CN106480328A - A kind of technique for reclaiming precious metal vanadium in flue gas desulphurization sludge - Google Patents
A kind of technique for reclaiming precious metal vanadium in flue gas desulphurization sludge Download PDFInfo
- Publication number
- CN106480328A CN106480328A CN201610669558.8A CN201610669558A CN106480328A CN 106480328 A CN106480328 A CN 106480328A CN 201610669558 A CN201610669558 A CN 201610669558A CN 106480328 A CN106480328 A CN 106480328A
- Authority
- CN
- China
- Prior art keywords
- sludge
- vanadium
- flue gas
- leaching
- technique
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention provides the technique for reclaiming precious metal vanadium in a kind of flue gas desulphurization sludge, mainly includes the following steps that：（1）Metallic element in spray liquid is enriched with coprecipitation mode, while being pre-processed；（2）By step（1）In sediment and sludge crush, grinding；（3）By step（2）In sludge raw material crush after add acid leaching agent carry out mixing leaching standing, supernatant remain neutralization, sink mud filtration washing；（4）By step（3）In leachate carry out ion exchange, extract containing vanadium ion；（5）By step（4）In organic phase solution carry out back extraction process, obtain the aqueous solution containing vanadium of high concentration；（6）To step（5）In the aqueous solution containing vanadium in add ammonium chloride, filter precipitation；（7）To step（6）Middle pentavalent vanadium precipitation carries out calcination, and vanadic anhydride is obtained.The rate of recovery of the present invention is high, with significant economic benefit；Reduce the harm to environment；Technological process is simple, as a result easily realizes.
Description
Technical field
The invention belongs to Solid Waste Treatment and resource field, valuable in more particularly to a kind of recovered flue gas desulfurization sludge
The method of vanadium metal, belongs to environmental protection, recycling field.
Background technology
Vanadium metal element is generally present in the mineral matters such as ore, oil, in thermal power plant, non-ferrous metal metallurgy, change
These raw material of the industries such as work are widely used.Precious metal vanadium as accompanying element, during mineral matter pyrolytic semlting,
Noble metal vanadium also can be entered in flue gas processing device with high-temperature gasification together with other flue gases.
Fume treatment typically adopts wet-treating, and in flue gas, main component is sulfur dioxide.Desulfurization spray liquid contains in a large number
Heavy metal contaminants in flue gas, if not treated just discharge, can cause the severe contamination of soil and water body, heavy metal
It is enriched with by food chain layer by layer, chronic/cumulative toxicity is produced, serious harm is caused to human health and bio-diversity.Very
In many industrial solid wastes, content of beary metal is of a relatively high, and the content of a lot of heavy metals alreadys exceed its product in metallic ore
Position.Heavy metal in heavy metal sludge is reclaimed, and not only can realize changing waste into resources utilization, moreover it is possible to reduce waste poison
Property, so as to reduce disposal costs, it is to kill two birds with one stone.
In the processing procedure of existing desulfurization spray liquid and desulfurization sludge, equal No Assets recycling step.For spray liquid, one
As be that the sewage treatment plant for entering plant area is processed, its spray liquid be high salinity waste water, can be to existing sewage treatment process
Produce certain impact；For the process of desulfurization sludge, modal mode is processed for outward transport, transfers to qualified associated companies
Collection is processed, and general whereabouts is landfill.
However, in these spray liquids and sludge, containing substantial amounts of precious metal, very polymetallic content alreadys exceed which
Grade in metallic ore, is directly processed or landfill causes the great wasting of resources.
