CN114106238A - Zwitterionic flocculant and preparation method thereof - Google Patents
Zwitterionic flocculant and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
A zwitterionic flocculant and a preparation method thereof belong to the technical field of oilfield produced liquid treatment. The zwitterionic flocculant is prepared by the following method: adding an unsaturated quaternary ammonium salt monomer, an unsaturated secondary amine monomer and hydrochloric acid into water, and polymerizing under the action of an initiator to obtain a polymer solution, wherein the total mass of the monomers is not less than 45% of the total mass of the whole solution; and adding sodium hydroxide into the polymer solution, cooling to 0-10 ℃, dropwise adding carbon disulfide, after dropwise adding the carbon disulfide, heating to room temperature, and reacting for 2-5 hours to obtain the catalyst. Compared with single cationic flocculant and single anionic flocculant, the zwitterionic flocculant provided by the invention has the advantages of small dosage, remarkable effect and convenience in filling.
Description
Technical Field
The invention relates to the technical field of oilfield produced liquid treatment, in particular to a zwitterionic flocculant and a preparation method and application thereof.
Background
With the development of oil fields, the produced water volume of the oil fields is larger and larger. Oilfield produced water contains a large amount of oil droplets and solids, and the oil content of the oilfield produced water needs to be effectively reduced before the oilfield produced water is reinjected or discharged. The flocculation method is one of important methods for effectively reducing the oil content of produced water by adding a flocculating agent into the produced water to promote oil drop aggregation and oil-water separation. Currently, the common flocculants used for oilfield treatment of produced water are mainly cationic polymers, nonionic polymers and anionic dithiocarbamate compounds. However, the single-type flocculant for treating the sewage system with coexisting anions and cations has the problems of large dosage and poor treatment effect. In order to solve the above problems, it is necessary to prepare a zwitterionic flocculant having both the characteristics of a cationic flocculant and an anionic flocculant.
Disclosure of Invention
In view of the above, the present invention aims to provide a zwitterionic flocculant, which uses quaternary ammonium salt cationic monomer and unsaturated secondary amine as comonomers, firstly synthesizes a cationic polymer with a secondary amine group on a side group by aqueous solution polymerization, and then utilizes CS2Secondary amine is modified to prepare the zwitterion polymer with the characteristics of quaternary ammonium salt cations and dithio carbamate anions.
The technical proposal provided by the invention is that the preparation method of the zwitterionic flocculant comprises the following steps,
adding an unsaturated quaternary ammonium salt monomer, an unsaturated secondary amine monomer and hydrochloric acid into water in a molar ratio of 5-10: 1:1, and polymerizing under the action of an initiator to obtain a polymer solution, wherein the total mass of the monomers is not less than 45% of the total mass of the whole solution;
adding sodium hydroxide into the polymer solution, cooling to 0-10 ℃, dropwise adding carbon disulfide, after dropwise adding the carbon disulfide, heating to room temperature, and reacting for 2-5 hours to obtain the catalyst; the molar ratio of the carbon disulfide to the sodium hydroxide to the unsaturated secondary amine monomer is 1:1 to 1.05.
In one embodiment of the present invention, the unsaturated quaternary ammonium salt monomer is one of methacryloyloxyethyl trimethyl ammonium chloride and diallyl dimethyl ammonium chloride.
Preferably, the unsaturated quaternary ammonium salt monomer is methacryloyloxyethyl trimethyl ammonium chloride.
In one embodiment of the invention, the water-soluble initiator is one of ammonium persulfate and potassium persulfate, and the addition amount of the water-soluble initiator is 0.4-1.2% of the total mass of the monomers.
In one embodiment of the present invention, the unsaturated secondary amine monomer is diallylamine.
One embodiment of the present invention is that the polymerization reaction time is 4 to 10 hours, and oxygen in the system is removed before polymerization.
It is another object of the present invention to disclose a zwitterionic flocculant prepared according to any of the methods described above.
The invention also discloses the application of the zwitterionic flocculant, which is used for oil-water separation of oily water, wherein the oily water contains ferrous ions with the concentration of not less than 0.5mg/L, and the ferrous ions can be contained in the oily sewage per se or added externally.
