CN103435016A - Method for extracting selenium from acid mud - Google Patents
Method for extracting selenium from acid mud Download PDFInfo
- Publication number
- CN103435016A CN103435016A CN2013103580165A CN201310358016A CN103435016A CN 103435016 A CN103435016 A CN 103435016A CN 2013103580165 A CN2013103580165 A CN 2013103580165A CN 201310358016 A CN201310358016 A CN 201310358016A CN 103435016 A CN103435016 A CN 103435016A
- Authority
- CN
- China
- Prior art keywords
- selenium
- mud
- time
- sour
- leaching
- 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.)
- Granted
Links
Images
Abstract
The invention discloses a method for extracting selenium from acid mud. The method comprises the following steps: nitric acid is added into a sulfuric acid solution to form a mixed solution, acid mud is put into the mixed solution for leaching treatment, and the liquid-solid weight ratio of the mixed solution in which the acid mud is input is (2.5-7.5) to 1, leaching liquid containing crude selenium is obtained after 2 to 7 hours of leaching treatment, and selenium is separated through reduction treatment on the leaching liquid.
Description
Technical field
The present invention relates to put forward the selenium technical field, relate in particular to a kind of method of extracting selenium from sour mud.
Background technology
Acid mud is by the relieving haperacidity of copper smelting exhaust gas, then water spray cleaning flue gas gained.The copper smelting plant of China is numerous, and the amount of producing sour mud per year is also not at decimal, contains Se in sour mud generally 3 ~ 6%, and minimum 1.5%, sour mud major ingredient is Pb, generally is greater than 50%.Sour mud is all as leady raw materials all the time, advance blast furnace, and selenium does not give recovery.
In the last few years, along with scientific and technological progress and social development, find that selenium has special purposes in some field, selenium demand and price have had very large lifting, more than the existing tens thousand of units of price per ton rise to hundreds of thousands of unit.If the selenium in sour mud can be extracted, will greatly improve the performance of enterprises, and can make resource be fully used, but, in prior art, the extraction yield that extracts selenium from sour mud is low, cost is high, causes resource to be wasted.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of method of extracting selenium from sour mud, be intended to solve in prior art and carry from sour mud that the extraction yield of selenium is low, cost is high, the problem of the wasting of resources.
Technical scheme of the present invention is as follows:
A kind of method of extracting selenium from sour mud wherein, comprises step:
Add nitric acid and form mixing solutions in sulphuric acid soln, sour mud is put in mixing solutions and leached processing, the solvent and solute weight ratio that drops into the mixing solutions after sour mud is 2.5 ~ 7.5:1, leaches to process within 2 ~ 7 hours, to obtain the leach liquor that contains thick selenium, leach liquor reduce to processing and separate out selenium.
The described method of extracting selenium from sour mud, wherein, described leaching is processed and is comprised that leaching for the first time processing processes with leaching for the second time, leach for the first time to process and form a leach liquor and a leached mud, one time leached mud forms secondary leach liquor and secondary leached mud through leaching for the second time to process, the secondary leached mud is returned and leaches for the first time processing, the secondary leached mud is reduced to process and separate out selenium.
The described method of extracting selenium from sour mud, wherein, leach the temperature of processing and be controlled at 80 ~ 90 ℃.
The described method of extracting selenium from sour mud, wherein, solvent and solute weight ratio is controlled at 5:1.
The described method of extracting selenium from sour mud, wherein, the time of leaching processing is greater than 3 hours.
The described method of extracting selenium from sour mud, wherein, the concentration >=500g/L of described sulphuric acid soln.
The described method of extracting selenium from sour mud, wherein, the addition of nitric acid is 7mL/100g acid mud.
The described method of extracting selenium from sour mud, wherein, described reduction is treated to: to leach liquor, pass into SO
2separate out selenium.
The described method of extracting selenium from sour mud, wherein, in sour mud, the massfraction of selenium is 3% ~ 6%.
Beneficial effect: the present invention leaches processing by the mixed solution that utilizes sulfuric acid and nitric acid to the selenium in sour mud, by suitable condition, make the casting yield of final selenium more than 83.36%, the cost that the present invention extracts selenium is low, yield is high, technological process is easily controlled, not only realized also having reclaimed precious resource for enterprise increases economic efficiency.
The accompanying drawing explanation
Fig. 1 is a kind of schema that extracts the method preferred embodiment of selenium from sour mud of the present invention.
