CN114471446B - Adsorption material, preparation method thereof, treatment method of dye wastewater and application thereof - Google Patents

Adsorption material, preparation method thereof, treatment method of dye wastewater and application thereof Download PDF

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Publication number
CN114471446B
CN114471446B CN202011164233.7A CN202011164233A CN114471446B CN 114471446 B CN114471446 B CN 114471446B CN 202011164233 A CN202011164233 A CN 202011164233A CN 114471446 B CN114471446 B CN 114471446B
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polyacrylamide
adsorbent material
adsorption
metal cations
impregnation
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CN114471446A (en
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胡潇雨
姜健准
殷杰
胡晨曦
随山红
孙姝琦
姚青
曾小强
白羽
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • B01J20/02—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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/28014—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 form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—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 relates to the technical field of adsorption separation, and discloses an adsorption material which comprises an alumina matrix, polyacrylamide supported on the alumina matrix and metal cations. The adsorption material provided by the invention has the advantages of high adsorption efficiency, large unit adsorption capacity, long continuous service life, simple preparation method, capability of being regenerated and reused for multiple times, stable performance after repeated use and the like. The method is particularly suitable for adsorption treatment of dye wastewater, and the treated wastewater can reach the standard of discharge or biochemical treatment, thereby being suitable for industrial mass production and application.

Description

Adsorption material, preparation method thereof, treatment method of dye wastewater and application thereof
Technical Field
The invention relates to the technical field of adsorption separation, in particular to an adsorption material, a preparation method thereof, a dye wastewater treatment method and application thereof.
Background
With the rapid development of textile industry, the variety and quantity of dye wastewater discharged into water bodies are increased, and the dye wastewater becomes one of heavy-point pollution sources of water environments. The dye wastewater has the characteristics of high water chromaticity, complex organic components, strong acid-base property, high salt content, low microbial degradation degree and the like, and is always a great difficulty in wastewater treatment of workers. For example, methyl red is an anionic organic dye commonly used in industry, and is widely used in textile, printing, dyeing, plastics and other fields. Methyl red is an anionic azo dye, the azo dye-containing waste water accounts for more than half of the total amount of printing and dyeing waste water, azo dye molecules have azo group structures, and degradation of the azo dye is difficult. At present, a large amount of waste water dye is generated in the fields of industrial papermaking, chemical industry, dyeing and weaving, and the like, so that the environmental problems of environmental pollution, reduced photosynthesis capability of aquatic plants and the like are caused, and the health problems of nausea, vomiting, cancer lesions and the like can be caused after human beings contact the waste water for a long time. Accordingly, there is a need for a method and product for effectively treating dye wastewater.
The adsorption separation technology is commonly used for treating dye wastewater, and has the characteristics of simple operation, low cost and the like, so that the technology is widely applied to industries at present. The adsorption material is the core and key of the adsorption separation technology, and the adsorption material commonly used at present mainly comprises high-porosity and high-specific surface area materials such as active carbon. However, although the activated carbon has a good adsorption effect, it cannot be reused, resulting in a problem of high adsorption separation cost. Furthermore, the adsorption efficiency, unit adsorption amount and continuous service life of the existing adsorption material are still to be further improved.
Disclosure of Invention
The invention aims to solve the problems that the adsorption material cannot be repeatedly used, has high cost, high adsorption efficiency, unit adsorption capacity, continuous service life and the like in the prior art, and provides an adsorption material which has the advantages of high adsorption efficiency, large unit adsorption capacity, long continuous service life, capability of being repeatedly regenerated and used for many times and the like.
In order to achieve the above object, an aspect of the present invention provides an adsorbent material comprising an alumina substrate and polyacrylamide and metal cations supported on the alumina substrate.
In a second aspect, the present invention provides a method for preparing an adsorbent material, the adsorbent material being as described above, the method comprising impregnating an alumina matrix in an impregnating solution comprising a polyacrylamide and a source of metal cations, and drying the impregnated product to obtain the adsorbent material.
In a third aspect the present invention provides a method of treating dye waste water, the method comprising contacting an adsorbent material with the waste water, wherein the adsorbent material is an adsorbent material as described above.
