CN108439523B - Application of composite adsorbent in treatment of oily wastewater - Google Patents

Application of composite adsorbent in treatment of oily wastewater Download PDF

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CN108439523B
CN108439523B CN201810281434.1A CN201810281434A CN108439523B CN 108439523 B CN108439523 B CN 108439523B CN 201810281434 A CN201810281434 A CN 201810281434A CN 108439523 B CN108439523 B CN 108439523B
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adsorbent
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rectorite
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sepiolite
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CN108439523A (en
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叶澄
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INNER MONGOLIA YONGJIANGJIAYUAN SCIENCE & TECHNOLOGY Co.,Ltd.
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Abstract

The invention provides application of a composite adsorbent, wherein the specific preparation steps of the adsorbent comprise: (1) preparing composite powder gel; (2) preparing a modified composite adsorbent; (3) preparing a magnetic composite cross-linked adsorbent; the adsorbent is prepared by compounding modified rectorite and modified sepiolite as a basic adsorbent raw material, wherein organic groups are introduced to the surface of the rectorite and the sepiolite after the rectorite and the sepiolite are modified, so that the surface properties of the rectorite and the sepiolite are greatly enriched, and the adsorption performance of the rectorite and the sepiolite is improved; the rectorite and the sepiolite are used jointly, the advantages of the rectorite and the sepiolite are exerted, the synergistic effect is achieved, the adsorption performance of the organic and inorganic pollutants with different types and molecular sizes can be selectively adsorbed, and the application range of the organic and inorganic pollutants is greatly expanded; in addition, the adsorbent has magnetism, so that after adsorption is finished, the adsorbent can be completely recovered in a magnetic field within 20 minutes without additional treatment such as filtration, sedimentation, centrifugation and the like.

Description

Application of composite adsorbent in treatment of oily wastewater
The application is a divisional application, the application number of the original application is 201610555322.1, the application date is 2016, 7 and 15, and the name of the invention is 'an adsorbent for petrochemical wastewater treatment and a preparation method thereof'.
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an application of a composite adsorbent in treating oily wastewater.
Background
With the development of economy, chemical plants in various regions are more and more, the treatment of industrial sewage becomes a hot point of attention of all the world, and the discharge amount of traditional electroplating, tanning, metal surface treatment, printing and dyeing, petrifaction and waste water containing other organic pollutants is increased day by day.
Petrochemical industry is an important component of chemical industry, plays an important role in the development of national economy, and is one of the prop industry departments in China. Petrochemical refers to the processing industry that produces petroleum products and petrochemical products from petroleum and natural gas. Petroleum products are also called oil products, and mainly comprise various fuel oils (gasoline, kerosene, diesel oil and the like), lubricating oil, liquefied petroleum gas, petroleum coke, paraffin, asphalt and the like. The process for producing these products is often referred to as petroleum refining, or refining for short. The petrochemical product is obtained by further chemically processing raw oil provided by an oil refining process. The first step in the production of petrochemical products is the cracking of feedstock oil and gas (such as propane, gasoline, diesel, etc.) to produce basic chemical materials, typically ethylene, propylene, butadiene, benzene, toluene, xylene. The second step is to produce various organic chemical materials (about 200 kinds) and synthetic materials (plastics, synthetic fibers, synthetic rubbers) from basic chemical materials. The production of these two-step products falls within the scope of petrochemical industry. The organic chemical raw materials can be processed continuously to prepare more chemical products, which are not in the range of petrochemical industry in habit. In some data, the synthesis of ammonia and urea from natural gas, light gasoline and heavy oil, and even the preparation of nitric acid, are also included in petrochemical industry. The existing petrochemical wastewater can not be thoroughly treated and is discharged during treatment, so that the environment is polluted, resources are wasted, and the environment is polluted.
The adsorption treatment technology is a simple and effective wastewater treatment technology and is widely applied to treatment of industrial wastewater, dye wastewater, petrochemical wastewater and the like containing heavy metal ions. Currently, the common techniques for industrial wastewater treatment include activated carbon adsorption, zeolite exchange, and the like. The activated carbon is difficult to use in large scale due to its high price and complex regeneration.