Content of the invention
The present invention can provide a kind of process for reclaiming noble metal vanadium from flue gas desulphurization sludge, with the invention choosing
Selecting property is high, simple to operation, it is easy to control cost, reduces secondary pollution, reducing energy consumption, Resource recovery.The present invention is main
Comprise the following steps,
（1）Metallic element in spray liquid is enriched with by way of precipitation, is formed precipitation and is reclaimed.Sediment and dirt
Mud is pre-processed simultaneously；
（2）By step（1）In sediment and sludge crush, grinding；
（3）By step（2）In desulfurization sludge raw material crush after add acid leaching agent to carry out mixing leaching, react 10-90min
Afterwards, until separation of solid and liquid, supernatant remains neutralization to standing, sinks mud filtration washing, as general fixed-end forces；
（4）By step（3）In leachate carry out ion exchange, adjust pH value of solution in 1-4, add P204, TBP and kerosene conduct
Extractant, in Extraction solvent containing vanadium ion；
（5）By step（4）In organic phase solution carry out back extraction process, add inorganic acid as strippant, obtain highly concentrated
The aqueous solution containing vanadium of degree；
（6）To step（5）In the aqueous solution containing vanadium in add ammonium chloride, in solution pentavalent vanadium with ammonium poly-vanadate form precipitate, mistake
Filter precipitation；
（7）To step（6）Middle pentavalent vanadium precipitation carries out calcination process, and vanadic anhydride of the purity more than 90% can be obtained.
Preferably, the selection of activated sludge for reclaiming vanadium is flue gas desulphurization sludge（Containing wet desulphurization and dry desulfurization）And desulfurization spray
Drench liquid；
Preferably, step（3）In acid leaching agent be sulfuric acid.
Preferably, step（3）Control mixeding liquid temperature be 60-90 degree, the reaction time be 30-60min.
Preferably, step（4）The volume ratio of the proportioning of middle extractant, P204, TBP and kerosene is 18:6:76, control reaction
PH is between 2-3.
Preferably, step（5）The extractant of reversed phase extraction is sulfuric acid or hydrochloric acid, the more preferably hydrochloric acid of 2mol/L,
Consumption is calculated with the amount of solute, be containing vanadium（Quality）3-5 times.
Preferably, step（3）In extraction be stage extraction, the process route of multilevel leaching is, by pretreatment process
Separation of solid and liquid after the pressed powder leaching of acquisition, supernatant send to neutralization；Lower floor's sludge wouldn't be discharged；Now with the leaching of new configuration
Take liquid carries out second leaching to described lower floor's sludge, and leaching is stood after finishing, and supernatant pumps out storage, enters for next group
The first time leaching of material；Leaching agent and conditioning agent are added in the filtrate of press filtration acquisition and mud cake cleaning solution, configure new leaching
Liquid, for second leaching of next group charging；So repeatedly.
Beneficial effects of the present invention：
1st, the rate of recovery is high, with significant economic benefit.Flue gas desulfurization can be successfully separated using the technique proposed in the present invention
Vanadium metal in sludge, it is achieved that changing waste into resources, the rate of recovery of vanadium are more than 90%, and vanadium is precious metal, and price per ton is 300
More than ten thousand, the product income of acquisition is more than operating cost, with actual application value.In present invention process, using multistage leaching
The technique for carrying, significantly improves the rate of recovery of vanadium, and achieves the sealing and circulating of medicament, and automaticity strengthens.
2nd, the residue after processing is general solid waste, reduces the harm to environment.In the residue after extraction, heavy metal
Element major part is transferred in solution, significantly reduces the heavy metal element in solid waste slag, and the solid waste quantity of slag is significantly reduced.Cause
This, after leaching, remaining filter residue, can processing as general waste, greatly reducing disposal costs, while reducing to environment
Harm.
3rd, the Extraction and back extraction technique of the present invention, greatly improves the selective extraction to vanadium, it is to avoid acid dissolution
In other valuable metal ions interference.
4th, present invention process flow process is simple, it is easy to which operational administrative, investment cost are low, as a result easily realizes.
Specific embodiment
With reference to specific embodiment, the present invention is further elucidated with, it should be understood that following specific embodiments are only used for
The bright present invention rather than restriction the scope of the present invention.
Embodiment 1
Power plant smoke desulfurization by wet method sludge portion about 5kg is taken, 50% sulfuric acid after being ground into powder, is used, solution is heated to
80 degree, extraction time is 60min, and sludge gives over to next Leaching tests use.Supernatant takes out, and adds extract 10L, extractant
The ratio of P204, TBP and kerosene is 18:6:76, pH control 2.5 or so, after stirring 10min, and water is mutually arranged by stratification
Go out, add 2mol/L sulfuric acid as strippant in organic phase, 10min is stirred, water tank is taken out after standing.Add ammonium chloride
300g, precipitation is taken out, and in Muffle furnace, 500 degree of calcination 6h, obtain white powder.By experimental analysis, V2O5Purity be more than
95%.
