CN108149018A - The recovery method of Ag in a kind of Bi systems superconducting line strips - Google Patents
The recovery method of Ag in a kind of Bi systems superconducting line strips Download PDFInfo
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- CN108149018A CN108149018A CN201711494494.3A CN201711494494A CN108149018A CN 108149018 A CN108149018 A CN 108149018A CN 201711494494 A CN201711494494 A CN 201711494494A CN 108149018 A CN108149018 A CN 108149018A
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- 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
- C22B7/007—Wet processes by acid leaching
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- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses the recovery method of Ag in a kind of Bi systems superconducting line strips, this method is：It first removes argentiferous or the Bi systems superconducting line strips of silver alloy degreases, after coating, then be heat-treated；It is then dissolved in concentrated nitric acid, evaporation, decomposition nitrate, the stirring ageing of whole plus water, filter in solution containing undecomposed silver nitrate, strontium nitrate, calcium nitrate, small part bismuth basic salt, concentrated hydrochloric acid generation silver nitride precipitation is added dropwise into solution, avoid light place is aged, and filtering precipitation is transferred in container, add in concentrated ammonia liquor covering sediment, it is heated to boiling, hydrazine hydrate is slowly added under stirring, until being generated there is no sediment, filtering, it is dry, sponge silver powder of the quality purity more than 99.95% is obtained, and the rate of recovery is as many as 99%.Silver-colored recycling in the suitable single of the present invention, multicore Bi systems argentiferous jacket can obtain mass, purity height, the uniform tiny sponge silver powder of crystal grain.
Description
Technical field
The invention belongs to silver recovery technical fields, and in particular to the recovery method of Ag in a kind of Bi systems superconducting line strips.
Background technology
Superconductor is the basis of superconductor technology application, with NbTi, Nb3Sn is for the low temperature superconducting material of representative and with MgB2
Medium temperature superconductor and BSCCO (Bi systems), the high temperature superconducting materia that YBCO (Y systems) is representative for representative have been enter into recent years
Or partly enter the pattern of industrialization, it is widely used in the fields such as electric power, communication, national defence, medical treatment, there is answering for more high added value
Use prospect.The ripe application of these technologies, experienced a longer R＆D process early period, put into a large amount of human and material resources,
Financial resources.Bi systems oxide superconductor is found in 1986, it in the application advantage of liquid nitrogen 77K warm areas by various countries scientific worker
Many energy has been poured into, has been done in crystal structure, characteristic electron, preparation method, mechanical performance, A.C.power loss, insulation etc.
A large amount of detailed researchs, China was in 2005《National Program for Medium-to Long-term Scientific and Technological Development》(2006-2020)
High temperature superconductor technology is asserted one of three cutting edge technologies of new material technology (smart material and structure technology, high-temperature superconductor skill
Art and efficient energy material technology), foreign countries, which have also established the company, carries out large-scale production (ASC companies of the U.S., SUMITOMO CHEMICAL public affairs
Department, German Trithor companies, annual output are more than 5000Km, are worth 200,000,000 dollars).
In above-mentioned high temperature superconducting oxide, Bi-2223 and Bi-2212 are using silver-colored or silver alloy as sheath material prepares line
Band, based on study, study its wire strip into phase mechanism, the preparation of front axle shell, the processing of wire strip and heat at
The A.C.power loss of reason, metal alloy sheath material, the flux pinning of wire strip, wire strip；As its mass of engineering Application Research
Preparation Technique of Powders, the thermal insulation coating technology of long band, finished product long band electrical isolation paint technology, improve band mechanical performance
WIT technologies.The research and development of each technology, which are required for preparing sample, to be tested, the feasibility of judgment technology, therefore is left a large amount of
Research and development sample, and in sample more than 70% be all silver, remaining is superconducting phase.Silver is noble metal, is prepared into silver-colored pipe price higher,
In order to reduce R＆D costs and loss, the silver wire band discarded after recycling purification experiment is necessary, the silver after purification
It can continue as scientific research, industrial production plays a role.
The purification of general Oily wastewater has pyrogenic process and wet method, and pyrometallurgical smelting temperature height (1000-1100 DEG C), energy consumption is big, into
This height need to add fluxing agent to improve the mobility of material, but satisfied fluxing effect is actually not achieved, and material residue is difficult to more effectively
Separation, the rate of recovery are relatively low.Wet-process purification method is more, and including electrolysis and chemical purification, the electrolytic recovery period is long, labor intensity
Greatly, scientific research sample complexity is not easy stationary electrolysis parameter, and the rate of recovery is indefinite.Chemical purification need to be suitble to according to sample into component selections
Reagent, some need high-temperature calcination or heating in vacuum after these reagents and silver reaction, some adds in aqueous slkali into AgCl,
But it needs just to can guarantee that it is unlikely to hydrolysis life in acidic environment for dissolving for a small amount of bismuth in the solution, when starting washing
Into precipitation, it is otherwise blended in the reduction purity influenced in silver chlorate thereafter.But the chemical method scope of application is wider, according to the spy of element
Property easily adjust preparation parameter, be also particularly suitable for small lot laboratory recycling, have flexible and changeable means.
Bi system high-temperature superconductings oxide include Bi-2223, Bi-2212, the former contain 4-5 kinds chemical element (Bi, Pb, Sr,
Ca, Cu), above-mentioned other 4 kind elements of the latter other than Pb.In order to improve pinning performance, some other members are also usually adulterated
Element.For sheath material other than fine silver jacket, also exploitation has AgMg alloys, AgAu alloys etc., therefore, silver-colored change in the presence of multielement
In method purification process, the control of temperature is a technological difficulties in recovery technology, same recovery technology, containing different
Element, each element interfere with each other, each have their own reaction characteristics, hold bad so that the purity of final silver cannot be guaranteed.
It was found that, when decomposing Bi system's superconducting line strips using nitric acid, the generated nitrate of reaction to temperature extremely
Sensitivity, when starting dissolving, five kinds or four kinds of elements first generate nitrate, with gradually rising for temperature, different nitrate from
Hydrolysis, decomposed, to resolve into completely oxide or simple substance experience temperature range it is larger, between 50 DEG C~700 DEG C, especially
It is bismuth nitrate, and basic salt (Bi is generated at 50 DEG C~80 DEG C6O6)2(NO3)11(OH).6H2O is precipitated, and also part salt dissolves,
77 DEG C~130 DEG C generate [Bi again6O6](NO3)6.3H2O, 400 DEG C~500 DEG C resolve into bismuth oxide.It is decomposed completely according to high temperature
During into oxide, silver is blended in simple substance or with silver oxide in oxide powder, and silver-colored simple substance can not be gone out with liquid phase separation.Text at present
Offering the silver recovery technology of record mainly has fixing solution, slag, metal alloy etc., and using silver or silver alloy as the Bi of sheath material
Series superconducting material, the interior recovery technology containing 30% or so high temperature superconducting oxide powder are also rarely reported.
Invention content
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, to provide a kind of superconduction of Bi systems
The recovery method of Ag in wire strip.The rate of recovery of the metal Ag of recovery method recycling is not less than 99%, and purity is up to
More than 99.95%, it is the uniform tiny sponge silver of crystal grain, and 18 kinds of impurity elements of spectral detection of the sponge silver recycled exist
0.001% hereinafter, wherein Bi is less than 0.0003wt%, and ICP detections Sr is less than 0.001wt%.
In order to solve the above technical problems, the technical solution adopted by the present invention is：Ag's returns in a kind of Bi systems superconducting line strips
Receiving method, which is characterized in that the recovery method includes the following steps：
Step 1: cut short Bi systems superconducting line strips, Bi systems superconducting line strips are to utilize single made of argentiferous jacket or more
Core Bi systems superconducting line strips；
Step 2: first remove step 1 in cut short after Bi systems superconducting line strips face coat and greasy dirt, then using go from
Sub- water cleans the Bi systems superconducting line strips after degreasing, and finally using dehydration of alcohol and dries；
It is 10 in vacuum degree Step 3: the Bi systems superconducting line strips after being dried in step 2 are placed in vacuum drying oven-3Pa、
Temperature is heat-treated 2h~4h under conditions of being 400 DEG C~600 DEG C, the gas adsorbed inside removal Bi systems superconducting line strips, moisture,
Stress；
Step 4: by step 3 be heat-treated after Bi systems superconducting line strips be added in concentrated nitric acid and be heated to 150 DEG C~
155 DEG C of heat preservations, until obtain yellow gum object, then add concentrated nitric acid and be heated to 160 DEG C~200 DEG C heat preservations, until
To dark brown jelly, then distilled water is added to stir evenly, 8h~10h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered to the precipitated liquid obtained in step 4, filter cake and filtrate are obtained, then using deionized water
The filter cake is rinsed, until filter cake is in neutrality, the deionized water after rinsing filter cake is collected and is mixed with the filtrate, mixed
Liquid；
Step 6: mixed liquor described in first heating stepses five is to 80 DEG C~100 DEG C, then dense salt is added in into the mixed liquor
Acid carries out precipitation reaction (AgNO3+ HCl (dense)=AgCl ↓+HNO3), ageing 5h~8h is protected from light after the completion of reaction to be precipitated, then
It is filtered and washs, obtain silver chlorate filter cake, the silver chlorate filter cake is in neutrality；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction (AgCl+2NH completely3.H2O=Ag (NH3)2Cl+2H2O), two ammino silver solution of chlorination is generated, then heats chlorination diamino
It closes silver-colored solution and removes extra ammonium hydroxide, then be slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to boiling
Hydrazine hydrate carries out precipitation reaction (2Ag (NH3)2Cl+2N2H4.H2O=2Ag ↓+2NH4Cl+N2↑+4NH3↑+2H2O), until there is no
Until sediment generates, postcooling reaction solution is completed in reaction to be precipitated, it is last it is filtered, wash and be dried to obtain sponge silver.
The recovery method of Ag in a kind of above-mentioned Bi systems superconducting line strips, it is characterized in that：Bi systems superconducting line described in step 1
Band is Bi-2223 superconducting line strips or Bi-2212 superconducting line strips.
The recovery method of Ag in a kind of above-mentioned Bi systems superconducting line strips, it is characterized in that：Step 2 removes cuts in step 1
The detailed process of Bi systems superconducting line strips face coat and greasy dirt after short is：First by mass concentration be 22%~25% dense ammonia
Water and deionized water press 1：10 volume ratio is uniformly mixed, and is used further to impregnate Bi system's superconducting line strips until the coating on surface is molten
Solution, then be washed with deionized 4 times, finally remove the oil on Bi systems superconducting line strips surface using metal detergent immersion 30min
It is dirty.
The recovery method of Ag in a kind of above-mentioned Bi systems superconducting line strips, it is characterized in that：What is added in twice in step 4 is dense
The total volume of nitric acid is 1 times of the quality of Bi systems superconducting line strips, and the volume for adding in the deionized water is the Bi systems
The unit of 5 times of the quality of superconducting line strips, the total volume of the concentrated nitric acid and the volume of deionized water is mL, the Bi systems
The unit of the quality of superconducting line strips is g, and the mass concentration of the concentrated nitric acid is 68%.
The recovery method of Ag in a kind of above-mentioned Bi systems superconducting line strips, it is characterized in that：Using paving when being filtered in step 5
There is the glass funnel of filter paper and filter cloth；Using the cloth funnel for being covered with two layers of filter paper when being filtered in step 6.
The recovery method of Ag in a kind of above-mentioned Bi systems superconducting line strips, it is characterized in that：Concentrated hydrochloric acid described in step 6
Dosage adds in the concentrated hydrochloric acid of 350mL~400mL for Bi systems superconducting line strips described in every 500 grams of step 1, the concentrated hydrochloric acid
Mass concentration is 50%.
The recovery method of Ag in a kind of above-mentioned Bi systems superconducting line strips, it is characterized in that：Hydrazine hydrate described in step 7
Mass concentration is 50%~80%, the temperature 60 C of the drying.
The principle of the present invention：
The distinguishing feature of the present invention is exactly four kinds of elements (Bi, Sr, Ca, Cu) or five kinds of elements in Bi systems superconducting line strips
The silver or silver alloy co-dissolve of (Bi, Pb, Sr, Ca, Cu) and jacket generate nitrate in nitric acid, in the relatively low steaming of the present invention
It sends out at 150 DEG C~200 DEG C of temperature, dissolves superconductive oxide powder, 150 DEG C~155 DEG C of first stage stage by stage, low temperature ensures line
Net material all dissolvings in band, equably generate nitrate, 160 DEG C~200 DEG C of second stage, except the nitrate of Ag, Sr, Ca
It does not decompose, ageing will be dissolved in water when placing, and Pb, Cu, Bi respectively can be with basic salt, decomposed or partial hydrolysis
Form precipitate and be separated off in water, reduce the possibility with silver-colored coprecipitation that hydrochloric acid precipitation silver causes as far as possible, carry
The high purity of silver.
Nitrate once shows several phenomenons:Evaporate the AgNO that does not decompose but can dissolve in water3、Sr(NO3)2；Or evaporation regardless of
Solution but the Pb (NO that easily hydrolysis generation precipitates in water3)2；Do not decomposed less than 170 DEG C or 170 DEG C~200 DEG C under conditions of part
Cu (the NO of decomposition3)2, occur insoluble and dissolving two states in subsequent water；Or Bi (the NO of evaporation, decomposition3)3Again in water
Middle most of generation basic salt precipitation not soluble in water, while there may also be a small amount of basic salt and be dissolved in water.Therefore it needs
Raw material acidolysis temperature is controlled, prevents impurity element from mixing in the subsequent precipitation reaction of silver, reduction reaction, so as to cause carrying for silver
Purity reduces.
In order to realize the purpose of high-purity recycling silver, avoid more than other elements interference, the technical side that uses of the present invention
Case is：The Bi systems superconducting line strips surface of argentiferous is degreased, after coating first, in vacuum degree 10-3Under the conditions of Pa, it is heat-treated
Temperature is 400 DEG C~600 DEG C, gas, moisture, the stress adsorbed inside heat preservation 2~4h removal wire strips；Subsequent sample is dissolved in
In concentrated nitric acid, 150 DEG C~200 DEG C evaporation, decomposition part nitrate, whole plus water stirring 8~10h of ageing is filtered in acquired solution
Containing undecomposed silver nitrate, strontium nitrate, calcium nitrate, small part bismuth basic salt, toward molten under conditions of 80 DEG C~100 DEG C of heating
Concentrated hydrochloric acid generation silver nitride precipitation is added dropwise in liquid, avoid light place is aged 5~8h.Filtering precipitation, is transferred in container, adds in dense ammonia
Water covers sediment, is heated to boiling, is slowly added to hydrazine hydrate under stirring on a small quantity, until being generated there is no sediment, then
Precipitated to sponge silver, filtering, 60 DEG C of dryings obtain sponge silver powder of the quality purity more than 99.95%, and the rate of recovery not under
In 99%.
Compared with the prior art, the present invention has the following advantages：
1st, the method period of recycling Ag of the invention is short, and low energy consumption, and no high-end complex device is used in this method, while real
Test that operating process is simple, and the rate of recovery of metal Ag, not less than 99%, purity is up to more than 99.95%, is that crystal grain is even and fine
Small sponge silver.
2nd, the sponge silver recycled to the present invention is detected, and the mass content of 19 detected kind impurity element is extremely low,
Mass content of the mass content of middle Bi less than 0.0003%, Sr is less than 0.001%, solves to be difficult in current technology recovery scheme
Effectively reduce the mass content of Bi and Sr in the Ag of recycling.
3rd, method of the invention is particular for the Bi systems superconducting line strips design of argentiferous or silver alloy jacket, and passes through
The temperature of concentrated nitric acid acidolysis twice is controlled so as to which the metallic element in Bi systems superconducting line strips be controlled to enter in subsequent reaction solution
The problem of forming impurity, causing the purity of metal Ag not high.
4th, slag charge and resulting product can be easily separated, and slag charge can caused by the intermediate steps in recovery method of the present invention
It purifies repeatedly, the rate of recovery of silver can be improved.
Technical scheme of the present invention is described in further detail below by embodiment.
Specific embodiment
Embodiment 1
The method of the present embodiment recycling Ag includes the following steps：
Step 1: cut short the Bi-2223 single superconducting tapes of 500 grams of jackets containing fine silver；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating Bi-2223 singles superconducting tape until the coating on surface dissolves, then is washed with deionized 4 times, finally using gold
Belong to detergent and impregnate the greasy dirt that 30min removes Bi-2223 single superconducting tapes surface, cleaned after oily waste degradation using deionized water
Bi-2223 single superconducting tapes after degreasing finally using dehydration of alcohol and are dried；
Step 3: sample is placed into vacuum drying oven, vacuum degree reaches 10-3400 DEG C/4h heat treatments are warming up to after Pa；
Step 4: the Bi-2223 single superconducting tapes after being heat-treated in step 3 are added in the concentrated nitric acid of 250mL and added
Heat is to 150 DEG C of heat preservations, until obtaining yellow gum object, then adding the concentrated nitric acid of 250mL and being heated to 160 DEG C of heat preservations, directly
To dark brown jelly is obtained, then the distilled water of 2500mL is added to stir evenly, 8h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 80 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 5h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
400mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.97%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Sr are respectively less than 0.001%, and the mass content of impurity Ni, Si and Cu are
Mass content of the mass content of 0.001%, impurity B i less than 0.0003%, Zr is less than 0.002%.
Embodiment 2
The method of the present embodiment recycling Ag includes the following steps：
Step 1: cut short the Bi-2223 multi-core superconducting wire rods of 500 grams of argentiferous magnesium alloy jacket；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating Bi-2223 multi-core superconductings wire rod until the coating on surface dissolves, then is washed with deionized 4 times, finally using gold
Belong to detergent and impregnate the greasy dirt that 30min removes Bi-2223 multi-core superconducting wire rods surface, cleaned after oily waste degradation using deionized water
Bi-2223 multi-core superconducting wire rods after degreasing finally using dehydration of alcohol and are dried；
Step 3: the Bi-2223 multi-core superconducting wire rods after being dried in step 2 are placed in vacuum drying oven, it is in vacuum degree
10-3Pa, temperature are heat-treated 3h under conditions of being 500 DEG C；
Step 4: the Bi-2223 multi-core superconducting wire rods after being heat-treated in step 3 are added in the concentrated nitric acid of 250mL and added
Heat is to 150 DEG C of heat preservations, until obtaining yellow gum object, then adding the concentrated nitric acid of 250mL and being heated to 180 DEG C of heat preservations, directly
To dark brown jelly is obtained, then the distilled water of 2500mL is added to stir evenly, 9h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 90 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 7h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.97%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Sr are respectively less than 0.001%, and the mass content of impurity Ni, Si and Cu are
Mass content of the mass content of 0.001%, impurity B i less than 0.0003%, Zr is less than 0.002%.
Embodiment 3
The method of the present embodiment recycling Ag includes the following steps：
Step 1: cut short the Bi-2212 superconduction multi-filamentary tapes of 500 grams of argentiferous gold jackets；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating Bi-2212 superconductions multi-filamentary tape until the coating on surface is dissolved, then washed after being washed with deionized 4 times using metal
It washs agent and impregnates 30min and remove the greasy dirt on Bi-2212 superconduction multi-filamentary tapes surface, removal is cleaned using deionized water after oily waste degradation
Bi-2212 superconduction multi-filamentary tapes after greasy dirt finally using dehydration of alcohol and are dried；
Step 3: the Bi-2212 superconduction multi-filamentary tapes after being dried in step 2 are placed in vacuum drying oven, it is in vacuum degree
10-3Pa, temperature are heat-treated 2h under conditions of being 600 DEG C；
Step 4: the Bi-2212 superconduction multi-filamentary tapes after being heat-treated in step 3 are added in the concentrated nitric acid of 250mL and added
Heat is to 150 DEG C of heat preservations, until obtaining yellow gum object, then adding the concentrated nitric acid of 250mL and being heated to 200 DEG C of heat preservations, directly
To dark brown jelly is obtained, then the distilled water of 2500mL is added to stir evenly, 10h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 100 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 8h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.97%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Sr are respectively less than 0.001%, and the mass content of impurity Ni and Si are
The mass content of 0.001%, impurity Cu are 0.002%, and the mass content of impurity B i is small less than the mass content of 0.0003%, Zr
In 0.002%.
Embodiment 4
The method of the present embodiment recycling Ag includes the following steps：
Step 1: cut short the Bi-2223 single superconducting tapes of 500 grams of jackets containing fine silver；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating Bi-2223 singles superconducting tape until the coating on surface is dissolved, then washed after being washed with deionized 4 times using metal
It washs agent and impregnates 30min and remove the greasy dirt on Bi-2223 single superconducting tapes surface, removal is cleaned using deionized water after oily waste degradation
Bi-2223 single superconducting tapes after greasy dirt finally using dehydration of alcohol and are dried；
Step 3: the Bi-2223 single superconducting tapes after being dried in step 2 are placed in vacuum drying oven, it is in vacuum degree
10-3Pa, temperature are heat-treated 4h under conditions of being 400 DEG C；
Step 4: the Bi-2223 single superconducting tapes after being heat-treated in step 3 are added in the concentrated nitric acid of 250mL and added
Heat is to 150 DEG C of heat preservations, until obtaining yellow gum object, then adding the concentrated nitric acid of 250mL and being heated to 160 DEG C of heat preservations, directly
To dark brown jelly is obtained, then the distilled water of 2500mL is added to stir evenly, 8h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 80 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 5h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
350mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.98%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Zr, Sr are respectively less than 0.001%, the mass content of impurity Ni, Si and Cu
It is 0.001%, the mass content of impurity B i is less than 0.0003%.
Embodiment 5
The method of the present embodiment recycling Ag includes the following steps：
Step 1: cut short the Bi-2223 multi-core superconductings wire rod and 250 grams of argentiferous magnesium of 250 grams of argentiferous magnesium alloy jacket
The Bi-2223 multi-core superconducting bands of metal alloy sheath, the multi-core superconducting wire strip mixed；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating the multi-core superconducting wire strip of mixing until the coating on surface dissolves, then uses metal after being washed with deionized 4 times
Detergent impregnates the greasy dirt that 30min removes the multiple core superconductive wire strip surface of mixing, is cleaned after oily waste degradation using deionized water
The multi-core superconducting wire strip of mixing after degreasing finally using dehydration of alcohol and is dried；
Step 3: the multi-core superconducting wire strip of the mixing after being dried in step 2 is placed in vacuum drying oven, it is in vacuum degree
10-3Pa, temperature are heat-treated 3h under conditions of being 500 DEG C；
Step 4: the multi-core superconducting wire strip of the mixing after being heat-treated in step 3 is added in the concentrated nitric acid of 250mL simultaneously
155 DEG C of heat preservations are heated to, until obtain yellow gum object, then add the concentrated nitric acid of 250mL and be heated to 180 DEG C of heat preservations,
Until obtaining dark brown jelly, then the distilled water of 2500mL is added to stir evenly, 9h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 90 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 7h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.97%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Sr are respectively less than 0.001%, and the mass content of impurity Ni, Si and Cu are
Mass content of the mass content of 0.001%, impurity B i less than 0.0003%, Zr is less than 0.002%.
Embodiment 6
The method of the present embodiment recycling Ag includes the following steps：
Step 1: the Bi-2223 multi-core superconductings band and 300 grams of Bi-2212 multi-core superconducting bands of 200 grams of argentiferous gold jackets
Material is cut short, the superconducting tape mixed；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating the superconducting tape of mixing until the coating on surface dissolves, then uses metal detergent after being washed with deionized 4 times
The greasy dirt that 30min removes the superconducting tape surface of mixing is impregnated, is cleaned after oily waste degradation using deionized water after degreasing
The superconducting tape of mixing finally using dehydration of alcohol and is dried；
It is 10 in vacuum degree Step 3: the superconducting tape of the mixing after being dried in step 2 is placed in vacuum drying oven-3Pa、
Temperature is heat-treated 2h under conditions of being 600 DEG C；
Step 4: the superconducting tape of the mixing after being heat-treated in step 3 is added in the concentrated nitric acid of 250mL and is heated to
155 DEG C of heat preservations, until obtain yellow gum object, then add the concentrated nitric acid of 250mL and be heated to 200 DEG C of heat preservations, until
To dark brown jelly, then the distilled water of 2500mL is added to stir evenly, 10h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 100 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 8h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.96%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Sr are respectively less than 0.001%, and the mass content of impurity Ni, Si and Cu are
Mass content of the mass content of 0.001%, impurity B i less than 0.0003%, Zr is less than 0.002%.
Embodiment 7
The method of the present embodiment recycling Ag includes the following steps：
Step 1: cut short the Bi-2223 single-core superconducting wire materials of 500 grams of jackets containing fine silver；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating Bi-2223 single-core superconducting wires material until the coating on surface is dissolved, then washed after being washed with deionized 4 times using metal
It washs agent and impregnates 30min and remove the greasy dirt on Bi-2223 single-core superconducting wire materials surface, removal is cleaned using deionized water after oily waste degradation
Bi-2223 single-core superconducting wire materials after greasy dirt finally using dehydration of alcohol and are dried；
Step 3: the Bi-2223 single-core superconducting wire materials after being dried in step 2 are placed in vacuum drying oven, it is in vacuum degree
10-3Pa, temperature are heat-treated 4h under conditions of being 400 DEG C；
Step 4: the Bi-2223 single-core superconducting wire materials after being heat-treated in step 3 are added in the concentrated nitric acid of 250mL and added
Heat is to 153 DEG C of heat preservations, until obtaining yellow gum object, then adding the concentrated nitric acid of 250mL and being heated to 160 DEG C of heat preservations, directly
To dark brown jelly is obtained, then the distilled water of 2500mL is added to stir evenly, 8h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 80 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 5h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
400mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.99%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Zr, Sr, Si are respectively less than 0.001%, the mass content of impurity Ni and Cu
It is 0.001%, the mass content of impurity B i is less than 0.0003%.
Comparative example 1
The recovery method of this comparative example A g and the difference of embodiment 7 are：Step 4: after being heat-treated in step 3
Bi series superconductive wires are added in the concentrated nitric acid of 500mL and are heated to 160 DEG C of heat preservations, until obtaining dark brown jelly, then add
The distilled water of 2500mL stirs evenly, and 8h is placed in finally ageing, obtains precipitated liquid；Remaining step is corresponding with embodiment 7
Step is identical.
The method that this comparative example takes step acidolysis recycling wire strip in step 4, its main feature is that each element starts in acidolysis
The excessively high easy splash of temperature and below after acidolysis since acidity variation causes Bi easily to hydrolyze the Bi contents of acquisition during reaction
Higher (spectrum analysis Bi 0.1%), and the rate of recovery and purity reduce.In addition, comparative example is without step 3, step three of the invention
The sulfuric horizon on supplied materials jacket surface can be removed and step 2 washes steam that material adsorbs in the process etc., therefore except step 3 and step
Four is different outer, remaining step of comparative example is identical with the embodiment：
Embodiment 8
The method of the present embodiment recycling Ag includes the following steps：
Step 1: cut short the Bi-2223 multi-core superconducting wire rods of 500 grams of argentiferous magnesium alloy jacket；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating Bi-2223 multi-core superconductings wire rod until the coating on surface is dissolved, then washed after being washed with deionized 4 times using metal
It washs agent and impregnates 30min and remove the greasy dirt on Bi-2223 multi-core superconducting wire rods surface, removal is cleaned using deionized water after oily waste degradation
Bi-2223 multi-core superconducting wire rods after greasy dirt finally using dehydration of alcohol and are dried；
Step 3: the Bi-2223 multi-core superconducting wire rods after being dried in step 2 are placed in vacuum drying oven, it is in vacuum degree
10-3Pa, temperature are heat-treated 3h under conditions of being 500 DEG C；
Step 4: the Bi-2223 multi-core superconducting wire rods after being heat-treated in step 3 are added in the concentrated nitric acid of 250mL and added
Heat is to 150 DEG C of heat preservations, until obtaining yellow gum object, then adding the concentrated nitric acid of 250mL and being heated to 180 DEG C of heat preservations, directly
To dark brown jelly is obtained, then the distilled water of 2500mL is added to stir evenly, 9h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 90 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 7h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
350mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.98%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Zr, Sr are respectively less than 0.001%, the mass content of impurity Ni, Si and Cu
It is 0.001%, the mass content of impurity B i is less than 0.0003%.
