CN107619068A - A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing - Google Patents
A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing Download PDFInfo
- Publication number
- CN107619068A CN107619068A CN201710914821.XA CN201710914821A CN107619068A CN 107619068 A CN107619068 A CN 107619068A CN 201710914821 A CN201710914821 A CN 201710914821A CN 107619068 A CN107619068 A CN 107619068A
- Authority
- CN
- China
- Prior art keywords
- iron
- sulfonium
- iron sulfonium
- hydrogen sulfide
- acid
- 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.)
- Pending
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of iron sulfonium to prepare method of the hydrogen sulfide for waste acid processing, mainly includes the following steps that (1) solid iron sulfonium crushes pulp；(2) iron sulfonium slurries leaching kettle acidic leaching prepares hydrogen sulfide；(3) hydrogen sulfide high-efficient purification waste acid；(4) valuable metal such as Slag recovering gold, silver after iron sulfonium leaching separation of solid and liquid；(5) iron sulfonium leachate freezing and crystallizing recovery ferrous sulfate；(6) liquid is used to prepare diluted acid after freezing and crystallizing, returns to iron sulfonium slurries leaching kettle.This method relies on Nonferrous Metallurgical Process, and the deep purifying of acid water is realized with extremely low cost, can reclaim the noble metals such as gold, silver, and recyclable water treatment agent ferrous sulfate simultaneously.The recycling of valuable element and the advanced treating of acid water are realized, operating cost is saved, reduces environmental risk, there is significant economy and environmental benefit.
Description
Technical field
The invention belongs to metallurgical engineering and environmental project crossing domain, and in particular to a kind of iron sulfonium prepares hydrogen sulfide and is used for dirt
The method of acid treatment.
Background technology
It is mostly sulphide ore that weight coloured (copper, lead, zinc), which is smelted, produces substantial amounts of sulfur dioxide flue gas in fusion process, and two
Sulfur oxide, which is prepared in sulfuric acid process, needs gas cleaning to wash, and washing process produces substantial amounts of acid water, and the waste water has containing weight
The features such as metal concentration is high, species is more, acidity is high, complex shape, and intractability is big, harm is big, main heavy metal ion is
The fluctuation of arsenic, copper, lead, zinc, cadmium etc., especially arsenic concentration is big, and concentration range can be from thousands of mg/L to mg/L up to ten thousand, wherein sulfuric acid matter
Amount concentration can reach 10-200g/L.
Flue Gas of Nonferrous Smelting washing acid water is the very strong a kind of heavy metal wastewater thereby of contaminative, also can even if concentration very little
Cause high risks.The discharge of the waste water containing heavy metal-polluted acid, had both been caused in the enterprises such as resource loss, equipment corrosion, pollution charge
Portion's economic loss, while can also pollute surrounding aqueous environment, and with the migration of heavy metal element, conversion and entering food chain after
Enrichment, seriously endanger ecological environment and health.
