CN116813018A - Semiconductor industrial production wastewater treatment process - Google Patents
Semiconductor industrial production wastewater treatment process Download PDFInfo
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- CN116813018A CN116813018A CN202311099577.8A CN202311099577A CN116813018A CN 116813018 A CN116813018 A CN 116813018A CN 202311099577 A CN202311099577 A CN 202311099577A CN 116813018 A CN116813018 A CN 116813018A
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000004065 semiconductor Substances 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims abstract description 25
- 238000004065 wastewater treatment Methods 0.000 title abstract description 13
- 238000009776 industrial production Methods 0.000 title abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 61
- 239000010457 zeolite Substances 0.000 claims abstract description 61
- 239000002351 wastewater Substances 0.000 claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000001509 sodium citrate Substances 0.000 claims abstract description 10
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 10
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims description 5
- 239000010842 industrial wastewater Substances 0.000 claims description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims 1
- 239000005052 trichlorosilane Substances 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 abstract description 11
- 239000011737 fluorine Substances 0.000 abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 fluoride ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a wastewater treatment process for semiconductor industrial production, which belongs to the technical field of wastewater treatment and comprises the following steps: firstly, mixing amino-functionalized 4A zeolite with anhydrous methanol under the protection of nitrogen, performing ultrasonic dispersion, adding anhydrous sodium sulfate, heating for reflux, adding salicylaldehyde, and performing reflux reaction to obtain modified 4A zeolite; soaking modified 4A zeolite in calcium chloride solution, taking out and drying; mixing the modified 4A zeolite and the trisodium citrate solution at room temperature, and drying to obtain an adsorption material; secondly, adding liquid alkali into the wastewater to adjust the pH value to 8-9; thirdly, adding an adsorption material into the wastewater with the pH adjusted, standing and settling for 1.5-2h, and then carrying out solid-liquid separation. The invention provides an adsorption material which not only has good adsorption performance, but also can treat the condition of a small amount of heavy metal ions in fluorine-containing wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a wastewater treatment process in semiconductor industrial production.
Background
In the semiconductor manufacturing technology, semiconductor chips having various functions are formed through a series of processes of photolithography, etching, deposition, ion implantation, grinding, cleaning, and the like, and then the semiconductor chips are packaged and electrically tested to form end products. Currently, a large amount of industrial wastewater is generated in the manufacturing process of semiconductor chips.
According to the characteristics of semiconductor sewage treatment enterprises, the semiconductor wastewater is divided into four categories, namely fluorine-containing wastewater, organic wastewater, ammonia-containing wastewater and metal ion wastewater which are generated in the production process. With the rapid development of the semiconductor industry, the related environmental problems are gradually developed, the too high fluoride ions not only affect the health of human bodies, but also affect the growth and development of plants, the fluoride-containing wastewater is generally treated by adopting a chemical sedimentation method, and calcium salt and fluoride ions in water are added to form CaF 2 . But CaF 2 Has certain solubility, is difficult to be lower than the emission standard, and has long time for balancing precipitation reaction, and excessive Ca needs to be added 2+ Increasing the reaction rate, resulting in a larger volume of the reaction tank, resulting in F - Is difficult to fall below the emission standard.
Disclosure of Invention
The invention aims to provide a treatment process of wastewater in semiconductor industry, which is used for coping with the situation of a small amount of heavy metal ions in low-concentration fluorine-containing wastewater and solving the problems that the treatment efficiency of the fluorine-containing wastewater is low and the emission standard is difficult to be lower than.
The aim of the invention can be achieved by the following technical scheme:
a process for treating wastewater in semiconductor industry comprises the following steps:
first, preparing an adsorption material:
mixing amino-functionalized 4A zeolite with anhydrous methanol under the protection of nitrogen, performing ultrasonic dispersion, adding anhydrous sodium sulfate, setting the temperature to 64 ℃, heating, refluxing and stirring for 10min, adding salicylaldehyde, performing reflux reaction for 12h, washing with water, washing with diethyl ether, and drying to obtain modified 4A zeolite;
soaking modified 4A zeolite in calcium chloride solution, taking out and drying; mixing the modified 4A zeolite and the trisodium citrate solution at room temperature, and drying to obtain an adsorption material;
secondly, adding liquid alkali into the wastewater to adjust the pH value to 8-9;
thirdly, adding an adsorption material into the wastewater with the pH adjusted, standing and settling for 1.5-2h, and then carrying out solid-liquid separation.
Further, the amino-functionalized 4A zeolite, anhydrous sodium sulfate and salicylaldehyde were used in the first step in a ratio of 30g:2g:4g.
