CN116196897A - Sludge cation adsorbent and preparation method thereof - Google Patents
Sludge cation adsorbent and preparation method thereof Download PDFInfo
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- CN116196897A CN116196897A CN202310073959.7A CN202310073959A CN116196897A CN 116196897 A CN116196897 A CN 116196897A CN 202310073959 A CN202310073959 A CN 202310073959A CN 116196897 A CN116196897 A CN 116196897A
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- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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Images
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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of environmental pollution treatment, in particular to a sludge cationic adsorbent and a preparation method thereof. The preparation method provided by the invention comprises the steps of mixing acrylamide with gelatin-TiO 2 The composite material reacts to obtain a cationic adsorbent. The adsorbent effectively improves the mechanical strength of the adsorption material and solves the problem of water absorption expansion of the adsorption material; meanwhile, the adsorbent contains rich functional group structures with chelating effect, so that more binding sites are provided for cations; the introduction of polyacrylamide leads the adsorbent to have excellent flocculation effect, and simultaneously, the semi-interpenetrating network structureThe structure has stronger stability and bridging capability than the polymer with a single network structure. The prepared cation adsorbent has the advantages of strong selectivity, high adsorption removal rate, simple and quick operation and good effect of removing Pb (II) and Ni (II) plasma in sludge.
Description
Technical Field
The invention relates to the technical field of environmental pollution treatment, in particular to a sludge cationic adsorbent and a preparation method thereof.
Background
Heavy metals are a significant factor causing environmental pollution, and are difficult to degrade, which is a serious problem. Stabilization of heavy metal solidification is an important requirement for sediment treatment and disposal. How to improve the environment and reduce the influence of heavy metal pollution on human beings and an ecological system becomes a problem to be solved urgently. Therefore, the method for removing the cationic pollutants contained in the sludge by adopting a proper method has important practical significance and application value for reducing water pollution and realizing sludge recycling.
At present, the most widely used method for treating heavy metals in the bottom mud is to add a heavy metal adsorbent to react with the heavy metals in the bottom mud to form insoluble compounds, so that the metal dissolution rate is reduced. Compared with the traditional synthetic adsorbent, the natural polymer-based adsorbent (usually in the form of gel or film) has the characteristics of wide source, high reactivity with pollutants, good treatment effect, easy separation and the like, has unique advantages in the aspects of heavy metal treatment and recovery, and becomes the focus of the current heavy metal and organic dye adsorbent research.
Natural biological materials are attracting attention because of their wide sources, renewable, degradable, safe and environment-friendly properties. Gelatin is a natural biopolymer which is easy to obtain and has the advantages of low cost, rich sources, environmental protection and the like. The presence of-OH in the gelatin moleculeNH 2 And COO - The group, which can provide a binding site with metal ions, is an excellent natural biological adsorbent and is widely concerned in the field of environmental management. However, the direct use of gelatin as an adsorbent has the problems of high water solubility, easy loss, low mechanical strength and the like, so that the treatment effect is very limited.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to providing a cationic adsorbent and a preparation method thereof, which are used for solving the problems of high water solubility, easy loss and low mechanical strength existing in the prior art when gelatin is directly used as an adsorbent.
To achieve the above and other related objects, the present invention provides a method for preparing a cationic adsorbent comprising mixing acrylamide with gelatin-TiO 2 The composite material reacts to obtain the cation adsorbent.
Preferably, the preparation method comprises the following steps:
1) gelatin-TiO 2 Preparing a composite solution:
1A) TiO is mixed with 2 Mixing with gelatin in acidic environment; preferably, the TiO is dispersed in an acid solution 2 Mixing with acidic gelatin solution;
1B) Mixing epoxy trimethoxy silane and silane coupling agent with the system in the step 1A), adjusting pH, and reacting to obtain gelatin-TiO 2 A composite material;
2) Cation adsorbent preparation: combining acrylamide and an initiator with the gelatin-TiO of step 1) 2 And (3) after the composite materials are mixed and reacted, separating to obtain the cation adsorbent.
The invention also provides a cationic adsorbent, which is obtained by the preparation method.
The invention also provides the application of the cation adsorbent in heavy metal ion adsorption or flocculation dehydration.
The invention also provides a method for adsorbing heavy metal ions in sludge or flocculating and dehydrating, which comprises the step of adding the cationic adsorbent into sludge.
As described above, the cation adsorbent and the preparation method thereof of the invention not only maintain excellent electric neutralization and adsorption bridging effects, but also can rapidly remove pollutants such as charged colloid, suspended particles and the like in the wastewater; meanwhile, the molecular chain of the cation adsorbent is rich in hydroxyl, carboxyl, sulfhydryl, amino and other groups, and has high-efficiency adsorption and complexation capability on heavy metal ions. The prepared cation adsorbent has good effect of adsorbing and removing Pb (II) and Ni (II) plasma in sludge, and has the following beneficial effects:
(1) The cation adsorbent prepared by the invention is rich in gelatin molecules and rich in-OH and-NH 2 And COO-groups and other functional groups, can provide binding sites with metal ions, and have good adsorption effect under different pH conditions; meanwhile, gelatin has sol-gel conversion characteristics, and the hydrogel structure of the gelatin can effectively adsorb pollutants such as heavy metals in sludge;
(2) The inorganic material is introduced into the gelatin molecules, so that the defects of high water solubility, low mechanical strength and poor thermal stability of the gelatin material as a single material are greatly improved, and the excellent mechanical strength and thermal stability of the material are endowed; meanwhile, the inorganic material endows the polymer with excellent adsorption characteristics due to the large specific surface area, and has definite synergic heavy metal adsorption effect;
(3) gelatin-TiO 2 The semi-interpenetrating network polymer formed by the polymer and the polyacrylamide has higher molecular weight and higher charge density, has stronger stability and bridging capacity than the polymer with a single network structure, and has obvious dehydration flocculation effect while strengthening adsorption;
(4) The cation adsorbent has the dual effects of flocculation and heavy metal adsorption, has the advantages of strong selectivity, high adsorption removal rate, simple and quick operation, mild synthesis conditions and strong application prospect in the treatment of sludge cation pollutants.
Drawings
FIG. 1 shows a schematic structure of a cation adsorbent of the present invention. Wherein, the black lines are polyacrylamide; the pink line is gelatin; yellow oval is TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The red rectangle is a bond.
Detailed Description
The invention provides a preparation method of a cation adsorbent, which comprises the steps of mixing acrylamide with gelatin-TiO 2 The composite material reacts to obtain the cation adsorbent.
The preparation method specifically comprises the following steps:
1) gelatin-TiO 2 Preparing a composite material:
1A) TiO is mixed with 2 Mixing with gelatin in acidic environment; preferably, the TiO is dispersed in an acid solution 2 Mixing with acidic gelatin solution;
1B) Mixing epoxy trimethoxy silane and silane coupling agent with the system in the step 1A), adjusting pH, and reacting to obtain gelatin-TiO 2 A composite material;
2) Cation adsorbent preparation: combining acrylamide and an initiator with the gelatin-TiO of step 1) 2 And (3) after the composite materials are mixed and reacted, separating to obtain the cation adsorbent.
In some embodiments, in step 1), the amount of gelatin is 60-140g/L based on the total volume of the reaction solution of step 1); and/or, tiO 2 The mass of the (B) is 0.8-1.7 times of the mass of the gelatin; and/or the dosage of the epoxy trimethoxysilane is 40-100ml/L; and/or the silane coupling agent is used in an amount of TiO 2 0.1 to 6 percent of the mass. More specifically, the dosage of gelatin is 60-80g/L, 80-100g/L, 100-120g/L or 120-140g/L; tiO (titanium dioxide) 2 The mass of the gel is 0.8 to 1, 1 to 1.2, 1.2 to 1.5 or 1.5 to 1.7 times of the mass of the gellan gum; the dosage of the epoxy trimethoxy silane is 40-50ml/L, 50-60ml/L, 60-70ml/L, 70-80ml/L, 80-90ml/L or 90-100ml/L; the mass of the silane coupling agent is TiO 2 0.1-1%, 1-2%, 2-3%, 3-4%, 4-5% or 5-6% of the mass.
In some embodiments, the foregoing TiO dispersed in an acid solution 2 TiO as dispersed in hydrochloric acid 2 . Preferably, tiO dispersed in hydrochloric acid 2 50-80g/L; the pH of the hydrochloric acid is 1-5.
Further, the TiO 2 Is nano TiO 2 . More specifically, the aforementioned TiO 2 TiO with the product number T299718 or T298674 of Aladin company 2 。
In some embodiments, the TiO 2 React with the acidic gelatin solution to form TiO dispersed in the acid solution 2 The acidic gelatin solution was added dropwise. Preferably, the acidic gelatin solution is a hydrochloric acid-gelatin solution, and the pH of hydrochloric acid is 1-5.
In some embodiments, the TiO of step 1) 2 The reaction time with the acidic gelatin solution is 25-35min; the method comprises the steps of carrying out a first treatment on the surface of the The reaction time for continuous reaction with epoxy trimethoxy silane and silane coupling agent is 25-35min; the pH is adjusted to 7-11; the reaction time of the reaction after the adjustment of the pH is 7-9h. More specifically, tiO 2 The reaction time with the acidic gelatin solution is 25-27min, 27-30min, 30-33min or 33-35min; 1A) The reaction time for continuous reaction with epoxy trimethoxy silane and silane coupling agent is 25-27min, 27-30min, 30-33min or 33-35min; the pH is adjusted to 7-8, 8-9, 9-10 or 10-11.
The silane coupling agent is selected from one or more of tetraethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (. Beta. -methoxyethoxy) silane and 3- (methacryloyloxy) propyltrimethoxysilane.
In some embodiments, the solvent for each of step 2) is methanol.
In some embodiments, in step 2), the gelatin-TiO in step 1) is based on the total volume of the reaction solution of step 2) 2 The composite material is 40-100g/L; the dosage of the acrylamide is 10-70g/L; the amount of the initiator is 0.1-2% of the sum of the mass of the dry matter and the mass of the acrylamide. More specifically, the aforementioned gelatin-TiO 2 The dosage of the composite material is 40-50g/L, 50-60g/L, 60-70g/L, 70-80g/L, 80-90g/L or 90-100g/L; the dosage of the acrylamide is 10-20g/L, 20-30g/L, 30-40g/L, 40-50g/L, 50-60g/L or 60-70g/L; the initiator is used in an amount of 0.1-0.5%, 0.5-1%, 1-1.5% or 1.5-2%.
In some embodiments, the aforementioned initiator is one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, t-butyl peroxybenzoate.
In some embodiments, the temperature of the mixing in step 2) is 55-85 ℃; heating the solution from 20-30 ℃ to 55-85 ℃ at a heating rate of 0.5-1.5 ℃/min in the mixed heating process; mixing for 5-7h; mixing and reacting under the condition of protective gas; the separation time is 22-26h. More specifically, the mixing temperature is 55-60deg.C, 60-65deg.C, 65-70deg.C, 70-75deg.C, 75-80deg.C or 80-85deg.C; the temperature rising speed is 0.5-0.7 ℃/min, 0.7-1 ℃/min, 1-1.2 ℃/min or 1.2-1.5 ℃/min; the separation time is 22-23h, 23-24h, 24-25h or 25-26h.
In some embodiments, the shielding gas is nitrogen. The separation method is extraction. The extractant used for extraction is one or more selected from N, N-dimethylformamide, dimethyl sulfoxide, ethyl acetate and pyridine.
The invention also provides the cation adsorbent prepared by the preparation method.
The cationic adsorbent is a polymer with a semi-interpenetrating network structure, as shown in fig. 1. Specifically, the polymer of the semi-interpenetrating network structure is a crosslinked polymer: gelatin and linear polymers: polyacrylamide is integrated to form a polymer.
The invention also provides application of the cation adsorbent in heavy metal ion adsorption or flocculation dehydration.
Preferably, the heavy metal ions adsorbed by the cation adsorbent are one or more selected from cadmium ions, mercury ions, iron ions, cobalt ions, zinc ions, copper ions, lead ions and nickel ions.
In some embodiments, the foregoing flocculation dewatering is flocculation dewatering in sludge.
The invention also provides a method for adsorbing heavy metal ions in sludge or flocculating and dehydrating, which is to add the cation adsorbent into sludge.
In some embodiments, the cationic adsorbent is added in the amount of 2-6g/L in the foregoing process. More specifically, the aforementioned addition amount is 2-3g/L, 3-4g/L, 4-5g/L or 5-6g/L.
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention; in the description and claims of the invention, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.
Example 1 preparation of cationic adsorbent A and Metal cationic curing Experimental results
8g of TiO 2 (Aladin company product number T299718 or T298674) nanometer powder is dispersed in 100mL hydrochloric acid solution with pH of 3.0, stirring for reaction, 10mL gelatin solution with concentration of 0.8g/mL is added dropwise into the solution, reaction is carried out for 30min, then 6mL epoxy trimethoxysilane and 0.22mL tetraethoxysilane are added, and the mixture is fully mixedStirring at room temperature for 30min, then dropwise adding ammonia water into the reaction system, adjusting the pH of the solution to 9, and continuing stirring for reacting for 8h to obtain gelatin-TiO 2 Washing the nano material solution with deionized water for many times to neutrality, and drying for later use.
100ml of methanol was added to a 500ml four-necked round bottom flask equipped with a magnetic stirring apparatus and a reflux condenser, and 7.5g of gelatin-TiO were added in sequence in proportion 2 Nanometer material, 5g acrylamide and 0.05g azodiisobutyronitrile, and stirring continuously for 15min to fully and uniformly mix the above reagents; introducing nitrogen into the reactor, heating the solution to 60 ℃ at a heating rate of 1 ℃/min, and stirring at constant temperature for 6 hours under the nitrogen atmosphere to obtain a mixed solution; adding an extractant (N, N-dimethylformamide: water=1:1) into the mixed solution, extracting for 24 hours, and finally drying the obtained nanocomposite at 80 ℃ to obtain gelatin-TiO 2 Nanoparticle and polyacrylamide grafted cation adsorbent A.
The sediment of a river or a lake of six amperes is taken as a simulation sample, and the water content of the raw mud is 80.2 percent. The water content is obtained by comparing the mud cake with the undried mud cake in a 105-DEG oven, and the calculation formula is as follows: (weight before drying-weight after drying)/weight before drying 100%. The gelatin-TiO prepared by the method 2 The nano composite material modified semi-interpenetrating network type cation adsorbent A is added into the sediment to carry out sediment dehydration experiment and heavy metal solidification leaching experiment (heavy metal leaching concentration after testing sediment sample maintenance for 7 days), and the addition amount of the adsorbent is 4g/L. The experimental results are: the water content of the mud cake is reduced to 66.0% from 80.2% of the original mud; the concentration of heavy metals Pb (II) and Ni (II) in the sludge leaching liquid is respectively reduced from 9.8mg/L and 35.4mg/L to 1.6mg/L and 6.7mg/L, which are respectively reduced by 83.9 percent and 81.1 percent.
EXAMPLE 2 preparation of cationic adsorbent B and Metal cation adsorption experiment results
8g of TiO 2 (Aladin company product No. T299718 or T298674) nanometer powder is dispersed in 100mL hydrochloric acid solution with pH of 3.0, stirring for reaction, adding 55mL gelatin solution with 0.12g/mL concentration dropwise for 30min, and adding 7.5mL epoxy trimethoxysilane and 0.28mL tetraethoxysilaneFully mixing, stirring at room temperature for 30min, then dropwise adding ammonia water into the reaction system, regulating the pH of the solution to 9, and continuously stirring for reaction for 8h to obtain gelatin-TiO 2 Washing the nano material solution with deionized water for many times to neutrality, and drying for later use.
100ml of methanol was added to a 500ml four-necked round bottom flask equipped with a magnetic stirring apparatus and a reflux condenser, and 7.5g of gelatin-TiO were added in sequence in proportion 2 Nanometer material, 4g acrylamide and 0.04g azodiisoheptonitrile, and stirring continuously for 15min to mix the above reagents completely and uniformly; introducing nitrogen into the reactor, heating the solution to 60 ℃ at a heating rate of 1 ℃/min, and stirring at constant temperature for 6 hours under the nitrogen atmosphere to obtain a mixed solution; adding an extractant (dimethyl sulfoxide: water=1:1) into the mixed solution, extracting for 24 hours, and finally drying the obtained nanocomposite at 80 ℃ to obtain gelatin-TiO 2 And (3) a cationic adsorbent B grafted by nano particles and polyacrylamide.
The method for obtaining the water content by taking the bottom mud of a river and a lake with six amperes as a simulation sample and the water content of the raw mud with 80.2 percent is the same as that of the embodiment 1. gelatin-TiO prepared in example 2 above 2 The nano composite material modified semi-interpenetrating network type cationic pollutant adsorbent is added into the sediment for a sediment dehydration experiment and a heavy metal solidification leaching experiment (the heavy metal leaching concentration after the sediment sample is tested and maintained for 7 days), and the addition amount of the adsorbent is 4g/L. The experimental results are: the water content of the mud cake is reduced to 67.3% from 80.2% of the original mud; the concentration of heavy metals Pb (II) and Ni (II)) in the sludge leaching liquid is respectively reduced from 9.8mg/L and 35.4mg/L to 1.7mg/L and 6.9mg/L, which are respectively reduced by 82.7 percent and 80.5 percent.
EXAMPLE 3 preparation of cationic adsorbent C and Metal cation adsorption experiment results
5g of TiO 2 Dispersing (Aladin company product number T299718 or T298674) nanometer powder in 100mL hydrochloric acid solution with pH of 3.0, stirring for reacting, dropwise adding 50mL gelatin solution with concentration of 0.10g/mL for 30min, adding 9mL epoxy trimethoxysilane and 0.21mL vinyl trimethoxysilane, mixing thoroughly, stirring at room temperature for 30min, adding ammonia water dropwise into the reaction system, adjusting pH to 9, and continuouslyContinuously stirring and reacting for 8 hours to obtain gelatin-TiO 2 Washing the nano material solution with deionized water for many times to neutrality, and drying for later use.
100ml of methanol was added to a 500ml four-necked round bottom flask equipped with a magnetic stirring apparatus and a reflux condenser, and 8.0g of gelatin-TiO were added in sequence in proportion 2 Nanometer material, 5g acrylamide and 0.05g dimethyl azodiisobutyrate, and stirring continuously for 15min to fully and uniformly mix the above reagents; introducing nitrogen into the reactor, heating the solution to 65 ℃ at a heating rate of 1 ℃/min, and stirring at constant temperature for 6 hours under the nitrogen atmosphere to obtain a mixed solution; adding an extractant (pyridine: water=1:1) into the mixed solution, extracting for 24 hours, and finally drying the obtained nanocomposite at 80 ℃ to obtain gelatin-TiO 2 And (3) a cationic adsorbent C grafted by nano particles and polyacrylamide.