Arsenic is also most difficult to handle based on arsenious acid in acid water, thus the handling process of domestic acid water mainly with
For the purpose of arsenic removal.At present, the method for domestic acid water arsenic removal commercial Application mainly have neutralisation, vulcanization-neutralisation, neutralization-
Molysite coprecipitation etc..To containing the very high waste water of arsenic concentration, using vulcanized sodium dearsenification, then after being mixed with other waste water in factory in the lump
Neutralisation treatment, to typically using lime-molysite coprecipitation containing the relatively low waste water of arsenic concentration.It is that waste acid is given up using vulcanization method dearsenification
The Main way of water dearsenification, vulcanizing agent used mainly have vulcanized sodium, barium sulphide, ferrous sulfide etc., but presently, there are one
Individual common problem is that the price of vulcanizing agent is higher, and especially for containing the high acid water of arsenic concentration, processing cost is higher, up to
More than 100 yuan/m3Waste water.Domestic scholars have also been made many work in the optimization that vulcanizing agent selects and applies, and noble thrifty wait uses
Ferrous sulfide fixed bed processing arsenic-containing waste water achieves preferable effect；Tao Xiucheng etc. prepares ferrous sulfide using pyrite, does
The work of exploration；River member you have studied the metamorphosis of arsenic in ferrous sulfide processing arsenic-containing waste water.Li Yalin etc. is studied
The process conditions of arsenic are reclaimed from acid water using ferrous sulfide, achieve preferable effect.A kind of high concentration contains arsenic acid
Property method of wastewater treatment and device (201310157992.4) disclose using ferrous sulfide packed bed processing arsenic-containing waste water side
Method.A kind of method (201710110032.0) that ferrous sulfide (FeS) oxidation dissolution removes water body middle and high concentration As (III) provides
A kind of method that water body middle and high concentration As (III) is removed using FeS oxidation dissolutions.Using simple first in anaerobism glove box
Chemical precipitation method synthesize armorphous, high activity FeS, then made a return journey using the reaction of its oxidation dissolution except the As in water body
(III) absorption property of the Fe to be formed (III) iron mineral, is mainly reacted by FeS and forms ferric arsenate arsenic removal, As's (III)
Removal effect shows that effect of removing arsenic is good and stably very well and without follow-up arsenic release phenomenon.Heavy metal-polluted acid waste water reclaiming reclaims
Method and device (201310501529.7) discloses a kind of heavy metal-polluted acid waste water reclaiming recovery method and its device first
It can be very good the acid in waste acid realizing separation by the selection of anions and canons film in electrodialytic process, containing the low of heavy metal
Acidity waste water utilization hydrogen sulfide gas and jet process integrated technology can quickly in Recycling of waste liquid valuable heavy metal, heavy metal
The rate of recovery of ion is up to more than 95%.
Existing research data is above studied in the preparation and application of ferrous sulfide, is all based on directly adding vulcanization Asia
Iron have impact on reuse sour in follow-up spent acid, and existing document all has the preparation work of ferrous sulfide applied to waste acid processing
The problems such as skill is complicated, application cost is higher, constrains its large-scale industrial application.In view of the intractability of waste acid is big and is processed into
This height, it has also become the subject matter in coloured industry pollution control, have impact on the sustainable development of coloured industry.Therefore research and develop low
Cost, efficient waste acid processing method are significant.
The content of the invention
The present invention, as main object, combines metallurgical work using acid water caused by nonferrous smelting process flue gas washing process
Journey and environment-friendly engineering, support make sulfonium and catch the iron sulfonium that gold and silver is rich in caused by golden new technology, and sulphur is prepared using malleation reaction kettle leaching
Change hydrogen for waste acid processing, there is provided a kind of new approaches and method of acid water processing.After processed by the invention, in iron sulfonium
It the rare precious metals such as gold and silver, can be effectively enriched with, generate hydrogen sulfide and be directly used in the weights such as acid water removing arsenic, copper, lead
Metal, ferrous sulfate by-product can be used as water treatment agent, realize efficient, the low-cost processes of waste acid, economy and Environmental Effect
It is beneficial notable.
A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing, comprises the following steps：
(1) solid iron sulfonium crushes pulp；
(2) iron sulfonium pulp liquid prepares hydrogen sulfide using acidic leaching；
(3) hydrogen sulfide carries out advanced treating to acid water, is purified waste acid and high-grade arsenic sulfide slag；
(4) liquid is after separation of solid and liquid after the iron sulfonium Leach reaction that step (2) obtains, Slag recovering gold, silver valuable metal；
(5) liquid recovery ferrous sulfate after the iron sulfonium after step (4) separation of solid and liquid leaches；
(6) liquid is used to prepare diluted acid, the acidic leaching of return to step (2) after reclaiming the freezing and crystallizing after ferrous sulfate.
Iron sulfonium catches golden yellow golden pyrometallurgical smelting process from making sulfonium in step (1), using including Gold Concentrate under Normal Pressure, iron ore, stone
Raw material including lime stone is in smelting furnace obtained by melting.
