CN118084258A - Comprehensive treatment system and method for semiconductor sulfuric acid waste liquid and TMAH waste liquid - Google Patents
Comprehensive treatment system and method for semiconductor sulfuric acid waste liquid and TMAH waste liquid Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 348
- 239000007788 liquid Substances 0.000 title claims abstract description 194
- 239000002699 waste material Substances 0.000 title claims abstract description 170
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 title claims abstract description 142
- 239000004065 semiconductor Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000010306 acid treatment Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims description 127
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 238000003860 storage Methods 0.000 claims description 33
- 238000007872 degassing Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000000108 ultra-filtration Methods 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 239000003814 drug Substances 0.000 claims description 9
- 239000002918 waste heat Substances 0.000 claims description 9
- 239000002912 waste gas Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 238000011403 purification operation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 claims 6
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention relates to the technical field of recycling of waste liquid in the semiconductor industry, in particular to a comprehensive treatment system and method for semiconductor sulfuric acid waste liquid and TMAH waste liquid, comprising the following contents: the device comprises a pretreatment unit, an anaerobic unit, a deep treatment unit, a denitrification unit and a sulfuric acid treatment unit. The pretreatment unit, the anaerobic unit, the advanced treatment unit and the denitrification unit are sequentially connected into a treatment part, the sulfuric acid treatment unit is connected to the treatment part, and the sulfuric acid treatment unit provides regenerated sulfuric acid for the treatment part. The system and the method can fully purify the semiconductor sulfuric acid waste liquid and utilize the generated sulfuric acid; simultaneously, the sulfuric acid waste liquid and the TMAH waste liquid are treated without adding other treatment equipment, so that the equipment cost is greatly reduced; the method does not need to entrust an external factory to process, reduces the transportation cost, and avoids the potential safety hazard and environmental pollution caused by leakage of waste liquid to pollute the environment. Realize the reduction emission and the recycling of the waste liquid in the semiconductor industry.
Description
Technical Field
The disclosure relates to the technical field of recycling of waste liquid in the semiconductor industry, in particular to a comprehensive treatment system and method for semiconductor sulfuric acid waste liquid and TMAH waste liquid.
Background
In recent years, the semiconductor industry, typified by wafer fabrication and package testing, has rapidly progressed. However, one of the raw materials required in the production process by these industries is sulfuric acid. Sulfuric acid (H 2SO4) is added with hydrogen peroxide (H 2O2) to form a strong oxidant, so that organic pollutants in products such as chips, wafers and the like are oxidized and decomposed into CO 2 and H 2 O, and finally so-called sulfuric acid waste liquid is generated. The content of the sulfuric acid (H 2SO4) in the waste liquid is about 60%, the hydrogen peroxide (H 2O2) accounts for about 5%, and the water and impurities are brought in the cleaning process. Therefore, the waste liquid is difficult to reuse in the production process of semiconductors. The discharge amount of the sulfuric acid waste liquid is increased year by year, and the sulfuric acid waste liquid belongs to dangerous waste, and has the characteristics of high acidity, strong corrosiveness, high treatment difficulty, high environmental protection requirement and high treatment cost. The hydrogen peroxide has poor stability in the sulfuric acid environment, and the explosion is easy to be caused by the existence of the hydrogen peroxide, so that the waste sulfuric acid containing the hydrogen peroxide needs to be recycled.
In addition, tetramethylammonium hydroxide (Tetramethylammonium hydroxide, hereinafter abbreviated as TMAH) is also widely used as a photo-developing agent and a wafer developing agent in the production process of semiconductors. It is a kind of organic nitrogen compound with strong alkalinity, corrosiveness and toxicity. TMAH dissociates into TMA + and OH -,OH- in water, which are the main causes of alkalinity and also raise the pH in water. And TMA + is organic nitrogen, and has the characteristics of biotoxicity and poor biodegradability. At present, many production plants directly transport TMAH waste liquid as hazardous waste, but high disposal cost is generated. With the rapid development of industry, the generation amount of TMAH waste liquid is increased year by year, and a plurality of treatment methods are gradually developed. For example: TMAH waste liquid is directly discharged into the organic wastewater treatment unit, but TMAH+ has strong alkalinity, biotoxicity and poor biodegradability, so that the paralysis of the existing organic wastewater treatment unit is often caused. Therefore, no matter from the economical or environmental protection point of view, reasonable waste sulfuric acid and TMAH waste liquid treatment modes are selected, so that the safe and reliable reuse of the waste sulfuric acid is realized, and the further optimization treatment of the TMAH waste liquid is a problem to be solved urgently.
