CN114789046A - Heavy metal trapping agent and application thereof - Google Patents
Heavy metal trapping agent and application thereof Download PDFInfo
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- CN114789046A CN114789046A CN202210564656.0A CN202210564656A CN114789046A CN 114789046 A CN114789046 A CN 114789046A CN 202210564656 A CN202210564656 A CN 202210564656A CN 114789046 A CN114789046 A CN 114789046A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 38
- 235000017060 Arachis glabrata Nutrition 0.000 claims abstract description 60
- 244000105624 Arachis hypogaea Species 0.000 claims abstract description 60
- 235000010777 Arachis hypogaea Nutrition 0.000 claims abstract description 60
- 235000018262 Arachis monticola Nutrition 0.000 claims abstract description 60
- 235000020232 peanut Nutrition 0.000 claims abstract description 60
- 244000302544 Luffa aegyptiaca Species 0.000 claims abstract description 58
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000012153 distilled water Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 235000003956 Luffa Nutrition 0.000 claims description 2
- 241000219138 Luffa Species 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 125000003700 epoxy group Chemical group 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 13
- 239000012265 solid product Substances 0.000 description 12
- 239000003463 adsorbent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000002154 agricultural waste Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 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
- 238000012271 agricultural production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction 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
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 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
- 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
- 239000010865 sewage Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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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
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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
- B01J20/26—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
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- 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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Abstract
The invention discloses a heavy metal trapping agent and application thereof, wherein the heavy metal trapping agent is polyhydroxy peanut shells or polyhydroxy vegetable sponge, potassium persulfate and sodium bisulfite are used as initiators, glycidyl methacrylate is used as a grafting monomer, GMA polymer chains containing a large number of epoxy groups are introduced into waste peanut shell powder or vegetable sponge powder, and the epoxy groups are further used as active points to perform a functional reaction with hydroxyl-terminated hyperbranched polyester rich in adsorption functional groups, so that the polyhydroxy peanut shells or the polyhydroxy vegetable sponge are obtained. By the modification method and the process route, the number of the adsorption groups introduced to the surface of the peanut shell or the loofah sponge is greatly increased, and the pair C of the modified peanut shell is obviously improvedu (II) has adsorption capacity and saturated adsorption capacity of 1400mg/g and 1482mg g ‑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
China is a big country for agricultural production, agricultural technology is continuously innovated, the degree of agricultural modernization is higher and higher, the yield of crops is increased day by day, and the total amount of agricultural wastes is increased gradually. However, the tendency that city-entering business workers become rural labor output in recent years leads to the shortage of rural labor force, so that the utilization rate of agricultural wastes is greatly reduced, and the phenomenon of random abandonment is increasingly serious. On the other hand, the pollution of underground water resources caused by the discharge of heavy metal wastewater generated by the development of the electroplating industry and the battery industry threatens the health of human beings all the time. The effective treatment means for reducing the concentration of heavy metals in wastewater is urgently sought.
The conventional method for treating heavy metal wastewater at present comprises the following steps: although the chemical method is easy to operate, simple in process and low in treatment cost, the discharged wastewater hardly meets 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. Although the polymer heavy metal trapping agent has stronger trapping capacity with heavy metal ions, the heavy metal ions can be selectively trapped and precipitated. 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 researchers turn the attention to the development and utilization of agricultural wastes, and prepare the heavy metal trapping agent by performing functional modification on the agricultural wastes. The hydroxyl-terminated hyperbranched polymer has a large number of adsorption functional groups (hydroxyl groups) and unique intramolecular nano micropores, has the structural characteristic of no chain winding, enables adsorption points to be exposed on the surface of a molecule, and is more favorable for fully adsorbing heavy metal ions.
Disclosure of Invention
The invention provides a heavy metal trapping agent and application thereof, aiming at overcoming the problems of insufficient quantity of introduced adsorption groups and low adsorption capacity on heavy metal ions in the process of modifying peanut shells or vegetable sponge in the prior art. The modifier adopted by the invention is hydroxyl-terminated hyperbranched polyester, the synthesis route is that potassium persulfate and sodium bisulfite are used as initiator, Glycidyl Methacrylate (GMA) is used as grafting monomer, GMA polymeric chain containing a large amount of epoxy groups is introduced into peanut shell powder or vegetable sponge powder, and further epoxy groups are used as active points to carry out functional reaction with hydroxyl-terminated hyperbranched polyester (Hyper H102) rich in adsorption functional groups, so as to prepare polyhydroxy peanut shell or polyhydroxy vegetable sponge.
The technical scheme of the invention is as follows:
the invention provides a heavy metal trapping agent, which is a polyhydroxy peanut shell or polyhydroxy loofah, and a preparation method of the heavy metal trapping agent comprises the following steps:
(1) soaking the peanut shell powder or the 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 the vegetable sponge;
(2) and (2) adding a mixed solution of dioxane and water into the GMA graft of the peanut shell or the loofah pulp in the step (1), stirring for swelling, adding the hydroxyl-terminated hyperbranched polyester at the temperature of 65-85 ℃, reacting, and obtaining the polyhydroxy peanut shell or the polyhydroxy loofah pulp after the reaction is finished.
Further, the mass ratio of the peanut shell powder or the loofah 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) to 2;
preferably, the mass ratio of potassium persulfate to sodium bisulfite in the mixture of potassium persulfate and sodium bisulfite is 2: 1-2: 3;
preferably, the emulsifier is OP-10;
preferably, the peanut shell powder or the vegetable sponge powder is powder passing through a 200-mesh sieve.
Further, in the step (1), the reaction time is 40-120 min under the constant temperature condition of 15-60 ℃;
preferably, when the GMA graft of the loofah sponge is prepared, the reaction temperature in the step (1) is 25-60 ℃.
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 luffa pith 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 solution of dioxane and water is 1: 4-1: 2;
preferably, the hydroxyl-terminated hyperbranched polyester is HyPer H102.
Further, the time for stirring and swelling in the step (2) is 4-6 hours;
the time for adding the terminal hydroxyl hyperbranched polyester in the step (2) to react is 15-30 h;
preferably, when the polyhydroxy loofah pulp is prepared, the time for adding the hydroxyl hyperbranched polyester in the end in the step (2) to react is 20-30 hours.
Further, after the reaction is finished at the constant temperature of 15-60 ℃ in the step (1), the reaction product is filtered and poured into absolute ethyl alcohol for soaking, then acetone is extracted to remove homopolymer, and the GMA graft of peanut shell or loofah sponge is obtained after drying.
Further, after the end of the hydroxyl hyperbranched polyester added in the step (2) is reacted, extracting and washing the reaction product in distilled water to be neutral, drying to constant weight, and grinding to obtain the polyhydroxy peanut shells or polyhydroxy loofah pulp.
The invention provides an application of the heavy metal trapping agent in heavy metal sewage treatment.
Further, the polyhydroxy peanut shell or polyhydroxy loofah is 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:
the method takes Glycidyl Methacrylate (GMA) as a bridge, and introduces GMA polymer containing a large amount of epoxy groups on peanut shells or loofah pith through free radical graft copolymerizationAnd (3) combining chains, further taking an epoxy group as an active point, and carrying 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 surface of the peanut shell or the vegetable sponge is greatly increased, and the peanut shell or the vegetable sponge has super-strong adsorption capacity on heavy metal ions. Through the modification method and the process route, the number of the introduced adsorption groups on the surface of the peanut shell or the loofah sponge is greatly increased, the adsorption capacity of the modified peanut shell or the loofah sponge on Cu (II) is remarkably improved, and when the pH of the adsorption solution is 5, the initial concentration of Cu (II) is 900 mg.L -1 The adsorption capacity of the adsorbent is respectively as high as 1400mg g -1 And 1482mg g -1 。
Drawings
FIG. 1 is a graph of the adsorption capacity of polyhydroxy peanut shells at various initial Cu (II) concentrations (25 ℃ C., solution pH 5).
FIG. 2 shows the adsorption capacity of polyhydroxy vegetable sponge (25 ℃ C., solution pH 5) at different initial Cu (II) concentrations.
Detailed Description
In order that the invention may be more clearly understood, it will now be further described with reference to the following examples and the accompanying drawings. The examples are given for the purpose of illustration only and are not intended to limit the invention in any way. In the examples, each raw reagent material is commercially available, and the experimental method not specifying the specific conditions is a conventional method and a conventional condition well known in the art, or a condition recommended by an instrument manufacturer.
Example 1
The waste peanut shells are cleaned, dried and smashed, and the powder which passes through a 200-mesh sieve is screened for standby. 4.0g of peanut shell powder is weighed into a four-neck flask filled with 80ml of distilled water, and 0.2g of emulsifier OP-10, 8.0g of GMA, 2.0g of potassium persulfate and 1.5g of sodium bisulfite are added in sequence (mass ratio is 1.3: 1). The reaction was carried out at a constant temperature of 25 ℃ for 80 minutes. And (3) pumping and filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol, soaking for 40min, extracting for 48h by using acetone to remove homopolymers, drying to obtain a peanut shell graft, and grinding for later use.
1.0g of the graft prepared above is weighed into a four-neck flask, 50ml of mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:4) is added, after the mixed solution is stirred and swelled by magnetic force for 6H, 6.0g of hydroxyl-terminated hyperbranched polyester (HyPer H102) (the molecular weight is 1100g/mol, the number of hydroxyl groups is 10-12/mol, the hydroxyl value is 600mgKOH/g, the acid value is less than 20mgKOH/g, Hangzhou subbond biotechnology limited) is added in batches at 85 ℃ (the mixture is divided into 5-10 parts and added in sequence at intervals of 3 min) to react for 25H. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying oven to constant weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified peanut shell adsorbent, namely the polyhydroxy peanut shell.
At different initial concentrations, the obtained polyhydroxy peanut shells are used for detecting the adsorption performance of Cu (II)
The method comprises the following specific steps: the different concentrations (50, 100, 200, 300, 400, 500, 600, 700, 800, 900 mg.L) of pH 5 were measured out separately -1 ) Each 40mL of the Cu (II) solution was added to each set of reaction vessels and 0.02g of each of the above-obtained polyhydroxylated peanut shells was added. Keeping the temperature at 25 ℃ and the rotation speed of an oscillator at 160 r.min -1 Shaking for 2 hr, centrifuging part of the solution for 60min, collecting supernatant, and detecting Cu (II) concentration with atomic absorption spectrometer. As shown in fig. 1.
As can be seen from FIG. 1, the adsorption capacity of the obtained polyhydroxy peanut shells increases with the increase of the initial concentration of Cu (II), and when the initial concentration is 900 mg.L -1 When the adsorption amount is 1400mg/g -1 Showing its super-strong adsorption capacity.
Example 2
The waste peanut shells are cleaned, dried and smashed, and the powder which passes through a 200-mesh sieve is screened for standby. 4.0g of peanut shell powder is weighed into a four-neck flask filled with 80ml of distilled water, and 0.15g of emulsifier OP-10, 2.0g of GMA, 2.33g of potassium persulfate and 1.17g of sodium bisulfite are added in sequence (mass ratio is about 2: 1). The reaction was carried out at 15 ℃ for 120 minutes. And (3) pumping and filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol, soaking for 40min, extracting for 48h by using acetone to remove homopolymers, drying to obtain a peanut shell graft, and grinding for later use.
Weighing 1.0g of the prepared graft, adding 60ml of mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:2), magnetically stirring and swelling for 4h, adding 4.0g of hydroxyl-terminated hyperbranched polyester (the molecular weight is 1100g/mol, the hydroxyl number is 10-12/mol, the hydroxyl value is 600mgKOH/g, the acid value is less than 20mgKOH/g, Hangzhou sub-bond biotechnology limited company) in batches at 75 ℃ (the mixture is divided into 5-10 parts and added in sequence at intervals of 3 min), and reacting for 15 h. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying oven to constant weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified peanut shell adsorbent, namely the polyhydroxy peanut shell.
Example 3
The waste peanut shells are cleaned, dried and smashed, and the powder passing through a 200-mesh sieve is screened for later use. 4.0g of peanut shell powder is weighed into a four-neck 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 (mass ratio of 2:3) are added in sequence. The reaction was carried out at a constant temperature of 60 ℃ for 40 minutes. And (3) pumping and filtering a solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol, soaking for 40min, extracting for 48h by using acetone to remove a homopolymer, drying to obtain a peanut shell graft, and grinding for later use.
Weighing 1.0g of the prepared graft, adding 40ml of mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:3), magnetically stirring and swelling for 5h, adding 2.0g of hydroxyl-terminated hyperbranched polyester (the molecular weight is 1100g/mol, the hydroxyl number is 10-12/mol, the hydroxyl value is 600mgKOH/g, the acid value is less than 20mgKOH/g, Hangzhou sub-bond biotechnology limited company) in batches at 65 ℃ (the mixture is divided into 5-10 parts and added in sequence at intervals of 3 min), and reacting for 30 h. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying oven to constant weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified peanut shell adsorbent, namely the polyhydroxy peanut shell.
