gold cyanidation effect is very poor.Orpiment is disturbed very big to gold cyanidation leaching effect, and its harm increases to 12 with cyaniding pH value by 10 and aggravates.Realgar only just has tangible disadvantageous effect when pH＞12, in view of cyaniding pH in the industrial production remains about 10, so the disadvantageous effect of realgar can be ignored.For containing the difficult metallurgical ore deposit of arsenic, industrial employing oxidizing roasting, pressure oxidation and three kinds of methods of microbiological oxidation are carried out dearsenification, carry out cyanidation gold-extracted thereafter again.
When the red arsenic such as orpiment that contain a great deal of in the arsenic-containing gold ore exist with arsenopyrite, should consider to select for use a kind of as cheap as dirt method preferentially to remove red arsenic, so as not to it and arsenopyrite one is reinstated the higher roasting method of tooling cost or the pressure oxidation method is carried out dearsenification: for the microbial oxidation in the industrial difficult metallurgical ore deposit that begins to grow up in recent years, because bacterium can not oxidation orpiment and realgar, only can arsenic oxide arsenoxide pyrite and pyrite etc., therefore, in the time deviating from red arsenic more in advance, microbial oxidation also can have been adopted technically in the difficult metallurgical ore deposit of this kind arsenopyrite and red arsenic.
Chemical metallurgy institute of Kazakhstan academy of sciences is to arsenic-containing gold concentrate (Ц BETH Ы E META Л Л Ы, 1990, No.8, C, research 43-47) concentrates on pyrogenic process, be the dearsenification roasting method etc. of heating under vacuum dearsenification, oxidation of sulfureted roasting method and high-sulfur gesture, what have enters half industrially scalable, but still can not eliminate pyrogenic process dearsenification inherent shortcomings such as investment is big, environmental practice is tight.
Aspect waste residue-arsenic slag (red arsenic) processing of non-ferrous metals smelting works, company of Furukawa Electronic foot tail copper work (non-ferrous metal, 1984 the 6th phases, the 12nd page) adopts pyrogenic attack to produce white arsenic, be stoving oven distillation-reverberatory furnace resublime method, require very tight environmental practice.Aspect wet processing, SUMITOMO CHEMICAL company gives in east the copper work at first with NaOH solution leaching arsenic sulfide slag, changes CuSO afterwards into
4Solution leaches (Mineral Processing and Extractive Metallurgy, p55,1984), and reagent is more expensive when obviously using NaOH; Use CuSO
4, process is complicated.
Aspect wet method, the patent report (SU1,481,206,1989) that extracts red arsenic from contain the tennantite ore pulp is arranged, method comprises with elementary sulfur handles ore pulp, and that continues leaches with NaOH under heating, uses H again
2SO
4The sulfide of arsenic is separated out in neutralization.Obviously, the shortcoming of this patent is to have consumed NaOH and H
2SO
4
Summarize it, develop a kind of cheap wet method and remove arsenones technology in the ore deposit, can significantly improve the technical indicator and the economic benefit that contain the difficult metallurgical ore deposit pre-oxidation operating unit of arsenic.For the copper mine of Containing Sulfur arsenic, when wet method dearsenication in advance that can be cheap, the arsenic oxide arsenoxide treatment capacity in the time of then can significantly reducing copper mine smelting.
The present invention seeks to shortcoming, adopt a kind of solvent extraction orpiment that can be recycled, can reduce production costs and reduce environmental pollution, and final arsenic product is purer orpiment at prior art.The present invention when containing the difficult metallurgical ore deposit of arsenic, after will orpiment wherein preferentially removing, then thereafter roasting or the used acid of wet method pressure oxidation operation or all corresponding reductions of consumption of base reagent and oxygen.
The used solvent of the present invention is an ammoniacal liquor.Weak ammonia does not dissolve realgar, but the solubilized orpiment is reacted as follows:
As
2S
3+6NH
4OH＝（NH
4）
3AsO
3+（NH
4）
3AsS
3+3H
2O [1]
Up to now, the data that still lack the solubility of orpiment in ammoniacal liquor in the related documents.Mensuration according to this patent inventor: under 10～100 ℃, contain 3～10%NH
3Ammoniacal liquor with after natural orpiment minal fully mixes mutually, solubilized 66～78g/lAs
2S
3, that is 40～48g/l As.Just (main component is As to this result with producing the arsenic slag with NaOH solution dissolving factory
2S
3) data conform to (Hydrometallurgy, 27(1) 6,1991), namely at 10～80 ℃, 3M NaOH leaches 90min, contains 41～52g/lAs in the solution, and NH is described under identical concentration
4OH and NaOH dissolving As
2S
3Ability close, and the impact of temperature is littler.Therefore can think, in practice the temperature of leaching height all can, in technological process, can be satisfied with the determined temperature requirement of thermal balance.