Existing published patent numbers: CN113788563a, name: a treatment device and a treatment process of TMAH-containing developing waste liquid, wherein sulfuric acid solution is adopted to adjust the pH of the waste liquid to be acidic, a potassium persulfate and ferrous sulfate reaction system is adopted to catalyze and oxidize the TMAH-containing developing waste liquid, meanwhile, the COD index content of the waste liquid is degraded, finally, calcium hydroxide and sodium hydroxide are used to adjust the pH of the system to be alkalescent, and three wastes of the system are effectively collected and treated in the whole reaction process, so that the operation environment is safe when the TMAH-containing developing waste liquid is treated. However, TMAH itself dissociates in water into TMA+ and OH-causing an increase in pH. Regardless of the physical and chemical treatment, a large amount of chemical is consumed to adjust the pH to a proper value. And it can not utilize sulfuric acid waste liquid simultaneously, still need add multiple material, need extra processing method, increased processing cost, can not effectively eliminate the danger, can not handle multiple waste liquid simultaneously, can not adapt to more application scenes, can not guarantee that there is the potential safety hazard in the processing procedure outside the commission.
Disclosure of Invention
Therefore, the disclosure provides a comprehensive treatment system and method for semiconductor sulfuric acid waste liquid and TMAH waste liquid to solve the above problems.
According to an aspect of the present disclosure, there is provided an integrated treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid, including: the device comprises a pretreatment unit, an anaerobic unit, a deep treatment unit, a denitrification unit and a sulfuric acid treatment unit;
The pretreatment unit, the anaerobic unit, the advanced treatment unit and the denitrification unit are all sequentially connected into a treatment part through a power pump, and the sulfuric acid treatment unit is connected to the treatment part;
the sulfuric acid treatment unit comprises a first heat exchanger, a first reaction tank, a second heat exchanger and a regenerated sulfuric acid storage tank, wherein the heat exchanger, the first reaction tank, the second heat exchanger and the regenerated sulfuric acid storage tank are sequentially connected;
The pretreatment unit comprises a pre-reaction tank, an air floatation tank and a first middle tank, wherein the pre-reaction tank, the air floatation tank and the first middle tank are sequentially connected;
the anaerobic unit comprises a UASB reaction tank and a precipitation tank, and the UASB reaction tank is connected with the precipitation tank;
The advanced treatment unit comprises a filter, an ultrafiltration structure and a second middle groove, and the filter, the ultrafiltration structure and the middle groove are sequentially connected;
the denitrification unit comprises two sections of degassing membranes which are connected in series;
wherein the sulfuric acid treatment unit supplies regenerated sulfuric acid to the treatment section.
Preferably, the sulfuric acid treatment unit receives sulfuric acid waste liquid, the front end of the sulfuric acid treatment unit is further provided with a power pump, the power pump is arranged at the upstream of the first heat exchanger, the first heat exchanger is connected with the power pump and the first reaction tank, and the first heat exchanger is further connected with a heat source;
the first heat exchanger is connected with the first reaction tank, the first reaction tank is connected with the second reaction tank, and the second reaction tank is connected with the regenerated sulfuric acid storage tank;
The second heater is arranged downstream of the second reaction tank, and the second heat exchanger outputs heat of the second reaction tank;
The first reaction tank and the second reaction tank are also connected with an exhaust gas washing tower, and hydrochloric acid is added into the first reaction tank and the second reaction tank;
And the upstream and downstream of the regenerated sulfuric acid storage tank are respectively provided with a power pump, and the first heat exchanger and the second heat exchanger are plate heat exchangers and/or tubular heat exchangers.
