Acidic copper-containing waste liquid and aluminum mud collaborative recovery treatment system and treatment process

Abstract

The invention relates to an acidic copper-containing waste liquid and aluminum mud collaborative recovery treatment system and process, the treatment system comprises an acidic copper-containing waste liquid collecting tank, the acidic copper-containing waste liquid collecting tank is sequentially connected with a first filter and a preheater, the preheater is respectively connected with a condenser and a multi-effect evaporator, and the first filter is connected with a second filter. The multi-effect evaporator is sequentially connected with a transfer tank, a washer and a second filter; the second filter is respectively connected with a sodium chloride solution storage tank and a copper sulfate preparation unit; the treatment system further comprises an aluminum mud bin connected with the acidification reaction kettle, the acidification reaction kettle is respectively connected with the first filter press and the condenser, the first filter press is connected with the evaporation concentration chamber, and the evaporation concentration chamber is respectively connected with the crystallized aluminum chloride preparation unit and the liquid polyaluminum chloride preparation unit. According to the treatment system and the treatment process, the acidic copper-containing waste liquid generated in the production process of the printed circuit board and the aluminum mud generated in the surface treatment industry are subjected to cooperative treatment, the recovery treatment efficiency is improved, resource utilization is achieved, and economic benefits are achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of surface treatment waste, and particularly relates to a system and a treatment process for co-recovering and treating acidic copper-containing waste liquid and aluminum sludge. Background Art

[0002] The acidic copper-containing waste liquid is generated during the preparation of circuit boards. This waste liquid is a highly copper-containing and highly acidic industrial wastewater generated during the etching of copper foils in the graphic transfer manufacturing process. It is a typical hazardous liquid waste, but this waste is also a high-value composite resource and has great potential in related technologies for resource recovery and etching regeneration.

[0003] Meanwhile, a large amount of aluminum sludge is generated in surface treatment industries such as metal surface treatment and heat treatment. A large amount of aluminum sludge causes great harm to the environment. Aluminum sludge is radioactive, which can cause air pollution, groundwater pollution, and damage to building surfaces and soil. If not properly disposed of and strictly controlled, it will inevitably have a serious impact on the environment and human health.

[0004] In the prior art, the acidic copper-containing waste liquid and aluminum sludge are generally separately recovered and treated, and there is no relevant patent that combines the acidic copper-containing waste liquid and aluminum sludge together. Summary of the Invention

[0005] The purpose of the present invention is to provide a system for co-recovering and treating acidic copper-containing waste liquid and aluminum sludge, which has high treatment efficiency, strong controllability, low treatment cost, no wastewater generation, and simultaneously recovers copper sulfate pentahydrate, sodium chloride and water, enabling rational utilization of resources and having environmental and economic benefits.

[0006] The technical solution adopted by the present invention to solve the above problems is as follows: A system for co-recovering and treating acidic copper-containing waste liquid and aluminum sludge, the recovery and treatment system includes an acidic copper-containing waste liquid collection tank, the acidic copper-containing waste liquid collection tank is sequentially connected to a first filter and a preheater, one outlet of the preheater is connected to a condenser, and the other outlet of the preheater is sequentially connected to a multi-effect evaporator, a transfer tank, a scrubber, and a second filter. The second filter is respectively connected to a sodium chloride solution storage tank and a copper sulfate preparation unit.

[0007] The recovery and treatment system further includes an aluminum sludge silo, the aluminum sludge silo is connected to an acidification reaction kettle, the acidification reaction kettle is respectively connected to a first filter press and the condenser, the first filter press is connected to an evaporation and concentration chamber, and the evaporation and concentration chamber is also respectively connected to a crystalline aluminum chloride preparation unit and a liquid polyaluminum chloride preparation unit.

[0008] Preferably, the connection between the aluminum sludge silo and the acidification reaction kettle is specifically: the aluminum sludge silo is connected to the acidification reaction kettle through a screw feeder.

