CN112588270B - Preparation method and application of attapulgite composite adsorbent material - Google Patents

Preparation method and application of attapulgite composite adsorbent material Download PDF

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CN112588270B
CN112588270B CN202011167500.6A CN202011167500A CN112588270B CN 112588270 B CN112588270 B CN 112588270B CN 202011167500 A CN202011167500 A CN 202011167500A CN 112588270 B CN112588270 B CN 112588270B
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attapulgite
silica gel
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CN112588270A (en
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谭立强
陈梓
徐婷婷
许莹
马喜君
彭喜花
谷亚昕
胡涛
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Huaiyin Institute of Technology
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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
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

Abstract

The invention discloses a preparation method and application of an attapulgite composite adsorbent material, wherein attapulgite is used as a raw material, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane is subjected to modification treatment to obtain amino-modified attapulgite, and glutaric anhydride and ferric chloride are added for further modification treatment to obtain carboxyl-modified magnetic attapulgite; then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution; and finally inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the compound feed. The adsorbent material can effectively remove dyes and heavy metals in printing and dyeing wastewater.

Description

Preparation method and application of attapulgite composite adsorbent material
Technical Field
The invention relates to a preparation method and application of an adsorbent, in particular to a preparation method and application of an attapulgite composite adsorbent.
Background
In recent years, the problem of environmental pollution caused by industrial wastewater is more and more serious, and the serious threat to human health and human survival is caused. The textile wastewater is mainly wastewater containing natural impurities, fat, starch and other organic matters generated in the processes of raw material cooking, rinsing, bleaching, sizing and the like; the printing and dyeing wastewater is generated in a plurality of processes such as washing, dyeing, printing, sizing and the like, contains inorganic pollutants (alkali, sulfide, various salts and the like) and a large amount of organic matters which are difficult to degrade (dye, starch, cellulose, lignin, detergent and the like), is mostly aromatic compounds, has chromogenic groups and has strong pollution. In addition, the printing and dyeing wastewater contains a lot of heavy metals, so that the environmental pollution is serious, and the treatment is particularly difficult.
At present, the treatment methods of printing and dyeing wastewater mainly comprise coagulation, adsorption, catalytic oxidation and the like. Coagulation is generally used for pretreatment, adsorption is generally used for advanced treatment of final effluent, and the quality of the final effluent is directly controlled; the catalytic oxidation is less adopted due to high cost; the adsorption method is an effective method for removing pollutants in water by utilizing porous solid substances. The adsorbent is usually a solid substance, is easy to remove by solid-liquid separation after water treatment, generally does not cause secondary pollution to the environment, and has better effect on advanced treatment of printing and dyeing wastewater. The traditional adsorbent is activated carbon, which has strong adsorption capacity and high removal rate, but the regeneration efficiency of the activated carbon is low, the treated water quality hardly meets the recycling requirement, the cost is high, and the application is limited.
Patent CN102211015A discloses a printing and dyeing wastewater adsorbent, which is a cyclodextrin functionalized graphene nano material, and the preparation method thereof comprises the following steps: treating graphite powder with strong acid and strong oxidant, ultrasonically stripping to obtain graphene oxide, adding cyclodextrin, and reducing to obtain cyclodextrin functionalized graphene. The adsorbent is used for treating printing and dyeing wastewater, and the removal rate of dye in the printing and dyeing wastewater can reach more than 96%. However, the adsorbent is mainly suitable for treatment of printing and dyeing wastewater generated from azo dyes, reactive dyes, triphenylmethane dyes, phthalocyanine dyes or anthraquinone dyes, and has a limited adsorption capacity for heavy metals.
Disclosure of Invention
The purpose of the invention is as follows: one of the purposes of the invention is to provide a preparation method of an attapulgite composite adsorbent material, which is used for treating printing and dyeing wastewater and can simultaneously realize the efficient removal of dyes and heavy metals in the printing and dyeing wastewater; the invention also aims to provide the application of the attapulgite composite adsorbent material.
The technical scheme is as follows: the invention relates to a preparation method of an attapulgite composite adsorbent material, which comprises the following steps:
(1) The pretreated attapulgite is used as a raw material, and a carboxyl modified magnetic attapulgite material is obtained through modification treatment;
(2) Taking carboxyl modified magnetic attapulgite, coconut shell powder, silica gel with surface hydroxyl modified and acrylic acid premixed liquid as raw materials, and carrying out polymerization reaction to obtain mixed liquid;
(3) Inoculating Candida utilis and Rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding, and sieving.
Wherein, in the step (1), the pretreatment of the attapulgite comprises grinding after removing impurities; adding attapulgite into a solvent, removing precipitates after ultrasonic oscillation, taking a suspension, performing microwave treatment, drying and grinding. The specific method comprises the following steps: adding attapulgite into water with the weight of 4-6 times of that of the attapulgite, carrying out ultrasonic oscillation at 500-800W for 50-80 minutes, standing for 20-30 minutes, carrying out solid-liquid separation to remove bottom sediment, retaining suspension, carrying out microwave treatment at 500-800W for 5-8 minutes, drying and grinding to below 1 mm.
In the step (1), the modification treatment comprises: the attapulgite is modified by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then glutaric anhydride and ferric chloride are added for further modification treatment to obtain carboxyl modified magnetic attapulgite.
Further, the preparation method of the amino modified attapulgite comprises the following steps: adding 0.01-0.02 part of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.008-0.01 part of attapulgite into 2-4 parts of solvent by weight, stirring and reacting for 8-12 hours at 60-80 ℃ under the atmosphere of inert gas, and centrifuging to obtain the catalyst. Optionally, the solvent is an aqueous solution of absolute ethanol.
