CN117682732B - Zero-emission treatment method for aluminum processing wastewater - Google Patents
Zero-emission treatment method for aluminum processing wastewater Download PDFInfo
- Publication number
- CN117682732B CN117682732B CN202410155085.4A CN202410155085A CN117682732B CN 117682732 B CN117682732 B CN 117682732B CN 202410155085 A CN202410155085 A CN 202410155085A CN 117682732 B CN117682732 B CN 117682732B
- Authority
- CN
- China
- Prior art keywords
- processing wastewater
- aluminum processing
- bentonite
- treatment
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 144
- 238000012545 processing Methods 0.000 title claims abstract description 143
- 239000002351 wastewater Substances 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 78
- 229910000281 calcium bentonite Inorganic materials 0.000 claims abstract description 60
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical class O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- -1 fluoride ions Chemical class 0.000 claims abstract description 40
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001669 calcium Chemical class 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 24
- 229920005610 lignin Polymers 0.000 claims abstract description 23
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000467 phytic acid Substances 0.000 claims abstract description 22
- 229940068041 phytic acid Drugs 0.000 claims abstract description 22
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 19
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 17
- 229910000280 sodium bentonite Inorganic materials 0.000 claims abstract description 17
- 229940080314 sodium bentonite Drugs 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 238000003825 pressing Methods 0.000 claims description 21
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 11
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a treatment method for zero emission of aluminum processing wastewater, which relates to the field of wastewater treatment and comprises the following steps: adding modified calcium bentonite into the aluminum processing wastewater for preliminary adsorption treatment, then adding a reducing agent for reduction treatment, then adding an alkaline agent, and then uniformly stirring until the pH value is 6.5-7.2 to obtain alkali-neutralized aluminum processing wastewater; adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization for deep adsorption treatment to obtain aluminum processing wastewater after deep adsorption; adding a decoloring agent into the deeply adsorbed aluminum processing wastewater to perform decoloring treatment to obtain treated water; the preparation raw materials of the modified calcium bentonite comprise 1, 6-hexamethylenediamine, calcium bentonite and lignin; the preparation raw materials of the modified sodium bentonite comprise p-phenylenediamine, sodium bentonite and phytic acid. The heavy chromate ions and fluoride ions in the treated water obtained by the treatment method provided by the invention are reduced to zero, so that zero emission of aluminum processing wastewater is realized.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a zero-emission treatment method for aluminum processing wastewater.
Background
The aluminum profile processing process needs to be subjected to surface treatment, a large amount of water is needed in the surface treatment process, an aluminum profile spraying factory is a large household of water all the time, and the zero-emission technology is to fully utilize limited water resources, reduce industrial water pressure, reduce sewage discharge and improve water quality, so that ecological harmony development is realized. The existing aluminum profile processing plants have high contents of dichromate ions and fluoride ions in the wastewater discharged, so that huge environmental risks are brought. In order to reduce environmental risks and save water resources, a zero-emission treatment method for aluminum processing wastewater is urgently needed.
In summary, through mass search by the applicant, the field at least has high contents of dichromate ions and fluoride ions in the wastewater discharged from the aluminum profile processing factory, so that the environment is polluted and water is wasted, and therefore, development or improvement of a zero-discharge treatment method for the aluminum processing wastewater is needed.
Disclosure of Invention
Based on the method, in order to solve the problem that the waste water from the aluminum profile processing factory is polluted by water due to high contents of dichromate ions and fluoride ions, the invention provides a zero-emission treatment method for aluminum processing waste water, which comprises the following specific technical scheme:
A treatment method for zero emission of aluminum processing wastewater comprises the following steps:
adding modified calcium bentonite into the aluminum processing wastewater to perform preliminary adsorption treatment to obtain the primarily adsorbed aluminum processing wastewater;
Adding a reducing agent into the aluminum processing wastewater after preliminary adsorption for reduction treatment to obtain reduced aluminum processing wastewater;
Adding an alkaline agent into the reduced aluminum processing wastewater, and uniformly stirring until the pH value is 6.5-7.2 to obtain alkali-neutralized aluminum processing wastewater;
Adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization for deep adsorption treatment to obtain aluminum processing wastewater after deep adsorption;
adding a decoloring agent into the deeply adsorbed aluminum processing wastewater to perform decoloring treatment to obtain treated water;
the preparation raw materials of the modified calcium bentonite comprise 1, 6-hexamethylenediamine, calcium bentonite and lignin;
the preparation raw materials of the modified sodium bentonite comprise p-phenylenediamine, sodium bentonite and phytic acid.
Further, the alkaline agent includes at least one of potassium hydroxide, sodium hydroxide, calcium oxide, and calcium hydroxide.
