Device for preparing copper oxide from ammonia alkaline etching waste liquid and recycling reaction residual liquid

Abstract

The utility model discloses a device for preparing copper oxide from ammonia alkaline etching waste liquid and recycling reaction residual liquid. The device comprises a solution pH value adjusting tank and a chemical reaction tank for reacting the etching waste liquid with an acid solution, the solid-liquid separator A is used for carrying out solid-liquid separation on the solid-liquid mixture from the solution pH value adjusting tank to obtain filter residue 1 # copper salt and filtrate 1 # ammonium salt solution; the heating ammonia distillation reaction kettle is used for carrying out heating reaction on the filter residue 1 # copper salt from the solid-liquid separator A and an alkaline compound solution to promote ammonia gas to escape from a reaction solution and react to synthesize a copper oxide product; the solid-liquid separator B is used for carrying out solid-liquid separation on the solid-liquid mixture in the heating ammonia distillation reaction kettle to obtain copper oxide powder; the ammonia gas absorber is used for absorbing ammonia gas escaped from the heating ammonia distillation reaction kettle; and the regenerated etching sub-liquid preparation tank is used for receiving the filtrate 1 # separated by the solid-liquid separator A and preparing regenerated etching sub-liquid according to process requirements.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the technical field of circuit board etching waste liquid treatment, and particularly relates to a device for preparing copper oxide from ammonia alkaline etching waste liquid and recycling reaction residual liquid. BACKGROUND

[0002] Circuit boards are prepared by etching after printing circuit patterns on copper-clad boards. Etching liquid includes acidic etching liquid and ammonia alkaline etching liquid, wherein the ammonia alkaline etching liquid can be subdivided into ammonia alkaline copper chloride ammonia etching liquid and ammonia alkaline sulfuric acid tetraammine copper etching liquid. The main components of the ammonia alkaline copper chloride ammonia etching liquid include ammonia water, ammonium chloride and copper chloride ammonia salt; the main components of the ammonia alkaline sulfuric acid tetraammine copper etching liquid include ammonium sulfate, ammonia water and sulfuric acid tetraammine copper salt. In the process of etching circuit boards, the copper-clad boards with printed patterns are put into etching machines for circuit etching; the etching liquid in the etching machines is called etching working liquid. In order to continuously etch, the etching machines need to be supplied with a mixed supplement liquid mainly containing ammonium salt and / or ammonia water, which is called etching sub-liquid in the industry. Due to the supplement of the etching sub-liquid, part of the etching working liquid overflows out of the etching machines, which is called etching waste liquid in the industry. As the etching production proceeds, the storage of etching waste liquid is continuously increased, so it is necessary to recycle metal copper and recycle the reaction residual liquid for environmental protection treatment of the etching waste liquid.

[0003] For the environmental protection treatment of etching waste liquid, the prior art has a process for preparing copper oxide from ammonia alkaline etching waste liquid, which specifically adds sodium hydroxide directly to the ammonia alkaline etching waste liquid and then performs heating ammonia evaporation treatment to obtain copper oxide powder, wherein the reaction process of heating ammonia evaporation is as follows:

[0004]

[0005] Or

[0006] From the chemical reaction formula of the prior art, it can be known that the prior art obtains copper oxide products and recycles ammonia gas from the ammonia alkaline etching waste liquid, but a large amount of sodium hydroxide and / or potassium hydroxide needs to be added, which leads to a relatively high treatment cost, and the ammonium salt in the waste liquid cannot be recycled, and high-concentration brine is also produced.

[0007] In view of the problems of the above existing process, the Chinese authorized patent CN111032917B discloses a kind of ammonia evaporation recovery cycle process of circuit board alkaline etching waste liquid, the process is first heated ammonia evaporation recovery ammonia gas to alkaline etching waste liquid, then the solid mixture left after heating ammonia evaporation is acidified to obtain basic copper chloride and / or copper hydroxide.It also discloses a kind of ammonia evaporation recovery cycle process system of circuit board alkaline etching waste liquid, including: heating evaporation tank, for concentrating heated alkaline etching waste liquid and separating waste liquid gas;Acid-base adjustment tank, for adjusting the pH value of the remaining liquid after alkaline etching waste liquid evaporation;Compound reaction tank, for manufacturing ammonium carbonate and / or ammonium bicarbonate;Filter, the filter is connected with acid-base adjustment tank.However, the recovered copper product obtained by the process and device of the above Chinese authorized patent CN111032917B is basic copper chloride and / or copper hydroxide, which has lower value than copper oxide. Utility model content

[0008] The utility model aims at providing a kind of ammonia alkaline etching waste liquid preparation copper oxide and reaction residual liquid recycling device, makes etching waste liquid recycling rate high, obtains high-value copper oxide, and reduces environmental pollution and saves production material.

[0009] A kind of ammonia alkaline etching waste liquid preparation copper oxide and reaction residual liquid recycling device, characterized by, including solution pH adjustment tank, solid-liquid separator A, solid-liquid separator B, regeneration etching sub-liquid preparation tank, ammonia gas absorber, heating ammonia evaporation reaction kettle;

[0010] The solution pH adjustment tank is a chemical reaction tank for etching waste liquid and acidic solution reaction, to reduce the pH value of etching waste liquid and generate copper salt precipitate;

[0011] The solid-liquid separator A is used for solid-liquid separation of solid-liquid mixture from the solution pH adjustment tank, and filter residue 1 # Copper salt and filtrate 1 # Ammonium salt solution;The feed pipe opening of solid-liquid separator A is connected with solution pH adjustment tank by pipeline, and the liquid outlet of which is connected with regeneration etching sub-liquid preparation tank by pipeline;

[0012] The heating ammonia evaporation reaction kettle is used for filter residue 1 # Copper salt and basic compound solution are heated to react, to make ammonia gas escape from reaction liquid and reaction synthesis copper oxide product;The heating ammonia evaporation reaction kettle is provided with a feed inlet for feeding solid or solid-liquid mixture, and a cold-hot temperature exchanger is installed in the heating ammonia evaporation reaction kettle to heat or cool the reaction liquid therein, and the exhaust pipe opening thereof is connected with the air suction pipe opening of ammonia gas absorber by pipeline, and the discharge pipe opening thereof is connected with the feed pipe opening of solid-liquid separator B by pipeline;

[0013] The solid-liquid separator B is used for solid-liquid separation of the solid-liquid mixture in the heating ammonia evaporation reactor, and the filter residue 2 is obtained # and the filtrate 2 # The main component of the filter residue 2 # is copper oxide powder, and the filtrate 2 # is waste brine; the feeding pipe of the solid-liquid separator B is connected with the heating ammonia evaporation reactor by pipeline, and the liquid outlet pipe is connected with the temporary storage tank and / or the liquid flow buffer tank by pipeline

[0014] The ammonia gas absorber is a gas-liquid mixer, which is used for absorbing the ammonia gas emitted from the heating ammonia evaporation reactor, and the ammonia gas absorbing pipe is connected with the exhaust pipe in the heating ammonia evaporation reactor by pipeline; the ammonia gas absorber can be a bubbling type gas-liquid mixer, a vacuum jet type gas-liquid mixer or a spray tower type gas-liquid mixer; the reaction solution for absorbing ammonia gas in the ammonia gas absorber is a solution in which ammonia gas is dissolved after reacting with ammonia gas, preferably the filtrate 1 # , or the regenerated etching sub-solution, or the reaction solution in the process of preparing the regenerated etching sub-solution;

[0015] The regenerated etching sub-solution preparation tank is used for receiving the filtrate 1 # separated by the solid-liquid separator A, and preparing the regenerated etching sub-solution according to the process requirements. The filtrate 1 # is specifically a solution with ammonium salt as the main component, and the concentration of ammonium salt and / or ammonia water and the concentration of additives in the obtained etching regenerated etching sub-solution meet the process requirements.

