CN108118154A - A kind of method using APT waste residues recycling rare metal - Google Patents
A kind of method using APT waste residues recycling rare metal Download PDFInfo
- Publication number
- CN108118154A CN108118154A CN201711410906.0A CN201711410906A CN108118154A CN 108118154 A CN108118154 A CN 108118154A CN 201711410906 A CN201711410906 A CN 201711410906A CN 108118154 A CN108118154 A CN 108118154A
- Authority
- CN
- China
- Prior art keywords
- solution
- rare metal
- waste residues
- tungsten
- apt
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a kind of method using APT waste residues recycling rare metal, copper is contained by what is generated during ammonium paratungstate production by grater, the waste residue of tungsten and molybdenum is levigate, slag charge containing copper carries out soda boiling leaching, wherein alkali is NaOH, when the concentration of alkali is in 35 45g/L, stop adding alkali, it boils and keeps the temperature 1.5 2.5h, copper sulfide is obtained after washing, molten cryolitic is solvent, aluminium oxide is solute, using carbon body as anode, molten aluminum is as cathode, after being passed through powerful direct current, add in the material for needing to purify, it need to constantly measure and adjust pH value with acid adding, generate MoS3Solution after precipitation is black-and-blue, and the MoS of brown can be observed3Precipitation.By the recycling to Copper Slag, tungsten and molybdenum element, the economic benefit of enterprise can be improved, very small for the pollution of environment, practical performance is excellent, novel in design, is a kind of good innovation scheme.
Description
Technical field
The present invention relates to metal purification technical field, more particularly to a kind of side using APT waste residues recycling rare metal
Method.
Background technology
Melting is to dissolve old metal material and other auxiliary materials input heating furnace and quenched, and furnace charge is in high temperature
Certain physics, chemical change, output crude metal or the fire of metal enrichment object and clinker occur for material in (1300-1600K) stove
Method metallurgical process, metallic copper, tungsten and molybdenum are important non-ferrous metals, and wherein tungsten and molybdenum also exists in addition to being used to manufacture steel alloy
Other aspects such as chemical industry widely use.
Cupric tungsten waste residue is mainly manufacturer's progress list that molybdenum has been sold in the form of byproduct in APT production technologies
One molybdenum recycling, significantly wastes copper and tungsten or waste residue is again returned to ball-milling technology, taken with tungsten concentrate
With processing.The shortcomings that processing method is substantial amounts of impurity element in waste residue, to the wound of resin in postorder ion-exchange process
Evil is bigger, be easy to cause resin poison, brings the economic loss of bigger, and adds labor intensity, is unfavorable for molybdenum and copper
Effectively recycling, there is deficiencies, it is impossible to the actual demand of society.
A kind of in conclusion the defects of for the prior art, it is accordingly required in particular to side using APT waste residues recycling rare metal
Method, to solve the deficiencies in the prior art.
The content of the invention
For existing existing deficiency, actual use is influenced, the present invention proposes a kind of rare using the recycling of APT waste residues
The method of metal, it is novel in design, to the rate of recovery for improving metal, improve benefit and reduce environmental pollution, it can be from APT waste residues
Recycle rare metal.
To achieve these goals, technical scheme is as follows：
A kind of method using APT waste residues recycling rare metal will be generated by grater during ammonium paratungstate production
The waste residue containing copper, tungsten and molybdenum it is levigate, slag charge containing copper carries out soda boiling leaching, and wherein alkali is NaOH, when the concentration of alkali exists
During 35-45g/L, stop adding alkali, boil and keep the temperature 1.5-2.5h, copper sulfide is obtained after washing, molten cryolitic is solvent, oxidation
Aluminium is solute, and using carbon body as anode, molten aluminum is as cathode, after being passed through powerful direct current, adds in the material for needing to purify,
It need to constantly measure and adjust pH value with acid adding, generate MoS3Solution after precipitation is black-and-blue, and the MoS of brown can be observed3It is heavy
It forms sediment, is separated by filtration to obtain containing MoS afterwards3Slag charge and tungstic acid, the HCl of 3-5mol can also be added in by solution ph
2.5-3 is transferred to, solid-liquid separator receives from slag charge and the aqueous solution of tungstic acid discharge and separates metallic, works as mixed solution
Temperature be 80 DEG C, and pH value be 3 when, be stirred for 1h, when mixed solution becomes light blue, then keep the temperature 1.5h, sediment analysis
Go out, slurries filtration, obtain ammonium molybdate filter cake.
Further, tungstic acid of the invention is supplied to anode and the reaction compartment between the cathode of the anode
When middle, receive from external aqueous solution, then reduced on the cathode surface and extract the metal ion in aqueous solution.
In mixed solution of the present invention in 150 DEG C of temperature, pressure 0.5MPa is 1 with liquid-solid ratio:1, it is added to hydrogen
Sodium hydroxide solution is sized mixing, and concentration >=500g/L of sodium hydroxide solution, in the case of stirring 1 is small in autoclave pressure, tungsten
Leaching rate is 85.2%, and the mother liquor generated after condensing crystallizing returns to leaching process and recycles.
It is -120 mesh >=95% in the levigate granularity of waste residue of the present invention, the acidolysis in the state of 90-95 DEG C is used
The concentration of nitric acid is 8-10wt%, and the solid-liquid mass ratio of acid hemolysis process is 1:3, reaction time 2.5h.
Further, the tungstic acid makees precipitating transforming agent using ammonium hydrogen carbonate, will convert tungsten in nitric acid solution mineral aggregate
When enter solution other precipitation by metallic ion recycling.
It is filtered in the slurry of the present invention using vacuum filter or line with rubber centrigugal swing dryer.
The beneficial effects of the invention are as follows：It is simple in structure, it can realize while three kinds of APT Copper Slags, tungsten and molybdenum metal members
Element efficiently reduces the wasting of resources so as to realize, improves the utilization rate of resource, by Copper Slag, tungsten and molybdenum element
Recycling, the economic benefit of enterprise can be improved, very small for the pollution of environment, practical performance is excellent, novel in design, is one
The good innovation scheme of kind.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
A kind of method using APT waste residues recycling rare metal will be generated by grater during ammonium paratungstate production
The waste residue containing copper, tungsten and molybdenum it is levigate, slag charge containing copper carries out soda boiling leaching, and wherein alkali is NaOH, when the concentration of alkali exists
During 35-45g/L, stop adding alkali, boil and keep the temperature 1.5-2.5h, copper sulfide is obtained after washing, molten cryolitic is solvent, oxidation
Aluminium is solute, and using carbon body as anode, molten aluminum is as cathode, after being passed through powerful direct current, adds in the material for needing to purify,
It need to constantly measure and adjust pH value with acid adding, generate MoS3Solution after precipitation is black-and-blue, and the MoS of brown can be observed3It is heavy
It forms sediment, is separated by filtration to obtain containing MoS afterwards3Slag charge and tungstic acid, the HCl of 3-5mol can also be added in by solution ph
2.5-3 is transferred to, solid-liquid separator receives from slag charge and the aqueous solution of tungstic acid discharge and separates metallic, works as mixed solution
Temperature be 80 DEG C, and pH value be 3 when, be stirred for 1h, when mixed solution becomes light blue, then keep the temperature 1.5h, sediment analysis
Go out, slurries filtration, obtain ammonium molybdate filter cake.Tungstic acid is supplied to anode and anti-between the cathode of the anode
When answering in space, receive from external aqueous solution, then reduced on the cathode surface and extract the metal in aqueous solution
Ion.Mixed solution is 1 with liquid-solid ratio in 150 DEG C of temperature, pressure 0.5MPa:1, it is added to sodium hydroxide solution and sizes mixing, and hydrogen
Concentration >=500g/L of sodium hydroxide solution, in the case of stirring 1 is small in autoclave pressure, the leaching rate of tungsten is 85.2%, concentration
The mother liquor generated after crystallization returns to leaching process and recycles.The granularity that waste residue is levigate is -120 mesh >=95%, at 90-95 DEG C
Acidolysis under state, the concentration of nitric acid used is 8- 10wt%, and the solid-liquid mass ratio of acid hemolysis process is 1:3, the reaction time is
2.5h.Tungstic acid makees precipitating transforming agent using ammonium hydrogen carbonate, will enter the other of solution when tungsten is converted in nitric acid solution mineral aggregate
Precipitation by metallic ion recycles.Slurry is filtered using vacuum filter or line with rubber centrigugal swing dryer.
Scruff is stabilizer by reducing agent, nonmetallic mineral of lignite, through reduce it is firm after, with sulfuric acid leaching tin, then pass through
Liquid phase oxidation, dehydrate stannic oxide or directly Sulphuric acid stannous, change into stannous chloride, sodium stannate product, produce
Exhaust gas, the waste liquid generated in the process uses corresponding last handling process, and practical performance is excellent.It is simple in structure, it can realize while APT
Three kinds of Copper Slag, tungsten and molybdenum metallic elements, efficiently reduce the wasting of resources so as to realize, improve the utilization rate of resource,
By the recycling to Copper Slag, tungsten and molybdenum element, the economic benefit of enterprise can be improved, it is unusual for the pollution of environment
Small, practical performance is excellent, novel in design, is a kind of good innovation scheme.
