CN111908499A - Method and device for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution - Google Patents
Method and device for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution Download PDFInfo
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 113
- 239000002699 waste material Substances 0.000 title claims abstract description 105
- 238000005530 etching Methods 0.000 title claims abstract description 74
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 51
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 51
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002253 acid Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 52
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 50
- 238000005406 washing Methods 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 39
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 230000002378 acidificating effect Effects 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 98
- 238000002425 crystallisation Methods 0.000 claims description 29
- 230000008025 crystallization Effects 0.000 claims description 29
- 239000012452 mother liquor Substances 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 16
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 238000011033 desalting Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- NZYJFRGHEGZHRV-UHFFFAOYSA-N [S-2].[Na+].[Cu+2] Chemical compound [S-2].[Na+].[Cu+2] NZYJFRGHEGZHRV-UHFFFAOYSA-N 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000001502 supplementing effect Effects 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005752 Copper oxychloride Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses a method and a device for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution, wherein the method comprises the following steps: (1) adding the waste alkaline etching solution into the waste acidic etching solution, stirring until the pH value reaches 5-6, stirring for reaction for 0.5-1 hour, filtering and washing to obtain basic copper chloride; (2) putting the basic copper chloride into sodium hydroxide, heating to above 60 ℃ until the pH of a reaction solution reaches 8-9, filtering, washing and drying to obtain a copper oxide product; (3) adding sodium sulfide into the basic copper chloride filtrate, stirring and reacting until the liquid is colorless and transparent, filtering, washing and recovering copper sulfide, and recovering the copper sulfide filtrate to prepare ammonium chloride; the method adopts two etching solutions with different acid and alkali properties to perform neutralization reaction with each other, so that the investment cost of an additional reagent is greatly reduced, valuable elements in the two waste solutions are well recycled, the treatment process is scientific and environment-friendly, the resource recovery is maximized, and the economic benefit and the environment-friendly benefit are very obvious.
Description
Technical Field
The invention relates to the technical field of environment-friendly treatment of waste acid and alkaline etching solution, in particular to a method and a device for preparing copper oxide and ammonium chloride by combining the waste acid and the alkaline etching solution.
Background
The waste acidic etching solution contains about 10% of copper, about 8% of free hydrochloric acid and about 2% of sodium chloride. The existing method for treating waste acidic etching solution comprises the following steps: the sponge copper is produced by using an iron replacement method, the wastewater containing a large amount of iron and trace copper after the sponge copper is recovered needs to be neutralized by calcium hydroxide to precipitate iron slag and is sent to landfill or recovery, and the wastewater is discharged to a sewage treatment plant. The method has high wastewater treatment cost, and the production environment is severe because hydrogen is generated in the production process of the sponge copper.
The main component of the waste alkaline etching solution is Cu (NH)3）4Cl2And Cu (NH)3）4CO3. The existing method for treating alkaline etching solution is as follows: adding sulfuric acid for acidification, precipitating basic copper chloride, removing trace copper from mother liquor, adding alkali, heating, evaporating, recovering ammonia water, and discharging the brine from which ammonia nitrogen is removed; the basic copper chloride is acidified by sulfuric acid to prepare copper sulfate, and after the copper sulfate is crystallized, the mother liquor continuously reacts with the alkaline etching solution, so that the circulation is realized. The main chemical reaction equation of the process principle is as follows:
4Cu（NH3）4Cl2 + 5H2SO4 = CuCl2 ·3Cu（OH）2↓+ 5（NH4）2SO4 + 6NH4Cl；
2Cu（NH3）4CO3 + 5H2SO4 = Cu2（OH）2SO4↓+ 4（NH4）2SO4 + 2CO2↑；
CuCl2 ·3Cu（OH）2 + 3H2SO4 =3CuSO4 + 2CuCl2 + 6H2O；
（NH4）2SO4 + NH4Cl +3NaOH = Na2SO4 + NaCl+ 3NH3 ↑+ 3H2O；
2NH3 + H2SO4 = （NH4）2SO4 。
although the copper sulfate product can be obtained in the treatment process, the content of chlorine seriously exceeds the standard, the copper sulfate can only be sold as a crude product or an agricultural product, and the relative value is low, more importantly, the waste liquid containing ammonium sulfate and ammonium chloride is difficult to process into a standard product, only the alkali is added and ammonia is evaporated for discharge, the treatment cost is extremely high, the waste of resources is also caused, and the economic cost is extremely low.
