CN114471449B - Adsorption material, preparation method thereof and application thereof in treatment of printing and dyeing wastewater - Google Patents

Adsorption material, preparation method thereof and application thereof in treatment of printing and dyeing wastewater Download PDF

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CN114471449B
CN114471449B CN202011150148.5A CN202011150148A CN114471449B CN 114471449 B CN114471449 B CN 114471449B CN 202011150148 A CN202011150148 A CN 202011150148A CN 114471449 B CN114471449 B CN 114471449B
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adsorbent material
temperature
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fly ash
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CN114471449A (en
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刘艳芳
侯吉礼
李红伟
崔龙鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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Abstract

The present disclosure relates to an adsorption material, a method for preparing the same, and an application thereof in treating printing and dyeing wastewater, the method comprising: under the condition of microwave heating, enabling the fly ash, the alkali solution and the oxidant to contact and react, and carrying out solid-liquid separation on the reacted product to obtain desilication ash and a first solution; mixing the first solution, the surfactant and optionally the pH regulator to obtain a second solution, wherein the pH value of the second solution is 10.0-11.3; the second solution is subjected to a hydrothermal treatment, and the solid product is collected and calcined. The adsorption material prepared by the method has the nano-sheet loaded nano-particle structure, and has the advantages of large specific surface area, good adsorption effect and high adsorption efficiency.

Description

Adsorption material, preparation method thereof and application thereof in treatment of printing and dyeing wastewater
Technical Field
The invention relates to an adsorption material, a preparation method thereof and application thereof in treating printing and dyeing wastewater.
Background
Fly ash is solid waste generated by coal combustion, and along with the continuous expansion of the scale of a thermal power plant, the discharge amount of the fly ash is increased sharply. According to statistics, the emission of the fly ash in China in 2015 reaches 6.2 hundred million tons, and the fly ash becomes the largest industrial solid waste in China nowadays. How to make comprehensive utilization of the fly ash becomes the focus of related enterprises and countries. Combined printout of the national Committee for improvement and the Ministry of industry and information of industry in 2019 on the notice of the development of the aggregation of the industry for promoting the comprehensive utilization of solid wastes in bulk industry, indicates that the comprehensive utilization of solid wastes in bulk is to be improvedThe utilization level is used for forming a comprehensive utilization development pattern of multiple paths and high additional value utilization. Currently, fly ash in China is mainly used for producing building materials, roadbed materials, backfill mining areas and the like, and a small part of fly ash is used for improving soil and extracting valuable components. By SiO in fly ash 2 And Al 2 O 3 The preparation of the adsorption material is one of important ways for high value-added utilization of the fly ash, and the adsorption material has recently gained extensive attention and research of students at home and abroad.
Patent CN103769045a describes a preparation method of a high-performance adsorption material by using fly ash, mixing the fly ash with alkali, melting at high temperature, using the dissolved solution as a silicon source, synthesizing a mesoporous adsorption material with large specific surface area under the action of a structure directing agent, ethanol and water, and using alkali to melt and activate can cause corrosion to a reactor, and the amount of the alkali used is large. CN103787354a discloses a method for preparing an MCM-41 molecular sieve by using fly ash and application thereof, and the MCM-41 molecular sieve is prepared by adopting fly ash alkali fusion activation, silica extraction and crystallization reaction, and has good adsorption capacity on hexavalent chromium, and also has the problem of corrosion caused by high-temperature fusion. Document (Journal of Environmental Chemical Engineering,5,2017, 391-399) describes a method for preparing a low-cost adsorbent by using fly ash, wherein silicon in the fly ash is dissolved by alkali, then a sodium metaaluminate solution is added to adjust the silicon-aluminum ratio, and the adsorbent capable of adsorbing mercury in wastewater is obtained by hydrothermal crystallization under the condition of microwave heating.
Disclosure of Invention
The invention aims to provide an adsorption material, a preparation method thereof and application thereof in treating printing and dyeing wastewater.