It is 10~200 mesh that step (1) iron sulfonium, which is crushed to specification, uses water iron sulfonium pulp after crushing sieving so that containing solid
It is 40~60% to measure mass fraction.
The dilute sulfuric acid reaction that 20%~50% mass concentration is added in step (2) prepares hydrogen sulfide.Dilute sulfuric acid is starched with iron sulfonium
The mass ratio for changing liquid is (1.5~5.8):1.
Reaction pressure is 0.05~0.2Mpa in step (2), and reaction temperature is 25~70 DEG C.
Iron sulfonium after pulp is sent into malleation Leach reaction kettle by step (2) using Pulp pump, is reacted in reactor.
Step (3) hydrogen sulfide carries out deep purifying to waste acid, controls vulcanization anti-by the way of oxidation reduction potential control
Terminal is answered, the control range of oxidation-reduction potential is -180~-250mv.
In step (5) when the concentration enrichment of iron ion in ferrous sulfate is to 100~120g/L, using the side of freezing and crystallizing
Formula reclaims ferrous sulfate, and cryogenic temperature is 0~15 DEG C.
Beneficial effects of the present invention
1st, hydrogen sulfide is prepared using iron sulfonium, the low cost for realizing vulcanizing agent is prepared (with 1200m3/ d waste acid treatment scales,
Arsenic content 8g/L is counted, then can save yuan/year of medicament expense about 31,680,000 compared with conventional vulcanized sodium vulcanization method using which),
Remarkable in economical benefits, for the processing of acid water, the deep purifying of waste acid can be achieved, while avoid the sulphur such as conventional vulcanized sodium
The impurity that agent enters, reduce the amount for producing arsenic sulfide slag, the cost of disposal of follow-up dangerous waste can be reduced；Sodium ion does not enter into
Waste acid, be advantageous to the concentration of waste acid and the reuse of water.
2nd, iron sulfonium prepares the process of hydrogen sulfide, generates leached mud and is enriched the noble metals such as gold, silver, is advantageous to your follow-up gold
The recovery of category, while the byproduct ferrous sulfate in recyclable leachate, can be used or sell as water treatment agent.
Brief description of the drawings
Fig. 1 is present invention process flow chart；
Liquid ferrous sulfate crystallization after Fig. 2 leaches for the present invention；
Liquid ferrous sulfate crystal analysis after Fig. 3 leaches for the present invention；
As seen from the figure, the crystal main component is ferrous sulfate, without other metal impurity components；
Fig. 4 is iron sulfonium material phase analysis；
Such as figure, XRD detections are mainly FeS peak, it was demonstrated that simple substance iron content is relatively low in the iron sulfonium.
Embodiment：
The present invention is intended to further illustrate with reference to embodiments, is not intended to limit the present invention.
Embodiment 1
Take a certain amount of iron sulfonium raw material and acid water, iron sulfonium main component is as shown in table 1, acid water essential element and
Concentration is as shown in table 2.
The iron sulfonium composition (unit of table 1：%)
The acid water essential element of table 2 and concentration (mg/L)
The iron sulfonium of certain mass is weighed, after crushing and screening, the particle diameter for controlling iron sulfonium particle is 10 mesh.According to 1:1 liquid is consolidated
Mass ratio is by iron sulfonium water slurry, with malleation Leach reaction kettle is pumped into, prepares the sulfuric acid weak solution that mass fraction is 20%, to
A certain amount of pickle is added in malleation Leach reaction kettle, produces hydrogen sulfide gas, controls the reaction temperature of malleation Leach reaction kettle
Spend for 65 DEG C, pressure 0.1Mpa.Caused hydrogen sulfide gas is passed through waste acid through piping and carries out reinforcing vulcanization reaction, passes through control
The amount that oxidation reduction potential control hydrogen sulfide gas passes through, it is dirty to strengthen the terminal of vulcanization reaction when controlling potential is -230mv
Ion concentration after acid treatment in solution is as shown in table 2.Liquid after vulcanization reaction is filtered, obtains liquid after arsenic sulfide slag and purification,
Liquid send subsequent handling after purification.Solution in malleation Leach reaction kettle filters through filter press, collects filter residue and does valuable metal recovery
(golden grade is 1160g/t in slag).Filtrate is used to prepare dilute sulfuric acid and circulate to occur for gas, by controlling in circulation solution
The concentration of ferrous ion is 120g/L, and copperas solution is carried out into freezing and crystallizing, and it is 5 DEG C to control crystallization temperature, separation of solid and liquid
Ferrous sulfate heptahydrate (content of ferrous sulfate heptahydrate is 99.5%) is obtained afterwards, and filtrate returns to diluted acid preparation process.