Therefore, the treatment methods of the waste acidic etching solution and the waste alkaline etching solution are relatively laggard at present, not only reasonable recycling of resources is not achieved, but also extra high treatment cost is brought, not only is no income created for enterprises, but also heavy burden is brought to the enterprises. Therefore, a new method and a new device for treating waste acidic etching solution and waste alkaline etching solution with low cost and environmental protection are developed to solve the above problems, which become a problem to be solved in the industry.
Disclosure of Invention
The invention aims to provide a method and a device for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution, aiming at the problems that the existing treatment methods of the waste acidic etching solution and the waste alkaline etching solution are relatively laggard, the reasonable recycling of resources is not achieved, and extra high treatment cost is brought.
The invention discloses a method for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution, which comprises the following steps:
(1) respectively collecting the waste acidic etching solution and the waste alkaline etching solution in a waste acid solution collecting tank and a waste alkaline solution collecting tank, adding the waste alkaline etching solution into the waste acidic etching solution, stirring and reacting until the pH value reaches 5-6, stopping adding the solution, stirring and reacting for 0.5-1 hour, discharging the materials to an alkali copper chloride filter, filtering and washing to obtain alkali copper chloride; respectively adding the next batch of waste acidic etching solution and waste alkaline etching solution into the waste acid solution collecting tank and the waste alkaline solution collecting tank for the next batch of treatment;
(2) putting basic copper chloride into a sodium hydroxide reaction tank, heating to above 60 ℃, stirring while heating until the pH of a reaction solution reaches 8-9, discharging the materials to a copper oxide filter, filtering and washing until the mass fraction of washing water chloride ions is less than or equal to 0.1%, and drying filter residues to obtain a copper oxide product;
(3) combining the basic copper chloride filtrate and the washing liquid obtained in the step (1), adding the basic copper chloride filtrate and the washing liquid into a sodium sulfide copper precipitation tank, detecting the content of copper ions in the liquid, adding sodium sulfide with the same molar amount of copper ions, stirring and reacting until the liquid is colorless and transparent, discharging the material to a copper sulfide filter, filtering, washing and recovering copper sulfide, and recovering the copper sulfide filtrate and the washing liquid to prepare ammonium chloride;
(4) and (3) combining the copper sulfide filtrate and the washing solution obtained in the step (3), adding the mixture into an ammonium chloride concentration tank for concentration, adding the mixture into an ammonium chloride crystallization tank for crystallization, centrifugally drying the crystals to obtain an ammonium chloride product, adding an ammonium chloride crystallization mother solution into an ammonium chloride desalting tank, detecting the sodium chloride content, adding ammonium sulfate with 0.5-time molar weight, supplementing water with 10% of the total solution amount, cooling to below 0 ℃, precipitating sodium sulfate decahydrate, centrifugally drying to obtain a sodium sulfate decahydrate product, and returning the desalted ammonium chloride crystallization mother solution to the ammonium chloride concentration tank to recover ammonium chloride or directly evaporating to recover ammonium chloride.
The waste acidic etching solution contains 8-12% of copper, 6-10% of free hydrochloric acid and 0.5-3% of sodium chloride.
The main component of the waste alkaline etching solution is Cu (NH)3）4Cl2And Cu (NH)3）4CO3。
The mass fraction of the sodium hydroxide in the step (2) is 3-15%.