Preferably, hydrochloric acid is added into the first reaction tank and the second reaction tank, the volume concentration of the hydrochloric acid is 0.3% -0.5%, and the reaction time of adding hydrochloric acid into the second reaction tank is longer than that of adding hydrochloric acid into the first reaction tank.
Preferably, the heat source of the first heat exchanger of the sulfuric acid treatment unit adopts waste heat in the second heat exchanger to heat the sulfuric acid waste liquid in the sulfuric acid treatment unit to 35-40 ℃.
Preferably, the pre-reaction tank is connected with the regenerated sulfuric acid storage tank, and PAC medicament, sodium hydroxide and PAM medicament are also added into the pre-reaction tank;
The pre-reaction tank receives the TMAH waste liquid, the TMAH waste liquid adjusts the PH value to 6-8 in the pre-reaction tank, the air floatation tank comprises a filtering structure, the first middle tank is connected with the regenerated sulfuric acid storage tank, sodium hydroxide is further added into the first middle tank, and the PH value of the first middle tank is adjusted to 6.5-7.5.
Preferably, the UASB reaction tank of the anaerobic unit is connected with the regenerated sulfuric acid storage tank and added with sodium hydroxide, the UASB reaction tank is connected with a methane collecting system, and the TOC treatment load of the UASB reaction tank is 1-4 kg/(m 3. D).
Preferably, sodium hydroxide is added to the second intermediate tank of the depth treatment unit and the PH is adjusted to 10-12.
Preferably, the denitrification unit is connected with the regenerated sulfuric acid storage tank, and the denitrification unit is connected with an output structure and/or a biochemical unit;
and two sections of degassing membranes of the denitrification unit are respectively connected with an ammonium sulfate collecting device.
According to an aspect of the present disclosure, there is provided a method for comprehensively treating semiconductor sulfuric acid waste liquid and TMAH waste liquid, for the above-mentioned comprehensive treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid, comprising the following steps:
S110, simultaneously collecting sulfuric acid waste liquid and sending the sulfuric acid waste liquid to a sulfuric acid treatment unit and collecting TMAH waste liquid and sending the TMAH waste liquid to a pretreatment unit, wherein the sulfuric acid waste liquid in the sulfuric acid treatment unit reacts with hydrochloric acid in the first reaction tank and the second reaction tank, the waste gas generated by the first reaction tank and the second reaction tank is collected by a waste gas washing tower, and the regenerated sulfuric acid storage tank is used for collecting regenerated sulfuric acid liquid; the TMAH waste liquid receives the regenerated sulfuric acid liquid in the regenerated sulfuric acid storage tank in the pre-reaction tank, PAC medicament, sodium hydroxide and PAM medicament are added, the PH value of the TMAH waste liquid is regulated to 6-8, the regulated liquid enters the air floatation tank to remove the scum, the liquid after the scum removal enters the first middle tank, and the first middle tank is also added with regenerated sulfuric acid and sodium hydroxide to stabilize the PH value of the liquid at 6.5-7.5;
S120, removing impurities in the waste liquid, collecting the waste liquid in the first middle tank into the anaerobic unit, adding regenerated sulfuric acid and sodium hydroxide into the UASB reaction tank, then sending biogas in the TMAH waste liquid to a biogas collecting system, changing macromolecular organic matters into micromolecular matters, and then sending the waste liquid into the precipitation tank for solid-liquid separation;
S130, performing deep purification operation, wherein the filter filters organic matters and suspended matters in the precipitation tank, filtered liquid enters the ultrafiltration structure, and sodium hydroxide is added into the second intermediate tank to adjust the pH value after the liquid is output from the ultrafiltration structure, so that the pH value is adjusted to 10-12;
S140, performing denitrification operation, wherein the liquid after PH adjustment enters two sections of degassing membranes which are connected in series and are of a degassing unit, generated ammonia gas and regenerated sulfuric acid in the regenerated sulfuric acid storage tank are subjected to mixed reaction, an ammonium sulfate waste liquid is formed and is sent to an ammonium sulfate collecting device, and the liquid is further subjected to ammonia nitrogen removal and then is output to external equipment.
Preferably, in the step S110, the first heat exchanger receives waste heat in the second heat exchanger to promote a reaction in the first reaction tank.
