CN112326399A - Rapid extraction pool dewatering method - Google Patents
Rapid extraction pool dewatering method Download PDFInfo
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Abstract
The invention discloses a rapid extraction tank dewatering method. The invention designs the bottom and top water absorption layers, integrates the two steps of dehydration and extraction, shortens the operation time of extracting the organic matters in the extracted substances, and is convenient for rapidly detecting the content of the organic matters in the extracted substances. The upper surface and the lower surface of the diatomite/Ca-LTA layer extract material are utilized to absorb water in a large range, water molecules are firmly combined, and the desorption rate is reduced, which is a first defense line for removing water; absorbing the water vapor analyzed or overflowed in the heating process by using the MIL-101/color-changing silica gel layer, and judging whether residual water molecules in the extract liquid are left or not from the color change, wherein the residual water molecules are the second defense line for removing water; in addition, the diatomite is purified, the introduction of other object molecules such as alkaline earth, alkaline metal, iron, organic matters and the like is eliminated, and the extraction substances are subjected to impurity removal by utilizing the metal adsorption of MIL-101 so as to enhance the accuracy and stability of the detection of the liquid to be detected.
Description
Technical Field
The invention relates to the field of soil pretreatment, in particular to a rapid extraction tank dewatering method.
Background
Soil is one of the factors which form the basic environment of an ecosystem and is the material basis for human beings to live on, so that the prevention and treatment of soil pollution is significant, wherein besides metal pollution, more pollution caused by organic matters remained in garbage decomposition is caused, and how to judge the organic matter pollution and the pollution severity needs to be judged by detecting the content of components.
Generally, the detection substance is obtained by extracting effective components from soil or other media through a solvent and then concentrating the effective components through nitrogen blowing so as to be analyzed by a next instrument. With this simultaneously, if it is unsatisfactory to appear the dewatering effect in the extraction process, then can lead to nitrogen to blow the process and go wrong, therefore lead to the experiment failure, influence the authenticity and the stability of detection data. At present, substances are generally pretreated by using a water removing agent to remove water, and then are extracted, so that the method is long in time consumption, and the extraction still has the risk that water molecules are easily introduced after water removal; in addition, the extracted substance generally contains trace metal impurities, which are not removed during extraction, and thus the service life of the detection instrument is easily affected, and the detection result is also affected.
Disclosure of Invention
The invention aims to provide a rapid extraction pond dewatering method to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a quick extraction pool water removal method comprises the following steps:
s1: preparing an extraction material;
s2: pressurized fluid extraction;
s3: first nitrogen-blowing concentration;
s4: purifying;
s5: and (5) performing nitrogen-blown concentration for the second time.
Preferably, the extraction substance is a composition of one or more substances in waste branches, waste leaves, stones and soil.
Preferably, the method comprises the following steps:
s1: preparing materials:
(1) preparation of extraction material: accurately weighing the extract to 0.01g, and grinding into fine particles for later use;
(2) preparation of diatomaceous earth/Ca-LTA: grinding diatomite in a ball mill and sieving the ground diatomite by a sieve to obtain diatomite powder; performing acid treatment on 20g of diatomite powder at 80-100 ℃ for 5-6 h by using 400mL of 4mol/L nicotinic acid; thoroughly washing the treated diatomite powder with deionized water until no chloride exists, and drying at 80-110 ℃ for 24-30 h to obtain acid-treated diatomite powder; putting the diatomite powder into a muffle furnace, and raising the temperature to 500-700 ℃ at a heating rate of 5-6 ℃/min for treatment for 2-3 h to obtain purified diatomite powder; mixing the diatomite/Ca-LTA and Ca-LTA by a mixer at a set rotating speed of 120-200 rmp and a temperature of 25-35 ℃ to prepare diatomite/Ca-LTA for later use;
(3) preparation of MIL-101/allochroic silica gel: accurately weighing 4.0g of terephthalic acid, 1.66g of chromium nitrate, 1mL of hydrochloric acid and 100mg of allochroic silica gel, sequentially adding the terephthalic acid, the chromium nitrate, the 1mL of hydrochloric acid and the 100mg of allochroic silica gel into 50mL of deionized water, ultrasonically dispersing for 45-75 min, reacting by a solvothermal method, setting the temperature to be 150-200 ℃, and setting the reaction time to be 12 h; after the reaction is finished, washing the product with DMF solution for 3 times at 60-65 ℃, washing the product with absolute ethyl alcohol for 2 times at room temperature, washing the product with deionized water for 2 times, and drying the product in vacuum for 5-10 hours at 120-150 ℃ to prepare MIL-101/allochroic silica gel for later use, wherein the MIL-101/allochroic silica gel can be prepared in an equal proportion according to the using amount;