Further, the preliminary adsorption treatment includes the steps of:
Adding modified calcium bentonite into the aluminum processing wastewater, uniformly stirring at the speed of 800-900 r/min, continuously stirring at the speed of 500-600 r/min for 8-12 h, adding a sedimentation tank to sediment for 15-18 h, and then performing filter pressing by using a filter press, wherein clear liquid is the primarily adsorbed aluminum processing wastewater.
Further, the reduction treatment includes the steps of:
And adding thioacetamide into the primarily adsorbed aluminum processing wastewater, stirring at the speed of 700-800 r/min for 5-7 h, then introducing nitrogen for 10-20 min, adding calcium sulfide, and continuously stirring at the speed of 700-800 r/min for 3-8 h to obtain the reduced aluminum processing wastewater.
Further, the deep adsorption process includes the steps of:
adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization, heating to 40-45 ℃, stirring for 3-7 h at 1000-1100 r/min, cooling to room temperature, continuously stirring for 5-7 h at 1000-1100 r/min, and then performing filter pressing by using a filter press, wherein clear liquid is the aluminum processing wastewater after deep absorption.
Further, the decoloring treatment includes the steps of:
Adding a decolorizing agent into the deeply adsorbed aluminum processing wastewater, stirring for 5-7 hours at the speed of 700-800 r/min, then reducing to the speed of 300-400 r/min, stirring for 3-4 hours, and then performing filter pressing by using a filter press, wherein clear liquid is the treated water.
Further, the preparation method of the modified calcium bentonite comprises the following steps:
adding calcium bentonite into water, carrying out ultrasonic treatment for 30-40 min at a frequency of 70-90 kHz, adding 1, 6-hexamethylenediamine and lignin, uniformly stirring at a speed of 850-950 r/min, heating to 120-130 ℃ for hydrothermal reaction for 6-8 h, heating to 600-700 ℃ in nitrogen atmosphere, calcining for 6-8 h, and cooling in nitrogen atmosphere to obtain the modified calcium bentonite;
the mass ratio of the 1, 6-hexamethylenediamine, the calcium bentonite and the lignin is 1-3: 12-15: 3-7.
Further, the preparation method of the modified sodium bentonite comprises the following steps:
adding sodium bentonite into ethanol, carrying out ultrasonic treatment at a frequency of 70-90 kHz for 20-30 min, adding p-phenylenediamine and phytic acid, uniformly stirring at a speed of 900-1000 r/min, heating to 100-110 ℃ for hydrothermal reaction for 2-3 h, and then drying at a temperature of 60-80 ℃ in a nitrogen atmosphere to obtain the modified sodium bentonite;
the mass ratio of the p-phenylenediamine to the sodium bentonite to the phytic acid is 1-3: 10-15: 5-10.
Further, the decoloring agent is at least one of polyaluminum chloride and polyferric chloride.
Further, the mass of the modified calcium bentonite is 1-3% based on the total mass of the aluminum processing wastewater;
the mass of the reducing agent is 0.3-0.7% based on the total mass of the primarily adsorbed aluminum processing wastewater;
The total mass of the aluminum processing wastewater after alkali neutralization is calculated as a percentage, and the mass of the modified sodium bentonite is 0.2-0.4%;
and the total mass of the deeply adsorbed aluminum processing wastewater is 1.2-1.8% of the mass of the decoloring agent.
The dichromate ions and the fluoride ions in the treated water obtained by the treatment method are reduced to zero, so that zero emission of aluminum processing wastewater is realized; specifically, the aluminum processing wastewater is subjected to preliminary adsorption through modified calcium bentonite, so that high-concentration dichromate ions and fluoride ions are removed, the subsequent reduction treatment and alkali neutralization are favorable for further removing the dichromate ions and the fluoride ions, the further advanced adsorption treatment is performed by modified sodium bentonite, low-concentration dichromate ions and fluoride ions can be removed, and the further decolorization treatment is performed to obtain treated water without the dichromate ions and the fluoride ions, so that zero emission of the aluminum processing wastewater is realized; more specifically, the 1, 6-hexamethylenediamine and lignin modified calcium bentonite have larger adsorption space size, so that the adsorption quantity is obviously increased; the p-phenylenediamine and the phytic acid modified sodium bentonite have smaller adsorption space size, and can more effectively capture low-concentration dichromate ions and fluoride ions, so that zero emission of aluminum processing wastewater is finally realized.
