CN112961345B - Chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater and quaternary ammonium salt thereof - Google Patents
Chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater and quaternary ammonium salt thereof Download PDFInfo
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Abstract
The invention discloses chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater, which is characterized in that chitosan is dispersed in a solvent, an aldehyde compound is added and uniformly mixed, an acrylate compound is added, a catalyst is added, the reaction is carried out under the illumination condition, and an ester-terminated chitosan intermediate is obtained by suction filtration after the reaction is finished; dispersing the end ester group chitosan intermediate into a solvent, adding a polybasic fatty amine and an acrylate compound, and carrying out ester exchange reaction at room temperature to obtain the chitosan group hyperbranched polyamidoamine. The invention also discloses a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier obtained by performing quaternary ammonium salt modification on chitosan-based hyperbranched polyamidoamine. The polysaccharide-based hyperbranched polyamidoamine takes chitosan as a core, takes aliphatic aldehyde or aromatic aldehyde and methyl acrylate to perform a reduction reaction under photocatalysis, has mild conditions and simple operation, and is convenient for subsequent industrial and large-scale production of products.
Description
Technical Field
The invention belongs to the technical field of oil-in-water wastewater treatment, and particularly relates to preparation of chitosan-based hyperbranched polyamidoamine and quaternary ammonium salt thereof and application of the chitosan-based hyperbranched polyamidoamine and the quaternary ammonium salt thereof in treatment of oil-in-water wastewater generated in a polymer flooding oil extraction technology.
Background
The adsorption and separation system of functional materials to environmental pollutants is taken as the advanced development field of the chemical science department. The environment-friendly, high-efficiency, low-toxicity and degradable demulsifier is the main development direction of oil-in-water (O/W) emulsion oil-water separation materials. The preparation of the green, high-efficiency and low-toxicity degradable bio-based demulsification material has important significance on the control of pollutants, the repair of water resources and the like.
Patent CN106279706A discloses a preparation method of polyether grafted chitosan derivative crude oil desalting demulsifier. The prepared demulsifier has good demulsification and dehydration effects, and has strong binding capacity for negatively charged ions such as metal cations, naphthenate radicals and the like and particles with surfaces being electronegative because molecules of the demulsifier contain a large amount of carboxyalkyl groups and quaternary ammonium salt groups, so that the demulsifier has the capacity of removing oil-soluble salts while demulsifying. However, the subsequent treatment process needs polar dialysis and freeze-drying treatment, and has high energy consumption and long time. And is mainly directed to the breaking of water-in-oil emulsions. In patent CN201610645442.0, glycidyl dimethyl alkyl ammonium chloride and polyether modified by nitrophenyl ester are grafted to carboxymethyl chitosan to obtain the high-efficiency crude oil desalting demulsifier. In patent CN201610645497.1, glycidyl dimethyl ammonium chloride and polyether after halogenation modification are grafted to carboxymethyl chitosan to obtain a chitosan natural polymer modified crude oil desalting demulsifier, and the demulsifiers also have demulsification effect mainly aiming at water-in-oil type emulsion.
The tertiary oil recovery technology widely adopts a large amount of added surfactants, alkalis, high molecular polymers and the like to improve the recovery rate of crude oil, but the surfactants, the alkalis, the high molecular polymers and the like generally reduce interfacial tension by gathering on an oil-water interface, and the formed oil-in-water (O/W) type emulsion is difficult to break. Therefore, chitosan-based hyperbranched polyamide amine with large specific surface area and more active sites and quaternary ammonium salt thereof are needed to realize efficient separation of the emulsion.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater and a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier prepared from the chitosan-based hyperbranched polyamidoamine. The polysaccharide-based hyperbranched polyamidoamine takes chitosan as a core, takes aliphatic aldehyde or aromatic aldehyde and methyl acrylate to carry out photocatalytic reduction reaction, has mild condition and simple operation, and is convenient for subsequent industrial and large-scale production of products.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater, wherein the chitosan-based hyperbranched polyamidoamine is a compound represented by formula I:
where m is a positive integer and is the substitution number of the chitosan-based hyperbranched polyamidoamine, for example, when m is 1, the resulting product is G1, which has two amine groups at its terminal.
