CN114426264B - Electronic acid waste liquid pretreatment module and electronic acid waste liquid recovery treatment method - Google Patents
Electronic acid waste liquid pretreatment module and electronic acid waste liquid recovery treatment method Download PDFInfo
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- CN114426264B CN114426264B CN202111604580.1A CN202111604580A CN114426264B CN 114426264 B CN114426264 B CN 114426264B CN 202111604580 A CN202111604580 A CN 202111604580A CN 114426264 B CN114426264 B CN 114426264B
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- 239000002253 acid Substances 0.000 title claims abstract description 171
- 239000002699 waste material Substances 0.000 title claims abstract description 129
- 239000007788 liquid Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000011084 recovery Methods 0.000 title claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 156
- 238000003860 storage Methods 0.000 claims abstract description 54
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000010521 absorption reaction Methods 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 42
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003546 flue gas Substances 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000012856 packing Methods 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 238000011278 co-treatment Methods 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 34
- 239000012535 impurity Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/775—Liquid phase contacting processes or wet catalysis processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention relates to the field of electronic acid waste liquid treatment, and provides a method for recycling and treating electronic acid waste liquid, which comprises the following steps: respectively conveying the pretreated electronic acid waste liquid to a circulating tank I with concentrated sulfuric acid at the bottom of a storage battery sulfuric acid absorption tower and a circulating tank II with dilute sulfuric acid at the bottom of a tail gas absorption tower, introducing flue gas produced by a sulfuric acid device into the storage battery sulfuric acid absorption tower, enabling acid liquor to reversely contact with the flue gas, and reacting sulfur trioxide with water in the concentrated sulfuric acid to generate sulfuric acid; and introducing the tail gas containing the sulfur dioxide after the reaction in the steps into a tail gas absorption tower, and reacting the sulfur dioxide in the packing layer II with hydrogen peroxide in the electronic acid waste liquid to generate sulfuric acid. The electronic acid waste liquid pretreatment module is applied to the electronic acid waste liquid recovery treatment method; after the electronic acid waste liquid is pretreated by the pretreatment module, acid is respectively supplied to the storage battery sulfuric acid absorption module and the tail gas absorption module; the beneficial effects are that: not only the sulfur trioxide and sulfur dioxide in the electronic acid waste liquid and the flue gas are recovered, but also the concentration of sulfuric acid is improved.
Description
Technical Field
The invention relates to the field of comprehensive treatment of electronic acid waste liquid and flue gas generated in the sulfuric acid production process, in particular to an electronic acid waste liquid pretreatment module and an electronic acid waste liquid recovery treatment method.
Background
Wet electronic chemical, electronic grade sulfuric acid is also known as high purity sulfuric acid and ultrapure sulfuric acid, and belongs to an ultrapure high purity reagent, which is an indispensable key basic chemical reagent in the development process of microelectronic technology, and is widely applied to the assembly and processing processes of semiconductors and very large scale integrated circuits, and also applied to the cleaning, photoetching and corrosion of silicon wafers, and the corrosion and electroplating cleaning of printed circuit boards.
The method is applied to a chemical industry enterprise specially producing electronic acid and sulfuric acid with various contents, the electronic acid sold at present is mainly used for cleaning electronic chips in the etching and cleaning processes by using electronic grade sulfuric acid, and then the generated electronic acid waste liquid is not reasonably recycled in China at present, so that the competitiveness of company products is improved, and the utilization rate of the acid is further improved by recycling the sold and used electronic acid waste liquid by the applicant.
Disclosure of Invention
The invention aims to provide a method for cooperatively recycling electronic acid waste liquid and flue gas, which does not need to be treated separately, and sulfur trioxide and sulfur dioxide in the electronic acid waste liquid and the flue gas can be recycled by the method.
In order to achieve the above object, the present invention has the following technical scheme:
an electronic acid waste liquid pretreatment module comprises at least one of a ceramic membrane filter, an activated carbon treatment unit and an ion exchange resin unit, wherein the ceramic membrane filter is a container internally provided with a microporous ceramic membrane, and the filtration grade of the microporous ceramic membrane is 50 nanometers; the active carbon treatment unit is a container with S-level active carbon arranged inside; the ion exchange resin unit is a container with built-in H-type exchange resin.