Embodiment 2
Take a certain amount of iron sulfonium raw material and acid water, iron sulfonium main component is as shown in table 3, acid water essential element and
Concentration is as shown in table 4.
The iron sulfonium composition (unit of table 3：%)
The acid water essential element of table 4 and concentration (mg/L)
The iron sulfonium of certain mass is weighed, after crushing and screening, the particle diameter for controlling iron sulfonium particle is 80 mesh.According to 1.2:1 liquid
Gu mass ratio is by iron sulfonium water slurry, with malleation Leach reaction kettle is pumped into, the sulfuric acid weak solution that mass fraction is 25% is prepared,
A certain amount of pickle is added into malleation Leach reaction kettle, produces hydrogen sulfide gas, controls the reaction of malleation Leach reaction kettle
Temperature is 60 DEG C, pressure 0.08Mpa.Caused hydrogen sulfide gas is sent into waste acid through piping, occurs to strengthen vulcanization reaction,
By the amount for controlling oxidation reduction potential control hydrogen sulfide gas to pass through, when controlling potential is -245mv, to strengthen vulcanization reaction
Terminal, the ion concentration after waste acid processing in solution is as shown in table 4.Liquid after vulcanization reaction is filtered, obtain arsenic sulfide slag and
Liquid after purification, liquid send subsequent handling after purification.Solution in malleation Leach reaction kettle filters through filter press, and collection filter residue does valuable
Metal recovery (golden grade is 1300g/t in slag).Filtrate is used to prepare dilute sulfuric acid and circulate to occur for gas, is followed by control
The concentration of ring solution ferrous ions is 115g/L, and copperas solution is carried out into freezing and crystallizing, and it is 0 DEG C to control crystallization temperature,
Ferrous sulfate heptahydrate (content of ferrous sulfate heptahydrate is 99.7%) is obtained after separation of solid and liquid, filtrate returns to diluted acid preparation process.
Claims (8)
1. a kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing, it is characterised in that comprises the following steps：
(1) solid iron sulfonium crushes pulp；
(2) iron sulfonium pulp liquid prepares hydrogen sulfide using acidic leaching；
(3) hydrogen sulfide carries out advanced treating to acid water, is purified waste acid and high-grade arsenic sulfide slag；
(4) liquid is after separation of solid and liquid after the iron sulfonium Leach reaction that step (2) obtains, Slag recovering gold, silver valuable metal；
(5) liquid recovery ferrous sulfate after the iron sulfonium after step (4) separation of solid and liquid leaches；
(6) liquid is used to prepare diluted acid, the acidic leaching of return to step (2) after reclaiming the freezing and crystallizing after ferrous sulfate.
2. according to the method for claim 1, it is characterised in that iron sulfonium catches golden yellow golden pyrogenic process from making sulfonium in step (1)
Fusion process, using the raw material including Gold Concentrate under Normal Pressure, iron ore, lime stone in smelting furnace obtained by melting.
3. method according to claim 1 or 2, it is characterised in that it is 10~200 mesh that step (1) iron sulfonium, which is crushed to specification,
Using water iron sulfonium pulp after broken sieving so that solid content mass fraction is 40~60%.