Example 4
Cutting Luffa cylindrica pulp into 2-3 cm long sections, cleaning, oven drying, crushing, and sieving to obtain 200 mesh powder. Weighing loofah powder 4.0g into a four-neck flask filled with 80ml of distilled water, and adding emulsifier OP-10, GMA 8.0g, potassium persulfate 2.0g and sodium bisulfite 1.5g (mass ratio of 1.3:1) 0.2 g. The reaction was carried out at a constant temperature of 35 ℃ for 80 minutes. And (3) pumping and filtering a solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol, soaking for 40min, extracting for 48h by using acetone to remove a homopolymer, drying to obtain a loofah sponge graft, and grinding for later use.
Weighing 1.0g of the prepared graft, adding 50ml of mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:4), magnetically stirring and swelling for 6H, adding 6.0g of hydroxyl-terminated hyperbranched polyester (HyPer H102) (the molecular weight is 1100g/mol, the number of hydroxyl groups is 10-12/mol, the hydroxyl value is 600mgKOH/g, the acid value is less than 20mgKOH/g, Hangzhou subbond biotechnology limited) in batches at 85 ℃ (evenly divided into 5-10 parts, and added sequentially at intervals of 3 min), and reacting for 25H. 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 constant weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified loofah sponge adsorbent, namely the polyhydroxy loofah sponge.
Detecting the adsorption performance of the modified vegetable sponge to Cu (II) at different initial concentrations
The method comprises the following specific steps: adjusting the pH value of the prepared Cu (II) solution with each concentration to 5, and measuring different concentrations (50, 100, 200, 300, 400, 500, 600, 700, 800 and 900 mg.L) respectively -1 ) 40mL of each of the Cu (II) solutions of (1) was added to each of the reaction vessels, and 0.02g of each of the adsorbents obtained in example 1 was added. Keeping the temperature at 25 ℃ and the rotation speed of an oscillator at 160 r.min -1 Oscillating for 2 hours, taking out part of the solution, centrifuging for 60min, taking supernatant, and detecting the Cu (II) concentration by using an atomic absorption spectrometer. As shown in fig. 2.
As can be seen from FIG. 2, the adsorption capacity of the obtained polyhydroxy loofah flesh increases with the initial concentration of Cu (II). Initial concentration of Cu (II) at 25 deg.C and pH 5 of 900 mg. L -1 When the adsorption quantity is up to 1482 mg/g -1 Showing super adsorption capability to Cu (II).
Example 5
Cutting Luffa cylindrica pulp into 2-3 cm long segments, cleaning, oven drying, crushing, and sieving to obtain 200 mesh powder. Weighing 4.0g of vegetable sponge powder into a four-neck flask filled with 80ml of distilled water, and sequentially adding 0.15g of emulsifier OP-4.0g of GMA, 2.33g of potassium persulfate and 1.17g of sodium bisulfite (the mass ratio is about 2: 1). The reaction was carried out at a constant temperature of 25 ℃ for 120 minutes. And (3) pumping and filtering a solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol, soaking for 40min, extracting for 48h by using acetone to remove a homopolymer, drying to obtain a loofah sponge graft, and grinding for later use.
Weighing 1.0g of the prepared graft, adding 60ml of mixed solution of dioxane and distilled water (the volume ratio of the distilled water to the dioxane is 1:2), stirring and swelling by magnetic force for 4 hours, adding 4.0g of hydroxyl-terminated hyperbranched polyester (with the molecular weight of 1100g/mol, the number of hydroxyl groups of 10-12/mol, the hydroxyl value of 600mgKOH/g, the acid value of less than 20mgKOH/g, Hangzhou subbond biotechnology limited company) in batches at 80 ℃, and reacting for 20 hours, wherein the parts are divided into 5-10 parts and are added in sequence at intervals of 3 minutes. And after the reaction is finished, extracting and washing the prepared sample in distilled water to be neutral, drying the sample in a drying oven to constant weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified loofah sponge adsorbent, namely the polyhydroxy loofah sponge.
Example 6
Cutting Luffa cylindrica pulp into 2-3 cm long sections, cleaning, oven drying, crushing, and sieving to obtain 200 mesh powder. Weighing 4.0g of loofah powder into a four-neck flask filled with 80ml of distilled water, and sequentially adding 0.1g of emulsifier OP-10, 6.0g of GMA, 1.4g of potassium persulfate and 2.1g of sodium bisulfite (the mass ratio is 2: 3). The reaction was carried out at a constant temperature of 60 ℃ for 40 minutes. And (3) pumping and filtering the solid product obtained by the reaction, pouring the solid product into absolute ethyl alcohol, soaking for 40min, then extracting for 48h by using acetone to remove homopolymers, drying to obtain a vegetable sponge graft, and grinding for later use.