In order to achieve the above object, a first aspect of the present invention provides a method of producing an adsorbent material, the method comprising:
(1) Under the condition of microwave heating, enabling the fly ash, the alkali solution and the oxidant to contact and react, and carrying out solid-liquid separation on the reacted product to obtain desilication ash and a first solution;
(2) Mixing the first solution, a surfactant and a pH regulator to obtain a second solution, wherein the pH value of the second solution is 10.0-11.3;
(3) Subjecting the second solution to hydrothermal treatment, collecting a solid product and roasting.
Optionally, in step (1), the conditions of microwave heating include: the temperature is 60-150 ℃, the time is 10-120 min, and the power is 200-850W;
preferably, the temperature is 80-130 ℃, the time is 15-60 min, and the power is 450-850W.
Optionally, in the step (1), the weight ratio of the fly ash to the alkali solution is 1: (0.25 to 1.25), wherein the alkali solution is calculated as alkali; the weight ratio of the fly ash to the oxidant is 1: (0.01-0.1).
Optionally, in step (2), the molar ratio of the surfactant to the amount of the first solution is (0.06-0.4): 1, the first solution is calculated by silicon element;
preferably, the molar ratio of the surfactant to the amount of the first solution is (0.1-0.2): 1.
optionally, in step (3), the conditions of the hydrothermal treatment include: the temperature is 50-150 ℃ and the time is 8-48h; preferably, the temperature is 80-120 ℃ and the time is 16-32h;
the roasting temperature is 400-650 ℃ and the roasting time is 1-10h; preferably, the temperature is 500-600 ℃ and the time is 2-6h.
Optionally, the content of the impurity element in the first solution is 10-100 mg/L; the impurity element includes one or more of Al, fe, mg, ti and Ca.
Optionally, the concentration of the alkali solution is 10-30 wt%; the alkali solution contains one or more of NaOH, KOH and RbOH, preferably NaOH and/or KOH;
the oxidizing agent is selected from hydrogen peroxide and/or NaClO, preferably hydrogen peroxide;
the surfactant is at least one selected from cetyltrimethylammonium bromide, cetyltriethylammonium bromide and cetylpyridinium bromide, preferably cetyltrimethylammonium bromide;
the pH regulator is an acid solution, and the acid solution contains one or more of acetic acid, sulfuric acid and hydrochloric acid.
The second aspect of the invention provides an adsorbent material prepared by the method of the first aspect of the invention.
Optionally, the specific surface area of the adsorption material is 900-1200 m 2 /g。
Optionally, the silica content of the adsorbent material is 80.2 to 99.6 wt% based on the total weight of the adsorbent material.
In a third aspect, the invention provides an application of the adsorption material provided by the second aspect in treating printing and dyeing wastewater.
According to the technical scheme, the method disclosed by the invention has the advantages that the fly ash is used as the raw material, the adsorption material with the nanosheet-loaded nanoparticle structure can be prepared relatively simply under the condition that a carbon source and a silicon source are not additionally added, the specific surface area is large, the adsorption performance is good, and when the adsorption material is used for treating dye wastewater, the removal rate of dye in the dye wastewater is high, the adsorption effect is good, and the adsorption efficiency is high.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is an SEM photograph (magnification of 10000 times) of an adsorbent material prepared according to example 1 of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In a first aspect, the present invention provides a method of preparing an adsorbent material, the method comprising:
(1) Under the condition of microwave heating, enabling the fly ash, the alkali solution and the oxidant to contact and react, and carrying out solid-liquid separation on the reacted product to obtain desilication ash and a first solution;
(2) Mixing the first solution, the surfactant and optionally the pH regulator to obtain a second solution, wherein the pH value of the second solution is 10.0-11.3;
(3) The second solution is subjected to a hydrothermal treatment, and the solid product is collected and calcined.
According to the method disclosed by the invention, silicon is extracted under the condition of microwave heating, so that the deep desilication can be realized in the extraction process of the silicon, the content of impurity elements in the first solution can be reduced, and the prepared adsorption material has a nano-sheet loaded nano-particle structure, and has higher adsorption efficiency and removal rate.
In one embodiment, when the pH of the mixture obtained after the first solution and the surfactant are mixed is 10.0 to 11.3, the pH adjuster may not be added, and the obtained mixture is the first solution.
The method of solid-liquid separation in step (1) is not particularly limited according to the present invention, and any method conventionally employed by those skilled in the art may be employed, for example, a method of centrifugal separation or filtration separation, and centrifugal separation is preferable. The centrifugation may be performed in a centrifuge, and conditions for the centrifugation are not particularly limited, and in one embodiment, the conditions for the centrifugation include: the rotating speed is 2000-6000r/min, and the time is 2-10min. In order to separate out the solid desilication ash more effectively, in one specific embodiment, the product obtained by the contact reaction of the fly ash with the alkali solution and the oxidant is diluted with a solvent and then subjected to solid-liquid separation. The solvent may be deionized water, distilled water, etc.
According to the present invention, in step (1), the conditions of microwave heating may include: the temperature is 60-150 ℃, the time is 10-120 min, and the power is 200-850W; in a preferred embodiment, the microwave heating is carried out at a temperature of 80 to 130℃for a period of 15 to 60 minutes and at a power of 450 to 850W. The microwave heating may be performed using equipment known to those skilled in the art, for example, on a microwave digestion instrument.
According to the invention, in step (1), the weight ratio of fly ash to alkali solution used may vary within a wide range, for example 1: (0.25 to 1.25), preferably 1: (0.5-1.0). The concentration of the alkali solution may vary within a wide range, and may be, for example, 10 to 30% by weight, preferably 15 to 25% by weight. The alkaline solution may be any alkaline containing solution, the alkaline contained in the alkaline solution may be NaOH, KOH or RbOH, or a combination of two or three thereof, preferably the alkaline contained is NaOH and/or KOH. The solvent for dissolving the alkali in the alkali solution can be deionized water or any organic solvent which does not participate in the reaction, and the organic solvent can be one or more of ethanol, methanol and glycerol. In a preferred embodiment, the alkaline solution is an aqueous solution of a base.
According to the invention, in step (1), the weight ratio of fly ash to oxidant amount may also vary within a wide range, for example 1: (0.01 to 0.1), preferably 1: (0.02-0.05). The oxidizing agent may be well known to those skilled in the art, and may be selected from hydrogen peroxide and/or sodium hypochlorite, preferably hydrogen peroxide, more preferably, an aqueous solution of hydrogen peroxide and/or sodium hypochlorite, and the concentration of the above solution is not particularly limited, and may be, for example, 10 to 30 wt%.
In one embodiment, the content of the impurity element in the first solution may be 10 to 100mg/L, preferably 20 to 90mg/L; the impurity element includes one or more of Al, fe, mg, ti and Ca. The content of the impurity element in the first solution is expressed by the content of the impurity element in the first solution after the first solution is fixed to 100 mL.
According to the invention, in step (2), the molar ratio of surfactant to the amount of first solution may vary within a wide range, for example (0.06-0.4): 1, the first solution is calculated by silicon element; preferably, the molar ratio of surfactant to the amount of first solution may be (0.1-0.2): 1. the surfactant may be various surfactants capable of achieving mesoporous silica synthesis, and may be at least one selected from cetyltrimethylammonium bromide, cetyltriethylammonium bromide and bromopyridyl, for example, preferably cetyltrimethylammonium bromide. The pH regulator may be an acid solution containing one or more of acetic acid, sulfuric acid and hydrochloric acid, preferably acetic acid. The concentration of the acid solution is not particularly limited, and may be selected according to actual needs.
According to the invention, in step (3), the hydrothermal treatment is well known to those skilled in the art and may be carried out in a heat-resistant closed vessel, such as an autoclave, a hydrothermal vessel. The conditions of the hydrothermal treatment may include: the temperature is 50-150 ℃ and the time is 8-48h; preferably, the temperature is 80-120 ℃ and the time is 16-32h. The pressure of the hydrothermal treatment is not particularly limited, and may be the autogenous pressure of the reaction system or the externally applied pressure, and is preferably performed under the autogenous pressure of the system.
According to the present invention, in step (3), the conditions of firing may include: the temperature can be 400-650 ℃ and the time can be 1-10h; preferably, the temperature is 500-600 ℃ and the time is 2-6h. The atmosphere for calcination is not particularly limited, and may be, for example, an air atmosphere or an inert atmosphere, and the inert gas contained in the inert atmosphere may be helium, argon, nitrogen, or the like. Calcination may be carried out in equipment conventionally employed by those skilled in the art, such as muffle furnaces, tube furnaces.
In a preferred embodiment, step (3) further comprises: the collected solid product is washed by a conventional means in the art, and the present invention is not particularly limited. The solvent used for the washing may be water (e.g., deionized water). Preferably, the washing supernatant is neutral.
In another preferred embodiment, step (3) further comprises: the solid product collected is dried, which may be carried out in a constant temperature oven. The drying conditions may include: the temperature is 70-150 ℃ and the time is 0.5-6h; further preferably, the conditions of drying include: the temperature is 80-120 ℃ and the time is 0.5-3h.
The second aspect of the invention provides an adsorbent material prepared by the method of the first aspect of the invention.
According to the invention, the adsorption material has a nano-sheet loaded nano-particle structure, and the specific surface area of the adsorption material can be 900-1200 m 2 /g; preferably, the specific surface area is 980-1125 m 2 And/g. The specific surface area of the adsorbent material can be determined by methods conventionally employed by those skilled in the art, such as low temperature static nitrogen adsorption capacity methods.
According to the present invention, the silica content of the adsorbent material may be 80.2 to 99.6 wt% based on the total weight of the adsorbent material. Preferably, the silica content of the adsorbent material is 86.0 to 99.0 wt.%
In a third aspect, the invention provides an application of the adsorption material provided by the second aspect in treating printing and dyeing wastewater. The method has good treatment effect on the wastewater, high dye adsorption speed and high removal rate.
In one embodiment, the adsorbent material is contacted with the printing and dyeing wastewater at 20-30 ℃, e.g., the adsorbent material is contacted with the printing and dyeing wastewater containing rhodamine B at 20-30 ℃.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
In the following examples and comparative examples, the contents of impurity elements and silicon in the first solution were measured by inductively coupled plasma emission spectrometry using an inductively coupled plasma emission spectrometer of model Optima5300DV of Perkinelmer, USA, with an incident power of 1500W and a carrier gas of argon at a flow rate of 0.8L/min.
The sample was 1.33X10 by using ASAP 2405N V1.01 automatic adsorbent, low temperature static nitrogen adsorption capacity method of Micromerics company -2 Vacuum degassing at 300 deg.C under Pa for 4 hr, and mixing with N 2 The adsorption-desorption isotherms of the samples were determined at 77.4K for the adsorption media. Calculating the specific surface area of the sample according to the BET formula (S BET )。
The fly ash used was collected from Ningxia chemical plant, and its main chemical components were tested by X-ray fluorescence method, and the results are shown in Table 1.
TABLE 1
Composition of the components SiO 2 Al 2 O 3 Fe 2 O 3 CaO MgO TiO 2 Na 2 O
Content/% 48.3 29.2 6.9 2.3 1.1 1.6 1.2
Example 1
(1) 3.0g of fly ash is weighed into a polytetrafluoroethylene digestion tube, 6mL of NaOH solution with the concentration of 20 wt% and 0.1mL of hydrogen peroxide solution with the mass fraction of 30% are added, the mixture is placed into a microwave digestion instrument for microwave heating assisted extraction, the reacted product is diluted by deionized water and then separated by a centrifuge, the rotational speed of the centrifuge is 4000r/min, the centrifugation time is 5min, and desilication ash and first solution with the silicon content of 5758mg/L are obtained. Wherein, the microwave heating conditions include: the microwave heating temperature is 110 ℃, the time is 30min, and the power is 850W. The first solution was fixed to 100mL with deionized water, and the content of impurity element (Al) in the first solution after the fixed volume was determined to be 29.8mg/L.
(2) 80mL of the first solution was measured, 0.96g of cetyltrimethylammonium bromide (CTAB) was added, and after stirring well, acetic acid was added to adjust the pH to 11.0, to obtain a second solution.
(3) The second solution is subjected to hydrothermal treatment at 110 ℃ for 24 hours, the obtained mixed product is separated by a centrifugal machine, the rotation speed of the centrifugal machine is 4000r/min, the centrifugal time is 5min, the solid product is obtained, the solid product is dried in an oven at 105 ℃ for 1 hour, and then is calcined in a muffle furnace at 550 ℃ for 5 hours, so that an adsorption material A is obtained, an SEM image of the adsorption material A is shown in figure 1, and the adsorption material prepared in the embodiment has a nano-sheet loaded nano-particle structure.
Example 2
(1) 3.0g of fly ash is weighed into a polytetrafluoroethylene digestion tube, 6mL of NaOH solution with the concentration of 17.3 weight percent and 0.1mL of hydrogen peroxide solution with the mass fraction of 30 percent are added, the mixture is placed into a microwave digestion instrument for microwave heating assisted extraction, the reacted product is diluted by deionized water and then separated by a centrifugal machine, the rotating speed of the centrifugal machine is 4000r/min, the centrifugal time is 5min, and desilication ash and first solution with the silicon content of 5632mg/L are obtained. Wherein, the microwave heating conditions include: the microwave heating temperature is 110 ℃, the time is 30min, and the power is 600W. The first solution was fixed to a volume of 100mL with deionized water, and the content of impurity element (Al) in the first solution after the volume was measured to be 24mg/L.
(2) 80mL of the first solution was measured, 0.99g of cetyltrimethylammonium bromide (CTAB) was added, and after stirring well, acetic acid was added to adjust the pH to 10.8, to obtain a second solution.
(3) And carrying out hydrothermal treatment on the second solution at 110 ℃ for 24 hours, separating the obtained mixture by using a centrifugal machine, wherein the rotation speed of the centrifugal machine is 4000r/min, the centrifugal time is 5min, obtaining a solid product, drying the solid product in an oven at 105 ℃ for 1 hour, and calcining the solid product in a muffle furnace at 550 ℃ for 5 hours to obtain the adsorption material B.
Example 3
(1) 3.0g of fly ash is weighed into a polytetrafluoroethylene digestion tube, 6mL of NaOH solution with the concentration of 33.3 weight percent and 0.1mL of hydrogen peroxide solution with the mass fraction of 30 percent are added, the mixture is placed into a microwave digestion instrument for microwave heating assisted extraction, the reacted product is diluted by deionized water and then separated by a centrifugal machine, the rotating speed of the centrifugal machine is 4000r/min, the centrifugal time is 5min, desilication ash is obtained, and the first solution with the silicon content of 6018mg/L is obtained. Wherein, the microwave heating conditions include: the microwave heating temperature is 110 ℃, the time is 30min, and the power is 600W. The first solution was fixed to a volume of 100mL with deionized water, and the content of impurity element (Al) in the first solution after the volume was measured to be 35.5mg/L.
(2) 80mL of the first solution was measured, 1.00g of CTAB was added, and after stirring well, acetic acid was added to adjust the pH to 11.0, to obtain a second solution.
(3) Carrying out hydrothermal treatment on the second solution at 110 ℃ for 24 hours, separating the obtained mixed product by using a centrifugal machine, wherein the rotation speed of the centrifugal machine is 4000r/min, the centrifugal time is 5min, obtaining a solid product, drying the solid product in an oven at 105 ℃ for 1 hour, and calcining the solid product in a muffle furnace at 550 ℃ for 5 hours, thus obtaining the adsorption material C.
Example 4
(1) 3.0g of fly ash is weighed into a polytetrafluoroethylene digestion tube, 6mL of NaOH solution with the concentration of 20 wt% and 0.1mL of hydrogen peroxide solution with the mass fraction of 30% are added, the mixture is placed into a microwave digestion instrument for microwave heating assisted extraction, the reacted product is diluted by deionized water and then separated by a centrifuge, the rotational speed of the centrifuge is 4000r/min, the centrifugation time is 5min, desilication ash and extract are obtained, the volume of the extract is fixed to 100mL, and a first solution with the silicon content of 6019mg/L is obtained. Wherein, the microwave heating conditions include: the microwave heating temperature is 130 ℃, the time is 30min, and the power is 850W. The first solution was fixed to 100mL with deionized water, and the content of impurity element (Al) in the first solution after the fixed volume was measured to be 35.8mg/L.
(2) 80mL of the first solution was measured, 1.03g of CTAB was added, and after stirring well, acetic acid was added to adjust the pH to 11.0, to obtain a second solution.
(3) And carrying out hydrothermal treatment on the second solution for 24 hours at 110 ℃, separating the obtained mixed product by using a centrifugal machine, wherein the rotation speed of the centrifugal machine is 4000r/min, and the centrifugal time is 5min, so as to obtain a solid product. The solid product was dried in an oven at 105 ℃ for 1 hour and calcined in a muffle furnace at 550 ℃ for 5 hours to give an adsorbent material D.
Example 5
The adsorbent E was prepared in the same manner as in example 1, except that in step (1), the microwave heating conditions include: the microwave heating temperature is 150 ℃, the time is 30min, and the power is 400W. The content of the impurity element in the first solution was 81.7mg/L.
Example 6
The adsorbent F was prepared in the same manner as in example 1, except that in step (1), the microwave heating conditions include: the microwave heating temperature is 200 ℃, the time is 30min, and the power is 450W. The content of the impurity element in the first solution was 108mg/L.
Example 7
The same method as in example 1 was used to prepare the adsorbent material G, except that in step (1), 3G of fly ash was weighed into a polytetrafluoroethylene digestion tube, 10mL of a 45 wt% NaOH solution and 0.1mL of a 30% mass fraction hydrogen peroxide solution were added, and the mixture was placed into a microwave digestion instrument to perform microwave heating assisted extraction, and the reacted product was diluted with deionized water, and then separated with a centrifuge at a centrifuge speed of 4000r/min for 5min to obtain desilication ash and a first solution having a silicon content of 8398mg/L. The first solution was fixed to a volume of 100mL with deionized water, and the content of impurity element (Al) in the first solution after the volume was determined to be 110mg/L.
Example 8
The same method as in example 1 was used to prepare the adsorbent material H, except that in step (1), 3.0g of fly ash was weighed into a polytetrafluoroethylene digestion tube, 6mL of a NaOH solution with a concentration of 20 wt% and 0.01mL of a hydrogen peroxide solution with a mass fraction of 30% were added, and the mixture was placed into a microwave digestion instrument to perform microwave heating assisted extraction, and the reacted product was diluted with deionized water, and then separated with a centrifuge at a centrifuge speed of 4000r/min for 5min to obtain desilicated ash and a first solution with a silicon content of 5732mg/L. The first solution was fixed to a volume of 100mL with deionized water, and the content of impurity element (Al) in the first solution after the volume was measured to be 26.2mg/L.
Example 9
An adsorbent I was prepared in the same manner as in example 1 except that in step (2), 80mL of the first solution was measured, 3.64g of cetyltrimethylammonium bromide (CTAB) was added, and after stirring uniformly, acetic acid was added to adjust the pH to 11.0, to obtain a second solution.
Comparative example 1
The comparative example adopts an alkali fusion method for desilication and a hydrothermal method for synthesizing the molecular sieve, and the specific implementation modes are as follows:
(1) Weighing 5.0g of fly ash and 2.5g of sodium hydroxide, uniformly mixing, calcining for 1h in a muffle furnace at 550 ℃, taking out, naturally cooling to room temperature, grinding into fine powder, and mixing according to a solid-liquid ratio of 1:4, mixing with deionized water, stirring for 24 hours, separating the mixture by adopting a centrifugal machine, wherein the rotating speed of the centrifugal machine is 4000rpm, centrifuging for 5 minutes to obtain an extracting solution and solid, and fixing the volume of the extracting solution to 100mL by using deionized water, wherein the content of impurity element (Al) in the extracting solution after fixing the volume is 462mg/L.
(2) 80mL of the first solution was measured, 1.78g of CTAB was added, and after stirring well, acetic acid was added to adjust the pH to 11.0, to obtain a mixture.
(3) And (3) carrying out hydrothermal treatment on the mixture obtained in the step (2) for 24 hours at 110 ℃, separating a product obtained by the hydrothermal treatment by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is 4000r/min, and the centrifugal time is 5min, so as to obtain a lower solid.
