CN112403033B - Composite solid phase extraction column and application thereof in separation of alkane/aromatic hydrocarbon mixture - Google Patents
Composite solid phase extraction column and application thereof in separation of alkane/aromatic hydrocarbon mixture Download PDFInfo
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Abstract
The invention discloses a composite solid-phase extraction column, which comprises a first-stage solid-phase extraction column and a second-stage solid-phase extraction column connected with the first-stage solid-phase extraction column in series; the stationary phase in the first-stage solid-phase extraction column is a first porous composite filler which takes porous alumina as a shell and porous silica as a core; the stationary phase in the second-stage solid-phase extraction column is a second porous composite filler which takes porous silicon oxide as a core and Co-MOF nano material as a shell and is loaded with silver nano particles. The filler in the solid phase extraction column has good adsorption selectivity, excellent stability and good separation efficiency.
Description
Technical Field
The invention relates to the field of separation of hydrocarbon mixtures, in particular to a composite solid-phase extraction column and application thereof in separation of alkane/aromatic hydrocarbon mixtures.
Background
In recent years, with the development of chemical and petrochemical industries, the demand for aromatic hydrocarbon products has been increasing. Aromatic hydrocarbons are the starting material for many polymer products, plastics, and fuels. Meanwhile, along with the continuous enhancement of health consciousness of people, the quality index of petroleum products is also continuously improved. In the field of automotive fuel, low aromatic content and high octane number are always the development directions of high quality gasoline. On the one hand, the higher boiling point of aromatic hydrocarbons affects the boiling point of gasoline to some extent, and the content thereof has been limited. On the other hand, most aromatic hydrocarbons are carcinogenic, and their combustion products lead to the emission of greenhouse gases and the formation of soot in diesel engines. Meanwhile, when gasoline is combusted, the higher the aromatic hydrocarbon content is, the lower the combustion efficiency of the gasoline is, and the more serious the pollution to the environment is.
Separation of aromatic/paraffinic mixtures is one of the most important processes in the petrochemical industry. Due to the close boiling points of the components and the existence of constant boiling components in the mixture, it is very difficult to achieve efficient separation, and a new and efficient separation method needs to be further explored. In recent years, many researchers have developed many new separation methods based on different principles for aromatic/paraffinic systems.
The solid phase extraction technology is a separation technology which is developed rapidly in recent years, is based on a liquid-color fixation spectrum theory, adopts selective adsorption and selective elution modes to enrich, separate and purify a sample, and is a physical extraction process comprising a liquid phase and a solid phase. Patent CN201310743588.5 provides a solid phase extraction column for solid phase extraction separation of different hydrocarbon components in diesel, which is composed of an upper solid phase extraction column and a lower solid phase extraction column, wherein the stationary phase of the upper solid phase extraction column is a mixture of silica gel and alumina, the alumina content is 1-40% by mass, the stationary phase of the lower solid phase extraction column is silica gel loaded with silver ions and treated with water, the silver content of the stationary phase calculated by taking silica gel as a reference is 1-12% by mass, and the water content is 4-15% by mass. Patent CN201210416516.5 provides a solid phase extraction column based on graphene bonded silica gel, which is used for the enrichment and separation of organic pollutants in an environmental water sample. According to the graphene bonded silica gel filler, 3-Aminopropyltriethoxysilane (APTES) is used as a cross-linking agent, graphene is bonded to the surface of silica gel, and then the product graphene bonded silica gel particles are uniformly filled in a solid-phase extraction column to obtain the graphene bonded silica gel solid-phase extraction column. It can be known from the prior art that the key point of the solid phase extraction technology is a solid phase extraction column with good adsorption performance and mechanical performance.
Disclosure of Invention
One of the technical problems to be solved by the invention is as follows: aiming at the defects in the prior art, the invention provides a composite solid-phase extraction column, which is characterized in that a core-shell material taking porous alumina as a shell and porous silica as a core is prepared as a first porous composite filler; porous silicon oxide is used as a core, a Co-MOF nano material is used as a shell, and a material coated with silver nano particles is used as a second porous composite filler; and then the first porous composite filler and the second porous composite filler are respectively filled into a first-stage solid-phase extraction column and a second-stage solid-phase extraction column and then connected in series to form the composite solid-phase extraction column.