Embodiment
The invention provides a kind of method of extracting selenium from sour mud, clearer, clear and definite for making purpose of the present invention, technical scheme and effect, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
A kind of method of extracting selenium from sour mud, it comprises step:
Add nitric acid and form mixing solutions in sulphuric acid soln, sour mud is put in mixing solutions and leached processing, the solvent and solute weight ratio that drops into the mixing solutions after sour mud is 2.5 ~ 7.5:1, leaches to process within 2 ~ 7 hours, to obtain the leach liquor that contains thick selenium, leach liquor reduce to processing and separate out selenium.
At H
2sO
4system under, what selenium and nitric acid occurred reacts mainly as follows:
3Se+4HNO
3+H
2O=3H
2SeO
3+NO （1） E=0.95V
Se+2HNO
3=H
2SeO
3+N
2O
3 （2）
Se+4HNO
3=H
2SeO
3+4NO
2 （3） E=0.77V
From above-mentioned reaction formula, selenium has all generated H by reaction
2seO
3, and NO
- 3in N generated NO, N
2o
3, NO
2, i.e. the N of divalence, trivalent, tetravalence, so to the Se of isodose, HNO
3consumption is respectively: 4/3,2,4.So, the HNO consumed in reaction formula (1)
3measure minimumly, oxidizing potential is the highest, the HNO consumed in reaction formula (3)
3measure the highest, so control HNO
3add-on makes the NO in solution
- 3while keeping lower concentration, reaction trend (1), on the contrary tend to (2), (3), in addition, sulfuric acid concentration, extraction time, extraction temperature, solvent and solute weight ratio etc. are also the important factors that affects the leaching yield of Se.
Below describe one by one.
1, H
2sO
4concentration, be 5:1 at solvent and solute weight ratio, and extraction temperature is 70 ℃, and extraction time is 2.5 hours, in sour mud, containing selenium, is the 2.44%(massfraction, lower with), oxygenant is HNO3(7ml/100g acid mud) condition under:
| H 2SO 4(acid of beginning) | In batches | Leached mud is containing Se% | Leaching yield is in slag % |
| 250g/L | 100g/ time | 1.4 | 44.87 |
| 500g/L | 100g/ time | 0.56 | 77.25 |
| 500g/L | 500g/ time | 0.55 | 78.29 |
| 500g/L | 200g/ time | 0.58 | 76.55 |
| 600g/L | 100g/ time | 0.42 | 82.79 |
As can be known from the above table, sulfuric acid concentration is higher, and Se leaching yield (calculate in leached mud and contain Se, then obtain the Se leaching yield in leach liquor, be lower same) is higher, and in industrial production, acid (H preferably will begin
2sO
4) be controlled at>=500g/L of concentration.
2, extraction temperature, be 5:1 at solvent and solute weight ratio, and extraction time is 2.5 hours, in sour mud, containing selenium, is 2.44%, H
2sO
4concentration 500g/L, oxygenant is HNO
3under the condition of (7ml/100g acid mud):
| Extraction temperature | In batches | Leached mud is containing Se% | Leaching yield is in slag % |
| 90℃ | 100g/ time | 0.34 | 86.75 |
| 70℃ | 100g/ time | 0.56 | 77.05 |
| 70℃ | 500g/ time | 0.55 | 78.29 |
| 50℃ | 200g/ time | 1.83 | 21.78 |
As can be known from the above table, extraction temperature also has obvious impact to the leaching yield of Se, and temperature is higher, and leaching yield is higher, in the present invention, preferably extraction temperature is controlled at more than 80 ℃ even highlyer, and for example 80 ~ 90 ℃ are applicable to industrial production.
3, HNO
3addition, be 2.5:1 at solvent and solute weight ratio, and extraction time is 2.5 hours, 70 ℃ of extraction temperatures, and sour mud 100g/ time, be 2.44%, H containing selenium in sour mud
2sO
4under the condition of concentration 500g/L:
| HNO 3Addition | 4ml | 6ml | 7ml | 9ml | 10ml | 12ml |
| Leached mud is containing Se% | 1.28 | 0.56 | 0.47 | 0.47 | 0.45 | 0.42 |
| Se leaching yield % | 21.93 | 76.64 | 80.74 | 80.35 | 81.19 | 82.96 |
As can be known from the above table, add 7mlHNO
3be a flex point, before 7ml, along with the increase of the addition of nitric acid, soak slag and descend containing Se, and after 7ml, soak that slag descends containing Se and not obvious.