[0009] Preferably, the multiple-effect evaporator is provided with a steam inlet and a steam outlet. The steam inlet is connected to a steam pipeline, and the steam outlet is connected to the condenser.

[0010] Preferably, the multiple-effect evaporator is a triple-effect evaporator, including a first-effect evaporator, a second-effect evaporator, and a third-effect evaporator. The steam inlet of the first-effect evaporator is connected to the steam pipeline. The steam outlet of the first-effect evaporator is connected to the steam inlet of the second-effect evaporator through a pipeline. The steam outlet of the second-effect evaporator is connected to the steam inlet of the third-effect evaporator through a pipeline. The steam outlet of the third-effect evaporator is connected to the condenser through a pipeline. The material inlet of the third-effect evaporator is connected to the preheater through a pipeline. The material outlet of the third-effect evaporator is connected to the material inlet of the second-effect evaporator through a pipeline. The material outlet of the second-effect evaporator is connected to the material inlet of the first-effect evaporator through a pipeline.

[0011] Preferably, the sodium chloride solution storage tank is also connected to a sodium chloride solid preparation unit.

[0012] Preferably, the acidification reactor is provided with a spiral stirring paddle.

[0013] Preferably, the crystalline aluminum chloride preparation unit includes a crystallizer and a centrifuge connected in sequence.

[0014] Preferably, the liquid polyaluminum chloride preparation unit includes a polymerization reactor and a second filter press connected in sequence.

[0015] Another object of the present invention is to provide a process for co-recovering and treating acidic copper-containing waste liquid and aluminum sludge, including the following steps: Step 1: The acidic copper-containing waste liquid in the acidic copper-containing waste liquid collection tank enters the first filter to remove solid impurities in the waste liquid.

[0016] Step 2: The waste liquid from which solid impurities have been removed enters the preheater for preliminary heating of the waste liquid. The acid mist HCl waste gas generated during this process enters the condenser for condensation.

[0017] Step 3: The preliminarily heated waste liquid enters the multiple-effect evaporator for evaporation and concentration. During this process, the steam in the steam pipeline enters the multiple-effect evaporator from the steam inlet. The residual heat in the steam and the generated acid mist HCl waste gas enter the condenser for condensation through the steam outlet.

[0018] Step 4: The waste liquid after evaporation and concentration enters the transfer tank, and then is washed by a scrubber and filtered by a second filter to obtain purified basic copper chloride and sodium chloride solution. The two respectively enter the copper sulfate preparation unit and the sodium chloride solution storage tank.

[0019] Step 5: The aluminum sludge in the aluminum sludge silo and the hydrochloric acid solution in the condenser both enter the acidification reactor. The aluminum sludge and the hydrochloric acid solution react in the acidification reactor to obtain aluminum chloride. After the reaction is completed, a heavy metal scavenger is added. The heavy metal scavenger reacts with heavy metal ions such as Cu 2+ , Cd 2+ , Hg 2+ , Pb 2+ , Mn 2+ , Ni 2+ , Zn 2+ , Cr 3+ in the mixed solution to form precipitates, which are removed by filtration through the first filter press. The filtrate enters the evaporation and concentration chamber for evaporation and concentration. Part of the evaporated and concentrated solution enters the crystalline aluminum chloride preparation unit, and the other part of the evaporated and concentrated solution enters the liquid polyaluminum chloride preparation unit.

[0020] Preferably, in Step 5, the part of the evaporated and concentrated solution that enters the crystalline aluminum chloride preparation unit and the other part of the evaporated and concentrated solution that enters the liquid polyaluminum chloride preparation unit are specifically as follows: The evaporated and concentrated solution that enters the crystalline aluminum chloride preparation unit is sequentially crystallized in a crystallizer and centrifuged by a centrifuge to obtain aluminum chloride crystals; The evaporated and concentrated solution that enters the liquid polyaluminum chloride preparation unit is sequentially subjected to a polymerization reaction in a polymerization reactor and filtered by a second filter press to obtain liquid polyaluminum chloride.