Obviously, in ammonia still or boiling vessel, reaction [1] is to As
2S
3The direction of separating out is carried out, thus make ammonia can Recycling in the leaching of orpiment, this is the outstanding advantages of ammonia solvent method, NaOH solution dissolving rule does not possess this advantage, only when with in the acid and Shi Caineng separate out As
2S
3
As is leached in the present invention
2S
3Operating condition can select as follows: dissolving behind grinde ore, is 20～50% with ammoniacal liquor furnishing pulp solids concentration during dearsenification in the ore deposit, contains 3～8%NH
3, 10～80 ℃ of temperature are dissolved 1～2h in closed container.When being one section dissolving, As
2S
3Dissolution rate～78%; It is two periods whens dissolving about 91%; When being the dissolving of three sections adverse currents about 100%.Pulp solids concentration during leaching is decided by the height of arsenic content in the ore deposit, and when arsenic content was higher, then pulp density will hang down, and ammonia concentration is high, and the dearsenification desired times then needs just can reach more than twice fully.
As is separated out in ammonia still process of the present invention
2S
3Condition as follows: ammonia still process is carried out under normal pressure and 83～100 ℃, steams to pH8～9 o'clock, contains NH in the raffinate
3Being lower than 0.01% gets final product.Thereafter with acid with raffinate pH value by 8～9 transfer to＜4, then separate out byssaceous orpiment sediment, and quite complete, filtration obtains As then
2S
3Utilize economic indicator of the present invention to be: whenever to obtain one ton of As
2S
3, consume approximately 2kgNH
3, 30kg H
2SO
4And 4 tons of steam.
Compare with the dearsenification of NaOH solution dissolution method, weak ammonia dissolution method dearsenification very economical of the present invention, solvent can be recycled, and need not consume a large amount of alkali and sour reagent.When the difficult metallurgical ore deposit that contains arsenic with oxidizing roasting method or the preliminary treatment of wet method pressure oxidation method, and arsenic mineral wherein then adopts the inventive method to remove orpiment when suitable orpiment is arranged, and can the utmost point reduces significantly pretreated unit consumption index and increases economic efficiency.For the difficult metallurgical concentrate that can not adopt microbe-preoxidation gold because containing orpiment and mispickel, adopt the present invention to remove after the orpiment, so that microbe-preoxidation gold becomes possibility technically.In addition, when processing the arsenic slag of non-ferrous metal factory with the inventive method, can obtain pure As
2S
3
Realize that above-mentioned technology sulphur journey of the present invention is by dissolving, Separation of Solid and Liquid, ammonia still process and As
2S
3Reclaiming four unit processes forms.
Extract As in the difficult metallurgical ore deposit of self-contained arsenic or the arsenic slag
2S
3The time, the technological principle flow process as shown in drawings, 1-dissolving tank wherein, 2-concentrator, 3-ammonia still, 4-neutralization chamber, the dense filter of 5-, A-arsenic-containing material, B-NH
3And H
2The O gaseous mixture, the ammoniacal liquor that C-replenishes, material after the D-dearsenification, the E-flocculant, F-steam, G-distills underflow, H-diluted acid, I-waste liquid.
Existing combined process schematic flow sheet further specifies the present invention.
During dissolving, arsenic-containing material behind the comminution [A] is added in the dissolving tank [1], come gas [B] to reach the ammoniacal liquor [C] that replenishes with water, distillation and carry out one section or the leaching of two-part adverse current, in equipment [2], carry out solid-liquid separation and washing afterwards, [D] is the material after the dearsenification, [E] needs the polyacrylamide of adding or the flocculation agent of its type for strengthening the solid-liquid separation process, and the arsenical ammonia solution of gained is delivered to and carried out the ammonia still process operation in the ammonia still [3], and equipment [3] is that screen formula distillation tower or two is imitated pulp digesters.The steam that [F] passes into for distillation, the ammonia gas [B] that contains that steams is delivered in the dissolving tank [1], returns for leaching; Distillation gained milkiness raffinate [G] is delivered to neutralization chamber [4], neutralizes with diluted acid [H] (sulfuric acid or other acid), the pH value of emulsion is transferred to＜4, in dense filter [5], carry out Separation of Solid and Liquid more thereafter, obtain As
2S
3Filtration rear filtrate major part is returned and is used for dissolving, and small part waste liquid [I] is abandoned it.