The second technical problem to be solved by the invention is to provide an application of the composite solid phase extraction column in the separation of alkane/arene mixtures, aiming at the defects of the prior art.
In order to solve the first technical problem, the invention adopts the technical scheme that:
a composite solid phase extraction column comprises a first-stage solid phase extraction column and a second-stage solid phase extraction column connected with the first-stage solid phase extraction column in series; the stationary phase in the first-stage solid-phase extraction column is a first porous composite filler which takes porous alumina as a shell and porous silica as a core; the stationary phase in the second-stage solid-phase extraction column is a second porous composite filler which takes porous silicon oxide as a core and Co-MOF nano material as a shell and is loaded with silver nano particles.
As a preferable mode of the above technical solution, the method for preparing the first porous composite filler includes the steps of:
dissolving P123 in acetic acid, then dropwise adding ammonia water under an ice bath condition, finally dropwise adding ethyl orthosilicate under a state of vigorous stirring, continuing to vigorously stir until the solution becomes clear after the dropwise adding is finished, finally transferring the solution into a hydrothermal kettle, heating for reaction, carrying out aging treatment after the reaction is finished, finally placing wet gel obtained by aging in a mixed solution of water and ethanol for solvent exchange, drying and then placing in a muffle furnace for calcining treatment; preparing graded porous silicon dioxide particles;
secondly, mixing the prepared porous silicon dioxide particles with absolute ethyl alcohol to prepare dispersion liquid; dissolving aluminum isopropoxide in isopropanol, adding dispersion liquid, uniformly mixing, adding urea, heating and reacting at 130-150 ℃ for 3-7min, filtering after the reaction is finished, drying the solid, and calcining in a muffle furnace to obtain the first porous composite filler.
Preferably, in the first step, the concentration of the ammonia water is 25 wt%, and the dosage ratio of the P123, the ammonia water and the tetraethoxysilane is (1-2) g: 5 ml: (2-3) ml.
Preferably, in the first step, the temperature of the heating reaction is 55-65 ℃, and the time of the heating reaction is 1-3 h; the temperature of the aging treatment is 55-65 ℃, and the time of the aging treatment is 5-6 d.
Preferably, in the first step, the conditions of the calcination treatment are as follows: firstly heating to 400 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation treatment for 10min, then heating to 600 ℃ at a heating rate of 7 ℃/min, carrying out heat preservation treatment for 10min, finally heating to 800 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation treatment for 1 h.
Preferably, in the second step, the mass ratio of the aluminum isopropoxide to the urea to the porous silica particles is (4-7): 1:3.
Preferably, in the second step, the conditions of the calcination treatment are as follows: firstly, heating to 300 ℃ at the speed of 1 ℃/min, carrying out heat preservation treatment for 30min, then heating to 500 ℃ at the speed of 5 ℃/min, and carrying out heat preservation treatment for 4 h.
As a preferable mode of the above technical solution, the method for preparing the second porous composite filler includes the steps of:
(a) dispersing the hierarchical porous silicon dioxide particles prepared in the first step in a solvent consisting of DMF and deionized water, then dropwise adding DMF solution of succinic anhydride and APTES, stirring at 30 +/-5 ℃ for 2-4h, finally filtering, directly dispersing the solid obtained by filtering in the aqueous solution of cobalt nitrate hexahydrate, adding DMF solution of 2-amino terephthalic acid, reacting at 90-100 ℃ for 20-30h, and after the reaction is finished, concentrating the reaction liquid to prepare a concentrated solution;
(b) adding the concentrated solution into 50mmol/L ethanol solution of silver nitrate, soaking at room temperature and 0.1-0.2MPa for 2-4 hr, and soaking at room temperature and normal pressure for 20-50 hr; filtering, washing the precipitate with absolute ethyl alcohol, and drying to obtain a second porous composite filler.
