CN113083263A - Magnetic adsorbent for treating industrial wastewater and preparation method and application thereof - Google Patents
Magnetic adsorbent for treating industrial wastewater and preparation method and application thereof Download PDFInfo
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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
- B01J20/28—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
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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
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4893—Residues derived from used synthetic products, e.g. rubber from used tyres
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a magnetic adsorbent for treating industrial wastewater, and a preparation method and application thereof; the preparation method comprises the following steps: (1) uniformly mixing iron-based Fischer-Tropsch synthesis waste catalyst wax and oil sludge to obtain a mixed raw material; (2) heating the obtained mixed raw material for carbonization treatment to obtain a carbonized product; (3) and grinding and screening the obtained carbonized product until the particle size is less than 250 mu m, and transferring the carbonized product to an activation furnace for activation treatment to prepare the magnetic adsorbent. The magnetic adsorbent prepared by the invention can adsorb phenolic compounds in wastewater, and realizes purification and impurity removal of industrial wastewater.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a magnetic adsorbent for treating industrial wastewater, and a preparation method and application thereof.
Background
Coal chemical industry is an important support for the development of economic society in China, but the implementation of the process inevitably produces coal chemical industry wastewater, wherein the wastewater contains a large amount of organic matters which are difficult to degrade, inorganic matters with biological toxicity and heavy metal salts, and the wastewater seriously threatens the ecological environment. The physicochemical pretreatment is combined with the A/O biochemical treatment to obviously reduce the content of organic matters in the wastewater, but partial pollutants which are difficult to treat still exist in the wastewater at the moment, and the discharge standard is not reached yet. The wastewater is further subjected to advanced treatment by adopting an adsorption method, so that the wastewater can be thoroughly and deeply purified, but the treatment mode has the problem that solid-liquid separation of an adsorbent and the wastewater is difficult. The magnetic adsorbent can be separated from the water body under the action of an external magnetic field, so that the adsorbent can be conveniently recovered. Therefore, the magnetic adsorbent is an ideal material for advanced treatment of coal chemical wastewater.
Chinese patent document CN 103285838B discloses a preparation method of a functional magnetic adsorbent for industrial wastewater treatment, the invention firstly needs to prepare a ferroferric oxide nano-crystal cluster by a solvothermal method, then uses a sol-gel method and a distillation precipitation polymerization method to carry out chemical modification and coating on the surface of the ferroferric oxide with a polymer shell layer, and finally carries out functional group modification on the surface of a microsphere shell layer to obtain the functional magnetic adsorbent; the prepared adsorbent can efficiently adsorb various heavy metals and organic pollutants, however, the method has complex operation steps and complex preparation flow, and is not beneficial to industrial scale-up production.
Chinese patent document CN 105749864B discloses a method for preparing a magnetic adsorbent or magnetic catalyst carrier with high specific surface area, the method comprises the steps of carrying out atomic layer deposition reaction on iron-containing metal organic compound steam and a carrier material with large specific surface area, and further carrying out oxidation reaction, thereby depositing a magnetic iron oxide film on the surface of the carrier. Although the preparation method can obtain the magnetic adsorbent with large specific surface area, the preparation method needs to use expensive metal organic compounds, and the production cost is high.
Therefore, a preparation method of the magnetic adsorbent suitable for advanced treatment of coal chemical wastewater needs to be further explored.
In the coal liquefaction industry, waste products such as iron-based Fischer-Tropsch synthesis spent catalyst wax, which is a mixture of mainly deactivated iron-based Fischer-Tropsch synthesis catalyst and entrained paraffin wax, are discharged. The iron-based Fischer-Tropsch synthesis waste catalyst has large wax discharge amount, belongs to dangerous solid waste, has higher disposal cost, and increases the operation cost of enterprises.
The oil-containing sludge is a multiphase mixture of oil, mud, sand and water generated in the processes of oil exploitation, storage and transportation, refining and the like. According to statistics, the generation amount of the oil sludge accounts for about 1.0 percent of the yield of the crude oil in the oil exploitation process, and the generation amount of the oil sludge in the petrochemical industry accounts for about 0.5 percent of the processing amount of the crude oil; therefore, the oil sludge yield is huge in China. The oil sludge has complex components, contains a large amount of crude oil and organic matters, belongs to dangerous waste, and can cause serious pollution to the surrounding environment if being stacked for a long time.
In conclusion, the existing preparation method of the magnetic adsorbent for advanced treatment of coal chemical wastewater has the defects of high production cost and complex preparation process. The resource utilization of the Fischer-Tropsch synthesis waste catalyst wax residue and the oil sludge is a problem which is urgently solved by the industries of coal indirect liquefaction, oil exploitation and refining. Therefore, it is a worthy direction to explore how to use the two wastes as raw materials to prepare magnetic carbon-based adsorbents and apply the magnetic carbon-based adsorbents to adsorption purification of coal chemical wastewater according to the composition characteristics of the two wastes.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a resource utilization method of iron-based Fischer-Tropsch synthesis waste catalyst wax and oil sludge, namely a magnetic adsorbent for treating industrial wastewater and a preparation method and application thereof, wherein the iron-based Fischer-Tropsch synthesis waste catalyst wax and oil sludge are used as raw materials, so that the resource utilization of wastes can be realized; meanwhile, the prepared magnetic adsorbent can adsorb phenolic compounds in the wastewater, so that the purification and impurity removal of the industrial wastewater are realized.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, a method for preparing a magnetic adsorbent for treating industrial wastewater is provided, which comprises the following steps:
(1) uniformly mixing iron-based Fischer-Tropsch synthesis waste catalyst wax and oil sludge to obtain a mixed raw material;
(2) heating the obtained mixed raw material for carbonization treatment to obtain a carbonized product;
(3) and grinding and screening the obtained carbonized product until the particle size is less than 250 mu m, and transferring the carbonized product to an activation furnace for activation treatment to prepare the magnetic adsorbent.
According to the preparation method of the invention, in some examples, in the step (1), the iron-based fischer-tropsch synthesis waste catalyst wax residue is deactivated iron-based fischer-tropsch waste catalyst wax-containing filter residue discharged from a fischer-tropsch synthesis process, and the preparation method comprises the following steps: iron and diatomaceous earth were precipitated and wrapped with paraffin. In some examples, the paraffin wax is present in an amount of 20 to 60 wt% (e.g., 27 wt%, 35 wt%, 50 wt%) based on 100 wt% of the total weight of the iron-based fischer-tropsch synthesis spent catalyst wax. In some examples, the iron-based Fischer-Tropsch synthesis waste catalyst residue wax also comprises a mineral component with a content of precipitated iron (calculated as Fe) based on 100 wt% of the total weight of the mineral component2O3Meter)Can be present in an amount of 30 wt% to 40 wt% (e.g., 35 wt%, 38 wt%).
In some examples, in step (1), the oil sludge is oil-containing sludge generated in the processes of crude oil extraction, refining, storage and transportation.
In some examples, the iron-based fischer-tropsch synthesis waste catalyst residue wax is blended in an amount of 5.0 wt% or more (e.g., 8.0 wt%, 10.0 wt%, 15.0 wt%, 20.0 wt%, 25.0 wt%, 45.0 wt%, 60.0 wt%) of the mixed raw material in step (1), based on the total weight of the mixed raw material being 100 wt%. Preferably, the blending amount of the iron-based Fischer-Tropsch synthesis waste catalyst residue wax is 5.0-30 wt% of the mixed raw material, and more preferably 5.0-20 wt% of the mixed raw material.
In some examples, step (1) grinds and screens the iron-based Fischer-Tropsch synthesis spent catalyst residue wax to a particle size of less than 75 μm (e.g., 1 μm, 5 μm, 10 μm, 25 μm, 45 μm, 65 μm, 74 μm) prior to mixing with the oil sludge. For example, the particles are sieved through a 75 μm mesh sieve.
Any experimental device/equipment capable of heating the mixed raw materials for carbonization can be used. In some examples, in step (2), the resulting mixed feedstock is placed in a corundum crucible and transferred to a tube furnace for heating.
In some examples, in step (2), the process conditions of the carbonization treatment include: the carbonization temperature is 300-600 deg.C (e.g., 350 deg.C, 400 deg.C, 450 deg.C, 550 deg.C), and the carbonization time is 1-3 h (e.g., 1.5h, 2h, 2.5 h). For example, in N2The temperature is raised at a certain temperature raising rate under the atmosphere, and carbonization treatment is carried out.
The carbonized product obtained may be crushed, ground and sieved before the activation treatment, for example, by sieving through a 250 μm mesh sieve to a particle size of less than 250 μm.
In some examples, in step (3), the process conditions of the activation treatment include: the activation temperature is 700-900 deg.C (e.g., 750 deg.C, 800 deg.C, 850 deg.C), the activation time is 10-60 min (e.g., 20min, 30min, 40min, 50min), and the activation atmosphere is CO2And H2One or two of O. For example, in N2At a certain liter under the atmosphereHeating at a high temperature rate, activating, and adding N2Atmosphere switching to CO2Atmosphere, continued activation, then sample at N2Cooling to room temperature under the atmosphere.
In another aspect, there is provided a magnetic adsorbent obtained by the above-described production method.
The invention also provides an application of the magnetic adsorbent prepared by the preparation method in adsorbing phenolic compounds in wastewater, which comprises the following steps: mixing the magnetic adsorbent with a wastewater solution to be treated, and adsorbing phenolic compounds in the wastewater by using the magnetic adsorbent to obtain an adsorbed mixture; and separating the magnetic adsorbent adsorbed with the phenolic compounds from the wastewater solution by the action of an external magnetic field on the obtained mixture subjected to adsorption treatment.
According to the application provided by the invention, preferably, the phenolic compound comprises one or more of phenol, cresol, aminophenol and nitrophenol.
In some examples, after the magnetic adsorbent is mixed with the wastewater solution to be treated, the mixture can be oscillated at 25 ℃ and an oscillation speed of 100-120r/min for 10-24h to obtain the mixture after adsorption treatment.
The process of passing the resulting mixture after adsorption treatment through the action of an applied magnetic field is well known to those skilled in the art and will not be described herein.
According to the application provided by the invention, the magnetic adsorbent can adsorb phenolic compounds in wastewater; in the mixture after adsorption treatment, most of the phenolic compounds can enter the magnetic adsorbent from the wastewater solution, and the magnetic adsorbent adsorbing the phenolic compounds can be separated from the wastewater in a mode of an external magnetic field, so that the phenolic compounds in the wastewater can be effectively removed.
The invention provides a technical scheme for synthesizing a magnetic adsorbent by taking two dangerous wastes, namely iron-based Fischer-Tropsch synthesis waste catalyst residue wax and oil sludge, as raw materials and using the two dangerous wastes as raw materials to remove phenolic compounds in wastewater, aiming at the current situations that the preparation cost of the magnetic adsorbent is high and the two dangerous solid wastes, namely the iron-based Fischer-Tropsch synthesis waste catalyst residue wax discharged in the coal indirect liquefaction industry and the oil-containing sludge generated in the petroleum and petrochemical industry, are in urgent need of treatment.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) the raw materials required by the magnetic adsorbent in the preparation process are hazardous wastes, so that the resource utilization of the hazardous wastes can be realized, and the damage of the wastes to the ecological environment is effectively avoided; (2) the magnetic adsorbent is used for adsorption and purification of industrial wastewater, so that a cyclic development system and a design concept of zero waste discharge are realized; (3) the iron element in the iron-based Fischer-Tropsch synthesis waste catalyst is fully utilized, the adsorbing material with excellent magnetism is prepared, and the separation of the adsorbing agent and the wastewater can be realized under the condition of an external magnetic field; (4) the preparation method of the magnetic adsorbent has the advantages of simple operation process, low cost and good economic benefit.
Drawings
FIG. 1 shows the results of evaluating the adsorption performance of the magnetic adsorbents obtained in comparative example 1 and examples 1, 2 and 3 of the present invention on phenol in wastewater;
FIG. 2 shows the magnetic properties of the magnetic adsorbents obtained in comparative example 1 and examples 1, 2 and 3 of the present invention under an applied magnetic field.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
< sources of raw materials >
In each example, the iron-based fischer-tropsch synthesis spent catalyst wax used was taken from a coal indirect liquefaction project, in which: the content of paraffin entrapped therein was 50.98%. The mineral composition in the residue wax is shown in Table 1, wherein Fe is calculated by the total amount of all mineral compositions being 100 wt%2O338.29% of the total weight of the product.
TABLE 1 mineral composition in Fischer-Tropsch Synthesis spent catalyst residue wax (wt%)
Crushing and grinding the Fischer-Tropsch synthesis waste catalyst wax residue, and then screening the crushed Fischer-Tropsch synthesis waste catalyst wax residue through a sieve with a mesh of 75 microns until the particle size is smaller than 75 microns for later use.
The oil sludge used was oil-containing sludge obtained from a certain oil production plant, and the results of the component analysis thereof are shown in table 2. Naturally drying the oil sludge, and further drying the oil sludge in a vacuum oven at 80 ℃ for 24 hours for later use.
TABLE 2 analysis results of the components of oily sludge
Comparative example 1
The preparation method of the magnetic adsorbent comprises the following steps:
(1) putting the iron-based Fischer-Tropsch waste catalyst slag wax into a corundum crucible, and putting the corundum crucible into a tube furnace, so that a sample is placed in a N state2Heating to 500 deg.C at a heating rate of 8 deg.C/min under atmosphere, and carbonizing for 180 min; the sample is then brought to N2Cooling to room temperature under the atmosphere to obtain a carbonized product;
(2) grinding the obtained carbonized product, sieving to obtain particles with particle size less than 250 μm, placing in an activation furnace, and adding into a reactor under N condition2Heating to 800 deg.C at a heating rate of 10 deg.C/min under atmosphere, activating, and adding N2The atmosphere was switched to CO at a flow rate of 200mL/min2Activating for 20min, and then putting the sample in N2And cooling to room temperature under the atmosphere to obtain the magnetic adsorbent MAD 0.
The application of the obtained magnetic adsorbent in adsorbing phenolic compounds in wastewater is as follows:
25mL of a 50mg/L phenol aqueous solution was used as a simulated solution of phenol-containing wastewater. 0.1g of the magnetic adsorbent MAD0 obtained as described above was taken and placed in 25mL of a 50mg/L phenol aqueous solution, and shaken at 25 ℃ at an oscillation speed of 120r/min for 12 hours. The magnetic adsorbent is separated from the wastewater simulation solution by a magnet, and the concentration of phenol in the separated wastewater simulation solution is tested by an ultraviolet spectrophotometer. The results of the performance evaluation are shown in FIG. 1, and the phenol removal rate is 8.16%.
Example 1
The preparation method of the magnetic adsorbent comprises the following steps:
(1) weighing the iron-based Fischer-Tropsch waste catalyst residue wax and the oil sludge for later use according to a proportion, and fully stirring and uniformly mixing to obtain a mixed raw material; wherein the mixing amount of the iron-based Fischer-Tropsch waste catalyst slag wax accounts for 5.0 wt% of the total weight of the mixed raw material slag wax and the oil sludge;
(2) transferring the obtained mixed raw material sample to a corundum crucible, placing the corundum crucible in a tube furnace, and enabling the sample to be in N2Heating to 550 ℃ at a heating rate of 8 ℃/min under the atmosphere, and carrying out carbonization treatment for 90 min; the sample is then brought to N2Cooling to room temperature under the atmosphere to obtain a carbonized product;
(3) grinding the obtained carbonized product, sieving to obtain particles with particle size less than 250 μm, placing in an activation furnace, and adding into a reactor under N condition2Heating to 800 deg.C at a heating rate of 10 deg.C/min under atmosphere, activating, and adding N2The atmosphere was switched to CO at a flow rate of 200mL/min2Atmosphere, continue activation for 18min, then let the sample in N2And cooling to room temperature under the atmosphere to obtain the magnetic adsorbent MAD 1.
The application of the obtained magnetic adsorbent in adsorbing phenolic compounds in wastewater is as follows:
25mL of a 50mg/L phenol aqueous solution was used as a simulated solution of phenol-containing wastewater. 0.1g of the magnetic adsorbent MAD1 thus obtained was taken and placed in 25mL of a 50mg/L aqueous phenol solution, and shaken at 25 ℃ at an oscillation speed of 120r/min for 12 hours. The magnetic adsorbent is separated from the wastewater simulation solution by a magnet, and the concentration of phenol in the separated wastewater simulation solution is tested by an ultraviolet spectrophotometer. The results of the performance evaluation are shown in FIG. 1, and the phenol removal rate is 97.5%.
Example 2
The preparation method of the magnetic adsorbent comprises the following steps:
(1) weighing the iron-based Fischer-Tropsch waste catalyst residue wax and the oil sludge for later use according to a proportion, and fully stirring and uniformly mixing to obtain a mixed raw material; wherein the mixing amount of the iron-based Fischer-Tropsch waste catalyst slag wax accounts for 10.0 wt% of the total weight of the mixed raw material slag wax and the oil sludge;
(2) transferring the obtained mixed raw material sample to a corundum crucible, placing the corundum crucible in a tube furnace, and enabling the sample to be in N2Heating to 500 deg.C at a rate of 5 deg.C/min under atmosphere, and carbonizing for 120 min; the sample is then brought to N2Cooling to room temperature under the atmosphere to obtain a carbonized product;
(3) grinding the obtained carbonized product, sieving to obtain particles with particle size less than 250 μm, placing in an activation furnace, and adding into a reactor under N condition2Heating to 800 deg.C at a heating rate of 10 deg.C/min under atmosphere, activating, and adding N2The atmosphere was switched to CO at a flow rate of 200mL/min2Activating for 10min, and then putting the sample in N2And cooling to room temperature under the atmosphere to obtain the magnetic adsorbent MAD 2.
The application of the obtained magnetic adsorbent in adsorbing phenolic compounds in wastewater is as follows:
25mL of a 50mg/L phenol aqueous solution was used as a simulated solution of phenol-containing wastewater. 0.1g of the magnetic adsorbent MAD2 thus obtained was taken and placed in 25mL of a 50mg/L aqueous phenol solution, and shaken at 25 ℃ at an oscillation speed of 120r/min for 12 hours. The magnetic adsorbent is separated from the wastewater simulation solution by a magnet, and the concentration of phenol in the separated wastewater simulation solution is tested by an ultraviolet spectrophotometer. The results of the performance evaluation are shown in FIG. 1, and the phenol removal rate is 99.1%.
Example 3
The preparation method of the magnetic adsorbent comprises the following steps:
(1) weighing the iron-based Fischer-Tropsch waste catalyst residue wax and the oil sludge for later use according to a proportion, and fully stirring and uniformly mixing to obtain a mixed raw material; wherein the mixing amount of the iron-based Fischer-Tropsch waste catalyst slag wax accounts for 20.0 wt% of the total weight of the mixed raw material slag wax and the oil sludge;
(2) transferring the obtained mixed raw material sample to a corundum crucible, placing the corundum crucible in a tube furnace, and enabling the sample to be in N2Heating to 600 deg.C at a heating rate of 10 deg.C/min under atmosphere, and carbonizing for 60 min; the sample is then brought to N2Cooling to room temperature under the atmosphere to obtain a carbonized product;
(3) grinding the obtained carbonized product, sieving to obtain particles with particle size less than 250 μm, placing in an activation furnace, and adding into a reactor under N condition2Heating to 850 deg.C at a heating rate of 10 deg.C/min under atmosphere, activating, and adding N2The atmosphere was switched to CO at a flow rate of 200mL/min2The atmosphere, activation for 15min, then the sample is placed in N2And cooling to room temperature under the atmosphere to obtain the magnetic adsorbent MAD 3.
The application of the obtained magnetic adsorbent in adsorbing phenolic compounds in wastewater is as follows:
25mL of a 50mg/L phenol aqueous solution was used as a simulated solution of phenol-containing wastewater. 0.1g of the magnetic adsorbent MAD3 thus obtained was taken and placed in 25mL of a 50mg/L aqueous phenol solution, and shaken at 25 ℃ at an oscillation speed of 120r/min for 12 hours. The magnetic adsorbent is separated from the wastewater simulation solution by a magnet, and the concentration of phenol in the separated wastewater simulation solution is tested by an ultraviolet spectrophotometer. The results of the performance evaluation are shown in FIG. 1, and the phenol removal rate is 95.4%.
From the results of the comparative example 1 and the examples 1 to 3, it can be seen that the magnetic adsorbent prepared from the iron-based Fischer-Tropsch waste catalyst residue wax and the oil sludge has more remarkable adsorption performance on phenol in the wastewater, and the removal rate of the phenol in the wastewater can reach more than 95%, which is much higher than the removal rate of the phenol by the magnetic adsorbent prepared from the iron-based Fischer-Tropsch waste catalyst residue wax alone.
Meanwhile, the magnetic adsorbent prepared in the embodiments 1 to 3 fully utilizes iron elements in the iron-based Fischer-Tropsch waste catalyst wax residue, has excellent magnetism, and can separate and recover the magnetic adsorbent adsorbed with the phenolic compounds from the wastewater by realizing the obvious separation of the adsorbent and the wastewater under the condition of an external magnetic field as shown in figure 2. The separation effect of the magnetic adsorbent obtained in comparative example 1 and wastewater is not as sufficient as that of the magnetic adsorbents prepared in examples 1 to 3.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A preparation method of a magnetic adsorbent for treating industrial wastewater is characterized by comprising the following steps:
(1) uniformly mixing iron-based Fischer-Tropsch synthesis waste catalyst wax and oil sludge to obtain a mixed raw material;
(2) heating the obtained mixed raw material for carbonization treatment to obtain a carbonized product;
(3) and grinding and screening the obtained carbonized product until the particle size is less than 250 mu m, and transferring the carbonized product to an activation furnace for activation treatment to prepare the magnetic adsorbent.
2. The preparation method according to claim 1, wherein in the step (1), the iron-based Fischer-Tropsch synthesis waste catalyst wax residue is deactivated iron-based Fischer-Tropsch waste catalyst wax-containing filter residue discharged from a Fischer-Tropsch synthesis process, and the preparation method comprises the following steps: precipitating iron and diatomite, and wrapping paraffin; and/or
The oil sludge is oil-containing sludge generated in the processes of crude oil exploitation, refining, storage and transportation.
3. The method according to claim 1, wherein the iron-based Fischer-Tropsch synthesis waste catalyst residue wax is blended in an amount of 5.0 wt% or more based on the total weight of the raw materials in the step (1).
4. The preparation method according to claim 1, wherein the iron-based Fischer-Tropsch synthesis waste catalyst wax is ground and sieved until the particle size is less than 75 μm in the step (1), and then is mixed with oil sludge.
5. A production method according to any one of claims 1 to 4, wherein in the step (2), the obtained mixed raw material is placed in a corundum crucible and transferred to a tube furnace to be heated.
6. The preparation method according to any one of claims 1 to 5, wherein in the step (2), the process conditions of the carbonization treatment include: the carbonization temperature is 300-600 ℃, and the carbonization time is 1-3 h.
7. The production method according to any one of claims 1 to 6, wherein in the step (3), the process conditions of the activation treatment include: the activation temperature is 700-900 ℃, the activation time is 10-60 min, and the activation atmosphere is CO2And H2One or two of O.
8. A magnetic adsorbent obtainable by the process according to any one of claims 1 to 7.
9. The application of the magnetic adsorbent prepared by the preparation method of any one of claims 1 to 7 in adsorbing phenolic compounds in wastewater, which comprises the following steps: mixing the magnetic adsorbent with a wastewater solution to be treated, and adsorbing phenolic compounds in the wastewater by using the magnetic adsorbent to obtain an adsorbed mixture; and separating the magnetic adsorbent adsorbed with the phenolic compounds from the wastewater solution by the action of an external magnetic field on the obtained mixture subjected to adsorption treatment.
10. Use according to claim 9, wherein the phenolic compound comprises one or more of phenol, cresol, aminophenol and nitrophenol.
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