Further, the preparation method of the carboxyl modified magnetic attapulgite comprises the following steps: according to parts by weight, 1 part of amino modified attapulgite is added into 10 to 15 parts of dimethylformamide, 1.5 to 2.2 parts of glutaric anhydride and 0.02 to 0.03 part of ferric chloride are added after ultrasonic treatment, stirred and reacted for 50 to 70 minutes at the temperature of 100 to 120 ℃, and then centrifuged, thus obtaining the modified attapulgite. Wherein the ultrasonic treatment is 500-800W ultrasonic oscillation for 40-60 minutes.
Wherein, in the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 3-5: 0.1-0.2: 0.3-0.4. The material proportion is related to the formation of a three-dimensional net structure, so that the adsorption and chelation effects on heavy metals, dye molecules and the like are influenced, and the adsorption effect of a product is influenced.
In the step (2), the polymerization conditions are as follows: stirring and reacting for 3-5 hours at 65-68 ℃.
Wherein, the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: firstly, naturally airing fresh coconut shells for 5-6 days under the sunlight condition, then cutting the coconut shells into small sections with the length of 1-2 cm, and mechanically crushing the coconut shells.
The preparation method of the acrylic acid premix comprises the following steps: according to parts by weight, 1 part of acrylic acid is stirred and dripped into 2-3 parts of 25-35% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then 0.008-0.01 part of N, N' -methylene bisacrylamide is added, the mixture is stirred in water bath at 60 ℃ until the mixture is dissolved, and finally 0.001-0.002 part of potassium persulfate is added, so that the acrylic acid premix is obtained. A large amount of carbon-carbon double bonds brought by the acrylic acid premixed solution are subjected to polymerization reaction, and meanwhile, amino groups brought by the acrylic acid premixed solution can chelate heavy metals, dye molecules and the like.
In the step (2), the preparation method of the surface hydroxylation modified silica gel comprises the following steps: activating silica gel, adding the activated silica gel into a tetramethylammonium hydroxide solution with the mass concentration of 12-15% and the weight of 0.8-1.2 times of the activated silica gel, reacting for 4-6 hours at the temperature of 130-140 ℃, filtering and washing to obtain the catalyst. The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by using deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (3), the fermentation treatment comprises: firstly, inoculating candida utilis and rhizopus oryzae in malt extract agar culture medium respectively, culturing to obtain candida utilis seed liquor and rhizopus oryzae seed liquor, then inoculating them into mixed liquor, fermenting for 2-3 hr at 32-35 deg.C.
Wherein, the inoculation amount (volume) of the candida utilis seed liquid and the rhizopus oryzae seed liquid in the mixed liquid is 5-8 percent and 2-3 percent respectively.
The preparation method of the candida utilis seed liquid comprises the following steps: inoculating the candida utilis into a malt extract agar culture medium, culturing for 18-22 hours at 28-32 ℃, rotating the shaking table at 200-250 rpm, and stopping culturing until logarithmic phase to obtain the candida utilis seed solution.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, the rhizopus oryzae is inoculated in a malt extract agar culture medium, the culture is carried out for 16 to 20 hours at the temperature of between 35 and 37 ℃, the rotation speed of a shaking table is 200 to 250rpm, and the culture is stopped when the culture reaches the logarithmic phase, thus obtaining the rhizopus oryzae seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 60-80 deg.c for 6-9 hr; grinding and sieving with a 200-300 mesh sieve.
The invention also provides application of the attapulgite composite adsorbent material in printing and dyeing wastewater treatment, wherein the attapulgite composite adsorbent material is prepared by the preparation method.
The method comprises the steps of firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino-modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl-modified magnetic attapulgite; then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution; and inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material which can be used for treating printing and dyeing wastewater and realizing the efficient removal of dyes and heavy metals in the printing and dyeing wastewater.
Has the advantages that:
(1) The attapulgite is a water-containing magnesium-aluminum-rich silicate clay mineral with a special chain lamellar structure, has a larger specific surface area due to a unique fibrous crystal structure and a natural nano channel, and has a certain adsorption capacity, but has a poor adsorption effect on dyes and heavy metals; according to the invention, the attapulgite is subjected to carboxyl modification, and ferric chloride is converted into magnetic ferroferric oxide in the process, so that the adsorbent material has magnetism and can be conveniently separated and removed after wastewater treatment is finished, thereby being recycled.
(2) And a large amount of carbon-carbon double bonds are polymerized by the acrylic acid premix, and meanwhile, amino groups brought by the acrylic acid premix have a chelating effect on heavy metals, dye molecules and the like. The attapulgite clay surface is modified with a large amount of carboxyl, the coconut shell powder contains a large amount of hydroxyl, the surface of the surface hydroxylation modified silica gel contains hydroxyl, the reaction between the hydroxyl and the carboxyl can be generated while the carbon-carbon double bond polymerization reaction is carried out, and finally, a three-dimensional network structure is formed by polymerization of the reactions, so that the specific surface area is further increased; in addition, the residue of part of the active groups also has adsorption and chelation effects on heavy metals, dye molecules and the like, and the adsorption effect is further improved by the combined action of the two aspects.
(3) The invention also accesses candida utilis and rhizopus oryzae for fermentation treatment, the candida utilis is fermented to generate a large amount of amino acid, the amino acid has good complexing action on heavy metal ions and can also generate glutathione, and the glutathione contains a large amount of amino, imino, hydroxyl and sulfydryl, so that the chelation action on the heavy metal ions and dye molecules is excellent; the rhizopus oryzae is fermented to produce organic acid, and has chelation effect on heavy metal, dye molecule, etc. In addition, rhizopus oryzae fermentation provides proper acidic conditions for candida utilis fermentation, promotes the generation of a large amount of glutathione, and improves the adsorption effect of products. Moreover, the fermentation products of the candida utilis and the rhizopus oryzae synergistically promote the adsorption effect on heavy metals and dye molecules.