Preferably, in the technical scheme, the mass ratio of the graded porous silica particles, succinic anhydride, APTES, cobalt nitrate hexahydrate, 2-amino terephthalic acid and silver nitrate is (4-5): (1-3): (3-4): 7: (0.5-0.8): 3.
in order to solve the second technical problem, the invention adopts the technical scheme that:
the application of the composite solid phase extraction column in the extraction separation of alkane/arene mixture comprises the following steps:
(1) 10-20g of first porous composite filler is filled in the first-stage solid-phase extraction column, and 10-20g of second porous composite filler is filled in the second-stage solid-phase extraction column; the first stage solid phase extraction column and the second stage solid phase extraction are connected in series;
(2) respectively wetting a first porous composite filler in a first-stage solid-phase extraction column and a second porous composite filler in a second-stage solid-phase extraction column by adopting n-pentane, diluting a mixture to be separated by adopting n-pentane, adding the diluted mixture from the upper end of the first-stage solid-phase extraction column, and performing adsorption treatment; eluting the first porous composite filler of the first-stage solid phase extraction column and the second porous composite filler in the second solid phase extraction column by using n-pentane to obtain a saturated hydrocarbon component; adopting n-pentane and toluene in a volume ratio of (15-5): eluting the first porous composite filler of the first-stage solid-phase extraction column and the second porous composite filler in the second solid-phase extraction column by using the eluent consisting of the eluent 1 to obtain the aromatic hydrocarbon component.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention provides a composite solid-phase extraction column, which comprises a first-stage solid-phase extraction column and a second-stage solid-phase extraction column connected with the first-stage solid-phase extraction column in series; the stationary phase in the first-stage solid-phase extraction column is a first porous composite filler which takes porous alumina as a shell and porous silica as a core; the stationary phase in the second-stage solid-phase extraction column is a second porous composite filler which takes porous silicon oxide as a core and Co-MOF nano material as a shell and is loaded with silver nano particles. The first porous composite filler has good mechanical property, large adsorption capacity and good thermal stability; the Co-MOF nano material in the second porous composite filler is uniformly dispersed on the surface of the porous silica, the specific surface area is large, and Co ions and aromatic hydrocarbon have good affinity, so that the selective adsorption property of the second porous composite filler is improved; the loading of the silver nanoparticles further improves the separation performance of the second porous composite filler, mainly due to the weak charge interaction between silver and pi electrons in unsaturated hydrocarbons. And the silver nanoparticles are stably dispersed in the pores of the Co-MOF nano material, and cannot be eluted after adsorption, so that the stable separation performance of the solid-phase extraction column is ensured.
The invention firstly takes tetraethoxysilane as a silicon source, takes P123 as a template, hydrolyzes under the action of urea and acetic acid, and then effectively controls the calcining condition, thereby preparing the porous silicon dioxide material with a stable pore structure, wherein the porous silicon dioxide has a stable hierarchical pore structure, specifically a 0.5-1 mu m macropore and a 5-10nm mesopore structure, the specific surface area reaches 425m2(ii)/g; and then a layer of porous alumina is coated on the surface of the first composite filler, so that the specific surface area of the first composite filler is increased, and the mechanical property of the first composite filler is improved. When the second porous composite filler is prepared, firstly, porous silicon dioxide with a hierarchical pore structure is dispersed, then, APTES is adopted for modification under the action of succinic anhydride, the surface of the modified porous silicon dioxide material has more active groups, so that the adsorption of 2-amino terephthalic acid and cobalt salt is facilitated, and further, a Co-MOF nano material is stably and uniformly formed on the surface of the porous silicon dioxide, and the Co-MOF nano material has good dispersibility, a stable porous structure and a large specific surface area. In order to further improve the selective adsorption of the second composite filler, the porous silicon dioxide coated by the Co-MOF nano material is placed in the ethanol solution of silver nitrate, firstly, impregnation treatment is carried out under certain pressure, silver ions stably enter the macropores and mesopores of the matrix, finally, under normal temperature and normal pressure, ethanol is adopted for slight reduction, and uniformly dispersed silver nanoparticles are formed in the pores.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
The mixture to be separated in the examples and comparative examples is a system containing 20% by weight of toluene/n-heptane.