In a fourth aspect the present invention provides the use of an adsorbent material and method as described above in wastewater treatment.
Through the technical scheme, the invention has the following beneficial effects:
(1) The adsorption material provided by the invention has the advantages of simple preparation method, low cost and strong adaptability, and is suitable for industrial mass production and application;
(2) The adsorption material provided by the invention has the advantages of high adsorption efficiency, large unit adsorption capacity and long continuous service life;
(3) The adsorption material provided by the invention can be regenerated and reused for a plurality of times, and the performance is still stable after repeated use for a plurality of times;
(4) The adsorption material provided by the invention is particularly used for dye wastewater with complex components, and wastewater treated by using the adsorption material provided by the invention can reach the discharge standard or biochemical treatment standard.
Drawings
FIGS. 1 to 17 are graphs showing changes in the content of methyl red-methylene blue in the system when the adsorption materials obtained in examples 1 to 14 and comparative examples 1 to 2 were subjected to simulated adsorption experiments using the alumina honeycomb ceramics used in the examples;
FIG. 18 is a schematic diagram of a simulated wastewater treatment adsorption apparatus employed in test example 2;
FIG. 19 is a graph comparing the total removal of methyl red-methylene blue per test in test example 3.
Description of the reference numerals
1 is an adsorption material; 2 is a stirrer; 3 is a temperature control heating rod; 4 is a reaction tank; and 5 is a control cabinet.
Detailed Description
The following detailed description of the invention is given with the understanding that the present description is to be taken merely as an illustration and not a limitation of the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The inventor of the invention skillfully discovers that when polyacrylamide and metal cations are loaded on an alumina matrix according to a certain proportion, the prepared adsorption material has good adsorption effect, and particularly has more obvious adsorption effect on waste water such as dye waste water, which has the characteristics of high water chromaticity, complex organic components, strong acid and alkali, and the like.
In a first aspect, the present invention provides an adsorbent material comprising an alumina matrix and a polyacrylamide and a metal cation supported on the alumina matrix.
According to a preferred embodiment of the present invention, the alumina substrate is a honeycomb ceramic of alumina material, the porosity is 50-80%, and the average pore diameter is 0.5-3mm.
According to a preferred embodiment of the present invention, wherein the polyacrylamide is at least one of nonionic polyacrylamide, anionic polyacrylamide and cationic polyacrylamide having a weight average molecular weight of 5 to 50 tens of thousands, preferably 10 to 20 tens of thousands.
Preferably, the polyacrylamide is a nonionic polyacrylamide.
According to a preferred embodiment of the invention, wherein the metal cation is selected from Mn 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ And Co 2 + At least one of them.
Preferably, the metal cations are present in the adsorbent material in the form of salts. Therefore, cl is also present in the adsorption material - 、SO 4 2- 、NO 3 - And (3) plasma anions.
According to a preferred embodiment of the present invention, wherein the alumina content is 70-95 wt%, based on the total weight of the adsorbent material.
According to a preferred embodiment of the present invention, wherein the total content of polyacrylamide and metal cations is 5-30 wt. -%, based on the total weight of the adsorption material.
According to a preferred embodiment of the present invention, wherein the polyacrylamide content is 1-5 wt.%, based on the total weight of the adsorbent material.
According to a preferred embodiment of the present invention, wherein Mn is based on the total weight of the adsorbent material 2+ The content of (2) is 1-5 wt%. Sn (Sn) 2+ The content of (2) is 1-5 wt%. Ni (Ni) 2+ The content of (2) is 1-5 wt%. Sb (Sb) 3+ The content of (2) is 1-3 wt%. Co (Co) 2+ The content of (2) is 1-3 wt%.
According to a preferred embodiment of the invention, mn in the adsorbent material 2+ And Sn (Sn) 2+ The weight ratio of (2) is 1:1-3, more preferably 1:1-1.5.