Compared with the prior art, the comprehensive treatment system and method for the semiconductor sulfuric acid waste liquid and the TMAH waste liquid disclosed in the embodiment of the disclosure have the beneficial effects that: the comprehensive treatment system and the comprehensive treatment method for the semiconductor sulfuric acid waste liquid and the TMAH waste liquid can fully purify the semiconductor sulfuric acid waste liquid and utilize the generated sulfuric acid waste liquid; simultaneously, the sulfuric acid waste liquid and the TMAH waste liquid are treated without adding other treatment equipment, so that the equipment cost is greatly reduced; the method does not need to entrust an external factory to process, reduces the processing cost and the transportation cost, and avoids the potential safety hazard of leakage of waste liquid and pollution to the environment. The system realizes the reduction emission and the recycling of the waste liquid in the semiconductor industry, reduces the environmental pollution, and simultaneously realizes the recycling of the waste water, energy conservation and emission reduction.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Other features and aspects of the present disclosure will become apparent from the following detailed description of exemplary embodiments, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the technical aspects of the disclosure.
FIG. 1 shows a schematic diagram of a comprehensive treatment system for semiconductor sulfuric acid waste liquid, TMAH waste liquid according to the present disclosure;
Fig. 2 shows a schematic flow chart of a method for integrated treatment of semiconductor sulfuric acid waste liquid, TMAH waste liquid according to the present disclosure.
Detailed Description
Various exemplary embodiments, features and aspects of the disclosure will be described in detail below with reference to the drawings. In the drawings, like reference numbers indicate identical or functionally similar elements. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The term "and/or" is herein merely an association relationship describing an associated object, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the term "at least one" herein means any one of a plurality or any combination of at least two of a plurality, for example, including at least one of A, B, C, may mean including any one or more elements selected from the group consisting of A, B and C.
Furthermore, numerous specific details are set forth in the following detailed description in order to provide a better understanding of the present disclosure. It will be understood by those skilled in the art that the present disclosure may be practiced without some of these specific details. In some instances, methods, means, elements, and circuits well known to those skilled in the art have not been described in detail in order not to obscure the present disclosure.
It will be appreciated that the above-mentioned method embodiments of the present disclosure may be combined with each other to form a combined embodiment without departing from the principle logic, and are limited to the description of the present disclosure.
In the semiconductor manufacturing process, a large amount of waste water and waste liquid are generated, and the waste water and waste liquid are generated at different stages of the semiconductor processing technology, so that the types of the waste water and the waste liquid are completely different. In the actual treatment process, different treatment systems are often formulated for various different types of waste water and waste liquid, but most of waste water and waste liquid are subjected to basic treatment and then are subjected to outsourcing treatment. The waste water and waste liquid after basic treatment still has a great threat to ecology, so a method capable of simultaneously treating various waste water and waste liquid is needed, potential safety hazards caused in outsourcing treatment are avoided, and the high-cost treatment mode that treatment equipment is required to be respectively arranged for different types of waste water and waste liquid is avoided. For this reason, this embodiment provides a comprehensive treatment system and method for semiconductor sulfuric acid waste liquid and TMAH waste liquid, as shown in fig. 1, in one aspect of this embodiment, a comprehensive treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid is disclosed, including: the device comprises a pretreatment unit, an anaerobic unit, a deep treatment unit, a denitrification unit and a sulfuric acid treatment unit; the pretreatment unit, the anaerobic unit, the advanced treatment unit and the denitrification unit are sequentially connected into a treatment part, and the sulfuric acid treatment unit is connected to the treatment part; the sulfuric acid treatment unit comprises a first heat exchanger, a first reaction tank, a second heat exchanger and a regenerated sulfuric acid storage tank, and the heat exchanger, the first reaction tank, the second heat exchanger and the regenerated sulfuric acid storage tank are sequentially connected through a power pump; the pretreatment unit comprises a pre-reaction tank, an air floatation tank and a first middle tank, and the pre-reaction tank, the air floatation tank and the first middle tank are sequentially connected; the anaerobic unit comprises a UASB reaction tank and a precipitation tank, and the UASB reaction tank is connected with the precipitation tank; the advanced treatment unit comprises a filter, an ultrafiltration structure and a second middle groove, and the filter, the ultrafiltration structure and the middle groove are sequentially connected. The denitrification unit comprises two sections of degassing membranes, and the degassing membranes at the two ends are connected in series; wherein the sulfuric acid treatment unit supplies regenerated sulfuric acid to the treatment section.
