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CN109354054A - A kind of method for preparing copper oxide powder by recovering copper from printing waste printing plate - Google Patents

A kind of method for preparing copper oxide powder by recovering copper from printing waste printing plate Download PDF

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Publication number
CN109354054A
CN109354054A CN201811484554.8A CN201811484554A CN109354054A CN 109354054 A CN109354054 A CN 109354054A CN 201811484554 A CN201811484554 A CN 201811484554A CN 109354054 A CN109354054 A CN 109354054A
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CN
China
Prior art keywords
copper
ammonia
oxide powder
printing
kun
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Pending
Application number
CN201811484554.8A
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Chinese (zh)
Inventor
王小亮
王伟
康勇
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Wenshui Xinbiao Renewable Resources Co Ltd
Shaanxi University of Technology
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Wenshui Xinbiao Renewable Resources Co Ltd
Shaanxi University of Technology
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Priority to CN201811484554.8A priority Critical patent/CN109354054A/en
Publication of CN109354054A publication Critical patent/CN109354054A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00Compounds of copper
    • C01G3/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of from printing with recycling copper in useless version Kun for the method for cupric oxide powder, uses useless version Kun acid processing by that will print, dissolves the chromium on surface, the obtained useless version Kun for removing surface chromium;The useless version Kun for removing surface chromium is placed in ammonia solution, and is passed through air and dissolves the useless surface version Kun copper, obtains ammonia formula carbonic acid copper solution;Ammonia formula carbonic acid copper solution is transferred in heating kettle, 100 DEG C are to slowly warm up in 1~2h, keeps the temperature 1h, Kocide SD is made after discharging ammonia completely, the ammonia of release is absorbed through absorption plant to be recycled;Kocide SD mixed liquor is transferred in settling tank through settling separated from the water, the Kocide SD that solid is dried powdered;Kocide SD is calcined at high temperature, cupric oxide powder is made.The method of the present invention is simple, easy to operate, and byproduct of reaction is less, and the yield of cupric oxide powder is up to 95%, purity up to 98% or more.

Description

A method of copper is recycled from printing in useless version Kun for cupric oxide powder
Technical field
The invention belongs to copper scrap resource reutilization technical fields, more particularly to one kind to recycle copper in useless version Kun from printing The method of standby cupric oxide powder.
Background technique
Useless version Kun is the waste as caused by large-sized print factory, annual to generate about few hundred thousand tonnes of, version Kun main component of giving up For iron, contain 0.3%~1.0% chromium and 2.5%~5% copper.The internal layer of useless version Kun is iron, iron surface successively copper facing, chromium.
Cupric oxide powder is mainly used for colorant, the You Jihe of fireworks, ceramics and glass as important Inorganic Chemicals At catalyst, the desulfurizing agent of oils, magnetic material, circuit version plating of electronic industry, manufacture artificial silk and gas analysis etc. Industry.The production method of cupric oxide powder mainly has the oxidizing process of molten state copper, the molten copper-of alkali precipitation-calcination method, ammonium hydroxide containing mantoquita Calcination method.Patent CN201310571018.2 disclose it is a kind of by waste and old red copper wire or red copper bar, by red copper wire or red copper bar It is cut into fritter, is put into embedded with being heated in copper lining board or high temperature resistant stainless steel copper lining board rotary furnace, and red copper is added in rotary furnace Ball is passed through oxygen reaction generation copper oxide after being heated to certain temperature as abrading-ball.Patent CN201410550840.5 is disclosed Using copper sheet as raw material, ammonia leaching process preparation copper ammonia complexation solution evaporates to obtain alkali formula carbon using tiny structure one kind by secondary filter Sour copper obtains active oxidation copper powder product through low temperature calcination, and the leaching copper raw material in the technique mainly is ammonium hydroxide, accurate overanxious institute Membrane aperture is 2~5 microns and is difficult to carry out.CN201410240133.6 is reported to be dissolved in industrial acetic copper or copper nitrate In pure water, powdery cocoanut active charcoal is added, with ammonium hydroxide or carbonic acid hydrogen ammonium tune pH value, and is precipitated under ultrasound condition, from anti- Collection target product high pure and ultra-fine cupric oxide powder in product is answered, ultrafine copper oxide powder purity is up to 99%.Patent CN102320644A is reported using copper sulphate as raw material, and using ammonium hydroxide as buffer, sodium hydroxide is precipitating reagent, reaction preparation oxidation Copper powder.However, the above-mentioned method raw materials for preparing copper oxide are high-purity red copper wire, red copper bar, copper sheet, copper acetate, nitric acid Copper or copper sulphate etc..
Summary of the invention
The purpose of the present invention is to provide a kind of from printing with recycling copper in useless version Kun for the method for cupric oxide powder, it is intended to Solving the existing method raw materials for preparing copper oxide is high-purity red copper wire, red copper bar, copper sheet, copper acetate, copper nitrate or sulphur The problem of sour copper etc..
The invention is realized in this way a method of copper is recycled from printing in useless version Kun for cupric oxide powder, the party Method the following steps are included:
(1) by printing useless version Kun acid processing, the chromium on surface is dissolved, the useless version Kun for removing surface chromium is made;
(2) the useless version Kun for removing surface chromium is placed in ammonia solution, and is passed through air and dissolves the useless surface version Kun copper, obtain ammonia Formula carbonic acid copper solution;Ammonia formula carbonic acid copper solution is transferred in heating kettle, 100 DEG C are to slowly warm up in 1~2h, 1h is kept the temperature, makes Kocide SD is made in ammonia after discharging completely, the ammonia of release is absorbed through absorption plant to be recycled;Kocide SD mixed liquor is turned Enter in settling tank through settling separated from the water, the Kocide SD that solid is dried powdered;
(3) Kocide SD is calcined at high temperature and cupric oxide powder is made.
Preferably, in step (1), the acid be mass concentration be 2~37% hydrochloric acid, 2~50% sulfuric acid and/or 2~30% nitric acid.
Preferably, in step (1), the mass ratio of the material of chromium and acid ion is 1:(2~6 in the useless version Kun).
Preferably, in step (1), the reaction temperature of the acid processing is 10~40 DEG C, the reaction time is 0.5~12h.
Preferably, in step (2), the ammonia solution be mass concentration be 2~17.8% ammonium hydrogencarbonate, 2~50% Carbonic acid ammonia and/or 2~25% ammonium hydroxide.
Preferably, in step (2), copper in the useless version Kun, oxygen in air, ammonium ion the mass ratio of the material be 1:(1 ~10): (4~20).
Preferably, in step (2), it is 10~45 DEG C that ammonia, which dissolves copper reaction temperature, and the reaction time is 4~48h.
Preferably, in step (3), calcined under the high temperature specifically: 300~800 DEG C of temperature lower calcinations 0.5~ 10h。
The present invention overcomes the deficiencies of the prior art and provide a kind of use in useless version Kun from printing and recycles copper for cupric oxide powder Method, comprising steps of dissolving the chromium on surface, chromous salts being made printing useless version Kun acid processing;The useless of surface chromium will be removed Version Kun, which is placed in ammonia solution and is passed through air, dissolves the useless surface version Kun copper, obtains ammonia formula carbonic acid copper solution;Then in heating condition Under release ammonia be made Kocide SD;Kocide SD obtained is calcined at high temperature is made cupric oxide powder.
Compared with the prior art the shortcomings that and deficiency, the invention has the following advantages:
(1) from the yield of useless version Kun recycling copper and obtained cupric oxide powder up to 95%, the purity of copper oxide reaches the method for the present invention 98% or more;
(2) the method for the present invention is simple, easy to operate, and byproduct of reaction is less, and correlated response product can be with repetitive cycling It uses, energy-efficient, cost is lower;
(3) remove surface chromium, copper useless version Kun main component iron content be 98% or more, can be used as excellent iron material Material.
Detailed description of the invention
Fig. 1 is the process flow chart that the useless version Kun of the present invention prepares cupric oxide powder.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
Embodiment
(1) it weighs the useless version Kun of 10.0kg to be placed in 5 liters of groove type reactors of glass, prepared acid solution is added, one It is reacted under fixed temperature and time, useless version Kun is rotated in reaction process.Concrete outcome is as shown in table 1 below:
The chromium experiment condition on the useless surface version Kun is dissolved in 1 acid processing of table
By the experimental result of embodiment 1~17 in table 1 provided it is found that well the surface useless version Kun in embodiment Chromium all dissolves, and the surface version Kun of giving up is in the copper color of glassy yellow.
(2) ammonium bicarbonate solution is added in 100L slot type stainless steel reactor, the useless version Kun of 10.0kg removal chromium is added, It is heated to the temperature of setting, air is periodically passed through, is reacted under setting time, end of reaction, removes useless version Kun, solution, which is transferred to, to be added It in hot kettle, is to slowly warm up to 100 DEG C (1~2h), keeps the temperature 1h, Kocide SD is made after discharging ammonia completely.Ammonia is through absorbing Device, which absorbs, to be recycled.Kocide SD is separated from the water through settling, and obtains powdered Kocide SD through drying.
Specific embodiment parameter and its reaction result such as following table 2-1, shown in table 2-2, table 2-3 and table 2-4:
The copper experiment condition on the useless surface version Kun is dissolved in the processing of table 2-1 ammonium hydrogencarbonate
The copper experiment condition on the useless surface version Kun is dissolved in table 2-2 carbonic acid ammonia treatment
Table 2-3 AMMONIA TREATMENT dissolves the copper experiment condition on the useless surface version Kun
The AMMONIA TREATMENT that table 2-4 recycles dissolves the copper experiment condition on the useless surface version Kun
Difference it can be seen from the quality of the reaction condition and Kocide SD that are provided by embodiment 18~68 in table 2-1~2-4 Give up under the concentration of ammonium hydrogencarbonate, differential responses temperature and differential responses time conditions the surface version Kun copper dissolved well under It is converted to four ammino copper, adds hydrogen to decompose and generate Kocide SD.
(3) Kocide SD made from is calcined in high-temperature calcination stove, sampling amount, calcination temperature, calcination time parameter and oxygen Change copper yield such as table 3.
3 different temperatures of table and Kocide SD is calcined under the time
It can be seen from embodiment 69~85 when 300~800 DEG C of calcination temperature, calcination time produces in 0.5~12h The yield of product copper oxide is 95.0% or more, and the purity of copper oxide is 98.0% or more.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (8)

1.一种从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,该方法包括以下步骤:1. a method for preparing copper oxide powder by reclaiming copper from printing waste printing plate is characterized in that, the method comprises the following steps: (1)将印刷用废版锟用酸处理,溶解表面的铬,制得除去表面铬的废版锟;(1) treating the waste printing plate with acid to dissolve the chromium on the surface to obtain the waste printing plate that removes the surface chromium; (2)将去除表面铬的废版锟置于氨溶液中,并通入空气溶解废版锟表面铜,获得氨式碳酸铜溶液;将氨式碳酸铜溶液转入加热釜中,在1~2h内缓慢升温至100℃,保温1h,使氨气完全释放后制得氢氧化铜,释放的氨气经吸收装置吸收再利用;将氢氧化铜混合液转入沉降池中经沉降与水相分离,固体经晾干得粉末状的氢氧化铜;(2) place the waste plate Kun that removes the surface chromium in ammonia solution, and pass into the air to dissolve the surface copper of the waste plate Kun to obtain ammonia copper carbonate solution; transfer the ammonia copper carbonate solution into the heating kettle, at 1 ~ The temperature was slowly raised to 100 °C within 2 hours, and the temperature was kept for 1 hour, so that the ammonia gas was completely released to obtain copper hydroxide. The released ammonia gas was absorbed and reused by the absorption device; the copper hydroxide mixed solution was transferred to the sedimentation tank for sedimentation and water phase Separation, the solid is dried to obtain powdered copper hydroxide; (3)将氢氧化铜在高温下煅烧制得氧化铜粉。(3) calcining copper hydroxide at high temperature to obtain copper oxide powder. 2.如权利要求1所述的从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,在步骤(1)中,所述酸为质量浓度为2~37%的盐酸、2~50%的硫酸和/或2~30%的硝酸。2. the method for preparing copper oxide powder from reclaiming copper from printing waste plate mill as claimed in claim 1, is characterized in that, in step (1), described acid is the hydrochloric acid that mass concentration is 2~37%, 2-50% sulfuric acid and/or 2-30% nitric acid. 3.如权利要求2所述的从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,在步骤(1)中,所述废版锟中铬与酸离子的物质的量比为1:(2~6)。3. the method for preparing copper oxide powder by reclaiming copper from printing waste plate mill as claimed in claim 2, is characterized in that, in step (1), the amount of substance of chromium and acid ion in described waste plate mill The ratio is 1:(2~6). 4.如权利要求3所述的从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,在步骤(1)中,所述酸处理的反应温度为10~40℃、反应时间为0.5~12h。4. the method for preparing copper oxide powder by reclaiming copper from printing waste plate mill as claimed in claim 3, is characterized in that, in step (1), the reaction temperature of described acid treatment is 10~40 ℃, reaction The time is 0.5 to 12 hours. 5.如权利要求1所述的从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,在步骤(2)中,所述氨溶液为质量浓度为2~17.8%的碳酸氢氨、2~50%的碳酸氨和/或2~25%的氨水。5. the method for preparing copper oxide powder by reclaiming copper from printing waste plate rolls as claimed in claim 1, is characterized in that, in step (2), described ammonia solution is the carbonic acid that mass concentration is 2~17.8% Hydrogen ammonia, 2-50% ammonia carbonate and/or 2-25% ammonia water. 6.如权利要求1所述的从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,在步骤(2)中,所述废版锟中铜、空气中氧气、氨离子的物质的量比为1:(1~10):(4~20)。6. the method for preparing copper oxide powder by reclaiming copper from printing waste printing plate as claimed in claim 1, is characterized in that, in step (2), in described waste printing plate copper, oxygen in the air, ammonia ion The amount ratio of the substances is 1:(1~10):(4~20). 7.如权利要求1所述的从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,在步骤(2)中,氨溶解铜反应温度为10~45℃,反应时间为4~48h。7. the method for preparing copper oxide powder by reclaiming copper from printing waste printing plate as claimed in claim 1, is characterized in that, in step (2), ammonia dissolved copper reaction temperature is 10~45 ℃, and the reaction time is 4~48h. 8.如权利要求1所述的从印刷用废版锟中回收铜制备氧化铜粉的方法,其特征在于,在步骤(3)中,所述高温下煅烧具体为:在300~800℃温度下煅烧0.5~10h。8. the method for preparing copper oxide powder by recovering copper from printing waste plate rolls as claimed in claim 1, is characterized in that, in step (3), calcining at described high temperature is specifically: at 300~800 ℃ temperature Lower calcination for 0.5-10h.
CN201811484554.8A 2018-12-06 2018-12-06 A kind of method for preparing copper oxide powder by recovering copper from printing waste printing plate Pending CN109354054A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110315243A (en) * 2019-07-03 2019-10-11 郑州机械研究所有限公司 The processing method of slag in a kind of copper-phosphorus brazing alloy
CN114804186A (en) * 2022-05-16 2022-07-29 吴江市威士达铜业科技有限公司 Production method and production device of copper oxide
CN115304093A (en) * 2022-08-10 2022-11-08 李晓清 Continuous production process of high-purity copper oxide based on ammonia circulation system
CN116422683A (en) * 2023-04-21 2023-07-14 重庆金美新材料科技有限公司 A kind of waste copper film recycling method

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CN1172074A (en) * 1997-08-15 1998-02-04 张礼英 Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion

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CN1172074A (en) * 1997-08-15 1998-02-04 张礼英 Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110315243A (en) * 2019-07-03 2019-10-11 郑州机械研究所有限公司 The processing method of slag in a kind of copper-phosphorus brazing alloy
CN110315243B (en) * 2019-07-03 2021-08-03 郑州机械研究所有限公司 A kind of processing method of slag in copper-phosphorus solder
CN114804186A (en) * 2022-05-16 2022-07-29 吴江市威士达铜业科技有限公司 Production method and production device of copper oxide
CN115304093A (en) * 2022-08-10 2022-11-08 李晓清 Continuous production process of high-purity copper oxide based on ammonia circulation system
CN116422683A (en) * 2023-04-21 2023-07-14 重庆金美新材料科技有限公司 A kind of waste copper film recycling method

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Application publication date: 20190219