4. according to the method for claim 1, it is characterised in that the dilute of 20%~50% mass concentration is added in step (2)
Sulfuric acid reaction prepares hydrogen sulfide, and the mass ratio of dilute sulfuric acid and iron sulfonium pulp liquid is (1.5~5.8):1.
5. the method according to claim 1 or 4, it is characterised in that reaction pressure is 0.05~0.2Mpa in step (2),
Reaction temperature is 25~70 DEG C.
6. according to the method for claim 5, it is characterised in that iron sulfonium after pulp is sent into just by step (2) using Pulp pump
Reactor is pressed, is reacted in reactor.
7. according to the method for claim 1, it is characterised in that step (3) hydrogen sulfide carries out deep purifying to waste acid, uses
The mode of oxidation reduction potential control controls vulcanization reaction terminal, and the control range of oxidation-reduction potential is -180~-250mv.
8. according to the method for claim 1, it is characterised in that the concentration in step (5) when iron ion in ferrous sulfate is rich
When collection is to 100~120g/L, ferrous sulfate is reclaimed by the way of freezing and crystallizing, cryogenic temperature is 0~15 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710914821.XA CN107619068A (en) | 2017-09-30 | 2017-09-30 | A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710914821.XA CN107619068A (en) | 2017-09-30 | 2017-09-30 | A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107619068A true CN107619068A (en) | 2018-01-23 |
Family
ID=61091707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710914821.XA Pending CN107619068A (en) | 2017-09-30 | 2017-09-30 | A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107619068A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285229A (en) * | 2018-02-09 | 2018-07-17 | 武汉飞博乐环保工程有限公司 | The waste acid processing method of nonferrous smelting |
| CN109055780A (en) * | 2018-07-18 | 2018-12-21 | 河南中原黄金冶炼厂有限责任公司 | A kind of method of iron sulfonium processing pyrometallurgical smelting acid making system spent acid containing arsenic |
| CN109402410A (en) * | 2018-08-10 | 2019-03-01 | 安徽工业大学 | A kind of method of iron sulfonium acid dissolution slag pretreatment enriching noble metals |
| CN113736999A (en) * | 2021-09-10 | 2021-12-03 | 山东国大黄金股份有限公司 | Method for cooperatively treating arsenic-silver-containing concentrate and waste acid by using sodium sulfide waste residues |
| CN115535967A (en) * | 2022-10-11 | 2022-12-30 | 有研资源环境技术研究院(北京)有限公司 | Method and device for preparing hydrogen sulfide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB656144A (en) * | 1946-12-09 | 1951-08-15 | Marvin J Udy | Improvements in metallurgy |
| GB656140A (en) * | 1946-12-09 | 1951-08-15 | Marvin J Udy | Improvements in the recovery of sulphur as hydrogen sulphide from iron-sulphide bearing material |
| CN103553248A (en) * | 2013-10-23 | 2014-02-05 | 中南大学 | Heavy metal waste acid and wastewater resource recycling method and device |
| CN107058730A (en) * | 2017-04-10 | 2017-08-18 | 中南大学 | A kind of method and its system comprehensively utilized to cu-ni sulphide ore |
-
2017
- 2017-09-30 CN CN201710914821.XA patent/CN107619068A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB656144A (en) * | 1946-12-09 | 1951-08-15 | Marvin J Udy | Improvements in metallurgy |
| GB656140A (en) * | 1946-12-09 | 1951-08-15 | Marvin J Udy | Improvements in the recovery of sulphur as hydrogen sulphide from iron-sulphide bearing material |
| CN103553248A (en) * | 2013-10-23 | 2014-02-05 | 中南大学 | Heavy metal waste acid and wastewater resource recycling method and device |
| CN107058730A (en) * | 2017-04-10 | 2017-08-18 | 中南大学 | A kind of method and its system comprehensively utilized to cu-ni sulphide ore |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285229A (en) * | 2018-02-09 | 2018-07-17 | 武汉飞博乐环保工程有限公司 | The waste acid processing method of nonferrous smelting |
| CN109055780A (en) * | 2018-07-18 | 2018-12-21 | 河南中原黄金冶炼厂有限责任公司 | A kind of method of iron sulfonium processing pyrometallurgical smelting acid making system spent acid containing arsenic |
