CN109134756B - Oil-water separating agent and preparation method and application thereof - Google Patents
Oil-water separating agent and preparation method and application thereof Download PDFInfo
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- CN109134756B CN109134756B CN201810744944.8A CN201810744944A CN109134756B CN 109134756 B CN109134756 B CN 109134756B CN 201810744944 A CN201810744944 A CN 201810744944A CN 109134756 B CN109134756 B CN 109134756B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The invention discloses an oil-water separating agent, and a preparation method and application thereof. The oil-water separating agent for treating acidic oily sewage generated after acidification operation of an oil field is prepared by using methyl methacrylate, methacrylic acid and chitosan as raw materials and using a cationic surfactant as an emulsifier through emulsion polymerization. The oil-water separating agent has good treatment effect when treating acidic oily sewage generated after acidification operation of an oil field.
Description
Technical Field
The invention relates to the technical field of petroleum industry, and relates to an oil-water separating agent, and a preparation method and application thereof.
Background
Acidification of oil wells is the main stimulation measure of oil fields, but acidification brings other problems to oil field production while increasing production, and the treatment of acidic oily sewage is one of the problems. At present, the oil-water separating agent for treating the conventional oily sewage (non-acidic oily sewage) mainly comprises compounds such as polyaluminium, polyferric and cationic polymer, but the compounds are not suitable for directly treating the acidic oily sewage. Therefore, the research on the oil-water separating agent for effectively treating the acidic oily sewage generated after the acidification operation of the oil field has important production significance for oil field production.
Disclosure of Invention
The invention aims to provide an oil-water separating agent, and a preparation method and application thereof.
The method for preparing the oil-water separating agent provided by the invention comprises the following steps:
in an inert atmosphere, adding an initiator into the water phase solution, dropwise adding the dropwise added phase solution, continuing to react for 3.5-4.5h after dropwise adding is finished, and cooling to obtain the oil-water separating agent;
the aqueous phase solution consists of chitosan, a cationic surfactant and an acetic acid aqueous solution;
the dropwise addition phase solution is composed of methacrylic acid and methyl methacrylate.
In the above method, the cationic surfactant is at least one selected from the group consisting of dodecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide;
the mass percentage concentration of the acetic acid aqueous solution is 0.5-1.5%; in particular to 1 percent;
the dosage of the cationic surfactant is 0.4 to 0.8 percent of the total mass of the reaction system; specifically, it was 0.5%.
The deacetylation degree of the chitosan is more than 90%; the chitosan is at least one of low-viscosity chitosan and medium-viscosity chitosan; the viscosity of the low viscosity chitosan is <0.25Pa · s; the viscosity of the medium-viscosity chitosan is 0.25-0.65 Pa.s, and the medium-viscosity chitosan can be purchased from various open commercial sources.
The dosage of the chitosan is 0.05-0.4% of the total mass of the reaction system; specifically, it was found to be 0.2%.
The total mass of the methyl methacrylate and the methacrylic acid accounts for 8-14% of the total mass of the reaction system; in particular 10 percent;
the mass ratio of the methyl methacrylate to the methacrylic acid is 0.4-0.8: 1; specifically 0.6: 1.
The initiator is potassium persulfate; the amount of the initiator is 0.1 to 0.6 percent of the total mass of the methacrylic acid and the methyl methacrylate; specifically, it was found to be 0.2%.
In the dripping step, the dripping speed is 0.25-0.28 g/min; in particular 0.27 g/min.
In the reaction step, the reaction temperature is 60 to 80 ℃; in particular 70 ℃. The reaction time may be specifically 4 h.
In addition, the oil-water separating agent prepared by the method and the application of the oil-water separating agent in separating oily sewage or acidic oily sewage also belong to the protection scope of the invention. Wherein the oil-water separating agent is emulsion or homogeneous aqueous solution; the particle size of the emulsion is 0.15-1.5 μm. NaOH is added into the oil-water separating agent to adjust the pH value to 7, the oil-water separating agent can be changed into homogeneous phase aqueous solution from white emulsion, and hydrochloric acid is added to adjust the pH value to 4, so that the homogeneous phase aqueous solution becomes turbid and is changed into white emulsion. The physical diagram is shown in figure 1. In the separation, the dosage of the oil-water separating agent is 200 mg/L.
The oil-water separating agent for treating acidic oily sewage generated after acidification operation of an oil field is prepared by using methyl methacrylate, methacrylic acid and chitosan as raw materials and using a cationic surfactant as an emulsifier through emulsion polymerization. The oil-water separating agent has good treatment effect when treating acidic oily sewage generated after acidification operation of an oil field.