s2: pressurized fluid extraction: vertically placing the cleaned and dried extraction tank on a horizontal plane; placing the glass fiber filter membrane at the bottom of the extraction tank, and screwing down the bottom cover; the MIL-101/allochroic silica gel is uniformly paved on a glass fiber filter membrane, and then diatomite/Ca-LTA is uniformly paved on the MIL-101/allochroic silica gel to be used as a bottom water absorption layer; then uniformly spreading the ground extract on diatomite/Ca-LTA to obtain an extract layer; uniformly paving the kieselguhr/Ca-LTA on the extraction substance, and then uniformly paving the MIL-101/allochroic silica gel on the kieselguhr/Ca-LTA to serve as a top water absorption layer; obtaining a loaded extraction tank; performing an extraction process by adopting a dichloromethane-acetone solution, and setting extraction conditions as follows: the carrier gas pressure is 0.4-0.6 MPa, the heating temperature is 110-130 ℃, and the working pressure is 100 bar; the static extraction is circulated for 2 times, and the solvent/gas is set to be 50sec/5 min; rinsing (RP) again for 1 time to obtain extract liquor;
s3: first nitrogen-blowing concentration: transferring the extract liquid in the step S2 to a concentration bottle, washing the extraction bottle with 10-15 mL of dichloromethane-acetone solution for 3-5 times, and transferring the obtained solution to the concentration bottle; placing the concentration bottle in a nitrogen blowing instrument for concentration, setting the working temperature to be 20-30 ℃ and the working pressure to be 20 Kpa; in the concentration process, 10-20 mL of dichloromethane solution is needed to rinse the inner wall of the nitrogen blowing pipe for 3-5 times, and the nitrogen blowing pipe is finally concentrated to 1mL to obtain a concentrated solution;
s4: purifying: pre-eluting the Florisl SPE small column by using 8-10 mL of dichloromethane solution, and pouring off the eluent; transferring the concentrated solution obtained in the step S3 to a Florisl SPE small column, rinsing the inner wall of a nitrogen blowing pipe for 3-5 times by using 4-8 mL of dichloromethane, and transferring the obtained liquid to the Florisl SPE small column; starting a vacuum pump to execute elution operation, setting the flow rate of a control valve, and collecting eluent; washing the wall of the Florisl SPE small column with 2mL of dichloromethane for 2 times, collecting and combining to obtain a purified solution;
s5: and (3) second nitrogen blowing concentration: performing secondary nitrogen-blowing concentration on the purified liquid in the step S4 according to the nitrogen-blowing concentration step in the step S3 to obtain 0.3-0.5 mL of concentrated liquid, adding an internal standard solution, uniformly mixing, and performing constant volume to 1mL by using a dichloromethane solution to obtain a constant solution; transferring the sample solution into a 2mL sample injection vial to obtain a solution to be detected; in addition, if the test is not performed immediately, the test solution should be stored at a temperature below 4 ℃.
Preferably, in step S1 (2), the aperture of the sieve is 50-80 μm.
Preferably, in step S1 (2), the ratio of diatomaceous earth in the diatomaceous earth/Ca-LTA is 15% to 25%.
Preferably, in step S2, the pore size of the glass fiber filter membrane is 0.45 μm.
Preferably, in step S2, the thickness of the diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silica gel in the bottom water absorption layer are respectively 1-2 cm and 2-4 cm; the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silica gel in the top water absorption layer are respectively 1-2 cm and 1-2 cm.
Preferably, in step S2, the static extraction time is 8-10 min.
Preferably, in step S4, the flow rate of the control valve is 4-6 mL/min.
In the technical scheme:
the technical scheme aims to combine the two steps of dehydration and extraction, save the step of dehydration by anhydrous sodium sulfate before the general extraction process, shorten the operation time of extraction of organic matters in the extracted substances and facilitate the rapid detection of the content of the organic matters in the extracted substances. The problem of the not ideal nitrogen that leads to of effect of common dewatering in-process blows the process and appears water simultaneously to lead to the deviation to appear in the testing process is solved.
The extraction tank is provided with a bottom water absorption layer and a top water absorption layer which are respectively arranged above and below the extraction material, the bottom water absorption layer and the top water absorption layer are symmetrically arranged and both consist of diatomite/Ca-LTA layers and MIL-101/allochroic silica gel layers, and the diatomite/Ca-LTA layers are arranged close to two sides of the extraction material.
Firstly, diatomite is an adsorbent capable of adsorbing water molecules, two water adsorption mechanisms of chemical adsorption and physical adsorption exist, the chemical adsorption is characterized in that the surface of a mineral substance and the water molecules are subjected to hydroxylation reaction and cannot be resolved, the physical adsorption is adsorption by van der waals force, the adsorption can also have desorption effect due to a pore channel, the desorbed water molecules can enter an extraction liquid along with a solvent during extraction, and the nitrogen blowing failure is caused because the nitrogen blowing temperature of the diatomite is only 30 ℃, so that the later detection result is influenced. Therefore, Ca-LTA (calcium exchange type molecular sieve) is introduced to strengthen the combination of water molecules and reduce the desorption rate, the Ca-LTA is also a water-absorbing substance, the Ca-LTA is mixed with diatomite, part of the sieved diatomite enters Ca-LTA pore channels, the mixed diatomite/Ca-LTA layer absorbs water on the upper surface and the lower surface of the extraction substance in a large range, and the movable non-framework cations and the framework oxygen ions of the diatomite in the Ca-LTA cavity can firmly combine the water molecules in the extraction substance to reduce the desorption rate, so that the first defense line for removing water is provided.