Example 1
(1) Dissolving 1g P123 in 10ml of acetic acid, then dripping 5ml of 25 wt% ammonia water under an ice bath condition, finally dripping 2ml of ethyl orthosilicate under a violent stirring state, continuing to stir violently until the solution becomes clear after the dripping is finished, finally transferring the solution into a hydrothermal kettle, heating and reacting for 1h at 55 ℃, aging for 5d at 55 ℃ after the reaction is finished, finally placing the wet gel obtained by aging into a mixed solution of water and ethanol for solvent exchange, drying and placing in a muffle furnace under an air atmosphere, firstly heating to 400 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation treatment for 10min, then heating to 600 ℃ at a heating rate of 7 ℃/min, carrying out heat preservation treatment for 10min, finally heating to 800 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation treatment for 1h to obtain porous silica particles with a hierarchical pore structure;
(2) mixing 3g of the porous silica particles prepared above with 50ml of absolute ethanol to prepare a dispersion; dissolving 4g of aluminum isopropoxide in 50ml of isopropanol, adding the dispersion, uniformly mixing, adding 1g of urea, heating to react at 130 ℃ for 3min, filtering after the reaction is finished, drying the solid, placing the dried solid in a muffle furnace under the air atmosphere, firstly heating to 300 ℃ at the speed of 1 ℃/min, carrying out heat preservation treatment for 30min, then heating to 500 ℃ at the speed of 5 ℃/min, and carrying out heat preservation treatment for 4h to obtain a first porous composite filler;
(3) dispersing 4g of the hierarchical porous silica particles prepared in the first step in a solvent consisting of 50ml of DMF and 20ml of deionized water, then dropwise adding a solution consisting of 1g of succinic anhydride, 3g of APTES and 50ml of DMF, stirring at 30 +/-5 ℃ for 2 hours, finally filtering, directly dispersing a solid obtained by filtering in a solution consisting of 7g of cobalt nitrate hexahydrate and 50ml of deionized water, adding a solution consisting of 0.5g of 2-aminoterephthalic acid and 30ml of DMF, reacting at 90 ℃ for 20 hours, and after the reaction is finished, concentrating the reaction solution to prepare a concentrated solution;
(4) adding the concentrated solution into 352ml of 50mmol/L silver nitrate ethanol solution, firstly performing immersion treatment for 2h at room temperature and under the pressure of 0.1MPa, and then performing immersion treatment for 20h at room temperature and under normal pressure; filtering, washing the precipitate with absolute ethyl alcohol, and drying to obtain a second porous composite filler;
(5) 10g of first porous composite filler is filled in the first-stage solid-phase extraction column, and 10g of second porous composite filler is filled in the second-stage solid-phase extraction column; the first stage solid phase extraction column and the second stage solid phase extraction are connected in series;
(6) wetting a first porous composite filler in a first-stage solid-phase extraction column and a second porous composite filler in a second-stage solid-phase extraction column respectively by using 100ml of n-pentane, diluting 12ml of a mixture to be separated by using 30ml of n-pentane, adding the diluted mixture from the upper end of the first-stage solid-phase extraction column, and eluting the first porous composite filler of the first-stage solid-phase extraction column and the second porous composite filler in the second solid-phase extraction column by using 170ml of n-pentane after adsorption treatment to obtain a saturated hydrocarbon component; eluting a first porous composite filler of the first-stage solid-phase extraction column and a second porous composite filler in the second solid-phase extraction column by using an eluent consisting of 225ml of n-pentane and 15ml of toluene to obtain an aromatic hydrocarbon component;
(7) and respectively removing the n-pentane solvent from the saturated hydrocarbon component and the aromatic hydrocarbon component obtained by elution by adopting a rotary evaporator to obtain a toluene component and an n-heptane component. The toluene recovery was 98.5%.