Drawings
FIG. 1 is a schematic diagram showing the sequential addition of NaOH and HCl to an oil-water separating agent.
FIG. 2 is a graph showing the particle size distribution of different oil-water separating agents.
FIG. 3 shows the effect of oil-water separation at different concentrations of the oil-water separating agent 2.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1 preparation of oil-water separating agent
0.8g of hexadecyl trimethyl ammonium bromide and 0.1g of low-viscosity chitosan are dissolved in 1 wt% acetic acid aqueous solution (135g), the water bath is heated to 70 ℃, nitrogen is introduced, oxygen is removed for 30min, 0.0326g of potassium persulfate is added, then the dropwise addition of the mixed solution (10g +6.3g) of methacrylic acid and methyl methacrylate is started, the dropwise addition speed is controlled, and the dropwise addition of the mixed solution is finished within 1 hour. And reacting at 70 ℃ for 4h after the dropwise addition is finished, and cooling to room temperature to obtain the oil-water separating agent 1. The median particle diameter of the oil-water separating agent 1 was 0.186. mu.m, and the intrinsic viscosity was 1.48 dL/g.
Example 2 preparation of oil-water separating agent
0.8g of hexadecyl trimethyl ammonium bromide and 0.3g of low-viscosity chitosan are dissolved in 1 wt% acetic acid aqueous solution (135g), the water bath is heated to 70 ℃, nitrogen is introduced, oxygen is removed for 30min, 0.0326g of potassium persulfate is added, then the dropwise addition of the mixed solution (10g +6.3g) of methacrylic acid and methyl methacrylate is started, the dropwise addition speed is controlled, and the dropwise addition of the mixed solution is finished within 1 hour. After the dropwise addition, the reaction is carried out for 4 hours at the temperature of 70 ℃, and the oil-water separating agent 2 is obtained after cooling to the room temperature. The median particle diameter of the oil-water separating agent 2 is 0.375 mu m, and the intrinsic viscosity is 2.13 dL/g.
Example 3 preparation of oil-water separating agent
0.8g of hexadecyl trimethyl ammonium bromide and 0.5g of low-viscosity chitosan are dissolved in 1 wt% acetic acid aqueous solution (135g), the water bath is heated to 70 ℃, nitrogen is introduced, oxygen is removed for 30min, 0.0326g of potassium persulfate is added, then the dropwise addition of the mixed solution of methacrylic acid and methyl methacrylate (10g +6.3g) is started, the dropwise addition speed is controlled, and the dropwise addition of the mixed solution is finished within 1 hour. And reacting at 70 ℃ for 4h after the dropwise addition is finished, and cooling to room temperature to obtain the oil-water separating agent 3. The median particle diameter of the oil-water separating agent 3 was 1.09. mu.m, and the intrinsic viscosity was 3.38 dL/g.
The particle size distribution of the oil-water separating agent 1-3 is shown in FIG. 2.
Example 4 evaluation of the Performance of the oil-water separating agent for treating acidic oily wastewater
Firstly, neutralizing an oil-water separating agent to be neutral by using a sodium hydroxide solution, and then preparing a 1% aqueous solution for later use; then, 100ml of acidic oily sewage (pH 4.2 and oil content 6400mg/L) generated in the acidification operation of a certain oil field is taken and poured into a 250ml beaker, and the beaker is placed at 40 ℃ for heat preservation for 10 min; and finally, adding 200mg/L of oil-water separating agent under the stirring of 150rpm, stirring for 10min, standing for 5min, taking a lower-layer water sample to measure the oil content and calculating the oil removal rate. The results of the oil removal rates of the different oil-water separating agents are shown in Table 1.
TABLE 1 oil removal rates of different agents for acidic oily wastewater
| Medicament | Polyaluminium chloride | Oil-water separating agent 1 | Oil-water separating agent 2 | Oil-water separating agent 3 |
| Oil removal Rate (%) | 12 | 83 | 92 | 92 |
As can be seen from Table 1, the oil removal rates of the oil-water separating agent provided by the invention are both significantly higher than those of polyaluminium, wherein the oil removal rates of the oil-water separating agent 2 and the oil-water separating agent 3 can reach 92%.