The water content of the sludge of a river or a lake in the Shanghai is 80.2% by using the sludge as a simulation sample, and the water content is obtained in the same manner as in example 1.. The gelatin-TiO prepared by the method 2 The nano composite material modified semi-interpenetrating network type cation adsorbent C is added into the sediment to carry out sediment dehydration experiment and heavy metal solidification leaching experiment (heavy metal leaching concentration after testing sediment sample maintenance for 7 days), and the addition amount of the adsorbent is 4g/L. The experimental results are: the water content of the mud cake is reduced from 79.1% of the original mud to 65.9%; the concentration of heavy metals Pb (II) and Ni (II)) in the sludge leaching liquid is respectively reduced from 10.3mg/L and 34.8mg/L to 1.6mg/L and 6.6mg/L, and respectively reduced by 84.5 percent and 81.0 percent.
The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. Further, various modifications of the methods set forth herein, as well as variations of the methods of the invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.
Claims (10)
1. A method for preparing a cation adsorbent, which is characterized by comprising the steps of mixing acrylamide with gelatin-TiO 2 The composite material reacts to obtain the cation adsorbent.
2. The method of preparation according to claim 1, characterized in that it comprises the steps of:
1) gelatin-TiO 2 Preparing a composite material:
1A) TiO is mixed with 2 Mixing with gelatin in acidic environment; preferably, the TiO is dispersed in an acid solution 2 Mixing with acidic gelatin solution;
1B) Mixing epoxy trimethoxy silane and silane coupling agent with the system in the step 1A), adjusting pH, and reacting to obtain gelatin-TiO 2 A composite material;
2) Cation adsorbent preparation: combining acrylamide and an initiator with the gelatin-TiO of step 1) 2 And (3) after the composite material is subjected to a mixing reaction, separating to obtain the cation adsorbent.
3. The method according to claim 2, wherein in step 1), the gelatin is used in an amount of 60 to 140g/L based on the total volume of the reaction liquid in step 1); and/or, tiO 2 The mass of the (B) is 0.8-1.7 times of the mass of the gelatin; and/or the dosage of the epoxy trimethoxysilane is 40-100ml/L; and/or the silane coupling agent is used in an amount of TiO 2 0.1% -6% of the mass; and/or, in step 1), tiO 2 The pH of the reaction with gelatin solution is 1-5; and/or, tiO 2 The reaction time with gelatin solution is 25-35min; and/or, 1A) continuously reacting with epoxy trimethoxy silane and a silane coupling agent for 25-35min; and/or adjusting the pH to 7-11; and/or the reaction time after pH adjustment is 7-9h.
4. The method of preparing according to claim 2, wherein the silane coupling agent is selected from one or more of tetraethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, and 3- (methacryloyloxy) propyltrimethoxysilane.
5. The process according to claim 2, wherein in step 2), the total volume of the reaction liquid in step 2) is taken as a reference, and the gelatin-TiO in step 1) is 2 The dosage of the dry matter of the composite material is 40-100g/L; and/or the dosage of acrylamide is 10-70g/L; and/or the amount of the initiator is 0.1-2% of the sum of the mass of the dry matter and the mass of the acrylamide.
6. The preparation method according to claim 2, wherein the initiator in the step 2) is one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide and tert-butyl peroxybenzoate.
7. The method according to claim 2, wherein the temperature of the mixing reaction in step 2) is 55 to 85 ℃;
and/or heating the solution from 20-30 ℃ to 55-85 ℃ at a heating rate of 0.5-1.5 ℃/min in the heating process of the mixing reaction; and/or, mixing and reacting under the condition of protective gas; and/or mixing reaction time is 5-7h; and/or the separation time is 22-26h.
8. A cationic adsorbent, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the cationic adsorbent of claim 8 for adsorption of heavy metal ions or flocculation dehydration.
10. A method for adsorbing heavy metal ions in sludge or flocculating and dewatering, which is characterized in that the cationic adsorbent of claim 8 is added into the sludge.
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