CN110029009A - It is a kind of to utilize waste and old circuit board recycling copper nanoparticle and selfreparing preparation of greases method - Google Patents
It is a kind of to utilize waste and old circuit board recycling copper nanoparticle and selfreparing preparation of greases method Download PDFInfo
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- CN110029009A CN110029009A CN201910317439.XA CN201910317439A CN110029009A CN 110029009 A CN110029009 A CN 110029009A CN 201910317439 A CN201910317439 A CN 201910317439A CN 110029009 A CN110029009 A CN 110029009A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/06—Mixtures of thickeners and additives
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
- C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
-
- 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
Waste and old circuit board recycling copper nanoparticle and selfreparing preparation of greases method are utilized the present invention relates to a kind of, including the waste and old circuit board of copper by pulverization process and is using the broken raw material of waterpower separation by shaking table, the powder of enriched in metals is isolated by density difference, then metal is ionized with leaching agent, it is extracted using extraction with back extraction and removes Salzburg vitriol, liquid phase reduction is further used to extract separation nano-metallic copper powder, good fortune reaction is recycled to produce lubricating grease, and copper nanoparticle is applied to lubricating grease and realizes self-repair function to improve recycling copper powder added value.Copper nanoparticle good dispersion prepared by the present invention, can be used in lubricating grease, and easy to operate, at low cost.
Description
Technical field
The present invention relates to a kind of recoverying and utilizing methods of copper powder, and in particular to a kind of to recycle Nanometer Copper using waste and old circuit board
Powder and selfreparing preparation of greases method.
Background technique
For circuit board from the perspective of resource reclaim, potential value is very high, is one containing your dilute gold such as gold, silver, platinum, rhodiums
Belong to, the resource concentration body of the base metals such as Yi Jitong, iron, aluminium, zinc, nickel.Compared with Metal Production is extracted in mine, from electronic waste
The secondary amount of waste generated in recycling metal process in object is less, and the content of noble metal is than the product in gold concentrate in waste printed circuit board
Position is taller.However, circuit board be metal and it is nonmetallic combine closely, separate hardly possible, be most complicated, most difficulty in electron wastes
Reason.
The recovery technology of discarded printed circuit boards mainly includes pyrogenic process, pyrolysismethod, wet process, microbial method and mechanical approach
Etc. technologies.Pyrogenic process recycles copper, although simple process, circuit board can generate a large amount of pollution gas during the burning process；Machine
Though there is no the risks of pollution environment for tool method, metal and nonmetallic can only be sorted roughly；And wet-treating waste and old printed circuit
Plate can not only obtain higher metal recovery rate and metal purity, but also equipment requirement is lower.Hydrometallurgic recovery was usually extracted
Leaching agent can only act on exposed metal surface in journey, if metal is wrapped up by resistant material ceramics etc., be difficult to leach
Out；There is corrosivity and toxicity easily to cause even more serious secondary pollution if dealing with improperly for leachate and residue.How to lead to
The copper in a kind of recycling waste printed circuit board of recovery method efficient pollution-free is crossed, and is able to achieve its value added applications, makes it
With good nano effect, recycle out copper nanoparticle and as lubricating grease self repairing agent be realize its high added value have efficacious prescriptions
Method.
Summary of the invention
Waste and old circuit board recycling copper nanoparticle and selfreparing preparation of greases are utilized the object of the present invention is to provide a kind of
Metal part in circuit board is enriched with using physical disruption methods, is then led to using waste in circuit board as research object by method
It crosses leaching agent and leaches copper ion, and Salzburg vitriol crystal is obtained using extraction, back extraction, then prepare copper nanoparticle, most
Afterwards using preparation selfreparing lubricating grease in lubricating grease.
To achieve the above object, present invention provide the technical scheme that
It is a kind of to utilize waste and old circuit board recycling copper nanoparticle and selfreparing preparation of greases method, comprising the following steps:
1) raw material is the particle that cupric waste and old circuit board is crushed to 0.8~1.2mm of average grain diameter with grinder；
2) above-mentioned particles with water power shaking table is sorted, weight density metal component and light close is sub-elected by density difference
Nonmetallic ingredient is spent, weight density components are the raw metal of leaching process；
3) certain density leaching agent is added in raw metal: hydrochloric acid, n-butylamine and anhydrous cupric sulfate pass through magnetic agitation
Device obtains copper ions solution after being stirred reaction a period of time at a certain temperature；
4) initial pH value that copper ions solution is adjusted by sulfuric acid and sodium hydroxide, passes through extractant LK-C2 and sulfonation
Copper in water phase copper ions solution is extracted into organic phase by kerosene organic phase；
5) it uses a certain amount of sulfuric acid as stripping agent, the copper ion in organic phase is stripped, back extraction ratio is by stripping agent sulphur
Acid concentration is affected, and control strip liquor is compared, and back-extraction time fullys shake and is stripped, and crystallization obtains five hydrated sulfuric acids
Copper；
6) step 5) is extracted to obtained Salzburg vitriol dissolution in deionized water and adds polyvinylpyrrolidone,
PH value is adjusted by nitric acid or ammonium hydroxide and reaches certain value, and oxidizing agent solution A is made；By the sodium borohydride of a certain amount of concentration
Reducing agent solution B, is slowly dropped in solution A, carries out magnetic agitation at a certain temperature and obtains the dispersion liquid containing copper powder；It connects down
Copper powder is obtained obtained copper dispersion liquid is passed through centrifuge separation, then is washed with deionized water three times, is washed one time with alcohol, it is last true
Sky, which is dried, can be obtained pure copper powder；
7) it takes a certain amount of normal octane and oleic acid to stir evenly and step 6) is added and recycle obtained copper nanoparticle, high-speed shearing machine stirs
It uniformly is placed in supersonic cleaning machine ultrasound certain time, is added into reaction kettle and base oil is added and stir evenly；Decompression is steamed
It evaporates, is all steamed to normal octane, obtain the lubricating oil of the powder containing Surface modification nanometer copper；
8) it takes a certain amount of ten dihydroxystearic acid, lithium hydroxide aqueous solution and base oil to be added in refining kettle and heats soap
Change after a certain period of time, the moisture after saponification is sloughed in heating；Then, extruding step-up temperature and addition obtain containing table with step 7)
The lubricating oil and a certain amount of base oil of the modified copper powder in face are uniformly mixed, then that mixture is cooling；This is mixed with three-roll mill
Object is uniformly dispersed, and prepares the selfreparing lubricating grease containing copper nanoparticle.
Hydrochloric acid described in step 3), nitric acid, n-butylamine, copper sulphate are that analysis is pure, and manufacturer is the examination of Chinese medicines group chemistry
Agent Co., Ltd.
Above-mentioned steps 3) in technical solution, the concentration of the anhydrous cupric sulfate is 5g~10g/L, preferably 6.25g/L；
Above-mentioned steps 3) in technical solution, the HCl solution concentration is 100g~200g/L, preferably 130g/L；Nitric acid is molten
Liquid concentration is 50g~200g/L, preferably 80g/L；
Above-mentioned steps 3) in technical solution, the n-butylamine concentration is 20g~100g/L, preferably 36g/L；
Above-mentioned steps 3) in technical solution, the reaction temperature is 10~60 DEG C, and preferably 50 DEG C of reaction time are 2~10h,
It is preferred that 5h；
Above-mentioned steps 3) in technical solution, it is described；Mixing speed is 400~600rpm, preferably 300rpm；
Above-mentioned steps 4) in technical solution, the sulfuric acid, sodium hydroxide are to analyze pure, and manufacturer is Chinese medicines group chemistry
Reagent Co., Ltd；
Above-mentioned steps 4) in technical solution, the oil is mutually and water phase volume ratio is 4:1~1:4, preferably 1:1；
Above-mentioned steps 4) in technical solution, volumetric concentration of the extractant LK-C2 in oily phase is in 3%~40% range
It is interior, preferably 18%；
Above-mentioned steps 4) in technical solution, extraction time is in 1~10min range, preferably 4min；
Above-mentioned steps 4) in technical solution, water phase initial pH value range is 0.2~4.0, preferably 3；
1. above-mentioned steps 5) stripping agent sulfuric acid concentration ranges are as follows: 0.3~4mol/L, preferably 3mol/L, strip liquor oil mutually with
Water phase is compared are as follows: 1:3~3:1, preferably 2:1, back-extraction time are as follows: 2~10min, preferably 3min.
Above-mentioned steps 6) in technical solution, nitric acid, ammonium hydroxide, sodium borohydride are to analyze pure, and manufacturer is Chinese medicines group
Learn reagent Co., Ltd；
Above-mentioned steps 6) in technical solution, the pH value range is 9~13, preferably 11；The concentration of Salzburg vitriol is
50~80g/L, preferably 60g/L；The mass ratio of polyvinylpyrrolidone and Salzburg vitriol is 1:5-1:10, preferably 1:10；
The molar ratio of sodium borohydride and Salzburg vitriol is 1:4~1:1, preferably 1:1.
With in step 7) technical solution, oleic acid is that analysis is pure, manufacturer is the sub- safe joint Chemical Co., Ltd. in Wuxi, just
Octane is that analysis is pure, and manufacturer is Sinopharm Chemical Reagent Co., Ltd.；
Above-mentioned steps 7) in technical solution, the copper powder is the 10~80% of oleic acid mass content, preferably 40%；When ultrasonic
Between are as follows: 20~60min, preferably 40min.
Above-mentioned steps 8) in technical solution, base oil 500SN, ten dihydroxystearic acids are technical grade, and lithium hydroxide is
It analyzes pure.
PERFORMANCE OF GREASES is evaluated by four ball-type friction wear testing machines, experiment condition is room temperature, secondary to friction
Apply the load of 140~490N, the friction selfreparing secondary to friction of 1200r/min revolving speed, preferably 392N loading analysis lubricating grease
The influence of performance；Copper nanoparticle additive amount is the 0.3~1% of quality of lubrication oil content, preferably 0.4%.
Compared with prior art, the beneficial effects of the present invention are:
It is of the present invention a kind of using waste and old circuit board recycling copper nanoparticle and selfreparing preparation of greases method, it is special
It is not a kind of method for recycling copper nanoparticle and improving its added value.The copper nanoparticle good dispersion of method preparation, can be used for
In lubricating grease, and experimental implementation is simple, at low cost.
Specific embodiment
Below by embodiment, the invention will be further described, but the present invention is not limited only to following Examples.Pass through this
A little embodiments can fully understand essence and invention scope of the invention, further appreciate that synthesis and separation of the present invention
The characteristics of technique.
Embodiment 1:
The extraction of Salzburg vitriol crystal in cupric waste and old circuit board:
Step 1, cupric waste and old circuit board is crushed to average grain diameter about 1mm with grinder；
Step 2, this powder raw material is sorted with waterpower shaking table in advance, weight density metal group is sub-elected by density difference
Divide and light density non-metallic component, weight density components are the raw metal of leaching process；
Step 3, anhydrous cupric sulfate 6.25g/L, HCl concentration 130g/L, n-butylamine concentration 36g/L, mixing speed are
300rpm, temperature 50 C, extraction time 5h, the leaching efficiency of copper is up to 97.7% in waste and old circuit board.
Step 4, extractant LK-C2 concentration is 18% (volume fraction), extraction time, initial pH value 3, organic phase and water
It is comparably 1:1, extraction time 4min, natural stratification, liquid separation sufficiently after oscillation obtain the organic phase of copper ions.
Step 5, using sulfuric acid as stripping agent, the copper ion in step 4 in organic phase is stripped to taking-up from organic phase, controlled
Organic phase is 2:1 compared with water in system back extraction liquid phase, and back-extraction time 3min fullys shake 10min and obtains strip liquor, evaporates this
After strip liquor to the 50% of original volume, it is put into gained Salzburg vitriol crystal after 0 DEG C of laboratory freezer crystallization.
Embodiment 2:
Salzburg vitriol crystal prepares copper nanoparticle:
It weighs Salzburg vitriol and 6gPVP prepared by 60g embodiment 1 and is made into copper in beaker with 1L deionized water dissolving
Solion, with ammonium hydroxide adjusting pH value to 11, wiring solution-forming A.1L deionized water is added in the sodium borohydride for separately weighing 9.06g, matches
At solution B.B solution is slowly dropped into solution A, 50 DEG C of constant temperature carry out magnetic agitation 1h, copper powder suspension is made.Then, by copper
Powder suspension is centrifugated out Cu particle, is cleaned 3 times with deionized water, and washes of absolute alcohol 1 time.Last 40 DEG C of vacuum drying,
Pure copper powder is obtained, it is 23nm that purity, which tests copper powder average grain diameter up to 99.91%, TEM,.
Embodiment 3:
Salzburg vitriol crystal prepares copper nanoparticle:
It weighs Salzburg vitriol and 3gPVP prepared by 60g embodiment 1 and is made into copper in beaker with 1L deionized water dissolving
Solion, with ammonium hydroxide adjusting pH value to 11, wiring solution-forming A.1L deionized water is added in the sodium borohydride for separately weighing 4.53g, matches
At solution B.B solution is slowly dropped into solution A, 50 DEG C of constant temperature carry out magnetic agitation 1h, copper powder suspension is made.Then, by copper
Powder suspension is centrifugated out Cu particle, is cleaned 3 times with deionized water, and washes of absolute alcohol 1 time.Last 40 DEG C of vacuum drying,
Pure copper powder is obtained, it is 52nm that purity, which tests copper powder average grain diameter up to 99.90%, TEM,.
Embodiment 4:
It is prepared by the lubricating oil of the powder containing Surface modification nanometer copper:
It takes 100g normal octane and 30g oleic acid to stir evenly and embodiment 2 is added and recycle obtained copper nanoparticle 12g, high speed shear
Machine, which stirs evenly, is placed in supersonic cleaning machine, and ultrasound 40min, is added into reaction kettle and is added the base of 1kg under the power of 560W
Plinth oil stirs evenly；Vacuum distillation, all steams to normal octane, obtains the lubricating oil containing copper nanoparticle.
Embodiment 5:
It is prepared by the lubricating oil of the powder containing Surface modification nanometer copper:
It takes 100g normal octane and 30g oleic acid to stir evenly and embodiment 2 is added and recycle obtained copper nanoparticle 24g, high speed shear
Machine, which stirs evenly, is placed in supersonic cleaning machine, and ultrasound 40min, is added into reaction kettle and is added the base of 1kg under the power of 560W
Plinth oil stirs evenly；Vacuum distillation, all steams to normal octane, obtains the lubricating oil containing copper nanoparticle.
Embodiment 6:
The selfreparing preparation of greases of modified 0.4% copper nanoparticle containing surface:
Ten dihydroxystearic acid of 300g is taken, the base oil of 40g lithium hydroxide, deionized water 200mL and 1kg is added to refining
110 DEG C of saponification 2h are heated in kettle.Then, 149 DEG C of moisture sloughed after saponification are warming up to.Then, extruding step-up temperature is simultaneously
1kg embodiment 4 is added and prepares the base oil containing copper nanoparticle.It is added in mixture, and will mix finally, 1kg base oil is added
Object is closed to cool down immediately.It is stirred the mixture for uniformly preparing the selfreparing lubricating grease containing 0.4% copper nanoparticle with three-roll mill.
This selfreparing lubricating grease load for applying 392N secondary to friction at room temperature, when 1200r/min revolving speed, wear scar diameter is
0.35mm, coefficient of friction 0.0665.
Comparative example 1:
Preparation without selfreparing lithium base grease:
Ten dihydroxystearic acid of 200g is taken, the base oil of 40g lithium hydroxide, deionized water 200mL and 1kg is added to refining
110 DEG C of saponification 2h are heated in kettle.Then, 149 DEG C of moisture sloughed after saponification are warming up to.Then, extruding step-up temperature is simultaneously
1kg base oil is added.Then mixture is cooled down immediately, this lithium base grease is secondary to friction at room temperature to apply 392N's
Load, when 1200r/min revolving speed, wear scar diameter 0.59mm, coefficient of friction 0.0993.
Comparative example 2:
The selfreparing preparation of greases of modified 0.8% copper nanoparticle containing surface:
Ten dihydroxystearic acid of 300g is taken, the base oil of 40g lithium hydroxide, deionized water 200mL and 1kg is added to refining
110 DEG C of saponification 2h are heated in kettle.Then, 149 DEG C of moisture sloughed after saponification are warming up to.Then, extruding step-up temperature is simultaneously
1kg embodiment 5 is added and prepares the base oil containing 0.8% copper nanoparticle.It is added in mixture finally, 1kg base oil is added, and
Mixture is cooled down immediately.Stir the mixture for uniformly preparing the lubrication of the selfreparing containing 0.8% copper nanoparticle with three-roll mill
Rouge.This selfreparing lubricating grease load for applying 392N secondary to friction at room temperature, when 1200r/min revolving speed, wear scar diameter
For 0.47mm, coefficient of friction 0.0811.
It can be seen that the selfreparing lubricating grease of 0.4% copper nanoparticle of addition (as implemented from embodiment 6 and 1 result of comparative example
Example 6) compared to copper nanoparticle (such as comparative example 1) lithium saponify is not added, wear scar diameter and coefficient of friction drop decline to a great extent；Together
When selfreparing lubricating grease (such as comparative example 2) relative to 0.8% copper nanoparticle, the selfreparing lubrication of 0.4% copper nanoparticle of addition
Rouge (such as embodiment 6) wear-resisting property is more excellent.
It is raw material that the present invention, which selects waste and old circuit board, and by crushing, leachate extraction, stripping agent separates copper ion, and leads to
It crosses chemical reduction method and extracts copper nanoparticle, the surfactant modified surface finish nano copper powder lubricating prepared is added
Oil；The lubricating grease of self repairing agent containing copper nanoparticle is prepared using saponification, realizes the lubricating grease self-healing properties secondary to friction, it is real
Test it is easy to operate, it is at low cost, be a kind of both economical preparation method.Meanwhile the present invention obtains waste and old circuit board recycling metal
Economic and environment-friendly, metal resource high added value recycle may be implemented in technique.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality
Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention
It is interior.
Claims (9)
1. a kind of utilize waste and old circuit board recycling copper nanoparticle and selfreparing preparation of greases method, it is characterised in that: including
Following steps:
1) raw material is the particle that cupric waste and old circuit board is crushed to 0.8~1.2mm of average grain diameter with grinder；
2) above-mentioned particles with water power shaking table is sorted, weight density metal component is sub-elected by density difference and light density is non-
Metal component, weight density components are the raw metal of leaching process；
3) certain density leaching agent: hydrochloric acid, n-butylamine and anhydrous cupric sulfate is added in raw metal, by magnetic stirring apparatus into
Row stirring obtains copper ions solution after reacting a period of time at a certain temperature；
4) initial pH value that copper ions solution is adjusted by sulfuric acid and sodium hydroxide, passes through extractant LK-C2 and sulfonated kerosene
Copper in water phase copper ions solution is extracted into organic phase by organic phase；
5) it uses a certain amount of sulfuric acid as stripping agent, the copper ion in organic phase is stripped, back extraction ratio is dense by stripping agent sulfuric acid
Degree is affected, and control strip liquor is compared, and back-extraction time fullys shake and is stripped, and crystallization obtains Salzburg vitriol；
6) step 5) is extracted to obtained Salzburg vitriol dissolution in deionized water and adds polyvinylpyrrolidone, is passed through
Nitric acid or ammonium hydroxide adjustment pH value reach certain value, and oxidizing agent solution A is made；By the sodium borohydride reduction of a certain amount of concentration
Agent solution B, is slowly dropped in solution A, carries out magnetic agitation at a certain temperature and obtains the dispersion liquid containing copper powder；Next handle
Obtained copper dispersion liquid obtains copper powder by centrifuge separation, then is washed with deionized water three times, is washed one time with alcohol, and last vacuum is dry
Dry processing can be obtained pure copper powder；
7) it takes a certain amount of normal octane and oleic acid to stir evenly and step 6) is added and recycle obtained copper nanoparticle, high-speed shearing machine stirs well even
It is placed in supersonic cleaning machine ultrasound certain time, is added into reaction kettle and base oil is added and stir evenly；Vacuum distillation, to
Normal octane all steams, and obtains the lubricating oil of the powder containing Surface modification nanometer copper；
8) a certain amount of ten dihydroxystearic acid, lithium hydroxide aqueous solution and base oil is taken to be added to heating saponification one in refining kettle
After fixing time, the moisture after saponification is sloughed in heating；Then, extruding step-up temperature and be added obtain changing containing surface with step 7)
Property copper powder lubricating oil and a certain amount of base oil be uniformly mixed, it is then that mixture is cooling；This mixture is divided with three-roll mill
It dissipates uniformly, prepares the selfreparing lubricating grease containing copper nanoparticle.
2. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: step 3) the HCl solution concentration is 100g~200g/L, the n-butylamine concentration is 20g~100g/L, the nothing
The concentration of brochanite is 5g~10g/L.
3. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: the step 3) mixing speed is 400~600rpm, reaction temperature is 10~60 DEG C.
4. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: step 4) initial pH value is 0.2~4.0；Oily is mutually 4:1~1:4 with water phase volume ratio.
5. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: step 4) extractant LK-C2 is in the volumetric concentration in oily phase in 3%~40% range；Extraction time 1~
10min range.
6. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: step 5) stripping agent sulfuric acid concentration ranges are as follows: 0.3~4mol/L, strip liquor oil is mutually compared with water phase are as follows: 1:3~
3:1, back-extraction time are as follows: 2~10min.
7. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: step 6) is 9~13 by the range that nitric acid or ammonium hydroxide adjust pH value.
8. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: the concentration of step 6) Salzburg vitriol is 50~80g/L；The quality of polyvinylpyrrolidone and Salzburg vitriol
Than for 1:5-1:10；The molar ratio of sodium borohydride and Salzburg vitriol is 1:4~1:1.
9. the recycling and selfreparing preparation of greases method of copper powder in waste and old circuit board according to claim 1, special
Sign is: copper powder is the 10~80% of oleic acid mass content, ultrasonic time are as follows: 20~60min in step 7).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111979027A (en) * | 2020-09-07 | 2020-11-24 | 上海中孚特种油品有限公司 | Long-acting electricity-saving two-for-one twister oil and preparation method thereof |
| CN113430044A (en) * | 2021-07-23 | 2021-09-24 | 西安热工研究院有限公司 | Method for removing metal impurity elements in wind power gear oil |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200670A (en) * | 2006-12-12 | 2008-06-18 | 中国石油天然气集团公司 | Composite lithium-base grease and method for making same |
| US20100298180A1 (en) * | 2006-12-01 | 2010-11-25 | Henkel Corporation | Anti-seize composition with nano-sized lubricating solid particles |
| US20140005083A1 (en) * | 2012-07-02 | 2014-01-02 | Nanomech, Inc. | Textured surfaces to enhance nano-lubrication |
| CN104629881A (en) * | 2015-01-29 | 2015-05-20 | 山东宏泽石油化工有限公司 | Anti-wear repairing high-speed special bearing grease and production method thereof |
| CN105925360A (en) * | 2016-05-04 | 2016-09-07 | 金陵科技学院 | Preparing method for lithium-base grease with self-repairing agent added |
| CN107400780A (en) * | 2017-07-18 | 2017-11-28 | 四川长虹电器股份有限公司 | A kind of method that gold, silver and bronze are extracted in the plate from cell phone lines |
| CN108559599A (en) * | 2018-05-31 | 2018-09-21 | 江苏大学 | A kind of preparation method of the complex lithium grease containing Nanometer Copper |
| CN108570560A (en) * | 2018-06-11 | 2018-09-25 | 李天麟 | A method of recycling copper from copper-bearing waste material |
-
2019
- 2019-04-19 CN CN201910317439.XA patent/CN110029009A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100298180A1 (en) * | 2006-12-01 | 2010-11-25 | Henkel Corporation | Anti-seize composition with nano-sized lubricating solid particles |
| CN101200670A (en) * | 2006-12-12 | 2008-06-18 | 中国石油天然气集团公司 | Composite lithium-base grease and method for making same |
| US20140005083A1 (en) * | 2012-07-02 | 2014-01-02 | Nanomech, Inc. | Textured surfaces to enhance nano-lubrication |
| CN104629881A (en) * | 2015-01-29 | 2015-05-20 | 山东宏泽石油化工有限公司 | Anti-wear repairing high-speed special bearing grease and production method thereof |
| CN105925360A (en) * | 2016-05-04 | 2016-09-07 | 金陵科技学院 | Preparing method for lithium-base grease with self-repairing agent added |
| CN107400780A (en) * | 2017-07-18 | 2017-11-28 | 四川长虹电器股份有限公司 | A kind of method that gold, silver and bronze are extracted in the plate from cell phone lines |
| CN108559599A (en) * | 2018-05-31 | 2018-09-21 | 江苏大学 | A kind of preparation method of the complex lithium grease containing Nanometer Copper |
| CN108570560A (en) * | 2018-06-11 | 2018-09-25 | 李天麟 | A method of recycling copper from copper-bearing waste material |
Non-Patent Citations (2)
| Title |
|---|
| 付云芝 等: "《应用化学综合实验教程》", 31 August 2012, 中国财富出版社 * |
| 杨乐: "废旧电路板中湿法冶金回收铜并制备超细铜粉的研究", 《中国学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111979027A (en) * | 2020-09-07 | 2020-11-24 | 上海中孚特种油品有限公司 | Long-acting electricity-saving two-for-one twister oil and preparation method thereof |
| CN111979027B (en) * | 2020-09-07 | 2022-08-23 | 上海中孚油品集团有限公司 | Long-acting electricity-saving two-for-one twister oil and preparation method thereof |
| CN113430044A (en) * | 2021-07-23 | 2021-09-24 | 西安热工研究院有限公司 | Method for removing metal impurity elements in wind power gear oil |
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