Embodiment 2
Power plant smoke desulfurization by wet method sludge portion about 5kg is taken, 50% sulfuric acid after being ground into powder, is used, solution is heated to
60 degree, extraction time is 90min, and sludge gives over to next Leaching tests use.Supernatant takes out, and adds extract 10L, extractant
The ratio of P204, TBP and kerosene is 18:6:76, pH control 3 or so, after stirring 10min, and water is mutually arranged by stratification
Go out, add 2mol/L hydrochloric acid as strippant in organic phase, 10min is stirred, water tank is taken out after standing.Add ammonium chloride
300g, precipitation is taken out, and in Muffle furnace, 500 degree of calcination 6h, obtain white powder.By experimental analysis, V2O5Purity be more than
95%.
Embodiment 3
Power plant smoke desulfurization by wet method sludge portion about 5kg is taken, 50% sulfuric acid after being ground into powder, is used, solution is heated to
90 degree, extraction time is 10min, and sludge gives over to next Leaching tests use.Supernatant takes out, and adds extract 10L, extractant
The ratio of P204, TBP and kerosene is 18:6:76, pH control 1 or so, after stirring 10min, and water is mutually arranged by stratification
Go out, add 2mol/L sulfuric acid as strippant in organic phase, 10min is stirred, water tank is taken out after standing.Add ammonium chloride
300g, precipitation is taken out, and in Muffle furnace, 500 degree of calcination 6h, obtain white powder.By experimental analysis, V2O5Purity be more than
90%.
Embodiment 4
Power plant smoke desulfurization by wet method sludge portion about 5kg is taken, 50% sulfuric acid after being ground into powder, is used, solution is heated to
70 degree, extraction time is 60min, and sludge gives over to next Leaching tests use.Supernatant takes out, and adds extract 10L, extractant
The ratio of P204, TBP and kerosene is 18:6:76, pH control 4 or so, after stirring 10min, and water is mutually arranged by stratification
Go out, add 2mol/L hydrochloric acid as strippant in organic phase, 10min is stirred, water tank is taken out after standing.Add ammonium chloride
300g, precipitation is taken out, and in Muffle furnace, 500 degree of calcination 6h, obtain white powder.By experimental analysis, V2O5Purity be more than
94%.
Embodiment 5
Power plant smoke desulfurization by wet method sludge portion about 5kg is taken, 50% sulfuric acid after being ground into powder, is used, solution is heated to
80 degree, extraction time is 30min, and sludge gives over to next Leaching tests use.Supernatant takes out, and adds extract 10L, extractant
The ratio of P204, TBP and kerosene is 18:6:76, pH control 2 or so, after stirring 10min, and water is mutually arranged by stratification
Go out, add 2mol/L sulfuric acid as strippant in organic phase, 10min is stirred, water tank is taken out after standing.Add ammonium chloride
300g, precipitation is taken out, and in Muffle furnace, 500 degree of calcination 6h, obtain white powder.By experimental analysis, V2O5Purity be more than
92%.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned embodiment, also includes
By the constituted technical scheme of above technical characteristic any combination.It should be pointed out that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (8)
1. the technique for reclaiming precious metal vanadium in a kind of flue gas desulphurization sludge, it is characterised in that mainly include the following steps that,
（1）Metallic element in spray liquid is enriched with by way of precipitation, is formed precipitation and is reclaimed；
Sediment is with sludge while pre-processed；
（2）By step（1）In sediment and sludge crush, grinding；
（3）By step（2）In sludge raw material crush after add acid leaching agent to carry out mixing leaching, after reaction 10-90min,
Until separation of solid and liquid, supernatant remains neutralization to standing, sinks mud filtration washing, as general fixed-end forces；
（4）By step（3）In leachate carry out ion exchange, adjust pH value of solution in 1-4, add P204, TBP and kerosene conduct
Extractant, in Extraction solvent containing vanadium ion；
（5）By step（4）In organic phase solution carry out back extraction process, add inorganic acid as strippant, obtain highly concentrated
The aqueous solution containing vanadium of degree；
（6）To step（5）In the aqueous solution containing vanadium in add ammonium chloride, in solution pentavalent vanadium with ammonium poly-vanadate form precipitate, mistake
Filter precipitation；
（7）To step（6）Middle pentavalent vanadium precipitation carries out calcination process, and vanadic anhydride is obtained.