According to a preferred embodiment of the present invention, wherein the specific surface area of the adsorbent material is 0.5-3cm 3 /g。
In a second aspect, the present invention provides a method for preparing an adsorbent material, the adsorbent material being as described above, the method comprising impregnating an alumina matrix in an impregnating solution comprising a polyacrylamide and a source of metal cations, and drying the impregnated product to obtain the adsorbent material.
According to a preferred embodiment of the invention, the impregnation fluid is an aqueous solution of polyacrylamide and a source of metal cations.
According to a preferred embodiment of the invention, wherein the source of metal cations is a water-soluble salt of the metal. Water-soluble salts of any of the above metal cations may be suitable for use in the methods provided herein.
Preferably, the metal cation source is selected from at least one of manganese dichloride, stannous sulfate, nickel nitrate, antimony trichloride, cobalt nitrate, and hydrates thereof.
According to a preferred embodiment of the invention, the concentration of polyacrylamide in the impregnation fluid is 10-50mg/L.
According to a preferred embodiment of the invention, the concentration of metal cations in the impregnation fluid is between 10 and 30mg/L.
Preferably, in the impregnation liquid, mn 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ And Co 2+ The weight ratio of (2) is 1-10:1-10:1-5:1-5:1. Preferably 1-9:1-9:2-3:2-3:1.
More preferably, in the impregnation liquid, mn 2+ And Sn (Sn) 2+ The weight ratio of (2) is 1:1-3, preferably 1:1-1.5.
According to a preferred embodiment of the invention, the impregnation is performed by isovolumetric impregnation and/or by overdose, preferably by overdose.
Preferably, the volume ratio of the impregnating solution to the alumina matrix is 5-20:1. Preferably 5-15:1. More preferably 10-15:1.
Preferably, the conditions of the impregnation include: the temperature is 10-50 ℃ and the time is 1-5h. Preferably at a temperature of 20-40℃for a period of 1-5 hours.
According to a preferred embodiment of the present invention, wherein the drying conditions include: the temperature is 80-120 ℃ and the time is 12-24 hours.
According to a preferred embodiment of the invention, the impregnated alumina honeycomb ceramic may be suspended and dried prior to said drying to remove excess solution.
According to a particularly preferred embodiment of the invention, the adsorbent material is prepared according to the following method:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 12-17 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2 + The mass ratio of (3-6:3-6:2-3:2-3:1), wherein the concentration of the nonionic polyacrylamide is 25-30mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ ) The total concentration of (2) is 25-30mg/L.
And (3) preparing an adsorption material: immersing an alumina honeycomb ceramic with a diameter of 2-3cm and a height of 1-2cm in the immersion liquid in an excessive immersion mode, wherein the volume ratio of the alumina honeycomb ceramic to the immersion liquid is about 1:8-12. The soaking time is 1-3h, and the temperature is 25-35 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 20-24 hours at 80-85 ℃. An adsorbent material is obtained.
In a third aspect the present invention provides a method of treating dye waste water, the method comprising contacting an adsorbent material with the dye waste water, wherein the adsorbent material is an adsorbent material as described above.
According to a preferred embodiment of the invention, wherein the conditions of the method comprise: the temperature is 20-50 ℃, the time is 1-5h, and the consumption of the adsorbing material is 50-300g relative to 1-10L of wastewater.
According to a preferred embodiment of the invention, the chromaticity in the dye wastewater is 150-200 DEG and the pH is 11-13. Any dye wastewater meeting the above conditions can be treated by the method provided by the invention, wherein the main component can be any dye existing in the field. Preferably, the dye component in the wastewater is mainly methyl red-methylene blue.
In a fourth aspect the present invention provides the use of an adsorbent material and method as described above in wastewater treatment.
According to a preferred embodiment of the invention, wherein the waste water is dye waste water. The dye wastewater features are as described above and will not be described in detail herein.
The adsorption material provided by the invention can be regenerated and reused for multiple times, and the adsorption effect is stable. Wherein the regeneration is to dry the adsorption material, preferably at 80-120 ℃ for 8-24h.
The present invention will be described in detail by examples. It should be understood that the following examples are provided for further explanation and illustration of the present invention and are not intended to limit the present invention.