Detailed Description
The present invention will be described in further detail with reference to the following examples thereof in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention relates to a treatment method for zero emission of aluminum processing wastewater, which comprises the following steps:
adding modified calcium bentonite into the aluminum processing wastewater to perform preliminary adsorption treatment to obtain the primarily adsorbed aluminum processing wastewater;
Adding a reducing agent into the aluminum processing wastewater after preliminary adsorption for reduction treatment to obtain reduced aluminum processing wastewater;
Adding an alkaline agent into the reduced aluminum processing wastewater, and uniformly stirring until the pH value is 6.5-7.2 to obtain alkali-neutralized aluminum processing wastewater;
Adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization for deep adsorption treatment to obtain aluminum processing wastewater after deep adsorption;
adding a decoloring agent into the deeply adsorbed aluminum processing wastewater to perform decoloring treatment to obtain treated water;
the preparation raw materials of the modified calcium bentonite comprise 1, 6-hexamethylenediamine, calcium bentonite and lignin;
the preparation raw materials of the modified sodium bentonite comprise p-phenylenediamine, sodium bentonite and phytic acid.
In one embodiment, the alkaline agent comprises at least one of potassium hydroxide, sodium hydroxide, calcium oxide, and calcium hydroxide.
In one embodiment, the preliminary adsorption treatment comprises the steps of:
Adding modified calcium bentonite into the aluminum processing wastewater, uniformly stirring at the speed of 800-900 r/min, continuously stirring at the speed of 500-600 r/min for 8-12 h, adding a sedimentation tank to sediment for 15-18 h, and then performing filter pressing by using a filter press, wherein clear liquid is the primarily adsorbed aluminum processing wastewater.
In one embodiment, the reduction process includes the steps of:
And adding thioacetamide into the primarily adsorbed aluminum processing wastewater, stirring at the speed of 700-800 r/min for 5-7 h, then introducing nitrogen for 10-20 min, adding calcium sulfide, and continuously stirring at the speed of 700-800 r/min for 3-8 h to obtain the reduced aluminum processing wastewater.
In one embodiment, the deep adsorption process comprises the steps of:
adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization, heating to 40-45 ℃, stirring for 3-7 h at 1000-1100 r/min, cooling to room temperature, continuously stirring for 5-7 h at 1000-1100 r/min, and then performing filter pressing by using a filter press, wherein clear liquid is the aluminum processing wastewater after deep absorption.
In one embodiment, the decolorizing process includes the steps of:
Adding a decolorizing agent into the deeply adsorbed aluminum processing wastewater, stirring for 5-7 hours at the speed of 700-800 r/min, then reducing to the speed of 300-400 r/min, stirring for 3-4 hours, and then performing filter pressing by using a filter press, wherein clear liquid is the treated water.
In one embodiment, the preparation method of the modified calcium bentonite comprises the following steps:
adding calcium bentonite into water, carrying out ultrasonic treatment for 30-40 min at a frequency of 70-90 kHz, adding 1, 6-hexamethylenediamine and lignin, uniformly stirring at a speed of 850-950 r/min, heating to 120-130 ℃ for hydrothermal reaction for 6-8 h, heating to 600-700 ℃ in nitrogen atmosphere, calcining for 6-8 h, and cooling in nitrogen atmosphere to obtain the modified calcium bentonite;
the mass ratio of the 1, 6-hexamethylenediamine, the calcium bentonite and the lignin is 1-3: 12-15: 3-7.
In one embodiment, the preparation method of the modified sodium bentonite comprises the following steps:
adding sodium bentonite into ethanol, carrying out ultrasonic treatment at a frequency of 70-90 kHz for 20-30 min, adding p-phenylenediamine and phytic acid, uniformly stirring at a speed of 900-1000 r/min, heating to 100-110 ℃ for hydrothermal reaction for 2-3 h, and then drying at a temperature of 60-80 ℃ in a nitrogen atmosphere to obtain the modified sodium bentonite;
the mass ratio of the p-phenylenediamine to the sodium bentonite to the phytic acid is 1-3: 10-15: 5-10.
In one embodiment, the decolorizing agent is at least one of polyaluminum chloride and polyferric chloride.