2. the technique for reclaiming precious metal vanadium in flue gas desulphurization sludge as claimed in claim 1, it is characterised in that the step
（1）Sludge used by middle recovery vanadium is flue gas desulphurization sludge, and the spray liquid is desulfurization spray liquid.
3. the technique for reclaiming precious metal vanadium in flue gas desulphurization sludge as claimed in claim 1, it is characterised in that the step
（3）In acid leaching agent be sulfuric acid.
4. the technique for reclaiming precious metal vanadium in flue gas desulphurization sludge as claimed in claim 1, it is characterised in that the step
（3）Middle control mixeding liquid temperature is 60-90 degree, and the reaction time is 30-60min.
5. the technique for reclaiming precious metal vanadium in flue gas desulphurization sludge as claimed in claim 1, it is characterised in that step（4）
The proportioning of middle extractant is 18 for the volume ratio of P204, TBP and kerosene:6:76, and control reaction pH between 2-3.
6. the technique for reclaiming precious metal vanadium in flue gas desulphurization sludge as claimed in claim 1, it is characterised in that the step
（5）The solvent selection of middle reversed phase extraction is hydrochloric acid or the sulfuric acid of 2mol/L.
7. the technique for reclaiming precious metal vanadium in the flue gas desulphurization sludge as described in claim 1 or 5, it is characterised in that described
Step（5）The solvent selection of middle reversed phase extraction is the hydrochloric acid of 2mol/L, and consumption is calculated with the amount of solute, is the 3- containing vanadium quality
5 times.
8. the technique for reclaiming precious metal vanadium in flue gas desulphurization sludge as claimed in claim 1, it is characterised in that step（3）
In extraction be stage extraction, the process route of multilevel leaching is, will the pressed powder that is obtained in pretreatment process leach after consolidate
Liquid is separated, and neutralization sent to by supernatant；Lower floor's sludge wouldn't be discharged；Now described lower floor's sludge is entered with the leaching liquid of new configuration
Row leaches for second, and leaching is stood after finishing, and supernatant pumps out storage, for the first time leaching of next group charging；To press filtration
Add leaching agent and conditioning agent in the filtrate of acquisition and mud cake cleaning solution, new leaching liquid is configured, for the of next group charging
Secondary leaching；So repeatedly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610669558.8A CN106480328A (en) | 2016-08-16 | 2016-08-16 | A kind of technique for reclaiming precious metal vanadium in flue gas desulphurization sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610669558.8A CN106480328A (en) | 2016-08-16 | 2016-08-16 | A kind of technique for reclaiming precious metal vanadium in flue gas desulphurization sludge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106480328A true CN106480328A (en) | 2017-03-08 |
Family
ID=58273263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610669558.8A Pending CN106480328A (en) | 2016-08-16 | 2016-08-16 | A kind of technique for reclaiming precious metal vanadium in flue gas desulphurization sludge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106480328A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746161A (en) * | 2017-09-12 | 2018-03-02 | 大唐环境产业集团股份有限公司 | A kind of chemical extraction method and system of desulfurization wastewater sludge heavy-metal |
| WO2021003789A1 (en) * | 2019-07-09 | 2021-01-14 | 中国科学院城市环境研究所 | Resource utilization method of sludge pyrolysis biochar |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289705A (en) * | 2007-04-20 | 2008-10-22 | 北京化工大学 | Process for abstracting vanadium from iron-smelting waste slag of vanadium -containing iron ore |
| CN101503762A (en) * | 2009-03-20 | 2009-08-12 | 湖南大学 | Desulphurization and vanadium extraction technique for calcinated vanadium ore |
| CN102011010A (en) * | 2009-09-07 | 2011-04-13 | 杨秋良 | Method for totally extracting vanadium, gallium and scandium by using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium |
| CN103952560A (en) * | 2014-04-23 | 2014-07-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium from vanadium slag |