The device used in the method for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution comprises a waste alkaline solution collecting tank and a waste acid solution collecting tank, wherein the waste acid solution collecting tank is provided with a stirring device, the top of the waste acid solution collecting tank is provided with a waste alkaline etching solution feeding port, the bottom of the waste acid solution collecting tank is provided with a discharge port, the discharge port is connected with an alkaline copper chloride filter through a pipeline, a sodium hydroxide reaction tank, a copper oxide filter and a copper oxide dryer are further arranged behind the discharge port of the alkaline copper chloride filter, and after alkaline copper chloride obtained by filtering is added into the sodium hydroxide reaction tank to generate copper oxide, the material is sent to the copper oxide filter to be filtered and washed and then sent to the copper oxide dryer to be dried; a liquid outlet pipe of the basic copper chloride filter is connected with a raw material inlet of a sodium sulfide copper deposition tank, and a discharge port of the sodium sulfide copper deposition tank is connected with the copper sulfide filter; the pipelines are provided with pumps and valves according to requirements.
The liquid outlet pipe of the copper sulfide filter is connected with a raw material inlet of an ammonium chloride concentration tank, concentrated ammonium chloride mother liquor is sent into an ammonium chloride crystallization tank for crystallization, crystallized ammonium chloride crystals and the crystallized mother liquor are sent into a centrifugal machine together for ammonium chloride recovery, the centrifuged ammonium chloride crystallized mother liquor is sent into an ammonium chloride desalting tank, the ammonium chloride desalting tank is provided with a cooling device, the top of the ammonium chloride desalting tank is provided with an ammonium sulfate feeding port, sodium chloride and ammonium sulfate in the ammonium chloride crystallized mother liquor react, sodium sulfate decahydrate is separated out at the temperature of below 0 ℃, the ammonium chloride crystallized mother liquor is sent into the centrifugal machine for centrifugal recovery of sodium sulfate decahydrate, and the desalted ammonium chloride crystallized mother liquor continuously returns to the raw material inlet of the ammonium chloride concentration tank for circular preparation of ammonium.
The process principle of the invention is as follows: mixing the waste alkaline etching solution and the waste acidic etching solution by utilizing the components of the waste alkaline etching solution and the waste acidic etching solution for neutralization reaction to generate basic copper chloride precipitate, filtering the basic copper chloride precipitate, and reacting the basic copper chloride precipitate with sodium hydroxide to prepare copper oxide; the liquid for filtering out the basic copper chloride contains trace copper ions besides the main component of ammonium chloride, filtrate with the main component of ammonium chloride is sent into an ammonium chloride concentration tank after sodium sulfide is adopted for decoppering, ammonium chloride is directly concentrated and crystallized and recovered, ammonium chloride crystallization mother liquor still contains more abundant sodium ions, sodium sulfide is generated by adopting a mode of adding ammonium sulfate, and after crystallization and removal, the ammonium chloride crystallization mother liquor is continuously returned to the ammonium chloride concentration tank to recycle the ammonium chloride; the main chemical reaction equations involved are as follows:
HCl + CuCl2+Cu（NH3）4Cl2+Cu（NH3）4CO3+H2O→CuCl2·3Cu（OH）2↓
+Cu（NH3）2Cl2+NH4Cl+CO2↑；
CuCl2·3Cu（OH）2+2NaOH
4CuO↓+2NaCl+4H2O；
Cu（NH3）2Cl2+Na2S+2H2O＝CuS↓+2NaCl+2NH3·H2O；
10H2O + 2NaCl+（NH4）2SO4 ＝Na2SO4·10H2O↓ + NH4cl (cooled below 0 ℃).
The method adopts alkaline etching solution and acidic etching solution to neutralize each other to generate copper chloride hydroxide precipitate, and the generated copper chloride hydroxide is converted into a copper oxide product by using sodium hydroxide; the method adopts two etching solutions with different acid and alkali properties to carry out neutralization reaction, greatly reduces the cost of an additional reagent, well recycles valuable elements in the two waste liquids, has scientific and environment-friendly treatment process, maximizes the resource recycling, and has very obvious economic benefit and environmental benefit.
Drawings
FIG. 1 is a process flow diagram of the present invention;
fig. 2 is a schematic view of the connection of the apparatus of the present invention.
In the figure: 1-waste lye collection tank, 2-waste acid liquid collection tank, 3-basic copper chloride filter, 4-sodium hydroxide reaction tank, 5-copper oxide filter, 6-copper oxide dryer, 7-sodium sulfide copper precipitation tank, 8-copper sulfide filter, 9-ammonium chloride concentration tank, 10-ammonium chloride crystallizing tank, 11-centrifuge, 12-ammonium chloride desalting tank, 13-centrifuge, 14-pump, 15-valve.