The rectorite mineral material is a natural product, has good compatibility with the environment, is an environmental material with a promising application prospect, and can be used as an adsorbent. Compared with active carbon, rectorite has the advantages of low price, strong adsorption capacity, rich sources, renewability and the like. The crystal structure of the rectorite contains a large hydrophilic surface, and the rectorite shows good hydrophilicity and high dispersibility in an aqueous solution. In the practice of wastewater treatment and sudden raw water pollution remediation, in order to improve the organic adsorption capacity of rectorite, people often adopt quaternary ammonium salts and the like to organically modify the rectorite to prepare the organic rectorite. The sepiolite is a magnesium-rich fibrous silicate clay mineral, has the characteristics of large specific surface area and good adsorbability, is lower than the commercial price of common active carbon, and has become a research hotspot for wastewater treatment. However, the sepiolite is difficult to recycle and regenerate, and is not suitable for industrialization, so that the popularization and application range of the sepiolite is hindered. Therefore, the sepiolite is used for developing a novel adsorbing material with low cost and high efficiency and is used for treating industrial wastewater, and has important practical significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an adsorbent and a preparation method thereof, wherein the adsorbent has the advantages of wide raw material source, simple preparation process, high adsorption capacity, low treatment cost and easy recovery.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of an adsorbent for petrochemical wastewater treatment comprises the following steps:
(1) preparing composite powder gel: dispersing 15-30 parts of modified rectorite powder and 20-40 parts of modified sepiolite powder in 180 parts of 100-one-phase solvent, ultrasonically shaking for 1-2 hours at room temperature, heating to 65-75 ℃, slowly dripping 20-30 parts of tetraethoxysilane, and continuously stirring until the solution becomes a solid phase; washing the solid phase with distilled water until the quality is unchanged, and drying at the temperature of 100-110 ℃ for 3-6 hours to obtain composite powder gel;
(2) preparing a modified composite adsorbent: adding the modified composite powder gel obtained in the step (1) into 10-15 parts of quaternary ammonium salt tetrameric surfactant, 6-12 parts of chitosan and 50-80 parts of toluene solvent, mixing and stirring uniformly, then transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction at 80-120 ℃ for 6-10h, centrifuging, washing and drying after the reaction is finished, and obtaining the modified composite adsorbent;
(3) preparing a magnetic composite cross-linked adsorbent: and (3) adding the modified composite adsorbent obtained in the step (2) into 30-40 parts of mixed iron salt solution, and stirring and reacting for 20-30 min at 40 ℃ under the protection of N2 to obtain the adsorbent for petrochemical wastewater treatment.
Wherein the preparation method of the quaternary ammonium salt tetrameric surfactant in the step (2) comprises the following steps: adding 40mL of absolute ethyl alcohol and 4.5g of ethylenediamine into a 250mL three-neck flask with a condenser tube, magnetically stirring at room temperature, adding 34.7g of epoxy chloropropane at a rate of 10 drops/min, carrying out reflux reaction at 50 ℃ for 4h after the dropwise addition is finished, carrying out reduced pressure distillation to obtain a tetrameric surfactant intermediate which is a light yellow semitransparent viscous liquid, taking 20g of the intermediate, adding 40mL of a mixed solution of absolute ethyl alcohol and deionized water with a volume ratio of 1: l as a solvent, dropwise adding 7.9g of N, N-dimethyl dodecyl tertiary amine, heating to 80 ℃, reacting for 1h, carrying out reduced pressure distillation, recrystallizing, and vacuum drying to obtain a white powdery solid, namely the quaternary ammonium salt tetrameric surfactant.
The modifier used for modifying the rectorite powder is one selected from the group consisting of dodecyl trimethyl phosphorus bromide, dodecyl trimethyl phosphorus chloride and hexadecyl triphenyl phosphorus chloride.
The modifier used for modifying the sepiolite powder is one of tetraethylenepentamine, triethylene tetramine, ethylenediamine or ethylenediamine tetraacetic acid.
After the mixed iron salt solution is added in the step (3), slowly dropwise adding 1-2 parts of ammonia water with the concentration of 28% in the stirring process, and heating to 40 ℃ after the ammonia water is added.
The mixed iron salt is a mixture of FeSO4 & 7H2O and FeC13 & 6H2O in a molar ratio of 1: 1.5-2.5.
In the step (1), the solvent is one or more of toluene, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran.