Further, the mass fraction of the liquid alkali is 10-15%.
Further, the concentration of the calcium chloride solution is 300-400g/L, the mass fraction of the trisodium citrate solution is 0.4%, and the dosage ratio of the modified 4A zeolite to the trisodium citrate solution is 30-32g:5-6mL.
Further, the soaking time of the zeolite in the calcium chloride solution is 40-50h.
Further, the amino-functionalized 4A zeolite is prepared by the steps of:
under the protection of nitrogen, the coupling agent is used for pre-treating the 4A zeolite and branched polyethyleneimine, the coupling agent is added into 50 mass percent methanol aqueous solution, the heating reflux reaction is carried out for 30 to 48 hours, and after the reaction is finished, the amino functional 4A zeolite is obtained through centrifugation, washing and drying.
Further, the coupling agent pre-treated 4A zeolite is prepared by the steps of:
adding trichloro (methyl) silane and 3-chloropropyl trichlorosilane into normal hexane, stirring and mixing to obtain a treatment solution, mixing 4A zeolite and normal hexane, stirring and dispersing, dripping the treatment solution at room temperature under the protection of nitrogen, stirring and reacting for 24 hours, and performing centrifugal separation and drying to obtain the coupling agent pretreated 4A zeolite.
Further, the usage ratio of the trichloro (methyl) silane, the 3-chloropropyl trichlorosilane and the 4A zeolite is 10mmol:1mmol:5g.
The invention has the beneficial effects that:
the invention provides a semiconductor industrial productionIn the wastewater treatment process, most of the fluorine-containing wastewater exists in the form of hydrofluoric acid in the semiconductor industrial wastewater, but also contains a small amount of heavy metal Pb 2+ 、Zn 2+ And the like, in the prior art, the production requirement is generally met by adding calcium chloride and auxiliary additives such as a flocculating agent, and the like, and the adsorption material provided by the invention not only has good adsorption performance, but also can cope with the situation of a small amount of heavy metal ions in low-concentration fluorine-containing wastewater.
The adsorption material in the invention takes zeolite as a carrier, carries out multiple modification on the surface of the zeolite, improves the adsorption capacity of the zeolite, and meets the requirements of different types of wastewater treatment. The zeolite after treatment can adsorb more calcium ions in the calcium chloride solution, and because the main Si, al and O framework structures in the crystal structure of the zeolite and metal cations outside the framework structures form catalytic active centers together with replaceable cations, the replaceable cations are in a highly dispersed state, the calcium ions can be slowly released within a certain time after being adsorbed, a certain concentration can be maintained, and a stable and continuous adsorption process can be formed.
In the process of treating zeolite, the amino-functionalized 4A zeolite with branched polyethylenimine as grafting monomer reacts with salicylaldehyde to form hyperbranched macromolecular bridged salicylaldehyde structure, which can chelate metal ions, and finally is separated by standing and sedimentation.
The adsorption material used in the wastewater treatment process in the semiconductor industry has the advantages of simple use method, convenient industrial production and high treatment efficiency of fluorine-containing wastewater.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a graph showing comparison of the adsorption amount of calcium ions measured by the adsorption material prepared by the invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
This example provides an amino-functionalized 4A zeolite prepared by the steps of:
adding 20mmol of trichloro (methyl) silane and 2mmol of 3-chloropropyl trichlorosilane into 30mL of normal hexane, stirring and mixing to obtain a treatment liquid, mixing 10g of 4A zeolite and 120mL of normal hexane, stirring and dispersing, dropwise adding the treatment liquid under the conditions of room temperature (25-30 ℃) and nitrogen protection, stirring and reacting for 24 hours, and centrifugally separating and drying to obtain the coupling agent pretreated 4A zeolite.
Under the protection of nitrogen, 10g of coupling agent is used for preprocessing 4A zeolite and 2g of branched polyethylenimine (average Mw 25,00), and the mixture is added into 100mL of 50% methanol water solution with mass fraction, heated and refluxed for 48h, and after the reaction is finished, the amino functionalized 4A zeolite is obtained through centrifugation, washing and drying.