In the following examples, alumina honeycomb ceramics were purchased from Henan Shannan environmental protection technologies Co., ltd, under the trademark 17-4. The nonionic polyacrylamide was purchased from nanjing Xiangshan chemical company, inc. Other chemicals used were purchased from regular chemical suppliers and were pure chemical.
Example 1
The adsorbent material A1 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Wherein the concentration of the nonionic polyacrylamide is 30mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The total concentration of (C) was 30mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent A1 was obtained.
Example 2
The adsorbent material A2 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Wherein the concentration of the nonionic polyacrylamide is 10mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The total concentration of (C) was 20mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent material A2 was obtained.
Example 3
The adsorbent material A3 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Is 5:5:2:2:1), wherein the concentration of the nonionic polyacrylamide is 45mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The concentration of (C) is 10mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent A3 was obtained.
Example 4
The adsorbent material A4 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Is 6:6:2:2:1), wherein the concentration of the nonionic polyacrylamide is 25mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The concentration of (C) was 25mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent material A4 was obtained.
Example 5
The adsorbent material A5 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ The mass ratio of (2:2:2:2:1), wherein the concentration of the nonionic polyacrylamide is 20mg/L, and the metal cations are as follows(Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The concentration of (C) is 10mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent material A5 was obtained.
Example 6
The adsorbent material A6 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Wherein the concentration of the nonionic polyacrylamide is 50mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The concentration of (C) is 10mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent material A6 was obtained.
Example 7
The adsorbent material A7 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Wherein the concentration of the nonionic polyacrylamide is 50mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The concentration of (C) is 10mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent material A7 was obtained.
Example 8
The adsorbent material A8 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into aqueous solution (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Wherein the concentration of the nonionic polyacrylamide is 30mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The concentration of (C) is 20mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent material A8 was obtained.
Example 9
The adsorbent material A9 was prepared as follows:
preparing an impregnating solution: preparing nonionic polyacrylamide with weight average molecular weight of 15 ten thousand, manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate into water-soluble preparationLiquid (Mn) 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ Wherein the concentration of the nonionic polyacrylamide is 20mg/L, and the metal cation (Mn 2+ 、Sn 2+ 、Ni 2 + 、Sb 3+ 、Co 2+ ) The concentration of (C) is 10mg/L.
And (3) preparing an adsorption material: alumina honeycomb ceramics with the diameter of 2.5+/-0.5 cm and the height of 1.5+/-0.5 cm are immersed in the impregnating solution in an excessive impregnation mode, and the volume ratio of the alumina honeycomb ceramics to the impregnating solution is about 1:10. the immersion time was 2h at 30 ℃. Hanging and airing the impregnated aluminum oxide honeycomb ceramic to remove redundant solution, and then putting the aluminum oxide honeycomb ceramic into an oven to be dried for 24 hours at 80 ℃. The adsorbent material A9 was obtained.
Example 10
The procedure of example 1 was followed except that no cobalt nitrate hexahydrate was added to prepare the impregnating solution. The total concentration of metal cations is still 30mg/L, mn 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ The mass ratio of (2) is 3:3:2:2. The adsorbent material a10 was obtained.
Example 11
The method of example 1 was used, except that Mn in the impregnation liquid was 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ 、Co 2+ The mass ratio of (2) is 1:3:5:7:9. the adsorbent a11 was obtained.
Example 12
The method of example 1 was used, except that the concentration of the nonionic polyacrylamide in the impregnation liquid was 2mg/L. The adsorbent material a12 was obtained.
Example 13
The method of example 1 was used, except that the concentration of metal cations in the impregnation fluid was 35mg/L. The adsorbent material a13 was obtained.
Example 14
The method of example 1 was used, except that Mn in the impregnation liquid was 2+ And Sn (Sn) 2+ The weight ratio of (2): 1. the adsorbent material a14 was obtained.
Comparative example 1
The procedure of example 1 was followed except that manganese dichloride tetrahydrate, stannous sulfate, nickel nitrate hexahydrate, antimony trichloride and cobalt nitrate hexahydrate were not added to the impregnation solution. The adsorbent D1 was obtained.