Example 5 evaluation of the Performance of the oil-water separating agent for treating acidic oily wastewater
Firstly, neutralizing an oil-water separating agent 2 to be neutral by using a sodium hydroxide solution, and then preparing a 1% aqueous solution for later use; then, 100ml of acidic oily sewage (pH 4.2 and oil content 6400mg/L) generated in the acidification operation of a certain oil field is taken and poured into a 250ml beaker, and the beaker is placed at 40 ℃ for heat preservation for 10 min; and finally, adding the oil-water separating agent 2 with different concentrations under the stirring of 150rpm, stirring for 10min, standing for 5min, taking a lower-layer water sample to measure the oil content and calculating the oil removal rate. The results of the oil removal rates of the different oil-water separating agents are shown in FIG. 3. The result of figure 3 shows that when the addition amount of the oil-water separating agent 2 is more than or less than 200mg/L, the oil drops float slowly.
In conclusion, the oil-water separating agent prepared by emulsion polymerization by taking methyl methacrylate, methacrylic acid and chitosan as raw materials and a cationic surfactant as an emulsifier has a good treatment effect on acidic oily sewage generated after oilfield acidification operation.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (16)
1. A method for preparing an oil-water separating agent comprises the following steps:
in an inert atmosphere, adding an initiator into the water phase solution, dropwise adding the dropwise added phase solution, continuing to react for 3.5-4.5h after dropwise adding is finished, and cooling to obtain the oil-water separating agent;
the aqueous phase solution consists of chitosan, a cationic surfactant and an acetic acid aqueous solution;
the dropwise addition phase solution is composed of methacrylic acid and methyl methacrylate.
2. The method of claim 1, wherein: the cationic surfactant is selected from at least one of dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide;
the mass percentage concentration of the acetic acid aqueous solution is 0.5-1.5%;
the dosage of the cationic surfactant is 0.4-0.8% of the total mass of the reaction system.
3. The method of claim 2, wherein: the mass percentage concentration of the acetic acid aqueous solution is 0.5-1.5%;
the dosage of the cationic surfactant is 0.5 percent of the total mass of the reaction system.
4. The method of claim 1, wherein: the deacetylation degree of the chitosan is more than 90%; the chitosan is at least one of low-viscosity chitosan and medium-viscosity chitosan; the dosage of the chitosan is 0.05-0.4% of the total mass of the reaction system.
5. The method of claim 4, wherein: the dosage of the chitosan is 0.2 percent of the total mass of the reaction system.
6. The method of claim 1, wherein: the total mass of the methyl methacrylate and the methacrylic acid accounts for 8-14% of the total mass of the reaction system;
the mass ratio of the methyl methacrylate to the methacrylic acid is 0.4-0.8: 1.
7. The method of claim 6, wherein: the total mass of the methyl methacrylate and the methacrylic acid accounts for 10% of the total mass of the reaction system;
the mass ratio of methyl methacrylate to methacrylic acid was 0.6: 1.
8. The method of claim 1, wherein: the initiator is potassium persulfate; the amount of the initiator is 0.1 to 0.6 percent of the total mass of the methacrylic acid and the methyl methacrylate.
9. The method of claim 8, wherein: the amount of the initiator is 0.2% of the total mass of the methacrylic acid and the methyl methacrylate.
10. The method of claim 1, wherein: in the dripping step, the dripping speed is 0.25-0.28 g/min.
11. The method of claim 10, wherein: in the dropping step, the dropping rate was 0.27 g/min.
12. The method according to any one of claims 1-11, wherein: in the reaction step, the reaction temperature is 60 to 80 ℃.
13. The method of claim 12, wherein: in the reaction step, the reaction temperature was 70 ℃.
14. An oil-water separating agent produced by the method according to any one of claims 1 to 13.
15. The oil-water separating agent according to claim 14, wherein: the oil-water separating agent is emulsion or homogeneous phase water solution; the particle size of the emulsion is 0.15-1.5 μm.
16. Use of the oil-water separating agent according to claim 14 or 15 for separating oily sewage or acidic oily sewage.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709310A (en) * | 2013-12-20 | 2014-04-09 | 西南石油大学 | Methacrylic acid-methyl methacrylate copolymer emulsion and preparation method and applications thereof |
| CN105461849A (en) * | 2015-12-28 | 2016-04-06 | 重庆市环境科学研究院 | Preparation method of hydrophobic oleophilic resin and application of hydrophobic oleophilic resin in oil-water separation material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5662504A (en) * | 1979-10-27 | 1981-05-28 | Tadashi Ijima | Oil-water separating material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709310A (en) * | 2013-12-20 | 2014-04-09 | 西南石油大学 | Methacrylic acid-methyl methacrylate copolymer emulsion and preparation method and applications thereof |
| CN105461849A (en) * | 2015-12-28 | 2016-04-06 | 重庆市环境科学研究院 | Preparation method of hydrophobic oleophilic resin and application of hydrophobic oleophilic resin in oil-water separation material |
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