[0016] The basic component combination of the device is as shown in Figure 1 .

[0017] The solid-liquid separator A and the solid-liquid separator B are divided by a centrifuge, a filter and a filter press in structure, and the specific selection is carried out according to the process design.

[0018] The alkaline compound used in the device is one or a mixture of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate. The acidic solution used is a solution of hydrochloric acid or sulfuric acid.

[0019] The utility model improves the shortcomings of the prior art ammonia alkaline etching waste liquid environmental protection treatment process. First, hydrochloric acid is added to the ammonia alkaline copper chloride ammonia etching waste liquid in the solution pH value adjusting tank, or sulfuric acid is added to the ammonia alkaline sulfuric acid tetraamine copper etching waste liquid to make the treatment liquid produce solid copper salt precipitate, and the solid-liquid mixture generated in the reaction is subjected to solid-liquid separation to obtain filtrate and filter residue; the filtrate is a mixed solution mainly containing ammonium chloride and a small amount of copper chloride ammonia salt or a mixed solution mainly containing ammonium sulfate and a small amount of sulfuric acid tetraamine copper salt, and the filter residue is solid copper salt. The above acid addition chemical reaction is as follows:

[0020] NH4OH + Cu(NH3)4Cl2 + HCl → NH4Cl + H2O + Cu(NH3)4Cl2↓;

[0021] Or 2NH4OH + Cu(NH3)4SO4 + H2SO4 → (NH4)2SO4 + 2H2O + Cu(NH3)4SO4↓.

[0022] First take the solution pH adjustment tank to add acidic solution to the etching waste liquid to generate ammonium salt, and then recycle the operation, which fully meets the requirements of the environmental protection process.

[0023] Unlike the prior art of heating ammonia and recovering ammonia gas from the alkaline etching waste liquid, the utility model is to filter residue 1 obtained by adding acid reaction in the solution pH adjustment tank and solid-liquid separation # The copper salt is added to the heating ammonia reaction kettle, and the sodium hydroxide or potassium hydroxide solution is heated to prepare copper oxide powder and collect the ammonia gas escaped during heating. The chemical reaction formula in the heating ammonia reaction kettle is as follows (taking the chloride salt as an example):

[0024]

[0025] From the improvement of the environmental protection treatment process using the device of the utility model, it can be seen that the improved device and the corresponding process can not only recover and prepare copper oxide powder, but also recycle the filtrate, and only a small amount of brine is produced in the process. The improved process can greatly reduce the consumption of alkaline compound raw materials and reduce the environmental protection treatment cost.

[0026] As a preferred embodiment of the utility model, the device of the utility model is integrated with the etching production line as a whole, specifically, the regenerated etching sub-solution preparation tank is connected with the etching production line through a pipeline or is connected with the etching production line through an added temporary tank and / or a liquid flow buffer tank, so that the regenerated etching sub-solution can be recycled in time.

[0027] The utility model can be improved as follows: a heating ammonia reaction kettle 2 for heating ammonia treatment of etching waste liquid is additionally arranged in the device # The cold and hot temperature exchanger is installed therein, so that the etching waste liquid with high ammonia concentration can be reacted with the acidic solution in the solution pH adjustment tank after evaporating part of ammonia, which is beneficial to the generation of copper salt precipitate. The improvement solves the problem that when the etching waste liquid contains high ammonia concentration, the amount of acidic solution added is large, the volume of the treatment liquid is increased, and the treatment liquid cannot be recycled in time. Therefore, the heating ammonia reaction kettle 2 for heating ammonia treatment of etching waste liquid is additionally arranged in the original basic equipment combination # (see Figure 2) and its exhaust port is connected with the suction port of the ammonia gas absorber by a pipeline, and its discharge port is directly connected with the solution pH adjusting tank or connected with the solution pH adjusting tank through a temporary storage tank and / or a liquid flow buffer tank, and finally the etching waste liquid treated by ammonia evaporation is introduced into the solution pH adjusting tank.

[0028] Since the ammonia alkaline etching liquid is often used for the etching pattern of the circuit board with tin resist layer, the tin particles not firmly combined with the surface of the resist layer are washed off during the spraying and impacting of the etching liquid, so that the fine tin powder is mixed in the etching working liquid. # The etching waste liquid temporary storage tank is connected with the solution pH adjusting tank or the heating ammonia evaporation reactor 2 # for heating ammonia evaporation treatment. # Preferably, a solid-liquid separator C is additionally arranged on the connecting pipeline between the etching waste liquid temporary storage tank and the heating ammonia evaporation reactor 2 Figure 3 .

[0029] The utility model can be improved as follows: a temporary storage tank and / or a liquid flow buffer tank are additionally arranged between the solution pH adjusting tank and the solid-liquid separator A and between the regenerated etching sub-liquid preparation tank and the solid-liquid separator A, so that the feeding port of the solid-liquid separator A is connected with the solution pH adjusting tank through the temporary storage tank and / or the liquid flow buffer tank, and the liquid outlet port is connected with the regenerated etching sub-liquid preparation tank through the temporary storage tank and / or the liquid flow buffer tank.

[0030] The utility model can be improved as follows: a temporary storage tank and / or a liquid flow buffer tank are additionally arranged between the heating ammonia evaporation reactor and the solid-liquid separator B, so that the feeding port of the solid-liquid separator B is connected with the heating ammonia evaporation reactor through the temporary storage tank and / or the liquid flow buffer tank.

[0031] The utility model can be further improved as follows: a plurality of ammonia gas absorbers are additionally arranged, the suction port of the primary ammonia gas absorber is connected with the exhaust port of the heating ammonia evaporation reactor, and the working gas pipeline of the remaining ammonia gas absorbers is connected in series, so as to absorb the ammonia gas escaped from the heating ammonia evaporation reactor in series.

[0032] The utility model discloses still can make the following improvement: add tail gas absorption groove, to the tail gas of temporary storage groove, solution pH adjustment groove, regenerative etching sub -liquid preparation groove in the device when working escapes environmental protection treatment. The specific tail gas absorption groove is equipped with vacuum jet or spray tower, and its suction pipe mouth is connected with the exhaust pipe mouth of temporary storage groove, solution pH adjustment groove, regenerative etching sub -liquid preparation groove respectively and makes pipeline connection.