And after the electronic acid waste liquid is pretreated by the electronic acid waste liquid pretreatment module, acid is respectively supplied to the storage battery sulfuric acid production module and the tail gas recovery module.
The electronic acid waste liquid recovery treatment method comprises the following steps:
(1) And (3) transporting the electronic acid waste liquid to a factory through a tank car or a ton barrel, and discharging the electronic acid waste liquid to a waste acid ground tank after the electronic acid waste liquid is checked to be qualified.
Starting a submerged centrifugal pump of the waste acid geosyncline, and conveying the electronic acid waste liquid into the waste acid storage tank from the top of the waste acid storage tank through a pipeline, so that the liquid level of the waste acid geosyncline keeps a reasonable index range until the electronic acid waste liquid in the tank wagon or the ton bucket is completely discharged;
(2) Opening an acid discharge valve at the bottom of the waste acid storage tank to enable the electronic acid waste liquid to flow into a waste acid ground tank, and simultaneously opening a submerged centrifugal pump of the waste acid ground tank to pretreat the electronic acid waste liquid and then respectively supply acid to a storage battery sulfuric acid production module and a tail gas recovery module through pipelines;
in the process, the liquid level of the waste acid ground tank is kept in a reasonable liquid level index range by adjusting the opening of the acid discharging valve and the opening of the acid supplying valve at the bottom of the waste acid storage tank.
Before acid is supplied to the storage battery sulfuric acid production module and the tail gas recovery module, the electronic acid waste liquid is subjected to pretreatment according to the inspection result and the visual color condition, and the treatment process is as follows: the electronic acid waste liquid sequentially passes through all three units of a ceramic membrane filter, an activated carbon treatment unit and an ion exchange resin unit or any 1-2 treatment units, so that solid mechanical impurities and/or organic matters and/or heavy metal ions possibly existing in the electronic acid waste liquid are removed.
(3) Electronic acid waste liquid and flue gas collaborative recovery procedure
(1) The co-processing process of the electronic acid waste liquid and the flue gas in the storage battery sulfuric acid production module is as follows:
respectively conveying the pretreated electronic acid waste liquid into a circulating tank I with concentrated sulfuric acid at the bottom of a storage battery sulfuric acid absorption tower and a circulating tank II with dilute sulfuric acid at the bottom of a tail gas absorption tower, pumping the acid liquor in the circulating tank I into the storage battery sulfuric acid absorption tower from the top of the storage battery sulfuric acid absorption tower through a centrifugal pump, simultaneously, introducing the flue gas containing sulfur trioxide and sulfur dioxide produced by a sulfuric acid device into the storage battery sulfuric acid absorption tower from the outside of the storage battery sulfuric acid absorption tower between a packing layer I and the circulating tank I, enabling the acid liquor to uniformly distribute through an acid distributor in the tower, enabling the acid liquor to reversely contact with the flue gas through the packing layer I in the tower by virtue of self gravity, and enabling the sulfur trioxide to react with water in the concentrated sulfuric acid to generate sulfuric acid and fall back into the circulating tank I;
(2) the co-treatment process of the electronic acid waste liquid and the tail gas in the tail gas recovery module is as follows:
the tail gas containing sulfur dioxide after reaction in the steps is discharged from the upper part of a storage battery sulfuric acid absorption tower and is introduced into the tail gas absorption tower from a circulating tank II through a pipeline, acid liquor in the circulating tank I is pumped into the storage battery sulfuric acid absorption tower from the top of the tail gas absorption tower through a centrifugal pump, and sulfur dioxide in the tail gas in a packing layer II reacts with hydrogen peroxide in electronic acid waste liquid to generate sulfuric acid and falls back into the circulating tank II;