In this embodiment, firstly, the sulfuric acid waste liquid and the TMAH waste liquid generated in the semiconductor production process can be collected rapidly at the same time, and the sulfuric acid waste liquid and the TMAH waste liquid can be sent to different units respectively. Specifically, the pretreatment unit receives TMAH waste liquid, the sulfuric acid treatment unit receives sulfuric acid waste liquid, a first heat exchanger and a second heat exchanger arranged in the sulfuric acid treatment unit are matched with each other, the sulfuric acid waste liquid is fully recovered and treated, the second heat exchanger sends the generated waste heat to the first heat exchanger, and other structures are not needed to be additionally arranged for recycling resources. The regenerated sulfuric acid is collected in the sulfuric acid waste liquid treatment unit, and is applied to the subsequent treatment unit. The pretreatment unit, the anaerobic unit, the advanced treatment unit and the denitrification unit are sequentially connected into a treatment part, the sulfuric acid treatment unit is connected into the treatment part, and regenerated sulfuric acid is used as a preparation material for participating in subsequent reactions, so that additional treatment equipment is avoided being added, and the cost is saved. In the pretreatment unit, TMAH waste liquid is collected into a pre-reaction tank, and regenerated sulfuric acid, PAC and PAM medicaments are added into the pre-reaction tank, wherein the TMAH waste liquid is sent into an air floatation tank after full reaction, and the pH value of the TMAH waste liquid is regulated by using the regenerated sulfuric acid before the TMAH waste liquid enters the air floatation tank. The waste residue and the like are further treated in a subsequent treatment unit, wherein the reaction is better carried out by using the regenerated sulfuric acid, and the waste liquid is further treated to achieve the expected treatment effect.
In the embodiment of the disclosure, as shown in fig. 1, in order to better treat the sulfuric acid waste liquid, in this embodiment, a sulfuric acid treatment unit is provided to receive the sulfuric acid waste liquid, and a power pump is further provided at the front end of the sulfuric acid treatment unit, where the power pump is used to provide sufficient power for the flow of the sulfuric acid waste liquid, so as to ensure the smooth operation of the sulfuric acid treatment unit. The power pump is arranged at the upstream of the first heat exchanger, the first heat exchanger is connected with the power pump and the first reaction tank, and the first heat exchanger is also connected with a heat source, wherein the heat source is waste heat emitted by the second heat exchanger. The first heat exchanger is connected with the first reaction tank, the first reaction tank is connected with the second reaction tank, the second reaction tank is connected with the regenerated sulfuric acid storage tank, the heat exchanger utilizes waste heat to promote sulfuric acid waste liquid to react in the first reaction tank and the second reaction tank, the second heater is arranged at the downstream of the second reaction tank, and the second heat exchanger outputs heat of the second reaction tank. The first reaction tank and the second reaction tank are arranged and are also connected with an exhaust gas washing tower, hydrochloric acid is added in the first reaction tank and the second reaction tank, and a power pump is arranged at the upstream and downstream of the regenerated sulfuric acid storage tank to promote the treatment efficiency of sulfuric acid waste liquid in the sulfuric acid treatment unit. Further, the first heat exchanger and the second heat exchanger are also provided as plate heat exchangers, or as tube heat exchangers. The two heat exchangers have small structure, small occupied area, high heat exchange efficiency and little heat loss, and can well promote the purification treatment operation of the sulfuric acid treatment unit.