[0033] The utility model discloses still can make the following improvement: add liquid flow buffer groove and solve the problem of liquid flow between tank. The liquid flow buffer groove is connected with various tank in the device according to need and makes pipeline connection.

[0034] The utility model discloses still can make the following improvement: add program logic controller PLC and sensor in the device, so that the device can run safely according to preprogram. The sensor is pH meter, specific gravity meter, oxidation-reduction potential meter (ORP meter), thermometer, liquid level meter, photoelectric colorimeter and ammonia gas concentration meter. The sensor is installed in the tank that needs to be detected and the production workshop site and exports the numerical value to control. Preferably, install pH meter in solution pH adjustment groove to control the acid solution and install thermometer in heating ammonia evaporation reaction kettle to control the temperature of reaction liquid. The signal output end of sensor is electrically connected with the signal input end of pump, valve and cold and hot temperature exchanger in the device.

[0035] The utility model discloses still can make the following improvement: add agitator, and the specific agitator is divided into impeller type and liquid flow type; can be installed in temporary storage groove, heating ammonia evaporation reaction kettle, solution pH adjustment groove and regenerative etching sub -liquid preparation groove.

[0036] The utility model discloses still can make the following improvement: add cold and hot temperature exchanger, so that the temperature of reaction liquid is controlled in the process range; be installed in the temporary storage groove, solution pH adjustment groove, regenerative etching sub -liquid preparation groove and etching production line that need.

[0037] The utility model discloses still can make the following improvement: add copper oxide cleaning groove and clean the copper oxide powder of filter residue 2 # The outlet pipe mouth of ammonia gas cleaning groove is connected with the inlet pipe mouth of added solid-liquid separator D and is separated to collect high-quality copper oxide product after cleaning and removing impurity.

[0038] The utility model discloses still can make the following improvement: for making the NH3 in etching waste liquid can reuse to the regenerative etching subliquid under the premise of ensuring quality, adds ammonia gas cleaning tank between the heating ammonia evaporation reactor and ammonia gas absorber, is used for washing and removing the ammonia gas that contains the alkaline compound impurity of alkaline compound solution under high temperature treatment copper salt from heating ammonia evaporation reactor, avoids the sodium and potassium ion of alkaline solution that hot and rising ammonia gas takes out and introduces to the regenerative etching subliquid, influences the etching reaction of recycling reuse.

[0039] The utility model discloses still can make the following improvement: to filtrate 2 # The trace ammonia nitrogen impurities in the waste brine are treated, and an appropriate amount of sodium hypochlorite solution is poured into the waste brine tank containing trace ammonia nitrogen pollutants to treat the ammonia nitrogen, so that the ammonia nitrogen concentration in the treated waste brine is reduced to below the requirement of the discharge standard.

[0040] Compared with the prior art, the utility model has the following beneficial effects:

[0041] 1. The device of the utility model can recycle and utilize the ammonia NH3 in etching waste liquid.

[0042] 2. In the process of treating ammonia alkaline etching waste liquid by the device of the utility model, no new pollution source is added, and the discharge amount of brine waste liquid is reduced, which meets the requirement of the environmental protection treatment process standard.

[0043] 3. The device of the utility model has small investment and low operating cost, and the implemented process is simple, safe and reliable.

[0044] 4. When treating ammonia alkaline etching waste liquid by the device of the utility model, no other impurities are added in the preparation of the regenerative etching subliquid, which completely meets and ensures the etching quality requirement, realizes recycling reuse, and achieves higher economic benefit. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 It is the basic structure schematic view of the device for preparing cupric oxide and reaction residual liquid from ammonia alkaline etching waste liquid.

[0046] Figure 2The utility model relates to a kind of copper oxide and reaction residual liquid recycling device for ammonia alkaline etching waste liquid preparation, and the structure schematic diagram of the structure of the improved etching waste liquid containing high concentration ammonia is shown.

[0047] Figure 3 The utility model relates to a kind of copper oxide and reaction residual liquid recycling device for ammonia alkaline etching waste liquid preparation, and the structure schematic diagram of the structure of the improved etching waste liquid containing trace tin powder is shown.

[0048] Figure 4 The utility model relates to a kind of copper oxide and reaction residual liquid recycling device for ammonia alkaline etching waste liquid preparation, and the structure schematic diagram of the structure of the improved etching waste liquid containing trace tin powder is shown. Figure 4-1 、4-2、4-3 and 4-4 are Figure 4 The partial view of the four constitutes complete device structure schematic diagram.

[0049] Reference signs

[0050] 1-solution pH value adjusting groove, 2-solid-liquid separator, 3-ammonia gas absorber, 4-heating ammonia evaporation reaction kettle, 5-regeneration etching sub-liquid preparation tank, 6-temporarily stored tank, 7-heating ammonia evaporation reaction kettle 2 # , 8-etching production line, 9-tail gas absorption tank, 10-PLC, 11-sensor, 12-impeller agitator, 13-liquid flow agitator, 14-cold and hot temperature exchanger, 15-valve, 16-pump, 17-fresh water, 18-alkaline compound solution, 19-acidic solution, 20-waste brine, 21-ammonia alkaline etching waste liquid, 22-ammonium salt, 23-ammonia water, 24-liquid ammonia, 25-regeneration etching sub-liquid, 26-filtrate 1 # , 27-filtrate 1 # , 28-filtrate 2 # , 29-filtrate 2 # , 30-refined copper oxide product, 31-bubbling pipe, 32-vacuum jet, 33-spraying tower, 34-circuit board, 35-copper oxide cleaning tank, 36-ammonia gas cleaning tank, 37-wastewater treatment tank, 38-etching waste liquid having been treated by heating ammonia evaporation, 39-solid-liquid separator C or D, 40-sodium hypochlorite solution, 41-tin powder, 42-additive, 43-blower, 44-liquid flow buffer tank.

[0051] When there are two or more same components or substances used in the device, the reference signs X-1 and X-2 are used for distinguishing in the drawings, wherein X is the serial number of the reference sign. DETAILED DESCRIPTION

[0052] The utility model is further described below through specific implementation.

[0053] The solution pH adjustment tank, heating ammonia stripping reactor, regenerated etching solution preparation tank, ammonia absorber, temporary storage tank, stirrer, liquid flow buffer tank, and exhaust gas processor used in the embodiments of this utility model are all products of Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd., Guangdong Province. The solid-liquid separator, etching production line, PLC, detection sensor, heat exchanger, pump, and valves are all commercially available products. The chemical raw materials used are commercially available. In addition to those listed above, those skilled in the art can also choose other products with similar performance to those listed above, based on conventional selection, to achieve the purpose of this utility model.