For specifying result of the present invention and advantage, embodiment is as follows:
Example one
Certain gold mine (8.7g/t Au, 13% As, 10% S) is to contain the arsenic difficulty to select the smelting ore deposit, is mainly orpiment in the arsenic mineral, and directly during cyaniding, gold leaching rate only is 20%.Condition is during with the ammoniacal liquor dearsenification: breeze granularity 95%-320 order, pulp solids concentration 20% contains 5%NH
3, 80 ℃ of following stirring and dissolving 1 hour, the decreasing ratio of arsenic was 75%; During two sections adverse current dissolvings, be same as under the above-mentioned condition, decreasing ratio is 90%; Then reach 97% in the time of three sections.Remove most of orpiment and after suitable processing, the gold cyanidation leaching rate can reach 90～95%.
Example two
With example one identical operations condition under, but 25 ℃ of following stirring and dissolving 2 hours, then arsenic decreasing ratio was 63%.
Example three
With example one same operation condition under, when pulp solids concentration brought up to 50% by 20%, then arsenic Leaching Removal rate was 50%.
Example four
Certain gold mine (4.9g/t Au, 1.93%As, 2.09%S) is difficultly selected and refractory arsenic ore, and orpiment accounts for major part in the arsenic mineral, and the gold leaching only is 15% during direct cyaniding.Adopt shown in the example one and carry out one section ammonia solvent dearsenification under the condition, then arsenic-removing rate is 67%, after the dearsenification with NaOH or Ca(OH)
2When carrying out alkaline pressure oxidation pre-treatment, the oxygen depletion in ore deposit per ton drops to 10 mark cubic meters by 30; NaOH consumes can reduce to 20kg by 53; Ca(OH)
2Consume and also can reduce to 20kg, can reach more than 85% through this pretreated golden cyaniding leaching yield by 60kg.
When obtaining the gold ore product of energy autogenous roasting when above-mentioned gold mine being strengthened flotation and suitable reduction gold recovery requirement, for example be about 30g/t Au, 10% As, the flotation concentrate product of 16%S, adopt shown in the example one and carry out one section ammoniacal liquor dearsenification under the condition, be 70% when then arsenic-removing rate is 57%, two section.Like this, adopt the gold ore after the inventive method dearsenification, arsenic content can reduce to 3% by 10%, and the gold floatation concentrate of the low arsenic content of this kind can allow to carry out the roasting pre-treatment in industrial practice, and that continues is cyanidation gold-extracted again.Desire to carry out one section or two-stage roasting as not adopting the step that removes orpiment in advance, because arsenic content up to 10%, be extremely difficult technically, and the golden cyaniding leaching yield of gained calcining and flue dust is also not high.
Example five
With the above-mentioned example one resulting 50g/l NH that contains
3And 32～64g/l As
2S
31 liter of solution pass into steam and carry out ammonia still process, 83～100 ℃ of lower distillations till the pH8, the ammon amount＜0.01g/l in this moment solution, the raffinate volume also is about 1 liter after the ammonia still process, drips sulfuric acid pH is transferred to＜4, this moment, emulsion became clear liquid, separated out cotton-shaped As
2S
3Precipitation, the As in the solution
2S
3Content is less than 28mg/l.Survey 1 liter of solution of every processing, the ammonia loss is about 0.1g, sulfuric acid 1g, and the liquid-vapour ratio of industrial ammonia still process can be (4～4.5) in addition: 1, can draw thus and reclaim one ton of As
2S
3The unit consumption index be about 1.5～3kgNH
3, 15～30kgH
2SO
4And 4～8 tons of steam.
With the above-mentioned example four resulting 38g/l As that contain
2S
3And 50g/l NH
3Solution, pass into steam and carry out ammonia still process operation, situation and distilled ammonia waste liquid composition are identical with above-mentioned situation, but reclaim one ton of As
2S
3Unit consumption be 2.6kgNH
3, 26kgH
2SO
4And 7 tons of steam.