Further, hydrochloric acid is added into both the first reaction tank and the second reaction tank, and the volume concentration of the hydrochloric acid is specifically set to be 0.3% -0.5%, and the reaction time of adding the hydrochloric acid into the second reaction tank is longer than that of adding the hydrochloric acid into the first reaction tank. The sulfuric acid waste liquid fully reacts, and the heat source of the first heat exchanger of the sulfuric acid treatment part adopts the waste heat in the second heat exchanger to heat the sulfuric acid waste liquid in the sulfuric acid treatment part to 35-40 ℃. Since the reaction of sulfuric acid is exothermic, the temperature of regenerated sulfuric acid increases after the entire reaction process is completed, and thus, the regenerated sulfuric acid enters the second heat exchanger again to lower the temperature thereof. Wherein, the reaction time of the second reaction tank is longer than that of the first reaction tank, so that the increase of chloride ions can be reduced. The first reaction tank and the second reaction tank of the sulfuric acid waste liquid treatment unit are connected to the waste gas washing tower in an exhausting mode, and waste gas generated in the reaction process is removed.
In the treatment portion of the embodiment of the present disclosure, as shown in fig. 1, a pre-reaction tank is connected to a regenerated sulfuric acid storage tank, PAC chemical, sodium hydroxide and PAM chemical are further added in the pre-reaction tank, the pre-reaction tank receives TMAH waste liquid, the TMAH waste liquid adjusts the PH value to 6-8 in the pre-reaction tank, the air flotation tank includes a filtering structure, the first intermediate tank is connected to the regenerated sulfuric acid storage tank and sodium hydroxide is added, and the PH value in the first intermediate tank is 6.5-7.5. The regenerated sulfuric acid and sodium hydroxide are utilized to adjust the PH value of TMAH waste liquid by connecting the regenerated sulfuric acid storage tank, so that the PH value of the waste liquid in the subsequent purification treatment process reaches an optimal value, and the purification efficiency is improved. A UASB reaction tank provided with an anaerobic unit decomposes substances in the liquid, the TOC treatment load of the UASB reaction tank is 1-4 kg/(m 3. D), and biogas generated in the UASB reaction tank is collected and treated. And the pH value of the sodium hydroxide added into the second middle tank of the advanced treatment unit is adjusted to 10-12 so that the purified liquid meets the use requirement. The denitrification unit is connected with the regenerated sulfuric acid storage tank, and the denitrification unit is connected with the output structure or the biochemical unit. Wherein the denitrification membrane is formed by connecting two sections in series, the denitrification rate is more than 97%, and the load of the subsequent biochemical units is greatly reduced. In the actual treatment process, ammonium sulfate is generated in the denitrification unit, and in order to further enhance the treatment effect of the waste liquid, an ammonium sulfate collecting device is arranged to collect the generated ammonium sulfate. And judging whether the liquid needs to be further treated according to the actual demand, so that the problem that the existing waste liquid needs to be collected and then treated outside is unified is effectively avoided.
In another aspect of the disclosure, as shown in fig. 2, there is provided a method for comprehensively treating semiconductor sulfuric acid waste liquid and TMAH waste liquid, which is applied to the above-mentioned comprehensive treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid, comprising the following steps:
S110, simultaneously collecting sulfuric acid waste liquid, sending the sulfuric acid waste liquid to a sulfuric acid treatment unit and collecting TMAH waste liquid, sending the sulfuric acid waste liquid in the sulfuric acid treatment unit to a pretreatment unit, reacting the sulfuric acid waste liquid with hydrochloric acid in a first reaction tank and a second reaction tank, collecting waste gas generated by the first reaction tank and the second reaction tank by a waste gas washing tower, and collecting regenerated sulfuric acid liquid by a regenerated sulfuric acid storage tank; the TMAH waste liquid receives the regenerated sulfuric acid liquid in the regenerated sulfuric acid storage tank in the pre-reaction tank, PAC medicament, sodium hydroxide and PAM medicament are added, the PH value of the TMAH waste liquid is regulated to 6-8, the regulated liquid enters the air floatation tank to remove scum, the liquid after scum removal enters the first middle tank, and the regenerated sulfuric acid and sodium hydroxide are also added in the first middle tank to stabilize the PH value of the liquid at 6.5-7.5;
S120, removing impurities in the waste liquid, collecting the waste liquid in the first middle tank into an anaerobic unit, adding regenerated sulfuric acid and sodium hydroxide into a UASB (upflow anaerobic sludge blanket) reaction tank, sending biogas in TMAH waste liquid into a biogas collecting system, changing macromolecular organic matters into micromolecular matters, and sending the waste liquid into a precipitation tank for solid-liquid separation operation;
S130, performing deep purification operation, wherein the filter filters organic matters and suspended matters in the precipitation tank, the filtered liquid enters an ultrafiltration structure, sodium hydroxide is added into a second intermediate tank for pH value adjustment after the liquid is output from the ultrafiltration structure, and the pH value is adjusted to 10-12;
S140, performing denitrification operation, wherein the liquid after PH adjustment enters two sections of degassing membranes which are connected in series and are of a degassing unit, generated ammonia gas and regenerated sulfuric acid in a regenerated sulfuric acid storage tank are subjected to mixed reaction, an ammonium sulfate waste liquid is formed and is sent to an ammonium sulfate collecting device, and the liquid is further removed of ammonia nitrogen and then is output to external equipment.