(4) The invention can simultaneously realize the high-efficiency removal of dye and heavy metal in the printing and dyeing wastewater, the adsorption amount of different dye molecules is higher than 150mg/g, and the adsorption amount of mercury ions and chromium ions is higher than 165mg/g.
Detailed Description
The present invention is described in further detail below with reference to examples.
The reagents and materials in the following examples and comparative examples are all commercially available. Wherein, the candida utilis, ATCC22023, is purchased from Beinoco biotechnology limited company in Shanghai; rhizopus oryzae, ATCC 9638, available from Sichuan Rui Nuo Sa Biotech Co. Saccharomyces cerevisiae, ATCC204991, available from Tokyo, inc.
Example 1:
a preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution;
(3) And inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the attapulgite is pretreated firstly, and the specific method comprises the following steps: adding attapulgite into water with the weight of 4 times, carrying out ultrasonic oscillation at 800W for 50 minutes, standing for 30 minutes, carrying out solid-liquid separation to remove bottom precipitate, retaining suspension, carrying out microwave treatment at 500W for 8 minutes, drying and grinding to below 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 2kg of water, adding 0.02kg of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.008kg of attapulgite, stirring and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: adding 1kg of amino modified attapulgite into 15kg of dimethylformamide, carrying out 500W ultrasonic oscillation for 60 minutes, then adding 1.5kg of glutaric anhydride and 0.03kg of ferric chloride, stirring at 100 ℃, reacting for 70 minutes, and centrifuging to obtain the modified attapulgite modified amino acid.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 3: 0.2: 0.3.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 68 ℃ for 3 hours.
In the step (2), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 6 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 1cm, and mechanically crushing the small sections.
In the step (2), the surface hydroxylation modified silica gel is obtained by the following preparation method: activating silica gel, adding the activated silica gel into a 1.2-time-by-weight 12% tetramethylammonium hydroxide solution, reacting for 4 hours at 140 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25 mass percent sodium hydroxide solution under the condition of ice-water bath, then adding 0.01kg of N, N' -methylene-bisacrylamide, stirring and dissolving in water bath at 60 ℃, and finally adding 0.001kg of potassium persulfate to obtain the acrylic acid premix.
In the step (3), the fermentation method comprises the following specific steps: the Candida utilis and the rhizopus oryzae are respectively inoculated into a malt extract agar culture medium to be cultured to obtain Candida utilis seed solution and rhizopus oryzae seed solution, and then the Candida utilis seed solution and the rhizopus oryzae seed solution are inoculated into the mixed solution to be fermented for 2 hours at 35 ℃.
The inoculation amounts (volumes) of the candida utilis seed solution and the rhizopus oryzae seed solution in the mixed solution are respectively 8 percent and 2 percent.
The preparation method of the candida utilis seed liquid comprises the following steps: inoculating the candida utilis into a malt extract agar culture medium, culturing for 18 hours at 32 ℃, rotating the shaking table at 250rpm, and stopping culturing when the culture reaches logarithmic phase to obtain the candida utilis seed solution.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, the rhizopus oryzae is inoculated in a malt extract agar culture medium, the culture is carried out for 20 hours at 35 ℃, the rotating speed of a shaking table is 200rpm, and the culture is stopped when the culture reaches logarithmic phase, thus obtaining the rhizopus oryzae seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 80 deg.C for 6 hr; grinding and sieving with 300 mesh sieve.
Example 2:
a preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution;
(3) And inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the attapulgite is pretreated firstly, and the specific method comprises the following steps: adding attapulgite into 6 times of water by weight, performing ultrasonic oscillation at 500W for 80 minutes, standing for 20 minutes, performing solid-liquid separation to remove bottom precipitate, retaining suspension, performing microwave treatment at 800W for 5 minutes, drying, and grinding to below 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 3kg of water, adding 0.01kg of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.01kg of attapulgite, stirring and reacting for 12 hours at 60 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: adding 1kg of amino modified attapulgite into 10kg of dimethylformamide, carrying out ultrasonic oscillation at 800W for 40 minutes, then adding 2.2kg of glutaric anhydride and 0.02kg of ferric chloride, stirring at 120 ℃ for reaction for 50 minutes, and centrifuging to obtain the modified attapulgite modified mineral water.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 5: 0.1: 0.4.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 65 ℃ for 5 hours.
In the step (2), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 5 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 2cm, and mechanically crushing the small sections.
In the step (2), the surface hydroxylation modified silica gel is prepared by the following preparation method: activating silica gel, adding the activated silica gel into a tetramethylammonium hydroxide solution with the mass concentration of 15% and the weight of 0.8 time, reacting for 6 hours at 130 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: 1kg of acrylic acid is stirred and dripped into 2kg of sodium hydroxide solution with the mass concentration of 35% under the condition of ice-water bath, then 0.008kg of N, N' -methylene bisacrylamide is added, the mixture is stirred in water bath at the temperature of 60 ℃ until the mixture is dissolved, and finally 0.002kg of potassium persulfate is added, thus obtaining the acrylic acid premix.
In the step (3), the fermentation method comprises the following steps: the Candida utilis and the rhizopus oryzae are respectively inoculated into a malt extract agar culture medium to be cultured to obtain Candida utilis seed solution and rhizopus oryzae seed solution, and then the Candida utilis seed solution and the rhizopus oryzae seed solution are inoculated into the mixed solution to be fermented for 3 hours at 32 ℃.