Detailed Description
The process of the present invention is further illustrated by the following specific examples, which are intended to be purely exemplary and are not intended to limit the invention in any way.
Example 1
Referring to fig. 1, a method for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution comprises the following steps:
(1) adding 500g (containing 12.1% of copper by mass) of waste alkaline etching solution into the waste acidic etching solution, stirring and reacting until the pH reaches 5.5, (consuming 556g of waste acidic etching solution, containing 10.15% of copper by mass), stopping adding liquid, stirring and reacting for 0.5 hour, discharging and filtering the materials, filtering and washing until the chlorine content of washing water is less than or equal to 0.2%, and obtaining basic copper chloride;
(2) putting copper oxychloride into 1250mL sodium hydroxide reaction tank with the mass fraction of 3%, heating to above 80 ℃, stirring while heating until the pH of a reaction liquid reaches 8.6 (stirring for reaction for about 2 hours), discharging the material, filtering and washing until the mass fraction of washing water chloride ions is less than or equal to 0.1% (washing water is discharged after meeting a silver nitrate test), drying (105 ℃, 4 hours) filter residue to obtain 144.1g of a copper oxide product, and detecting that the mass fraction of the copper oxide is 98.54%;
(3) combining the basic copper chloride filtrate and the washing liquid obtained in the step (1), adding the basic copper chloride filtrate and the washing liquid into a sodium sulfide copper precipitation tank, detecting the content of copper ions in the liquid, adding 7.3g of sodium sulfide with the mass fraction of 60%, stirring and reacting until the liquid is colorless and transparent, discharging the material to a copper sulfide filter, filtering, washing and recovering copper sulfide, and drying to obtain 5.5g of copper sulfide, wherein the detected mass fraction of the copper sulfide is 98.8%;
(4) and (3) combining the copper sulfide filtrate obtained in the step (3) with washing liquid, adding the mixture into an ammonium chloride concentration tank for concentration, adding the mixture into an ammonium chloride crystallization tank for crystallization, centrifugally drying crystals to obtain 193.6g (with the content of 99.5%) of an ammonium chloride product, adding ammonium chloride crystallization mother liquor into an ammonium chloride desalting tank, detecting the content of sodium chloride, adding ammonium sulfate with 0.5-time molar weight, supplementing water with the total liquor amount of 10%, cooling to below 0 ℃, precipitating sodium sulfate decahydrate, centrifugally drying to obtain 43.5g of a sodium sulfate decahydrate product, and returning the desalted ammonium chloride crystallization mother liquor to the ammonium chloride concentration tank to recover ammonium chloride.
Example 2
Referring to fig. 1 and 2, a method for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution comprises the following steps:
(1) respectively collecting waste acidic etching solution and waste alkaline etching solution in a waste acid solution collecting tank 2 and a waste alkaline solution collecting tank 1, adding the waste alkaline etching solution (450.6 kg is consumed and 12.1% of copper is contained) into the waste acidic etching solution (500 kg is consumed and 10.15% of copper is contained), stirring and reacting until the pH value reaches 6.0, stopping adding the solution, stirring and reacting for 1 hour, discharging the material to a basic copper chloride filter 3, filtering and washing to obtain basic copper chloride; respectively adding the next batch of waste acidic etching solution and waste alkaline etching solution into the waste acid solution collecting tank and the waste alkaline solution collecting tank for the next batch of treatment;
(2) putting 340kg of sodium hydroxide reaction tank 4 with the mass fraction of 10% into an alkali copper chloride, heating to above 70 ℃, stirring while heating until the pH of a reaction liquid reaches 9 (the time is about 2.5 hours), discharging the material to a copper oxide filter 5, filtering and washing until the mass fraction of washing water chloride ions is less than or equal to 0.1% (the washing water is discharged after being detected to be qualified by silver nitrate), putting the washing water into a copper oxide dryer 6, drying filter residues to obtain 129.6kg of copper oxide products, and detecting that the content of copper oxide is 98.86%;