Example 2
(1) Dissolving 2g P123 in 10ml of acetic acid, then dripping 5ml of 25 wt% ammonia water under an ice bath condition, finally dripping 3ml of ethyl orthosilicate under a violent stirring state, continuing to stir violently until the solution becomes clear after dripping is finished, finally transferring the solution into a hydrothermal kettle, heating and reacting for 3h at 65 ℃, carrying out ageing treatment for 6d at 65 ℃ after the reaction is finished, finally placing the wet gel obtained by ageing in a mixed solution of water and ethanol for solvent exchange, drying and placing in a muffle furnace under an air atmosphere, firstly heating to 400 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation treatment for 10min, then heating to 600 ℃ at a heating rate of 7 ℃/min, carrying out heat preservation treatment for 10min, finally heating to 800 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation treatment for 1h to obtain porous silica particles with a hierarchical pore structure;
(2) mixing 3g of the porous silica particles prepared above with 50ml of absolute ethanol to prepare a dispersion; dissolving 7g of aluminum isopropoxide in 50ml of isopropanol, adding the dispersion, uniformly mixing, adding 1g of urea, heating to react for 7min at 150 ℃, filtering after the reaction is finished, drying the solid, placing the dried solid in a muffle furnace under the air atmosphere, firstly heating to 300 ℃ at the speed of 1 ℃/min, carrying out heat preservation treatment for 30min, then heating to 500 ℃ at the speed of 5 ℃/min, and carrying out heat preservation treatment for 4h to obtain a first porous composite filler;
(3) dispersing 5g of the hierarchical porous silica particles prepared in the first step in a solvent consisting of 50ml of DMF and 20ml of deionized water, then dropwise adding a solution consisting of 3g of succinic anhydride, 4g of APTES and 50ml of DMF, stirring at 30 +/-5 ℃ for 4 hours, finally filtering, directly dispersing a solid obtained by filtering in a solution consisting of 7g of cobalt nitrate hexahydrate and 50ml of deionized water, adding a solution consisting of 0.8g of 2-aminoterephthalic acid and 30ml of DMF, reacting at 100 ℃ for 30 hours, and after the reaction is finished, concentrating the reaction solution to prepare a concentrated solution;
(4) adding the concentrated solution into 352ml of 50mmol/L silver nitrate ethanol solution, firstly performing immersion treatment for 4h at room temperature and under the pressure of 0.2MPa, and then performing immersion treatment for 50h at room temperature and under normal pressure; filtering, washing the precipitate with absolute ethyl alcohol, and drying to obtain a second porous composite filler;
(5) 20g of first porous composite filler is filled in the first-stage solid-phase extraction column, and 20g of second porous composite filler is filled in the second-stage solid-phase extraction column; the first stage solid phase extraction column and the second stage solid phase extraction are connected in series;
(6) wetting a first porous composite filler in a first-stage solid-phase extraction column and a second porous composite filler in a second-stage solid-phase extraction column respectively by using 100ml of n-pentane, diluting 12ml of a mixture to be separated by using 30ml of n-pentane, adding the diluted mixture from the upper end of the first-stage solid-phase extraction column, and eluting the first porous composite filler of the first-stage solid-phase extraction column and the second porous composite filler in the second solid-phase extraction column by using 170ml of n-pentane after adsorption treatment to obtain a saturated hydrocarbon component; eluting a first porous composite filler of the first-stage solid-phase extraction column and a second porous composite filler in the second solid-phase extraction column by using an eluent consisting of 225ml of n-pentane and 15ml of toluene to obtain an aromatic hydrocarbon component;
(7) and respectively removing the n-pentane solvent from the saturated hydrocarbon component and the aromatic hydrocarbon component obtained by elution by adopting a rotary evaporator to obtain a toluene component and an n-heptane component. The toluene recovery was 98.7%.