So, for this batch materials, HNO
3addition the best is 7ml/100g acid mud, but different batches acid mud preferably can carry out lab scale, selects preferably consumption.If add excessive HNO
3the SO of respective amount will be consumed
2, and produce brown N
2o
3, NO
2gas, so HNO
3addition needs strict control.
4, extraction time, be 5:1 at solvent and solute weight ratio, 90 ℃ of extraction temperatures, and sour mud 200g, be 5.38%, H containing selenium in sour mud
2sO
4concentration 250g/L, oxygenant is HNO
3under the condition of (7ml/100g acid mud):
| Time/h | 1 | 2 | 3 | 4 |
| Leach liquor is containing Se g/L | 8.43 | 9.02 | 9.04 | 9.28 |
| In liquid leaching yield % | 74.26 | 79.46 | 79.63 | 81.75 |
| In slag leaching yield % | 78.23 | 80.55 | 80.68 | 82.63 |
As can be known from the above table, extraction time is when being greater than 1 hour, and Se is most of the leaching, and along with the time increases, leaching yield can slowly increase, and the present invention preferably is controlled at and is greater than 3 hours, to reach than high rate.
5, solvent and solute weight ratio, 90 ℃ of extraction temperatures, sour mud 200g, be 2.44%, H containing selenium in sour mud
2sO
4concentration 500g/L, oxygenant is HNO
3under the condition of (7ml/100g acid mud):
| Extraction temperature | Solvent and solute weight ratio | Soaking slag goes out containing Se% | Leached mud is on average containing Se% | Leaching yield is in slag % |
| 70℃ | 2.5:1 | 0.66，0.44 | 0.55 | 74.80 |
| 70℃ | 5:1 | 0.23，0.20 | 0.215 | 90.48 |
| 90℃ | 2.5:1 | 0.46，0.59 | 0.325 | 77.25 |
| 90℃ | 5:1 | 0.20，0.36 | 0.28 | 88.52 |
As can be known from the above table, in the present invention, preferably adopt the scheme that solvent and solute weight ratio is 5:1, be conducive to improve the leaching yield of Se.
After at the mixing solutions by sulfuric acid and nitric acid, sour mud being leached processing, obtain the leach liquor containing thick selenium, then need leach liquor is reduced and processes to extract the selenium in leach liquor.The present invention is by leach liquor, passing into SO
2reduced; Separate out red Se, the cohesion of then heating is transformed into coarse grain black Se.Concrete reaction formula is as follows:
SO
2+H
2O=H
2SO
3
H
2SeO
3+2H
2SO
3=2H
2SO
3+Se↓+H
2O
To sum up, in the present invention, leaching the preferred processing condition of processing is H
2sO
4>=500g/L, solvent and solute weight ratio is 5:1, and extraction temperature is 80 ~ 90 ℃, and extraction time is 3 ~ 5 hours, HNO
3addition 7ml/100g acid mud.
As the preferred embodiment of the present invention, the invention provides the scheme that a kind of secondary leaches, leach processing and be divided into two steps, leach for the first time and process and leach for the second time processing.As shown in Figure 1, leaching for the first time and processing sour mud used is to process by leaching for the second time the secondary leached mud formed to be prepared, leach for the first time to process and form a leach liquor and a leached mud, one time leached mud returns blast furnace utilized as the Pb raw material, one time leach liquor will add sour mud to leach for the second time processing formation secondary leached mud and secondary leach liquor, and the secondary leach liquor will pass into SO
2reduce and process the thick selenium of formation and the rear liquid of reduction, the rear liquid of reduction can return as leaching for the first time the raw material of processing or turning back in the dust treatment system and be re-used.It should be noted that, leaching for the first time during secondary leaches processed and leached for the second time the condition of processing, identical with the condition that adopts a leaching scheme, just leaches for the second time the extraction time of processing and can foreshorten in 1 ~ 1.5 hour.
The embodiment that secondary leaches:
Leaching for the first time the condition of processing is: secondary leached mud 200g is adjusted to H after the reduction of secondary leach liquor
2sO
4500g/L, HNO
3addition be 5.5ml/100g acid mud, extraction time is 3 hours, extraction temperature is 90 ℃.