[0021] Preferably, the mass ratio of the acidic copper-containing waste liquid to the aluminum sludge is 3 - 4:1.

[0022] Preferably, the heating temperature in Step 2 is 60 - 70°C; the reaction temperature in Step 5 is 80°C, and the reaction time is 40 - 50 min.

[0023] Compared with the prior art, the advantages of the present invention are as follows: The recovery and treatment system of the present invention co-treats the acidic copper-containing waste liquid generated in the printed circuit board production process and the aluminum sludge generated in the surface treatment industry, which helps to improve the recovery and treatment efficiency, realize resource utilization, and has economic benefits. Brief Description of the Drawings

[0024] Figure 1 It is a schematic structural diagram of the co-recovery and treatment system for acidic copper-containing waste liquid and aluminum sludge in the embodiment of the present invention.

[0025] Wherein: 1 is an acidic copper-containing waste liquid collection tank, 2 is a first filter, 3 is a preheater, 4 is a condenser, 5 is a multi-effect evaporator, 5-1 is a steam inlet, 5-2 is a steam outlet, 6 is a transfer tank, 7 is a scrubber, 8 is a second filter, 9 is a sodium chloride solution storage tank, 10 is a copper sulfate preparation unit, 11 is an aluminum sludge bin, 12 is an acidification reactor, 13 is a first filter press, 14 is an evaporation and concentration chamber, 15 is a crystalline aluminum chloride preparation unit, 15-1 is a crystallizer, 15-2 is a centrifuge, 16 is a liquid polyaluminum chloride preparation unit, 16-1 is a polymerization reactor, 16-2 is a second filter press. Detailed implementation mode

[0026] The present invention will be further described in detail below in conjunction with the embodiments with reference to the drawings.

[0027] As Figure 1 shown, it is a schematic structural diagram of the acidic copper-containing waste liquid and aluminum sludge co-recovery treatment system in this embodiment.

[0028] An acidic copper-containing waste liquid and aluminum sludge co-recovery treatment system, the recovery treatment system includes an acidic copper-containing waste liquid collection tank 1, the acidic copper-containing waste liquid collection tank 1 is sequentially connected to a first filter 2 and a preheater 3, one outlet of the preheater 3 is connected to a condenser 4, and the other outlet of the preheater 3 is sequentially connected to a multi-effect evaporator 5, a transfer tank 6, a scrubber 7, and a second filter 8, and the second filter 8 is respectively connected to a sodium chloride solution storage tank 9 and a copper sulfate preparation unit 10.

[0029] The recovery treatment system further includes an aluminum sludge bin 11, the aluminum sludge bin 11 is connected to an acidification reactor 12, the acidification reactor 12 is provided with a spiral agitator, the acidification reactor 12 is respectively connected to a first filter press 13 and the condenser 4, the first filter press 13 is connected to an evaporation and concentration chamber 14, the evaporation and concentration chamber 14 is also respectively connected to a crystalline aluminum chloride preparation unit 15 and a liquid polyaluminum chloride preparation unit 16, the crystalline aluminum chloride preparation unit 15 includes a crystallizer 15-1 and a centrifuge 15-2 connected in sequence, and the liquid polyaluminum chloride preparation unit 16 includes a polymerization reactor 16-1 and a second filter press 16-2 connected in sequence.

[0030] Among them, the multi-effect evaporator 5 is provided with a steam inlet 5-1 and a steam outlet 5-2. The steam inlet 5-1 is connected to a steam pipeline, and the steam outlet 5-2 is connected to the condenser 4. The multi-effect evaporator 5 is a triple-effect evaporator, including a first-effect evaporator, a second-effect evaporator, and a third-effect evaporator. The steam inlet of the first-effect evaporator (i.e., the steam inlet 5-1 of the multi-effect evaporator 5) is connected to the steam pipeline. The steam outlet of the first-effect evaporator is connected to the steam inlet of the second-effect evaporator through a pipeline. The steam outlet of the second-effect evaporator is connected to the steam inlet of the third-effect evaporator through a pipeline. The steam outlet of the third-effect evaporator (i.e., the steam outlet 5-2 of the multi-effect evaporator 5) is connected to the condenser 4 through a pipeline. The material inlet of the third-effect evaporator is connected to the preheater 3 through a pipeline. The material outlet of the third-effect evaporator is connected to the material inlet of the second-effect evaporator through a pipeline. The material outlet of the second-effect evaporator is connected to the material inlet of the first-effect evaporator through a pipeline.

[0031] An acidic copper-containing waste liquid and aluminum sludge co-recovery treatment process includes the following steps: Step 1: The acidic copper-containing waste liquid in the acidic copper-containing waste liquid collection tank 1 enters the first filter 2 to remove solid impurities in the waste liquid.

[0032] Step 2: The waste liquid from which solid impurities have been removed enters the preheater 3 for preliminary heating of the waste liquid. The heating temperature is 70°C. The acid mist HCl waste gas generated during this process enters the condenser 4 for condensation.

[0033] Step 3: The preliminarily heated waste liquid enters the multi-effect evaporator 5 for evaporation and concentration. During this process, the steam in the steam pipeline enters the multi-effect evaporator 5 from the steam inlet 5-1. The residual heat in the steam and the generated acid mist HCl waste gas enter the condenser 4 for condensation through the steam outlet 5-2.

[0034] Step 4: The waste liquid after evaporation and concentration enters the transfer tank 6, and then is washed by the washer 7 and filtered by the second filter 8 in sequence to obtain purified basic copper chloride and sodium chloride solution, and the two respectively enter the copper sulfate preparation unit 10 and the sodium chloride solution storage tank 9.

[0035] Step 5: The aluminum sludge in the aluminum sludge bin 11 and the hydrochloric acid solution in the condenser 4 both enter the acidification reaction kettle 12. The aluminum sludge and the hydrochloric acid solution react in the acidification reaction kettle 12 to obtain aluminum chloride. The reaction temperature is 80°C, and the reaction time is 50 min. After the reaction is completed, a heavy metal scavenger is added. The heavy metal scavenger reacts with Cu 2+ , Cd 2+ , Hg 2+ , Pb 2+ , Mn 2+ , Ni 2+ , Zn 2+ , Cr 3+It reacts with heavy metal ions such as to form a precipitate, which is removed by pressure filtration through the first pressure filter 13. The filtrate enters the evaporation and concentration chamber 14 for evaporation and concentration. 83.2% (mass fraction) of the evaporated and concentrated liquid enters the crystalline aluminum chloride preparation unit 15, and successively undergoes crystallization in the crystallizer 15-1 and centrifugation in the centrifuge 15-2 to obtain the crystalline aluminum chloride product. The remaining evaporated and concentrated liquid enters the liquid polyaluminum chloride preparation unit 16, and successively undergoes a polymerization reaction in the polymerization reactor 16-1 and pressure filtration through the second pressure filter 16-2 to obtain the liquid polyaluminum chloride.

[0036] Among them, the mass ratio of the acidic copper-containing waste liquid to the aluminum mud is 4:1.

[0037] In addition to the above embodiments, the present invention also includes other embodiments. Any technical solutions formed by equivalent transformation or equivalent substitution shall fall within the protection scope of the claims of the present invention.

Claims

1. A system for the coordinated recovery and treatment of acidic copper-containing waste liquid and aluminum mud, characterized in that: The recovery and treatment system comprises an acidic copper-containing waste liquid collection tank (1), wherein the acidic copper-containing waste liquid collection tank (1) is sequentially connected to a first filter (2) and a preheater (3), wherein one outlet of the preheater (3) is connected to a condenser (4), and another outlet of the preheater (2) is sequentially connected to a multiple-effect evaporator (5), a transfer tank (6), a scrubber (7), and a second filter (8), wherein the second filter (8) is respectively connected to a sodium chloride solution storage tank (9) and a copper sulfate preparation unit (10); The recycling and processing system further comprises an aluminum sludge silo (11), the aluminum sludge silo (11) being connected to an acidification reaction kettle (12), the acidification reaction kettle (12) being respectively connected to a first filter press (13) and the condenser (4), the first filter press (13) being connected to an evaporation concentration chamber (14), and the evaporation concentration chamber (14) being respectively connected to a crystalline aluminum chloride preparation unit (15) and a liquid polyaluminum chloride preparation unit (15).