Example 3
(1) Dissolving 1.5g P123 in 10ml of acetic acid, then dripping 5ml of 25 wt% ammonia water under an ice bath condition, finally dripping 2ml of ethyl orthosilicate under a violent stirring state, continuing to stir violently until the solution becomes clear after the dripping is finished, finally transferring the solution into a hydrothermal kettle, heating and reacting for 1h at 60 ℃, aging for 5d at 60 ℃ after the reaction is finished, finally placing the wet gel obtained by aging into a mixed solution of water and ethanol for solvent exchange, drying and placing in a muffle furnace under an air atmosphere, firstly heating to 400 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation treatment for 10min, then heating to 600 ℃ at a heating rate of 7 ℃/min, carrying out heat preservation treatment for 10min, finally heating to 800 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation treatment for 1h to obtain porous silica particles with a hierarchical pore structure;
(2) mixing 3g of the porous silica particles prepared above with 50ml of absolute ethanol to prepare a dispersion; dissolving 5g of aluminum isopropoxide in 50ml of isopropanol, adding the dispersion, uniformly mixing, adding 1g of urea, heating to react for 5min at 130 ℃, filtering after the reaction is finished, drying the solid, placing the dried solid in a muffle furnace under the air atmosphere, firstly heating to 300 ℃ at the speed of 1 ℃/min, carrying out heat preservation treatment for 30min, then heating to 500 ℃ at the speed of 5 ℃/min, and carrying out heat preservation treatment for 4h to obtain a first porous composite filler;
(3) dispersing 4g of the hierarchical porous silica particles prepared in the first step in a solvent consisting of 50ml of DMF and 20ml of deionized water, then dropwise adding a solution consisting of 3g of succinic anhydride, 3g of APTES and 50ml of DMF, stirring at 30 +/-5 ℃ for 3 hours, finally filtering, directly dispersing a solid obtained by filtering in a solution consisting of 7g of cobalt nitrate hexahydrate and 50ml of deionized water, adding a solution consisting of 0.6g of 2-aminoterephthalic acid and 30ml of DMF, reacting at 90 ℃ for 25 hours, and after the reaction is finished, concentrating the reaction solution to prepare a concentrated solution;
(4) adding the concentrated solution into 352ml of 50mmol/L silver nitrate ethanol solution, firstly performing immersion treatment for 3h at room temperature and under the pressure of 0.1MPa, and then performing immersion treatment for 30h at room temperature and under normal pressure; filtering, washing the precipitate with absolute ethyl alcohol, and drying to obtain a second porous composite filler;
(5) 15g of first porous composite filler is filled in the first-stage solid-phase extraction column, and 15g of second porous composite filler is filled in the second-stage solid-phase extraction column; the first stage solid phase extraction column and the second stage solid phase extraction are connected in series;
(6) wetting a first porous composite filler in a first-stage solid-phase extraction column and a second porous composite filler in a second-stage solid-phase extraction column respectively by using 100ml of n-pentane, diluting 12ml of a mixture to be separated by using 30ml of n-pentane, adding the diluted mixture from the upper end of the first-stage solid-phase extraction column, and eluting the first porous composite filler of the first-stage solid-phase extraction column and the second porous composite filler in the second solid-phase extraction column by using 170ml of n-pentane after adsorption treatment to obtain a saturated hydrocarbon component; eluting a first porous composite filler of the first-stage solid-phase extraction column and a second porous composite filler in the second solid-phase extraction column by using an eluent consisting of 225ml of n-pentane and 15ml of toluene to obtain an aromatic hydrocarbon component;
(7) and respectively removing the n-pentane solvent from the saturated hydrocarbon component and the aromatic hydrocarbon component obtained by elution by adopting a rotary evaporator to obtain a toluene component and an n-heptane component. The toluene recovery was 98.9%.
Example 4
(1) Dissolving 2g P123 in 10ml of acetic acid, then dripping 5ml of 25 wt% ammonia water under an ice bath condition, finally dripping 2ml of ethyl orthosilicate under a violent stirring state, continuing to stir violently until the solution becomes clear after the dripping is finished, finally transferring the solution into a hydrothermal kettle, heating and reacting for 2h at 60 ℃, carrying out ageing treatment for 6d at 60 ℃ after the reaction is finished, finally placing the wet gel obtained by ageing in a mixed solution of water and ethanol for solvent exchange, drying and placing in a muffle furnace under an air atmosphere, firstly heating to 400 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation treatment for 10min, then heating to 600 ℃ at a heating rate of 7 ℃/min, carrying out heat preservation treatment for 10min, finally heating to 800 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation treatment for 1h to obtain porous silica particles with a hierarchical pore structure;