The inoculation amounts (volumes) of the candida utilis seed solution and the rhizopus oryzae seed solution in the mixed solution are respectively 5 percent and 3 percent.
The preparation method of the candida utilis seed liquid comprises the following steps: inoculating the candida utilis into a malt extract agar culture medium, culturing for 22 hours at 28 ℃, rotating the shaking table at 200rpm, and stopping culturing when the culture reaches logarithmic phase to obtain the candida utilis seed solution.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, inoculating rhizopus oryzae into a malt extract agar culture medium, culturing for 16 hours at 37 ℃, rotating the rotary speed of a shaking table at 250rpm, and stopping culturing when the culture reaches logarithmic phase to obtain rhizopus oryzae seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 60 deg.C for 9 hr; grinding and sieving with 200 mesh sieve.
Example 3:
a preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution;
(3) And inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the attapulgite is pretreated firstly, and the specific method comprises the following steps: adding attapulgite into water with the weight 5 times that of the attapulgite, carrying out 700W ultrasonic oscillation for 60 minutes, standing for 25 minutes, carrying out solid-liquid separation to remove bottom sediment, retaining suspension, carrying out 750W microwave treatment for 6 minutes, drying and grinding to below 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 2.5kg of water, adding 0.015kg of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.009kg of attapulgite, stirring and reacting for 10 hours at 70 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: firstly, 1kg of amino modified attapulgite is added into 12kg of dimethylformamide, 750W of ultrasonic oscillation is carried out for 50 minutes, then 1.8kg of glutaric anhydride and 0.025kg of ferric chloride are added, stirring reaction is carried out for 60 minutes at 110 ℃, and centrifugation is carried out, thus obtaining the modified attapulgite.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 4: 0.15: 0.35.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 66 ℃ for 4 hours.
In the step (2), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 5 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 1.5cm, and mechanically crushing the small sections.
In the step (2), the surface hydroxylation modified silica gel is obtained by the following preparation method: activating silica gel, adding the activated silica gel into a 1-time-by-weight tetramethyl ammonium hydroxide solution with the mass concentration of 13%, reacting for 5 hours at 135 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dropping 1kg of acrylic acid into 2.5kg of sodium hydroxide solution with the mass concentration of 30% under the condition of ice-water bath, then adding 0.009kg of N, N' -methylene bisacrylamide, stirring and dissolving in water bath at 60 ℃, and finally adding 0.0015kg of potassium persulfate to obtain the acrylic acid premix.
In the step (3), the fermentation method comprises the following specific steps: the Candida utilis and the rhizopus oryzae are respectively inoculated into a malt extract agar culture medium to be cultured to obtain Candida utilis seed solution and rhizopus oryzae seed solution, and then the Candida utilis seed solution and the rhizopus oryzae seed solution are inoculated into the mixed solution to be fermented for 2.5 hours at 33 ℃.
The inoculation amounts (volumes) of the candida utilis seed liquid and the rhizopus oryzae seed liquid in the mixed liquid are respectively 6 percent and 2.5 percent.
The preparation method of the candida utilis seed liquid comprises the following steps: inoculating the candida utilis yeast into a malt extract agar culture medium, culturing for 20 hours at 30 ℃, rotating the shaking table at 220rpm, and stopping culturing when the culture reaches the logarithmic phase to obtain the candida utilis yeast seed solution.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, the rhizopus oryzae is inoculated in a malt extract agar culture medium, the culture is carried out for 18 hours at 36 ℃, the rotating speed of a shaking table is 220rpm, and the culture is stopped when the culture reaches logarithmic phase, thus obtaining the rhizopus oryzae seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 70 deg.C for 8 hr; grinding and sieving with 300 mesh sieve.
Comparative example 1:
a preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, carrying out polymerization reaction on attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution serving as raw materials to obtain mixed solution;
(2) And inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the mass ratio of the attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 3: 0.2: 0.3.
In the step (1), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 68 ℃ for 3 hours.
In the step (1), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 6 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 1cm, and mechanically crushing the small sections.
In the step (1), the surface hydroxylation modified silica gel is obtained by the following preparation method: activating silica gel, adding the activated silica gel into 1.2 times of 12% tetramethylammonium hydroxide solution by weight, reacting for 4 hours at 140 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (1), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of N, N' -methylene bisacrylamide, stirring in water bath at 60 ℃ until the acrylic acid is dissolved, and finally adding 0.001kg of potassium persulfate to obtain the acrylic acid premix.
In the step (2), the fermentation method comprises the following specific steps: the Candida utilis and the rhizopus oryzae are respectively inoculated into a malt extract agar culture medium to be cultured to obtain Candida utilis seed solution and rhizopus oryzae seed solution, and then the Candida utilis seed solution and the rhizopus oryzae seed solution are inoculated into the mixed solution to be fermented for 2 hours at 35 ℃.
The inoculation amounts (volumes) of the candida utilis seed liquid and the rhizopus oryzae seed liquid in the mixed liquid are 8 percent and 2 percent respectively.
The preparation method of the candida utilis seed solution comprises the following steps of: inoculating the candida utilis into a malt extract agar culture medium, culturing for 18 hours at 32 ℃, rotating the shaking table at 250rpm, and stopping culturing when the culture reaches logarithmic phase to obtain the candida utilis seed solution.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, inoculating rhizopus oryzae into a malt extract agar culture medium, culturing for 20 hours at 35 ℃, rotating the shaking table at 200rpm, and stopping culturing when the culture reaches logarithmic phase to obtain rhizopus oryzae seed solution.
In the step (2), the drying process conditions are as follows: vacuum drying at 80 deg.C for 6 hr; grinding and sieving with a 300-mesh sieve.