[0054] Example 1

[0055] like Figure 1 The diagram shows a schematic of the apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue in this embodiment. It includes a solution pH adjustment tank 1, two solid-liquid separators 2, an ammonia absorber 3, a heated ammonia stripping reactor 4, a regenerated etching solution preparation tank 5, two temporary storage tanks 6, a blower 43, and multiple valves and pumps. The ammonia absorber 3 is a bubbling gas-liquid mixing reactor with a bubbling pipe 31. The heated ammonia stripping reactor 4 has an inlet for feeding solids or solid-liquid mixtures and contains a heat exchanger 14. The solid-liquid separator 2-1 (solid-liquid separator A) is a filter press, and the solid-liquid separator 2-2 (solid-liquid separator B) is a centrifuge.

[0056] In the device, the pH adjustment tank 1 is connected to the inlet of the solid-liquid separator 2-1 via a pipe, and the outlet of the solid-liquid separator 2-1 is connected to the regenerated etching solution preparation tank 5 via a pipe. The exhaust port of the heated ammonia stripping reactor 4 is connected to the suction port of the ammonia absorber 3 via a blower 43, the discharge port of the heated ammonia stripping reactor 4 is connected to the inlet of the solid-liquid separator 2-2 via a pipe, and the outlet of the solid-liquid separator 2-2 is connected to the temporary storage tank 6-3 via a pipe. The temporary storage tanks 6-1 and 6-2 are used to load the filter residue separated by the solid-liquid separators 2-1 and 2-2, respectively.

[0057] The ammonia-alkaline etching waste liquid 21 processed by the device in this embodiment is a weakly alkaline copper chloride ammonia etching waste liquid with a pH of 7.3. Its main components are ammonia water, ammonium chloride, ammonium carbonate, and a mixture of copper chloride and ammonia. The alkaline compound solution 18 used is a sodium hydroxide solution. The acidic solution 19 is hydrochloric acid, the ammonium salt 22 is a mixture of ammonium chloride and ammonium bicarbonate, the ammonia source replenishment substance is ammonia water 23, and the additive 42 is an etching additive.

[0058] The steps for treating ammonia-alkaline etching waste liquid using the apparatus of this embodiment are as follows:

[0059] 1. The etching waste liquid 21 is added into the solution pH adjusting tank 1, and then hydrochloric acid is added for neutralization reaction, so that the solution reacts to precipitate copper mud.

[0060] 2. The solid-liquid mixture in the solution pH adjusting tank 1 is separated by a solid-liquid separator 2-1 to obtain a filtrate 1 # ammonium salt solution and a filter residue 1 # copper salt.

[0061] 3. The filter residue 1 # copper salt is added into the heated ammonia evaporation reactor 4 to mix with a sodium hydroxide solution under heating; the ammonia gas released from the heated ammonia evaporation reactor 4 is introduced into an ammonia gas absorber for absorption until the reaction liquid in the heated ammonia evaporation reactor 4 reaches the ammonia removal process index in the sampling detection, which is regarded as complete, and the copper salt in the reactor is changed into copper oxide.

[0062] 4. The mixture in the heated ammonia evaporation reactor 4 is separated by a solid-liquid separator 2-2 to obtain a filter residue 2 #

[0063] copper oxide and a filtrate 2 # alkali waste liquid containing salt.

[0064] 5. The filtrate 1 # ammonium salt solution is introduced into the regenerated etching sub-liquid preparation tank 5, and ammonium salt 22, ammonia water 23 and additive 42 are added for preparation, so that a regenerated etching sub-liquid 25 is prepared according to the process requirements and is used in the next process.

[0065] After the above steps, the ammonia alkaline etching waste liquid is recovered to obtain copper oxide product, and the reaction residual liquid of the etching waste liquid is recycled.

[0066] Example 2

[0067] As Figure 2 shown in the figure, the device structure schematic diagram for preparing copper oxide and recycling reaction residual liquid from ammonia alkaline etching waste liquid in the present embodiment includes a solution pH adjusting tank 1, two solid-liquid separators 2, an ammonia gas absorber 3, a heated ammonia evaporation reactor 4, a regenerated etching sub-liquid preparation tank 5, a temporary storage tank 6, another heated ammonia evaporation reactor 7, three sensing detectors 11, two cold and hot temperature exchangers 14, multiple valves and pumps.

[0068] The ammonia gas absorber 3 is a vacuum jet type gas-liquid mixer, which includes a vacuum jet 32.

[0069] The sensors 11-1 and 11-3 are thermometers respectively installed in the heated ammonia evaporation reactor 2 # 7 and the heated ammonia evaporation reactor 4, and the sensor 11-2 is a pH meter installed in the solution pH adjusting tank 1. The heated ammonia evaporation reactor 2 #7 and heating ammonia evaporation reactor 4 is provided with a feeding port for feeding solid or solid-liquid mixture, and cold and hot temperature exchangers 14-1 and 14-2 are arranged in the feeding port respectively.

[0070] The solid-liquid separator 2-1 is a solid-liquid separator A, and the solid-liquid separator 2-2 is a solid-liquid separator B, both of which are filter machines.

[0071] The heating ammonia evaporation reactor 2 # 7 is connected with the solution pH value adjusting tank 1 through a pipeline, the solution pH value adjusting tank 1 is connected with the feeding port of the solid-liquid separator 2-1 through a pipeline, the liquid outlet of the solid-liquid separator 2-1 is connected with the regenerative etching sub-solution preparation tank 5 through a pipeline, and the heating ammonia evaporation reactor 2 # 7 and the exhaust port of the heating ammonia evaporation reactor 4 are connected with the gas suction port of the ammonia gas absorber 3 through a gas pipeline, the discharging port of the heating ammonia evaporation reactor 4 is connected with the feeding port of the solid-liquid separator 2-2 through a pipeline, and the solid-liquid separator 2-2 is connected with the temporary storage tank 6 through a pipeline.

[0072] The ammonia alkaline etching waste liquid 21 treated by the device of the embodiment is a high-ammonia pH 9.2 alkaline tetraammine copper sulfate etching waste liquid, and the main components of the ammonia alkaline etching waste liquid 21 are a mixture of ammonia, ammonium sulfate and tetraammine copper sulfate; the alkaline compound solution 18 used is a mixed solution of sodium hydroxide, potassium carbonate and sodium bicarbonate, and the acidic solution 19 is sulfuric acid.

[0073] The ammonium salt 22 is ammonium sulfate, and the ammonia source supplement is ammonia water 23.

[0074] The embodiment adopts an improvement that the etching waste liquid is first treated by heating ammonia evaporation, and then sulfuric acid 19 is added for neutralization and precipitation reaction, and the steps for treating the ammonia alkaline etching waste liquid by using the device of the embodiment are as follows:

[0075] 1. The etching waste liquid 21 is fed into the heating ammonia evaporation reactor 2 # 7 for ammonia evaporation treatment, and after the ammonia concentration is reduced, the solution in the heating ammonia evaporation reactor 2 # 7 is introduced into the solution pH value adjusting tank 1 for neutralization reaction by adding sulfuric acid, so that copper salt precipitates are generated in the solution; the ammonia gas emitted from the heating ammonia evaporation reactor 2 # 7 is introduced into the ammonia gas absorber 3 for treatment.