The invention has the technical effects that: (1) the adsorbent is prepared by compounding modified rectorite and modified sepiolite as a basic adsorbent raw material, wherein organic groups are introduced to the surface of the rectorite and the sepiolite after the rectorite and the sepiolite are modified, so that the surface properties of the rectorite and the sepiolite are greatly enriched, and the adsorption performance of the rectorite and the sepiolite is improved; the rectorite and the sepiolite are used jointly, the advantages of the rectorite and the sepiolite are exerted, the synergistic effect is achieved, the adsorption performance of the organic and inorganic pollutants of different types and molecular sizes can be selectively adsorbed, and the application range of the organic and inorganic pollutants is greatly expanded; in addition, the quaternary ammonium salt tetrameric surfactant and chitosan are adopted to carry out secondary crosslinking modification on the modified rectorite and modified sepiolite compound, so that organic groups with very large molecular weight are further embedded on the surface of the compound, the alternation performance and the adsorption performance of the compound are improved, the stability and the strength of the compound are improved, and the obtained adsorbent can stably and efficiently adsorb and remove petrochemical wastewater.
(2) The adsorbent of the invention adopts a hydrothermal reaction method when carrying out secondary modification, and the method can excellently anchor the active group of the modifier on the compound of the modified rectorite and the modified sepiolite and is very stable.
(3) The adsorbent has magnetism, so that after adsorption is finished, the adsorbent can be completely recovered in a magnetic field within 20 minutes without additional treatment such as filtration, sedimentation, centrifugation and the like.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment as follows:
example 1
A preparation method of an adsorbent for petrochemical wastewater treatment comprises the following steps:
(1) preparing composite powder gel: dispersing 15 parts of decaalkyltrimethyl phosphorus bromide modified rectorite powder and 20 parts of tetraethylenepentamine modified sepiolite powder in 100 parts of toluene, ultrasonically shaking for 1 hour at room temperature, heating to 65 ℃, slowly dripping 20 parts of tetraethoxysilane, and continuously stirring until the solution becomes a solid phase; washing the solid phase with distilled water until the mass is unchanged, and drying at 100 ℃ for 3 hours to obtain composite powder gel;
(2) preparing a modified composite adsorbent: adding the modified composite powder gel obtained in the step (1) into 10 parts of quaternary ammonium salt tetramer surfactant, 6 parts of chitosan and 50 parts of toluene solvent, mixing and stirring uniformly, then transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction at 80 ℃ for 6h, centrifuging, washing and drying after the reaction is finished, thus obtaining the modified composite adsorbent;
(3) preparing a magnetic composite cross-linked adsorbent: and (3) adding the modified composite adsorbent obtained in the step (2) into 30 parts of mixed iron salt solution, slowly dropwise adding 1 part of ammonia water with the concentration of 28% in the stirring process under the protection of N2, and stirring and reacting for 20min at the temperature of 40 ℃ to obtain the adsorbent for treating the petrochemical wastewater.
Example 2
A preparation method of an adsorbent for petrochemical wastewater treatment comprises the following steps:
(1) preparing composite powder gel: dispersing 30 parts of decaalkyl trimethyl phosphorus chloride modified rectorite powder and 20-40 parts of triethylene tetramine modified sepiolite powder in 180 parts of N, N-dimethylformamide, ultrasonically shaking for 2 hours at room temperature, then heating to 75 ℃, slowly dripping 30 parts of tetraethoxysilane, and continuously stirring until the solution becomes a solid phase; washing the solid phase with distilled water until the mass is unchanged, and drying at 110 ℃ for 3 hours to obtain composite powder gel;
(2) preparing a modified composite adsorbent: adding the modified composite powder gel obtained in the step (1) into 15 parts of quaternary ammonium salt tetrameric surfactant, 12 parts of chitosan and 80 parts of toluene solvent, mixing and stirring uniformly, then transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 10 hours, and after the reaction is finished, centrifuging, washing and drying to obtain a modified composite adsorbent;
(3) preparing a magnetic composite cross-linked adsorbent: and (3) adding the modified composite adsorbent obtained in the step (2) into 40 parts of mixed iron salt solution, slowly dropwise adding 2 parts of ammonia water with the concentration of 28% in the stirring process under the protection of N2, and stirring and reacting at 40 ℃ for 27 min to obtain the adsorbent for treating the petrochemical wastewater.
Example 3
A preparation method of an adsorbent for petrochemical wastewater treatment comprises the following steps:
(1) preparing composite powder gel: dispersing 20 parts of hexadecyl triphenyl phosphonium chloride modified rectorite powder and 30 parts of ethylenediamine modified sepiolite powder into 140 parts of N, N-dimethylacetamide, ultrasonically shaking for 1.5h at room temperature, heating to 70 ℃, slowly dripping 25 parts of tetraethoxysilane, and continuously stirring until the solution becomes a solid phase; washing the solid phase with distilled water until the quality is unchanged, and drying at 105 ℃ for 5 hours to obtain composite powder gel;
(2) preparing a modified composite adsorbent: adding the modified composite powder gel obtained in the step (1) into 12 parts of quaternary ammonium salt tetramer surfactant, 9 parts of chitosan and 70 parts of toluene solvent, mixing and stirring uniformly, then transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 8 hours, and centrifuging, washing and drying after the reaction is finished to obtain the modified composite adsorbent;
(3) preparing a magnetic composite cross-linked adsorbent: and (3) adding the modified composite adsorbent obtained in the step (2) into 35 parts of mixed iron salt solution, slowly dropwise adding 1.5 parts of ammonia water with the concentration of 28% in the stirring process under the protection of N2, and stirring and reacting for 25 min at 40 ℃ to obtain the adsorbent for treating the petrochemical wastewater.
Example 4
A preparation method of an adsorbent for petrochemical wastewater treatment comprises the following steps:
(1) preparing composite powder gel: dispersing 25 parts of decaalkyltrimethyl phosphorus bromide modified rectorite powder and 35 parts of ethylenediamine tetraacetic acid modified sepiolite powder in 160 parts of tetrahydrofuran, ultrasonically shaking for 1.8 hours at room temperature, heating to 70 ℃, slowly dripping 28 parts of tetraethoxysilane, and continuously stirring until the solution becomes a solid phase; washing the solid phase with distilled water until the mass is unchanged, and drying at 110 ℃ for 5 hours to obtain composite powder gel;
(2) preparing a modified composite adsorbent: adding the modified composite powder gel obtained in the step (1) into 14 parts of quaternary ammonium salt tetrameric surfactant, 10 parts of chitosan and 70 parts of toluene solvent, mixing and stirring uniformly, then transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction at 110 ℃ for 9 hours, and after the reaction is finished, centrifuging, washing and drying to obtain the modified composite adsorbent;
(3) preparing a magnetic composite cross-linked adsorbent: and (3) adding the modified composite adsorbent obtained in the step (2) into 38 parts of mixed iron salt solution, slowly dropwise adding 1.5 parts of ammonia water with the concentration of 28% in the stirring process under the protection of N2, and stirring and reacting for 25 min at 40 ℃ to obtain the adsorbent for treating the petrochemical wastewater.
Example 5
A preparation method of an adsorbent for petrochemical wastewater treatment comprises the following steps:
(1) preparing composite powder gel: dispersing 18 parts of decaalkyltrimethyl phosphorus chloride modified rectorite powder and 25 parts of ethylenediamine tetraacetic acid modified sepiolite powder in 130 parts of N, N-dimethylacetamide, ultrasonically shaking for 1h at room temperature, heating to 75 ℃, slowly dripping 25 parts of tetraethoxysilane, and continuously stirring until the solution becomes a solid phase; washing the solid phase with distilled water until the mass is unchanged, and drying at 105 ℃ for 4 hours to obtain composite powder gel;
(2) preparing a modified composite adsorbent: adding the modified composite powder gel obtained in the step (1) into 12 parts of quaternary ammonium salt tetramer surfactant, 9 parts of chitosan and 60 parts of toluene solvent, mixing and stirring uniformly, then transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction at 90 ℃ for 10 hours, and centrifuging, washing and drying after the reaction is finished to obtain the modified composite adsorbent;
(3) preparing a magnetic composite cross-linked adsorbent: and (3) adding the modified composite adsorbent obtained in the step (2) into 33 parts of mixed iron salt solution, slowly dropwise adding 1.5 parts of ammonia water with the concentration of 28% in the stirring process under the protection of N2, and stirring and reacting at 40 ℃ for 22 min to obtain the adsorbent for treating the petrochemical wastewater.
Comparative example 1
The preparation method is the same as that of example 1, and the only difference is that the raw material adopts single sepiolite.
Comparative example 2
The preparation method is the same as that of the example 1, and the only difference is that only quaternary ammonium salt tetrameric surfactant is adopted as the modified raw material in the step (2).
Comparative example 3
The preparation method is the same as that of the example 1, and the only difference is that the hydrothermal reaction in the step (2) is changed into a normal-pressure water bath reaction.
Adsorption experiment I: examples 1-5 and comparative examples 1-3 simulate the adsorption of wastewater containing water.