Comparative example 2:
a preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder and acrylic acid premixed liquid as raw materials to obtain mixed liquid;
(3) And inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the attapulgite is pretreated firstly, and the specific method is as follows: adding attapulgite into water with the weight of 4 times, carrying out ultrasonic oscillation at 800W for 50 minutes, standing for 30 minutes, carrying out solid-liquid separation to remove bottom precipitate, retaining suspension, carrying out microwave treatment at 500W for 8 minutes, drying and grinding to below 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 2kg of water, adding 0.02kg of N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane and 0.008kg of attapulgite, stirring and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: firstly, 1kg of amino modified attapulgite is added into 15kg of dimethylformamide, 500W of ultrasonic oscillation is carried out for 60 minutes, then 1.5kg of glutaric anhydride and 0.03kg of ferric chloride are added, stirring reaction is carried out for 70 minutes at 100 ℃, and centrifugation is carried out, thus obtaining the modified attapulgite.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder and the acrylic acid premixed solution is 1: 3: 0.3.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 68 ℃ for 3 hours.
In the step (2), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 6 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 1cm, and mechanically crushing the small sections.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of N, N' -methylene bisacrylamide, stirring in water bath at 60 ℃ until the acrylic acid is dissolved, and finally adding 0.001kg of potassium persulfate to obtain the acrylic acid premix.
In the step (3), the fermentation method comprises the following specific steps: the candida utilis and the rhizopus oryzae are respectively inoculated in malt extract agar culture media to be cultured to obtain candida utilis seed solution and rhizopus oryzae seed solution, and then the candida utilis seed solution and the rhizopus oryzae seed solution are inoculated into mixed liquor to be fermented for 2 hours at 35 ℃.
The inoculation amounts (volumes) of the candida utilis seed solution and the rhizopus oryzae seed solution in the mixed solution are respectively 8 percent and 2 percent.
The preparation method of the candida utilis seed liquid comprises the following steps: inoculating the candida utilis yeast into a malt extract agar culture medium, culturing for 18 hours at 32 ℃, rotating the shaking table at 250rpm, and stopping culturing when the culture reaches the logarithmic phase to obtain the candida utilis yeast seed solution.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, inoculating rhizopus oryzae into a malt extract agar culture medium, culturing for 20 hours at 35 ℃, rotating the shaking table at 200rpm, and stopping culturing when the culture reaches logarithmic phase to obtain rhizopus oryzae seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 80 deg.C for 6 hr; grinding and sieving with a 300-mesh sieve.
Comparative example 3:
a preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, carboxyl modified magnetic attapulgite, surface hydroxylation modified silica gel and acrylic acid premixed solution are used as raw materials, polymerization reaction, filtering, drying, grinding and sieving are carried out, and the attapulgite composite adsorbent material is obtained.
In the step (1), the attapulgite is pretreated firstly, and the specific method comprises the following steps: adding attapulgite into water with the weight of 4 times, carrying out ultrasonic oscillation at 800W for 50 minutes, standing for 30 minutes, carrying out solid-liquid separation to remove bottom precipitate, retaining suspension, carrying out microwave treatment at 500W for 8 minutes, drying and grinding to below 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 2kg of water, adding 0.02kg of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.008kg of attapulgite, stirring and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: firstly, 1kg of amino modified attapulgite is added into 15kg of dimethylformamide, 500W of ultrasonic oscillation is carried out for 60 minutes, then 1.5kg of glutaric anhydride and 0.03kg of ferric chloride are added, stirring reaction is carried out for 70 minutes at 100 ℃, and centrifugation is carried out, thus obtaining the modified attapulgite.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 0.2: 0.3.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 68 ℃ for 3 hours.
In the step (2), the surface hydroxylation modified silica gel is obtained by the following preparation method: activating silica gel, adding the activated silica gel into 1.2 times of 12% tetramethylammonium hydroxide solution by weight, reacting for 4 hours at 140 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25 mass percent sodium hydroxide solution under the condition of ice-water bath, then adding 0.01kg of N, N' -methylene-bisacrylamide, stirring and dissolving in water bath at 60 ℃, and finally adding 0.001kg of potassium persulfate to obtain the acrylic acid premix.
Comparative example 4:
this comparative example is essentially the same as example 1, except that the fermenting species is Saccharomyces cerevisiae.
A preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution;
(3) And then adding saccharomyces cerevisiae (ATCC 204991, purchased from Shanghai Xuan Biotechnology Co., ltd.) and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the attapulgite is pretreated firstly, and the specific method comprises the following steps: adding attapulgite into water with the weight of 4 times, carrying out ultrasonic oscillation at 800W for 50 minutes, standing for 30 minutes, carrying out solid-liquid separation to remove bottom precipitate, retaining suspension, carrying out microwave treatment at 500W for 8 minutes, drying and grinding to below 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 2kg of water, adding 0.02kg of N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane and 0.008kg of attapulgite, stirring and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: adding 1kg of amino modified attapulgite into 15kg of dimethylformamide, carrying out 500W ultrasonic oscillation for 60 minutes, then adding 1.5kg of glutaric anhydride and 0.03kg of ferric chloride, stirring at 100 ℃, reacting for 70 minutes, and centrifuging to obtain the modified attapulgite modified amino acid.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 3: 0.2: 0.3.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 68 ℃ for 3 hours.
In the step (2), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 6 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 1cm, and mechanically crushing the small sections.
In the step (2), the surface hydroxylation modified silica gel is obtained by the following preparation method: activating silica gel, adding the activated silica gel into a 1.2-time-by-weight 12% tetramethylammonium hydroxide solution, reacting for 4 hours at 140 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of N, N' -methylene bisacrylamide, stirring in water bath at 60 ℃ until the acrylic acid is dissolved, and finally adding 0.001kg of potassium persulfate to obtain the acrylic acid premix.