[0076] 2. The solid-liquid mixture in the solution pH value adjusting tank 1 is separated by the solid-liquid separator 2-1 to obtain the filter residue 1 # in which the copper salt is intercepted, and the filtrate 1 # is introduced into the regenerative etching sub-solution preparation tank 5.

[0077] 3. The ammonium salt 22, ammonia 23, and additives 42 are respectively put into the regeneration etching sub-liquid preparation tank 5 to prepare the regeneration etching sub-liquid according to the process requirements.

[0078] 4. The copper salt of the filter residue 1 is put into the heated ammonia evaporation reactor 4 to react with the alkaline compound solution, the cold and hot temperature exchanger 14-2 is started to make the reaction liquid to react to remove ammonia while the copper salt is converted into copper oxide product, the ammonia gas released from the heated ammonia evaporation reactor 4 is also introduced into the ammonia gas absorber 3 for treatment; the regeneration etching sub-liquid is used as the ammonia absorption reaction liquid of the ammonia gas absorber 3, and after absorbing the ammonia gas, the pH value of the prepared regeneration etching sub-liquid is increased to the high ammonia concentration standard required by the process.

[0079] 5. The mixture in the heated ammonia evaporation reactor 4 is separated by the solid-liquid separator 2-2 to obtain the filter residue 2 #

[0080] Copper oxide and filter liquor 2 # Salt-containing alkaline waste liquid (regeneration etching sub-liquid), copper oxide powder product, and preparation for recycling the regeneration etching sub-liquid.

[0081] After the above steps, the ammonia alkaline etching waste liquid is recycled to obtain copper oxide product and the reaction residual liquid of the etching waste liquid.

[0082] Example 3

[0083] As Figure 3 shown, it is a device structure schematic diagram for preparing copper oxide and recycling the reaction residual liquid of the ammonia alkaline etching waste liquid, which includes a solution pH value adjusting tank 1, two solid-liquid separators 2, an ammonia gas absorber 3, a heated ammonia evaporation reactor 4, a regeneration etching sub-liquid preparation tank 5, four temporary storage tanks 6, a heated ammonia evaporation reactor 2 # 7, an impeller agitator 12, a liquid flow agitator 13, two cold and hot temperature exchangers 14, a solid-liquid separator C 39, and multiple valves and pumps.

[0084] The ammonia gas absorber 33 is a spray tower type gas-liquid mixer, which includes a spray tower 33 and a liquid flow agitator 13, and is used for absorbing and treating the ammonia gas released from the two heated ammonia evaporation reactors; the absorption reaction liquid used is hydrochloric acid 19. The gas inlet pipe of the ammonia gas absorber 3 is connected with the exhaust pipe of the two heated ammonia evaporation reactors by pipelines.

[0085] The heated ammonia evaporation reactor 2 # 7 and the heated ammonia evaporation reactor 4 are provided with material inlets for feeding solid or solid-liquid mixture, and are respectively provided with cold and hot temperature exchangers 14-1 and 14-2. The regeneration etching sub-liquid preparation tank 5 is provided with an impeller agitator 12.

[0086] The four temporary storage tanks 6 are used in common. The temporary storage tank 6-1 is used for the separation of tin powder in the etching waste liquid by sedimentation and stratification, and is connected to the feed port of the solid-liquid separator C 39 by a valve and a pump.

[0087] The sensor 11-1 is a liquid level meter, which is arranged in the temporary storage tank 6-1. The sensors 11-2 and 11-4 are thermometers, which are arranged in the heating ammonia evaporation reactor 2 # 7 and the heating ammonia evaporation reactor 4, respectively. The sensor 11-3 is a pH meter, which is arranged in the solution pH value adjusting tank 1.

[0088] The solid-liquid separator 2-1 is a centrifuge. The solid-liquid separator 2-2 is a filter press. The solid-liquid separator C 39 is a filter, which is used for filtering and removing the trace tin powder in the etching waste liquid.

[0089] The temporary storage tank 6-1 is connected to the feed port of the solid-liquid separator C 39 by a pipeline. The liquid outlet port of the solid-liquid separator C 39 is connected to the heating ammonia evaporation reactor 2 # 7 by a pipeline. The liquid outlet port of the heating ammonia evaporation reactor 2 # 7 is connected to the feed port of the solution pH value adjusting tank 1 by a pipeline. The liquid outlet port of the solution pH value adjusting tank 1 is connected to the feed port of the solid-liquid separator 2-1 by a pipeline. The liquid outlet port of the solid-liquid separator 2-1 is connected to the feed port of the regenerated etching sub-liquid preparation tank 5 by a pipeline. The liquid outlet port of the heating ammonia evaporation reactor 4 is connected to the feed port of the solid-liquid separator 2-2 by a pipeline. The liquid outlet port of the solid-liquid separator 2-2 is connected to the temporary storage tank 6-4 by a pipeline. The temporary storage tanks 6-2 and 6-3 are used for temporarily storing the filter residues separated by the solid-liquid separators 2-1 and 2-2, respectively.

[0090] The ammonia alkaline etching waste liquid 21 treated in the embodiment is an alkaline copper chloride ammonia etching waste liquid, which is used for etching a tin resist layer circuit board. The pH value of the etching waste liquid is pH 8.7. The main components of the etching waste liquid are a mixture of ammonium chloride, ammonia water and copper salt, and the etching waste liquid contains trace tin powder. The acid solution 19 used in the embodiment is hydrochloric acid. The alkaline compound solution 18 is a potassium hydroxide solution.

[0091] In the embodiment, the improved process is used to remove the tin powder in the etching waste liquid by precipitation and filtration, and to remove ammonia from the waste liquid by heating. The steps of using the device of the embodiment to treat the ammonia alkaline etching waste liquid are as follows:

[0092] 1. The etching waste liquid 21 is added to the temporary storage tank 6-1 for the treatment of tin powder by sedimentation. After the tin powder is settled at the bottom of the tank, the pump 16-1 is started to send the waste liquid in the tank to the solid-liquid separator C 39 for filtration. Then, the waste liquid is added to the heating ammonia evaporation reactor 2 #7 is treated to remove ammonia, and the thermometer 11-2 is adjusted to 85°C to carry out the ammonia evaporation reaction. The ammonia gas is led to the ammonia absorber 3 for treatment.

[0093] 2. The ammonia evaporation reactor 2 is heated # 7 is treated to remove ammonia, and the thermometer 11-2 is adjusted to 85°C to carry out the ammonia evaporation reaction. The ammonia gas is led to the ammonia absorber 3 for treatment.

[0094] 3. When the pH meter in the solution pH adjustment tank 1 is adjusted to pH 5.5, it is considered that the neutralization and precipitation treatment is completed, and the valve 15-6 and the pump 16-3 are opened to pump the solid-liquid mixture into the solid-liquid separator 2-1 for separation, and the filter residue 1 # The copper salt is stored in the temporary storage tank 6-2, and the filtrate 1 # The ammonium salt solution is led to the regenerated etching sub-solution preparation tank 5 and ammonia water and ammonium salt are added to prepare the regenerated etching sub-solution.

[0095] 4. The filter residue 1 # The copper salt is added to the heated ammonia evaporation reactor 4 to react with the potassium hydroxide solution inside. The temperature in the reactor is adjusted to 75°C according to the thermometer, so that the reaction liquid changes from copper salt to copper oxide, and the ammonia gas is led to the ammonia absorber 3 for treatment. The reaction liquid in the ammonia absorber 3 is ammonium chloride generated by the reaction of hydrochloric acid and ammonia gas for reuse.

[0096] 5. After the copper salt in the heated ammonia evaporation reactor 4 is converted to copper oxide, the valve 15-8 and the pump 16-4 are opened to pump the solid-liquid mixture in the reactor 4 to the solid-liquid separator 2-2 for solid-liquid separation, and the filter residue 2 # The copper oxide is stored in the temporary storage tank 6-3, and the filtrate 2 # The salt-containing waste liquid is led to the temporary storage tank 6-4 for storage.

[0097] 6. The copper oxide powder is collected and the regenerated etching sub-solution in the regenerated etching sub-solution preparation tank 5 is prepared for reuse.

[0098] After the above steps, the ammonia alkaline etching waste liquid is recycled to produce copper oxide products, and the reaction residue of the etching waste liquid is recycled.

[0099] Example 4

[0100] As Figure 4The device structure schematic diagram of the preparation of copper oxide and the reuse of the reaction residual liquid from the ammonia alkaline etching waste liquid is shown in the embodiment, including a solution pH value adjusting tank 1, four solid-liquid separators 2, two ammonia gas absorbers 3, a heating ammonia evaporation reaction kettle 4, a regenerated etching sub-solution preparation tank 5, eleven temporary storage tanks 6, other heating ammonia evaporation reaction kettles 7, a tail gas absorption tank 9, a PLC 10, twenty-one sensors 11, three impeller stirrers 12, seven liquid flow stirrers 13, four cold and hot temperature exchangers 14, a copper oxide powder cleaning tank 35, an ammonia gas cleaning tank 36, a solid-liquid separator C 39-1, and a plurality of valves and pumps.

[0101] The solution pH value adjusting tank 1 is provided with a liquid flow stirrer 13-1 and a sensor 11-8 pH meter, and the feed port and the discharge port of the solution pH value adjusting tank 1 are respectively connected to the temporary storage tank 6-3 and the solid-liquid separator 2-1 through pipelines.

[0102] The solid-liquid separators 2-1 and 2-2 are both solid-liquid separator A, which are a filter press and a filter respectively, and are used for the solid-liquid separation of the solid-liquid mixture from the solution pH value adjusting tank 1, to obtain the filter residue 1 # Copper salt and filtrate 1 # Ammonium salt solution. The solid-liquid separators 2-1 and 2-2 are connected in series to make the ammonium salt solution and the solid copper salt be more completely separated, and the liquid outlet of the solid-liquid separator 2-2 is connected to the temporary storage tank 6-5 through a pipeline. The solid-liquid separators 2-3 and 2-4 are a filter press and a filter respectively, and are used for the separation of the solid-liquid mixture in the heating ammonia evaporation reaction kettle 4, to obtain the filter residue 2 # Copper oxide 29 and filtrate 2 # Waste brine containing ammonia nitrogen impurities. The solid-liquid separators 2-3 and 2-4 are connected in series to make the copper oxide powder and the waste brine containing ammonia nitrogen impurities be more completely separated, and the feed port of the solid-liquid separator 2-3 is connected to the discharge port of the heating ammonia evaporation reaction kettle 4 through a pipeline, and the liquid outlet of the solid-liquid separator 2-4 is connected to the temporary storage tank 6-9 through a pipeline.

[0103] The ammonia gas pipeline and the material pipeline of the ammonia gas absorbers 3-1 and 3-2 are connected in series. The ammonia gas absorber 3-1 is a vacuum jet gas-liquid mixer, including a vacuum jet 32, and is provided with a liquid level meter sensor 11-9 and a pH meter sensor 11-10 inside. The ammonia gas absorber 3-2 is a spray tower gas-liquid mixer, including a spray tower 33-1, and is provided with a liquid level meter sensor 11-11 and a pH meter sensor 11-12 inside. Both of them use the filtrate 1 #The ammonium salt solution is used as ammonia gas absorbing liquid. The ammonia gas absorbing pipe of the ammonia gas absorber 3-1 is connected with the exhaust pipe of the two heating ammonia evaporation reactors, and the feeding pipe is connected with the temporary storage tank 6-5 through pipeline. The ammonia gas absorbing pipe of the ammonia gas absorber 3-2 is connected with the exhaust pipe of the ammonia gas absorber 3-1, and the discharging pipe is connected with the temporary storage tank 6-6 through the valve 15-8 and the pump 16-10.

[0104] The heating ammonia evaporation reactor 4 is used for preparing copper oxide powder, and is provided with a feeding port, in which an impeller agitator 12-2, a cold and hot temperature exchanger 14-4, sensors 11-17, 11-18 and 11-19 are installed. The sensors are respectively liquid level meter, pH meter and photoelectric colorimeter. The exhaust pipe of the heating ammonia evaporation reactor 4 is connected with the ammonia gas cleaning tank 36 through gas pipe, and the discharging pipe is connected with the feeding pipe of the solid-liquid separator 2-3 through pipeline.

[0105] The regenerative etching sub-liquid preparation tank 5 is provided with a cold and hot temperature exchanger 14-3 and sensors 11-13, 11-4, 11-15 and 11-16, which are respectively liquid level meter, pH meter, thermometer and specific gravity meter. The sensors are used for controlling and detecting the preparation process of the etching sub-liquid. The feeding pipe of the regenerative etching sub-liquid preparation tank 5 is connected with the temporary storage tank 6-6, the discharging pipe is connected with the temporary storage tank 6-7, and the ammonia gas escaping pipe is connected with the tail gas absorbing tank 9 through gas pipe.

[0106] The heating ammonia evaporation reactor 2 # 7 is used for ammonia evaporation treatment of etching waste liquid, and is provided with a feeding port, in which an impeller agitator 12-1, a cold and hot temperature exchanger 14-2, and sensors 11-4, 11-5 and 11-6 are installed. The sensors are respectively liquid level meter, pH meter and thermometer. The exhaust pipe of the heating ammonia evaporation reactor 2 is connected with the ammonia gas absorbing pipe of the ammonia gas absorber 3-1 through gas pipe, the feeding pipe is connected with the solid-liquid separator C 39-1 (filter) through pipeline, and the discharging pipe is connected with the temporary storage tank 6-3 through pipeline with valve and pump.