The invention has the technical effects that:
1. a more efficient flocculating agent is needed aiming at the increase of the produced water yield, and a composite flocculating agent with different characteristics is one of important development directions. The product of the invention is a zwitterionic flocculant integrating the adsorption bridging flocculation capability of quaternary ammonium salt ions and the net catching and flocculation of dithiocarbamate.
2. Compared with single cationic flocculant and single anionic flocculant, the product of the invention has the advantages of small dosage, obvious effect and convenient filling.
3. The produced water treatment process is simple, only a certain amount of the product of the invention needs to be added into the produced water, the product is fully stirred to quickly generate insoluble flocs, and the insoluble flocs are settled, separated and filtered without complex equipment and procedures.
4. The raw materials used in the invention are easy to obtain, and the synthesis process is simple.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a chart of the infrared spectrum of the product of example 1;
FIG. 2 is a diagram of the mechanism of action of the zwitterionic flocculants of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
In the invention, the unsaturated secondary amine monomer is a monomer which contains a secondary amine group and an unsaturated double bond and can carry out polymerization reaction, and the structural formula of the unsaturated secondary amine monomer is shown as a formula 1.
In formula 1, R represents an unsaturated secondary amine monomer1And R2Are respectively and independently one of linear alkyl, branched alkyl and alkenyl, and R1And R2At least one of which is an alkylene group;
R1-NH-R2formula 1
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the following examples, the oily wastewater was provided by Beijing research center of general oil Co., China, which contains emulsifier, and has stable system, oil content of 2780mg/L and ferrous ion content of 0.7 mg/L.
In the following examples, methacryloyloxyethyl trimethylammonium chloride was used as an aqueous solution thereof, and the effective content was 80%.
In the following examples, acryloyloxyethyltrimethyl ammonium chloride was used as an aqueous solution thereof, and the effective content was 80%.
In the following examples, diallyldimethylammonium chloride was used as an aqueous solution thereof, and the effective content was 65%.
Example 1 preparation of zwitterionic flocculant 1
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterionic flocculant 1.
The reaction sequence in example 1 is as follows:
to further illustrate the product, an infrared spectrum scan was performed, and the scan results are shown in fig. 1.
In the figure, at 3453cm-1The peak of (a) is produced by N-H stretching vibration of the secondary amine; 1729cm-1The peak of (a) belongs to the stretching vibration peak of C ═ O; 1631cm-1The peak of (a) belongs to the out-of-plane bending vibration peak of the C-N bond of the secondary amine; 1482cm-1The peak of (A) belongs to-CH3Out-of-plane bending vibration peaks of (a); 1151cm-1The peak of (a) belongs to the C-O stretching vibration peak; 950cm-1The stretching vibration peak of the C-S bond appears. The synthesis of the product was successful by combining the above.
Example 2 preparation of zwitterionic flocculant 2
Taking 52g of an acryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of a carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterionic flocculant 2.
Example 3 preparation of zwitterionic flocculant 3
Taking 64g of diallyl dimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 19g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterionic flocculant 3.
Example 4 preparation of zwitterionic flocculant 4
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of N, N-dimethylallylamine, 32.96g of deionized water and 6.56g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 2.73g of sodium hydroxide, stirring for dissolving, dropwise adding 5.06g of carbon disulfide aqueous solution into the reaction system, heating to room temperature after dropwise adding, and reacting for 3h to obtain the zwitterionic flocculant 4.
Example 5 preparation of zwitterionic flocculant 5
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g N-ethyl methyl acrylamide, 31.29g of deionized water and 8.23g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen to remove oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.44g of sodium hydroxide, stirring to dissolve, dropwise adding 6.39g of carbon disulfide aqueous solution into the reaction system, after dropwise adding, heating to room temperature, and reacting for 3h to obtain the zwitterionic flocculant 5.
Example 6 preparation of zwitterionic flocculant 6
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 56.03g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, heating to room temperature after dropwise adding is finished, and reacting for 3h to obtain the zwitterion flocculant 6.