In the step (3), the fermentation method comprises the following specific steps: firstly, respectively inoculating saccharomyces cerevisiae and rhizopus oryzae in a malt extract agar culture medium, culturing to obtain saccharomyces cerevisiae seed liquid and rhizopus oryzae seed liquid, inoculating the saccharomyces cerevisiae seed liquid and rhizopus oryzae seed liquid into the mixed liquid, and fermenting for 2 hours at 35 ℃.
The inoculation amounts (volumes) of the saccharomyces cerevisiae seed solution and the rhizopus oryzae seed solution in the mixed solution are 8 percent and 2 percent respectively.
The preparation method of the saccharomyces cerevisiae seed liquid comprises the following steps: firstly, inoculating the saccharomyces cerevisiae into a malt extract agar culture medium, culturing for 18 hours at 32 ℃, rotating the rotary speed of a shaking table at 250rpm, and stopping culturing when the saccharomyces cerevisiae is cultured to a logarithmic phase to obtain saccharomyces cerevisiae seed liquid.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, inoculating rhizopus oryzae into a malt extract agar culture medium, culturing for 20 hours at 35 ℃, rotating the shaking table at 200rpm, and stopping culturing when the culture reaches logarithmic phase to obtain rhizopus oryzae seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 80 deg.C for 6 hr; grinding and sieving with a 300-mesh sieve.
Comparative example 5:
the comparative example is substantially the same as example 1, except that only Candida utilis was added without Rhizopus oryzae during the fermentation treatment.
A preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution;
(3) And inoculating candida utilis into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the attapulgite is pretreated firstly, and the specific method comprises the following steps: adding attapulgite into water with the weight of 4 times of that of the attapulgite, carrying out ultrasonic oscillation at 800W for 50 minutes, standing for 30 minutes, carrying out solid-liquid separation to remove bottom sediment, retaining suspension, carrying out microwave treatment at 500W for 8 minutes, drying and grinding to be less than 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 2kg of water, adding 0.02kg of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.008kg of attapulgite, stirring and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: adding 1kg of amino modified attapulgite into 15kg of dimethylformamide, carrying out 500W ultrasonic oscillation for 60 minutes, then adding 1.5kg of glutaric anhydride and 0.03kg of ferric chloride, stirring at 100 ℃, reacting for 70 minutes, and centrifuging to obtain the modified attapulgite modified amino acid.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 3: 0.2: 0.3.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 68 ℃ for 3 hours.
In the step (2), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 6 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 1cm, and mechanically crushing the small sections.
In the step (2), the surface hydroxylation modified silica gel is prepared by the following preparation method: activating silica gel, adding the activated silica gel into 1.2 times of 12% tetramethylammonium hydroxide solution by weight, reacting for 4 hours at 140 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by using deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then adding 0.01kg of N, N' -methylene bisacrylamide, stirring in water bath at 60 ℃ until the acrylic acid is dissolved, and finally adding 0.001kg of potassium persulfate to obtain the acrylic acid premix.
In the step (3), the fermentation method comprises the following specific steps: inoculating candida utilis to a malt extract agar culture medium, culturing to obtain candida utilis seed solution, inoculating to the mixed solution, and fermenting for 2 hours at 35 ℃.
The inoculation amount (volume) of the candida utilis seed liquid in the mixed liquid is 8 percent.
The preparation method of the candida utilis seed liquid comprises the following steps: inoculating the candida utilis into a malt extract agar culture medium, culturing for 18 hours at 32 ℃, rotating the shaking table at 250rpm, and stopping culturing when the culture reaches logarithmic phase to obtain the candida utilis seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 80 deg.C for 6 hr; grinding and sieving with 300 mesh sieve.
Comparative example 6:
the comparative example is substantially the same as example 1, except that in step (2), the mass ratio of the carboxyl-modified magnetic attapulgite, the coconut shell powder, the surface-hydroxylated-modified silica gel and the acrylic acid premix is 1: 6: 0.1: 0.5.
A preparation method of an attapulgite composite adsorbent material comprises the following specific steps:
(1) Firstly, taking attapulgite as a raw material, carrying out modification treatment on the attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and then adding glutaric anhydride and ferric chloride for further modification treatment to obtain carboxyl modified magnetic attapulgite;
(2) Then, performing polymerization reaction by taking carboxyl modified magnetic attapulgite, coconut shell powder, surface hydroxylation modified silica gel and acrylic acid premixed solution as raw materials to obtain mixed solution;
(3) And inoculating candida utilis and rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding and sieving to obtain the attapulgite composite adsorbent material.
In the step (1), the attapulgite is pretreated firstly, and the specific method comprises the following steps: adding attapulgite into water with the weight of 4 times, carrying out ultrasonic oscillation at 800W for 50 minutes, standing for 30 minutes, carrying out solid-liquid separation to remove bottom precipitate, retaining suspension, carrying out microwave treatment at 500W for 8 minutes, drying and grinding to below 1 mm.
In the step (1), the amino modified attapulgite is prepared by the following method: mixing 1kg of absolute ethyl alcohol and 2kg of water, adding 0.02kg of N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane and 0.008kg of attapulgite, stirring and reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, and centrifuging to obtain the catalyst.
In the step (1), the carboxyl modified magnetic attapulgite is prepared by the following method: adding 1kg of amino modified attapulgite into 15kg of dimethylformamide, carrying out 500W ultrasonic oscillation for 60 minutes, then adding 1.5kg of glutaric anhydride and 0.03kg of ferric chloride, stirring at 100 ℃, reacting for 70 minutes, and centrifuging to obtain the modified attapulgite modified amino acid.