Secondly, because the temperature in the extraction condition is heated to 120 ℃, the water analysis can change along with the temperature rise, and part of water vapor overflows, the MIL-101/allochroic silica gel layer is arranged on the other side of the diatomite/Ca-LTA layer, the MIL-101 has strong adsorption to the water vapor, and the MIL-101 is extremely sensitive to trace water vapor after being activated at 100 ℃, so that the water vapor can be effectively organized to enter the extraction liquid along with the solvent to influence the nitrogen blowing process, and the water removal is a second defense line. In addition, the allochroic silicagel is embedded in the structure of the MIL-101 in the synthesis process, so that the stability of the structure of the MIL-101 is enhanced, the service life of the material is prolonged, and the allochroic silicagel can react with the allochroic silicagel after the MIL-101 grasps water molecules to generate color changes of different degrees, so that whether water exists or not can be judged, and whether trace water vapor exists in the extraction liquid or not can be known in time. Therefore, the reason why the MIL-101/color-changing silica gel layer with the thickness of 2-4 cm is arranged in the bottom water absorption layer can be judged according to the color depth and the color-changing area.
Meanwhile, the MIL-101/allochroic silica gel has a certain adsorption effect on metals, and if trace metal impurities exist in the extracted substances, the impurities can be removed in time, so that the phenomenon that trace non-volatile matters pollute a gasification chamber during detection is prevented, and the service life of a detection instrument is shortened; or blocking the air inlet, so that the detection result is abnormal.
Finally, in the process operation: (1) before the diatomite is used, purification treatment is carried out on the premise of not changing the structure of the diatomite, and the purpose is to eliminate other object molecules such as alkaline earth, alkaline metal, iron, organic matters and the like and prevent new impurities from being introduced during extraction to influence the analysis of a sample to be detected; (2) in the MIL-101 washing process, DMF solution washing is used for removing unreacted terephthalic acid, and absolute ethyl alcohol washing is used for removing surface impurities.
Compared with the prior art, the invention has the following beneficial effects: the invention designs the two water absorption layers at the bottom and the top, integrates the dehydration step and the extraction step, omits the dehydration step by using anhydrous sodium sulfate before the general extraction process, shortens the operation time of extracting the organic matters in the extracted substances, and is convenient for rapidly detecting the content of the organic matters in the extracted substances. The upper surface and the lower surface of the diatomite/Ca-LTA layer extraction material are utilized to absorb water in a large range, water molecules are firmly combined in the gap between the two materials, and the desorption rate is reduced, so that the first defense line for removing water is provided; absorbing the water vapor analyzed or overflowed in the heating process by using the MIL-101/color-changing silica gel layer, and judging whether residual water molecules in the extract liquid are left or not from the color change, wherein the residual water molecules are the second defense line for removing water; in addition, the diatomite is purified to eliminate introduction of other object molecules such as alkaline earth, alkaline metal, iron, organic matters and the like, and the extraction substances are subjected to impurity removal by utilizing the metal adsorption of MIL-101 so as to enhance the accuracy of the liquid to be detected.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
step 1: preparing materials:
(1) preparation of extraction material: accurately weighing the extract to 0.01g, and grinding into fine particles for later use;
(2) preparation of diatomaceous earth/Ca-LTA: grinding diatomite in a ball mill and sieving the ground diatomite by a sieve to obtain diatomite powder; the diatomite powder is subjected to acid treatment at 80 ℃ for 5 hours in a ratio of 400mL of 4mol/L nicotinic acid for every 20g of diatomite powder; thoroughly washing the treated diatomite powder by using deionized water until no chloride exists, and drying the diatomite powder for 24 hours at 80 ℃ to obtain acid-treated diatomite powder; putting the diatomite powder into a muffle furnace, and heating to 500 ℃ at a heating rate of 5 ℃/min for treatment for 2h to obtain purified diatomite powder; mixing the diatomite powder and Ca-LTA by a mixer at a set rotation speed of 120rmp and a temperature of 25 ℃ to prepare diatomite/Ca-LTA for later use;