The condition of leach processing for the second time is: containing the sour mud of selenium 2.44% 200g/ time, a leach liquor, extraction time is 1 ~ 1.15 hour, and extraction temperature is 90 ℃.
The condition that reduction is processed is: at room temperature to the secondary leach liquor, pass into SO
2to redfree, Se separates out, and heats and boils, and cohesion Se, catch up with except remaining SO
2can filter, filtrate can be used as leaches the raw material of processing for the first time.
Through evidence, the average leaching yield that secondary leaches is 84.68%, thick selenium is about 81.36% containing selenium, all high than the scheme once leached, the rate of recovery of selenium is 83.39%, so, the scheme that secondary leaches not only can improve the grade of leaching yield, casting yield Se, can also reduce cost consumption, also pollution-free to environment, there is stronger practicality.
The present invention leaches processing by the mixed solution that utilizes sulfuric acid and nitric acid to the selenium in sour mud, by suitable condition, make the casting yield of final selenium more than 83.36%, the cost that the present invention extracts selenium is low, yield is high, technological process is easily controlled, not only realized also having reclaimed precious resource for enterprise increases economic efficiency.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (9)
1. a method of extracting selenium from sour mud, is characterized in that, comprises step:
Add nitric acid and form mixing solutions in sulphuric acid soln, sour mud is put in mixing solutions and leached processing, the solvent and solute weight ratio that drops into the mixing solutions after sour mud is 2.5 ~ 7.5:1, leaches to process within 2 ~ 7 hours, to obtain the leach liquor that contains thick selenium, leach liquor reduce to processing and separate out selenium.
2. the method for extracting selenium from sour mud according to claim 1, it is characterized in that, described leaching is processed and is comprised that leaching for the first time processing processes with leaching for the second time, leach for the first time to process and form a leach liquor and a leached mud, one time leached mud forms secondary leach liquor and secondary leached mud through leaching for the second time to process, the secondary leached mud is returned and leaches for the first time processing, the secondary leached mud is reduced to process and separate out selenium.
3. the method for extracting selenium from sour mud according to claim 1, is characterized in that, leaches the temperature of processing and be controlled at 80 ~ 90 ℃.
4. the method for extracting selenium from sour mud according to claim 1, is characterized in that, solvent and solute weight ratio is controlled at 5:1.
5. the method for extracting selenium from sour mud according to claim 1, is characterized in that, the time of leaching processing is greater than 3 hours.
6. the method for extracting selenium from sour mud according to claim 1, is characterized in that the concentration >=500g/L of described sulphuric acid soln.
7. the method for extracting selenium from sour mud according to claim 1, is characterized in that, the addition of nitric acid is 7mL/100g acid mud.
8. the method for extracting selenium from sour mud according to claim 1, is characterized in that, described reduction is treated to: to leach liquor, pass into SO
2separate out selenium.
9. the method for extracting selenium from sour mud according to claim 1, is characterized in that, in sour mud, the massfraction of selenium is 3% ~ 6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310358016.5A CN103435016B (en) | 2013-08-16 | 2013-08-16 | A kind of method extracting selenium from acid mud |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310358016.5A CN103435016B (en) | 2013-08-16 | 2013-08-16 | A kind of method extracting selenium from acid mud |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103435016A true CN103435016A (en) | 2013-12-11 |
| CN103435016B CN103435016B (en) | 2016-08-17 |
Family
ID=49688770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310358016.5A Active CN103435016B (en) | 2013-08-16 | 2013-08-16 | A kind of method extracting selenium from acid mud |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435016B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445103A (en) * | 2014-12-09 | 2015-03-25 | 郴州市金贵银业股份有限公司 | Method for preparing selenium |
| CN104498722A (en) * | 2014-12-16 | 2015-04-08 | 贵州重力科技环保有限公司 | Method for comprehensively recovering mercury and selenium from metallurgical slag |
