CN108149018B - The recovery method of Ag in a kind of Bi system superconducting line strips - Google Patents
The recovery method of Ag in a kind of Bi system superconducting line strips Download PDFInfo
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- CN108149018B CN108149018B CN201711494494.3A CN201711494494A CN108149018B CN 108149018 B CN108149018 B CN 108149018B CN 201711494494 A CN201711494494 A CN 201711494494A CN 108149018 B CN108149018 B CN 108149018B
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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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- 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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Abstract
The invention discloses the recovery method of Ag in a kind of Bi system superconducting line strips, this method are as follows: first removes argentiferous or the Bi system superconducting line strips of silver alloy degrease, after coating, then be heat-treated；It is then dissolved in concentrated nitric acid, evaporation, decomposition nitrate, entirety adds water and stirs ageing, filter in solution containing undecomposed silver nitrate, strontium nitrate, calcium nitrate, small part bismuth basic salt, concentrated hydrochloric acid is added dropwise into solution and generates silver nitride precipitation, avoid light place ageing, filtering precipitating, is transferred in container, concentrated ammonia liquor is added and covers sediment, it is heated to boiling, is slowly added to hydrazine hydrate under stirring, until being generated there is no sediment, filtering, it is dry, sponge silver powder of the quality purity 99.95% or more is obtained, and the rate of recovery is as many as 99%.The present invention is suitble to single, recycling silver-colored in multicore Bi system argentiferous jacket, can get mass, purity is high, crystal grain uniformly tiny sponge silver powder.
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 system superconducting line strips.
Background technique
Superconductor is the basis of superconductor technology application, with NbTi, Nb3Sn is for the low temperature superconducting material of representative and with MgB2
Enter in recent years for the medium temperature superconductor and BSCCO (Bi system) of representative, the high temperature superconducting materia that YBCO (Y system) is representative
Or partly enter the mode of industrialization, it is widely used in the fields such as electric power, communication, national defence, medical treatment, answering with more high added value
Use prospect.The mature 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 system oxide superconductor is found in 1986, it in the application advantage of liquid nitrogen 77K warm area by various countries scientific worker
Poured into many energy, crystal structure, characteristic electron, preparation method, mechanical performance, A.C.power loss, in terms of do
A large amount of detailed researchs, China 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 company, the U.S., SUMITOMO CHEMICAL public affairs
Department, German Trithor company, annual output is more than 5000Km, is 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 preparation line
Band, based on study, study its wire strip at 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 technology.The research and development of every kind of technology, which require to prepare sample, to be tested, the feasibility of judgment technology, therefore is left a large amount of
Research and development sample, and in sample 70% or more be all silver, remaining is superconducting phase.Silver is noble metal, and it is higher to be prepared into silver-colored pipe price,
In order to reduce research and development cost 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 process, and pyrometallurgical smelting temperature is high (1000-1100 DEG C), and energy consumption is high, at
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 lower.Wet-process purification method is more, including electrolysis and chemical purification, and 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 at component selections
Reagent, some need high-temperature calcination or heating in vacuum after these reagents and silver reaction, aqueous slkali is added into AgCl some,
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
At precipitating, the reduction purity influenced thereafter is otherwise blended in silver chlorate.But the chemical method scope of application is wider, according to the spy of element
Property be easy adjust preparation parameter, be also particularly suitable for small lot laboratory recycling, have flexible and changeable means.
Bi system high-temperature superconducting oxide includes Bi-2223, Bi-2212, the former contain 4-5 kind 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.Sheath material is other than fine silver jacket, and also exploitation has AgMg alloy, AgAu alloy 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, and holding the bad purity for making final silver cannot be guaranteed.
It was found that, reacting nitrate generated to temperature extremely when decomposing Bi system superconducting line strips using nitric acid
Sensitivity, when starting dissolution, five kinds or four kinds of elements first generate nitrate, as the temperature gradually increases, different nitrate from
Hydrolysis, decomposed, to resolving into completely, the temperature range that oxide or simple substance are undergone is larger, between 50 DEG C~700 DEG C, especially
It is bismuth nitrate, in 50 DEG C~80 DEG C generation basic salt (Bi6O6)2(NO3)11(OH).6H2O precipitating, there are also the dissolution of part salt,
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
When at oxide, silver is blended in oxide powder with simple substance or with silver oxide, and silver-colored simple substance can not be gone out with liquid phase separation.Text at present
The silver recovery technology for offering 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.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of superconduction of Bi system
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
99.95% or more, 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 detects Sr and is less than 0.001wt%.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: Ag's returns in a kind of Bi system superconducting line strips
Receiving method, which is characterized in that the recovery method the following steps are included:
Step 1: cut short Bi system superconducting line strips, Bi system superconducting line strips are to utilize single made of argentiferous jacket or more
Core Bi system superconducting line strips；
Step 2: first remove step 1 in cut short after Bi system superconducting line strips surface covering and greasy dirt, then using go from
Sub- water cleans the Bi system superconducting line strips after degreasing, and finally uses dehydration of alcohol and dries；
It is 10 in vacuum degree Step 3: the Bi system superconducting line strips after drying in step 2 are placed in vacuum drying oven-3Pa、
Temperature be 400 DEG C~600 DEG C under conditions of be heat-treated 2h~4h, removal Bi system superconducting line strips inside adsorb gas, moisture,
Stress；
Step 4: by step 3 be heat-treated after Bi system 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 plus distilled water stir evenly, finally ageing place 8h~10h, obtain precipitated liquid；
Step 5: being filtered to precipitated liquid obtained in step 4, filter cake and filtrate are obtained, then uses 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 into the mixed liquor
Acid carries out precipitation reaction (AgNO3+ HCl (dense)=AgCl ↓+HNO3), it is to be precipitated to be protected from light ageing 5h~8h after the reaction was completed, then
It is filtered and washed, obtains silver chlorate filter cake, the silver chlorate filter cake is in neutrality；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, chlorination diamino is then heated
It closes silver-colored solution and removes extra ammonium hydroxide to boiling, then be slowly added dropwise under conditions of being stirred continuously into two ammino silver solution of chlorination
Hydrazine hydrate carries out precipitation reaction (2Ag (NH3)2Cl+2N2H4.H2O=2Ag ↓+2NH4Cl+N2↑+4NH3↑+2H2O), until there is no
It is to be precipitated to cool down reaction solution after the reaction was completed until sediment generates, finally it is filtered, washed and is dried to obtain sponge silver.
The recovery method of Ag in a kind of above-mentioned Bi system superconducting line strips, it is characterized in that: Bi system 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 system superconducting line strips is cut in step 1 it is characterized in that: step 2 removes
The detailed process of Bi system superconducting line strips surface covering and greasy dirt after short are as follows: the dense ammonia for being first 22%~25% by mass concentration
Water and deionized water are uniformly mixed by the volume ratio of 1:10, are used further to impregnate Bi system superconducting line strips until the coating on surface is molten
Solution, then be washed with deionized 4 times, the oil that 30min removes Bi system superconducting line strips surface is finally impregnated using metal detergent
It is dirty.
The recovery method of Ag in a kind of above-mentioned Bi system superconducting line strips, it is characterized in that: what is be added twice in step 4 is dense
The total volume of nitric acid is 1 times of the quality of Bi system superconducting line strips, and the volume that the deionized water is added is the Bi system
The unit of 5 times of the quality of superconducting line strips, the volume of the total volume and deionized water of the concentrated nitric acid is mL, the Bi system
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 system 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 Buchner 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 system superconducting line strips, it is characterized in that: concentrated hydrochloric acid described in step 6
Dosage is the concentrated hydrochloric acid that 350mL~400mL is added in Bi system 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 system 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:
Distinguishing feature of the invention is exactly four kinds of elements (Bi, Sr, Ca, Cu) or five kinds of elements in Bi system 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 lower steaming of the present invention
At 150 DEG C~200 DEG C of temperature of hair, superconductive oxide powder is dissolved stage by stage, 150 DEG C~155 DEG C of the first stage, low temperature guarantees line
Net material in band all dissolves, and equably generates nitrate, and 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, as far as possible reduction hydrochloric acid precipitation silver cause the possibility with silver-colored coprecipitation, mention
The high purity of silver.
Nitrate once shows several phenomenons: the AgNO that evaporation is not decomposed but can be dissolved in water3、Sr(NO3)2；Or evaporation regardless of
Solution but the Pb (NO for being easy hydrolysis generation precipitating 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 dissolution two states in subsequent water；Or Bi (the NO of evaporation, decomposition3)3Again in water
Middle most of generation basic salt precipitating not soluble in water, while there may also be a small amount of basic salt and being 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 mentioning for silver
Purity reduces.
In order to realize the purpose of high-purity recycling silver, the interference of above other elements, the technical side that the present invention uses are avoided
Case is: the Bi system superconducting line strips surface of argentiferous degreasing, 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, the moisture, stress adsorbed inside heat preservation 2~4h removal wire strip；Subsequent sample is dissolved in
In concentrated nitric acid, 150 DEG C~200 DEG C evaporation, decomposition part nitrate integrally add water and stir 8~10h of ageing, filter 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 is added dropwise in liquid and generates silver nitride precipitation, avoid light place is aged 5~8h.Filtering precipitating, is transferred in container, dense ammonia is added
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 99.95% or more, and the rate of recovery not under
In 99%.
Compared with the prior art, the present invention has the following advantages:
1, 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 is not less than 99%, purity is up to 99.95% or more, is that crystal grain is uniformly thin
Small sponge silver.
2, the sponge silver recycled to the present invention detects, 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 solves to be difficult in current technology recovery scheme less than 0.001%
The mass content of Bi and Sr in the Ag of recycling is effectively reduced.
3, method of the invention is designed particular for the Bi system superconducting line strips of argentiferous or silver alloy jacket, and is passed through
The temperature of concentrated nitric acid acidolysis twice is controlled to enter in subsequent reaction solution to control the metallic element in Bi system superconducting line strips
Form impurity, the problem for causing the purity of metal Ag not high.
4, slag charge and resulting product caused by the intermediate steps in recovery method of the present invention can be easily separated, and slag charge can
It purifies repeatedly, can be improved the rate of recovery of silver.
Technical solution of the present invention is described in further detail below by embodiment.
Specific embodiment
Embodiment 1
The present embodiment recycle Ag method the following steps are included:
Step 1: cutting short the Bi-2223 single superconducting tape of 500 grams of jackets containing fine silver；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating Bi-2223 single 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 tape surface, adopts and be washed with deionized water after oily waste degradation
Bi-2223 single superconducting tape after degreasing finally uses dehydration of alcohol and dries；
Step 3: sample is placed into vacuum drying oven, vacuum degree reaches 10-3400 DEG C/4h heat treatment is warming up to after Pa；
Step 4: the Bi-2223 single superconducting tape after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL and add
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 obtaining dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 8h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 5h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
400mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 less than 0.0003%, Zr of 0.001%, impurity B i are less than 0.002%.
Embodiment 2
The present embodiment recycle Ag method the following steps are included:
Step 1: cutting short the Bi-2223 multi-core superconducting wire rod of 500 grams of argentiferous magnesium alloy jacket；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating Bi-2223 multi-core superconducting 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 rod surface, adopts and be washed with deionized water after oily waste degradation
Bi-2223 multi-core superconducting wire rod after degreasing finally uses dehydration of alcohol and dries；
Step 3: the Bi-2223 multi-core superconducting wire rod after drying 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 Bi-2223 multi-core superconducting wire rod after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL and add
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 obtaining dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 9h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 7h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 less than 0.0003%, Zr of 0.001%, impurity B i are less than 0.002%.
Embodiment 3
The present embodiment recycle Ag method the following steps are included:
Step 1: cutting short the Bi-2212 superconduction multi-filamentary tape of 500 grams of argentiferous gold jackets；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating Bi-2212 superconduction multi-filamentary tape until the coating on surface dissolves, then washes after being washed with deionized 4 times using metal
It washs agent and impregnates the greasy dirt that 30min removes Bi-2212 superconduction multi-filamentary tape surface, adopted after oily waste degradation and be washed with deionized water removal
Bi-2212 superconduction multi-filamentary tape after greasy dirt finally uses dehydration of alcohol and dries；
Step 3: the Bi-2212 superconduction multi-filamentary tape after drying in step 2 is 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 tape after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL and add
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 obtaining dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 10h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 8h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 present embodiment recycle Ag method the following steps are included:
Step 1: cutting short the Bi-2223 single superconducting tape of 500 grams of jackets containing fine silver；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating Bi-2223 single superconducting tape until the coating on surface dissolves, then washes after being washed with deionized 4 times using metal
It washs agent and impregnates the greasy dirt that 30min removes Bi-2223 single superconducting tape surface, adopted after oily waste degradation and be washed with deionized water removal
Bi-2223 single superconducting tape after greasy dirt finally uses dehydration of alcohol and dries；
Step 3: the Bi-2223 single superconducting tape after drying in step 2 is 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 tape after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL and add
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 obtaining dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 8h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 5h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
350mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 present embodiment recycle Ag method the following steps are included:
Step 1: cutting short the Bi-2223 multi-core superconducting wire rod and 250 grams of argentiferous magnesium of 250 grams of argentiferous magnesium alloy jacket
The Bi-2223 multi-core superconducting band of metal alloy sheath, mixed multi-core superconducting wire strip；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating mixed multi-core superconducting wire strip 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, adopts and is washed with deionized water after oily waste degradation
Mixed multi-core superconducting wire strip after degreasing finally uses dehydration of alcohol and dries；
Step 3: the mixed multi-core superconducting wire strip after drying 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 mixed multi-core superconducting wire strip 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 obtain dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 9h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 7h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 less than 0.0003%, Zr of 0.001%, impurity B i are less than 0.002%.
