CN111672484A - Desulfurization wastewater heavy metal adsorbent - Google Patents
Desulfurization wastewater heavy metal adsorbent Download PDFInfo
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- CN111672484A CN111672484A CN202010492348.2A CN202010492348A CN111672484A CN 111672484 A CN111672484 A CN 111672484A CN 202010492348 A CN202010492348 A CN 202010492348A CN 111672484 A CN111672484 A CN 111672484A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 41
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 23
- 230000023556 desulfurization Effects 0.000 title claims abstract description 23
- 239000002351 wastewater Substances 0.000 title claims abstract description 23
- 239000003463 adsorbent Substances 0.000 title claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 61
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 35
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 35
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000002522 swelling effect Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 206010048282 zoonosis Diseases 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of a desulfurization wastewater heavy metal adsorbent, which comprises the following steps: respectively preparing polyvinyl alcohol and polyvinylamine into solutions, then adding sodium lignosulfonate, uniformly mixing, heating to 50-80 ℃ while stirring, adding a silane coupling agent and sodium hydroxide to prepare a mixed solution, continuously stirring, preparing glutaraldehyde into an aqueous solution, adding the aqueous solution into the mixed solution, continuously stirring at a constant temperature for 1-3 hours, then pouring the solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a drying oven, drying at 40-50 ℃ for 10-20 hours, heating to 90-120 ℃, drying for 1-9 hours, cooling to room temperature, taking down an adsorption film, and preparing a heavy metal adsorption film or grinding the film to prepare heavy metal adsorption particles. The adsorbent prepared by the method has the advantages of good water swelling property, uniform pore diameter, high porosity and strong adsorption capacity.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a heavy metal adsorbent for desulfurization wastewater.
Background
The desulfurization wastewater contains a certain amount of heavy metals, and the incomplete removal of the heavy metals can cause great harm to the environment and human bodies. Heavy metals flowing into the soil will generate H in plants2O2、C2H2And the heavy metal with higher concentration can inhibit the absorption of the plant to the mineral substances and influence the growth of the plant. Heavy metals reduce the diversity of soil zoonosis and threaten the existence of biological life. Heavy metals easily enter a human body to threaten the health of the human body, and when excessive cadmium enters the human body, the heavy metals can cause the pathological changes of organs of the human body and reduce the density and the hardness of bones; excessive intake of lead can cause a series of diseases such as reduction of reproductive function, reduction of immunity of the organism, hypomnesis and the like. Therefore, the collection and treatment of heavy metals is of great importance.
At present, the main methods for removing heavy metal ions in desulfurization wastewater include alkaline coagulation, oxidation reduction and adsorption, wherein the alkaline coagulation is realized by adding NaOH and Ca (OH)2Neutralizing agent with pH value to make heavy metal ion form sludge precipitate; the redox process mainly utilizes the strong redox property of coagulant to change the heavy metal with high toxicity into micro toxicity, and then adds coagulant aid to make it precipitate and separate. The method has high cost of adding chemical reagents, difficult post-treatment and secondary pollution. Adsorption technology is of great interest because of its ease of operation, high efficiency, reusability, and low cost. In the prior art, a plurality of adsorption films for adsorbing heavy metals exist, but the application methods are different. Chinese patent CN 108187641A uses sodium alginate to prepare a sodium alginate/polyvinyl alcohol @ polyacrylamide gel bead with a core-shell structure, improves the mechanical strength of the sodium alginate gel bead, but the preparation method requires special precision and is not suitable for large-scale production; chinese patent 200710056397.6 discloses a heavy metal adsorption film prepared by reacting polyvinylamine with an amino polymer under acidic conditions, which effectively improves the water swelling property of the adsorption film, but the adsorption film prepared by the method has a wider application range than that of the adsorption filmIs more limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the desulfurization wastewater heavy metal adsorbent which has the advantages of good water swelling property, uniform pore diameter, high porosity and strong adsorption capacity.
The invention is realized by the following technical scheme:
a preparation method of a desulfurization wastewater heavy metal adsorbent comprises the following steps:
(1) preparing polyvinyl alcohol and polyvinylamine into a solution with the mass fraction of 3-15% according to the mass ratio of 100: 5-100: 30, uniformly mixing, adding sodium lignosulfonate with the mass of 10-50% of polyvinyl alcohol, continuously stirring for 4-8 h, heating to 50-80 ℃ while stirring, adding a silane coupling agent with the mass of 1-5% of polyvinyl alcohol and sodium hydroxide with the mass of 10-30% of polyvinyl alcohol to prepare a mixed solution, continuously stirring, preparing glutaraldehyde with the mass of 5-50% of polyvinyl alcohol into an aqueous solution, adding the aqueous solution into the mixed solution, continuously stirring at a constant temperature for 1-3 h, pouring the solution on a polytetrafluoroethylene plate with the wet thickness of 500-2000 mu m, putting the polytetrafluoroethylene plate into a drying oven, drying at 40-50 ℃ for 10-20 h, heating to 90-130 ℃, drying for 1-9 h, cooling to room temperature, taking down an adsorption film, making into heavy metal adsorption film or grinding the film to obtain heavy metal adsorption granule.