In the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1: 6: 0.1: 0.5.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was stirred at 68 ℃ for 3 hours.
In the step (2), the particle size of the coconut shell powder is less than 1mm, and the preparation method comprises the following steps: the method comprises the steps of naturally airing fresh coconut shells for 6 days under the sunlight condition, then cutting the fresh coconut shells into small sections with the length of 1cm, and mechanically crushing the small sections.
In the step (2), the surface hydroxylation modified silica gel is prepared by the following preparation method: activating silica gel, adding the activated silica gel into 1.2 times of 12% tetramethylammonium hydroxide solution by weight, reacting for 4 hours at 140 ℃, filtering and washing to obtain the catalyst.
The activation method of the silica gel comprises the following steps: firstly, soaking silica gel in 6mol/L hydrochloric acid solution for 4 hours, then washing the silica gel to be neutral by deionized water, and drying the silica gel for 2 hours at 130 ℃ to obtain the activated silica gel.
In the step (2), the preparation method of the acrylic acid premix liquid comprises the following steps: stirring and dripping 1kg of acrylic acid into 3kg of 25 mass percent sodium hydroxide solution under the condition of ice-water bath, then adding 0.01kg of N, N' -methylene-bisacrylamide, stirring and dissolving in water bath at 60 ℃, and finally adding 0.001kg of potassium persulfate to obtain the acrylic acid premix.
In the step (3), the fermentation method comprises the following steps: the Candida utilis and the rhizopus oryzae are respectively inoculated into a malt extract agar culture medium to be cultured to obtain Candida utilis seed solution and rhizopus oryzae seed solution, and then the Candida utilis seed solution and the rhizopus oryzae seed solution are inoculated into the mixed solution to be fermented for 2 hours at 35 ℃.
The inoculation amounts (volumes) of the candida utilis seed solution and the rhizopus oryzae seed solution in the mixed solution are respectively 8 percent and 2 percent.
The preparation method of the candida utilis seed liquid comprises the following steps: inoculating the candida utilis into a malt extract agar culture medium, culturing for 18 hours at 32 ℃, rotating the shaking table at 250rpm, and stopping culturing when the culture reaches logarithmic phase to obtain the candida utilis seed solution.
The preparation method of the rhizopus oryzae seed liquid comprises the following steps: firstly, inoculating rhizopus oryzae into a malt extract agar culture medium, culturing for 20 hours at 35 ℃, rotating the shaking table at 200rpm, and stopping culturing when the culture reaches logarithmic phase to obtain rhizopus oryzae seed solution.
In the step (3), the drying process conditions are as follows: vacuum drying at 80 deg.C for 6 hr; grinding and sieving with 300 mesh sieve.
Test example:
the adsorption performance of the adsorbent materials obtained in examples 1 to 3 and comparative examples 1 to 6 was measured for adsorption effect.
(1) Dye adsorption experiments:
respectively preparing 650 mg.L of acid pink FG (anionic dye), methyl orange (cationic dye) and disperse orange (disperse dye) -1 The simulated dye wastewater. Measuring 50mL of a simulated dye wastewater sample into a conical flask, respectively adding 0.2g of adsorbent material, standing for 3 hours, then carrying out magnetic separation, taking supernatant, measuring the initial and equilibrium dye concentrations of each water sample at the maximum absorption wavelength by using a spectrophotometer, and calculating the adsorption amount of the dye according to the following formula, wherein the results are shown in Table 1 below.
Wherein q is e ＝(C 0 -C e ) X V/m, wherein q e As adsorption amount, C 0 The original concentration (mg/L) of the dye solution, C e Is the equilibrium concentration (mg/L) of the dye solution, V is the volume (L) of the dye solution, and m is the addition amount (g) of the adsorbent.
TABLE 1 dye adsorption test results
Figure BDA0002744027200000141
Figure BDA0002744027200000151
(2) Adsorption experiment of heavy metal ions
Weighing 40mg of adsorbing material, respectively adding 20mL of 360mg/L heavy metal ion solution, standing for 3 hours, carrying out magnetic separation, and determining the concentration of metal ions in the solution. The amount of heavy metal adsorbed was calculated from the change in the metal ion concentration before and after adsorption according to the following formula, and the results are shown in Table 2.
Wherein q is e ＝(C 0 -C e ) X V/m; in the formula, q e As adsorption amount, C 0 Concentration of heavy metal ion before adsorption (mg/L), C e Is the concentration (mg/L) of the adsorbed metal ion, V is the volume (L) of the dye solution, and m is the addition amount (g) of the adsorbent.
TABLE 2 adsorption results of heavy metal ions
Mercury ion adsorption capacity (mg/g) Adsorption capacity of chromium ion (mg/g)
Example 1 167.1 175.3
Example 2 168.2 177.8
Example 3 170.4 179.2
Comparative example 1 114.3 111.5
Comparative example 2 119.2 116.8
Comparative example 3 123.5 122.9
Comparative example 4 115.8 121.6
Comparative example 5 110.7 116.4
Comparative example 6 119.2 125.8
As can be seen from tables 1 and 2, the adsorbent materials obtained in examples 1 to 3 have better adsorption effects on dye molecules and heavy metal ions; wherein, the adsorption capacity of different dye molecules is higher than 150mg/g, and the adsorption capacity of mercury ions and chromium ions is higher than 165mg/g.
In the comparative example 1, the attapulgite is used for replacing carboxyl modified magnetic attapulgite, so that the system compatibility is poor; comparative example 2 omits surface hydroxylation modified silica gel, and influences the construction of a three-dimensional network structure; comparative example 3 in the step (2), coconut shell powder was omitted and the fermentation step was omitted, and glutathione, organic acids, etc. were not produced, and the adsorption effect of the product was remarkably deteriorated. Comparative example 4, the candida utilis is replaced by the saccharomyces cerevisiae, and in the comparative example 5, rhizopus oryzae is omitted in the step (3), so that the adsorption effect of the product is obviously poor, and the adsorption effect is improved by the cooperation of the saccharomyces cerevisiae and the rhizopus oryzae in the fermentation treatment process; comparative example 6 in the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premix is 1: 6: 0.1: 0.5, so that the adsorption effect of the product is obviously poor, and the material ratio of the invention can obtain better adsorption effect.

Claims (8)

1. A preparation method of an attapulgite composite adsorbent material is characterized by comprising the following steps: the method comprises the following steps:
(1) The pretreated attapulgite is used as a raw material, and a magnetic attapulgite material modified by carboxyl is obtained through modification treatment;
(2) Taking carboxyl modified magnetic attapulgite, coconut shell powder, silica gel with surface hydroxyl modified and acrylic acid premixed liquid as raw materials, and carrying out polymerization reaction to obtain mixed liquid;
(3) Inoculating Candida utilis and Rhizopus oryzae into the mixed solution, fermenting, filtering, drying, grinding, and sieving to obtain the final product;
the modification treatment in the step (1) comprises the following steps: modifying attapulgite by N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to obtain amino modified attapulgite, and adding glutaric anhydride and ferric chloride for further modification to obtain carboxyl modified magnetic attapulgite;
in the step (2), the mass ratio of the carboxyl modified magnetic attapulgite, the coconut shell powder, the surface hydroxylation modified silica gel and the acrylic acid premixed solution is 1:3 to 5:0.1 to 0.2:0.3 to 0.4.
2. The method for preparing the attapulgite composite adsorbent material according to claim 1, wherein: the preparation method of the amino modified attapulgite comprises the following steps: adding 0.01-0.02 part of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.008-0.01 part of attapulgite into 2-4 parts of solvent by weight, stirring and reacting for 8-12 hours at 60-80 ℃ under the atmosphere of inert gas, and centrifuging to obtain the catalyst.
3. The method for preparing the attapulgite composite adsorbent material according to claim 1, wherein: the preparation method of the carboxyl modified magnetic attapulgite comprises the following steps: according to parts by weight, firstly adding 1 part of amino modified attapulgite into 10-15 parts of dimethylformamide, adding 1.5-2.2 parts of glutaric anhydride and 0.02-0.03 part of ferric chloride after ultrasonic treatment, stirring and reacting at 100-120 ℃ for 50-70 minutes, and centrifuging to obtain the modified attapulgite.
4. The method for preparing the attapulgite composite adsorbent material according to claim 1, wherein: in the step (2), the polymerization conditions are as follows: stirring and reacting for 3-5 hours at 65-68 ℃.
5. The method for preparing the attapulgite composite adsorbent material according to claim 1, wherein: in the step (2), the preparation method of the surface hydroxylation modified silica gel comprises the following steps: activating silica gel, adding the activated silica gel into a tetramethylammonium hydroxide solution with the mass concentration of 12-15% and the weight of 0.8-1.2 times of the activated silica gel, reacting for 4-6 hours at the temperature of 130-140 ℃, filtering and washing to obtain the catalyst.
6. The method for preparing the attapulgite composite adsorbent material according to claim 1, wherein: in the step (3), the fermentation treatment comprises: firstly, the candida utilis yeast and the rhizopus oryzae are respectively inoculated in a culture medium to be cultured to obtain candida utilis yeast seed solution and rhizopus oryzae seed solution, and then the candida utilis yeast seed solution and the rhizopus oryzae seed solution are inoculated into mixed solution to be fermented for 2 to 3 hours at the temperature of between 32 and 35 ℃.
7. The method for preparing the attapulgite composite adsorbent material according to claim 1, wherein: in the step (2), the preparation method of the acrylic acid premix comprises the following steps: according to parts by weight, 1 part of acrylic acid is stirred and dripped into 2-3 parts of 25-35% sodium hydroxide solution with mass concentration under the condition of ice-water bath, then 0.008-0.01 part of N, N' -methylene bisacrylamide is added, the mixture is stirred in water bath until being dissolved, and finally 0.001-0.002 part of potassium persulfate is added, so that the acrylic acid premix is obtained.
8. The use of the attapulgite composite adsorbent material prepared by the preparation method of any one of claims 1 to 7 in printing and dyeing wastewater treatment.
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CN106000359A (en) * 2016-07-09 2016-10-12 成都育芽科技有限公司 Adsorbent for treating petrochemical engineering wastewater and preparing method of adsorbent
CN107236071A (en) * 2017-05-27 2017-10-10 淮阴工学院 The preparation method and products obtained therefrom of the recessed native polystyrene resin of magnetic based on the recessed native surface modification of magnetic
CN110339825A (en) * 2019-07-25 2019-10-18 杭州电子科技大学 A kind of adsorbent and preparation method thereof suitable for textile printing and dyeing wastewater processing

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CN106000359A (en) * 2016-07-09 2016-10-12 成都育芽科技有限公司 Adsorbent for treating petrochemical engineering wastewater and preparing method of adsorbent
CN107236071A (en) * 2017-05-27 2017-10-10 淮阴工学院 The preparation method and products obtained therefrom of the recessed native polystyrene resin of magnetic based on the recessed native surface modification of magnetic
CN110339825A (en) * 2019-07-25 2019-10-18 杭州电子科技大学 A kind of adsorbent and preparation method thereof suitable for textile printing and dyeing wastewater processing

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