CN114789046B - Heavy metal trapping agent and application thereof - Google Patents
Heavy metal trapping agent and application thereof Download PDFInfo
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- CN114789046B CN114789046B CN202210564656.0A CN202210564656A CN114789046B CN 114789046 B CN114789046 B CN 114789046B CN 202210564656 A CN202210564656 A CN 202210564656A CN 114789046 B CN114789046 B CN 114789046B
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 37
- 235000017060 Arachis glabrata Nutrition 0.000 claims abstract description 59
- 244000105624 Arachis hypogaea Species 0.000 claims abstract description 59
- 235000010777 Arachis hypogaea Nutrition 0.000 claims abstract description 59
- 235000018262 Arachis monticola Nutrition 0.000 claims abstract description 59
- 235000020232 peanut Nutrition 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 38
- 244000302544 Luffa aegyptiaca Species 0.000 claims abstract description 32
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims abstract description 32
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 27
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 16
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 16
- 235000003956 Luffa Nutrition 0.000 claims abstract description 15
- 241000219138 Luffa Species 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000008961 swelling Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 125000003700 epoxy group Chemical group 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000007306 functionalization reaction Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 238000000227 grinding Methods 0.000 description 12
- 239000012265 solid product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000002154 agricultural waste Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920000587 hyperbranched polymer Polymers 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 3
- 244000241257 Cucumis melo Species 0.000 description 2
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 2
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
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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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a heavy metal trapping agent and application thereof, wherein the heavy metal trapping agent is polyhydroxy peanut shell or polyhydroxy luffa pulp, the preparation of the heavy metal trapping agent firstly takes potassium persulfate and sodium bisulphite as initiators, glycidyl methacrylate as grafting monomers, GMA polymeric chains containing a large number of epoxy groups are introduced into waste peanut shell powder or luffa pulp powder, and further epoxy groups are taken as active points to carry out functionalization reaction with hydroxyl-terminated hyperbranched polyester rich in adsorption functional groups, so as to obtain polyhydroxy peanut shell or polyhydroxy luffa pulp. The modification method and the process route of the invention realize the great increase of the quantity of the adsorption groups introduced into the surface of the peanut shell or the vegetable sponge, obviously improve the adsorption capacity of the modified peanut shell to Cu (II), and respectively reach 1400mg/g and 1482 mg.g in saturated adsorption capacity ‑1 。
Description
Technical Field
The invention belongs to the technical field of heavy metal wastewater treatment, and particularly relates to a heavy metal trapping agent and application thereof.
Background
The agricultural technology is continuously innovated, the agricultural modernization degree is higher and higher, the yield of crops is increased, and the total amount of agricultural wastes is increased gradually. However, urban workers become the trend of rural labor output in recent years, so that the lack of rural labor is caused, the utilization rate of agricultural wastes is greatly reduced, and the random abandonment phenomenon is increasingly serious. On the other hand, the pollution to underground water resources caused by the discharge of heavy metal wastewater generated by the development of electroplating and battery industries threatens the health of human beings at any moment. It is urgent to find an effective treatment means for reducing the concentration of heavy metals in wastewater.
At present, the conventional method for treating heavy metal wastewater comprises the following steps: the chemical method has the advantages of easy operation, simple process and low treatment cost, but the discharged wastewater is difficult to meet the discharge standard. The membrane filtration method has good effect of removing heavy metal ions, but the permeable membrane needs to be replaced periodically, and the membrane is expensive. The high molecular heavy metal trapping agent has strong trapping capacity with heavy metal ions, and can selectively trap and precipitate the heavy metal ions. However, the monomer has high toxicity, difficult degradation, expensive raw materials and high treatment cost, and is difficult to be accepted by the market. More and more scientific researchers turn the eyes to the development and utilization of agricultural wastes, and heavy metal trapping agents are prepared by carrying out functional modification on the agricultural wastes. The hydroxyl-terminated hyperbranched polymer has a large number of adsorption functional groups (hydroxyl groups) and unique nanometer micropores in molecules, has the structural characteristics of chainless winding, enables adsorption points to be exposed on the surfaces of the molecules, is more beneficial to fully adsorbing heavy metal ions, and is expected to endow the hyperbranched polymer with extremely high adsorption capacity to the agricultural wastes if the hyperbranched polymer is used for realizing functional modification of the agricultural wastes, so that the hyperbranched polymer can be widely applied to the field of heavy metal sewage treatment.