| CN109402410A (en) * | 2018-08-10 | 2019-03-01 | 安徽工业大学 | A kind of method of iron sulfonium acid dissolution slag pretreatment enriching noble metals |
| CN109402410B (en) * | 2018-08-10 | 2020-09-22 | 安徽工业大学 | Method for enriching precious metals through iron matte acid slag pretreatment |
| CN113736999A (en) * | 2021-09-10 | 2021-12-03 | 山东国大黄金股份有限公司 | Method for cooperatively treating arsenic-silver-containing concentrate and waste acid by using sodium sulfide waste residues |
| CN113736999B (en) * | 2021-09-10 | 2022-09-27 | 山东国大黄金股份有限公司 | Method for cooperatively treating arsenic-silver-containing concentrate and waste acid by using sodium sulfide waste residues |
| CN115535967A (en) * | 2022-10-11 | 2022-12-30 | 有研资源环境技术研究院(北京)有限公司 | Method and device for preparing hydrogen sulfide |
| CN115535967B (en) * | 2022-10-11 | 2024-03-12 | 有研资源环境技术研究院(北京)有限公司 | Method and device for preparing hydrogen sulfide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106868307B (en) | A kind of comprehensive utilization process of pyrite cinder arsenic removal enrichment gold and silver | |
| CN107619068A (en) | A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing | |
| CN104831075B (en) | A kind of vanadium of useless vanadium molybdenum system SCR catalyst, molybdenum are separated and method of purification | |
| CN101503761B (en) | Method for separating and recycling valuable metal from pressure leached high sulphur slag | |
| CN102747226B (en) | Method for treating zinc hydrometallurgy waste residue by using alkali ammonium sulfur coupling method | |
| CN103526017A (en) | Extraction method of valuable elements from acid mud produced in sulfuric acid production by copper smelting flue gas | |
| CN101407355B (en) | Method for comprehensively utilizing iron vitriol dreg of yellow sodium | |
| CN106048217B (en) | The comprehensive reutilization method of oxide powder and zinc | |
| CN102925686B (en) | Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium | |
| CN107400780A (en) | A kind of method that gold, silver and bronze are extracted in the plate from cell phone lines | |
| CN110090548B (en) | Method for wet desulphurization and zinc sulfate recovery of copper slag tailings and zinc smelting fly ash | |
| CN102912133A (en) | Method for classifying and purifying heavy metals in electroplating sludge | |
| CN102094128A (en) | Method for comprehensively recovering various valuable metals from germanium-containing material by wet process | |
| CN102061388A (en) | Method for smelting ferromolybdenum by utilizing molybdenum scrap | |
| CN108249480A (en) | A kind of comprehensive recovering process of Copper making arsenic sulfide slag, flue dust leachate arsenic | |
| CN103194602A (en) | Method for removing iron and recovering iron-enriched iron scum in wet-method zinc smelting process | |
| CN102816931A (en) | Method for recovering copper and iron from copper-containing acid wastewater and producing gypsum | |
| CN109722528A (en) | While a kind of integrated conduct method containing trivalent and pentavalent arsenic solid waste | |
| CN103343242B (en) | Method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate | |
| CN101545038B (en) | Method for producing iron ore concentrate by using poor-tin sulfide ore tailings | |
| CN103805789B (en) | A kind of method of comprehensively recovering valuable metal of copper nickel slag | |
| CN109930007A (en) | A kind of processing method of Copper making electric dust | |
| CN101314820A (en) | Method for producing zinc finemeal with zinc oxide mine or zinc slag | |
| CN101545037B (en) | Method for producing iron ore concentrate by using poor-tin oxidized ore tailings | |
| CN105110300A (en) | Method for extracting manganese and sulfur from composite manganese mine containing manganese sulfide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180123 |
|
| RJ01 | Rejection of invention patent application after publication |