(3) combining the basic copper chloride filtrate and the washing liquid obtained in the step (1), adding the basic copper chloride filtrate and the washing liquid into a sodium sulfide copper precipitation tank 7, detecting the copper ion content in the liquid, adding 6.5kg of sodium sulfide with the mass fraction of 60%, stirring and reacting until the liquid is colorless and transparent, discharging the material to a copper sulfide filter 8, filtering, washing, drying and recovering 4.8kg of copper sulfide (the detected copper sulfide content is 98.7%);
(4) and (3) combining the copper sulfide filtrate and the washing solution obtained in the step (3), adding the mixture into an ammonium chloride concentration tank 9 for concentration, adding the mixture into an ammonium chloride crystallization tank 10 for crystallization, adding the crystals into a centrifuge 11 for centrifugal drying to obtain 172kg of ammonium chloride products (the ammonium chloride content is 99.3% through detection), adding the ammonium chloride crystallization mother liquor into an ammonium chloride desalting tank 12 for detection of the sodium chloride content, adding 16kg of ammonium sulfate, supplementing 45L of water of the total liquor amount, cooling to below 0 ℃, precipitating sodium sulfate decahydrate, adding a centrifuge 13 for centrifugal drying to obtain 39kg of sodium sulfate decahydrate, evaporating the desalted ammonium chloride crystallization mother liquor to dryness to obtain 81.6kg of ammonium chloride, and detecting that the ammonium chloride content is 97.4%.
Example 3
Referring to fig. 1 and 2, a method for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution comprises the following steps:
(1) respectively collecting waste acidic etching solution and waste alkaline etching solution in a waste acid solution collecting tank and a waste alkaline solution collecting tank, adding the waste alkaline etching solution (451.7 kg is consumed, copper content is 12.2 percent) into the waste acidic etching solution (500 kg is consumed, copper content is 10.17 percent), stirring and reacting until the pH value reaches 5.0, stopping adding the solution, stirring and reacting for 1 hour, discharging the material to an alkaline copper chloride filter, filtering and washing to obtain alkaline copper chloride; respectively adding the next batch of waste acidic etching solution and waste alkaline etching solution into the waste acid solution collecting tank and the waste alkaline solution collecting tank for the next batch of treatment;
(2) putting 672kg of basic copper chloride into a 5% sodium hydroxide reaction tank, heating to above 60 ℃, stirring while heating until the pH of a reaction liquid reaches 8 (about 3 hours), discharging the material to a copper oxide filter, filtering and washing until the mass fraction of washing water chloride ions is less than or equal to 0.1% (washing water is discharged after being detected to be qualified by silver nitrate), and drying filter residues to obtain 128.87kg of a copper oxide product, wherein the copper oxide content is detected to be 98.47%;
(3) combining the basic copper chloride filtrate and the washing liquid obtained in the step (1), adding the basic copper chloride filtrate and the washing liquid into a sodium sulfide copper precipitation tank, detecting the content of copper ions in the liquid, adding 6.9kg of sodium sulfide with the mass fraction of 60%, stirring and reacting until the liquid is colorless and transparent, discharging the material to a copper sulfide filter, filtering, washing, drying and recovering 5.1kg of copper sulfide (the content of the copper sulfide is 98.6% through detection);
(4) and (3) combining the copper sulfide filtrate and the washing solution obtained in the step (3), adding the mixture into an ammonium chloride concentration tank for concentration, adding the mixture into an ammonium chloride crystallization tank for crystallization, carrying out centrifugal drying on the crystals to obtain 169kg of ammonium chloride products (the ammonium chloride content is 99.6% through detection), adding ammonium chloride crystallization mother liquor into an ammonium chloride desalting tank, detecting the sodium chloride content, adding 16kg of ammonium sulfate, supplementing 45L of water in the total liquor amount, cooling to below 0 ℃, precipitating sodium sulfate decahydrate, carrying out centrifugal drying to obtain 39.8kg of sodium sulfate decahydrate, and evaporating the desalted ammonium chloride crystallization mother liquor to dryness to obtain 81.4kg of ammonium chloride, wherein the ammonium chloride content is 97.5% through detection.