Preferably, the mass ratio of the polyvinyl alcohol to the polyvinyl amine is 100:5-30, and more preferably, the mass ratio of the polyvinyl alcohol to the polyvinyl amine is 100: 20. Preferably, the polytetrafluoroethylene plate is placed in an oven and dried at 45 ℃ for 18h, then warmed to 120 ℃ and dried for 5 h.
The solution is sealed in the heating and stirring process to prevent the water from volatilizing in the form of water vapor. The sodium lignosulfonate is added in advance, so that the sodium lignosulfonate is uniformly distributed in the solution, and the finally prepared heavy metal adsorption particles contain uniform amount of sodium lignosulfonate.
The adsorbent prepared by the preparation method is applied to removing heavy metals in desulfurization wastewater.
Advantageous effects
(1) According to the invention, polyvinyl alcohol and polyvinylamine are uniformly mixed, then silane coupling agent, sodium lignosulfonate and glutaraldehyde are added to react under an alkaline condition, and the adsorbent is dried at a proper gradient temperature, so that the prepared adsorbent has large swelling degree, good toughness and better performance. The proper temperature gradient can ensure that the molecular weight is smooth during polymerization, and meanwhile, the prepared adsorbent has uniform aperture, higher porosity, increased micropore surface area and good adsorption performance, and micropores are not inconsistent in size or larger in pore size. Meanwhile, the added silane coupling agent can also play a role in promoting the uniformity of the pore diameter at a proper temperature.
(2) The polyvinyl alcohol is an environment-friendly polymer, does not harm the environment, has good hydrophilicity and flexibility, and has the function of adsorbing heavy metals in water by hydroxyl on the surface of the polyvinyl alcohol, polyvinylamine and amino on the surface of the silane coupling agent.
(3) The lignosulfonate is rich in content and low in price, and also contains a plurality of oxygen-containing groups such as carbonyl, phenolic hydroxyl, alcoholic hydroxyl and the like, and an unshared electron pair exists on an oxygen atom of the lignosulfonate, and can be coordinated with metal ions to form a chelate so as to have a certain adsorption effect and become a water treatment agent.
(4) The novel heavy metal adsorbent has strong adsorption capacity on various harmful metal ions such as chromium, lead, cadmium, copper, nickel and the like.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following preferred embodiments further illustrate the specific implementation, structure, features and effects of the system for treating desulfurization waste water by using waste heat of flue gas according to the present invention.
Example 1
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 3% according to the mass ratio of 100:10, mechanically stirring and uniformly mixing the two solutions, then adding sodium lignosulfonate with the mass of 10% of the polyvinyl alcohol, continuously stirring for 6h, then placing the mixture into a magnetic stirrer, continuously stirring, heating to 60 ℃, adding a silane coupling agent (kh 550) with the mass of 2% of the polyvinyl alcohol and sodium hydroxide with the mass of 10% of the polyvinyl alcohol after the temperature is stable, and continuously stirring. Preparing glutaraldehyde with the mass of 20% of polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven with the wet thickness of 1500 mu m at 40 ℃ for 20h, then heating to 90 ℃, drying for 3h, taking down a membrane after the polytetrafluoroethylene plate is cooled to the room temperature, and grinding with a mortar to obtain the desulfurization wastewater heavy metal adsorption particles.
Example 2
Preparing polyvinyl alcohol and polyvinylamine into an aqueous solution with the mass fraction of 5% according to the mass ratio of 100:20, mechanically stirring and uniformly mixing the two solutions, and then adding sodium lignin sulfonate with the mass fraction of 20% of the polyvinyl alcohol. Stirring for 6 hours, then putting the mixture into a magnetic stirrer, stirring continuously, heating to 70 ℃, adding a silane coupling agent (kh 550) accounting for 5 percent of the mass of the polyvinyl alcohol and sodium hydroxide accounting for 15 percent of the mass of the polyvinyl alcohol after the temperature is stable, and stirring continuously. Preparing glutaraldehyde with the mass of 30% of polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven at the wet thickness of 1500 mu m for 10h at 50 ℃, then heating to 90 ℃, drying for 5h, and taking down the membrane after the polytetrafluoroethylene plate is cooled to the room temperature to obtain the desulfurization wastewater heavy metal adsorption particles.
