CN109987687B - Composite coagulant and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a composite coagulant and a preparation method and application thereof, wherein chitosan is used as a raw material, the chitosan is sequentially subjected to sulfation reaction and nucleophilic reaction to obtain the composite coagulant, and the sulfation reaction comprises the following steps: dissolving chitosan in N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on the chitosan solution and an esterification reagent, cooling the reaction solution to room temperature after the reaction is finished, and then adjusting the pH value of the reaction solution to be neutral to obtain sulfated chitosan; a nucleophilic reaction step: adding the cationic dimeric polymer and the sulfated chitosan into a round-bottom flask filled with a methanol solution, and heating and refluxing to prepare the composite coagulant. The composite coagulant of the invention contains rich hydroxyl, amino, sulfate and other functional groups and a loose porous structure, has extremely strong adsorption and bridging capacity, and has good flocculation, coagulation and adsorption properties.
Description
Technical Field
The invention relates to a coagulant, in particular to a composite coagulant and a preparation method and application thereof.
Background
The chitosan is used as a natural polysaccharide, and has wide application prospect in the field of environmental protection due to the stability, adsorption bridging, biodegradability and safety. The chitosan has low water solubility and poor adsorbability, so the unmodified chitosan has certain application limitation. Although chemical modifications such as acetylation and carboxymethylation have been mostly studied to increase the solubility of chitosan and to provide a large number of functional groups, sulfated chitosan is not available and modification of chitosan with cationic gemini polymers has been rarely studied.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a composite coagulant which contains abundant functional groups such as hydroxyl, amino, sulfate and the like and a loose porous structure, has extremely strong adsorption bridging capacity and has good flocculation, coagulation and adsorption properties.
The invention also aims to provide a preparation method of the composite coagulant, which synthesizes high-energy, high-efficiency, low-cost and low-ecological-load saccharide raw material sources by using natural resources, is beneficial to the conventional use of saccharides by optimizing synthesis steps and selecting high-efficiency catalysts, and gradually replaces petrochemical products with large load on ecological environment.
The invention also aims to provide an application of the composite coagulant.
One of the purposes of the invention is realized by adopting the following technical scheme:
the composite coagulant is characterized in that chitosan is used as a raw material, and the composite coagulant is obtained by sequentially carrying out sulfuric acid esterification reaction and nucleophilic reaction on the chitosan.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the composite coagulant is characterized by comprising the following steps:
and (3) carrying out a sulfation reaction: dissolving chitosan in N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on a chitosan solution and an esterification reagent, cooling reaction liquid to room temperature after the reaction is finished, and then adjusting the pH value of the reaction liquid to be neutral to obtain sulfated chitosan;
a nucleophilic reaction step: adding 0.5-1.0moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 200 plus 300mL of absolute ethanol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70-80 ℃, dropwise adding 0.5-1.2moL of bromoalkane, stirring while dropwise adding, after dropwise adding, stirring and reacting for 2-4 hours under the condition of constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow; and then adding the cationic dimeric polymer and the sulfated chitosan into a round-bottom flask filled with a methanol solution, and heating and refluxing for 8 hours to prepare the composite coagulant.
Further, in the step of sulfation reaction, the preparation method of the esterification reagent is as follows: adding pyridine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, placing the flask in a saline ice bath for cooling, dropwise adding chlorosulfonic acid under the stirring condition, wherein the volume ratio of the chlorosulfonic acid to the pyridine is 1:4-6, and obtaining an esterification reagent for later use after the reaction is finished.
Further, the preparation method of the esterification reagent needs to complete the whole operation process within 40 min.
Further, in the step of the sulfation reaction, the reaction temperature of the sulfation reaction is 50-90 ℃.
Further, in the step of sulfation reaction, the reaction time of the sulfation reaction is 2-5 h.
Further, in the step of sulfation reaction, the volume ratio of the esterification reagent to the chitosan solution is 5-7: 4.
Further, in the step of sulfation reaction, after the reaction is finished, the reaction solution is cooled to room temperature, 150mL of precooled water is added into the reaction solution, and then the pH value of the reaction solution is adjusted to be neutral by using a 20% NaOH solution, so that the sulfated chitosan is obtained.
Further, in the nucleophilic reaction step, the molar ratio of the cationic Gemini polymer to the sulfated chitosan sulfuric acid is 1.5-2.5: 1.