In one embodiment, the mass of the modified calcium bentonite is 1-3% based on the total mass of the aluminum processing wastewater as a percentage;
the mass of the reducing agent is 0.3-0.7% based on the total mass of the primarily adsorbed aluminum processing wastewater;
The total mass of the aluminum processing wastewater after alkali neutralization is calculated as a percentage, and the mass of the modified sodium bentonite is 0.2-0.4%;
and the total mass of the deeply adsorbed aluminum processing wastewater is 1.2-1.8% of the mass of the decoloring agent.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
Adding calcium bentonite into water, carrying out ultrasonic treatment at a frequency of 80kHz for 35min, adding 1, 6-hexamethylenediamine and lignin, uniformly stirring at a speed of 900r/min, heating to 125 ℃ for hydrothermal reaction for 7h, heating to 650 ℃ under nitrogen atmosphere for calcination for 7h, and cooling under nitrogen atmosphere to obtain modified calcium bentonite, wherein the mass ratio of 1, 6-hexamethylenediamine to calcium bentonite to lignin is 2:13:5, a step of;
adding sodium bentonite into ethanol, carrying out ultrasonic treatment at 80kHz for 25min, adding p-phenylenediamine and phytic acid, uniformly stirring at 950r/min, heating to 105 ℃ for hydrothermal reaction for 2.5h, and drying at 70 ℃ under nitrogen atmosphere to obtain modified sodium bentonite, wherein the mass ratio of p-phenylenediamine to sodium bentonite to phytic acid is 2:12:7, preparing a base material;
Adding modified calcium bentonite into aluminum processing wastewater, uniformly stirring at a speed of 850r/min, continuously stirring at a speed of 550r/min for 10 hours, adding into a sedimentation tank for sedimentation for 17 hours, and then performing filter pressing by using a filter press to obtain clear liquid which is the aluminum processing wastewater after preliminary absorption; adding thioacetamide into the aluminum processing wastewater after primary adsorption, stirring for 6 hours at the speed of 750r/min, then introducing nitrogen for 15min, then adding calcium sulfide, and continuously stirring for 5 hours at the speed of 750r/min to obtain reduced aluminum processing wastewater; adding sodium hydroxide into the aluminum processing wastewater after reduction, and then uniformly stirring until the pH value is 6.8 to obtain aluminum processing wastewater after alkali neutralization; adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization, heating to 43 ℃, stirring for 5 hours at 1050r/min, cooling to room temperature, continuously stirring for 6 hours at 1050r/min, and then performing filter pressing by using a filter press, wherein clear liquid is the aluminum processing wastewater after deep absorption; adding polyaluminium chloride and polyferric chloride into the deeply adsorbed aluminum processing wastewater, stirring for 6 hours at the speed of 750r/min, then reducing to the speed of 350r/min, stirring for 3.5 hours, and then performing filter pressing by using a filter press to obtain clear liquid as processed water, wherein the mass of the modified calcium bentonite is 2% based on the total mass of the aluminum processing wastewater; the total mass of the aluminum processing wastewater after preliminary adsorption is calculated as percentage, the mass of thioacetamide is 0.3 percent, and the mass of calcium sulfide is 0.2 percent; the mass of the modified sodium bentonite is 0.3 percent based on the percentage by weight of the total mass of the aluminum processing wastewater after alkali neutralization; the total mass of the deeply adsorbed aluminum processing wastewater is 0.8 percent, and the mass of the polyaluminum chloride is 0.7 percent.
Comparative example 1:
Adding calcium bentonite into water, carrying out ultrasonic treatment at a frequency of 80kHz for 35min, adding 1, 6-hexamethylenediamine and lignin, uniformly stirring at a speed of 900r/min, heating to 125 ℃ for hydrothermal reaction for 7h, heating to 650 ℃ under nitrogen atmosphere for calcination for 7h, and cooling under nitrogen atmosphere to obtain modified calcium bentonite, wherein the mass ratio of 1, 6-hexamethylenediamine to calcium bentonite to lignin is 2:13:5, a step of;
Adding sodium bentonite into ethanol, carrying out ultrasonic treatment at the frequency of 80kHz for 25min, then adding p-phenylenediamine, uniformly stirring at the speed of 950r/min, then heating to 105 ℃ for hydrothermal reaction for 2.5h, and then drying at the temperature of 70 ℃ under the atmosphere of nitrogen to obtain modified sodium bentonite, wherein the mass ratio of the p-phenylenediamine to the sodium bentonite is 2:12;
Adding modified calcium bentonite into aluminum processing wastewater, uniformly stirring at a speed of 850r/min, continuously stirring at a speed of 550r/min for 10 hours, adding into a sedimentation tank for sedimentation for 17 hours, and then performing filter pressing by using a filter press to obtain clear liquid which is the aluminum processing wastewater after preliminary absorption; adding thioacetamide into the aluminum processing wastewater after primary adsorption, stirring for 6 hours at the speed of 750r/min, then introducing nitrogen for 15min, then adding calcium sulfide, and continuously stirring for 5 hours at the speed of 750r/min to obtain reduced aluminum processing wastewater; adding sodium hydroxide into the aluminum processing wastewater after reduction, and then uniformly stirring until the pH value is 6.8 to obtain aluminum processing wastewater after alkali neutralization; adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization, heating to 43 ℃, stirring for 5 hours at 1050r/min, cooling to room temperature, continuously stirring for 6 hours at 1050r/min, and then performing filter pressing by using a filter press, wherein clear liquid is the aluminum processing wastewater after deep absorption; adding polyaluminium chloride and polyferric chloride into the deeply adsorbed aluminum processing wastewater, stirring for 6 hours at the speed of 750r/min, then reducing to the speed of 350r/min, stirring for 3.5 hours, and then performing filter pressing by using a filter press to obtain clear liquid as processed water, wherein the mass of the modified calcium bentonite is 2% based on the total mass of the aluminum processing wastewater; the total mass of the aluminum processing wastewater after preliminary adsorption is calculated as percentage, the mass of thioacetamide is 0.3 percent, and the mass of calcium sulfide is 0.2 percent; the mass of the modified sodium bentonite is 0.3 percent based on the percentage by weight of the total mass of the aluminum processing wastewater after alkali neutralization; the total mass of the deeply adsorbed aluminum processing wastewater is 0.8 percent, and the mass of the polyaluminum chloride is 0.7 percent.