Embodiment 9
The method of the present embodiment recycling Ag includes the following steps：
Step 1: the Bi-2223 multi-core superconductings band and 400 grams of Bi-2212 multi-core superconducting bands of 100 grams of argentiferous gold jackets
Material is cut short, the multi-core superconducting band mixed；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating the multi-core superconducting band of mixing until the coating on surface is dissolved, then washed after being washed with deionized 4 times using metal
It washs agent and impregnates the greasy dirt that 30min removes the multi-core superconducting strip surface of mixing, removal is cleaned using deionized water after oily waste degradation
The multi-core superconducting band of mixing after greasy dirt finally using dehydration of alcohol and is dried；
It is 10 in vacuum degree Step 3: the multi-core superconducting band of the mixing after being dried in step 2 is placed in vacuum drying oven- 3Pa, temperature are heat-treated 3h under conditions of being 600 DEG C；
Step 4: the multi-core superconducting band of the mixing after being heat-treated in step 3 is added in the concentrated nitric acid of 250mL and added
Heat is to 150 DEG C of heat preservations, until obtaining yellow gum object, then adding the concentrated nitric acid of 250mL and being heated to 200 DEG C of heat preservations, directly
To dark brown jelly is obtained, then the distilled water of 2500mL is added to stir evenly, 10h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 100 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 8h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.97%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Sr are respectively less than 0.001%, and the mass content of impurity Ni, Si and Cu are
Mass content of the mass content of 0.001%, impurity B i less than 0.0003%, Zr is less than 0.002%.
Embodiment 10
The method of the present embodiment recycling Ag includes the following steps：
Step 1: by the Bi-2223 singles superconducting tape of 300 grams of argentiferous magnesium alloy jackets, 100 grams of argentiferous billons
The Bi-2223 single superconducting tapes of Bi-2223 singles superconducting tape and 100 grams of the jacket containing fine silver are cut short, the Bi- mixed
2223 single superconducting tapes；
Step 2: concentrated ammonia liquor and deionized water that mass concentration is 25% are first pressed 1：10 volume ratio is uniformly mixed, then
For impregnating the Bi-2223 singles superconducting tape of mixing until the coating on surface dissolves, then used after being washed with deionized 4 times
Metal detergent impregnates the greasy dirt that 30min removes the Bi-2223 single superconducting tapes surface of mixing, after oily waste degradation using go from
Sub- water cleans the Bi-2223 single superconducting tapes of the mixing after degreasing, and finally using dehydration of alcohol and dries；
Step 3: the Bi-2223 single superconducting tapes mixed after being dried in step 2 are placed in vacuum drying oven, in vacuum degree
It is 10-3Pa, temperature are heat-treated 3h under conditions of being 600 DEG C；
Step 4: the Bi-2223 single superconducting tapes of the mixing after being heat-treated in step 3 are added to the concentrated nitric acid of 250mL
In and be heated to 155 DEG C of heat preservations, until obtain yellow gum object, then add the concentrated nitric acid of 250mL and be heated to 200 DEG C of guarantors
Temperature until obtaining dark brown jelly, then adds the distilled water of 2500mL to stir evenly, and 10h is placed in finally ageing, is precipitated
Liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to the precipitated liquid obtained in step 4, obtain
To filter cake and filtrate, the filter cake is then rinsed using deionized water, until filter cake is in neutrality, collect after rinsing filter cake go from
Sub- water is simultaneously mixed with the filtrate, obtains mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 100 DEG C, then adds in concentrated hydrochloric acid into the mixed liquor and carry out
Precipitation reaction is protected from light ageing 8h, is then filtered using the cloth funnel for being covered with two layers of filter paper after the completion of reaction to be precipitated, then
It adopts and is washed with deionized to neutrality, obtain silver chlorate filter cake；The mass concentration of the concentrated hydrochloric acid is 50%, adds in volume and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide
Reaction completely generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide to boiling, then
The hydrazine hydrate that mass concentration is 50% is slowly added dropwise into two ammino silver solution of chlorination under conditions of being stirred continuously to be precipitated
Reaction, until being generated there is no sediment, postcooling reaction solution is completed in reaction to be precipitated, finally using Buchner funnel mistake
Filter, deionized water washing and 60 DEG C are dried to obtain sponge silver.
The quality purity for the sponge silver that the present embodiment recycles be 99.98%, wherein impurity Sb, Fe, Mn, Mg, Pb,
The mass content of Sn, Au, Al, Ca, Ir, Rh, Pt, Pd, Zr, Sr are respectively less than 0.001%, the mass content of impurity Ni, Si and Cu
It is 0.001%, the mass content of impurity B i is less than 0.0003%.
The above is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art substantially makees above example, still fall within technical solution of the present invention
Protection domain in.
Claims (7)
1. the recovery method of Ag in a kind of Bi systems superconducting line strips, it is characterized in that, which includes the following steps：
Step 1: cutting short Bi systems superconducting line strips, Bi systems superconducting line strips are argentiferous jacket or the single of silver alloy jacket
Or multicore Bi systems superconducting line strips；
Step 2: Bi systems superconducting line strips face coat and greasy dirt after being cut short in step 1 are first removed, then using deionized water
The Bi systems superconducting line strips after degreasing are cleaned, finally using dehydration of alcohol and are dried；
It is 10 in vacuum degree Step 3: the Bi systems superconducting line strips after being dried in step 2 are placed in vacuum drying oven-3Pa, temperature
2h~4h is heat-treated under conditions of being 400 DEG C~600 DEG C；
Step 4: the Bi systems superconducting line strips after being heat-treated in step 3 are added in concentrated nitric acid and are heated to 150 DEG C~155 DEG C
Heat preservation, until obtaining yellow gum object, then adding concentrated nitric acid and being heated to 160 DEG C~200 DEG C heat preservations, until obtaining dark brown
Color jelly, then distilled water is added to stir evenly, 8h~10h is placed in finally ageing, obtains precipitated liquid；
Step 5: being filtered to the precipitated liquid obtained in step 4, filter cake and filtrate are obtained, is then rinsed using deionized water
The filter cake until filter cake is in neutrality, is collected the deionized water after rinsing filter cake and is mixed with the filtrate, obtain mixed liquor；
Step 6: mixed liquor described in first heating stepses five is to 80 DEG C~100 DEG C, then add in into the mixed liquor concentrated hydrochloric acid into
Row precipitation reaction is protected from light ageing 5h~8h, is then filtered and washs, obtain silver chlorate filter cake after the completion of reaction to be precipitated,
The silver chlorate filter cake is in neutrality；
Step 7: ammonium hydroxide is slowly added dropwise in the silver chlorate filter cake obtained into step 6, until silver chlorate filter cake and ammonium hydroxide are complete
Reaction generates two ammino silver solution of chlorination, then heats two ammino silver solution of chlorination and removes extra ammonium hydroxide, then not to boiling
Hydrazine hydrate is slowly added dropwise into two ammino silver solution of chlorination under conditions of disconnected stirring and carries out precipitation reaction, until there is no sediments
Until generation, postcooling reaction solution is completed in reaction to be precipitated, it is last it is filtered, wash and be dried to obtain sponge silver.
2. the recovery method of Ag in a kind of Bi systems superconducting line strips according to claim 1, it is characterized in that：Described in step 1
Bi systems superconducting line strips are Bi-2223 superconducting line strips or Bi-2212 superconducting line strips.
3. the recovery method of Ag in a kind of Bi systems superconducting line strips according to claim 1, it is characterized in that：Step 2 removes
The detailed process of Bi systems superconducting line strips face coat and greasy dirt after being cut short in step 1 is：First by mass concentration for 22%~
25% concentrated ammonia liquor and deionized water presses 1：10 volume ratio is uniformly mixed, and is used further to impregnate Bi system's superconducting line strips until surface
Coating dissolving, then be washed with deionized 4 times, 30min finally impregnated using metal detergent and removes Bi systems superconducting line strips
The greasy dirt on surface.
4. the recovery method of Ag in a kind of Bi systems superconducting line strips according to claim 1, it is characterized in that：Two in step 4
The total volume of the concentrated nitric acid of secondary addition is 1 times of the quality of Bi systems superconducting line strips, adds in the volume of the deionized water
The unit of 5 times of quality for Bi systems superconducting line strips, the total volume of the concentrated nitric acid and the volume of deionized water is
ML, the unit of the quality of Bi systems superconducting line strips is g, and the mass concentration of the concentrated nitric acid is 68%.
5. the recovery method of Ag in a kind of Bi systems superconducting line strips according to claim 1, it is characterized in that：Mistake in step 5
Using the glass funnel for being covered with filter paper and filter cloth during filter, using the cloth funnel for being covered with two layers of filter paper when being filtered in step 6.
6. the recovery method of Ag in a kind of Bi systems superconducting line strips according to claim 1, it is characterized in that：Institute in step 6
The dosage for stating concentrated hydrochloric acid adds in the concentrated hydrochloric acid of 350mL~400mL, institute for Bi systems superconducting line strips described in every 500 grams of step 1
The mass concentration for stating concentrated hydrochloric acid is 50%.
7. the recovery method of Ag in a kind of Bi systems superconducting line strips according to claim 1, it is characterized in that：Institute in step 7
The mass concentration for stating hydrazine hydrate is 50%~80%, the temperature 60 C of the drying.
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| CN112939057A (en) * | 2021-03-26 | 2021-06-11 | 重庆烯宇新材料科技有限公司 | Method for recycling nano silver wire waste |
| CN113270235A (en) * | 2021-05-12 | 2021-08-17 | 中国科学院合肥物质科学研究院 | Method for separating superconducting phase from silver-based copper oxide superconducting material |
| CN113270235B (en) * | 2021-05-12 | 2022-10-11 | 中国科学院合肥物质科学研究院 | Method for separating superconducting phase from silver-based copper oxide superconducting material |
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