Comparative example 2
The method of example 1 was used, except that no nonionic polyacrylamide was added to the impregnating solution. The adsorbent material D2 was obtained.
Test example 1
The contents of the matrix and the support (i.e., the total content of polyacrylamide and metal cations) in the adsorption material obtained in the above examples were detected by weighing before and after the support, respectively, to calculate the weight difference. The results are detailed in Table 1 below.
TABLE 1 adsorbent material parameters
Material numbering Base (weight%) Load (weight%)
A1 95 5
A2 96 4
A3 98 2
A4 95 5
A5 97 3
A6 99 1
A7 98 2
A8 96 4
A9 97 3
A10 98 2
A11 97 3
A12 95 5
A13 96 4
A14 97 3
D1 97 3
D2 95 5
Test example 2
The adsorption performance of the adsorption material provided by the invention is illustrated by using a simulated wastewater treatment adsorption device (a schematic diagram is shown in figure 18, wherein the simulated wastewater treatment adsorption device comprises a reaction tank 4 and a control cabinet 5 connected with the reaction tank, the reaction tank comprises an adsorption material 1 placed in the reaction tank, a stirrer 2 arranged at the bottom of the reaction tank and a temperature control heating rod 3 arranged at the bottom of the reaction tank, the wall of the reaction tank is a10 mm polypropylene plate), the adsorption performance of the adsorption material is illustrated by using the adsorption material obtained in the embodiment as a reference group in a simulated treatment system with the tank temperature of 25 ℃, the stirring speed of 500rpm, the initial pH of water inlet of 12+/-0.5 and the total reaction time of 150 min. The simulated wastewater amount in the simulated treatment system is 3L, and the consumption of the adsorption material is 50g. The content of the methyl red-methylene blue in the system is measured by sampling every 30min (the detection method is an ultraviolet-visible spectrophotometer detection method). The methyl red-methylene blue content in the simulated wastewater after 150min of adsorption is shown in the following table 2; FIGS. 1-16 show time-dependent changes in methyl red-methylene blue content of the adsorption system, wherein the adsorption materials used in FIGS. 1-16 are A1-A14 and D1, D2, and the adsorption material used in FIG. 17 is alumina honeycomb ceramic which is not loaded with polyacrylamide and metal ions.
TABLE 2 Water quality parameters at the end of treatment
Test example 3
The method of test example 2 was used to perform 10 continuous simulated wastewater treatment tests on the adsorbent A1, each for 150 minutes, and after each treatment, the adsorbent A1 was dried (100 ℃ C., 12 hours) and then subjected to the next test. The concentration of methyl red-methylene blue in the wastewater was measured every 30min, and the total methyl red-methylene blue removal rate (calculation method is as follows) was calculated for each test, and the results are shown in FIG. 19.
Total removal of methyl red-methylene blue = methyl red-methylene blue removal 30min Removal of +methyl Red-methylene blue 60min Removal of +methyl Red-methylene blue 90min Removal of +methyl Red-methylene blue 120min Removal of +methyl Red-methylene blue 150min
As can be seen from fig. 19, the total removal rate of methyl red-methylene blue in 10 tests varies less, thus demonstrating that the adsorption material provided by the invention has higher stability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (18)

1. An adsorption material, characterized in that the adsorption material comprises an alumina matrix, polyacrylamide and metal cations loaded on the alumina matrix, the alumina matrix is honeycomb ceramics of alumina material, and the goldThe metal cation is Mn 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ And Co 2+ ；
Mn based on the total weight of the adsorption material 2+ Is 1-5 wt% Sn 2+ The content of (C) is 1-5 wt%, ni 2+ Is 1-5 wt% of Sb 3+ Is 1-3 wt%, co 2+ The content of (2) is 1-3 wt%.
2. The adsorbent material of claim 1, wherein the alumina matrix has a porosity of 50-80% and an average pore size of 0.5-3mm;
and/or the weight average molecular weight of the polyacrylamide is 5 ten thousand to 50 ten thousand, and the polyacrylamide is at least one selected from nonionic polyacrylamide, anionic polyacrylamide and cationic polyacrylamide;
3. the adsorption material of claim 2, wherein the polyacrylamide has a weight average molecular weight of 10-20 tens of thousands;
and/or, the polyacrylamide is nonionic polyacrylamide.