(The monomer concentration is 40%)
Example 7 preparation of zwitterionic flocculant 7
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 42.16g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, heating to room temperature after dropwise adding is finished, and reacting for 3h to obtain the zwitterion flocculant 7.
(monomer concentration 45%)
Example 8 preparation of zwitterionic flocculant 8
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.2g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterionic flocculant 8.
(initiator concentration 0.4%)
Example 9 preparation of zwitterionic flocculant 9
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.3g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterion flocculant 9.
(initiator concentration 0.6%)
Example 10 preparation of zwitterionic flocculant 10
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 50 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterionic flocculant 10. (The temperature is 50 DEG C)
EXAMPLE 11 preparation of zwitterionic flocculant 11
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 70 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterionic flocculant 11.(temperature 70 ℃ C.)
Example 12 preparation of amphoteric flocculant 12
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 16.64g of diallylamine, 30.95g of deionized water and 16.89g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 7.02g of sodium hydroxide, stirring for dissolving, dropwise adding 13.04g of carbon disulfide aqueous solution into the reaction system, heating to room temperature after dropwise adding is finished, and reacting for 3h to obtain the zwitterionic flocculant 12.(Yang: Secondary amine ═ 2.5:1)
Example 13 preparation of amphoteric flocculant 13
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 5.55g of diallylamine, 31.12g of deionized water and 5.63g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 4h, cooling to 0 ℃, adding 2.34g of sodium hydroxide, stirring for dissolving, dropwise adding 4.35g of carbon disulfide aqueous solution into the reaction system, heating to room temperature after dropwise adding is finished, and reacting for 3h to obtain the zwitterion flocculant 13.(Yang: Secondary amine ═ 7.5:1)
Example 14 preparation of zwitterionic flocculant 14
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, initiating polymerization for 6h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring for dissolving, dropwise adding 6.52g of carbon disulfide aqueous solution into the reaction system, and heating to room temperature for reaction for 3h after dropwise adding is finished to obtain the zwitterionic flocculant 14.(time 6h)
Example 15 preparation of zwitterionic flocculant 15
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31.08g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen to remove nitrogenAnd adding 0.4g of ammonium persulfate after 20min of oxygen, initiating polymerization for 8h, cooling to 0 ℃, adding 3.51g of sodium hydroxide, stirring to dissolve, dropwise adding 6.52g of carbon disulfide solution into the reaction system, and heating to room temperature after dropwise adding to react for 3h to obtain the zwitterion flocculant 15.(time 8h)
Example 16 preparation of comparative cationic flocculant 1
Taking 52g of methacryloyloxyethyl trimethyl ammonium chloride aqueous solution, adding 8.32g of diallylamine, 31g of deionized water and 8.45g of hydrochloric acid, after the hydrochloric acid is completely dissolved in the system, opening a heating switch, keeping the temperature at 60 ℃, introducing nitrogen, removing oxygen for 20min, adding 0.4g of ammonium persulfate, and initiating polymerization for 4h to obtain the cationic flocculant 1.
To further illustrate the effectiveness of the present invention, the following tests were conducted on the oil removal rates of the flocculants prepared in examples 1-16 above.
The following method was used for the measurement of oil removal rate: first, 10ml of oily sewage (in which the ferrous ion concentration is 0.7mg/L) was added to a colorimetric tube, and the temperature was maintained at 60 ℃ for 10 min. Adding 180mg/L of zwitterionic flocculant, shaking by hand for 30s, and keeping the temperature at 60 ℃ for 25 min. Taking the liquid at the bottom of the colorimetric cylinder, and measuring the OIL content of the liquid by using a JC-OIL-6 type infrared spectrophotometry OIL meter.
The final measurement results are shown in table 1.
TABLE 1 measurement of oil removal Rate
1. By comparing the results of the oil removal rates of flocculant 1, flocculant 2 and flocculant 3 synthesized under different cationic monomers, the flocculant synthesized when methacryloyloxyethyl trimethyl ammonium chloride is used as the cationic monomer has the highest oil removal rate.
2. Compared with the flocculating agent 1, the flocculating agent 4 and the flocculating agent 5 are obtained by changing the type of the unsaturated secondary amine, and the oil removal rate of the synthesized flocculating agent is highest when the diallyl amine is used as the unsaturated secondary amine monomer.
3. Compared with the flocculating agent 1, the flocculating agent 6 and the flocculating agent 7 are obtained by changing the total concentration of the monomers, the flocculating effect is better along with the increase of the concentration of the monomers, and the oil removal rate is higher. This is because the higher the monomer concentration in the polymerization system and thus the higher the average molecular weight of the synthesized polymer, the more favorable the cationic groups in flocculation in wastewater treatment are to exert the "bridging" effect.
4. Compared with the flocculating agent 1, the flocculating agent 8 and the flocculating agent 9 are obtained by changing the concentration of the initiating agent, and when the concentration of the initiating agent is 0.4 percent, the flocculating effect is best and the sewage treatment is better. However, when the initiator concentration is increased, the oil removal rate is reduced, which is probably because the excessive initiator concentration may cause the branching and crosslinking of the flocculant molecular chains, and when the initiator concentration is increased, the molecular weight of the polymerization product is reduced, thereby causing the reduction of the flocculation property of the flocculant bridging.
5. Compared with flocculant 1, flocculant 10 and flocculant 11 are obtained by changing the polymerization temperature, and the treatment effect is best when the reaction temperature is 60 ℃. This is because when the temperature is too low, the decomposition of the initiator ammonium persulfate is too slow or when the temperature is too low, the decomposition is not caused, and the polymerization conversion is low in the same period of time. When the temperature is too high, the initiator is decomposed too fast, and the molecular weight of a polymerization product is low, so that the oil removal rate is not high. Therefore, the result of the preferred temperature is 60 ℃.
6. Compared with the flocculating agent 1, the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the diallyl amine is changed to obtain the flocculating agent 12 and the flocculating agent 13, when the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the diallyl amine is 2.5:1, the deoiling rate is very low, which indicates that the high content of dithiocarbamate in the flocculating agent is not beneficial to the flocculation performance. The interaction between the dithiocarbamate and the quat molecule can cause a contraction in polymer conformation, which is detrimental to flocculation. The shrink content increases with increasing dithiocarbamate content. Therefore, when the mass ratio of methacryloyloxyethyltrimethyl ammonium chloride to diallylamine is 2.5:1, the oil removal rate is very low. When the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the diallylamine is more than 2.5:1, the polymer conformation is relatively prolonged, bridging and net capturing simultaneously act, and the flocculating agent has good flocculation performance.
7. Compared with the flocculating agent 1, the flocculating agent 14 and the flocculating agent 15 are obtained by changing the polymerization time, and the free radicals of the system are gradually increased along with the extension of the reaction time, so that the polymerization reaction is facilitated, and the synthesized flocculating agent has a good oil removing effect. 8. Compared with the zwitterionic flocculant 1, the cationic flocculant has a lower flocculation effect than the zwitterionic flocculant under the condition of the same dosage of the medicament.
The above data are measured under the condition that the dosage is 180mg/L, and in fact, when the dosage of the zwitterionic flocculant in the example 1 is increased to 300mg/L, the whole solution becomes clear and transparent, and the oil removal rate can reach 99.54% through the test.
To further illustrate the role of ferrous ions in the flocculation process, the zwitterionic flocculant from example 1 was used to illustrate different cationic-containing wastewater, and the results are shown in Table 2.
TABLE 2 oil-water separation effect of zwitterionic flocculants for different cationic-containing sewage
| Kind of oily wastewater | Oil removal rate% |
| Ferrous ion (0.7mg/L) | 95.87 |
| Iron ion (0.7mg/L) | 72.31 |
| Aluminum ion (0.7mg/L) | 66.51 |
| Ferrous ion (0mg/L) | 74.51 |
As can be seen from Table 2, when the zwitterionic flocculant is only used for oily sewage containing ferrous ions, the amphoteric flocculant has a good oil removal effect, and the final oil removal rate can reach more than 95%; when the zwitterionic flocculant is used for oily sewage containing other metal ions such as ferric ions, aluminum ions and the like, the effect is relatively poor.
The above results are due to the specific structure of the zwitterionic flocculant of the invention and the unique oil removal mechanism, as shown in fig. 2, the oil removal mechanism of the invention is: the cationic flocculant has the electric neutralization effect of the conventional cationic flocculant, reduces negative charges on the surfaces of oil drops, compresses a double electric layer, and reduces repulsive force among the oil drops, so that a system is destabilized; meanwhile, the zwitterionic flocculant can be matched with ferrous ions to react quickly to generate flocs, crude oil and colloidal particles in sewage are continuously coalesced in the stirring process, and oil drops float up quickly under the wrapping and trapping effects of the flocs.
Therefore, under the action of the two mechanisms, the zwitterionic flocculant has high oil removal effect.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the embodiments of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of a zwitterionic flocculant is characterized by comprising the following steps,
adding an unsaturated quaternary ammonium salt monomer, an unsaturated secondary amine monomer and hydrochloric acid into water in a molar ratio of 5-10: 1:1, and polymerizing under the action of an initiator to obtain a polymer solution, wherein the total mass of the monomers is not less than 45% of the total mass of the whole solution;
adding sodium hydroxide into the polymer solution, cooling to 0-10 ℃, dropwise adding carbon disulfide, after dropwise adding the carbon disulfide, heating to room temperature, and reacting for 2-5 hours to obtain the catalyst; the molar ratio of the carbon disulfide to the sodium hydroxide to the unsaturated secondary amine monomer is 1:1 to 1.05.
2. The method of claim 1, wherein the unsaturated quaternary ammonium salt monomer is one of methacryloyloxyethyl trimethyl ammonium chloride and diallyl dimethyl ammonium chloride.
3. The method of claim 2, wherein the unsaturated quaternary ammonium salt monomer is methacryloyloxyethyl trimethyl ammonium chloride.
4. The method according to claim 1, wherein the water-soluble initiator is one of ammonium persulfate and potassium persulfate, the polymerization temperature is 50-70 ℃, and the addition amount of the water-soluble initiator is 0.4-1.2% of the total mass of the monomers.
5. The method of claim 1, wherein the unsaturated secondary amine monomer is diallylamine.
6. The method according to claim 1, wherein the polymerization reaction time is 4 to 10 hours and oxygen in the system is removed before the polymerization.
7. A zwitterionic flocculant prepared according to any one of claims 1 to 6.
8. The use of an ionic flocculant according to claim 7, wherein the zwitterionic flocculant is used for the separation of oil and water in oily water containing ferrous ions at a concentration of not less than 0.5 mg/L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07213897A (en) * | 1994-01-31 | 1995-08-15 | Nitto Boseki Co Ltd | Polymer heavy metal collecting agent, alkali metal dithiocarbramate polymer and their production |
| CN101585572A (en) * | 2009-06-09 | 2009-11-25 | 湖南科技大学 | A kind of amphiprotic high-molecule chelated flocculating agent and preparation method thereof |
| CN103112937A (en) * | 2013-03-11 | 2013-05-22 | 湖南科技大学 | Ethyl polyethylene polyamine polymethacrylate chelating flocculant and preparation method thereof |
| CN107399801A (en) * | 2016-05-18 | 2017-11-28 | 东莞市顶盛环保科技有限公司 | Industrial waste water treatment agent based on multiple-effect dephosphorization |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07213897A (en) * | 1994-01-31 | 1995-08-15 | Nitto Boseki Co Ltd | Polymer heavy metal collecting agent, alkali metal dithiocarbramate polymer and their production |
| CN101585572A (en) * | 2009-06-09 | 2009-11-25 | 湖南科技大学 | A kind of amphiprotic high-molecule chelated flocculating agent and preparation method thereof |
| CN103112937A (en) * | 2013-03-11 | 2013-05-22 | 湖南科技大学 | Ethyl polyethylene polyamine polymethacrylate chelating flocculant and preparation method thereof |
| CN107399801A (en) * | 2016-05-18 | 2017-11-28 | 东莞市顶盛环保科技有限公司 | Industrial waste water treatment agent based on multiple-effect dephosphorization |
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