Disclosure of Invention
The invention provides a heavy metal trapping agent and application thereof, and aims to solve the problems of insufficient quantity of adsorption groups and low adsorption capacity for heavy metal ions introduced in the modification process of peanut shells or vegetable sponge in the prior art. The modifier is hydroxyl-terminated hyperbranched polyester, and the synthetic route is that firstly potassium persulfate and sodium bisulphite are used as an initiator, glycidyl Methacrylate (GMA) is used as a grafting monomer, GMA polymeric chains containing a large number of epoxy groups are introduced into peanut shell powder or loofah sponge powder, and further the epoxy groups are used as active points to perform functionalization reaction with hydroxyl-terminated hyperbranched polyester (Hyper H102) rich in adsorption functional groups, so as to prepare polyhydroxy peanut shells or polyhydroxy luffa pulp.
The technical scheme of the invention is as follows:
the first aspect of the invention provides a heavy metal trapping agent which is polyhydroxy peanut shells or polyhydroxy luffa pulp, and a preparation method of the heavy metal trapping agent comprises the following steps:
(1) Soaking peanut shell powder or vegetable sponge powder in distilled water, adding a mixture of an emulsifier, glycidyl methacrylate, potassium persulfate and sodium bisulfite, and reacting at a constant temperature of 15-60 ℃ to obtain a GMA graft of the peanut shell or vegetable sponge;
(2) Adding a mixed solution of dioxane and water into the GMA graft of the peanut shell or the vegetable sponge in the step (1), stirring and swelling, adding hydroxyl-terminated hyperbranched polyester for reaction at 65-85 ℃, and obtaining the polyhydroxy peanut shell or the polyhydroxy vegetable sponge after the reaction is finished.
Further, the mass ratio of the peanut shell powder or the vegetable sponge powder to the glycidyl methacrylate is 2 (1-4);
the mass ratio of the emulsifier to the peanut shell powder or the vegetable sponge powder is 1 (20-40);
the mass ratio of the mixture of the potassium persulfate and the sodium bisulfite to the peanut shell powder or the vegetable sponge powder is (1-3) 2;
preferably, the mass ratio of the potassium persulfate to the sodium bisulfite in the mixture of the potassium persulfate and the sodium bisulfite is 2:1-2:3;
preferably, the emulsifier is OP-10;
preferably, the peanut shell powder or vegetable sponge powder is a powder that passes through a 200 mesh screen.
Further, the reaction time in the step (1) is 40-120 min under the constant temperature condition of 15-60 ℃;
preferably, the reaction temperature in step (1) is 25-60 ℃ when preparing the GMA graft of the wire pulp.
Further, the mass ratio of the peanut shell GMA graft to the hydroxyl-terminated hyperbranched polyester is 1 (2-8);
the mass volume ratio of the peanut shell GMA graft or the vegetable sponge GMA graft to the mixed solution of dioxane and water is 1 (40-60) g/mL;
preferably, the volume ratio of water to dioxane in the mixed liquid of dioxane and water is 1:4-1:2;
preferably, the hydroxyl-terminated hyperbranched polyester is HyPer H102.
Further, the time of stirring and swelling in the step (2) is 4-6 hours;
adding hydroxyl-terminated hyperbranched polyester in the step (2) for 15-30 hours;
preferably, when preparing the polyhydroxy silk melon pulp, the reaction time of adding the hydroxyl-terminated hyperbranched polyester in the step (2) is 20-30 hours.
Further, after the reaction in the step (1) is finished under the constant temperature condition of 15-60 ℃, pouring the reaction product into absolute ethyl alcohol for soaking after suction filtration, then extracting with acetone to remove homopolymer, and drying to obtain the GMA graft of peanut shells or vegetable sponge.