The activated adsorbent particles are adopted to treat simulated oily wastewater, and main parameters of the simulated oily water sample are as follows: the COD concentration is 1500.Omg & L < -1 >, the oil concentration is 982.0mg & L < -1 >, and 40mL of water sample is taken.
The dosage of the adsorbent and the adsorption conditions comprise: the dosage of the adsorbent particles is 25g/L, 1g of the adsorbent is counted, the adsorption temperature is 40 ℃, the adsorption time is 120min, and the experimental results are shown in the following table 1.
Figure DEST_PATH_IMAGE002
As can be seen from Table 1, the adsorbents of examples 1 to 5 showed good adsorption performance for both COD and oil in petrochemical wastewater, and were superior to the adsorbents of comparative examples 1 to 3.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. The application of the composite adsorbent in oily wastewater is characterized in that activated adsorbent particles are adopted to treat simulated oily wastewater, and main parameters of a simulated oily water sample are as follows: the COD concentration is 1500.0 mg.L-1The oil concentration was 982.0 mg.L-1Taking 40mL of water sample, wherein the dosage and adsorption conditions of the adsorbent comprise: the dosage of the adsorbent particles is 25g/L, and the dosage is 1g of adsorbent and the adsorption temperatureThe degree is 40 ℃, the adsorption time is 120min, wherein the preparation method of the composite adsorbent comprises the following steps:
(1) preparing composite powder gel: dispersing 15-30 parts of modified rectorite powder and 20-40 parts of modified sepiolite powder in 180 parts of 100-one-phase solvent, ultrasonically shaking for 1-2 hours at room temperature, heating to 65-75 ℃, slowly dripping 20-30 parts of tetraethoxysilane, and continuously stirring until the solution becomes a solid phase; washing the solid phase with distilled water until the quality is unchanged, and drying at the temperature of 100-110 ℃ for 3-6 hours to obtain composite powder gel;
(2) preparing a modified composite adsorbent: adding the composite powder gel obtained in the step (1) into 10-15 parts of quaternary ammonium salt tetramer surfactant, 6-12 parts of chitosan and 50-80 parts of toluene solvent, mixing and stirring uniformly, then transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction at 80-120 ℃ for 6-10h, centrifuging, washing and drying after the reaction is finished, thus obtaining the modified composite adsorbent;
(3) preparing a magnetic composite adsorbent: adding the modified composite adsorbent obtained in the step (2) into 30-40 parts of mixed iron salt solution in N2Stirring and reacting for 20-30 min at 40 ℃ under protection;
wherein the modifier used for modifying the rectorite powder is one selected from the group consisting of dodecyl trimethyl phosphorus bromide, dodecyl trimethyl phosphorus chloride and hexadecyl triphenyl phosphorus chloride;
wherein the modifier used for modifying the sepiolite powder is one selected from tetraethylenepentamine, triethylene tetramine, ethylenediamine or ethylenediamine tetraacetic acid;
after the mixed iron salt solution is added in the step (3), slowly dropwise adding 1-2 parts of 28% ammonia water in the stirring process, and heating to 40 ℃ after the ammonia water is added.
2. The use according to claim 1, wherein the quaternary ammonium salt tetrameric surfactant in the step (2) is prepared by: adding 40mL of absolute ethyl alcohol and 4.5g of ethylenediamine into a 250mL three-neck flask with a condenser tube, magnetically stirring at room temperature, adding 34.7g of epoxy chloropropane at a rate of 10 drops/min, carrying out reflux reaction at 50 ℃ for 4h after the dropwise addition is finished, carrying out reduced pressure distillation to obtain a tetrameric surfactant intermediate which is a light yellow semitransparent viscous liquid, taking 20g of the intermediate, adding 40mL of a mixed solution of absolute ethyl alcohol and deionized water with a volume ratio of 1:1 as a solvent, dropwise adding 7.9g of N, N-dimethyl dodecyl tertiary amine, heating to 80 ℃, reacting for 1h, carrying out reduced pressure distillation, recrystallizing, and carrying out vacuum drying to obtain a white powdery solid, namely the quaternary ammonium salt tetrameric surfactant.
3. The use of claim 1, wherein the mixed iron salt is FeSO in a molar ratio of 1:1.5-2.54· 7H2O and FeCl3· 6H2A mixture of O.
4. The use according to claim 1, wherein the solvent in step (1) is one or more of toluene, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran.
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