Example 2
The embodiment provides a wastewater treatment process in semiconductor industrial production, which comprises the following steps:
first, preparing an adsorption material:
under the protection of nitrogen, mixing 30g of amino-functionalized 4A zeolite prepared according to the method disclosed in the example 1 with 500mL of anhydrous methanol, performing ultrasonic dispersion for 10min, adding 2g of anhydrous sodium sulfate, setting the temperature to 64 ℃, heating, refluxing and stirring for 10min, adding 4g of salicylaldehyde, performing reflux reaction for 12h, washing with water, washing with diethyl ether, and drying to obtain modified 4A zeolite;
soaking 30g of modified 4A zeolite in 300g/L calcium chloride solution for 40h, taking out and drying; mixing 30g of modified 4A zeolite and 5mL of 0.4% trisodium citrate solution at room temperature (25-30 ℃), and drying to obtain an adsorption material;
second, adjusting pH: adding 10% liquid caustic soda by mass percent into the wastewater to adjust the pH value to 8;
thirdly, adding an adsorbing material (10 g of the adsorbing material is added to each liter of wastewater) into the wastewater with the pH adjusted, wherein the wastewater is low-concentration fluorine-containing wastewater treated conventionally, standing and settling for 1.5h, and then carrying out solid-liquid separation.
The test results are shown in table 1 below:
TABLE 1
Example 3
The embodiment provides a wastewater treatment process in semiconductor industrial production, which comprises the following steps:
first, preparing an adsorption material:
under the protection of nitrogen, mixing 30g of amino-functionalized 4A zeolite prepared according to the method disclosed in the example 1 with 500mL of anhydrous methanol, performing ultrasonic dispersion for 10min, adding 2g of anhydrous sodium sulfate, setting the temperature to 64 ℃, heating, refluxing and stirring for 10min, adding 4g of salicylaldehyde, performing reflux reaction for 12h, washing with water, washing with diethyl ether, and drying to obtain modified 4A zeolite;
soaking 30g of modified 4A zeolite in a calcium chloride solution with the concentration of 350g/L for 45h, taking out and drying; 31g of modified 4A zeolite and 6mL of 0.4% trisodium citrate solution are mixed at room temperature (25-30 ℃) and dried to obtain an adsorption material;
second, adjusting pH: adding liquid caustic soda with the mass fraction of 15% into the wastewater to adjust the pH value to 9;
thirdly, adding an adsorbing material (10 g of the adsorbing material is added to each liter of wastewater) into the wastewater with the pH adjusted, wherein the wastewater is low-concentration fluorine-containing wastewater treated conventionally, standing and settling for 2 hours, and then carrying out solid-liquid separation.
The test results are shown in table 2 below:
TABLE 2
Example 4
The embodiment provides a wastewater treatment process in semiconductor industrial production, which comprises the following steps:
first, preparing an adsorption material:
under the protection of nitrogen, mixing 30g of amino-functionalized 4A zeolite prepared according to the method disclosed in the example 1 with 500mL of anhydrous methanol, performing ultrasonic dispersion for 10min, adding 2g of anhydrous sodium sulfate, setting the temperature to 64 ℃, heating, refluxing and stirring for 10min, adding 4g of salicylaldehyde, performing reflux reaction for 12h, washing with water, washing with diethyl ether, and drying to obtain modified 4A zeolite;
soaking 30g of modified 4A zeolite in 400g/L calcium chloride solution for 50h, taking out and drying; mixing 32g of modified 4A zeolite and 6mL of 0.4% trisodium citrate solution at room temperature (25-30 ℃), and drying to obtain an adsorption material;
second, adjusting pH: adding liquid caustic soda with the mass fraction of 15% into the wastewater to adjust the pH value to 9;
thirdly, adding an adsorbing material (10 g of the adsorbing material is added to each liter of wastewater) into the wastewater with the pH adjusted, wherein the wastewater is low-concentration fluorine-containing wastewater treated conventionally, standing and settling for 2 hours, and then carrying out solid-liquid separation.
The test results are shown in table 3 below:
TABLE 3 Table 3
The test results of examples 2-4 show that the adsorption material used in the wastewater treatment process of the semiconductor industry has large adsorption capacity and can adsorb a certain amount of metal ions to meet the production requirement.
Comparative example 1
In this comparative example, the modified 4A zeolite was changed to zeolite as in example 2, and the original raw materials and the production process were the same as in example 2.
The test results are shown in table 4 below:
TABLE 4 Table 4
Compared with the adsorption material prepared in the example of the invention, the adsorption capacity of the untreated 4A zeolite in comparative example 1 is limited, the effect of adsorbing calcium ions is slightly poorer, the effect of releasing calcium ions is poorer, and the effect of treating wastewater is also relatively poorer.