Weighing 1.0g of the prepared graft, adding 50ml of mixed solution of dioxane and distilled water (the volume ratio of water to dioxane is 1:3), magnetically stirring and swelling for 5h, adding 2.0g of hydroxyl-terminated hyperbranched polyester (the molecular weight is 1100g/mol, the hydroxyl number is 10-12/mol, the hydroxyl value is 600mgKOH/g, the acid value is less than 20mgKOH/g, Hangzhou sub-bond biotechnology limited company) in batches at 65 ℃ (the mixture is divided into 5-10 parts and added in sequence at intervals of 3 min), and reacting for 30 h. 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 constant weight, and grinding the sample to obtain the hydroxyl-terminated hyperbranched polyester modified loofah sponge adsorbent, namely the polyhydroxy loofah sponge.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The heavy metal trapping agent is characterized by being polyhydroxy peanut shells or polyhydroxy loofah flesh, and the preparation method of the heavy metal trapping agent comprises the following steps:
(1) soaking the peanut shell powder or the loofah powder in distilled water, adding a mixture of an emulsifier, glycidyl methacrylate, potassium persulfate and sodium bisulfite into the distilled water, and reacting at a constant temperature of 15-60 ℃ to obtain a GMA graft of the peanut shell or the loofah;
(2) and (2) adding a mixed solution of dioxane and water into the GMA graft of the peanut shell or the loofah pulp obtained in the step (1), stirring for swelling, adding the hydroxyl-terminated hyperbranched polyester at 65-85 ℃ for reaction, and obtaining the polyhydroxy peanut shell or the polyhydroxy loofah pulp after the reaction is finished.
2. The heavy metal collector according to claim 1, wherein the mass ratio of the peanut shell powder or the loofah 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 loofah powder is (1-3) to 2;
preferably, the mass ratio of potassium persulfate to sodium bisulfite in the mixture of potassium persulfate and sodium bisulfite is 2: 1-2: 3;
preferably, the emulsifier is OP-10;
preferably, the peanut shell powder or the vegetable sponge powder is powder passing through a 200-mesh sieve.
3. The heavy metal trapping agent according to claim 1, wherein the reaction time in step (1) is 40-120 min at a constant temperature of 15-60 ℃;
preferably, when the GMA graft of the loofah sponge is prepared, the reaction temperature in the step (1) is 25-60 ℃.
4. The heavy metal trapping agent according to claim 1, wherein the mass ratio of the peanut shell GMA graft or the loofah flesh GMA graft to the hydroxyl-terminated hyperbranched polyester is 1 (2-8);
the mass volume ratio of the peanut shell GMA graft or the luffa flesh 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 solution of dioxane and water is 1: 4-1: 2;
preferably, the hydroxyl-terminated hyperbranched polyester is HyPer H102.
5. The heavy metal trapping agent according to claim 1, wherein the time for swelling by stirring in step (2) is 4 to 6 hours;
the time for adding the terminal hydroxyl hyperbranched polyester in the step (2) to react is 15-30 h.
6. The heavy metal trapping agent according to claim 1, wherein in the step (1), after the reaction is finished at a constant temperature of 15-60 ℃, the reaction product is filtered, poured into absolute ethyl alcohol for soaking, then acetone is used for extracting and removing a homopolymer, and the GMA graft of the peanut shell or the loofah pulp is obtained after drying.
7. The heavy metal collector of claim 1, wherein after the end of the hydroxyl hyperbranched polyester added in step (2) is reacted, the reaction product is extracted and washed in distilled water to be neutral, dried to constant weight, and ground to obtain the polyhydroxy peanut shells or polyhydroxy loofah pulp.
8. The use of the heavy metal trapping agent of claim 1 in heavy metal wastewater treatment.
9. The use of claim 8, wherein the polyhydroxy peanut shells or polyhydroxy loofah are used for adsorbing heavy metal ions, so as to capture and separate the heavy metal ions, and the pH value of the adsorption reaction is 5.
10. Use according to claim 9, wherein the heavy metal ions are cu (ii), pb (ii) or cd (ii).
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