Comparative example 2:
Adding calcium bentonite into water, carrying out ultrasonic treatment at a frequency of 80kHz for 35min, adding 1, 6-hexamethylenediamine and lignin, uniformly stirring at a speed of 900r/min, heating to 125 ℃ for hydrothermal reaction for 7h, heating to 650 ℃ under nitrogen atmosphere for calcination for 7h, and cooling under nitrogen atmosphere to obtain modified calcium bentonite, wherein the mass ratio of 1, 6-hexamethylenediamine to calcium bentonite to lignin is 2:13:5, a step of;
Adding sodium bentonite into ethanol, carrying out ultrasonic treatment at 80kHz frequency for 25min, adding phytic acid, stirring uniformly at 950r/min, heating to 105 ℃ for hydrothermal reaction for 2.5h, and drying at 70 ℃ under nitrogen atmosphere to obtain modified sodium bentonite, wherein the mass ratio of the sodium bentonite to the phytic acid is 12:7, preparing a base material;
Adding modified calcium bentonite into aluminum processing wastewater, uniformly stirring at a speed of 850r/min, continuously stirring at a speed of 550r/min for 10 hours, adding into a sedimentation tank for sedimentation for 17 hours, and then performing filter pressing by using a filter press to obtain clear liquid which is the aluminum processing wastewater after preliminary absorption; adding thioacetamide into the aluminum processing wastewater after primary adsorption, stirring for 6 hours at the speed of 750r/min, then introducing nitrogen for 15min, then adding calcium sulfide, and continuously stirring for 5 hours at the speed of 750r/min to obtain reduced aluminum processing wastewater; adding sodium hydroxide into the aluminum processing wastewater after reduction, and then uniformly stirring until the pH value is 6.8 to obtain aluminum processing wastewater after alkali neutralization; adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization, heating to 43 ℃, stirring for 5 hours at 1050r/min, cooling to room temperature, continuously stirring for 6 hours at 1050r/min, and then performing filter pressing by using a filter press, wherein clear liquid is the aluminum processing wastewater after deep absorption; adding polyaluminium chloride and polyferric chloride into the deeply adsorbed aluminum processing wastewater, stirring for 6 hours at the speed of 750r/min, then reducing to the speed of 350r/min, stirring for 3.5 hours, and then performing filter pressing by using a filter press to obtain clear liquid as processed water, wherein the mass of the modified calcium bentonite is 2% based on the total mass of the aluminum processing wastewater; the total mass of the aluminum processing wastewater after preliminary adsorption is calculated as percentage, the mass of thioacetamide is 0.3 percent, and the mass of calcium sulfide is 0.2 percent; the mass of the modified sodium bentonite is 0.3 percent based on the percentage by weight of the total mass of the aluminum processing wastewater after alkali neutralization; the total mass of the deeply adsorbed aluminum processing wastewater is 0.8 percent, and the mass of the polyaluminum chloride is 0.7 percent.