Comparative example 1
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 3% according to the mass ratio of 100:5, mechanically stirring and uniformly mixing the two solutions, then adding sodium lignosulfonate with the mass of 10% of the polyvinyl alcohol, continuously stirring for 6h, then placing the mixture into a magnetic stirrer, continuously stirring, heating to 50 ℃, adding a silane coupling agent (kh 550) with the mass of 2% of the polyvinyl alcohol and hydrochloric acid with the mass of 1% of the polyvinyl alcohol after the temperature is stable, and continuously stirring. Preparing glutaraldehyde with the mass of 5% of the polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven at the wet thickness of 1000 microns for 10h at 50 ℃, then heating to 90 ℃, drying for 5h, and taking down the membrane after the polytetrafluoroethylene plate is cooled to the room temperature to obtain the desulfurization wastewater heavy metal adsorption particles.
Comparative example 2
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 3% according to the mass ratio of 100:10, mechanically stirring and uniformly mixing the two solutions, then placing the two solutions into a magnetic stirrer to be continuously stirred, heating the solution to 60 ℃, adding a silane coupling agent (kh 550) with the mass of 2% of the polyvinyl alcohol and sodium hydroxide with the mass of 10% of the polyvinyl alcohol after the temperature is stable, and continuously stirring the solution. Preparing glutaraldehyde with the mass of 20% of polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven with the wet thickness of 1500 mu m at 40 ℃ for 20h, then heating to 90 ℃, drying for 3h, taking down a membrane after the polytetrafluoroethylene plate is cooled to the room temperature, and grinding with a mortar to obtain the desulfurization wastewater heavy metal adsorption particles.
Comparative example 3
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 3% according to the mass ratio of 100:10, mechanically stirring and uniformly mixing the two solutions, then adding sodium lignosulfonate with the mass fraction of 10% of the polyvinyl alcohol, continuously stirring for 6 hours, then placing the mixture into a magnetic stirrer, continuously stirring, heating to 60 ℃, adding sodium hydroxide with the mass fraction of 10% of the polyvinyl alcohol after the temperature is stable, and continuously stirring. Preparing glutaraldehyde with the mass of 20% of polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven with the wet thickness of 1500 mu m at 40 ℃ for 20h, then heating to 90 ℃, drying for 3h, taking down a membrane after the polytetrafluoroethylene plate is cooled to the room temperature, and grinding with a mortar to obtain the desulfurization wastewater heavy metal adsorption particles.
Comparative example 4
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 3% according to the mass ratio of 100:10, mechanically stirring and uniformly mixing the two solutions, then adding sodium lignosulfonate with the mass of 10% of the polyvinyl alcohol, continuously stirring for 6h, then placing the mixture into a magnetic stirrer, continuously stirring, heating to 60 ℃, adding a silane coupling agent (kh 550) with the mass of 2% of the polyvinyl alcohol and sodium hydroxide with the mass of 10% of the polyvinyl alcohol after the temperature is stable, and continuously stirring. Preparing glutaraldehyde with the mass of 20% of polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven at the wet thickness of 1500 mu m for 20h at 40 ℃, then heating to 60 ℃, drying for 3h, taking down a membrane after the polytetrafluoroethylene plate is cooled to the room temperature, and grinding with a mortar to obtain the desulfurization wastewater heavy metal adsorption particles.
Comparative example 5
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 3% according to the mass ratio of 100:10, mechanically stirring and uniformly mixing the two solutions, then adding sodium lignosulfonate with the mass of 10% of the polyvinyl alcohol, continuously stirring for 6h, then placing the mixture into a magnetic stirrer, continuously stirring, heating to 60 ℃, adding a silane coupling agent (kh 550) with the mass of 2% of the polyvinyl alcohol and sodium hydroxide with the mass of 10% of the polyvinyl alcohol after the temperature is stable, and continuously stirring. Preparing glutaraldehyde with the mass of 20% of polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven at the wet thickness of 1500 mu m for 20h at 40 ℃, then heating to 150 ℃, drying for 3h, taking down a membrane after the polytetrafluoroethylene plate is cooled to the room temperature, and grinding with a mortar to obtain the desulfurization wastewater heavy metal adsorption particles.