| CN105803209A (en) * | 2016-04-21 | 2016-07-27 | 西北矿冶研究院 | Method for recovering rare and precious metals from acid mud |
| CN106282579A (en) * | 2016-09-09 | 2017-01-04 | 大冶有色金属有限责任公司 | A kind of method that the degree of depth reclaims rhenium and selenium from Copper making waste acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338368A (en) * | 2008-08-08 | 2009-01-07 | 中南大学 | Method for preprocessing anode sludge and recovering dissipated metal |
| CN102515117A (en) * | 2012-01-12 | 2012-06-27 | 伍代明 | Method for extracting selenium from material containing arsenic, selenium and aluminum |
| CN102828029A (en) * | 2012-07-27 | 2012-12-19 | 紫金矿业集团股份有限公司 | Method for preliminarily separating valuable metals from copper anode slime |
-
2013
- 2013-08-16 CN CN201310358016.5A patent/CN103435016B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338368A (en) * | 2008-08-08 | 2009-01-07 | 中南大学 | Method for preprocessing anode sludge and recovering dissipated metal |
| CN102515117A (en) * | 2012-01-12 | 2012-06-27 | 伍代明 | Method for extracting selenium from material containing arsenic, selenium and aluminum |
| CN102828029A (en) * | 2012-07-27 | 2012-12-19 | 紫金矿业集团股份有限公司 | Method for preliminarily separating valuable metals from copper anode slime |
Non-Patent Citations (1)
| Title |
|---|
| 李倩等: "硒酸泥制备粗硒新工艺", 《中南大学学报（自然科学版）》, vol. 42, no. 8, 31 August 2011 (2011-08-31), pages 2209 - 2214 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445103A (en) * | 2014-12-09 | 2015-03-25 | 郴州市金贵银业股份有限公司 | Method for preparing selenium |
| CN104498722A (en) * | 2014-12-16 | 2015-04-08 | 贵州重力科技环保有限公司 | Method for comprehensively recovering mercury and selenium from metallurgical slag |
| CN105803209A (en) * | 2016-04-21 | 2016-07-27 | 西北矿冶研究院 | Method for recovering rare and precious metals from acid mud |
| CN106282579A (en) * | 2016-09-09 | 2017-01-04 | 大冶有色金属有限责任公司 | A kind of method that the degree of depth reclaims rhenium and selenium from Copper making waste acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103435016B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103526013B (en) | Comprehensive recovery method of complex molybdenum sulfide ore | |
| CN101289705B (en) | Process for abstracting vanadium from iron-smelting waste slag of vanadium -containing iron ore | |
| CN103451438B (en) | A kind of microwave treatment that adopts extracts the method reclaiming copper and selenium from copper anode mud | |
| CN101914678B (en) | Method for producing industry molybdenum oxide from molybdenum concentrate | |
| CN101914695B (en) | Method for recycling vanadium from vanadium ore containing high silicon and high carbon via wet process | |
| CN102277483B (en) | Method for preparing rare earth chloride by using Baiyunebo rare earth concentrate | |
| CN104071832B (en) | The method extracting metal-oxide from discarded SCR denitration | |
| CN101736153B (en) | Method for extracting ammonium molybdate from molybdenum concentrate by pressure ammonia leaching | |
| CN104775026A (en) | Method for extracting high-purity uranium, thorium and mixed rare earths from excellent molten slag | |
| CN101092248A (en) | Technique for producing vanadium pentoxide | |
| CN106636691A (en) | Method used for extracting uranium and niobium from low-grade ore | |
| CN103993182B (en) | The comprehensive recovering process of secondary resource in a kind of iron vitriol slag | |
| CN103435016A (en) | Method for extracting selenium from acid mud | |
| CN103966421A (en) | Comprehensive recovery method of ferrous metallurgical solid wastes | |
| CN103572064B (en) | Method for enriching lead and recovering rare earth from rare earth lead slag | |
| CN102674480A (en) | Method for extracting and separating iron from industrial waste iron sludge and preparing ferrous sulfate and iron oxide red | |
| CN111321296A (en) | Method for recovering vanadium and nickel from waste petroleum catalyst | |
| CN103805774B (en) | A kind of method of low carbon number organism collaborative SCM pyrolusite | |
| CN107758705B (en) | Zinnwaldite extracts lithium carbonate technique | |
| CN102303908A (en) | Method for preparing high-solubility industrial molybdenum oxide | |
| CN109609754B (en) | Waste recovery process generated in precious metal extraction process | |
| CN102703716B (en) | Method for extracting rhenium from rhenium-containing smoke tail gas | |
| CN104745807A (en) | Method for extracting valuable metal elements in niobium-tantalum ore | |
| CN105274343A (en) | Method for extracting tungsten and nickel from petroleum hydrogenation waste catalyst | |
| CN104711437A (en) | Environmentally friendly one-time stone coal roasting and vanadium acid-leaching method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |