阅读说明：本技术 一种己二酸铵废液的纯化方法及其回收处理装置 (Purification method of ammonium adipate waste liquid and recovery processing device thereof ) 是由 慈敦锋 于 2019-09-18 设计创作，主要内容包括：本发明公开了一种己二酸铵废液的纯化方法及其回收处理装置,将待处理的己二酸铵废液进行过滤,去除己二酸铵废液中固体的杂质,往过滤后的己二酸铵废液中加入酸性调节液,随后将乙二酸废液依次通过双极膜电渗析装置和扩散渗析器,将废液经过酸性阳离子交换柱,将废液中的Cl<Sup>-</Sup>和Al<Sup>3+</Sup>去除,对过滤后的废液进行加热,本发明涉及有机废液回收技术领域。该己二酸铵废液的纯化方法及其回收处理装置通过将废液依次通过双击膜电渗析装置、扩散渗析器和离子交换柱,可以减少废液中氯离子、铝离以及其余离子,从而可以对废液进行提纯,并且在提纯前通过添加酸性调节液,可以保证废液的PH值,同时可以保证了纯化后电解质的品质。(The invention discloses a purification method of ammonium adipate waste liquid and a recovery processing device thereof, wherein the ammonium adipate waste liquid to be processed is filtered to remove solid impurities in the ammonium adipate waste liquid, acidic conditioning liquid is added into the filtered ammonium adipate waste liquid, then oxalic acid waste liquid sequentially passes through a bipolar membrane electrodialysis device and a diffusion dialyzer, the waste liquid passes through an acidic cation exchange column, and Cl in the waste liquid is treated ‑ And Al 3+ Removing, to the filteredThe invention discloses heating of waste liquid, and relates to the technical field of organic waste liquid recovery. This purification method of ammonium adipate waste liquid and recovery processing device thereof can reduce chloride ion, aluminium ion and other ions in the waste liquid through looping the waste liquid through double-impact membrane electrodialysis device, diffusion dialyzer and ion exchange column to can purify the waste liquid, and through adding acidic conditioning fluid before the purification, can guarantee the pH value of waste liquid, can guarantee the quality of electrolyte after the purification simultaneously.)

1. A purification method of ammonium adipate waste liquid is characterized by comprising the following steps: the method comprises the following steps:

filtering the ammonium adipate waste liquid to be treated to remove solid impurities in the ammonium adipate waste liquid;

step two, adding an acidic conditioning solution into the filtered ammonium adipate waste liquid, and then sequentially passing the oxalic acid waste liquid through a bipolar membrane electrodialysis device (3) and a diffusion dialyzer (4);

step three, passing the waste liquid through an acidic cation exchange column to remove Cl in the waste liquid^-And Al³⁺Removing;

step four, heating the filtered waste liquid to reduce the water content in the waste liquid;

step five, cooling the waste liquid, separating out crystals, and then carrying out solid-liquid separation to obtain ammonium adipate crystals;

and step six, dehydrating and drying the separated ammonium adipate crystals to obtain finished ammonium adipate.

2. The method for purifying the ammonium adipate waste liquid according to claim 1, which is characterized in that: the acidic regulating solution is one of nitric acid, sulfuric acid and hydrochloric acid.

3. The method for purifying the ammonium adipate waste liquid according to claim 1, which is characterized in that: and D, after the fifth step is finished, detecting the purity of the ammonium adipate crystal, and if the purity of the ammonium adipate crystal is lower than 95%, injecting pure water again to repeat the fourth step and the fifth step for purification again.

4. The method for purifying the ammonium adipate waste liquid according to claim 1, which is characterized in that: the ammonium adipate crystal needs to be kept at 45-55 ℃ during dehydration, drying is carried out by using drying air, and meanwhile, the drying air needs to be discharged after being treated by waste gas after being dried.

5. The method for purifying the ammonium adipate waste liquid according to claim 1, which is characterized in that: the density of the waste liquid after being heated needs to reach 0.9-1.5 g/cm³。

6. A recycling treatment device for ammonium adipate waste liquid comprises a waste liquid tank (1), a filter box (2), a bipolar membrane electrodialysis device (3), a diffusion dialyzer (4), an ion exchange column (5), a heater (6), an evaporator (7), a solid-liquid separator (8), a dryer (9), a water vapor recycling device (10), a pure water tank (11) and a waste gas treatment device (12), wherein the filter box (2) is communicated with the waste liquid tank (1), the bipolar membrane electrodialysis device (3) is communicated with the filter box (2), the diffusion dialyzer (4) is communicated with the bipolar membrane electrodialysis device (3), the ion exchange column (5) is communicated with the diffusion dialyzer (4), the heater (6) is communicated with the ion exchange column (5), the evaporator (7) is communicated with the heater (6), and the solid-liquid separator (8) is communicated with the evaporator (7), the dryer (9) is communicated with the solid-liquid separator (8).

7. The apparatus according to claim 6, wherein said apparatus comprises: the evaporator (7) is further communicated with a water vapor recovery device (10), the water vapor recovery device (10) is communicated with a pure water tank (11), the pure water tank (11) is communicated with the heater (6), and the dryer (9) is further communicated with an exhaust gas treatment device (12).

8. The apparatus according to claim 7, wherein said apparatus comprises: the ion exchange column (5) comprises a cation exchange column and an anion exchange column inside.

9. The apparatus according to claim 8, wherein said apparatus comprises: and an anion exchange membrane is arranged in the bipolar membrane electrodialysis device (3), and is a non-crosslinked polysulfone quaternary ammonium type anion membrane.

10. The apparatus according to claim 9, wherein said apparatus comprises: the inside of vapor recovery unit (10) includes condenser pipe and filter equipment, and filter equipment is provided with two sets ofly and sets up respectively at the both ends of condenser pipe.

Technical Field

The invention relates to the technical field of organic waste liquid recovery, in particular to a purification method of ammonium adipate waste liquid and a recovery processing device thereof.

Background

An aluminum electrolytic capacitor is a capacitor made by using an aluminum cylinder as a negative electrode, filling liquid electrolyte in the aluminum cylinder and inserting a bent aluminum strip as a positive electrode, and is called as an aluminum electrolytic capacitor. The production process of the anode aluminum foil for the aluminum electrolytic capacitor mainly comprises the steps of corrosion and formation. The electrolyte is required to be adopted in the aluminum foil formation process, the main component of the electrolyte in the medium-low pressure formation process is ammonium adipate, the concentration of the ammonium adipate is usually as high as 100g/L, more aluminum ions, chloride ions and other impurities can be mixed after the electrolyte is used for a period of time, so that the performance of the electrolyte cannot meet the requirement, a new ammonium adipate electrolyte needs to be prepared, the production cost can be increased and the product competitiveness can be reduced if the new electrolyte is used, a large amount of harmful substances are contained in the waste electrolyte and can be discharged after harmless treatment, and otherwise serious pollution can be caused to the environment.

Chinese patent discloses a purification method of ammonium adipate waste liquid and a recovery processing device thereof (publication number: CN109053423A), which divides the ammonium adipate waste liquid to be processed into a waste liquid a and a waste liquid B, adds ammonia water or NH3 gas into the waste liquid a to make the pH thereof slightly basic, and generates al (oh)3 precipitate; filtering to remove Al (OH)3 precipitate to obtain filtrate A; mixing the waste liquid B with the filtrate A to ensure that the pH of the obtained solution is 6.5-7.5; removing solid suspended substances contained in the mixed solution by using a fine filter, taking the filtrate as a feed liquid, taking Cl-free clean water as a receiving cleaning liquid, and introducing the clean water into a diffusion dialyzer to remove Cl < - > so as to obtain a recovered liquid.

The conventional method has various defects that in order to reduce the problem that the acid radical ions of the waste liquid are neutralized by adding alkaline liquid into the waste liquid to reduce the chloride ions, the number of the acid radical ions in the waste liquid is reduced, the pH value of the waste liquid is increased to cause the loss of the waste liquid to be increased, a large amount of water vapor is generated during evaporative crystallization in the conventional method, but the water vapor cannot be secondarily utilized, so that the energy consumption is increased and the waste is caused.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a purification method of ammonium adipate waste liquid and a recovery treatment device thereof, which solve the problems that the prior method has various defects, the acid radical ions in the waste liquid are neutralized due to the addition of alkaline liquid into the waste liquid for reducing the chloride ions, the number of the acid radical ions in the waste liquid is reduced, the PH value of the waste liquid is increased, the loss of the waste liquid is increased, and the traditional method can generate a large amount of water vapor during evaporation crystallization, but cannot perform secondary utilization on the water vapor, so that the energy consumption is increased and the waste is caused.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme: a purification method of ammonium adipate waste liquid comprises the following steps:

filtering the ammonium adipate waste liquid to be treated to remove solid impurities in the ammonium adipate waste liquid;

secondly, adding an acidic conditioning solution into the filtered ammonium adipate waste liquid, and then sequentially passing the oxalic acid waste liquid through a bipolar membrane electrodialysis device and a diffusion dialyzer;

step three, passing the waste liquid through an acidic cation exchange column to remove Cl in the waste liquid^-And Al³⁺Removing;

step four, heating the filtered waste liquid to reduce the water content in the waste liquid;

step five, cooling the waste liquid, separating out crystals, and then carrying out solid-liquid separation to obtain ammonium adipate crystals;

and step six, dehydrating and drying the separated ammonium adipate crystals to obtain finished ammonium adipate.

Preferably, the acidic conditioning solution is one of nitric acid, sulfuric acid and hydrochloric acid.

Preferably, the purity of the ammonium adipate crystals is detected after the fifth step, and if the purity of the ammonium adipate crystals is lower than 95%, pure water is injected again to repeat the fourth step and the fifth step for purification again.

Preferably, the ammonium adipate crystal is maintained at 45-55 ℃ during dehydration, and is dried by using drying air, and the drying air is discharged after being treated by waste gas after being dried.

Preferably, the density of the waste liquid after being heated needs to reach 0.9 g-1.5 g/cm³。

The invention also discloses a recycling treatment device of the ammonium adipate waste liquid, which comprises a waste liquid tank, a filter box, a bipolar membrane electrodialysis device, a diffusion dialyzer, an ion exchange column, a heater, an evaporator, a solid-liquid separator, a dryer, a water vapor recycling device, a pure water tank and a waste gas treatment device, wherein the filter box is communicated with the waste liquid tank, the bipolar membrane electrodialysis device is communicated with the filter box, the diffusion dialyzer is communicated with the bipolar membrane electrodialysis device, the ion exchange column is communicated with the diffusion dialyzer, the heater is communicated with the ion exchange column, the evaporator is communicated with the heater, the solid-liquid separator is communicated with the evaporator, and the dryer is communicated with the solid-liquid separator.

Preferably, the evaporator is further communicated with a water vapor recovery device, the water vapor recovery device is communicated with a pure water tank, the pure water tank is communicated with the heater, and the dryer is further communicated with the waste gas treatment device.

Preferably, the ion exchange column comprises a cation exchange column and an anion exchange column inside.

Preferably, an anion exchange membrane is arranged in the bipolar membrane electrodialysis device, and the anion exchange membrane is a non-crosslinked polysulfone quaternary ammonium type anion membrane.

Preferably, the inside of the water vapor recovery device comprises a condensation pipe and a filtering device, the filtering device is provided with two groups of water vapor recovery devices and is respectively arranged at two ends of the condensation pipe, and the condensation pipe is communicated with the pure water tank.

(III) advantageous effects

The invention provides a purification method of ammonium adipate waste liquid and a recovery processing device thereof. The method has the following beneficial effects:

(1) the ammonium adipate waste liquid to be treated is filtered to remove solid impurities in the ammonium adipate waste liquid, and filtered adipic acid isAdding acidic regulating solution into the ammonium acid waste liquid, sequentially passing the oxalic acid waste liquid through a bipolar membrane electrodialysis device and a diffusion dialyzer, passing the waste liquid through an acidic cation exchange column, and carrying out ion exchange on Cl in the waste liquid^-And Al³⁺The method comprises the steps of removing, wherein a filter box is communicated with a waste liquid tank, a bipolar membrane electrodialysis device is communicated with the filter box, a diffusion dialyzer is communicated with the bipolar membrane electrodialysis device, an ion exchange column is communicated with the diffusion dialyzer, a heater is communicated with the ion exchange column, and the ion exchange column internally comprises a cation exchange column and an anion exchange column.

(2) The purification method of the ammonium adipate waste liquid and the recovery processing device thereof have the advantages that the purity of ammonium adipate crystals needs to be detected after the fifth step is finished, if the purity of the ammonium adipate crystals is lower than 95%, pure water needs to be injected again to repeat the fourth step and the fifth step for purification again, the ammonium adipate crystals need to be kept at 45-55 ℃ when being dehydrated, drying air is used for drying, meanwhile, the drying air needs to be discharged after waste gas treatment after being dried, the heater is communicated with the ion exchange column, the evaporator is communicated with the heater, the evaporator is also communicated with the water vapor recovery device, the water vapor recovery device is communicated with the pure water tank, the pure water tank is communicated with the heater, the dryer is also communicated with the waste gas processing device, the device is additionally provided with the water vapor recovery device and the waste gas processing device on the basis of traditional evaporation precipitated crystals, the water vapor recovery device can condense and recover water vapor generated by the, and mix into the pure water tank with the comdenstion water to can utilize it repeatedly, reduce the loss, exhaust treatment device can carry out innocent treatment with the stoving waste gas of discharging in the desicator simultaneously and discharge, can avoid the polluted environment.

(3) The purification method of the ammonium adipate waste liquid and the recovery processing device thereof add acidic conditioning liquid into the filtered ammonium adipate waste liquid, then sequentially pass the oxalic acid waste liquid through a bipolar membrane electrodialysis device and a diffusion dialyzer, heat the filtered waste liquid, reduce the water content in the waste liquid, precipitate crystals after the waste liquid is cooled, then separate the ammonium adipate crystals by solid-liquid separation, dehydrate and dry the separated ammonium adipate crystals to obtain the finished product ammonium adipate, and the recovery processing device comprises a waste liquid tank, a filter box, a bipolar membrane electrodialysis device, a diffusion dialyzer, an ion exchange column, a heater, an evaporator, a solid-liquid separator, a dryer, a water vapor recovery device, a pure water tank and a waste gas processing device, wherein the interior of the water vapor recovery device comprises a condensation pipe and a filter device, and the filter device is provided with two groups and is respectively arranged at two ends of the condensation pipe, the condensation pipe is communicated with the pure water tank, only the acidic conditioning liquid and the pure water need to be added in the purification process, the secondary pollution to the waste liquid can be reduced, other impurities are not generated in the purification process, the purification efficiency is high, and the purification effect is good.

Drawings

FIG. 1 is a schematic flow chart of a recycling apparatus according to the present invention.

In the figure, 1, a waste liquid tank; 2. a filter box; 3. a bipolar membrane electrodialysis device; 4. a diffusion dialyzer; 5. an ion exchange column; 6. a heater; 7. an evaporator; 8. a solid-liquid separator; 9. a dryer; 10. a water vapor recovery device; 11. a pure water tank; 12. an exhaust gas treatment device.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to fig. 1, an embodiment of the present invention provides a technical solution: a recycling treatment device of ammonium adipate waste liquid comprises a waste liquid tank 1, a filter box 2, a bipolar membrane electrodialysis device 3, a diffusion dialyzer 4, an ion exchange column 5, a heater 6, an evaporator 7, a solid-liquid separator 8, a dryer 9, a water vapor recycling device 10, a pure water tank 11 and a waste gas treatment device 12, wherein the filter box 2 is communicated with the waste liquid tank 1, the bipolar membrane electrodialysis device 3 is communicated with the filter box 2, an anion exchange membrane is arranged inside the bipolar membrane electrodialysis device 3 and is a polysulfone quaternary ammonium type anion-exchange membrane without cross-linking, the diffusion dialyzer 4 is communicated with the bipolar membrane electrodialysis device 3, the ion exchange column 5 is communicated with the diffusion dialyzer 4, the ion exchange column 5 comprises a cation exchange column and an anion exchange column inside, the heater 6 is communicated with the ion exchange column 5, the evaporator 7 is communicated with the heater 6, the solid-liquid separator 8 is communicated with the evaporator 7, the desicator 9 communicates with solid-liquid separator 8, and evaporimeter 7 still communicates with steam recovery unit 10, and steam recovery unit 10 communicates with pure water tank 11, and steam recovery unit 10's inside includes condenser pipe and filter equipment, and filter equipment is provided with two sets ofly and sets up respectively at the both ends of condenser pipe, and condenser pipe and 11 intercommunication pure water tank 10, pure water tank 11 and heater 6 intercommunication, desicator 9 still communicates with exhaust treatment device 12.

A purification method of ammonium adipate waste liquid is characterized in that waste liquid raw materials in a waste liquid tank 1 are introduced into a filter box 2, solid impurities in the ammonium adipate waste liquid are removed after the waste liquid raw materials are filtered in the filter box 2, an acidic regulating liquid is added into the filtered waste liquid, the acidic regulating liquid is nitric acid, then the oxalic acid waste liquid sequentially passes through a bipolar membrane electrodialysis device 3 and a diffusion dialyzer 4, an anion exchange membrane is arranged inside the bipolar membrane electrodialysis device 3 and is a polysulfone quaternary ammonium type anion membrane without cross-linking, salts in the waste liquid can be converted into corresponding acid and alkali, the rest salts are filtered after the oxalic acid waste liquid passes through the diffusion dialyzer 4, the waste liquid passes through an acidic cation exchange column, and when the waste liquid passes through an ion exchange column 5, Cl in the waste liquid can be filtered through the cation exchange column and the anion exchange column inside the waste liquid^-And Al³⁺Get rid of, purify the waste liquid, heat the waste liquid after the filtration, the waste liquid shifts to evaporimeter 7 in after heater 6 heats, and the water in the waste liquid evaporates into vapor with heat to reduce the content of waste liquid normal water, back in vapor recovery device 10 is shifted to vapor, vapor behind filter equipment, in the condenser pipe in vapor recovery device 10Condensed into pure water and sent to a pure water tank 11 after being filtered by a second group of filtering devices, crystals are precipitated after the waste liquid is cooled, ammonium adipate crystals are separated by a solid-liquid separator 8, and part of ammonium adipate crystals are taken out to be detected, after inspection, the purity of the ammonium adipate crystals is found to be 90 percent and is lower, and less than 95%, pure water is re-injected, ammonium adipate crystals are dissolved and then sent to the heater 6 to be reheated, and then sent to the evaporator 7 again, ammonium adipate crystals precipitated after cooling, which were checked for a purity of 96% above the standard value of 95%, and were subsequently transferred to a dryer 9, the dryer 9 is maintained at 50 ℃, then the ammonium adipate crystals are dried by a fan, and the exhaust gas is discharged after being subjected to harmless treatment by an exhaust gas treatment device 12 after being dried.