It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, above-described embodiment and explanation
Merely illustrating the principles of the invention described in book, it is of the invention without departing from the spirit and scope of the present invention also to have respectively
Kind changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by
Appended claims and its equivalent define.
Claims (6)
- A kind of 1. method using APT waste residues recycling rare metal, it is characterised in that：By grater by ammonium paratungstate production mistake The waste residue containing copper, tungsten and molybdenum generated in journey is levigate, and the slag charge containing copper carries out soda boiling leaching, and wherein alkali is NaOH, works as alkali Concentration in 35-45g/L, stop plus alkali, boil and keep the temperature 1.5-2.5h, copper sulfide is obtained after washing, molten cryolitic is Solvent, aluminium oxide are solutes, and using carbon body as anode, molten aluminum is as cathode, and after being passed through powerful direct current, adding in needs to carry Pure material need to be measured constantly and adjust pH value with acid adding, generate MoS3Solution after precipitation is black-and-blue, and brown can be observed MoS3Precipitation, is separated by filtration to obtain containing MoS afterwards3Slag charge and tungstic acid, can also add in 3-5mol HCl will Solution ph is transferred to 2.5-3, and solid-liquid separator receives from slag charge and the aqueous solution of tungstic acid discharge and separates metallic, when Mixed solution temperature be 80 DEG C, and pH value be 3 when, be stirred for 1h, when mixed solution becomes light blue, then keep the temperature 1.5h, Sediment is precipitated, and slurries filtration, obtains ammonium molybdate filter cake.
- 2. a kind of method using APT waste residues recycling rare metal according to claim 1, it is characterised in that：Tungstic acid When being supplied in anode and reaction compartment between the cathode of the anode, receive from external aqueous solution, then It is reduced on the cathode surface and extracts the metal ion in aqueous solution.
- 3. a kind of method using APT waste residues recycling rare metal according to claim 1, it is characterised in that：Mixed solution In 150 DEG C of temperature, pressure 0.5MPa is 1 with liquid-solid ratio:1, it is added to sodium hydroxide solution and sizes mixing, and sodium hydroxide solution Concentration >=500g/L, in the case of stirring 1 is small in autoclave pressure, the leaching rate of tungsten is 85.2%, is generated after condensing crystallizing Mother liquor returns to leaching process and recycles.
- 4. a kind of method using APT waste residues recycling rare metal according to claim 1, it is characterised in that：Waste residue is levigate Granularity for -120 mesh >=95%, the acidolysis in the state of 90-95 DEG C, the concentration of nitric acid used is 8-10wt%, acid hemolysis process Solid-liquid mass ratio be 1:3, reaction time 2.5h.
- 5. a kind of method using APT waste residues recycling rare metal according to claim 1, it is characterised in that：Tungstic acid Precipitating transforming agent is made using ammonium hydrogen carbonate, other precipitation by metallic ion that solution is entered when tungsten is converted in nitric acid solution mineral aggregate are returned It receives.
- 6. a kind of method using APT waste residues recycling rare metal according to claim 1, it is characterised in that：Slurry uses Vacuum filter or the filtering of line with rubber centrigugal swing dryer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711410906.0A CN108118154A (en) | 2017-12-23 | 2017-12-23 | A kind of method using APT waste residues recycling rare metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711410906.0A CN108118154A (en) | 2017-12-23 | 2017-12-23 | A kind of method using APT waste residues recycling rare metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108118154A true CN108118154A (en) | 2018-06-05 |
Family
ID=62231390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711410906.0A Pending CN108118154A (en) | 2017-12-23 | 2017-12-23 | A kind of method using APT waste residues recycling rare metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108118154A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109987880A (en) * | 2019-02-25 | 2019-07-09 | 杨帮燕 | A kind of cracking resistance fiberglass asphalt tile |
| CN110735052A (en) * | 2019-10-16 | 2020-01-31 | 清远市恒德环保科技有限公司 | Method for enriching tungsten in low-grade APT slag |
| CN115109931A (en) * | 2022-06-21 | 2022-09-27 | 厦门钨业股份有限公司 | Method for recovering multiple metals from tungsten-molybdenum waste residue |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103358A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering metal by use of APT (ammonium paratungstate) waste slag |