R represents a chain segment with aromatic ring or fat. Wherein, the aromatic ring can be phenyl, benzyl, phenethyl, hydroxybenzyl and the like, and the aliphatic chain segment is an aliphatic chain with the carbon number more than or equal to 0; the fatty segment is preferably selected from methyl, ethyl, propyl or butyl.
In a second aspect of the present invention, a method for preparing the chitosan-based hyperbranched polyamidoamine is provided, which includes the following steps:
(1) dispersing chitosan in a solvent, adding an aldehyde compound, uniformly mixing, adding an acrylate compound, adding a catalyst, carrying out a light reaction, and carrying out suction filtration after the reaction is finished to obtain an end ester group chitosan intermediate;
(2) dispersing the end ester group chitosan intermediate obtained in the step (1) in a solvent, adding polybasic fatty amine, and carrying out ester exchange reaction at room temperature to obtain first-generation chitosan group hyperbranched polyamidoamine;
(3) and (3) carrying out Michael addition and ester exchange reaction on the first-generation chitosan-based hyperbranched polyamidoamine obtained in the step (2), an acrylate compound and the multi-element fatty amine at room temperature to obtain second-generation and above-generation chitosan-based hyperbranched polyamidoamine.
Preferably, in the step (1), the molar ratio of the chitosan to the aldehyde compound to the acrylate compound is 1:2: 2; the catalyst is selected from acetic acid, hydrochloric acid, sulfuric acid or iridium tris (2-phenylpyridine);
the illumination is natural light or blue light, the temperature of the illumination reaction is 20-50 ℃, and the illumination time is 3-10 h.
Preferably, the aldehyde compound is an aliphatic aldehyde or an aromatic aldehyde;
the acrylate compound is methyl acrylate or methyl methacrylate;
preferably, the fatty aldehyde is selected from formaldehyde, acetaldehyde, propionaldehyde or butyraldehyde;
the aromatic aldehyde is selected from benzaldehyde, phenylacetaldehyde or salicylaldehyde;
the solvent is selected from alcohol solvents or water;
more preferably, the alcohol solvent is methanol or ethanol.
Preferably, in the step (2), the molar ratio of the poly aliphatic amine to the terminal ester group chitosan intermediate is (1-2): 1; the polybasic aliphatic amine is selected from ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine or triethylenetetramine;
the solvent is selected from alcohol solvents or water.
Preferably, in the step (3), the molar ratio of the poly aliphatic amine to the acrylate compound is 2 m ：(2 m ～2 m +1 )；
The acrylate compound is methyl acrylate or methyl methacrylate.
Wherein m is an integer more than or equal to 2, and when m is 2, the second generation of chitosan-based hyperbranched amidoamine is obtained; when m is 3, the third generation of chitosan-based hyperbranched amidoamine is obtained; and so on.
In a third aspect of the invention, an application of chitosan-based hyperbranched polyamidoamine in demulsification of oil-in-water type emulsion generated by oil displacement technology is provided.
The fourth aspect of the invention provides a low-temperature efficient quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier, which is prepared by the following method:
dispersing chitosan-based hyperbranched polyamidoamine in a solvent, adding formaldehyde and dialkylamine to obtain a terminal tertiary amine structure, reacting the terminal tertiary amine structure with epoxy halopropane to obtain a terminal epoxy group intermediate, and carrying out an open-loop reaction with organic amine to obtain a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier;
or dispersing chitosan-based hyperbranched polyamidoamine in a solvent, adding epoxy chloropropane and triethylamine, and reacting to obtain a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier;
or dispersing chitosan-based hyperbranched polyamidoamine in a solvent, adding 2, 3-epoxypropyl ammonium chloride, and carrying out ring-opening reaction to obtain the low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier.
Preferably, the molar ratio of the chitosan-based hyperbranched polyamidoamine to the formaldehyde to the dimethylamine to the epichlorohydrin is 1 (2) m-1 ～2 m+1 ):(2 m-1 ～2 m+1 ):(2 m-1 ～2 m+1 ) The molar ratio of the epoxy-terminated intermediate to the organic amine is 1: 1;
the molar ratio of the chitosan-based hyperbranched polyamidoamine to the epoxy chloropropane to the triethylamine is 1 (2) m-1 ～2 m+1 ):(2 m-1 ～2 m+1 )；
The molar ratio of the chitosan-based hyperbranched polyamidoamine to the 2, 3-epoxypropylammonium chloride is 1 (2) m-1 ～2 m+1 ) (ii) a m is an integer greater than or equal to 1; m represents the generation number of the quaternary ammonium salt modified chitosan-based hyperbranched amidoamine; when m is 1, obtaining the first generation of quaternary ammonium salt modified chitosan-based hyperbranched amidoamine; when m is 2, obtaining second generation quaternary ammonium salt modified chitosan group hyperbranched amidoamine; and so on.
Preferably, the epihalohydrin is epichlorohydrin.
Preferably, the organic amine is selected from one of ethylenediamine, propylenediamine, butylenediamine, ethanolamine, diethanolamine, triethanolamine, ethylene glycol, polyethylene glycol, glycerol, butylamine, hexylamine, octylamine, dodecylamine, tetradecylamine, hexadecylamine, or octadecylamine.
The fifth aspect of the invention provides an application of the low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier in demulsification of oil-in-water emulsions generated by oil displacement and recovery technology.
The invention has the beneficial effects that:
1. the invention provides a preparation method of chitosan hyperbranched polyamidoamine, which takes chitosan as a core, takes aliphatic aldehyde or aromatic aldehyde and methyl acrylate to carry out photocatalytic reduction reaction, has mild condition and simple operation, and is convenient for subsequent industrial and large-scale production of products;
2. the invention provides chitosan-based hyperbranched polyamidoamine, which is polyamidoamine with a hyperbranched structure, wherein the end group of the polyamidoamine is an amino group, and the polyamidoamine has more cavity structures and amino-terminated structures;
3. the invention provides quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine, which has a polyamide with a subsurface layer of which the terminal group of a cationic group is an amino group.
4. The invention provides quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine, which has polyamidoamine with a cationic group on the surface layer.
5. The invention provides application of chitosan-based hyperbranched polyamidoamine and a quaternary ammonium salt modified product thereof in treatment of wastewater of O/W type emulsion generated by a polymer flooding oil extraction technology.
Drawings
FIG. 1 is a synthetic circuit diagram of chitosan-based hyperbranched polyamidoamine prepared by the present invention;
FIG. 2 is a synthetic circuit diagram of the quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine prepared by the present invention (first preparation method);
FIG. 3 is a synthetic circuit diagram of the quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine prepared by the invention (two preparation methods);
FIG. 4 is a synthetic circuit diagram of the quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine prepared by the present invention (third preparation method);
FIG. 5 is an infrared spectrogram of a quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine prepared in example 2 of the present invention;
FIG. 6 shows that the quaternary ammonium salt modified chitosan based hyperbranched polyamidoamine prepared in example 6 of the present invention 1 H NMR chart.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As introduced in the background section, with the application of tertiary oil recovery technology, most of various chemical additives in polymer flooding, steam flooding, active flooding, alkali flooding and thick oil emulsification and viscosity reduction are O/W type emulsifiers, so that the formation of O/W type emulsions is promoted. At present, the research on demulsifiers at home and abroad mainly focuses on the aspect of block polyether and is not suitable for the treatment of O/W type oil extraction sewage. Therefore, the development of the O/W type demulsifier with a novel chemical structure has important significance.
Based on the above, the invention aims to provide chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater and a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier prepared from the chitosan-based hyperbranched polyamidoamine. The chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater comprises the following steps:
(1) dispersing chitosan in a solvent, adding an aldehyde compound, uniformly mixing, adding an acrylate compound, adding a catalyst, carrying out a light reaction, and carrying out suction filtration after the reaction is finished to obtain an end ester group chitosan intermediate;
(2) dispersing the end ester group chitosan intermediate obtained in the step (1) in a solvent, adding polybasic fatty amine, and carrying out ester exchange reaction at room temperature to obtain first-generation chitosan group hyperbranched polyamidoamine;
(3) and (3) carrying out Michael addition and ester exchange reaction on the first-generation chitosan-based hyperbranched polyamidoamine obtained in the step (2), an acrylate compound and the multi-element fatty amine at room temperature to obtain second-generation and above-generation chitosan-based hyperbranched polyamidoamine.
The specific synthetic route is shown in fig. 1, and as can be seen from fig. 1, when the reaction in the step (1) is finished, the hydrophobic group is grafted on the surface of the chitosan, and when the aldehyde compound is aromatic aldehyde, the benzene ring on the surface of the chitosan can be combined with the asphaltene surfactant phase (i.e. natural surfactant) in the oil displacement chemical auxiliary agent (i.e. emulsion) so as to break emulsion; when the aldehyde compound is fatty aldehyde, the fatty carbon chain on the surface of the chitosan can be combined with the polymer surfactant (namely, the artificial surfactant) in the oil displacement chemical auxiliary agent so as to demulsify. And (3) after the reaction in the step (2) or (3) is finished, connecting the outermost layer of the chitosan with hydrophilic amino, wherein the hydrophilic amino can enable the chitosan-based hyperbranched polyamidoamine to quickly reach the interface between the emulsion and water, and further improving the demulsification effect.
The quaternary ammonium salt modification of the chitosan-based hyperbranched amidoamine to prepare the demulsifier provides the following three methods:
the first preparation method (the specific synthetic route is shown in figure 2): dispersing chitosan-based hyperbranched polyamidoamine in a solvent, adding formaldehyde and dialkylamine to obtain a terminal tertiary amine structure, reacting the terminal tertiary amine structure with epoxy halopropane to obtain a terminal epoxy group intermediate, and carrying out an open-loop reaction with organic amine to obtain a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier;
the second preparation method (the specific synthetic route is shown in figure 3): dispersing chitosan-based hyperbranched polyamidoamine in a solvent, adding epoxy chloropropane and triethylamine, and reacting to obtain a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier;
the third preparation method (the specific synthetic route is shown in figure 4): dispersing chitosan-based hyperbranched polyamidoamine in a solvent, adding 2, 3-epoxypropyl ammonium chloride, and carrying out a ring-opening reaction to obtain the low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier.
As shown in fig. 2 to 4, after quaternary ammonium salt modification is performed on the basis of demulsification of chitosan-based hyperbranched amidoamine, the demulsifiers obtained by the three preparation methods contain cations on the outermost layer or subsurface layer of chitosan, and can be electrostatically combined with anions in the emulsion, so that demulsification is performed, and the demulsification effect is further improved.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
Description of the drawings: the chitosan viscosity average molecular weight used in the examples was 1.32X10 5 。
Example 1
1.79g (containing about 10mmol of amine group) of chitosan is dispersed in 10mL of methanol, after complete dispersion, 0.6g (20mmol) of formaldehyde and 1.72g (20mmol) of methyl acrylate are added, 0.1% of acetic acid is added as a catalyst, reaction is carried out at 50 ℃ for 10h under natural light conditions, and then filtration is carried out to obtain 10mmol of end ester group chitosan intermediate. Dispersing the chitosan-based hyperbranched polyamide amine in 10mL of methanol, adding 1.2G (20mmol) of ethylenediamine after complete dispersion, reacting at 30 ℃ for 10h, and performing suction filtration to obtain chitosan-based hyperbranched polyamide amine HP-G1.
3.72G (10mmol) of HP-G1 was dispersed in 10mL of methanol and after complete dispersion, 1.2G (40mmol) of formaldehyde and 1.8G (40mmol) of dimethylamine were added and reacted at 50 ℃ for 2 hours, 3.7G (40mmol) of epichlorohydrin was added and reacted at 70 ℃ for 4 hours to give the epoxy terminated intermediate HP-G1-PO,
10.42G (10mmol) of HP-G1-PO is dispersed in 20mL of methanol, after complete dispersion, 2.4G (40mmol) of Ethylenediamine (EDA) is added, and reaction is carried out for 4h at 40 ℃ to obtain the amino-terminated chitosan hyperbranched polyamidoamine with the sub-surface being cationic groups, HP-EDA.
Example 2
Dispersing 10mmol HP-G1-PO in 10mL methanol, adding 40mmol divinyl Diamine (DETA) after complete dispersion, and reacting at 60 ℃ for 7h to obtain the amino-terminated chitosan hyperbranched polyamidoamine with the sub-surface being a cationic group, HP-DETA. The infrared spectrum of HP-DETA is shown in FIG. 5.
Example 3
Dispersing 10mmol of HP-G1 in 10mL of methanol, adding 40mmol of methyl acrylate after complete dispersion, reacting at 50 ℃ for 24h, and performing suction filtration to obtain 10mmol of a half-generation product HP-G1.5 of a terminal ester group; dispersing the mixture in 10mL of methanol, adding 40mmol of ethylenediamine after complete dispersion, reacting for 48h at room temperature, and performing suction filtration to obtain 10mmol of amino-terminated product HP-G2; dispersing the chitosan-terminated hyperbranched polyamide in 10mL of methanol, after complete dispersion, adding 80mmol of formaldehyde and 80mmol of dimethylamine, reacting for 2h at 50 ℃, adding 4mol of epoxy chloropropane, reacting for 4h at 70 ℃ to obtain 10mmol of epoxy-terminated intermediate HP-G2-PO, adding 80mmol of Ethanolamine (EOA), and reacting for 4h at 80 ℃ to obtain amino-terminated chitosan-based hyperbranched polyamide with a sub-surface being a cationic group, HP-EOA.
Example 4
Dispersing 10mmol HP-G1-PO in 10mL methanol, adding 20mmol dodecanol (C12) after complete dispersion, and reacting at 50 ℃ for 10h to obtain chitosan hyperbranched polyamidoamine with a terminal hydrophobic group and a cationic group on the subsurface, HP-C12.
Example 5
Dispersing 10mmol HP-G2-PO in 10mL methanol, adding 40mmol octadecanol (C18) after complete dispersion, and reacting for 4h at 80 ℃ to obtain chitosan-based hyperbranched polyamidoamine with a terminal hydrophobic group and a cationic group on the subsurface, HP-C18.
Example 6
1.79g (containing about 10mmol of amine group) of chitosan was dispersed in 10mL of methanol, and after complete dispersion, 2.12g (20mmol) of benzaldehyde and 2.0g (20mmol) of methyl methacrylate were added, followed by addition of0.1% of tris (2-phenylpyridine) iridium as a catalyst, reacting for 8h at 40 ℃ under the irradiation of blue light, and filtering to obtain 10mmol of end ester group chitosan intermediate. Dispersing the chitosan-based hyperbranched polyamide amine in 10mL of methanol, adding 1.76g (20mmol) of butanediamine after complete dispersion, reacting for 6h at 50 ℃, and performing suction filtration to obtain chitosan-based hyperbranched polyamide amine, HP-2. Of HP-2 1 The H NMR chart is shown in FIG. 6.
Example 7
Dispersing 10mmol of HP-2 in 10mL of methanol, adding 40mmol of epoxy chloropropane and 40mmol of triethylamine after complete dispersion, and reacting for 2h at 60 ℃ to obtain chitosan-based hyperbranched polyamidoamine, HP-HA, with a subsurface as a hydrophobic group and a terminal group as a cationic group.
Example 8
1.79g (containing about 10mmol of amine group) of chitosan was dispersed in 10mL of methanol, and after complete dispersion, 2.44g (20mmol) of salicylaldehyde and 2.0g (20mmol) of methyl methacrylate were added, and 0.1% of tris (2-phenylpyridine) iridium was added as a catalyst, and after reaction at 50 ℃ for 7 hours under irradiation of blue light, the reaction mixture was suction-filtered to obtain 10mmol of an end ester group-terminated chitosan intermediate. Dispersing the chitosan-based hyperbranched polyamide amine in 10mL of methanol, adding 2.06g (20mmol) of diethylenetriamine after complete dispersion, reacting for 2h at 50 ℃, and performing suction filtration to obtain chitosan-based hyperbranched polyamide amine, HP-3.
Example 9
Dispersing 10mmol HP-3 in 10mL methanol, adding 3.03g (20mmol) of 2, 3-epoxypropyltrimethylammonium chloride after complete dispersion, and reacting for 2h at 70 ℃ to obtain chitosan-based hyperbranched polyamidoamine, HP-ETA, with the subsurface being hydrophobic groups and the end group being cationic groups.
Test examples
According to the crude oil demulsifier use performance detection bottle test method of the oil and gas industry standard SY/T5281-2000 of the people's republic of China, the demulsifier obtained in the above example 1-9 and the commercial quaternary ammonium salt demulsifier CW-01 are used for carrying out demulsification experiments on sewage in the victory oil field under the same test conditions, then the oil content is measured according to the spectrophotometry of SY/T5329-94, and the oil removal rate is correspondingly calculated. The oil removal performance of examples 1-9 and the commercial quat demulsifier CW-01 are shown in Table 1.
TABLE 1 demulsifying Effect
| Reagent | Dosage of | Temperature of emulsion breaking | Time of emulsion breaking | Oil removal rate |
| CW-01 | 80ppm | At room temperature | 10min | >97％ |
| HP-G1 (example 1) | 80ppm | At room temperature | 10min | >95％ |
| HP-EDA (example 1) | 80ppm | At room temperature | 10min | >99％ |
| HP-DETA (example 2) | 80ppm | At room temperature | 10min | >99％ |
| HP-EOA (example 3) | 80ppm | At room temperature | 10min | >99％ |
| HP-G2 (example 3) | 80ppm | At room temperature | 10min | >98％ |
| HP-C12 (example 4) | 80ppm | At room temperature | 10min | >98％ |
| HP-C18 (example 5) | 80ppm | At room temperature | 10min | >98％ |
| HP-2 (example 6) | 80ppm | At room temperature | 10min | >97％ |
| HP-HA (example 7) | 80ppm | At room temperature | 10min | >99％ |
| HP-3 (example 8) | 80ppm | At room temperature | 10min | >97％ |
| HP-ETA (example 9) | 80ppm | At room temperature | 10min | >99％ |
As can be seen from table 1, the demulsifier provided in the embodiment of the present invention can rapidly and efficiently demulsify an O/W emulsion or a microemulsion formed by triple-displacement at room temperature, the demulsification time only needs about 10 minutes, the oil removal rate of the first-generation chitosan-based hyperbranched polyamidoamine can be as high as 95%, the oil removal rate of the second-generation chitosan-based hyperbranched polyamidoamine can be as high as 97%, and the oil removal rates of the first-generation quaternary ammonium salt-modified chitosan-based hyperbranched polyamidoamine and the second-generation quaternary ammonium salt-modified chitosan-based hyperbranched polyamidoamine are both 99% or more, so that the demulsifier can be effectively used in the demulsification process of an oil-in-water emulsion or a microemulsion. However, from the viewpoint of raw material cost and process cost (mainly preparation time and the like) of the product, the first generation or second generation chitosan-based hyperbranched polyamidoamine, or the first generation quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine, or the second generation quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine can meet the requirement of demulsification and is more suitable for industrial production. Compared with the commercial quaternary ammonium salt demulsifier CW-01, the invention has the advantages of simple preparation method, low cost and short preparation time, and is more suitable for large-scale industrial popularization.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A chitosan-based hyperbranched polyamidoamine for demulsification of oil-in-water wastewater is characterized in that the chitosan-based hyperbranched polyamidoamine is a compound shown as a formula I:
wherein m is a positive integer and represents the generation number of the chitosan-based hyperbranched polyamidoamine; r is an aromatic ring or an aliphatic chain segment; wherein the aromatic ring is phenyl, benzyl or hydroxyphenyl, and the aliphatic chain segment is an aliphatic chain with the carbon number more than or equal to 0.
2. The method for preparing chitosan-based hyperbranched polyamidoamine according to claim 1, comprising the steps of:
(1) dispersing chitosan in a solvent, adding an aldehyde compound, uniformly mixing, adding an acrylate compound, adding a catalyst, reacting under the illumination condition, and performing suction filtration after the reaction is finished to obtain an end ester group chitosan intermediate; the molar ratio of the chitosan to the aldehyde compound to the acrylate compound is 1:2: 2; the catalyst is selected from acetic acid, hydrochloric acid, sulfuric acid or iridium tris (2-phenylpyridine); the illumination is natural light or blue light, the reaction temperature under the illumination condition is 20-50 ℃, and the illumination time is 3-10 h; the aldehyde compound is aliphatic aldehyde or aromatic aldehyde; the acrylate compound is methyl acrylate; the fatty aldehyde is selected from formaldehyde, acetaldehyde, propionaldehyde or butyraldehyde; the aromatic aldehyde is selected from benzaldehyde, phenylacetaldehyde or salicylaldehyde; the solvent is selected from alcohol solvents or water;
(2) dispersing the end ester group chitosan intermediate obtained in the step (1) in a solvent, adding polybasic fatty amine, and carrying out ester exchange reaction at room temperature to obtain first-generation chitosan group hyperbranched polyamidoamine;
(3) and (3) carrying out Michael addition and ester exchange reaction on the first-generation chitosan-based hyperbranched polyamidoamine obtained in the step (2), an acrylate compound and the multi-element fatty amine at room temperature to obtain second-generation and above-generation chitosan-based hyperbranched polyamidoamine.
3. The preparation method according to claim 2, wherein in the step (2), the molar ratio of the poly aliphatic amine to the terminal ester group chitosan intermediate is (1-2): 1;
the polybasic aliphatic amine is selected from ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine or triethylenetetramine;
the solvent is selected from alcohol solvents or water.
4. The method according to claim 2, wherein in the step (3), the molar ratio of the acrylate compound to the poly-aliphatic amine is 2 m ：（2 m ~2 m+1 ) (ii) a m is an integer greater than or equal to 2;
the acrylate compound is methyl acrylate.
5. The low-temperature efficient quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier is characterized by being prepared by the following method:
dispersing the chitosan-based hyperbranched polyamidoamine of claim 1 in a solvent, adding formaldehyde and dialkylamine to obtain a terminal tertiary amine structure, reacting the terminal tertiary amine structure with epihalohydrin to obtain a terminal epoxy group intermediate, and performing a ring-opening reaction with organic amine to obtain a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier;
or dispersing the chitosan-based hyperbranched polyamidoamine of claim 1 in a solvent, adding epoxy chloropropane and triethylamine, and reacting to obtain a low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched polyamidoamine demulsifier;
or dispersing the chitosan-based hyperbranched polyamidoamine of claim 1 in a solvent, adding 2, 3-epoxypropylammonium chloride, and performing a ring-opening reaction to obtain the low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier.
6. The low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier of claim 5, wherein the molar ratio of the chitosan-based hyperbranched polyamidoamine to formaldehyde to dimethylamine to epichlorohydrin is 1 (2) m-1 ~2m ): (2 m-1 ~2 m ): (2 m-1 ~2 m ) The molar ratio of the epoxy-terminated intermediate to the organic amine is 1: 1;
the molar ratio of the chitosan-based hyperbranched polyamidoamine to the epoxy chloropropane to the triethylamine is 1 (2) m-1 ~2 m ): (2 m-1 ~2 m )；
The molar ratio of the chitosan-based hyperbranched polyamidoamine to the 2, 3-epoxypropylammonium chloride is 1 (2) m-1 ~2 m ) (ii) a m is an integer of 1 or more.
7. The low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier of claim 6, wherein the organic amine is selected from one of ethylenediamine, propylenediamine, butylenediamine, ethanolamine, diethanolamine, triethanolamine, butylamine, hexylamine, octylamine, dodecylamine, tetradecylamine, hexadecylamine, or octadecylamine.
8. The application of the chitosan-based hyperbranched polyamidoamine of claim 1 or the low-temperature high-efficiency quaternary ammonium salt modified chitosan-based hyperbranched amidoamine demulsifier of any one of claims 5 to 7 in oil-in-water emulsion demulsification.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188552A (en) * | 2016-08-09 | 2016-12-07 | 武汉工程大学 | The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier |
| CN110183652A (en) * | 2019-06-10 | 2019-08-30 | 威海晨源分子新材料有限公司 | Ultrabranching polyamide-amine, modified ultra-branching polyamide-amide, preparation method and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188552A (en) * | 2016-08-09 | 2016-12-07 | 武汉工程大学 | The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier |
| CN110183652A (en) * | 2019-06-10 | 2019-08-30 | 威海晨源分子新材料有限公司 | Ultrabranching polyamide-amine, modified ultra-branching polyamide-amide, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Chitosan-modifications and applications: Opportunities galore;V.K.Mourya et al.,;《Reactive & Functional Polymers》;20080313;第68卷;第1013-1051页 * |
| Functionalization of chitosan polymer and their applications;Shanta Pokhrel et al.,;《Journal of Macromolecular Science, Part A:Pure and Applied Chemistry》;20190319;第1-27页 * |
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