(4) Drying the lower layer solid in the step (3) in an oven at 105 ℃ for 1 hour, and calcining in a muffle furnace at 550 ℃ for 5 hours to obtain the adsorption material a.
Comparative example 2
(1) 3.0g of fly ash is weighed into a polytetrafluoroethylene digestion tube, 6mL of NaOH solution with the concentration of 20 wt% is added, the mixture is placed into a microwave digestion instrument for microwave heating auxiliary extraction, the reacted product is diluted by deionized water and then separated by a centrifuge, the rotational speed of the centrifuge is 4000r/min, and the centrifugation time is 5min, so that desilication ash and a first solution are obtained. Wherein, the microwave heating conditions include: the microwave heating temperature is 110 ℃, the time is 30min, and the power is 850W. The first solution was fixed to a volume of 100mL with deionized water, and the content of impurity element (Al) in the first solution after the volume was measured to be 20mg/L.
(2) 80mL of the first solution was measured, 0.96g of CTAB was added, and after stirring well, acetic acid was added to adjust the pH to 11.0, to obtain a second solution.
(3) And carrying out hydrothermal treatment on the second solution for 24 hours at 110 ℃, separating the obtained mixed product by using a centrifugal machine, wherein the rotation speed of the centrifugal machine is 4000r/min, and the centrifugal time is 5min, so as to obtain a solid product. The solid product was dried in an oven at 105 ℃ for 1h and calcined in a muffle furnace at 550 ℃ for 5h to give the adsorbent material b.
Comparative example 3
The same method as in example 1 was used to prepare the adsorbent material c, except that in step (1), 3.0g of fly ash was weighed into a 100mL hydrothermal reaction vessel, 6mL of a 20 wt% NaOH solution and 0.1mL of a 30% hydrogen peroxide solution were added, the reaction was performed at 110 ℃ for half an hour after sealing, the reacted product was diluted with deionized water, and then separated by a centrifuge at a centrifuge speed of 4000r/min for 5min to obtain desilication ash and a first solution. The first solution was fixed to 100mL with deionized water, and the content of impurity element (Al) in the first solution after the fixed volume was measured to be 109mg/L.
Test case
This test example is used to illustrate the application of the adsorption materials prepared in the examples and comparative examples provided by the present invention to adsorbing dyes in wastewater.
The adsorption process is as follows: accurately weighing 0.1g of the examples and comparative examplesThe prepared adsorbent material was added to 100mL of a solution containing 1X 10 -5 Stirring (the speed is 300 r/min) is started in a mol/L rhodamine B aqueous solution, timing is started, and the rhodamine B aqueous solution is adsorbed at a constant temperature of 25 ℃; after 10min, 5mL of the suspension was removed with a pipette, and the supernatant was obtained by centrifugation. Rhodamine B concentration in the solution before and after adsorption was measured by using a Lambda35 uv-vis spectrophotometer from PerkinElmer company, and the removal rate of rhodamine B was calculated from the concentration difference before and after adsorption, and the result is shown in table 2.
Removal rate%rhodamine B = (concentration of rhodamine B in solution before test adsorption-concentration of rhodamine B in solution after test adsorption)/concentration of rhodamine B in solution before test adsorption × 100%
TABLE 2
Adsorption material numbering Specific surface area, m 2 /g Silica content, percent Removal rate%
Example 1 A 1125 98.2 98
Example 2 B 1107 98.7 95
Example 3 C 1042 92.1 93
Example 4 D 1066 91.2 93
Example 5 E 980 86.5 88
Example 6 F 755 80.1 73
Example 7 G 1022 75.2 90
Example 8 H 878 98.8 80
Example 9 I 721 97.9 71
Comparative example 1 a 619 70.2 56
Comparative example 2 b 863 98.6 75
Comparative example 3 c 688 76.3 70
The first solution has low impurity content in the preparation process of the method, and the prepared adsorption material has higher specific surface area, high impurity removal rate and good adsorption effect.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (15)

1. A method of making an adsorbent material, the method comprising:
(1) Under the condition of microwave heating, enabling the fly ash, the alkali solution and the oxidant to contact and react, and carrying out solid-liquid separation on the reacted product to obtain desilication ash and a first solution; the conditions of the microwave heating include: the temperature is 60-150 ℃, the time is 10-120 min, and the power is 200-850W; the content of impurity elements in the first solution is 10-100 mg/L; the oxidizing agent is selected from hydrogen peroxide;
(2) Mixing the first solution, a surfactant and a pH regulator to obtain a second solution, wherein the pH value of the second solution is 10.0-11.3; the surfactant is at least one selected from cetyltrimethylammonium bromide, cetyltriethylammonium bromide and cetylpyridinium bromide;
(3) Subjecting the second solution to hydrothermal treatment, collecting a solid product and roasting; the conditions of the hydrothermal treatment include: the temperature is 50-150 ℃ and the time is 8-48h.
2. The method according to claim 1, wherein in the step (1), the temperature is 80-130 ℃, the time is 15-60 min, and the power is 450-850W.
3. The method of claim 1, wherein in step (1), the weight ratio of the fly ash to the alkali solution is 1: (0.25 to 1.25), wherein the alkali solution is calculated as alkali; the weight ratio of the fly ash to the oxidant is 1: (0.01-0.1).
4. The method of claim 1, wherein in step (2), the molar ratio of the surfactant to the amount of the first solution is (0.06-0.4): 1, the first solution is calculated by silicon element.
5. The method of claim 1, wherein the molar ratio of the surfactant to the amount of the first solution is (0.1-0.2): 1, the first solution is calculated by silicon element.
6. The method of claim 1, wherein in step (3), the conditions of the hydrothermal treatment comprise: the temperature is 80-120 ℃ and the time is 16-32h;
the roasting conditions include: the temperature is 400-650 ℃ and the time is 1-10h.
7. The method of claim 1, wherein the firing conditions include: the temperature is 500-600 ℃ and the time is 2-6h.
8. The method according to claim 1, wherein the impurity element includes one or more of Al, fe, mg, ti and Ca.
9. The method according to claim 1, wherein the concentration of the alkali solution is 10 to 30 wt%; the alkali solution contains one or more of NaOH, KOH and RbOH;
the pH regulator is an acid solution, and the acid solution contains one or more of acetic acid, sulfuric acid and hydrochloric acid.
10. The method according to claim 1, wherein the alkaline solution contains NaOH and/or KOH.
11. The method of claim 1, wherein the surfactant is cetyltrimethylammonium bromide.
12. An adsorbent material prepared by the method of any one of claims 1-11.
13. The adsorbent material of claim 12, wherein the adsorbent material has a specific surface area of 900-1200 m 2 /g。
14. The adsorbent material of claim 12, wherein the silica content of the adsorbent material is 80.2 to 99.6 wt% based on the total weight of the adsorbent material.
15. Use of the adsorbent material of claim 12 for treating printing and dyeing wastewater.
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Publication number Priority date Publication date Assignee Title
CN108928834A (en) * 2017-05-24 2018-12-04 神华集团有限责任公司 MCM-41 mesopore molecular sieve and its preparation method and application
CN108993457A (en) * 2018-07-27 2018-12-14 河北科技大学 A method of adsorbent is prepared by raw material of flyash
CN110040743A (en) * 2019-04-25 2019-07-23 太原理工大学 A kind of coal ash for manufacturing for SSZ-13 molecular sieve method
CN110639599A (en) * 2019-10-19 2020-01-03 青岛科技大学 Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108928834A (en) * 2017-05-24 2018-12-04 神华集团有限责任公司 MCM-41 mesopore molecular sieve and its preparation method and application
CN108993457A (en) * 2018-07-27 2018-12-14 河北科技大学 A method of adsorbent is prepared by raw material of flyash
CN110040743A (en) * 2019-04-25 2019-07-23 太原理工大学 A kind of coal ash for manufacturing for SSZ-13 molecular sieve method
AU2020100373A4 (en) * 2019-04-25 2020-04-16 Taiyuan University Of Technology Method for preparing ssz-13 molecular sieve by using fly ash
CN110639599A (en) * 2019-10-19 2020-01-03 青岛科技大学 Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof

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