4. The adsorbent material according to claim 1 or 2, wherein the alumina content is 70-95 wt% and the total content of polyacrylamide and metal cations is 5-30 wt%, based on the total weight of the adsorbent material;
and/or the polyacrylamide content is 1-5 wt%, based on the total weight of the adsorbent material.
5. The adsorbent material of claim 1, wherein Mn in the adsorbent material 2+ And Sn (Sn) 2+ The weight ratio of (2) is 1:1-3.
6. The adsorbent material of claim 5, wherein the adsorbent material comprises Mn 2+ And Sn (Sn) 2+ The weight ratio of (2) is 1:1-1.5.
7. The adsorbent material of claim 1, wherein,the specific surface area of the adsorption material is 0.5-3cm 3 /g。
8. A method for preparing an adsorbent material according to any one of claims 1 to 7, comprising impregnating an alumina matrix in an impregnating solution comprising a polyacrylamide and a source of metal cations, and drying the impregnated product to obtain the adsorbent material.
9. The method of claim 8, wherein the impregnating solution is an aqueous solution of polyacrylamide and a source of metal cations;
and/or the source of metal cations is a water soluble salt of a metal.
10. The method of claim 9, wherein the source of metal cations is selected from at least one of manganese dichloride, stannous sulfate, nickel nitrate, antimony trichloride, cobalt nitrate, and hydrates thereof.
11. The method according to claim 8 or 9, wherein the concentration of polyacrylamide in the impregnation fluid is 10-50mg/L;
and/or, the concentration of metal cations in the impregnating solution is 10-30mg/L.
12. The method of claim 11, wherein in the impregnating solution, mn 2+ 、Sn 2+ 、Ni 2+ 、Sb 3+ And Co 2+ The weight ratio of (2) is 1-10:1-10:1-5:1-5:1.
13. The method of claim 12, wherein in the impregnating solution, mn 2+ And Sn (Sn) 2+ The weight ratio of (2) is 1:1-3.
14. The method of claim 13, wherein in the impregnating solution, mn 2+ And Sn (Sn) 2+ The weight ratio of (2) is 1:1-1.5.
15. The method according to claim 8, wherein the impregnation is by isovolumetric impregnation and/or by overdose impregnation;
and/or, the drying conditions include: the temperature is 80-120 ℃ and the time is 12-24 hours.
16. The method of claim 15, wherein the impregnating is by means of excess impregnation;
and/or, the conditions of the impregnation include: the temperature is 10-50 ℃ and the time is 1-5h.
17. A method for treating dye wastewater, comprising contacting an adsorbent material with the dye wastewater, wherein the adsorbent material is the adsorbent material of any one of claims 1-7.
18. Use of an adsorbent material according to any one of claims 1-7 in wastewater treatment.
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CN104448131A (en) * 2014-11-11 2015-03-25 南京工业大学 Preparation method of porous magnetic polyacrylamide (PAM) microsphere adsorbent
CN106140113A (en) * 2016-07-27 2016-11-23 山东理工大学 A kind of graphene oxide/polymer gel and its preparation method and application
CN106345485A (en) * 2016-08-25 2017-01-25 万华化学集团股份有限公司 Catalyst for catalytic oxidation treatment of organic waste water, and preparation method and purpose thereof

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN102343266A (en) * 2010-07-29 2012-02-08 比亚迪股份有限公司 Preparation method of supported catalyst and supported catalyst
CN102872896A (en) * 2012-09-25 2013-01-16 东南大学 Catalyst for catalytic oxidation of printing and dyeing wastewater and preparation method for catalyst
CN104448131A (en) * 2014-11-11 2015-03-25 南京工业大学 Preparation method of porous magnetic polyacrylamide (PAM) microsphere adsorbent
CN106140113A (en) * 2016-07-27 2016-11-23 山东理工大学 A kind of graphene oxide/polymer gel and its preparation method and application
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