(3) preparation of MIL-101/allochroic silica gel: accurately weighing 4.0g of terephthalic acid, 1.66g of chromium nitrate, 1mL of hydrochloric acid and 100mg of allochroic silica gel, sequentially adding the terephthalic acid, the chromium nitrate, the 1mL of hydrochloric acid and the 100mg of allochroic silica gel into 50mL of deionized water, carrying out ultrasonic dispersion for 45min, and carrying out a reaction by a solvothermal method, wherein the reaction temperature is set to be 150 ℃, and the reaction time is 12 h; after the reaction is finished, washing the product with DMF solution for 3 times at 60 ℃, washing the product with absolute ethyl alcohol for 2 times at room temperature, washing the product with deionized water for 2 times, and drying the product in vacuum for 5 hours at 120 ℃ to prepare MIL-101/allochroic silica gel for later use, wherein the MIL-101/allochroic silica gel can be proportionally amplified according to the required amount;
step 2: pressurized fluid extraction: vertically placing the cleaned and dried extraction tank on a horizontal plane; placing the glass fiber filter membrane at the bottom of the extraction tank, and screwing down the bottom cover; the MIL-101/allochroic silica gel is uniformly paved on a glass fiber filter membrane, and then diatomite/Ca-LTA is uniformly paved on the MIL-101/allochroic silica gel to be used as a bottom water absorption layer; then uniformly spreading the ground extract on diatomite/Ca-LTA to obtain an extract layer; uniformly paving the kieselguhr/Ca-LTA on the extraction substance, and then uniformly paving the MIL-101/allochroic silica gel on the kieselguhr/Ca-LTA to serve as a top water absorption layer; obtaining a loaded extraction tank; performing an extraction process by adopting a dichloromethane-acetone solution, and setting extraction conditions as follows: the pressure of carrier gas is 0.4MPa, the heating temperature is 110 ℃, and the working pressure is 100 bar; the static extraction is circulated for 2 times, and the solvent/gas is set to be 50sec/5 min; rinsing (RP) again for 1 time to obtain extract liquor;
and step 3: first nitrogen-blowing concentration: transferring the extract liquid into a concentration bottle, washing the extraction bottle for 3 times by using 10mL of dichloromethane-acetone solution, and transferring the obtained solution into the concentration bottle; placing the concentration bottle in a nitrogen blowing instrument for concentration, setting the working temperature at 20 ℃ and the working pressure at 20 Kpa; in the concentration process, 10mL of dichloromethane solution is needed to rinse the inner wall of the nitrogen blowing pipe for 3 times, and the nitrogen blowing pipe is finally concentrated to 1mL to obtain concentrated solution;
and 4, step 4: purifying: pre-eluting the Florisl SPE cartridge by using 8mL of dichloromethane solution, and pouring off the eluent; transferring the concentrated solution to a Florisl SPE small column, rinsing the inner wall of a nitrogen blowing pipe for 3 times by using 4mL of dichloromethane, and transferring the obtained liquid to the Florisl SPE small column; starting a vacuum pump to execute elution operation, setting the flow rate of a control valve, and collecting eluent; washing the wall of the Florisl SPE small column with 2mL of dichloromethane for 2 times, collecting and combining to obtain a purified solution;
and 5: and (3) second nitrogen blowing concentration: performing secondary nitrogen-blowing concentration on the purified solution according to the nitrogen-blowing concentration step in the step 3 to obtain 0.3mL of concentrated solution, adding an internal standard solution, uniformly mixing, and performing constant volume to 1mL by using a dichloromethane solution to obtain a constant solution; transferring the sample solution into a 2mL sample injection vial to obtain a solution to be detected; in addition, if the test is not performed immediately, the test solution should be stored at a temperature below 4 ℃.
In this embodiment, the extraction substance is a composition of a plurality of substances including waste branches, waste leaves and soil;
the proportion of the diatomite in the diatomite/Ca-LTA is 15 percent;
the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silicagel of the bottom water absorption layer are respectively 1cm and 2 cm; the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silicagel of the top water absorption layer are respectively 1cm and 1 cm;
the static extraction time is 8 min;
the flow rate of the control valve is 4 mL/min.
Example 2:
step 1: preparing materials:
(1) preparation of extraction material: accurately weighing the extract to 0.01g, and grinding into fine particles for later use;
(2) preparation of diatomaceous earth/Ca-LTA: grinding diatomite in a ball mill and sieving the ground diatomite by a sieve to obtain diatomite powder; performing acid treatment on 20g of diatomite powder at 100 ℃ for 5-6 h by using 400mL of 4mol/L nicotinic acid; thoroughly washing the treated diatomite powder by using deionized water until no chloride exists, and drying the diatomite powder for 30 hours at 110 ℃ to obtain acid-treated diatomite powder; putting the diatomite powder into a muffle furnace, and heating to 700 ℃ at the heating rate of 6 ℃/min for treatment for 3h to obtain purified diatomite powder; mixing the diatomite/Ca-LTA and Ca-LTA by a mixer at a set rotation speed of 200rmp and a temperature of 35 ℃ to prepare diatomite/Ca-LTA for later use;
(3) preparation of MIL-101/allochroic silica gel: accurately weighing 4.0g of terephthalic acid, 1.66g of chromium nitrate, 1mL of hydrochloric acid and 100mg of allochroic silica gel, sequentially adding the terephthalic acid, the chromium nitrate, the 1mL of hydrochloric acid and the 100mg of allochroic silica gel into 50mL of deionized water, ultrasonically dispersing for 75min, and reacting by a solvothermal method, wherein the reaction temperature is set to be 200 ℃, and the reaction time is 12 hours; after the reaction is finished, washing the product with DMF solution for 3 times at 65 ℃, washing the product with absolute ethyl alcohol for 2 times at room temperature, washing the product with deionized water for 2 times, and drying the product in vacuum for 10 hours at 150 ℃ to prepare MIL-101/allochroic silicagel for later use, wherein the MIL-101/allochroic silicagel can be proportionally amplified according to the required amount;
step 2: pressurized fluid extraction: vertically placing the cleaned and dried extraction tank on a horizontal plane; placing the glass fiber filter membrane at the bottom of the extraction tank, and screwing down the bottom cover; the MIL-101/allochroic silica gel is uniformly paved on a glass fiber filter membrane, and then diatomite/Ca-LTA is uniformly paved on the MIL-101/allochroic silica gel to be used as a bottom water absorption layer; then uniformly spreading the ground extract on diatomite/Ca-LTA to obtain an extract layer; uniformly paving the kieselguhr/Ca-LTA on the extraction substance, and then uniformly paving the MIL-101/allochroic silica gel on the kieselguhr/Ca-LTA to serve as a top water absorption layer; obtaining a loaded extraction tank; performing an extraction process by adopting a dichloromethane-acetone solution, and setting extraction conditions as follows: the pressure of carrier gas is 0.6MPa, the heating temperature is 130 ℃, and the working pressure is 100 bar; the static extraction is circulated for 2 times, and the solvent/gas is set to be 50sec/5 min; rinsing (RP) again for 1 time to obtain extract liquor;
and step 3: first nitrogen-blowing concentration: transferring the extract liquid into a concentration bottle, washing the extraction bottle for 5 times by using 15mL of dichloromethane-acetone solution, and transferring the obtained solution into the concentration bottle; placing the concentration bottle in a nitrogen blowing instrument for concentration, setting the working temperature at 30 ℃ and the working pressure at 20 Kpa; in the concentration process, 20mL of dichloromethane solution is needed to rinse the inner wall of the nitrogen blow pipe for 5 times, and the concentration is finally carried out to 1mL to obtain concentrated solution;
and 4, step 4: purifying: pre-eluting the Florisl SPE cartridge by using 10mL of dichloromethane solution, and pouring off the eluent; transferring the concentrated solution to a Florisl SPE small column, using 8mL of dichloromethane to rinse the inner wall of a nitrogen blowing pipe for 5 times, and transferring the obtained liquid to the Florisl SPE small column; starting a vacuum pump to execute elution operation, setting the flow rate of a control valve, and collecting eluent; washing the wall of the Florisl SPE small column with 2mL of dichloromethane for 2 times, collecting and combining to obtain a purified solution;
and 5: and (3) second nitrogen blowing concentration: performing secondary nitrogen-blowing concentration on the purified solution according to the nitrogen-blowing concentration step in the step 3 to obtain 0.5mL of concentrated solution, adding an internal standard solution, uniformly mixing, and performing constant volume to 1mL by using a dichloromethane solution to obtain a constant solution; transferring the sample solution into a 2mL sample injection vial to obtain a solution to be detected; in addition, if the test is not performed immediately, the test solution should be stored at a temperature below 4 ℃.
In this embodiment, the extraction substance is a composition of a plurality of substances including waste branches, waste leaves and stones;
the proportion of the diatomite in the diatomite/Ca-LTA is 25 percent;
the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silicagel of the bottom water absorption layer are respectively 2cm and 4 cm; the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silicagel of the top water absorption layer are respectively 2cm and 2 cm;
the static extraction time is 10 min;
the flow rate of the control valve is 6 mL/min.
Example 3:
step 1: preparing materials:
(1) preparation of extraction material: accurately weighing the extract to 0.01g, and grinding into fine particles for later use;
(2) preparation of diatomaceous earth/Ca-LTA: grinding diatomite in a ball mill and sieving the ground diatomite by a sieve to obtain diatomite powder; the diatomite powder is subjected to acid treatment at 90 ℃ for 5.5h by using 400mL of 4mol/L nicotinic acid per 20g of diatomite powder; thoroughly washing the treated diatomite powder by using deionized water until no chloride exists, and drying at 95 ℃ for 27h to obtain acid-treated diatomite powder; putting the diatomite powder into a muffle furnace, and heating to 600 ℃ at the heating rate of 5 ℃/min for treatment for 2.3h to obtain purified diatomite powder; mixing the diatomite/Ca-LTA and the Ca-LTA by a mixer at a set rotating speed of 160rmp and a temperature of 30 ℃ to prepare diatomite/Ca-LTA for later use;
(3) preparation of MIL-101/allochroic silica gel: accurately weighing 4.0g of terephthalic acid, 1.66g of chromium nitrate, 1mL of hydrochloric acid and 100mg of allochroic silica gel, sequentially adding the terephthalic acid, the chromium nitrate, the 1mL of hydrochloric acid and the 100mg of allochroic silica gel into 50mL of deionized water, carrying out ultrasonic dispersion for 60min, and carrying out a reaction by a solvothermal method, wherein the reaction temperature is set to be 180 ℃, and the reaction time is 12 hours; after the reaction is finished, washing the product with DMF solution for 3 times at 62 ℃, washing the product with absolute ethyl alcohol for 2 times at room temperature, washing the product with deionized water for 2 times, and drying the product in vacuum for 8 hours at 135 ℃ to prepare MIL-101/allochroic silicagel for later use, wherein the MIL-101/allochroic silicagel can be proportionally amplified according to the required amount;
step 2: pressurized fluid extraction: vertically placing the cleaned and dried extraction tank on a horizontal plane; placing the glass fiber filter membrane at the bottom of the extraction tank, and screwing down the bottom cover; the MIL-101/allochroic silica gel is uniformly paved on a glass fiber filter membrane, and then diatomite/Ca-LTA is uniformly paved on the MIL-101/allochroic silica gel to be used as a bottom water absorption layer; then uniformly spreading the ground extract on diatomite/Ca-LTA to obtain an extract layer; uniformly paving the kieselguhr/Ca-LTA on the extraction substance, and then uniformly paving the MIL-101/allochroic silica gel on the kieselguhr/Ca-LTA to serve as a top water absorption layer; obtaining a loaded extraction tank; performing an extraction process by adopting a dichloromethane-acetone solution, and setting extraction conditions as follows: the pressure of carrier gas is 0.5MPa, the heating temperature is 120 ℃, and the working pressure is 100 bar; the static extraction is circulated for 2 times, and the solvent/gas is set to be 50sec/5 min; rinsing (RP) again for 1 time to obtain extract liquor;
and step 3: first nitrogen-blowing concentration: transferring the extract liquid into a concentration bottle, washing the extraction bottle 4 times by using 12mL of dichloromethane-acetone solution, and transferring the obtained solution into the concentration bottle; placing the concentration bottle in a nitrogen blowing instrument for concentration, setting the working temperature at 25 ℃ and the working pressure at 20 Kpa; in the concentration process, the inner wall of the nitrogen blowing pipe must be rinsed 4 times by 15mL of dichloromethane solution, and finally concentrated to 1mL to obtain concentrated solution;
and 4, step 4: purifying: pre-eluting the Florisl SPE cartridge by using 9mL of dichloromethane solution, and pouring off the eluent; transferring the concentrated solution to a Florisl SPE small column, using 6mL of dichloromethane to rinse the inner wall of a nitrogen blowing pipe for 4 times, and transferring the obtained liquid to the Florisl SPE small column; starting a vacuum pump to execute elution operation, setting the flow rate of a control valve, and collecting eluent; washing the wall of the Florisl SPE small column with 2mL of dichloromethane for 2 times, collecting and combining to obtain a purified solution;
and 5: and (3) second nitrogen blowing concentration: performing secondary nitrogen-blowing concentration on the purified solution according to the nitrogen-blowing concentration step in the step 3 to obtain 0.4mL of concentrated solution, adding an internal standard solution, uniformly mixing, and performing constant volume to 1mL by using a dichloromethane solution to obtain a constant solution; transferring the sample solution into a 2mL sample injection vial to obtain a solution to be detected; in addition, if the test is not performed immediately, the test solution should be stored at a temperature below 4 ℃.
In this embodiment, the extraction material is a composition of a plurality of materials, such as waste leaves, stones and soil;
the proportion of the diatomite in the diatomite/Ca-LTA is 20 percent;
the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silicagel of the bottom water absorption layer are respectively 1.5cm and 3 cm; the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silicagel of the top water absorption layer are respectively 1.cm and 1.5 cm;
the static extraction time is 9 min;
the flow rate of the control valve is 5 mL/min.
Experiment 1:
the water content of the extract obtained in examples 1 to 3 was measured by a Karl Fischer water content meter, and the results were 0.05%, 0.03%, and 0.04%; in addition, the MIL-101/color-changing silica gel layer in the water absorbing layer at the bottom is provided with 0.3-0.8 cm of non-color-changing areas.
And (4) conclusion: the diatomite/Ca-LTA layer has strong water removal performance, and the MIL-101/color-changing silica gel layer effectively prevents trace water vapor from entering the extraction liquid along with the solvent.
In addition, the deviation can be found to be less than 1% from the gas chromatogram detected by the liquid to be detected, the chromatogram data obtained by the method is stable, and the water removal method can effectively improve the accuracy and stability of the measurement of the liquid to be detected.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the 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 (9)
1. A quick extraction pool water removal method is characterized in that: the method comprises the following steps:
s1: preparing an extraction material;
s2: pressurized fluid extraction;
s3: first nitrogen-blowing concentration;
s4: purifying;
s5: and (5) performing nitrogen-blown concentration for the second time.
2. The rapid extraction cell dewatering method of claim 1, further comprising: the extraction substance is a composition of one or more substances in waste branches, waste leaves, stones and soil.
3. The rapid extraction cell dewatering method of claim 1, further comprising: the method comprises the following steps:
s1: preparing materials:
(1) preparation of extraction material: accurately weighing the extract to 0.01g, and grinding into fine particles for later use;
(2) preparation of diatomaceous earth/Ca-LTA: grinding diatomite in a ball mill and sieving the ground diatomite by a sieve to obtain diatomite powder; performing acid treatment on 20g of diatomite powder at 80-100 ℃ for 5-6 h by using 400mL of 4mol/L nicotinic acid; thoroughly washing the treated diatomite powder with deionized water until no chloride exists, and drying at 80-110 ℃ for 24-30 h to obtain acid-treated diatomite powder; putting the diatomite powder into a muffle furnace, and raising the temperature to 500-700 ℃ at a heating rate of 5-6 ℃/min for treatment for 2-3 h to obtain purified diatomite powder; mixing the diatomite/Ca-LTA and Ca-LTA by a mixer at a set rotating speed of 120-200 rmp and a temperature of 25-35 ℃ to prepare diatomite/Ca-LTA for later use;
(3) preparation of MIL-101/allochroic silica gel: accurately weighing terephthalic acid, chromic nitrate, hydrochloric acid and allochroic silica gel, sequentially adding the terephthalic acid, chromic nitrate, hydrochloric acid and allochroic silica gel into deionized water, ultrasonically dispersing for 45-75 min, reacting by a solvothermal method, setting the temperature to be 150-200 ℃, and setting the reaction time to be 12 h; after the reaction is finished, washing the product with DMF solution for 3 times at 60-65 ℃, washing with absolute ethyl alcohol for 2 times at room temperature, washing with deionized water for 2 times, and vacuum-drying at 120-150 ℃ for 5-10 h to prepare MIL-101/allochroic silica gel for later use;
s2: pressurized fluid extraction: vertically placing the cleaned and dried extraction tank on a horizontal plane; placing the glass fiber filter membrane at the bottom of the extraction tank, and screwing down the bottom cover; the MIL-101/allochroic silica gel is uniformly paved on a glass fiber filter membrane, and then diatomite/Ca-LTA is uniformly paved on the MIL-101/allochroic silica gel to be used as a bottom water absorption layer; then uniformly spreading the ground extract on diatomite/Ca-LTA to obtain an extract layer; uniformly paving the kieselguhr/Ca-LTA on the extraction substance, and then uniformly paving the MIL-101/allochroic silica gel on the kieselguhr/Ca-LTA to serve as a top water absorption layer; obtaining a loaded extraction tank; performing an extraction process by adopting a dichloromethane-acetone solution, and setting extraction conditions as follows: the carrier gas pressure is 0.4-0.6 MPa, the heating temperature is 110-130 ℃, and the working pressure is 100 bar; the static extraction is circulated for 2 times, and the solvent/gas is set to be 50sec/5 min; rinsing (RP) again for 1 time to obtain extract liquor;
s3: first nitrogen-blowing concentration: transferring the extract liquid in the step S2 to a concentration bottle, washing the extraction bottle with 10-15 mL of dichloromethane-acetone solution for 3-5 times, and transferring the obtained solution to the concentration bottle; placing the concentration bottle in a nitrogen blowing instrument for concentration, setting the working temperature to be 20-30 ℃ and the working pressure to be 20 Kpa; in the concentration process, 10-20 mL of dichloromethane solution is needed to rinse the inner wall of the nitrogen blowing pipe for 3-5 times, and the nitrogen blowing pipe is finally concentrated to 1mL to obtain a concentrated solution;
s4: purifying: pre-eluting the Florisl SPE small column by using 8-10 mL of dichloromethane solution, and pouring off the eluent; transferring the concentrated solution obtained in the step S3 to a Florisl SPE small column, rinsing the inner wall of a nitrogen blowing pipe for 3-5 times by using 4-8 mL of dichloromethane, and transferring the obtained liquid to the Florisl SPE small column; starting a vacuum pump to execute elution operation, setting the flow rate of a control valve, and collecting eluent; washing the wall of the Florisl SPE small column with 2mL of dichloromethane for 2 times, collecting and combining to obtain a purified solution;
s5: and (3) second nitrogen blowing concentration: performing secondary nitrogen-blowing concentration on the purified liquid in the step S4 according to the nitrogen-blowing concentration step in the step S3 to obtain 0.3-0.5 mL of concentrated liquid, adding an internal standard solution, uniformly mixing, and performing constant volume to 1mL by using a dichloromethane solution to obtain a constant solution; transferring the sample solution into a 2mL sample injection vial to obtain a solution to be detected; in addition, if the test is not performed immediately, the test solution should be stored at a temperature below 4 ℃.
4. The rapid extraction cell dewatering method of claim 3, further comprising: in step S1 (2), the aperture of the sieve is 50-80 μm.
5. The rapid extraction cell dewatering method of claim 3, further comprising: in step S1 (2), the ratio of diatomaceous earth in the diatomaceous earth/Ca-LTA is 15% to 25%.
6. The rapid extraction cell dewatering method of claim 3, further comprising: in step S2, the pore size of the glass fiber filter membrane is 0.45 μm.
7. The rapid extraction cell dewatering method of claim 3, further comprising: in the step S2, the thickness of the diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silicagel in the bottom water absorption layer are respectively 1-2 cm and 2-4 cm; the thickness of the middle diatomite/Ca-LTA and the thickness of the MIL-101/allochroic silica gel in the top water absorption layer are respectively 1-2 cm and 1-2 cm.
8. The rapid extraction cell dewatering method of claim 3, further comprising: in step S2, the static extraction time is 8-10 min.
9. The rapid extraction cell dewatering method of claim 3, further comprising: in step S4, the flow rate of the control valve is 4-6 mL/min.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB636752A (en) * | 1946-06-21 | 1950-05-03 | Bataafsche Petroleum | A process for reactivating a spent refining adsorbent |
| US4056468A (en) * | 1974-03-02 | 1977-11-01 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Isolation of component materials of aqueous solutions soluble in lipophilic solvents |
| JP2002336834A (en) * | 2001-05-16 | 2002-11-26 | Kawasaki Heavy Ind Ltd | Treatment method and equipment for organic chlorine compound in soil, solid and fly ash |
| CN102520101A (en) * | 2011-12-14 | 2012-06-27 | 广西壮族自治区环境监测中心站 | Pre-treatment and analysis methods of organochlorine pesticides in soil |
| US20160000713A1 (en) * | 2014-07-07 | 2016-01-07 | AntriaBio | Solvent extraction from biodegradable microparticles |
| CN106526060A (en) * | 2016-09-21 | 2017-03-22 | 中国人民解放军第二军医大学 | eTLC-SERS method |
| CN108982707A (en) * | 2018-09-14 | 2018-12-11 | 广东利诚检测技术有限公司 | A kind of method of 15 kinds of polycyclic aromatic hydrocarbons in measurement soil |
| CN109012162A (en) * | 2018-08-29 | 2018-12-18 | 西北工业大学 | A kind of multistage removal indoor formaldehyde device of band sterilization |
| CN111272909A (en) * | 2020-04-23 | 2020-06-12 | 上海国齐检测技术有限公司 | Method for detecting anthraquinone and anthrone substances in soil and sediment |
-
2020
- 2020-10-21 CN CN202011129081.7A patent/CN112326399B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB636752A (en) * | 1946-06-21 | 1950-05-03 | Bataafsche Petroleum | A process for reactivating a spent refining adsorbent |
| US4056468A (en) * | 1974-03-02 | 1977-11-01 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Isolation of component materials of aqueous solutions soluble in lipophilic solvents |
| JP2002336834A (en) * | 2001-05-16 | 2002-11-26 | Kawasaki Heavy Ind Ltd | Treatment method and equipment for organic chlorine compound in soil, solid and fly ash |
| CN102520101A (en) * | 2011-12-14 | 2012-06-27 | 广西壮族自治区环境监测中心站 | Pre-treatment and analysis methods of organochlorine pesticides in soil |
| US20160000713A1 (en) * | 2014-07-07 | 2016-01-07 | AntriaBio | Solvent extraction from biodegradable microparticles |
| CN106526060A (en) * | 2016-09-21 | 2017-03-22 | 中国人民解放军第二军医大学 | eTLC-SERS method |
| CN109012162A (en) * | 2018-08-29 | 2018-12-18 | 西北工业大学 | A kind of multistage removal indoor formaldehyde device of band sterilization |
| CN108982707A (en) * | 2018-09-14 | 2018-12-11 | 广东利诚检测技术有限公司 | A kind of method of 15 kinds of polycyclic aromatic hydrocarbons in measurement soil |
| CN111272909A (en) * | 2020-04-23 | 2020-06-12 | 上海国齐检测技术有限公司 | Method for detecting anthraquinone and anthrone substances in soil and sediment |
Non-Patent Citations (1)
| Title |
|---|
| FAYZA BABAA, ET AL: "Water adsorption and antibacterial activity studies for characterization of Ca-LTA zeolite/diatomite adsorbents", 《COLLOID AND INTERFACE SCIENCE COMMUNICATIONS》 * |
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