Specifically, in step S110, the first heat exchanger receives waste heat in the second heat exchanger, and promotes the reaction in the first reaction tank. In this example, the sulfuric acid waste liquid was recycled, and H 2O2 was removed and then used in the treatment process of TMAH waste liquid. Not only can reduce the cost of waste sulfuric acid, but also can realize the recycling of resources.
The foregoing description of the embodiments of the present disclosure has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvement of the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. A comprehensive treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid is characterized by comprising the following components: the device comprises a pretreatment unit, an anaerobic unit, a deep treatment unit, a denitrification unit and a sulfuric acid treatment unit;
The pretreatment unit, the anaerobic unit, the advanced treatment unit and the denitrification unit are all sequentially connected into a treatment part through a power pump, and the sulfuric acid treatment unit is connected to the treatment part;
the sulfuric acid treatment unit comprises a first heat exchanger, a first reaction tank, a second heat exchanger and a regenerated sulfuric acid storage tank, wherein the heat exchanger, the first reaction tank, the second heat exchanger and the regenerated sulfuric acid storage tank are sequentially connected;
The pretreatment unit comprises a pre-reaction tank, an air floatation tank and a first middle tank, wherein the pre-reaction tank, the air floatation tank and the first middle tank are sequentially connected;
the anaerobic unit comprises a UASB reaction tank and a precipitation tank, and the UASB reaction tank is connected with the precipitation tank;
The advanced treatment unit comprises a filter, an ultrafiltration structure and a second middle groove, and the filter, the ultrafiltration structure and the middle groove are sequentially connected;
the denitrification unit comprises two sections of degassing membranes which are connected in series;
wherein the sulfuric acid treatment unit supplies regenerated sulfuric acid to the treatment section.
2. The comprehensive treatment system for the semiconductor sulfuric acid waste liquid and the TMAH waste liquid according to claim 1, wherein the sulfuric acid treatment unit receives the sulfuric acid waste liquid, a power pump is further arranged at the front end of the sulfuric acid treatment unit, the power pump is arranged at the upstream of the first heat exchanger, the first heat exchanger is connected with the power pump and the first reaction tank, and the first heat exchanger is further connected with a heat source;
the first heat exchanger is connected with the first reaction tank, the first reaction tank is connected with the second reaction tank, and the second reaction tank is connected with the regenerated sulfuric acid storage tank;
The second heater is arranged downstream of the second reaction tank, and the second heat exchanger outputs heat of the second reaction tank;
The first reaction tank and the second reaction tank are also connected with an exhaust gas washing tower, and hydrochloric acid is added into the first reaction tank and the second reaction tank;
And the upstream and downstream of the regenerated sulfuric acid storage tank are respectively provided with a power pump, and the first heat exchanger and the second heat exchanger are plate heat exchangers and/or tubular heat exchangers.
3. The comprehensive treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid according to claim 2, wherein hydrochloric acid is added into the first reaction tank and the second reaction tank, the volume concentration of the hydrochloric acid is 0.3-0.5%, and the reaction time of adding hydrochloric acid into the second reaction tank is longer than that of adding hydrochloric acid into the first reaction tank.
4. The integrated treatment system for semiconductor waste sulfuric acid and TMAH waste liquid according to claim 3, wherein the heat source of the first heat exchanger of the sulfuric acid treatment unit is waste heat of the second heat exchanger, and the waste sulfuric acid in the sulfuric acid treatment unit is heated to 35 ℃ to 40 ℃.