the concentration of the acid liquor is reduced and controlled within a certain range by adding desalted water into the circulating tank II;
further, in the above process, the concentration sensor is arranged in the circulating tank I and the circulating tank II;
further, liquid level sensors are arranged in the circulating tank I and the circulating tank II, and the centrifugal pump is controlled by the liquid level sensors to enable the circulating tank I and the circulating tank II to keep certain liquid level;
finally, the concentrated sulfuric acid in the circulating tank I is discharged to a metering tank, and the tail gas after the reaction in the tail gas absorption tower is discharged to an electric demisting system;
furthermore, the device also comprises 1 heat exchanger, the acid liquor with the temperature increased after the reaction in the circulating groove I enters the heat exchanger for cooling, and is pumped into the storage battery sulfuric acid absorption tower from the top of the storage battery sulfuric acid absorption tower; the desalted water is added into the heat exchanger before being added into the circulating tank II, and then enters the circulating tank II after being heated;
the beneficial effects of the invention are as follows:
in the storage battery sulfuric acid absorption tower, sulfuric acid device produces sulfur trioxide in the flue gas and a part of 2% water contained in concentrated sulfuric acid react to generate sulfuric acid to promote acid liquor concentration, sulfur dioxide is contained in tail gas after the reaction, the tail gas is introduced into the flue gas absorption tower, trace sulfur dioxide reacts with hydrogen peroxide in electronic acid waste liquid to generate sulfuric acid, dilute sulfuric acid with concentration enriched after the reaction is maintained in concentration by adding desalted water, the process reduces the additional adding amount of hydrogen peroxide, the absorption process of sulfuric acid cannot be influenced, the conversion rate of sulfur dioxide and sulfur trioxide in the flue gas reaches 99.5% through the treatment line, and the emission of sulfur dioxide and sulfur trioxide in the flue gas is further reduced.
Drawings
FIG. 1 is a schematic diagram of a process for the co-recovery treatment of electronic acid waste liquid and flue gas;
FIG. 2 is a graph comparing mechanical impurities in spent acid;
in the figure:
1. waste acid geosyncline 2, submerged centrifugal pump 3 and waste acid storage tank
4. Ceramic membrane filter 5, activated carbon treatment unit 6, and ion exchange resin unit
7. Storage battery sulfuric acid absorption tower 7-1, circulating tank I7-2 and packing layer I
8. Tail gas absorption tower 8-1, circulation tank II 8-2 and packing layer II
8-3, air chamber
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
The electronic acid waste liquid recovery treatment method comprises the following steps:
(1) And (3) transporting the electronic acid waste liquid to a factory through a tank car, and discharging the electronic acid waste liquid to a waste acid ground tank after the electronic acid waste liquid is checked to be qualified.
Starting a submerged centrifugal pump of the waste acid geosyncline, and conveying the electronic acid waste liquid into the waste acid storage tank from the top of the waste acid storage tank through a pipeline, so that the liquid level of the waste acid geosyncline keeps a reasonable index range until the electronic acid waste liquid in the tank wagon or the ton bucket is completely discharged;
(2) Opening an acid discharge valve at the bottom of the waste acid storage tank to enable the electronic acid waste liquid to flow into the waste acid ground tank, and simultaneously opening a submerged centrifugal pump of the waste acid ground tank to supply acid to the storage battery sulfuric acid production module and the tail gas recovery module respectively through pipelines;
in the process, the liquid level of the waste acid ground tank is kept in a reasonable liquid level index range by adjusting the opening of the acid discharging valve and the opening of the acid supplying valve at the bottom of the waste acid storage tank.
Before acid is supplied to the storage battery sulfuric acid production module and the tail gas recovery module, through inspection, the electronic acid waste liquid contains solid mechanical impurities, colored organic matters and heavy metal ions, and the liquid is yellowish, so that the pretreatment is carried out, and experiments are carried out before the pretreatment, and the experimental process and the results are as follows:
(1) removing mechanical impurities in the electronic acid waste liquid by using a tetrafluoro filtering material, a microporous ceramic membrane filtering material and a ceramic tube filtering material respectively
Adding 200ml of electronic acid waste liquid into experimental equipment of tetrafluoro filtering materials, microporous ceramic membrane filtering materials and ceramic tube filtering materials respectively, vacuumizing the other side of the experimental equipment by a vacuum pump so as to filter the waste acid, and detecting the waste acid by using a transmittance detector before and after filtration, wherein the detection data are as follows:
| material of material | Tetrafluoro-based filter material | Microporous ceramic membrane filtering material | Ceramic tube filter material |
| Dosage of waste acid (ml) | 200 | 200 | 200 |
| Transmittance before filtration | 29 | 29 | 29 |
| Transmittance after filtration | 26 | 7 | 24.5 |
As shown in fig. 2, 3 arcs from top to bottom are in turn of tetrafluoro-based filter material, ceramic tube filter material and microporous ceramic membrane filter material, so that the microporous ceramic membrane filter material can remove mechanical impurities in electronic acid waste liquid more effectively than tetrafluoro-based filter material and ceramic tube filter material.
(2) The diatomite material and the active carbon filter material with different grades are used for respectively removing colored organic matters in the electronic acid waste liquid
The diatomite material and the activated carbon material are respectively weighed to be 10g, added into 200ml of electronic acid waste liquid, fully stirred, and kept stand for 3 hours, and the supernatant is observed as follows:
| material name | Diatomite material | Activated carbon material |
| Waste acid addition (ml) | 200 | 200 |
| Material addition (g) | 10 | 10 |
| Supernatant after standing | Yellowish light yellow | Colorless transparent liquid |
Taking 40g of P-grade active carbon filter material and 40g of S-grade active carbon filter material, respectively, adding the P-grade active carbon filter material and the S-grade active carbon filter material into 200ml of electronic acid waste liquid, wherein bubbles are generated after the P-grade active carbon filter material is added, and no gas is generated after the S-grade active carbon filter material is added:
| addition amount of activated carbon material | 40g (P grade) | 40g (S level) |
| Bubble generation condition | Has the following components | Without any means for |
From the above experiments, it was concluded that the S-stage activated carbon filter material was more effective than the diatomaceous earth material in removing colored organic substances from waste acid without generating bubbles.
(3) Removing metal ions from electronic acid waste liquid by using W-type resin and H-type resin respectively
Before removal, the standard solution with 30ml of standard acid solution containing 0.0001% of Cu ions and 0.0001% of Fe ions is prepared by respectively placing 25mlW type resin and 25ml of H type resin into a burette, dripping the electronic acid waste liquid, contacting the electronic acid waste liquid with the resin from top to bottom by utilizing natural attraction, and detecting metal ions of the exchanged standard solution. The test data are as follows: .
Conclusion of experiment: the H-type exchange resin can more effectively remove metal ions in the electronic acid waste liquid.
(4) Hydrogen peroxide removal experiment
Introducing 3 parts of 500ml of electronic acid waste liquid into the waste gas containing sulfur dioxide respectively to detect the change of the hydrogen peroxide content;
according to the test, the content of hydrogen peroxide is reduced to the minimum value after the waste gas containing sulfur dioxide is introduced into 500ml of electronic acid waste liquid for 90 seconds.
Thus the filtration grade of the microporous ceramic membrane filter is 50 nanometers; adsorbing colored organic matters in the electronic acid waste liquid by using the adsorptivity of the S-level activated carbon to remove the colored organic matters in the electronic acid waste liquid; and removing metal ions in the electronic acid waste liquid through ion exchange of H-type exchange resin.
(3) Electronic acid waste liquid and flue gas collaborative recovery procedure
The flue gas is generated in the sulfuric acid production process, and contains a large amount of sulfur trioxide and a small amount of sulfur dioxide, and further, the concentration of the sulfur trioxide and the sulfur dioxide in the flue gas is 55%, wherein the 55% contains 95% of sulfur trioxide and 5% of sulfur dioxide;
(1) the co-processing process of the electronic acid waste liquid and the flue gas in the storage battery sulfuric acid production module is as follows:
respectively conveying the pretreated electronic acid waste liquid into a circulating tank I filled with 98% of concentrated sulfuric acid at the bottom of a storage battery sulfuric acid absorption tower and a circulating tank II filled with 30% of dilute sulfuric acid at the bottom of a tail gas absorption tower, pumping acid liquor in the circulating tank I into the storage battery sulfuric acid absorption tower from the top of the storage battery sulfuric acid absorption tower through a centrifugal pump to enable the acid liquor to continuously circulate in the storage battery sulfuric acid absorption tower, simultaneously, introducing flue gas containing sulfur trioxide and sulfur dioxide produced by a sulfuric acid device into the storage battery sulfuric acid absorption tower from the outside of the storage battery sulfuric acid absorption tower between a packing layer I and the circulating tank I, enabling the acid liquor to be uniformly distributed through a splitter in the tower, enabling the acid liquor to reversely contact with the flue gas through the packing layer I in the tower by virtue of self gravity, and reacting the sulfur trioxide with water in the concentrated sulfuric acid to generate sulfuric acid;
(2) the co-treatment process of the electronic acid waste liquid and the tail gas in the tail gas recovery module is as follows:
introducing the tail gas containing a small amount of sulfur dioxide after the reaction in the step into a tail gas absorption tower from the upper part of the storage battery sulfuric acid absorption tower through a pipeline from a circulation tank II, pumping acid liquor in the circulation tank I into the storage battery sulfuric acid absorption tower from the top of the tail gas absorption tower through a centrifugal pump, continuously circulating the acid liquor in the tail gas absorption tower, and returning sulfuric acid generated by the reaction of sulfur dioxide in the tail gas in a filler layer II and hydrogen peroxide in electronic acid waste liquid into the circulation tank II; after the reaction, the conversion rate of sulfur dioxide in the flue gas reaches 99.5 percent.
The concentration of the acid liquor is reduced and controlled at 30% by adding desalted water into the packing layer I;
finally, the recovery rate of the electronic acid waste liquid is 100%, the conversion rate of sulfur trioxide in the flue gas is 100%, the conversion rate of sulfur dioxide is 99.5%, and when 98% sulfuric acid in the storage battery sulfuric acid absorption tower reaches a certain liquid level, the 98% sulfuric acid is discharged to a metering tank through a pipeline, the flue gas is discharged into a tail gas treatment system, and the tail gas in the tail gas absorption tower is discharged to a de-electric defogging system.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather to cover all modifications and equivalents falling within the spirit and scope of the present invention.
Claims (8)
1. A method for recycling and treating electronic acid waste liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) the co-processing process of the electronic acid waste liquid and the flue gas in the storage battery sulfuric acid production module is as follows:
respectively conveying the pretreated electronic acid waste liquid into a circulating tank I with concentrated sulfuric acid at the bottom of a storage battery sulfuric acid absorption tower and a circulating tank II with dilute sulfuric acid at the bottom of a tail gas absorption tower, pumping acid liquor in the circulating tank I into the storage battery sulfuric acid absorption tower from the top of the storage battery sulfuric acid absorption tower, simultaneously, introducing flue gas containing sulfur trioxide and sulfur dioxide produced by a sulfuric acid device into the storage battery sulfuric acid absorption tower from the outside of the storage battery sulfuric acid absorption tower between a packing layer I and the circulating tank I, enabling the acid liquor to uniformly distribute through an acid distributor in the tower, enabling the acid liquor to reversely contact with the flue gas by virtue of the packing layer I in the tower by virtue of self gravity, and enabling sulfuric acid produced by the reaction of sulfur trioxide and water in the concentrated sulfuric acid to fall back into the circulating tank I;
the concentration of sulfur trioxide and sulfur dioxide in the flue gas is 55%, wherein 55% of the flue gas contains 95% of sulfur trioxide and 5% of sulfur dioxide;
(2) the co-treatment process of the electronic acid waste liquid and the tail gas in the tail gas recovery module is as follows:
and (3) discharging the tail gas containing sulfur dioxide after the reaction in the step from the upper part of the storage battery sulfuric acid absorption tower, introducing the tail gas into the tail gas absorption tower from the circulation tank II through a pipeline, pumping acid liquor in the circulation tank I into the storage battery sulfuric acid absorption tower from the top of the tail gas absorption tower through a centrifugal pump, and returning sulfuric acid generated by the reaction of sulfur dioxide in the tail gas in the filler layer II and hydrogen peroxide in the electronic acid waste liquid to the circulation tank II.
2. The method for recycling and treating electronic acid waste liquid according to claim 1, which is characterized in that: the electronic acid waste liquid is derived from waste liquid after electronic chip etching and cleaning processes using electronic grade sulfuric acid.
3. The method for recycling and treating electronic acid waste liquid according to claim 2, which is characterized in that: the concentration of the acid liquor is reduced and controlled by adding desalted water into the circulating tank II.
4. A method for recycling electronic acid waste liquid according to any one of claims 1 to 3, characterized in that: the method comprises the following steps of:
(1) Transporting the electronic acid waste liquid to a factory through a tank car or a ton barrel, and discharging the electronic acid waste liquid to a waste acid ground tank after the electronic acid waste liquid is checked to be qualified;
starting a submerged centrifugal pump of the waste acid geosyncline, and conveying the electronic acid waste liquid into the waste acid storage tank from the top of the waste acid storage tank through a pipeline, so that the liquid level of the waste acid geosyncline keeps a reasonable index range until the electronic acid waste liquid in the tank wagon or the ton bucket is completely discharged;
(2) Opening an acid discharging valve at the bottom of the waste acid storage tank to enable the electronic acid waste liquid to flow into the waste acid geosyncline, and simultaneously opening a submerged centrifugal pump of the waste acid geosyncline, and keeping the liquid level of the waste acid geosyncline within a reasonable liquid level index range by adjusting the opening of the acid discharging valve and the acid supplying valve at the bottom of the waste acid storage tank.
5. The method for recycling and treating electronic acid waste liquid according to claim 4, wherein the method comprises the following steps: liquid level sensors are arranged in the circulating tank I and the circulating tank II, and the centrifugal pump is controlled by the liquid level sensors to enable the circulating tank I and the circulating tank II to keep certain liquid level.
6. The method for recycling and treating electronic acid waste liquid according to claim 5, wherein the method comprises the following steps: the device also comprises 1 heat exchanger, wherein the acid liquor with the temperature increased after the reaction in the circulating groove I enters the heat exchanger for cooling and is pumped into the storage battery sulfuric acid absorption tower from the top of the storage battery sulfuric acid absorption tower; the desalted water is added into the heat exchanger before being added into the circulating tank II, and then enters the circulating tank II after being heated.
7. An electronic acid waste liquid pretreatment module which is characterized in that: the method is applied to the method for recycling the electronic acid waste liquid according to any one of claims 1 to 6, and comprises at least one of a ceramic membrane filter, an activated carbon treatment unit and an ion exchange resin unit, wherein the electronic acid waste liquid is subjected to pretreatment by the electronic acid waste liquid pretreatment module and then is respectively supplied to the storage battery sulfuric acid production module and the tail gas recycling module.
8. The electronic acid waste liquid pretreatment module according to claim 7, wherein: the ceramic membrane filter is a container with a built-in microporous ceramic membrane, and the filtration grade of the microporous ceramic membrane is 50 nanometers; the active carbon treatment unit is a container with S-level active carbon arranged inside; the ion exchange resin unit is a container with built-in H-type exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111604580.1A CN114426264B (en) | 2021-12-24 | 2021-12-24 | Electronic acid waste liquid pretreatment module and electronic acid waste liquid recovery treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111604580.1A CN114426264B (en) | 2021-12-24 | 2021-12-24 | Electronic acid waste liquid pretreatment module and electronic acid waste liquid recovery treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114426264A CN114426264A (en) | 2022-05-03 |
| CN114426264B true CN114426264B (en) | 2023-07-14 |
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Denomination of invention: A pre-treatment module for electronic acid waste liquid and a method for recovering and treating electronic acid waste liquid Effective date of registration: 20240102 Granted publication date: 20230714 Pledgee: Qilu Bank Co.,Ltd. Tianjin Nankai Branch Pledgor: Tianjin Huanbo New Material Co.,Ltd. Registration number: Y2023980075773 |