[0107] The device uses eleven temporary storage tanks. The temporary storage tank 6-1 is used for receiving etching waste liquid for temporary storage. The temporary storage tank 6-2 is used for etching waste liquid, and is used for settling tin powder in the etching waste liquid. The feeding pipe of the temporary storage tank 6-1 is connected with the etching production line 8 through the liquid flow buffer tank 44, the discharging pipe is connected with the feeding pipe of the temporary storage tank 6-2 through pipeline, and the discharging pipe of the temporary storage tank 6-2 is connected with the feeding pipe of the solid-liquid separator C 39-1 through pipeline. # The temporary storage tank 6-3 is used for storing etching waste liquid which has been treated by ammonia evaporation, and is provided with a sensor 11-7 which is liquid level meter. The discharging pipe of the temporary storage tank 6-3 is connected with the feeding pipe of the solution pH value adjusting tank 1 through pipeline, and the feeding pipe of the temporary storage tank 6-4 is connected with the feeding pipe of the regenerative etching sub-liquid preparation tank 5 through pipeline. #26, and the gas outlet of the ammonia gas absorber 3-1, and the gas inlet of the tail gas absorption tank 9. The temporary storage tank 6-6 is arranged on the pipeline connecting the ammonia gas absorber 3-2 and the regenerative etching sub-liquid preparation tank 5, and is connected with the liquid outlet of the ammonia gas absorber 3-2 and the liquid inlet of the regenerative etching sub-liquid preparation tank 5. The temporary storage tank 6-7 is a regenerative etching sub-liquid temporary storage tank, and is arranged on the pipeline connecting the regenerative etching sub-liquid preparation tank 5 and the etching production line 8. The temporary storage tank 6-9 is a filtrate 2 # containing ammonia-nitrogen impurities, and is sent to the temporary storage tank 6-9 and added with a small amount of sodium hypochlorite solution 40, and the ammonia-nitrogen impurities in the waste brine are removed through the sensor 11-20 (ORP meter) control, so that the ammonia-nitrogen impurities in the waste brine reach the process requirement, and the liquid inlet and the liquid outlet are connected with the solid-liquid separator 2-4 and the waste water treatment tank 37. The temporary storage tanks 6-4, 6-10 and 6-11 are used for temporarily storing materials. #

[0108] The tail gas absorption tank 9 is connected with the tail gas outlet G of a plurality of tanks in the device by a gas pipe, and the tail gas absorption tank 9 is provided with a spray tower 33-2.

[0109] The copper oxide cleaning tank 35 is provided with an impeller agitator 12-3, which is connected with the liquid inlet of the solid-liquid separator D 39-2, the liquid outlet of the solid-liquid separator D 39-2 is connected with the liquid inlet of the solid-liquid separator D 39-3, and the solid-liquid separator D 39-2 and 39-3 are a filter press and a filter respectively, and high-quality copper oxide powder is collected through two-stage solid-liquid separation of the filter press and the filter. The waste liquid in the copper oxide cleaning tank 35 after cleaning is subjected to environmental protection treatment.

[0110] The ammonia gas cleaning tank 36 is a spray tower type gas-liquid mixer, and is provided with a spray tower 33-3, and uses clean water 17 as the washing liquid; the gas outlet is connected with the gas inlet of the ammonia gas absorber 3-1 by a pipeline, and the gas inlet is connected with the gas outlet of the heated ammonia evaporation reactor 4 by a gas pipe.

[0111] The sensor 11-21 is an ammonia gas concentration detector, which is used for detecting the ammonia concentration of the air in the workshop.

[0112] The device of the embodiment further comprises a PLC 10, which is electrically connected with the components in the device, and controls the device to operate according to the pre-programmed program.

[0113] ​The etching waste liquid treated in the embodiment is a copper chloride ammonia etching waste liquid for etching a tin resist layer circuit board, the pH value of the waste liquid is pH 8.2, and the main components of the waste liquid are a mixture of ammonia, ammonium chloride, additives and copper chloride ammonia complex and contain trace tin powder; the adopted alkaline compound solution 18 is a sodium hydroxide solution, and the acidic solution 19 is hydrochloric acid. The ammonia source supplement is liquid ammonia 24, and the ammonium salt 22 is ammonium chloride and ammonium bicarbonate.

[0114] The embodiment is a comprehensive improvement on the process, and the improvement contents include separating and treating the trace tin powder in the waste liquid, treating the ammonia in the high-concentration ammonia waste liquid, cleaning and removing impurities from the recovered ammonia gas, and cleaning and improving the product quality of the copper oxide. The steps of treating the ammonia alkaline etching waste liquid by using the device of the embodiment are as follows:

[0115] 1. Turn on the power supply of the device to make the PLC enter the working state and process the data transmitted by each sensor in the device, and make the device run according to the pre-programmed program after safety detection.

[0116] 2. Start the etching production line 8 and put the circuit board into the etching production line to produce the etching waste liquid, and pump the etching waste liquid to the temporary storage tank 6-1 through the liquid buffer tank 44.

[0117] 3. Pump the waste liquid in the temporary storage tank 6-1 to the temporary storage tank 6-2 through the pump 16-2 to separate and settle the tin powder, and pump the solution in the temporary storage tank 6-2 to the heating ammonia evaporation reactor 2 # 7 after filtration, and start the stirrer 12-1 and the cold and hot temperature exchanger 14-2, heat to 90°C for ammonia treatment, and open two ammonia gas absorbers for ammonia absorption treatment, during which the detection data of the pH meter in the reactor are sent to the PLC for processing and compared with the process set value pH 6.2 for determination.

[0118] 4. When the pH value of the solution in the heating ammonia evaporation reactor 2 # 7 decreases to pH 6.2, the PLC controls to stop the operation of the heating ammonia evaporation reactor 2 # 7 and opens the valve 15-3 and starts the pump 16-4 to pump the solution in the reactor to the temporary storage tank 6-3 for temporary storage.

[0119] 5. Pump part of the solution in the temporary storage tank 6-3 to the solution pH value adjusting tank 1 to react with hydrochloric acid, and control the pH meter in the tank to pH 5.2 during the operation to make the solution react to precipitate copper mud.

[0120] 6. Separate the solid-liquid mixture in the solution pH value adjusting tank 1 through the solid-liquid separators 2-1 and 2-2 to obtain the filter residue 1 # copper salt and the filtrate 1 # ammonium salt solution, and introduce the filtrate 1 # to the temporary storage tank 6-5 for temporary storage, and introduce the filter residue 1 #Copper salt 27 is put into the heating ammonia evaporation reactor 4.

[0121] 7. The ammonia absorption solution of ammonia absorbers 3-1 and 3-2 is the solution in temporary storage tank 6-5, and the replacement of the ammonia absorption solution during operation is controlled by the pH meter in the ammonia absorber. When the pH value of the ammonia absorption solution of ammonia absorber 3-2 rises to the process set pH value, pump 16-10 is started to draw part of the solution into temporary storage tank 6-6, and then pump 16-9 is started to supplement the liquid level of ammonia absorber 3-2 and pump 16-8 is started to supplement the liquid level of ammonia absorber 3-1.

[0122] 8. Part of the solution in temporary storage tank 6-6 is drawn into regeneration etching sub-solution preparation tank 5 to prepare the regeneration etching sub-solution, and ammonium chloride 22, liquid ammonia 24 and additive 42 are added, and stirrer 13-4 and cold and hot temperature exchanger 14-3 are started to adjust. The regeneration etching sub-solution 25 is prepared by comparing the on-site detection value of the sensor with the process set value during the reaction.