Further, after the reaction of adding the hydroxyl-terminated hyperbranched polyester in the step (2) is finished, the reaction product is extracted and washed to be neutral in distilled water, dried to be constant weight and ground to obtain the polyhydroxy peanut shell or polyhydroxy wire melon pulp.
The second aspect of the invention provides application of the heavy metal trapping agent in heavy metal sewage treatment.
Further, the polyhydroxy peanut shells or polyhydroxy luffa pulp are adopted to adsorb heavy metal ions, so that the heavy metal ions are captured and separated, and the pH value of the adsorption reaction is 5.
Further, the heavy metal ion is Cu (II), pb (II) or Cd (II).
Compared with the prior art, the invention has the following advantages:
according to the invention, glycidyl Methacrylate (GMA) is used as a bridge, a GMA polymerization chain containing a large amount of epoxy groups is introduced into peanut shells or luffa pulp through a free radical graft copolymerization reaction, and further epoxy groups are used as active points to carry out a ring opening reaction with hydroxyl-terminated hyperbranched polyester HyPer H102 rich in adsorption functional groups, so that the number of hydroxyl groups on the surfaces of the peanut shells or luffa pulp is greatly increased, and the peanut shells or luffa pulp has super-strong adsorption capacity on heavy metal ions. The modification method and the process route of the invention realize the great increase of the quantity of the adsorption groups introduced into the surface of the peanut shell or the vegetable sponge, obviously improve the adsorption capacity of the modified peanut shell or the vegetable sponge to Cu (II), and when the pH of the adsorption solution is 5, the initial concentration of Cu (II) is 900 mg.L -1 The adsorption capacity is up to 1400 mg.g respectively -1 And 1482 mg.g -1 。
Drawings
FIG. 1 is the adsorption capacity (25 ℃ C., solution pH 5) of polyhydroxy peanut shells at various initial Cu (II) concentrations.
FIG. 2 is the adsorption of polyhydroxy luffa pulp at various initial Cu (II) concentrations (25 ℃, solution pH 5).
Detailed Description
For a clearer understanding of the present invention, the present invention will now be further described with reference to the following examples and drawings. The examples are for illustration only and are not intended to limit the invention in any way. In the examples, each of the starting reagent materials is commercially available, and the experimental methods without specifying the specific conditions are conventional methods and conventional conditions well known in the art, or according to the conditions recommended by the instrument manufacturer.
Example 1
Cleaning the abandoned peanut shells, drying, crushing, and sieving the powder passing through a 200-mesh sieve for standby. 4.0g of peanut shell powder is weighed into a four-necked flask containing 80ml of distilled water, and 0.2g of dripping emulsifier OP-10, 8.0g of GMA,2.0g of potassium persulfate and 1.5g of sodium bisulfite are sequentially added (the mass ratio is 1.3:1). The reaction was carried out at a constant temperature of 25℃for 80 minutes. Filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol to soak for 40min, extracting with acetone for 48h to remove homopolymer, drying to obtain peanut shell graft, and grinding for later use.
1.0g of the prepared graft is weighed into a four-necked flask, 50ml of a mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:4) is added, and after magnetic stirring and swelling are carried out for 6 hours, 6.0g of hydroxyl-terminated hyperbranched polyester (HyPer H102) (molecular weight: 1100g/mol, hydroxyl number: 10-12/mol, hydroxyl value: 600mgKOH/g, acid value: 20mgKOH/g, hangzhou sub-bond biotechnology Co., ltd.) is added in batches (equally divided into 5-10 parts, added sequentially at intervals of 3 minutes) at 85 ℃ for reaction for 25 hours. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying box to be constant in weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified peanut shell adsorbent, namely the polyhydroxy peanut shell.