Calcium ion adsorption performance test:
the adsorption materials of example 2 and comparative example 1 were tested for the amount of calcium ion adsorption Q (mg/g) in calcium chloride solutions of different concentrations C (150-400 g/L), the mass of the adsorption material in a single adsorption experiment was 20g, example 2 was designated as group A, comparative example 1 was designated as group B, the adsorption time was 40h, and the recorded test results were shown in FIG. 1. As can be seen from the analysis of the recorded results of examples 2-4 and comparative example 1, the adsorption capacity of the treated modified 4A zeolite increases, and a higher adsorption level can be achieved in the treatment of fluorine-containing wastewater, and the branched structure in the modified 4A zeolite structure has a specific structure to F - The adsorption of the catalyst has positive promotion effect, and the amino-functionalized 4A zeolite with branched polyethyleneimine as a grafting monomer reacts with salicylaldehyde to form a hyperbranched macromolecular bridged salicylaldehyde structure, so that metal ions can be chelated, and finally, the metal ions can be subjected to standing sedimentation and separation, so that the treatment requirement of metal wastewater can be met.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The process for treating the wastewater in the semiconductor industry is characterized by comprising the following steps of:
first, preparing an adsorption material:
under the protection of nitrogen, mixing amino-functionalized 4A zeolite with anhydrous methanol, performing ultrasonic dispersion, adding anhydrous sodium sulfate, heating, refluxing and stirring, adding salicylaldehyde, performing reflux reaction for 12 hours, washing with water and diethyl ether after the reaction is finished, and drying to obtain modified 4A zeolite;
soaking modified 4A zeolite in calcium chloride solution, taking out and drying; mixing the modified 4A zeolite and the trisodium citrate solution at room temperature, and drying to obtain an adsorption material;
secondly, adding liquid alkali into the wastewater to adjust the pH value to 8-9;
thirdly, adding an adsorption material into the wastewater with the pH adjusted, standing and settling for 1.5-2h, and then carrying out solid-liquid separation.
2. The process for treating industrial wastewater of semiconductors according to claim 1, wherein the dosage ratio of the amino-functionalized 4A zeolite, anhydrous sodium sulfate and salicylaldehyde in the first step is 30g:2g:4g.
3. The process for treating wastewater from semiconductor industry according to claim 1, wherein the mass fraction of the liquid alkali is 10-15%.
4. The process for treating the wastewater in the semiconductor industry according to claim 1, wherein the concentration of the calcium chloride solution is 300-400g/L, the mass fraction of the trisodium citrate solution is 0.4%, and the dosage ratio of the modified 4A zeolite to the trisodium citrate solution is 30-32g:5-6mL.
5. The process for treating wastewater from semiconductor industry as claimed in claim 1, wherein the soaking time of the modified 4A zeolite in the calcium chloride solution is 40-50 hours.
6. The process for treating wastewater from semiconductor industry according to claim 1, wherein the amino-functionalized 4A zeolite is prepared by:
under the protection of nitrogen, the coupling agent is used for pre-treating the 4A zeolite and branched polyethyleneimine, the coupling agent is added into 50 mass percent methanol aqueous solution, the heating reflux reaction is carried out for 30 to 48 hours, and after the reaction is finished, the amino functional 4A zeolite is obtained through centrifugation, washing and drying.
7. The process for treating wastewater from semiconductor industry according to claim 6, wherein the coupling agent pretreatment of the 4A zeolite is prepared by:
adding trichloro (methyl) silane and 3-chloropropyl trichlorosilane into normal hexane, stirring and mixing to obtain a treatment solution, mixing 4A zeolite and normal hexane, stirring and dispersing, dripping the treatment solution at room temperature under the protection of nitrogen, stirring and reacting for 24 hours, and performing centrifugal separation and drying to obtain the coupling agent pretreated 4A zeolite.
8. The process for treating industrial wastewater of semiconductors according to claim 7, wherein the usage ratio of the trichlorosilane, the 3-chloropropyl trichlorosilane and the 4A zeolite is 10mmol:1mmol:5g.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360844A (en) * | 1970-08-28 | 1974-07-24 | Nippon Soda Co | Process for adsorbing free chlorine heavy metals and compounds of heavy metals |
| CN111170530A (en) * | 2018-11-13 | 2020-05-19 | 上海朗蔚环保科技有限公司 | Electroplating wastewater treatment system |
| CN111514867A (en) * | 2020-06-03 | 2020-08-11 | 李娟� | Polyethyleneimine grafted nano Fe3O4-graphene adsorption material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360844A (en) * | 1970-08-28 | 1974-07-24 | Nippon Soda Co | Process for adsorbing free chlorine heavy metals and compounds of heavy metals |
| CN111170530A (en) * | 2018-11-13 | 2020-05-19 | 上海朗蔚环保科技有限公司 | Electroplating wastewater treatment system |
| CN111514867A (en) * | 2020-06-03 | 2020-08-11 | 李娟� | Polyethyleneimine grafted nano Fe3O4-graphene adsorption material and preparation method thereof |
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