Comparative example 3:
Adding calcium bentonite into water, carrying out ultrasonic treatment at a frequency of 80kHz for 35min, adding 1, 6-hexamethylenediamine and lignin, uniformly stirring at a speed of 900r/min, heating to 125 ℃ for hydrothermal reaction for 7h, heating to 650 ℃ under nitrogen atmosphere for calcination for 7h, and cooling under nitrogen atmosphere to obtain lignin modified calcium bentonite, wherein the mass ratio of 1, 6-hexamethylenediamine to calcium bentonite to lignin is 2:13:5, a step of;
adding calcium bentonite into ethanol, carrying out ultrasonic treatment at 80kHz for 25min, adding p-phenylenediamine and phytic acid, uniformly stirring at 950r/min, heating to 105 ℃ for hydrothermal reaction for 2.5h, and drying at 70 ℃ under nitrogen atmosphere to obtain phytic acid modified calcium bentonite, wherein the mass ratio of p-phenylenediamine to calcium bentonite to phytic acid is 2:12:7, preparing a base material;
Adding lignin modified calcium bentonite into aluminum processing wastewater, uniformly stirring at a speed of 850r/min, continuously stirring at a speed of 550r/min for 10 hours, adding a sedimentation tank to sediment for 17 hours, and then performing filter pressing by using a filter press to obtain clear liquid which is the aluminum processing wastewater after preliminary absorption; adding thioacetamide into the aluminum processing wastewater after primary adsorption, stirring for 6 hours at the speed of 750r/min, then introducing nitrogen for 15min, then adding calcium sulfide, and continuously stirring for 5 hours at the speed of 750r/min to obtain reduced aluminum processing wastewater; adding sodium hydroxide into the aluminum processing wastewater after reduction, and then uniformly stirring until the pH value is 6.8 to obtain aluminum processing wastewater after alkali neutralization; adding phytic acid modified calcium bentonite into the aluminum processing wastewater after alkali neutralization, heating to 43 ℃, stirring at 1050r/min for 5 hours, cooling to room temperature, continuously stirring at 1050r/min for 6 hours, and then performing filter pressing by using a filter press, wherein clear liquid is the aluminum processing wastewater after deep absorption; adding polyaluminium chloride and polyferric chloride into the deeply adsorbed aluminum processing wastewater, stirring for 6 hours at the speed of 750r/min, then reducing to the speed of 350r/min, stirring for 3.5 hours, and then performing filter pressing by using a filter press to obtain clear liquid as processed water, wherein the mass of lignin modified calcium bentonite is 2% based on the total mass of the aluminum processing wastewater; the total mass of the aluminum processing wastewater after preliminary adsorption is calculated as percentage, the mass of thioacetamide is 0.3 percent, and the mass of calcium sulfide is 0.2 percent; the mass of the phytic acid modified calcium bentonite is 0.3 percent based on the percentage by weight of the total mass of the aluminum processing wastewater after alkali neutralization; the total mass of the deeply adsorbed aluminum processing wastewater is 0.8 percent, and the mass of the polyaluminum chloride is 0.7 percent.
The contents of dichromate ions and fluoride ions in the aluminum processing wastewater and the treated water obtained in example 1 and comparative examples 1 to 3 were measured, and the measurement results are shown in table 1.
Table 1:
From the above table, it can be seen that the dichromate ions and fluoride ions in the treated water obtained by the treatment method provided in example 1 are reduced to zero, thereby realizing zero emission of aluminum processing wastewater; specifically, the aluminum processing wastewater is subjected to preliminary adsorption through modified calcium bentonite, so that high-concentration dichromate ions and fluoride ions are removed, the subsequent reduction treatment and alkali neutralization are favorable for further removing the dichromate ions and the fluoride ions, the further advanced adsorption treatment is performed by modified sodium bentonite, low-concentration dichromate ions and fluoride ions can be removed, and the further decolorization treatment is performed to obtain treated water without the dichromate ions and the fluoride ions, so that zero emission of the aluminum processing wastewater is realized; more specifically, the 1, 6-hexamethylenediamine and lignin modified calcium bentonite have larger adsorption space size, so that the adsorption quantity is obviously increased; the p-phenylenediamine and the phytic acid modified sodium bentonite have smaller adsorption space size, and can more effectively capture low-concentration dichromate ions and fluoride ions, so that zero emission of aluminum processing wastewater is finally realized. From example 1 and comparative examples 1 to 2, the modified sodium bentonite requires both phytic acid and p-phenylenediamine, thereby effectively constructing a small-sized adsorption space. From example 1 and comparative example 3, sodium bentonite is more suitable for constructing a small-sized adsorption space than calcium bentonite.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The zero-emission treatment method for the aluminum processing wastewater is characterized by comprising the following steps of:
adding modified calcium bentonite into the aluminum processing wastewater to perform preliminary adsorption treatment to obtain the primarily adsorbed aluminum processing wastewater;
Adding a reducing agent into the aluminum processing wastewater after preliminary adsorption for reduction treatment to obtain reduced aluminum processing wastewater;
Adding an alkaline agent into the reduced aluminum processing wastewater, and uniformly stirring until the pH value is 6.5-7.2 to obtain alkali-neutralized aluminum processing wastewater;
Adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization for deep adsorption treatment to obtain aluminum processing wastewater after deep adsorption;
adding a decoloring agent into the deeply adsorbed aluminum processing wastewater to perform decoloring treatment to obtain treated water;
the preparation raw materials of the modified calcium bentonite comprise 1, 6-hexamethylenediamine, calcium bentonite and lignin;
the preparation raw materials of the modified sodium bentonite comprise p-phenylenediamine, sodium bentonite and phytic acid;
The reduction treatment comprises the following steps:
Adding thioacetamide into the primarily adsorbed aluminum processing wastewater, stirring at the speed of 700-800 r/min for 5-7 h, then introducing nitrogen for 10-20 min, then adding calcium sulfide, and continuously stirring at the speed of 700-800 r/min for 3-8 h to obtain the reduced aluminum processing wastewater;
the preparation method of the modified calcium bentonite comprises the following steps:
adding calcium bentonite into water, carrying out ultrasonic treatment for 30-40 min at a frequency of 70-90 kHz, adding 1, 6-hexamethylenediamine and lignin, uniformly stirring at a speed of 850-950 r/min, heating to 120-130 ℃ for hydrothermal reaction for 6-8 h, heating to 600-700 ℃ in nitrogen atmosphere, calcining for 6-8 h, and cooling in nitrogen atmosphere to obtain the modified calcium bentonite;
The mass ratio of the 1, 6-hexamethylenediamine, the calcium bentonite and the lignin is 1-3: 12-15: 3-7;
the preparation method of the modified sodium bentonite comprises the following steps:
adding sodium bentonite into ethanol, carrying out ultrasonic treatment at a frequency of 70-90 kHz for 20-30 min, adding p-phenylenediamine and phytic acid, uniformly stirring at a speed of 900-1000 r/min, heating to 100-110 ℃ for hydrothermal reaction for 2-3 h, and then drying at a temperature of 60-80 ℃ in a nitrogen atmosphere to obtain the modified sodium bentonite;
the mass ratio of the p-phenylenediamine to the sodium bentonite to the phytic acid is 1-3: 10-15: 5-10.
2. The method of claim 1, wherein the alkaline agent comprises at least one of potassium hydroxide, sodium hydroxide, calcium oxide, and calcium hydroxide.
3. The method of treatment according to claim 1, wherein the preliminary adsorption treatment comprises the steps of:
Adding modified calcium bentonite into the aluminum processing wastewater, uniformly stirring at the speed of 800-900 r/min, continuously stirring at the speed of 500-600 r/min for 8-12 h, adding a sedimentation tank to sediment for 15-18 h, and then performing filter pressing by using a filter press, wherein clear liquid is the primarily adsorbed aluminum processing wastewater.
4. The method according to claim 1, wherein the deep adsorption treatment comprises the steps of:
adding modified sodium bentonite into the aluminum processing wastewater after alkali neutralization, heating to 40-45 ℃, stirring for 3-7 h at 1000-1100 r/min, cooling to room temperature, continuously stirring for 5-7 h at 1000-1100 r/min, and then performing filter pressing by using a filter press, wherein clear liquid is the aluminum processing wastewater after deep absorption.
5. The method according to claim 1, wherein the decoloring treatment comprises the steps of:
Adding a decolorizing agent into the deeply adsorbed aluminum processing wastewater, stirring for 5-7 hours at the speed of 700-800 r/min, then reducing to the speed of 300-400 r/min, stirring for 3-4 hours, and then performing filter pressing by using a filter press, wherein clear liquid is the treated water.
6. The method according to claim 1, wherein the decoloring agent is at least one of polyaluminum chloride and polyferric chloride.