Claims (3)
1, a kind of method of alkaline solution dearsenification is characterized in that under normal pressure and 10～80 ℃, with containing 3～8%NH
3Ammoniacal liquor will contain arsenic ore or materials allocating becomes slurries, its solid concentration is 20～50% to carry out one-level, two-stage or multi-stage countercurrent dissolving, obtains containing As
2S
3Ammonia solution, the recovery rate of its orpiment can reach 97%.
2, according to right 1 said method, its characteristic is the As that contains to obtaining
2S
3Ammonia solution, under normal pressure and 83～100 ℃, pass into steam and distill, the ammonia that distillates is cycled to used in dissolving: the pH after the distillation is about 8～9 raffinate, with acid pH is adjusted to＜4.
3, by right 1 and 2 said methods, applicable to handle arsenic-containing gold ore, contain tennantite, the red arsenic waste residue of non-ferrous metal factory, and the purification processing of natural arsenic trisulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92103508A CN1027702C (en) | 1992-05-16 | 1992-05-16 | Technology for removing and recoverying orpiment assenblende from metallurgical mine containing arsnide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92103508A CN1027702C (en) | 1992-05-16 | 1992-05-16 | Technology for removing and recoverying orpiment assenblende from metallurgical mine containing arsnide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1079004A true CN1079004A (en) | 1993-12-01 |
| CN1027702C CN1027702C (en) | 1995-02-22 |
Family
ID=4940245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92103508A Expired - Fee Related CN1027702C (en) | 1992-05-16 | 1992-05-16 | Technology for removing and recoverying orpiment assenblende from metallurgical mine containing arsnide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027702C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786659B (en) * | 2009-11-16 | 2012-01-18 | 瓮福（集团）有限责任公司 | Method for recovering arsenic sulfide from arsenic-containing waste residue |
| CN103910383A (en) * | 2013-01-05 | 2014-07-09 | 伍以炳 | Technology and equipment for purification of realgar ore by sealed smelting |
| CN104749013A (en) * | 2015-04-16 | 2015-07-01 | 陕西省地质矿产实验研究所 | Method for selectively separating chemical phases of orpiment and orpiment |
| CN108950200A (en) * | 2018-08-21 | 2018-12-07 | 紫金矿业集团股份有限公司 | A method of it carrying golden high arsenic-and copper-bearing concentrate dearsenification and recycles associated gold |
| CN110923440A (en) * | 2019-11-22 | 2020-03-27 | 西北矿冶研究院 | Method for removing arsenic and recovering heavy metal from copper smelting wastewater |
| CN111233034A (en) * | 2020-03-24 | 2020-06-05 | 中南大学 | Method for preparing yolk crystal by hydrothermal method |
| CN113549777A (en) * | 2021-08-06 | 2021-10-26 | 武汉中地水石环保科技有限公司 | Device and method for reducing arsenic content of rock |
-
1992
- 1992-05-16 CN CN92103508A patent/CN1027702C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786659B (en) * | 2009-11-16 | 2012-01-18 | 瓮福（集团）有限责任公司 | Method for recovering arsenic sulfide from arsenic-containing waste residue |
| CN103910383A (en) * | 2013-01-05 | 2014-07-09 | 伍以炳 | Technology and equipment for purification of realgar ore by sealed smelting |
| CN104749013A (en) * | 2015-04-16 | 2015-07-01 | 陕西省地质矿产实验研究所 | Method for selectively separating chemical phases of orpiment and orpiment |
| CN104749013B (en) * | 2015-04-16 | 2018-01-12 | 陕西省地质矿产实验研究所 | Method for selectively separating chemical phases of orpiment and orpiment |
| CN108950200A (en) * | 2018-08-21 | 2018-12-07 | 紫金矿业集团股份有限公司 | A method of it carrying golden high arsenic-and copper-bearing concentrate dearsenification and recycles associated gold |
| CN110923440A (en) * | 2019-11-22 | 2020-03-27 | 西北矿冶研究院 | Method for removing arsenic and recovering heavy metal from copper smelting wastewater |
| CN111233034A (en) * | 2020-03-24 | 2020-06-05 | 中南大学 | Method for preparing yolk crystal by hydrothermal method |
| CN113549777A (en) * | 2021-08-06 | 2021-10-26 | 武汉中地水石环保科技有限公司 | Device and method for reducing arsenic content of rock |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1027702C (en) | 1995-02-22 |
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