5. The integrated treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid according to claim 4, wherein said pre-reaction tank is connected with said regenerated sulfuric acid storage tank, and PAC agent, sodium hydroxide and PAM agent are added in said pre-reaction tank;
The pre-reaction tank receives the TMAH waste liquid, the TMAH waste liquid adjusts the PH value to 6-8 in the pre-reaction tank, the air floatation tank comprises a filtering structure, the first middle tank is connected with the regenerated sulfuric acid storage tank, sodium hydroxide is further added into the first middle tank, and the PH value of the first middle tank is adjusted to 6.5-7.5.
6. The integrated treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid according to claim 5, wherein said UASB reaction tank of said anaerobic unit is connected with said regenerated sulfuric acid storage tank and added with sodium hydroxide, said UASB reaction tank is connected with a methane collection system, and TOC treatment load of said UASB reaction tank is 1-4 kg/(m 3. D).
7. The integrated treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid according to claim 6, wherein sodium hydroxide is added into said second intermediate tank of said advanced treatment unit and the pH value is adjusted to 10-12.
8. The integrated treatment system for semiconductor sulfuric acid waste liquid and TMAH waste liquid according to claim 7, wherein the denitrification unit is connected with the regenerated sulfuric acid storage tank, the denitrification unit is connected with an output structure, and/or a biochemical unit;
and two sections of degassing membranes of the denitrification unit are respectively connected with an ammonium sulfate collecting device.
9. A method for comprehensively treating semiconductor sulfuric acid waste liquid and TMAH waste liquid, which is used for the comprehensive treatment system of the semiconductor sulfuric acid waste liquid and the TMAH waste liquid, and is characterized by comprising the following steps:
S110, simultaneously collecting sulfuric acid waste liquid and sending the sulfuric acid waste liquid to a sulfuric acid treatment unit and collecting TMAH waste liquid and sending the TMAH waste liquid to a pretreatment unit, wherein the sulfuric acid waste liquid in the sulfuric acid treatment unit reacts with hydrochloric acid in the first reaction tank and the second reaction tank, the waste gas generated by the first reaction tank and the second reaction tank is collected by a waste gas washing tower, and the regenerated sulfuric acid storage tank is used for collecting regenerated sulfuric acid liquid; the TMAH waste liquid receives the regenerated sulfuric acid liquid in the regenerated sulfuric acid storage tank in the pre-reaction tank, PAC medicament, sodium hydroxide and PAM medicament are added, the PH value of the TMAH waste liquid is regulated to 6-8, the regulated liquid enters the air floatation tank to remove the scum, the liquid after the scum removal enters the first middle tank, and the first middle tank is also added with regenerated sulfuric acid and sodium hydroxide to stabilize the PH value of the liquid at 6.5-7.5;
S120, removing impurities in the waste liquid, collecting the waste liquid in the first middle tank into the anaerobic unit, adding regenerated sulfuric acid and sodium hydroxide into the UASB reaction tank, then sending biogas in the TMAH waste liquid to a biogas collecting system, changing macromolecular organic matters into micromolecular matters, and then sending the waste liquid into the precipitation tank for solid-liquid separation;
S130, performing deep purification operation, wherein the filter filters organic matters and suspended matters in the precipitation tank, filtered liquid enters the ultrafiltration structure, and sodium hydroxide is added into the second intermediate tank to adjust the pH value after the liquid is output from the ultrafiltration structure, so that the pH value is adjusted to 10-12;
S140, performing denitrification operation, wherein the liquid after PH adjustment enters two sections of degassing membranes which are connected in series and are of a degassing unit, generated ammonia gas and regenerated sulfuric acid in the regenerated sulfuric acid storage tank are subjected to mixed reaction, an ammonium sulfate waste liquid is formed and is sent to an ammonium sulfate collecting device, and the liquid is further subjected to ammonia nitrogen removal and then is output to external equipment.
10. The method according to claim 7, wherein in step S110, the first heat exchanger receives waste heat from the second heat exchanger and promotes a reaction in the first reaction tank.
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