Comparative example 6
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 3% according to the mass ratio of 100:10, mechanically stirring and uniformly mixing the two solutions, then adding sodium lignosulfonate with the mass of 10% of the polyvinyl alcohol, continuously stirring for 6h, then placing the mixture into a magnetic stirrer, continuously stirring, heating to 60 ℃, adding a silane coupling agent (kh 550) with the mass of 2% of the polyvinyl alcohol and sodium hydroxide with the mass of 10% of the polyvinyl alcohol after the temperature is stable, and continuously stirring. Preparing glutaraldehyde with the mass of 20% of polyvinyl alcohol into an aqueous solution, uniformly adding the aqueous solution into the mixed solution, continuously stirring for 1h at constant temperature, taking the solution down, pouring the solution on a polytetrafluoroethylene plate, drying the polytetrafluoroethylene plate in a drying oven at the wet thickness of 1500 mu m for 20h at 40 ℃, then heating to 200 ℃, drying for 3h, taking down a membrane after the polytetrafluoroethylene plate is cooled to the room temperature, and grinding with a mortar to obtain the desulfurization wastewater heavy metal adsorption particles.
Comparative example 7
Preparing polyvinyl alcohol and polyvinylamine into aqueous solution with the mass fraction of 5% according to the mass ratio of 100:5, mechanically stirring and uniformly mixing the two solutions, then adding a silane coupling agent (kh 550) with the mass of 5% of the polyvinyl alcohol and sodium hydroxide with the mass of 10% of the polyvinyl alcohol, then adding sodium lignin sulfonate with the mass of 10 percent of the polyvinyl alcohol, continuously stirring for 8 hours, heating to 80 ℃, after the temperature is stable, glutaraldehyde with the mass of 30 percent of the polyvinyl alcohol is prepared into water solution, the water solution is evenly added into the mixed solution, the constant-temperature stirring is continued for 1.5 hours, then the solution is taken down and poured on a polytetrafluoroethylene plate, the wet thickness is 1000 mu m, the polytetrafluoroethylene plate is put into an oven, drying at 50 ℃ for 10h, then heating to 100 ℃, drying for 7h, taking off the membrane after the polytetrafluoroethylene plate is cooled to room temperature, and grinding with a mortar to obtain the desulfurization wastewater heavy metal adsorption particles.
And (3) testing the adsorption performance of the prepared heavy metal adsorbent: measuring the concentration of cadmium ions and the content of copper ions in the desulfurization wastewater to be 1.5mg/L and 5mg/L, respectively placing the desulfurization wastewater into 8 shake flasks, weighing the adsorption films prepared in the examples 1-2 and the comparative examples 1-7, placing the adsorption films into the shake flasks, shaking the shake flasks at 25 ℃ and 100r/min for 24 hours, fully washing the shake flasks with deionized water, and measuring the ion adsorption capacity by using an inductively coupled plasma emission spectrometer, wherein the test results are shown in the following table:
Claims (5)
1. the preparation method of the desulfurization wastewater heavy metal adsorbent is characterized by comprising the following steps:
(1) preparing polyvinyl alcohol and polyvinylamine into an aqueous solution with the mass fraction of 3-15%, uniformly mixing, then adding sodium lignosulfonate accounting for 10-50% of the mass of the polyvinyl alcohol, continuously stirring for 4-8 hours, then heating to 50-80 ℃ while stirring, adding a silane coupling agent accounting for 1-5% of the mass of the polyvinyl alcohol and sodium hydroxide accounting for 10-30% of the mass of the polyvinyl alcohol to prepare a mixed solution, continuously stirring, preparing glutaraldehyde accounting for 5-50% of the mass of the polyvinyl alcohol into an aqueous solution, adding the aqueous solution into the mixed solution, continuously stirring at constant temperature for 1-3 hours, then pouring the solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into an oven with the wet thickness of 500-2000 mu m, drying for 10-20 h at 40-50 ℃, then heating to 90-130 ℃, drying for 1-9 h, cooling to room temperature, taking down the adsorption film, and preparing the heavy metal adsorption film or grinding the film to obtain heavy metal adsorption particles.
2. The preparation method according to claim 1, wherein the mass ratio of the polyvinyl alcohol to the polyvinyl amine is 100: 5-30.
3. The method of claim 1, wherein the polytetrafluoroethylene sheet is placed in an oven and dried at 45 ℃ for 18 hours, then warmed to 120 ℃ and dried for 5 hours.
4. The method according to claim 1, wherein the sealing is performed during the heating and stirring of the solution.
5. Use of the adsorbent prepared by the preparation method according to any one of claims 1 to 4 for removing heavy metals from desulfurization waste water.
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