Example 4
Referring to fig. 2, a device used in a method for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution comprises a waste alkaline solution collecting tank 1 and a waste acid solution collecting tank 2, wherein the waste acid solution collecting tank is provided with a stirring device, the top of the waste acid solution collecting tank is provided with a waste alkaline etching solution feeding port, the bottom of the waste acid solution collecting tank is provided with a discharge port, the discharge port is connected with an alkaline copper chloride filter 3 through a pipeline, a sodium hydroxide reaction tank 4, a copper oxide filter 5 and a copper oxide dryer 6 are further arranged behind the discharge port of the alkaline copper chloride filter, and after the filtered alkaline copper chloride is added into the sodium hydroxide reaction tank to generate copper oxide, the material is sent to the copper oxide filter to be filtered and washed and then sent to the copper oxide dryer; the liquid outlet pipe of the basic copper chloride filter is connected with the raw material inlet of a sodium sulfide copper deposition tank 7, and the discharge port of the sodium sulfide copper deposition tank is connected with a copper sulfide filter 8.
A liquid outlet pipe of the copper sulfide filter 8 is connected with a raw material inlet of an ammonium chloride concentration tank 9, concentrated ammonium chloride mother liquor is sent into an ammonium chloride crystallization tank 10 for crystallization, crystallized ammonium chloride crystals and the crystallized mother liquor are sent into a centrifugal machine 11 together for ammonium chloride recovery, the centrifuged ammonium chloride crystallized mother liquor is sent into an ammonium chloride desalting tank 12, the ammonium chloride desalting tank is provided with a cooling device, the top of the ammonium chloride desalting tank is provided with an ammonium sulfate feeding port, sodium chloride and ammonium sulfate in the ammonium chloride crystallized mother liquor react and are sent into a centrifugal machine 13 for centrifugal recovery of sodium sulfate decahydrate after sodium sulfate decahydrate is separated out at the temperature of below 0 ℃, and the desalted ammonium chloride crystallized mother liquor continuously returns to the raw material inlet of the ammonium chloride concentration tank 9 for circular preparation of ammonium chloride; the pipes are provided with a pump 14 and a valve 15 as required.
The above-described embodiments are not intended to limit the present invention in any way, and any process or apparatus similar or equivalent to the principles of the present invention, which is carried out under the principles of the claims, is considered to fall within the scope of the claims.
Claims (7)
1. A method for preparing copper oxide and ammonium chloride by combining waste acid and alkaline etching solution is characterized by comprising the following steps:
(1) respectively collecting the waste acidic etching solution and the waste alkaline etching solution in a waste acid solution collecting tank and a waste alkaline solution collecting tank, adding the waste alkaline etching solution into the waste acidic etching solution, stirring and reacting until the pH value reaches 5-6, stopping adding the solution, stirring and reacting for 0.5-1 hour, discharging the materials to an alkali copper chloride filter, filtering and washing to obtain alkali copper chloride; respectively adding the next batch of waste acidic etching solution and waste alkaline etching solution into the waste acid solution collecting tank and the waste alkaline solution collecting tank for the next batch of treatment;
(2) putting basic copper chloride into a sodium hydroxide reaction tank, heating to above 60 ℃, stirring while heating until the pH of a reaction solution reaches 8-9, discharging the materials to a copper oxide filter, filtering and washing until the mass fraction of washing water chloride ions is less than or equal to 0.1%, and drying filter residues to obtain a copper oxide product;
(3) and (2) combining the basic copper chloride filtrate and the washing liquid obtained in the step (1), adding the basic copper chloride filtrate and the washing liquid into a sodium sulfide copper precipitation tank, detecting the content of copper ions in the liquid, adding sodium sulfide with the same molar amount of copper ions, stirring and reacting until the liquid is colorless and transparent, discharging the material to a copper sulfide filter, filtering, washing and recovering copper sulfide, and recovering the copper sulfide filtrate and the washing liquid to prepare ammonium chloride.