[0123] 9. The prepared regeneration etching sub-solution 25 is temporarily stored in temporary storage tank 6-7, and is put back into the etching production line 8 according to the PLC control to participate in the etching reaction and produce etching waste liquid 21.

[0124] 10. The copper salt 27 of the filter residue 1 # and sodium hydroxide solution are put into the heating ammonia evaporation reactor 4, and impeller stirrer 12-2 and cold and hot temperature exchanger 14-4 are started to make the reaction liquid at a temperature of 87℃, to carry out ammonia removal treatment and copper oxide synthesis reaction, and the escaped ammonia gas is sent to ammonia cleaning tank 36 for cleaning and then introduced into vacuum jet 32 of ammonia absorber 3-1 for absorption treatment; after all the copper salt in the heating ammonia evaporation reactor 4 is converted into copper oxide powder, the solid-liquid mixture in the reactor is separated by solid-liquid separator 2-3 and 2-4 to obtain filter residue 2 # coarse copper oxide and filtrate 2 # containing trace ammonia nitrogen pollution impurities.

[0125] 11. The filtrate 2 # is introduced into temporary storage tank 6-9, and sodium hypochlorite solution is put into the tank under the control of the ORP meter to carry out ammonia removal treatment, so that the reaction liquid reaches the discharge standard of allowable concentration of ammonia nitrogen pollutants.

[0126] 12. The salt-containing solution in temporary storage tank 6-9 that has reached the standard after treatment is introduced into wastewater treatment tank 37 for centralized treatment.

[0127] 13. The filter residue 2 # coarse copper oxide is sent to copper oxide cleaning tank for water washing, and the filtrate 2

[0128] 39-2 and 39-3 are separated by solid-liquid separator to obtain fine copper oxide, and the filtrate 2# The effluent is drained into the temporary tank 6-11.

[0129] 14. The effluent from all the tank vents G in the device is drained into the effluent treatment tank 9 for environmental treatment.

[0130] After the above steps, the ammonia alkaline etching waste liquid recovery copper oxide product and the reaction residual liquid of the etching waste liquid are recycled.

Claims

1. An apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and for recycling the reaction residue, characterized in that, Includes a solution pH adjustment tank, solid-liquid separator A, solid-liquid separator B, regenerated etching solution preparation tank, ammonia absorber, and heated ammonia stripping reactor; The pH adjustment tank is a chemical reaction tank used to react the etching waste liquid with an acidic solution, thereby lowering the pH value of the etching waste liquid and generating copper salt precipitates. The solid-liquid separator A is used to separate the solid-liquid mixture from the solution pH adjustment tank and obtain filter residue 1. # Copper salt and filtrate 1 # Ammonium salt solution; the feed port of solid-liquid separator A is connected to the solution pH adjustment tank by a pipeline, and its outlet port is connected to the regeneration etching sub-solution preparation tank by a pipeline; The heated ammonia stripping reactor is used to process the filter residue 1 from the solid-liquid separator A. # Copper salt reacts with an alkaline compound solution under heat, causing ammonia to escape from the reaction liquid and react to synthesize copper oxide products; the heated ammonia stripping reactor is equipped with an inlet for feeding solids or solid-liquid mixtures, a heat exchanger is installed in the heated ammonia stripping reactor, and its exhaust port is connected to the intake port of the ammonia absorber, and its discharge port is connected to the inlet of the solid-liquid separator B. The solid-liquid separator B is used to separate the solid-liquid mixture in the heated ammonia-steaming reactor to obtain copper oxide powder; the feed port of the solid-liquid separator B is connected to the heated ammonia-steaming reactor via a pipeline. The ammonia absorber is a gas-liquid mixer used to absorb the ammonia gas escaping from the heated ammonia vaporizing reactor. Its ammonia absorption port is connected to the exhaust port in the heated ammonia vaporizing reactor. The regenerated etching solution preparation tank is used to receive the filtrate 1 separated by solid-liquid separator A. # And prepare the regenerated etching solution according to the process requirements.

2. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 1, characterized in that, The solid-liquid separator A and solid-liquid separator B are selected from centrifuges, filters and filter presses; the ammonia absorber is selected from bubble gas-liquid mixers, vacuum jet gas-liquid mixers and spray tower gas-liquid mixers.

3. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 2, characterized in that, The regenerated etching solution preparation tank is integrated into the etching production line as a whole. Specifically, the regenerated etching solution preparation tank is connected to the etching production line through a pipeline or through an additional temporary storage tank and / or liquid flow buffer tank, so that the regenerated etching solution can be recycled in a timely manner.

4. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 3, characterized in that, Add a heated ammonia stripping reactor 2 for heating and ammonia stripping treatment of etching waste liquid. # It is equipped with a heat exchanger; heating ammonia vaporizing reactor 2 # The exhaust port is connected to the intake port of the ammonia absorber by a pipeline, while its discharge port is directly connected to the solution pH adjustment tank by a pipeline or connected to the solution pH adjustment tank through a temporary storage tank and / or a liquid flow buffer tank.

5. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 4, characterized in that, An additional etching waste liquid temporary storage tank is added to precipitate and stratify the tin powder in the etching waste liquid. Its outlet is connected to a solution pH adjustment tank or a heated ammonia stripping reactor. # .

6. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 5, characterized in that, in Etching waste liquid temporary storage tank and additional heated ammonia stripping reactor 2 # A solid-liquid separator C is installed on the connecting pipe between the etching waste liquid storage tank and the solution pH adjustment tank.

7. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 6, characterized in that, A multi-stage ammonia absorber is added, with the intake port of the primary ammonia absorber connected to the exhaust port of the heated ammonia vaporizing reactor, and the working gas pipelines of the remaining ammonia absorbers connected in a series combination structure.

8. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 7, characterized in that, An exhaust gas absorption tank is added to provide environmentally friendly treatment for the exhaust gases emitted during operation from the temporary storage tank, solution pH adjustment tank, and regenerated etching solution preparation tank in the device.

9. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 8, characterized in that, Add a copper oxide cleaning tank for filter residue 2 # Copper oxide powder is used for cleaning; an ammonia cleaning tank is added between the heated ammonia steaming reactor and the ammonia absorber to wash away impurities containing alkaline compounds escaping from the heated ammonia steaming reactor. The ammonia cleaning tank is a gas-liquid mixing reactor.

10. The apparatus for producing copper oxide from ammonia-alkaline etching waste liquid and reusing the reaction residue according to claim 9, characterized in that, The device is equipped with a programmable logic controller (PLC) and sensors to enable it to operate safely according to a pre-programmed sequence. The sensors are installed in the tanks and production workshops within the device and are selected from pH meters, hydrometers, redox potentiometers, thermometers, level gauges, photoelectric colorimeters, and ammonia concentration meters. The signal input terminals of the PLC are electrically connected to the signal output terminals of the sensors, and the signal output terminals of the PLC are also electrically connected to the signal input terminals of the pumps, valves, and heat exchangers within the device.

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