Detecting the adsorption performance of the obtained polyhydroxy peanut shells on Cu (II) at different initial concentrations
The method comprises the following specific steps: different concentrations (50, 100, 200, 300, 400, 500, 600, 700, 800, 900 mg.L.) of pH 5 were measured separately -1 ) 40mL of each Cu (II) solution was added to each group of reaction vessels, and 0.02g of each of the above-obtained polyhydroxypeanut shells was added. Constant temperature at 25deg.C, and rotational speed of oscillator 160 r.min -1 Shaking for 2 hours, taking out part of the solution, centrifuging for 60 minutes, taking out supernatant, and detecting the concentration of Cu (II) by using an atomic absorption spectrometer. As shown in fig. 1.
As can be seen from FIG. 1, the adsorption amount of the obtained polyhydroxy peanut shell increases with the increase of the initial Cu (II) concentration, and the initial concentration is 900 mg.L -1 When the adsorption amount is up to 1400 mg.g -1 Showing its super strong adsorption capacity.
Example 2
Cleaning the abandoned peanut shells, drying, crushing, and sieving the powder passing through a 200-mesh sieve for standby. 4.0g of peanut shell powder is weighed into a four-necked flask containing 80ml of distilled water, and 0.15g of a drop emulsifier OP-10, 2.0g of GMA,2.33g of potassium persulfate and 1.17g of sodium bisulfite are sequentially added (the mass ratio is about 2:1). The reaction was carried out at a constant temperature of 15℃for 120 minutes. Filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol to soak for 40min, extracting with acetone for 48h to remove homopolymer, drying to obtain peanut shell graft, and grinding for later use.
1.0g of the prepared graft is weighed into a four-necked flask, 60ml of a mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:2) is added, after magnetic stirring and swelling for 4 hours, 4.0g of hydroxyl-terminated hyperbranched polyester (molecular weight: 1100g/mol, hydroxyl number: 10-12, hydroxyl number: 600mgKOH/g, acid value: 20mgKOH/g, hangzhou sub-bond biotechnology Co., ltd.) is added in batches (equally divided into 5-10 parts, added sequentially at intervals of 3 minutes) at 75 ℃ for reaction for 15 hours. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying box to be constant in weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified peanut shell adsorbent, namely the polyhydroxy peanut shell.
Example 3
Cleaning the abandoned peanut shells, drying, crushing, and sieving the powder passing through a 200-mesh sieve for standby. 4.0g of peanut shell powder is weighed into a four-necked flask containing 80mL of distilled water, and 0.1g of dripping emulsifier OP-10, 6.0g of GMA,1.4g of potassium persulfate and 2.1g of sodium bisulfite are sequentially added (the mass ratio is 2:3). The reaction was carried out at a constant temperature of 60℃for 40 minutes. Filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol to soak for 40min, extracting with acetone for 48h to remove homopolymer, drying to obtain peanut shell graft, and grinding for later use.
1.0g of the prepared graft is weighed into a four-necked flask, 40ml of mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:3) is added, after magnetic stirring and swelling are carried out for 5 hours, 2.0g of hydroxyl-terminated hyperbranched polyester (molecular weight: 1100g/mol, hydroxyl number: 10-12 g/mol, hydroxyl value: 600mgKOH/g, acid value: 20mgKOH/g, hangzhou sub-bond biotechnology Co., ltd.) is added in batches (equally divided into 5-10 parts, added sequentially at intervals of 3 minutes) at 65 ℃ for 30 hours. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying box to be constant in weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified peanut shell adsorbent, namely the polyhydroxy peanut shell.
Example 4
Cutting the pulp into 2-3 cm long pieces, cleaning, oven drying, crushing, and sieving to obtain 200 mesh powder. 4.0g of vegetable sponge powder is weighed into a four-necked flask filled with 80ml of distilled water, and 0.2g of dripping emulsifier OP-10, 8.0g of GMA,2.0g of potassium persulfate and 1.5g of sodium bisulfite are sequentially added (the mass ratio is 1.3:1). The reaction was carried out at a constant temperature of 35℃for 80 minutes. Filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol to soak for 40min, extracting with acetone for 48h to remove homopolymer, drying to obtain a vegetable sponge graft, and grinding for later use.