7. The treatment method according to any one of claims 1 to 6, characterized in that the mass of the modified calcium bentonite is 1 to 3% based on the total mass of the aluminum processing wastewater;
the mass of the reducing agent is 0.3-0.7% based on the total mass of the primarily adsorbed aluminum processing wastewater;
The total mass of the aluminum processing wastewater after alkali neutralization is calculated as a percentage, and the mass of the modified sodium bentonite is 0.2-0.4%;
the total mass of the deeply adsorbed aluminum processing wastewater is 1.2-1.8% of the mass of the decoloring agent;
The concentration of dichromate ions in the aluminum processing wastewater is 512.8mg/L;
the concentration of fluoride ions in the aluminum processing wastewater is 206.7mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410155085.4A CN117682732B (en) | 2024-02-04 | 2024-02-04 | Zero-emission treatment method for aluminum processing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410155085.4A CN117682732B (en) | 2024-02-04 | 2024-02-04 | Zero-emission treatment method for aluminum processing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117682732A CN117682732A (en) | 2024-03-12 |
| CN117682732B true CN117682732B (en) | 2024-04-19 |
Family
ID=90137558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410155085.4A Active CN117682732B (en) | 2024-02-04 | 2024-02-04 | Zero-emission treatment method for aluminum processing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117682732B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19629723C1 (en) * | 1996-07-23 | 1998-04-02 | August Hoellerich | Sewage sludge conditioning method for fertiliser production |
| CN102320702A (en) * | 2011-08-23 | 2012-01-18 | 辽宁科技大学 | The method of Coagulation and Adsorption and chemical oxidation associating advanced treatment on coking wastewater |
| CN106430698A (en) * | 2016-08-03 | 2017-02-22 | 张海棠 | Special water purifying agent for chloroprene rubber production and wastewater treatment method |
| EP3296013A1 (en) * | 2012-06-25 | 2018-03-21 | Nissan Chemical Industries, Ltd. | Dispersion and method for forming hydrogel |
| CN111704193A (en) * | 2020-06-30 | 2020-09-25 | 广西夏阳环保科技有限公司 | Composite sewage treatment agent based on modified bentonite and application |
| CN116284880A (en) * | 2023-03-20 | 2023-06-23 | 吉林大学 | Method for preparing halogen-free flame-retardant polystyrene beads and expandable polystyrene beads from waste polystyrene |
-
2024
- 2024-02-04 CN CN202410155085.4A patent/CN117682732B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19629723C1 (en) * | 1996-07-23 | 1998-04-02 | August Hoellerich | Sewage sludge conditioning method for fertiliser production |
| CN102320702A (en) * | 2011-08-23 | 2012-01-18 | 辽宁科技大学 | The method of Coagulation and Adsorption and chemical oxidation associating advanced treatment on coking wastewater |
| EP3296013A1 (en) * | 2012-06-25 | 2018-03-21 | Nissan Chemical Industries, Ltd. | Dispersion and method for forming hydrogel |
| CN106430698A (en) * | 2016-08-03 | 2017-02-22 | 张海棠 | Special water purifying agent for chloroprene rubber production and wastewater treatment method |
| CN111704193A (en) * | 2020-06-30 | 2020-09-25 | 广西夏阳环保科技有限公司 | Composite sewage treatment agent based on modified bentonite and application |
| CN116284880A (en) * | 2023-03-20 | 2023-06-23 | 吉林大学 | Method for preparing halogen-free flame-retardant polystyrene beads and expandable polystyrene beads from waste polystyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117682732A (en) | 2024-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112408401B (en) | Method for preparing silicon dioxide aerogel by utilizing industrial solid waste fly ash and silicon dioxide aerogel prepared by method | |
| CN1225405C (en) | Magnesium sulfate production method using magnesium oxide and desulfurated waste fluid | |
| CN103232065A (en) | Method for recycling before-kiln dehydration filtrate and method for producing titanium dioxide | |
| CN105293797A (en) | Method for co-production of aluminum potassium sulfate and gypsum through activated clay production mother liquid | |
| CN117682732B (en) | Zero-emission treatment method for aluminum processing wastewater | |
| CN113105020A (en) | Method for recycling nickel resources in waste acid system | |
| CN105271342A (en) | Method for preparing alum by utilization of activated clay waste acid mother solution | |
| CN111574879B (en) | Semi-dry desulfurization ash-based interior wall putty powder without oxidation treatment and preparation method thereof | |
| CN1127726A (en) | Method for producing manganese sulfate using waste residue from production of potassium permanganate | |
| CN1105341A (en) | Process for producing cuprous chloride using waste etching liquid of copper chloride plate | |
| CN109970383B (en) | Production process for manufacturing accelerating agent by using water purifying agent waste residues | |
| CN104591462A (en) | Fluoride coprecipitation method for treating strong-acidity high-fluorine wastewater | |
| CN114226421A (en) | Treatment method of semidry desulfurization ash | |
| CN113716665B (en) | Method for preparing flocculant by utilizing phosphorus-sulfur-containing strong-acid wastewater | |
| CN113461021A (en) | Method for extracting white carbon black from fluorine-containing silicon slag through sulfur-adding wet purification | |
| CN105384184A (en) | Method for preparing alum from mother solution produced by activated clay | |
| CN103663662A (en) | Method for degrading heavy metal lead by silicon tetrachloride hydrolysis products | |
| CN115716697A (en) | Preparation method of low-chlorination external-drainage recycled circulating water | |
| CN103803737A (en) | Treatment method of copper-containing etching liquid | |
| CN103073588A (en) | Functional ionic liquid and its application | |
| CN1107121A (en) | Method of preparing refined brine by using bittern | |
| CN112374679A (en) | Treatment method of wastewater generated in cobaltosic oxide preparation process | |
| CN113480279B (en) | Aluminum foil sludge-based cementing material and preparation method thereof | |
| CN219631306U (en) | Fluorination circulation device for preparing rare earth polishing powder by tail gas recycling acid | |
| CN110282949B (en) | Recycling treatment method of magnesium-process desulfurization waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |