Recovery system for copper in tin stripping wastewater by using waste ammonia water and use method of recovery system

Abstract

The invention relates to a recovery system for copper in tin stripping wastewater by using waste ammonia water and a use method thereof.The recovery system comprises a tin deposition reaction tank, a first filter pressing system, a first-stage copper deposition system, a second-stage copper deposition system and an ammonium nitrate storage tank, the whole system introduces a waste ammonia water storage tank and a connecting pipeline thereof, the collected waste ammonia water is used as a raw material, and the waste ammonia water is recycled. According to the invention, the copper-containing sludge is used as a raw material and participates in the first-stage copper deposition step of the tin-stripping wastewater process, the original industrial ammonia water is replaced as the raw material, the ammonia consumption during the production of the copper-containing sludge can be greatly reduced, the copper deposition effect and the back-end production are not influenced, the use demand of the industrial ammonia water can be reduced, and the production cost can also be reduced.

Description

Technical Field

[0001] The present application relates to the technical field of metal recovery in tin stripping wastewater, and in particular to a copper recovery system in tin stripping wastewater using waste ammonia water and a method for using the system. Background Art

[0002] Waste ammonia water comes from a wide range of sources, usually from by-products and wastes in industrial production processes. Waste ammonia water is often produced in the manufacturing process of chemical products such as fertilizers, pesticides, and dyes. For example, waste water containing ammonia may be produced in the production of synthetic ammonia and urea; ammonia or its derivatives are also used as raw materials in the synthesis of some drugs, and these processes may produce waste liquid containing ammonia; in some dyeing and finishing processes, in order to achieve specific effects, ammonia water is used to adjust the pH value, thereby producing waste ammonia water; ammonia water may also be used in metal surface treatment (such as electroplating, cleaning), thereby producing waste ammonia water; in some food processing processes (such as dairy processing), a small amount of waste ammonia water may also be produced. The management of waste ammonia water is crucial because it poses a potential threat to the natural environment. High concentrations of ammonia nitrogen can cause eutrophication of water bodies, damage water quality, and have adverse effects on aquatic biological systems. Therefore, the waste ammonia water generated must be effectively treated to avoid environmental pollution.

[0003] In the prior art, waste ammonia water can be used for energy recovery, industrial reuse, environmental remediation, and wastewater treatment. Rational use of waste ammonia water can not only reduce environmental pollution, but also create economic value and realize the recycling of resources. Waste ammonia water can not only reduce the impact on the environment through treatment, but also be converted into valuable resources through rational use. For example, tin stripping waste liquid is a kind of dangerous waste liquid with very high acidity produced in the PCB production process, which contains a large amount of metal compounds such as tin, copper, iron, and various organic substances such as stabilizers and corrosion inhibitors. The composition is complex and comprehensive recovery is difficult. In the tin stripping wastewater process, purchased industrial ammonia water is used as raw material to produce copper-containing sludge and tin products. When producing copper-containing sludge, the pH needs to be adjusted, the ammonia consumption is large, and the cost is high. In view of this, in order to reduce the ammonia consumption in production and thus reduce production costs, the present application aims to improve the copper precipitation process in the tin stripping wastewater process using waste ammonia water. Summary of the invention

[0004] The technical problem to be solved by the present application is that waste ammonia water has a wide range of sources and, if not properly utilized and managed, will cause serious damage to the natural environment and living environment.

[0005] In order to solve the above technical problems, according to one aspect of the present application, a system for recovering copper from tin stripping wastewater using waste ammonia water is provided, comprising: a tin precipitation reaction tank, connected to the tin stripping wastewater through a pipeline, the tin precipitation reaction tank is connected to a flocculant preparation tank and a waste ammonia water storage tank; a first filter press system, comprising a first filter press and a filtrate tank connected in sequence, the first filter press being connected to the output end of the tin precipitation reaction tank as a tin sludge recovery device, and the filtrate in the filter press flowing into the filtrate tank; a primary copper precipitation system, comprising a first copper precipitation tank, a second filter press connected in sequence, The filter machine comprises a first copper precipitation tank, an input end of which is connected to a filtrate tank and a waste ammonia water storage tank, an output end of which is connected to a second filter press, and the copper mud processed by the second filter press is output to a copper salt production line; a secondary copper precipitation system comprises a second copper precipitation tank and a third filter press which are connected in sequence, an input end of the second copper precipitation tank is connected to the second filter press, an output end of the second copper precipitation tank is connected to the third filter press, and the copper mud processed by the third filter press is output to a copper salt production line; an ammonium nitrate storage tank is used to receive the filtrate from the third filter press for further impurity removal and purification.

[0006] Among them, the tin precipitation reaction tank is used to precipitate tin in the tin stripping wastewater. The tin precipitation reaction tank is connected to the first filter press system, and the filter press system is used to perform filter press treatment on the pre-treated tin stripping wastewater; the first filter press system is connected to the first-level copper precipitation system, and the wastewater after the first-level copper removal is pumped into the second-level copper precipitation system for further copper removal. The purified liquid treated by the second-level copper precipitation system is pumped into the ammonium nitrate storage tank, and is further purified by the formulation system to meet the production parameter requirements. The liquid can then be returned to the production line for reuse.

[0007] According to the embodiments of the present application, the average ammonia content of the waste ammonia water used is between 12% and 18%.

[0008] According to an embodiment of the present application, the first filter press is a filter cake chamber filter press, which presses the tin mud into a filter cake for output, and the slurry produced by pressing the filter cake is returned to the tin precipitation reaction tank after desolventizing.

[0009] According to an embodiment of the present application, a back-pressure pipeline is connected between the filtrate tank and the first filter press.

[0010] According to an embodiment of the present application, the tin precipitation reaction tank, the first copper precipitation tank, the second copper precipitation tank and the ammonium nitrate storage tank are all provided with a stirring device.

[0011] According to another aspect of the present application, a method for recovering copper from tin stripping wastewater using waste ammonia water is provided, which uses a system for recovering copper from tin stripping wastewater using waste ammonia water as described above, comprising the following steps:

[0012] S1: Add water and flocculant into the flocculant preparation tank to prepare a viscous flocculant;

[0013] S2: introducing tin stripping wastewater into the tin precipitation reaction tank, adding alkaline solution to the tin stripping wastewater while stirring for neutralization, adjusting the pH value of the tin stripping wastewater to 1.5-2, adding the prepared flocculant, stirring evenly and then settling;

[0014] S3: After the sedimentation is completed, the transfer pump is turned on to introduce the above-mentioned fully treated mixed liquid into the first filter for pressure filtration to obtain a tin mud filter cake, and the filtrate is introduced into the filtrate tank;

[0015] S4: The clear water in the filtrate tank is introduced into the first copper precipitation tank, the stirring device is turned on, and an alkaline solution is added for neutralization. When the pH value is controlled in the range of 5.0-5.4, the addition of the alkaline solution is stopped, the stirring is stopped, and the precipitation is carried out;

[0016] S5: filtering the mixed solution neutralized in step S4 with a second filter press to obtain copper mud, and the copper mud is reversely dissolved to a copper salt production line for treatment;

[0017] S6: The filtrate of step S5 enters the second copper precipitation tank, solid sodium sulfide is added from the top of the second copper precipitation tank while stirring, and during the addition process, a portable ORP meter is used to detect the ORP value, and when the ORP value is controlled between -180 and -110, the addition of sodium sulfide is stopped; after the addition is completed, the reaction is stirred for 30 minutes; after the reaction is completed, the third filter press is introduced for filtration treatment to obtain copper sulfide mud, and the copper sulfide mud is reversely dissolved to the copper salt production line for treatment;

[0018] S7: The filtrate of step S6 is introduced into an ammonium nitrate storage tank for further purification and reuse.

[0019] According to an embodiment of the present application, the alkaline solution is a waste ammonia solution.

[0020] According to an embodiment of the present application, the mass ratio of the tin stripping wastewater, the alkaline solution, and the flocculant in step 2 is 4.21:1:0.56.

[0021] According to an embodiment of the present application, the mass ratio of the filtrate to the alkaline solution in step S4 is 16-19.6:1.

[0022] According to an embodiment of the present application, the flocculant in step S1 is composed of polyacrylamide, acrylamide, a cross-linking agent, an initiator, a stabilizer, a pH regulator and water.

[0023] Compared with the prior art, the technical solution of the present application has the following beneficial effects:

[0024] 1. The present invention utilizes waste ammonia water as the raw material in the tin stripping wastewater recycling process, which belongs to the recycling of waste liquid. This can greatly reduce the treatment cost of tin stripping wastewater, reduce ammonia consumption in production and treatment, reduce the impact of waste ammonia water on the environment, and reduce production costs.

[0025] 2. The recycling method of the present invention can quickly, efficiently and safely treat the tin stripping wastewater, recycle copper, and turn waste into treasure, which not only protects the environment but also saves energy. In addition, the recycling method has low recycling cost, small equipment investment, low energy consumption, and high promotion and application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings of the embodiments will be briefly introduced below. Obviously, the drawings in the following description only relate to some embodiments of the present application, rather than limiting the present application.

[0027] Figure 1 The present invention is a flowchart of the steps of a method for recovering copper from tin stripping wastewater using waste ammonia water. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical scheme and advantages of the embodiment of the present application clearer, the technical scheme of the embodiment of the present application will be clearly and completely described in conjunction with the drawings of the embodiment of the present application. Obviously, the described embodiment is a part of the embodiment of the present application, not all of the embodiments. Based on the described embodiment of the present application, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of this application.

[0029] Unless otherwise defined, the technical or scientific terms used herein shall have the common meanings understood by persons with ordinary skills in the field to which this application belongs. The words "first", "second" and similar words used in the patent application specification and claims of this application do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, words such as "one" or "an" do not indicate a quantity limitation, but indicate the existence of at least one.

[0030] As shown in the figure, a copper recovery system for tin stripping wastewater using waste ammonia water in the present invention includes a tin precipitation reaction tank, a first filter press system, a primary copper precipitation system, a secondary copper precipitation system and an ammonium nitrate storage tank. The whole system introduces a waste ammonia water storage tank and its connecting pipes, and the collected waste ammonia water is used as raw material. On the one hand, the waste ammonia water is effectively utilized to reduce the environmental burden, and on the other hand, the industrial ammonia consumption in production is reduced, thereby reducing production costs.

[0031] In the present embodiment, a copper recovery system in tin stripping wastewater using waste ammonia water comprises: a tin precipitation reaction tank, connected to the tin stripping wastewater through a pipeline, the tin precipitation reaction tank is connected to a flocculant preparation tank and a waste ammonia water storage tank; a first filter press system, comprising a first filter press and a filtrate tank connected in sequence, the first filter press is connected to the output end of the tin precipitation reaction tank as a tin mud recovery device, and the filtrate in the filter press flows into the filtrate tank; a primary copper precipitation system, comprising a first copper precipitation tank and a second filter press connected in sequence, the input end of the first copper precipitation tank is connected to the filtrate tank and the waste ammonia water delivery pipeline, the output end of the first copper precipitation tank is connected to the second filter press, and the copper mud processed by the second filter press is output to a copper salt production line; a secondary copper precipitation system, comprising a second copper precipitation tank and a third filter press connected in sequence, the input end of the second copper precipitation tank is connected to the second filter press, the output end of the second copper precipitation tank is connected to the third filter press, and the copper mud processed by the third filter press is output to a copper salt production line; an ammonium nitrate storage tank is used to receive the filtrate of the third filter press for further impurity removal and purification.

[0032] Among them: the tin precipitation reaction tank is used to precipitate tin in the tin stripping wastewater, the chemical tin precipitation reaction tank is connected to the first filter press system, and the filter press system is used to perform filter press treatment on the pre-treated tin stripping wastewater; the first filter press system is connected to the primary copper precipitation system, and the wastewater after the primary copper removal is pumped into the secondary copper precipitation system for further copper removal, and the purified liquid treated by the secondary copper precipitation system is pumped into the ammonium nitrate storage tank for further purification to meet the production parameter requirements, and can then be returned to the production line for reuse.

[0033] Specifically, the average ammonia content of the waste ammonia water used is between 12% and 18%.

[0034] Specifically, the first filter press is a filter cake chamber filter press, which presses the tin mud into filter cakes for output, and the slurry produced by pressing the filter cakes is returned to the tin precipitation reaction tank after reverse dissolution.

[0035] Specifically, in the primary copper precipitation system, a special copper precipitation agent is added to the first copper precipitation tank to precipitate copper in the wastewater.

[0036] Specifically, a back pressure pipeline is connected between the filtrate tank and the first filter press.

[0037] Specifically, the tin precipitation reaction tank, the first copper precipitation tank, the second copper precipitation tank and the ammonium nitrate storage tank are all provided with stirring devices.

[0038] Another aspect of the present application discloses a method for recovering copper from tin stripping wastewater using waste ammonia water, which adopts the above-mentioned system for recovering copper from tin stripping wastewater using waste ammonia water, and is characterized in that it comprises the following steps:

[0039] S1: Add water and flocculant into the flocculant preparation tank to prepare a viscous flocculant;

[0040] S2: introducing tin stripping wastewater into the tin precipitation reaction tank, adding alkaline solution to the tin stripping wastewater while stirring for neutralization, adjusting the pH value of the tin stripping wastewater to 1.5-2, adding the prepared flocculant, stirring evenly and then settling;

[0041] S3: After the sedimentation is completed, the transfer pump is turned on to introduce the above-mentioned fully treated mixed liquid into the first filter for pressure filtration to obtain a tin mud filter cake, and the filtrate is introduced into the filtrate tank;

[0042] S4: The clear water in the filtrate tank is introduced into the first copper precipitation tank, the stirring device is turned on, and an alkaline solution is added for neutralization. When the pH value is controlled in the range of 5.0-5.4, the addition of the alkaline solution is stopped, the stirring is stopped, and the precipitation is carried out;

[0043] S5: filtering the mixed solution neutralized in step S4 with a second filter press to obtain copper mud, and the copper mud is reversely dissolved to a copper salt production line for treatment;

[0044] S6: The filtrate of step S5 enters the second copper precipitation tank, solid sodium sulfide is added from the top of the second copper precipitation tank while stirring, and during the addition process, a portable ORP meter is used to detect the ORP value, and when the ORP value is controlled between -180 and -110, the addition of sodium sulfide is stopped; after the addition is completed, the reaction is stirred for 30 minutes; after the reaction is completed, the third filter press is introduced for filtration treatment to obtain copper sulfide mud, and the copper sulfide mud is reversely dissolved to the copper salt production line for treatment;

[0045] S7: The filtrate of step S6 is introduced into an ammonium nitrate storage tank for further purification and reuse.

[0046] Specifically, in step S1, water is first added to the flocculant preparation tank for stirring, and the flocculant is added while stirring until a viscous state appears, and then the addition is stopped.

[0047] Specifically, Figure 1 As shown, the slurry in the tin hydroxide filter cake filtered in step S3 can be de-dissolved and then added to the tin precipitation reaction tank for recycling.

[0048] Specifically, Figure 1 As shown, in step S3, a filtrate tank is connected between the first filter press and the first copper precipitation tank. When the filtrate of the first filter press enters the filtrate tank, leakage may occur. After precipitation in the filtrate tank, the lower layer can be recycled into the first filter press.

[0049] Specifically, the alkaline solution is a waste ammonia solution, which is placed in a waste ammonia storage tank and transported to a corresponding reaction tank through a pipeline.

[0050] Specifically, the present application conducts the following small test of using waste ammonia water to recover copper from tin stripping wastewater, adjusts the pH, and confirms the proportion of waste ammonia water added.

[0051] Step 1: Open the ammonia feed valve on the tin precipitation reaction tank, pump the waste ammonia into the tin precipitation reaction tank, and stop adding the waste ammonia when the black spots disappear completely; adjust the pH value of the tin stripping wastewater to 1.5-2, add the prepared flocculant, stir evenly and then settle;

[0052] Step 2: After adjustment, turn off the mixer and let it settle for a while depending on the difficulty of settling. After settling, turn on the drainage pump to drain the supernatant into the supernatant tank. During the drainage process, adjust the insertion depth of the supernatant pipe to drain the supernatant as much as possible without pumping out tin sludge.

[0053] Step 3: After the supernatant is drained, turn off the supernatant pump, turn on the tin sludge transfer pump, transfer the tin sludge to the temporary storage tank, and turn on the temporary storage tank mixer at the same time;

[0054] Step 4: Turn on the transfer pump of the supernatant tank, transfer the tin precipitation supernatant to the first copper precipitation tank, and reserve space for adding ammonia water; turn on the agitator of the copper precipitation adjustment tank, open the waste ammonia water feed valve on the tank top, turn on the ammonia water pump, and add ammonia water; when the pH value of the sample is 5.0-5.4, close the waste ammonia water feed pump and feed valve; stir and settle, and after the settlement is completed, extract the supernatant and transfer it to the second copper precipitation tank;

[0055] Step 5: Add solid sodium sulfide to the top funnel of the second copper precipitation reaction tank, stirring while adding. During the addition process, use a portable ORP meter to detect the ORP value. When the ORP value is controlled between -180 and -110, stop adding sodium sulfide; after the addition is completed, stir the reaction for 30 minutes.

[0056] Through small-scale tests, the appropriate amount of additives can be tested. Specifically, the mass ratio of tin stripping wastewater, alkaline solution, and flocculant in step S2 is 4.21:1:0.56; the mass ratio of filtrate and alkaline solution in step S4 is 16-19.6:1.

[0057] Specifically, in step S1, the flocculant is composed of polyacrylamide, acrylamide, a cross-linking agent, an initiator, a stabilizer, a pH regulator and water.

[0058] In summary, the technical solution of the present application has the following beneficial effects:

[0059] 1. The present invention utilizes waste ammonia water as the raw material in the tin stripping wastewater recycling process, which belongs to the recycling of waste liquid. This can greatly reduce the treatment cost of tin stripping wastewater, reduce ammonia consumption in production and treatment, reduce the impact of waste ammonia water on the environment, and reduce production costs.

[0060] 2. The recycling method of the present invention can quickly, efficiently and safely treat the tin stripping wastewater, recycle copper, and turn waste into treasure, which not only protects the environment but also saves energy. In addition, the recycling method has low recycling cost, small equipment investment, low energy consumption, and high promotion and application value.

[0061] The above are merely exemplary embodiments of the present application and are not intended to limit the protection scope of the present application. The protection scope of the present application is determined by the appended claims.

Claims

1. A copper recovery system in tin stripping wastewater using waste ammonia water, characterized in that: include: A tin precipitation reaction tank is connected to the tin stripping wastewater through a pipeline, and the tin precipitation reaction tank is connected to a flocculant preparation tank and a waste ammonia water storage tank; The first filter press system comprises a first filter press and a filtrate tank connected in sequence, wherein the first filter press is connected to the output end of the tin precipitation reaction tank as a tin sludge recovery device, and the filtrate in the filter press flows into the filtrate tank; A primary copper precipitation system comprises a first copper precipitation tank and a second filter press connected in sequence, wherein the input end of the first copper precipitation tank is connected to the filtrate tank and the waste ammonia water storage tank, the output end of the first copper precipitation tank is connected to the second filter press, and the copper mud processed by the second filter press is output to the copper salt production line; A secondary copper precipitation system comprises a second copper precipitation tank and a third filter press connected in sequence, wherein the input end of the second copper precipitation tank is connected to the second filter press, the output end of the second copper precipitation tank is connected to the third filter press, and the copper mud processed by the third filter press is output to the copper salt production line; The ammonium nitrate storage tank is used to receive the filtrate from the third filter press for further impurity removal and purification. Among them: the tin precipitation reaction tank is used to precipitate tin in the tin stripping wastewater, the tin precipitation reaction tank is connected to the first filter press system, and the filter press system is used to perform filter press treatment on the pre-treated tin stripping wastewater; the first filter press system is connected to the primary copper precipitation system, and the wastewater after the primary copper removal is pumped into the secondary copper precipitation system for further copper removal, and the purified liquid treated by the secondary copper precipitation system is pumped into the ammonium nitrate storage tank, and is further purified by the formulation system to meet the production parameter requirements, and can be returned to the production line for reuse.

2. A copper recovery system in tin stripping wastewater using waste ammonia water according to claim 1, characterized in that: The average ammonia content of the waste ammonia water used is between 12% and 18%.

3. A copper recovery system in tin stripping wastewater using waste ammonia water according to claim 1, characterized in that: The first filter press is a filter cake chamber filter press, which presses the tin mud into a filter cake for output, and the slurry produced by pressing the filter cake is returned to the tin precipitation reaction tank after reverse dissolution.

4. A copper recovery system in tin stripping wastewater using waste ammonia water according to claim 1, characterized in that: A back pressure pipeline is connected between the filtrate tank and the first filter press.

5. A copper recovery system in tin stripping wastewater using waste ammonia water according to claim 1, characterized in that: The tin precipitation reaction tank, the first copper precipitation tank, the second copper precipitation tank and the ammonium nitrate storage tank are all provided with stirring devices.

6. A method for recovering copper from tin stripping wastewater using waste ammonia water, using a system for recovering copper from tin stripping wastewater using waste ammonia water as described in any one of claims 1 to 5, characterized in that: The following steps are involved: S1: Add water and flocculant into the flocculant preparation tank to prepare a viscous flocculant; S2: introducing tin stripping wastewater into the tin precipitation reaction tank, adding alkaline solution to the tin stripping wastewater while stirring for neutralization, adjusting the pH value of the tin stripping wastewater to 1.5-2, adding the prepared flocculant, stirring evenly and then settling; S3: After the sedimentation is completed, the transfer pump is turned on to introduce the above-mentioned fully treated mixed liquid into the first filter for pressure filtration to obtain a tin mud filter cake, and the filtrate is introduced into the filtrate tank; S4: The clear water in the filtrate tank is introduced into the first copper precipitation tank, the stirring device is turned on, and an alkaline solution is added for neutralization. When the pH value is controlled in the range of 5.0-5.4, the addition of the alkaline solution is stopped, the stirring is stopped, and the precipitation is carried out; S5: filtering the mixed solution neutralized in step S4 with a second filter press to obtain copper mud, and the copper mud is reversely dissolved to a copper salt production line for treatment; S6: The filtrate of step S5 enters the second copper precipitation tank, solid sodium sulfide is added from the top of the second copper precipitation tank while stirring, and during the addition process, a portable ORP meter is used to detect the ORP value, and when the ORP value is controlled between -180 and -110, the addition of sodium sulfide is stopped; after the addition is completed, the reaction is stirred for 30 minutes; after the reaction is completed, the third filter press is introduced for filtration treatment to obtain copper sulfide mud, and the copper sulfide mud is reversely dissolved to the copper salt production line for treatment; S7: The filtrate of step S6 is introduced into an ammonium nitrate storage tank for further purification and reuse.

7. A method for recovering copper from tin stripping wastewater using waste ammonia water according to claim 6, characterized in that: The alkaline solution is a waste ammonia solution.

8. A method for recovering copper from tin stripping wastewater using waste ammonia water according to claim 7, characterized in that: The mass ratio of the tin stripping wastewater, alkaline solution and flocculant described in step S2 is 4.21:1:0.

56.

9. A method for recovering copper from tin stripping wastewater using waste ammonia water according to claim 7, characterized in that: In step S4, the mass ratio of the filtrate to the alkaline solution is 16-19.6:

1.

10. A method for recovering copper from tin stripping wastewater using waste ammonia water according to claim 6, characterized in that: In step S1, the flocculant is composed of polyacrylamide, acrylamide, a cross-linking agent, an initiator, a stabilizer, a pH regulator and water.

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