2. The method for jointly preparing copper oxide and ammonium chloride by using waste acid and alkaline etching solution as claimed in claim 1, wherein the method comprises the following steps: and (3) combining the copper sulfide filtrate and the washing solution obtained in the step (3), adding the mixture into an ammonium chloride concentration tank for concentration, adding the mixture into an ammonium chloride crystallization tank for crystallization, centrifugally drying the crystals to obtain an ammonium chloride product, adding an ammonium chloride crystallization mother solution into an ammonium chloride desalting tank, detecting the sodium chloride content, adding ammonium sulfate with 0.5-time molar weight, supplementing water with 10% of the total solution amount, cooling to below 0 ℃, precipitating sodium sulfate decahydrate, centrifugally drying to obtain a sodium sulfate decahydrate product, and returning the desalted ammonium chloride crystallization mother solution to the ammonium chloride concentration tank to recover ammonium chloride or directly evaporating to recover ammonium chloride.
3. The method for jointly preparing copper oxide and ammonium chloride by using waste acid and alkaline etching solution as claimed in claim 1, wherein the method comprises the following steps: the waste acidic etching solution contains 8-12% of copper, 6-10% of free hydrochloric acid and 0.5-3% of sodium chloride.
4. The method for jointly preparing copper oxide and ammonium chloride by using waste acid and alkaline etching solution as claimed in claim 1, wherein the method comprises the following steps: the main component of the waste alkaline etching solution is Cu (NH)3）4Cl2And Cu (NH)3）4CO3。
5. The method for jointly preparing copper oxide and ammonium chloride by using waste acid and alkaline etching solution as claimed in claim 1, wherein the method comprises the following steps: the mass fraction of the sodium hydroxide in the step (2) is 3-15%.
6. The device for the combined preparation method of copper oxide and ammonium chloride by using the waste acid and the alkaline etching solution as claimed in any one of claims 1 to 4, which comprises a waste alkali solution collecting tank and a waste acid solution collecting tank, and is characterized in that: the waste acid liquid collecting tank is provided with a stirring device, the top of the waste acid liquid collecting tank is provided with a waste alkaline etching liquid feeding port, the bottom of the waste acid liquid collecting tank is provided with a discharge port, the discharge port is connected with an alkaline copper chloride filter through a pipeline, a sodium hydroxide reaction tank, a copper oxide filter and a copper oxide dryer are further arranged behind the slag outlet of the alkaline copper chloride filter, the filtered alkaline copper chloride is added into the sodium hydroxide reaction tank to generate copper oxide, and then the material is sent to the copper oxide filter to be filtered and washed and is sent to the copper oxide dryer to be dried; a liquid outlet pipe of the basic copper chloride filter is connected with a raw material inlet of a sodium sulfide copper deposition tank, and a discharge port of the sodium sulfide copper deposition tank is connected with the copper sulfide filter; the pipelines are provided with pumps and valves according to requirements.
7. The device for the combined preparation method of the copper oxide and the ammonium chloride by the waste acid and the alkaline etching solution according to claim 6, is characterized in that: the liquid outlet pipe of the copper sulfide filter is connected with a raw material inlet of an ammonium chloride concentration tank, concentrated ammonium chloride mother liquor is sent into an ammonium chloride crystallization tank for crystallization, crystallized ammonium chloride crystals and the crystallized mother liquor are sent into a centrifugal machine together for ammonium chloride recovery, the centrifuged ammonium chloride crystallized mother liquor is sent into an ammonium chloride desalting tank, the ammonium chloride desalting tank is provided with a cooling device, the top of the ammonium chloride desalting tank is provided with an ammonium sulfate feeding port, sodium chloride and ammonium sulfate in the ammonium chloride crystallized mother liquor react, sodium sulfate decahydrate is separated out at the temperature of below 0 ℃, the ammonium chloride crystallized mother liquor is sent into the centrifugal machine for centrifugal recovery of sodium sulfate decahydrate, and the desalted ammonium chloride crystallized mother liquor continuously returns to the raw material inlet of the ammonium chloride concentration tank for circular preparation of ammonium.
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