| CN103103360A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering copper, tungsten and molybdenum by use of APT (ammonium paratungstate) waste slag |
| CN103484671A (en) * | 2013-08-25 | 2014-01-01 | 云南锡业集团有限责任公司研究设计院 | Method for separating tungsten and tin from tungsten/tin-containing concentrate |
| CN103725879A (en) * | 2013-12-24 | 2014-04-16 | 戴元宁 | Method for producing tungsten and tin chemical products through chemical metallurgical separation of tungsten-tin paragenic ore |
| CN105849318A (en) * | 2013-12-23 | 2016-08-10 | 韩国地质资源研究院 | Metal recovery reactor and metal recovery system |
-
2017
- 2017-12-23 CN CN201711410906.0A patent/CN108118154A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103358A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering metal by use of APT (ammonium paratungstate) waste slag |
| CN103103360A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering copper, tungsten and molybdenum by use of APT (ammonium paratungstate) waste slag |
| CN103484671A (en) * | 2013-08-25 | 2014-01-01 | 云南锡业集团有限责任公司研究设计院 | Method for separating tungsten and tin from tungsten/tin-containing concentrate |
| CN105849318A (en) * | 2013-12-23 | 2016-08-10 | 韩国地质资源研究院 | Metal recovery reactor and metal recovery system |
| CN103725879A (en) * | 2013-12-24 | 2014-04-16 | 戴元宁 | Method for producing tungsten and tin chemical products through chemical metallurgical separation of tungsten-tin paragenic ore |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109987880A (en) * | 2019-02-25 | 2019-07-09 | 杨帮燕 | A kind of cracking resistance fiberglass asphalt tile |
| CN110735052A (en) * | 2019-10-16 | 2020-01-31 | 清远市恒德环保科技有限公司 | Method for enriching tungsten in low-grade APT slag |
| CN110735052B (en) * | 2019-10-16 | 2021-08-24 | 清远市恒德环保科技有限公司 | Method for enriching tungsten in low-grade APT slag |
| CN115109931A (en) * | 2022-06-21 | 2022-09-27 | 厦门钨业股份有限公司 | Method for recovering multiple metals from tungsten-molybdenum waste residue |
| CN115109931B (en) * | 2022-06-21 | 2023-12-08 | 厦门钨业股份有限公司 | Method for recycling multiple metals from tungsten-molybdenum waste residues |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020102180A4 (en) | Method for leaching manganese from electrolytic manganese anode slag | |
| CN102956936B (en) | Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile | |
| CN104498718A (en) | Method for treating hard alloy grinding material | |
| CN103290223B (en) | Comprehensive recovery method for multiple metals of waste catalyst | |
| CN101648702B (en) | Method for preparing tellurium dioxide by using crude tellurium as raw material | |
| CN103911514B (en) | The recovery and treatment method of scrap hard alloy grinding material | |
| CN104911359A (en) | Process method for extracting cobalt and nickel from manganese waste slag | |
| CN112831660B (en) | Process for comprehensively utilizing molybdenum ore leaching slag | |
| CN110578058B (en) | Method for recovering titanium, tungsten, vanadium and silicon in waste catalyst for coal-fired flue gas denitration | |
| CN108118154A (en) | A kind of method using APT waste residues recycling rare metal | |
| US20240063455A1 (en) | Method for recovering valuable metals from spent lithium ion batteries | |
| CN102876896B (en) | Method for recovering vanadium by decomposing vanadium extraction tailings by using sodium hydroxide solution | |
| CN115259230B (en) | Impurity removal method for producing trimanganese tetroxide for soft magnetism from electrolytic manganese anode mud by utilizing molten acid leaching | |
| CN115011799B (en) | Method for producing soft magnetic trimanganese tetroxide by using electrolytic manganese anode slime | |
| CN112708786A (en) | Method for recycling scandium from aluminum-scandium alloy target material waste | |
| CN108707753B (en) | Process for recovering rare earth-containing waste material by solvent extraction | |
| CN105197987A (en) | Separation method of PbO, PbSO4 and PbO2 mixture | |
| CN115784267A (en) | Process method for recovering lithium iron phosphorus from waste lithium iron phosphate anode material | |
| CN116334410A (en) | Method for separating lithium from lithium-containing electrolyte waste residues in aluminum electrolysis | |
| CN115652077A (en) | Method for selectively separating and recovering lithium and manganese from waste lithium manganate battery | |
| CN111304446A (en) | Method for comprehensively utilizing high-temperature alloy waste through segmented leaching | |
| CN109182868B (en) | Low-impurity vanadium-aluminum alloy and preparation method thereof | |
| CN111394569A (en) | Roasting method for producing vanadium pentoxide | |
| CN114369729B (en) | Process for removing potassium from leaching solution by utilizing lithium slag | |
| CN114525408B (en) | Method for combined treatment of waste lithium cobalt oxide anode material and tungsten-containing solid waste |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180605 |