2. The system for coordinating the recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 1 is characterized in that: The multiple-effect evaporator (5) is provided with a steam inlet (5-1) and a steam outlet (5-2), the steam inlet (5-1) is connected to a steam pipeline, and the steam outlet (5-2) is connected to the condenser (4).

3. The system for coordinating the recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 1 is characterized in that: The multi-effect evaporator (5) is a three-effect evaporator, including a first-effect evaporator, a second-effect evaporator and a third-effect evaporator.

4. The system for coordinating the recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 1 is characterized in that: The sodium chloride solution storage tank (9) is also connected to a sodium chloride solid preparation unit.

5. The system for coordinating the recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 1 is characterized in that: The acidification reactor (12) is provided with a screw stirring paddle.

6. The system for coordinating the recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 1 is characterized in that: The crystalline aluminum chloride preparation unit (15) comprises a crystallizer (15-1) and a centrifuge (15-2) which are connected in sequence.

7. The system for coordinating the recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 1 is characterized in that: The liquid polyaluminium chloride preparation unit (16) comprises a polymerization reaction kettle (16-1) and a filter press (16-2) which are connected in sequence.

8. A process for the coordinated recovery and treatment of acidic copper-containing waste liquid and aluminum mud, characterized in that: The following steps are involved: Step 1: the acidic copper-containing waste liquid in the acidic copper-containing waste liquid collection tank (1) enters the first filter (2) to remove solid impurities in the waste liquid; Step 2: The waste liquid from which solid impurities have been removed enters the preheater (3) to preliminarily heat the waste liquid, and the acid mist HCl waste gas generated in the process enters the condenser (4) to be condensed; Step 3: The preliminarily heated waste liquid enters the multiple-effect evaporator (5) for evaporation and concentration. During this process, the steam in the steam pipe enters the multiple-effect evaporator (5) from the steam inlet (5-1), and the residual heat in the steam and the generated acid mist HCl waste gas enter the condenser (4) through the steam outlet (5-2) for condensation; Step 4: the waste liquid after evaporation and concentration enters the transfer tank (6), and then is washed by the scrubber (7) and filtered by the second filter (8) to obtain purified basic copper chloride and sodium chloride solution, which enter the copper sulfate preparation unit (10) and the sodium chloride solution storage tank (9) respectively; Step 5: The aluminum sludge in the aluminum sludge silo (11) and the hydrochloric acid solution in the condenser (4) are both introduced into the acidification reactor (12). The aluminum sludge and the hydrochloric acid solution react in the acidification reactor (12) to obtain aluminum chloride. A heavy metal scavenger is then added. The heavy metal scavenger reacts with heavy metal ions in the mixed solution to generate a precipitate, which is filtered out by a first filter press (13). The filtrate enters the evaporation concentration chamber (14) for evaporation and concentration. A portion of the evaporation concentrate enters the crystalline aluminum chloride preparation unit (15) to obtain a crystalline aluminum chloride product. Another portion of the evaporation concentrate enters the liquid polyaluminum chloride preparation unit (16) to obtain liquid aluminum chloride.

9. The process for the coordinated recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 8, characterized in that: The mass ratio of the acidic copper-containing waste liquid to the aluminum mud is 3-4:

1.

10. The process for the coordinated recovery and treatment of acidic copper-containing waste liquid and aluminum mud according to claim 8, characterized in that: The heating temperature in step 2 is 60-70°C; the reaction temperature in step 5 is 80°C, and the reaction time is 40-50min.

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