(2) mixing 3g of the porous silica particles prepared above with 50ml of absolute ethanol to prepare a dispersion; dissolving 6g of aluminum isopropoxide in 50ml of isopropanol, adding the dispersion, uniformly mixing, adding 1g of urea, heating to react at 140 ℃ for 5min, filtering after the reaction is finished, drying the solid, placing the dried solid in a muffle furnace under the air atmosphere, firstly heating to 300 ℃ at the speed of 1 ℃/min, carrying out heat preservation treatment for 30min, then heating to 500 ℃ at the speed of 5 ℃/min, and carrying out heat preservation treatment for 4h to obtain a first porous composite filler;
(3) dispersing 4.5g of the hierarchical porous silica particles prepared in the first step in a solvent consisting of 50ml of DMF and 20ml of deionized water, then dropwise adding a solution consisting of 2g of succinic anhydride, 3.5g of APTES and 50ml of DMF, stirring at 30 +/-5 ℃ for 3 hours, finally filtering, directly dispersing a solid obtained by filtering in a solution consisting of 7g of cobalt nitrate hexahydrate and 50ml of deionized water, adding a solution consisting of 0.7g of 2-aminoterephthalic acid and 30ml of DMF, reacting at 100 ℃ for 25 hours, and after the reaction is finished, concentrating the reaction liquid to prepare a concentrated solution;
(4) adding the concentrated solution into 352ml of 50mmol/L silver nitrate ethanol solution, firstly performing immersion treatment for 3h at room temperature and under the pressure of 0.2MPa, and then performing immersion treatment for 40h at room temperature and under normal pressure; filtering, washing the precipitate with absolute ethyl alcohol, and drying to obtain a second porous composite filler;
(5) 15g of first porous composite filler is filled in the first-stage solid-phase extraction column, and 15g of second porous composite filler is filled in the second-stage solid-phase extraction column; the first stage solid phase extraction column and the second stage solid phase extraction are connected in series;
(6) wetting a first porous composite filler in a first-stage solid-phase extraction column and a second porous composite filler in a second-stage solid-phase extraction column respectively by using 100ml of n-pentane, diluting 12ml of a mixture to be separated by using 30ml of n-pentane, adding the diluted mixture from the upper end of the first-stage solid-phase extraction column, and eluting the first porous composite filler of the first-stage solid-phase extraction column and the second porous composite filler in the second solid-phase extraction column by using 170ml of n-pentane after adsorption treatment to obtain a saturated hydrocarbon component; eluting a first porous composite filler of the first-stage solid-phase extraction column and a second porous composite filler in the second solid-phase extraction column by using an eluent consisting of 225ml of n-pentane and 15ml of toluene to obtain an aromatic hydrocarbon component;
(7) and respectively removing the n-pentane solvent from the saturated hydrocarbon component and the aromatic hydrocarbon component obtained by elution by adopting a rotary evaporator to obtain a toluene component and an n-heptane component. The toluene recovery was 98.5%.
Comparative example 1
The stationary phase in the second stage solid phase extraction column adopts a silver nanoparticle composite material loaded by porous silica, and other conditions are the same as those in example 4. The toluene recovery rate was found to be 73.5%.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (10)
1. A composite solid phase extraction column is characterized in that: comprises a first-stage solid-phase extraction column and a second-stage solid-phase extraction column connected with the first-stage solid-phase extraction column in series; the stationary phase in the first-stage solid-phase extraction column is a first porous composite filler which takes porous alumina as a shell and porous silica as a core; the stationary phase in the second-stage solid-phase extraction column is a second porous composite filler which takes porous silicon oxide as a core and Co-MOF nano material as a shell and is loaded with silver nano particles.
2. The composite solid phase extraction column of claim 1, wherein: the preparation method of the first porous composite filler comprises the following steps:
dissolving P123 in acetic acid, then dropwise adding ammonia water under an ice bath condition, finally dropwise adding ethyl orthosilicate under a state of vigorous stirring, continuing to vigorously stir until the solution becomes clear after the dropwise adding is finished, finally transferring the solution into a hydrothermal kettle, heating for reaction, carrying out aging treatment after the reaction is finished, finally placing wet gel obtained by aging in a mixed solution of water and ethanol for solvent exchange, drying and then placing in a muffle furnace for calcining treatment; preparing graded porous silicon dioxide particles;
secondly, mixing the prepared porous silicon dioxide particles with absolute ethyl alcohol to prepare dispersion liquid; dissolving aluminum isopropoxide in isopropanol, adding dispersion liquid, uniformly mixing, adding urea, heating and reacting at 130-150 ℃ for 3-7min, filtering after the reaction is finished, drying the solid, and calcining in a muffle furnace to obtain the first porous composite filler.
3. The composite solid phase extraction column of claim 2, wherein: in the first step, the concentration of the ammonia water is 25 wt%, and the dosage ratio of the P123, the ammonia water and the tetraethoxysilane is (1-2) g: 5 ml: (2-3) ml.
4. The composite solid phase extraction column of claim 2, wherein: in the first step, the temperature of the heating reaction is 55-65 ℃, and the time of the heating reaction is 1-3 h; the temperature of the aging treatment is 55-65 ℃, and the time of the aging treatment is 5-6 d.
5. The composite solid phase extraction column of claim 2, wherein: in the first step, the calcination treatment conditions are as follows: firstly heating to 400 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation treatment for 10min, then heating to 600 ℃ at a heating rate of 7 ℃/min, carrying out heat preservation treatment for 10min, finally heating to 800 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation treatment for 1 h.
6. The composite solid phase extraction column of claim 2, wherein: in the second step, the mass ratio of the aluminum isopropoxide to the urea to the porous silica particles is (4-7): 1:3.
7. The composite solid phase extraction column of claim 2, wherein: in the second step, the calcination treatment conditions are as follows: firstly, heating to 300 ℃ at the speed of 1 ℃/min, carrying out heat preservation treatment for 30min, then heating to 500 ℃ at the speed of 5 ℃/min, and carrying out heat preservation treatment for 4 h.
8. The composite solid phase extraction column of claim 2, wherein: the preparation method of the second porous composite filler comprises the following steps:
(a) dispersing the hierarchical porous silicon dioxide particles prepared in the first step in a solvent consisting of DMF and deionized water, then dropwise adding DMF solution of succinic anhydride and APTES, stirring at 30 +/-5 ℃ for 2-4h, finally filtering, directly dispersing the solid obtained by filtering in the aqueous solution of cobalt nitrate hexahydrate, adding DMF solution of 2-amino terephthalic acid, reacting at 90-100 ℃ for 20-30h, and after the reaction is finished, concentrating the reaction liquid to prepare a concentrated solution;
(b) adding the concentrated solution into 50mmol/L ethanol solution of silver nitrate, soaking at room temperature and 0.1-0.2MPa for 2-4 hr, and soaking at room temperature and normal pressure for 20-50 hr; filtering, washing the precipitate with absolute ethyl alcohol, and drying to obtain a second porous composite filler.
9. The composite solid phase extraction column of claim 8, wherein: the mass ratio of the graded porous silica particles, succinic anhydride, APTES, cobalt nitrate hexahydrate, 2-amino terephthalic acid and silver nitrate is (4-5): (1-3): (3-4): 7: (0.5-0.8): 3.
10. use of a composite solid phase extraction column according to any one of claims 1 to 9 for the separation of alkane/arene mixtures by extraction, comprising the following steps:
(1) 10-20g of first porous composite filler is filled in the first-stage solid-phase extraction column, and 10-20g of second porous composite filler is filled in the second-stage solid-phase extraction column; the first stage solid phase extraction column and the second stage solid phase extraction are connected in series;
(2) respectively wetting a first porous composite filler in a first-stage solid-phase extraction column and a second porous composite filler in a second-stage solid-phase extraction column by adopting n-pentane, diluting a mixture to be separated by adopting n-pentane, adding the diluted mixture from the upper end of the first-stage solid-phase extraction column, and performing adsorption treatment; eluting the first porous composite filler of the first-stage solid phase extraction column and the second porous composite filler in the second solid phase extraction column by using n-pentane to obtain a saturated hydrocarbon component; adopting n-pentane and toluene in a volume ratio of (15-5): eluting the first porous composite filler of the first-stage solid-phase extraction column and the second porous composite filler in the second solid-phase extraction column by using the eluent consisting of the eluent 1 to obtain the aromatic hydrocarbon component.
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| CN104208905B (en) * | 2013-06-05 | 2016-05-11 | 中国石油天然气股份有限公司 | Silver ion-loaded solid-phase extraction column and preparation and application thereof |
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