| CN104164571A (en) * | 2014-08-12 | 2014-11-26 | 东北大学 | Method for recovering valuable metal elements in converter vanadium slag |
-
2016
- 2016-08-16 CN CN201610669558.8A patent/CN106480328A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289705A (en) * | 2007-04-20 | 2008-10-22 | 北京化工大学 | Process for abstracting vanadium from iron-smelting waste slag of vanadium -containing iron ore |
| CN101503762A (en) * | 2009-03-20 | 2009-08-12 | 湖南大学 | Desulphurization and vanadium extraction technique for calcinated vanadium ore |
| CN102011010A (en) * | 2009-09-07 | 2011-04-13 | 杨秋良 | Method for totally extracting vanadium, gallium and scandium by using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium |
| CN103952560A (en) * | 2014-04-23 | 2014-07-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium from vanadium slag |
| CN104164571A (en) * | 2014-08-12 | 2014-11-26 | 东北大学 | Method for recovering valuable metal elements in converter vanadium slag |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746161A (en) * | 2017-09-12 | 2018-03-02 | 大唐环境产业集团股份有限公司 | A kind of chemical extraction method and system of desulfurization wastewater sludge heavy-metal |
| WO2021003789A1 (en) * | 2019-07-09 | 2021-01-14 | 中国科学院城市环境研究所 | Resource utilization method of sludge pyrolysis biochar |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103316907B (en) | Heavy-metal-polluted site soil leaching remediation method and device | |
| CN106868307B (en) | A kind of comprehensive utilization process of pyrite cinder arsenic removal enrichment gold and silver | |
| CN101314818B (en) | Golden shifting process of biological oxidation-torrefaction-cyanidation | |
| CN101274778B (en) | Method for extracting vanadic anhydride from stone coal | |
| CN104984992B (en) | A kind of method that heavy-metal contaminated soil press filtration elution is repaired | |
| Binnemans et al. | The twelve principles of circular hydrometallurgy | |
| CN104831075A (en) | Method for separating and purifying vanadium and molybdenum of waste vanadium-molybdenum SCR (selective catalytic reduction) catalyst | |
| CN102107208A (en) | Method for restoring heavy metal polluted soil in mine field | |
| Shadrunova et al. | A process for advanced recycling of water originating from mining operations, with metal recovery | |
| CN106480328A (en) | A kind of technique for reclaiming precious metal vanadium in flue gas desulphurization sludge | |
| CN107815554A (en) | The gold extracting method of high antimony golden ore concentrate hard to treat containing arsenic | |
| CN100998914A (en) | Treatment method of low grade titanium-riched material chlorination dust collecting slag | |
| CN106215863B (en) | A kind of heavy metal absorbent of purification diluted sulfric acid and its application | |
| CN102583598A (en) | Cycle production method for recovering zinc from beneficiation wastewater of high leaching slag | |
| Li et al. | A review on the treatments and minimization techniques of stainless steel pickling sludge | |
| Hakeem et al. | Investigations into the closed-loop hydrometallurgical process for heavy metals removal and recovery from biosolids via mild acid pre-treatment | |
| Adams et al. | Cyanide recovery by tailings washing and pond stripping | |
| CN102295969B (en) | Method for simultaneous removal of sulfur and arsenic in sulfur coal with high removal rate and little time | |
| CN103540751A (en) | Method for treating titanium tetrachloride refining tailings | |
| CN104876365A (en) | High-concentration cyanogen-contained tailing slurry treatment method for gold industry | |
| CN107326178B (en) | A kind of method that tail gas recycle utilizes during Zinc Hydrometallurgy Residue reducing leaching | |
| CN105439345A (en) | Recycling method for removing lead from acid cleaning waste liquid of lead-containing steel wire ropes | |
| CN102268538A (en) | Boiling furnace device used for roasting nickel-molybdenum concentrate and method for roasting nickel-molybdenum concentrate | |
| YANG et al. | Zinc removal from hyperaccumulator Sedum alfredii Hance biomass | |
| CN107841626B (en) | A kind of method of zinc hydrometallurgy kiln slag and waste acid Combined Treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170308 |