1.0g of the prepared graft is weighed into a four-necked flask, 50ml of a mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:4) is added, and after magnetic stirring and swelling are carried out for 6 hours, 6.0g of hydroxyl-terminated hyperbranched polyester (HyPer H102) (molecular weight: 1100g/mol, hydroxyl number: 10-12/mol, hydroxyl value: 600mgKOH/g, acid value: 20mgKOH/g, hangzhou sub-bond biotechnology Co., ltd.) is added in batches (equally divided into 5-10 parts, added sequentially at intervals of 3 minutes) at 85 ℃ for reaction for 25 hours. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying box to be constant in weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified wire pulp adsorbent, namely the polyhydroxy wire pulp.
Detection of Cu (II) adsorption performance of modified luffa pulp at different initial concentrations
The method comprises the following specific steps: the pH of the prepared Cu (II) solution with each concentration is adjusted to 5, and the Cu (II) solution with different concentrations (50, 100, 200, 300, 400, 500, 600, 700, 800, 900 mg.L) -1 ) 40mL of each Cu (II) solution was added to each set of reaction vessels, and 0.02g of each of the adsorbents obtained in example 1 was added. Constant temperature at 25deg.C, and rotational speed of oscillator 160 r.min -1 Shaking for 2 hours, taking out part of the solution, centrifuging for 60 minutes, taking out supernatant, and detecting the concentration of Cu (II) by using an atomic absorption spectrometer. As shown in fig. 2.
As can be seen from FIG. 2, the amount of polyhydroxy luffa pulp adsorbed increases as the initial Cu (II) concentration increases. At a temperature of 25 ℃, ph=5, initial concentration of cu (II) 900mg·l -1 When the adsorption amount is up to 1482 mg.g -1 Shows the super-strong adsorption capacity to Cu (II).
Example 5
Cutting the pulp into 2-3 cm long pieces, cleaning, oven drying, crushing, and sieving to obtain 200 mesh powder. 4.0g of vegetable sponge powder is weighed into a four-necked flask containing 80ml of distilled water, and 0.15g of emulsifier OP-4.0g of GMA,2.33g of potassium persulfate and 1.17g of sodium bisulfite (mass ratio of about 2:1) are sequentially added. The reaction was carried out at a constant temperature of 25℃for 120 minutes. Filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol to soak for 40min, extracting with acetone for 48h to remove homopolymer, drying to obtain a vegetable sponge graft, and grinding for later use.
1.0g of the prepared graft is weighed into a four-necked flask, 60ml of a mixed solution of dioxane and distilled water (the volume ratio of distilled water to dioxane is 1:2) is added, after magnetic stirring and swelling for 4 hours, 4.0g of hydroxyl-terminated hyperbranched polyester (molecular weight: 1100g/mol, hydroxyl number: 10-12, hydroxyl number: 600mgKOH/g, acid value: 20mgKOH/g, hangzhou sub-bond biotechnology Co., ltd.) is added in batches (equally divided into 5-10 parts, and added sequentially at intervals of 3 minutes) at 80 ℃ for reaction for 20 hours. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying box to be constant in weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified wire pulp adsorbent, namely the polyhydroxy wire pulp.
Example 6
Cutting the pulp into 2-3 cm long pieces, cleaning, oven drying, crushing, and sieving to obtain 200 mesh powder. 4.0g of vegetable sponge powder is weighed into a four-necked flask filled with 80ml of distilled water, and 0.1g of emulsifier OP-10, 6.0g of GMA,1.4g of potassium persulfate and 2.1g of sodium bisulfite are sequentially added (the mass ratio is 2:3). The reaction was carried out at a constant temperature of 60℃for 40 minutes. Filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol to soak for 40min, extracting with acetone for 48h to remove homopolymer, drying to obtain a vegetable sponge graft, and grinding for later use.
1.0g of the prepared graft is weighed into a four-necked flask, 50ml of mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:3) is added, after magnetic stirring and swelling are carried out for 5 hours, 2.0g of hydroxyl-terminated hyperbranched polyester (molecular weight: 1100g/mol, hydroxyl number: 10-12 g/mol, hydroxyl value: 600mgKOH/g, acid value: 20mgKOH/g, hangzhou sub-bond biotechnology Co., ltd.) is added in batches (equally divided into 5-10 parts, added sequentially at intervals of 3 minutes) at 65 ℃ for 30 hours. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying box to be constant in weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified wire pulp adsorbent, namely the polyhydroxy wire pulp.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. The heavy metal trapping agent is characterized by being polyhydroxy peanut shells or polyhydroxy luffa pulp, and the preparation method of the heavy metal trapping agent comprises the following steps of:
(1) Soaking peanut shell powder or vegetable sponge powder in distilled water, adding a mixture of an emulsifier, glycidyl methacrylate, potassium persulfate and sodium bisulfite, and reacting at a constant temperature of 15-60 ℃ to obtain a GMA graft of the peanut shell or vegetable sponge;
the mass ratio of the peanut shell powder or the vegetable sponge powder to the glycidyl methacrylate is 2 (1-4);
the mass ratio of the emulsifier to the peanut shell powder or the vegetable sponge powder is 1 (20-40);
the mass ratio of the mixture of the potassium persulfate and the sodium bisulfite to the peanut shell powder or the vegetable sponge powder is (1-3) 2;
the mass ratio of the potassium persulfate to the sodium bisulfite in the mixture of the potassium persulfate and the sodium bisulfite is 2:1-2:3;
the reaction time is 40-120 min under the constant temperature condition of 15-60 ℃;
(2) Adding a mixed solution of dioxane and water into the GMA graft of the peanut shell or the vegetable sponge in the step (1), stirring and swelling, adding hydroxyl-terminated hyperbranched polyester for reaction at 65-85 ℃, and obtaining the polyhydroxy peanut shell or the polyhydroxy vegetable sponge after the reaction is finished;
the mass ratio of the peanut shell GMA graft or the vegetable sponge GMA graft to the hydroxyl-terminated hyperbranched polyester is 1 (2-8);
the mass volume ratio of the peanut shell GMA graft or the vegetable sponge GMA graft to the mixed solution of dioxane and water is 1 (40-60) g/mL;
the volume ratio of water to dioxane in the mixed liquid of dioxane and water is 1:4-1:2;
the hydroxyl-terminated hyperbranched polyester is HyPer H102;
the time of stirring and swelling is 4-6 hours;
the reaction time of adding the hydroxyl-terminated hyperbranched polyester is 15-30 hours.
2. The heavy metal collector as recited in claim 1, wherein the emulsifier is OP-10;
the peanut shell powder or the vegetable sponge powder is powder passing through a 200-mesh sieve.
3. The heavy metal collector as recited in claim 1, wherein the reaction temperature in the step (1) is 25 to 60 ℃.
4. The heavy metal trapping agent according to claim 1, wherein after the reaction in the step (1) is finished at a constant temperature of 15-60 ℃, the reaction product is filtered by suction and then poured into absolute ethyl alcohol for soaking, then acetone is used for extraction to remove homopolymer, and the GMA graft of peanut shells or vegetable sponge is obtained by drying.
5. The heavy metal trapping agent according to claim 1, wherein after the reaction of adding the hydroxyl-terminated hyperbranched polyester in the step (2) is finished, the reaction product is extracted and washed to be neutral in distilled water, dried to be constant weight, and ground to obtain the polyhydroxy peanut shell or polyhydroxy luffa pulp.
6. The use of the heavy metal trapping agent according to claim 1 in heavy metal sewage treatment.
7. The use according to claim 6, wherein heavy metal ions are captured and separated by adsorption with the polyhydroxy peanut hulls or polyhydroxy luffa pulp, the pH of the adsorption reaction being 5.
8. The use according to claim 7, wherein the heavy metal ion is Cu (II), pb (II) or Cd (II).
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