The third purpose of the invention can be achieved by adopting the following technical scheme:
the application of the composite coagulant of one of the purposes of the invention is as follows: it is used as coagulant for treating oily waste water or garbage percolate.
The invention has the beneficial effects that:
the action mechanism of the composite coagulant is mainly the electric neutralization of dication charges, two hydrophobic chains are connected by a linking group to prepare a long-chain intermediate containing two reaction sites, and the intermediate is subjected to nucleophilic reaction with a saccharide derivative to prepare the cationic dimeric polymer with two hydrophilic groups. In consideration of space effect, the activity of reaction sites constrained by long chains on two sides is reduced, so the reaction sites need to react with sulfated chitosan with stronger activity to prepare the composite coagulant with higher activity, and the composite coagulant contains rich functional groups such as hydroxyl, amino, sulfate and the like and a loose porous structure, has extremely strong adsorption bridging capacity and has good flocculation, coagulation and adsorption. Meanwhile, the compound coagulant selects a sugar raw material source which is synthesized by natural resources and has high energy, high efficiency, low cost and low ecological load, a suitable synthesis method and a high-efficiency catalyst, thereby being beneficial to the conventional use of sugar and gradually replacing petrochemical products with large load on the ecological environment.
Drawings
FIG. 1 is a comparative graph of the effect of different coagulant samples on the flocculation performance of oily wastewater;
in fig. 1, a1 is the coagulant sample of example 1, a2 is the coagulant sample of example 2, A3 is the coagulant sample of example 3, a4 is the coagulant sample of example 4;
FIG. 2 is a comparative graph showing the effect of different coagulant samples on the removal rate of COD in landfill leachate;
in fig. 2, B1 is the coagulant sample of example 1, B2 is the coagulant sample of example 2, B3 is the coagulant sample of example 3, and B4 is the coagulant sample of example 4.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, various embodiments or technical features described below may be arbitrarily combined to form a new embodiment.
A composite coagulant is prepared from chitosan through sulfuric acid esterification and nucleophilic reaction.
The composite coagulant is a cationic gemini polymer modified sulfated chitosan composite coagulant, firstly, chitosan is fully called polyglucosamine (1-4) -2 amino-beta-D glucose and is the only cationic polysaccharide in the nature, the chitosan can form a polymer with polyanion with negative electricity by the characteristic, but the chitosan has low water solubility and poor adsorbability, so the sulfated chitosan modified by the chitosan has loose structure, a large amount of charges and increased water solubility; and secondly, connecting the two hydrophobic chains by using a linking group to prepare a long-chain intermediate containing two reaction sites, and carrying out nucleophilic reaction on the intermediate and a saccharide derivative to prepare the cationic dimeric polymer with two hydrophilic groups. The glycosylation reaction can adjust the space structure and the hydrophilic-hydrophobic balance of the cationic dimeric polymer, is possibly more beneficial to the adsorption of the polymer on an oil-water interface, and has good flocculation, coagulation and adsorption.
The cationic Gemini polymer modified sulfated chitosan composite coagulant is an environment-friendly green coagulant prepared by taking natural renewable saccharides as raw materials. The product takes glycosyl group as hydrophilic head group and has special polyhydroxy and sulfate group structure, thereby obviously improving the surface activity of the product. In addition, the biological safety, biocompatibility and biodegradability 'green chemistry' principle are met, and the method has wide application prospect in the field of environmental protection.
A preparation method of a composite coagulant comprises the following steps:
and (3) carrying out a sulfation reaction: dissolving chitosan in N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on the chitosan solution and an esterification reagent, cooling the reaction solution to room temperature after the reaction is finished, and then adjusting the pH value of the reaction solution to be neutral to obtain sulfated chitosan;
a nucleophilic reaction step: adding 0.5-1.0moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 200 plus 300mL of absolute ethanol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70-80 ℃, dropwise adding 0.5-1.2moL of bromoalkane, stirring while dropwise adding, after dropwise adding, stirring and reacting for 2-4 hours under the condition of constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow; and then adding the cationic dimeric polymer and the sulfated chitosan into a round-bottom flask filled with a methanol solution, and heating and refluxing for 8 hours to prepare the composite coagulant.
As a further embodiment, in the step of sulfation, the preparation method of the esterification reagent is as follows: adding pyridine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, placing the flask in a saline ice bath for cooling, dropwise adding chlorosulfonic acid under the stirring condition, wherein the volume ratio of the chlorosulfonic acid to the pyridine is 1:4-6, and obtaining an esterification reagent for later use after the reaction is finished.
As a further embodiment, the preparation method of the esterification reagent requires the whole operation process to be completed within 40 min.
As a further embodiment, in the sulfation reaction step, the reaction temperature of the sulfation reaction is 50-90 ℃.
As a further embodiment, in the sulfation reaction step, the reaction time of the sulfation reaction is 2-5 h.
As a further embodiment, in the step of sulfation reaction, the volume ratio of the esterification reagent to the chitosan solution is 5-7: 4.
In a further embodiment, in the sulfation reaction step, after the reaction is finished, the reaction solution is cooled to room temperature, 150mL of pre-cooled water is added into the reaction solution, and then the pH value of the reaction solution is adjusted to be neutral by using a 20% NaOH solution, so as to obtain the sulfated chitosan.
As a further embodiment, in the nucleophilic reaction step, the molar ratio of the cationic gemini polymer to the sulfated chitosan sulfuric acid is 1.5-2.5: 1.
As a further embodiment, in the nucleophilic reaction step, the alkyl bromide is dodecyl bromide or tetradecane bromide.
The application of the composite coagulant comprises the following steps: it is used as coagulant for treating oily waste water or garbage percolate.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Example 1:
the preparation method of the composite coagulant comprises the following steps:
1) and (3) carrying out a sulfation reaction:
1-1) adding 10mL of pyridine into a 250mL flask in a three-neck round-bottom flask provided with an electric stirrer and a thermometer, placing the flask in a saline ice bath for cooling, dropwise adding chlorosulfonic acid under the stirring condition, wherein the volume ratio of the chlorosulfonic acid to the pyridine is 1:6, and obtaining an esterification reagent for later use after the reaction is finished; the whole operation process is completed within 40 min;
1-2) dissolving chitosan in 40mL of N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on a chitosan solution and an esterification reagent, wherein the volume ratio of the esterification reagent to the chitosan solution is 6:4, the reaction temperature is 50 ℃, the reaction time is 3h, after the reaction is finished, cooling the reaction liquid to room temperature, adding 150mL of precooled water into the reaction liquid, and then adjusting the pH value of the reaction liquid to be neutral by using a NaOH solution with the concentration of 20% to obtain sulfated chitosan;
2) a nucleophilic reaction step:
2-1) adding 0.5moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 200mL of absolute ethyl alcohol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70 ℃, adding 0.6moL of bromoalkane dropwise, stirring while dropwise adding, after dropwise adding, stirring and reacting for 3 hours at the constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow;
2-2) then adding 1.5moL of cationic Gemini polymer and 1.0moL of sulfated chitosan into a round-bottom flask filled with methanol solution, heating and refluxing for 8h to prepare the composite coagulant.
Example 2:
a preparation method of a composite coagulant comprises the following steps:
1) and (3) carrying out a sulfation reaction:
1-1) adding 10mL of pyridine into a 250mL flask in a three-neck round-bottom flask provided with an electric stirrer and a thermometer, placing the flask in a saline ice bath for cooling, dropwise adding chlorosulfonic acid under the stirring condition, wherein the volume ratio of the chlorosulfonic acid to the pyridine is 1:4, and obtaining an esterification reagent for later use after the reaction is finished; the whole operation process is completed within 40 min;
1-2) dissolving chitosan in 40mL of N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on a chitosan solution and an esterification reagent, wherein the volume ratio of the esterification reagent to the chitosan solution is 5:4, the reaction temperature is 50 ℃, the reaction time is 2 hours, after the reaction is finished, cooling the reaction liquid to room temperature, adding 150mL of precooled water into the reaction liquid, and then adjusting the pH value of the reaction liquid to be neutral by using a 20% NaOH solution to obtain sulfated chitosan;
2) a nucleophilic reaction step:
2-1) adding 1.0moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 250mL of absolute ethyl alcohol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70 ℃, adding 1.2moL of bromoalkane dropwise, stirring while dropwise adding, after dropwise adding, stirring and reacting for 2 hours at the constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow;
2-2) then adding 2.0moL of cationic Gemini polymer and 1.0moL of sulfated chitosan into a round bottom flask filled with methanol solution, heating and refluxing for 8 hours to prepare the composite coagulant.
Example 3:
a preparation method of a composite coagulant comprises the following steps:
1) and (3) carrying out a sulfation reaction:
1-1) adding 10mL of pyridine into a 250mL flask in a three-neck round-bottom flask provided with an electric stirrer and a thermometer, placing the flask in a saline ice bath for cooling, dropwise adding chlorosulfonic acid under the stirring condition, wherein the volume ratio of the chlorosulfonic acid to the pyridine is 1:5, and obtaining an esterification reagent for later use after the reaction is finished; the whole operation process is completed within 40 min;
1-2) dissolving chitosan in 40mL of N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on a chitosan solution and an esterification reagent, wherein the volume ratio of the esterification reagent to the chitosan solution is 7:4, the reaction temperature is 80 ℃, the reaction time is 5 hours, after the reaction is finished, cooling the reaction liquid to room temperature, adding 150mL of precooled water into the reaction liquid, and then adjusting the pH value of the reaction liquid to be neutral by using a 20% NaOH solution to obtain sulfated chitosan;
2) a nucleophilic reaction step:
2-1) adding 0.8moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 300mL of absolute ethyl alcohol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70 ℃, adding 1.0moL of bromoalkane dropwise, stirring while dropwise adding, after dropwise adding, stirring and reacting for 3 hours at the constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow;
2-2) then adding 2.5moL of cationic Gemini polymer and 1.0moL of sulfated chitosan into a round-bottom flask filled with methanol solution, heating and refluxing for 8h to prepare the composite coagulant.
Example 4:
a preparation method of a composite coagulant comprises the following steps:
1) and (3) carrying out sulfation reaction:
1-1) adding 10mL of pyridine into a 250mL flask in a three-neck round-bottom flask provided with an electric stirrer and a thermometer, placing the flask in a saline ice bath for cooling, dropwise adding chlorosulfonic acid under the stirring condition, wherein the volume ratio of the chlorosulfonic acid to the pyridine is 1:5, and obtaining an esterification reagent for later use after the reaction is finished; the whole operation process is completed within 40 min;
1-2) dissolving chitosan in 40mL of N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on a chitosan solution and an esterification reagent, wherein the volume ratio of the esterification reagent to the chitosan solution is 6.5:4, the reaction temperature is 90 ℃, the reaction time is 4 hours, after the reaction is finished, cooling the reaction liquid to room temperature, adding 150mL of precooled water into the reaction liquid, and then adjusting the pH value of the reaction liquid to be neutral by using a 20% NaOH solution to obtain sulfated chitosan;
2) a nucleophilic reaction step:
2-1) adding 0.5moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 250mL of absolute ethyl alcohol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70 ℃, adding 0.5moL of bromoalkane dropwise while stirring, after dropwise addition is finished, stirring and reacting for 4 hours at the constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow;
2-2) then adding 1.8moL of cationic Gemini polymer and 1.0moL of sulfated chitosan into a round-bottom flask filled with methanol solution, heating and refluxing for 8h to prepare the composite coagulant.
Effect verification:
in order to examine the influence of different coagulant samples on the coagulation effect, under a certain condition (room temperature), according to different adding amounts, the oil content of the wastewater water sample before and after treatment by using different samples is measured, the oil removal rate is calculated, and the coagulation effect is evaluated.
As can be seen from FIG. 1, as the sample dosage is increased, the oil removing effect on the oily wastewater is also increased; under the low input, the oil removal rate increases comparatively rapidly, increases to behind 30mg/L when the input, and the oil removal rate reaches the biggest, and the flocculating agent quantity continues to increase, increases comparatively gently and finally reaches stably, and the oil removal rate increases unobviously. This may be combined with the electrical neutralization of the cationic groups of the polymer and the binding ability of the gemini groups to oil droplets to remove oil, which is beneficial to improving the oil removal effect.
Under certain conditions, four coagulant samples are used for carrying out coagulation experiments on the landfill leachate, the volume fraction of each coagulant is respectively 0.02%, 0.04%, 0.06%, 0.08% and 0.1% of 5 series, and the COD removal rate (%) is determined after treatment.
As can be seen from FIG. 2, the COD removal rate is highest when the volume fraction of the four coagulant samples is basically 0.04%, which is probably because the polymer provides a hydrophilic space due to sulfate groups and cationic gemini groups, and the adsorption capacity of the polymer on organic matters is increased; the COD removal rate is all the lower when the volume fraction is increased, which may be due to increased solubilization when the volume fraction is increased, which may cause electrical sign change of colloidal particles, resulting in protection and reduced coagulation.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (8)
1. A compound coagulant is characterized in that chitosan is used as a raw material, and the compound coagulant is obtained by sequentially carrying out sulfation reaction and nucleophilic reaction on the chitosan;
the preparation method of the composite coagulant comprises the following steps:
and (3) carrying out a sulfation reaction: dissolving chitosan in N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on the chitosan solution and an esterification reagent, cooling the reaction solution to room temperature after the reaction is finished, and then adjusting the pH value of the reaction solution to be neutral to obtain sulfated chitosan; the esterification reagent consists of chlorosulfonic acid and pyridine in a volume ratio of 1: 4-6;
a nucleophilic reaction step: adding 0.5-1.0moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 200 plus 300mL of absolute ethanol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70-80 ℃, dropwise adding 0.5-1.2moL of bromoalkane, stirring while dropwise adding, after dropwise adding, stirring and reacting for 2-4 hours under the condition of constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow; then adding the cationic dimeric polymer and the sulfated chitosan into a round-bottom flask filled with a methanol solution, and heating and refluxing for 8 hours to prepare a composite coagulant;
in the step of sulfation reaction, the volume ratio of an esterification reagent to the chitosan solution is 5-7: 4;
in the nucleophilic reaction step, the molar ratio of the cationic Gemini polymer to the sulfated chitosan sulfuric acid is 1.5-2.5: 1.
2. A method for preparing a composite coagulant according to claim 1, characterized by comprising the following steps:
and (3) carrying out a sulfation reaction: dissolving chitosan in N, N-dimethylformamide to obtain a chitosan solution; carrying out sulfation reaction on the chitosan solution and an esterification reagent, cooling the reaction solution to room temperature after the reaction is finished, and then adjusting the pH value of the reaction solution to be neutral to obtain sulfated chitosan;
a nucleophilic reaction step: adding 0.5-1.0moL of tetramethylethylenediamine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, adding 200 plus 300mL of absolute ethanol as a reaction solvent, uniformly stirring, adding 40g of sodium carbonate powder, stirring, heating to 70-80 ℃, dropwise adding 0.5-1.2moL of bromoalkane, stirring while dropwise adding, after dropwise adding, stirring and reacting for 2-4 hours under the condition of constant temperature of 80 ℃, and obtaining the cationic dimeric polymer after the reaction liquid is light yellow; and then adding the cationic dimeric polymer and the sulfated chitosan into a round-bottom flask filled with a methanol solution, and heating and refluxing for 8 hours to prepare the composite coagulant.
3. A method for preparing a composite coagulant according to claim 2, wherein in the step of sulfation, the method for preparing the esterification reagent is as follows: adding pyridine into a three-neck round-bottom flask provided with an electric stirrer and a thermometer, placing the flask in a saline ice bath for cooling, dropwise adding chlorosulfonic acid under the stirring condition, wherein the volume ratio of the chlorosulfonic acid to the pyridine is 1:4-6, and obtaining an esterification reagent for later use after the reaction is finished.
4. A process for the preparation of a composite coagulant as claimed in claim 3 where the process for the preparation of the esterifying reagent requires the entire process to be completed within 40 min.
5. The method for preparing a composite coagulant according to claim 2, wherein in the step of sulfation reaction, the reaction temperature of the sulfation reaction is 50-90 ℃.
6. The method for preparing a composite coagulant according to claim 2, wherein in the step of sulfation reaction, the reaction time of the sulfation reaction is 2 to 5 hours.
7. The method for preparing a composite coagulant according to claim 2, wherein in the step of sulfation reaction, after the reaction is finished, the reaction solution is cooled to room temperature, 150mL of precooled water is added into the reaction solution, and then the pH value of the reaction solution is adjusted to be neutral by using a 20% NaOH solution, so as to obtain the sulfated chitosan.
8. Use of a composite coagulant according to claim 1 wherein: it is used as coagulant for treating oily waste water or garbage percolate.
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| CN103012619A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
| CN104528863A (en) * | 2014-12-09 | 2015-04-22 | 厦门理工学院 | Method for removing heavy metals in garbage percolate through surfactant-modified attapulgite |
| CN108651462A (en) * | 2017-03-27 | 2018-10-16 | 中国石油化工股份有限公司 | Chitosan amphoteric ion fungicide and the preparation method and application thereof |
| CN108654703A (en) * | 2017-03-31 | 2018-10-16 | 南京理工大学 | A kind of preparation method of Gemini surface active agent pillared modification montmorillonite |
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