Embodiment 6
The present embodiment recycle Ag method the following steps are included:
Step 1: the Bi-2223 multi-core superconducting band and 300 grams of Bi-2212 multi-core superconducting band of 200 grams of argentiferous gold jackets
Material is cut short, mixed superconducting tape；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating mixed superconducting tape 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 adopted after oily waste degradation after being washed with deionized water and degreasing
Mixed superconducting tape finally uses dehydration of alcohol and dries；
It is 10 in vacuum degree Step 3: the mixed superconducting tape after drying 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 mixed superconducting tape after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL 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 heat preservations, until
To dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 10h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 8h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 less than 0.0003%, Zr of 0.001%, impurity B i are less than 0.002%.
Embodiment 7
The present embodiment recycle Ag method the following steps are included:
Step 1: cutting short the Bi-2223 single-core superconducting wire material of 500 grams of jackets containing fine silver；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating Bi-2223 single-core superconducting wire material until the coating on surface dissolves, then washes after being washed with deionized 4 times using metal
It washs agent and impregnates the greasy dirt that 30min removes Bi-2223 single-core superconducting wire material surface, adopted after oily waste degradation and be washed with deionized water removal
Bi-2223 single-core superconducting wire material after greasy dirt finally uses dehydration of alcohol and dries；
Step 3: the Bi-2223 single-core superconducting wire material after drying in step 2 is 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 material after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL and add
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 obtaining dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 8h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 5h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
400mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 wire is added in the concentrated nitric acid of 500mL and is heated to 160 DEG C of heat preservations, until dark brown jelly is obtained, then plus
The distilled water of 2500mL stirs evenly, and finally 8h is placed in 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
When reaction the excessively high easy splash of temperature and below after acidolysis due to acidity variation cause Bi be easy hydrolysis obtain Bi content
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 and step 2 that supplied materials jacket surface can be removed wash the steam etc. adsorbed during material, therefore remove step 3 and step
Four is different outer, remaining step of comparative example is identical as the embodiment:
Embodiment 8
The present embodiment recycle Ag method the following steps are included:
Step 1: cutting short the Bi-2223 multi-core superconducting wire rod of 500 grams of argentiferous magnesium alloy jacket；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating Bi-2223 multi-core superconducting wire rod until the coating on surface dissolves, then washes after being washed with deionized 4 times using metal
It washs agent and impregnates the greasy dirt that 30min removes Bi-2223 multi-core superconducting wire rod surface, adopted after oily waste degradation and be washed with deionized water removal
Bi-2223 multi-core superconducting wire rod after greasy dirt finally uses dehydration of alcohol and dries；
Step 3: the Bi-2223 multi-core superconducting wire rod after drying 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 Bi-2223 multi-core superconducting wire rod after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL and add
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 obtaining dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 9h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 7h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
350mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 present embodiment recycle Ag method the following steps are included:
Step 1: the Bi-2223 multi-core superconducting band and 400 grams of Bi-2212 multi-core superconducting band of 100 grams of argentiferous gold jackets
Material is cut short, mixed multi-core superconducting band；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating mixed multi-core superconducting band until the coating on surface dissolves, then washes 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, adopted after oily waste degradation and be washed with deionized water removal
Mixed multi-core superconducting band after greasy dirt finally uses dehydration of alcohol and dries；
It is 10 in vacuum degree Step 3: the mixed multi-core superconducting band after drying 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 mixed multi-core superconducting band after being heat-treated in step 3 to be added in the concentrated nitric acid of 250mL and add
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 obtaining dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 10h is placed in ageing, obtains precipitated liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 8h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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 less than 0.0003%, Zr of 0.001%, impurity B i are less than 0.002%.
Embodiment 10
The present embodiment recycle Ag method the following steps are included:
Step 1: by the Bi-2223 single superconducting tape of 300 grams of argentiferous magnesium alloy jackets, 100 grams of argentiferous billons
The Bi-2223 single superconducting tape of Bi-2223 single superconducting tape and 100 grams of the jacket containing fine silver is cut short, mixed Bi-
2223 single superconducting tapes；
Step 2: be first uniformly mixed mass concentration by the volume ratio of 1:10 for 25% concentrated ammonia liquor and deionized water, then
For impregnating mixed Bi-2223 single superconducting tape until the coating on surface dissolves, then uses after being washed with deionized 4 times
Metal detergent impregnates the greasy dirt that 30min removes the Bi-2223 single superconducting tape surface of mixing, after oily waste degradation using go from
Sub- water cleans the mixed Bi-2223 single superconducting tape after degreasing, and finally uses dehydration of alcohol and dries；
Step 3: the Bi-2223 single superconducting tape mixed after drying in step 2 is 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 mixed Bi-2223 single superconducting tape after being heat-treated in step 3 to be 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 obtain dark brown jelly, then plus the distilled water of 2500mL stir evenly, finally 10h is placed in ageing, is precipitated
Liquid；
Step 5: being filtered using the glass funnel for being covered with filter paper and filter cloth to 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 into the mixed liquor, addition concentrated hydrochloric acid is carried out
Precipitation reaction, it is to be precipitated to be protected from light ageing 8h after the reaction was completed, then filtered using the Buchner funnel for being covered with two layers of filter paper, 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%, and volume is added and is
380mL；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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, it is to be precipitated to cool down reaction solution after the reaction was completed until being generated there is no sediment, finally use 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, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (7)
1. the recovery method of Ag in a kind of Bi system superconducting line strips, characterized in that the recovery method the following steps are included:
Step 1: cutting short Bi system superconducting line strips, Bi system superconducting line strips are the single of argentiferous jacket or silver alloy jacket
Or multicore Bi system superconducting line strips；
Step 2: first removing Bi system superconducting line strips surface covering and greasy dirt after cutting short in step 1, then use deionized water
The Bi system superconducting line strips after degreasing are cleaned, dehydration of alcohol is finally used and are dried；
It is 10 in vacuum degree Step 3: the Bi system superconducting line strips after drying 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 system 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 plus distilled water stir evenly, finally ageing place 8h~10h, obtain precipitated liquid；
Step 5: being filtered to precipitated liquid obtained in step 4, filter cake and filtrate are obtained, is then rinsed using deionized water
The filter cake is collected the deionized water after rinsing filter cake and is mixed with the filtrate, obtain mixed liquor until filter cake is in neutrality；
Step 6: mixed liquor described in first heating stepses five is to 80 DEG C~100 DEG C, then be added into the mixed liquor concentrated hydrochloric acid into
Row precipitation reaction, it is to be precipitated to be protected from light ageing 5h~8h after the reaction was completed, it is then filtered and washed, obtains silver chlorate filter cake,
The silver chlorate filter cake is in neutrality；
Step 7: ammonium hydroxide is slowly added dropwise into silver chlorate filter cake obtained in 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 to boiling, then not
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
It is to be precipitated to cool down reaction solution after the reaction was completed until generation, finally it is filtered, washed and is dried to obtain sponge silver.
2. the recovery method of Ag in a kind of Bi system superconducting line strips according to claim 1, it is characterized in that: described in step 1
Bi system 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 system superconducting line strips according to claim 1, it is characterized in that: step 2 removes
The detailed process of Bi system superconducting line strips surface covering and greasy dirt after being cut short in step 1 are as follows: first by mass concentration be 22%~
25% concentrated ammonia liquor and deionized water is uniformly mixed by the volume ratio of 1:10, is used further to impregnate Bi system superconducting line strips until surface
Coating dissolution, then be washed with deionized 4 times, 30min finally impregnated using metal detergent and removes Bi system superconducting line strips
The greasy dirt on surface.
4. the recovery method of Ag in a kind of Bi system 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 system superconducting line strips, and the volume of the deionized water is added
It is 5 times of the quality of Bi system superconducting line strips, the unit of the volume of the total volume and deionized water of the concentrated nitric acid is
ML, the unit of the quality of Bi system superconducting line strips are g, and the mass concentration of the concentrated nitric acid is 68%.
5. the recovery method of Ag in a kind of Bi system 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 when filter, using the Buchner 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 system superconducting line strips according to claim 1, it is characterized in that: institute in step 6
The dosage for stating concentrated hydrochloric acid is the concentrated hydrochloric acid of the addition of Bi system superconducting line strips described in every 500 grams of step 1 350mL~400mL, institute
The mass concentration for stating concentrated hydrochloric acid is 50%.
7. the recovery method of Ag in a kind of Bi system 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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| US5942466A (en) * | 1994-10-28 | 1999-08-24 | American Superconductor Corporation | Processing of (Bi,Pb) SCCO superconductor in wires and tapes |
| CN101353727A (en) * | 2008-09-18 | 2009-01-28 | 西部金属材料股份有限公司 | Method for reclaiming silver and copper in silver-copper alloy scrap |
| CN102277497B (en) * | 2011-08-05 | 2013-03-13 | 武汉格林美资源循环有限公司 | Method of reclaiming gold, palladium, platinum and silver from waste circuit board |
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