CN108864421B - Multi-branched cationic polyether reverse demulsifier and preparation method and application thereof - Google Patents
Multi-branched cationic polyether reverse demulsifier and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a multi-branched cationic polyether reverse demulsifier, a preparation method and application thereof. The method firstly prepares hydroxymethyl BPA, and then reacts with polyene amine to prepare multi-branched BPA type phenol amine resin, the synthesis process of the phenol amine resin effectively avoids the side reaction of formaldehyde and ethylene amine, and can ensure that the ortho position of phenolic hydroxyl group is completely reacted. The BPA type phenol amine resin is reacted with ethylene oxide to obtain a multi-branched polyether demulsifier, and the polyether reverse demulsifier is subjected to cationic modification by adopting quaternary ammonium salt and is applied to the treatment of oily sewage in oilfield produced liquid. The method not only ensures the requirement of the offshore platform on the oil recovery rate, but also solves the difficult problems that the demulsification and the dewatering are difficult to recover and directly discharge.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and relates to a multi-branched cationic polyether reverse demulsifier, and a preparation method and application thereof.
Background
Along with the wide application of the tertiary oil recovery technology in China, the types of oil field produced fluids are increasingly complex and mainly comprise different complex types of emulsions such as water-in-oil (W/O), oil-in-water (O/W), water-in-oil-in-water (W/O/W) and the like while the crude oil recovery rate is continuously improved, and the demulsification difficulty is correspondingly increased. Meanwhile, the oil field also enters a high water content development period, and the proportion of O/W emulsion in produced liquid is increased, so that the reduction of the oil content in water also becomes an important means for improving the yield of crude oil. The traditional oily sewage treatment agents mainly comprise inorganic flocculant, organic flocculant, surfactant, biological flocculant and the like, but because the stability of emulsified oil drops is improved by the existence of polymers, the agents generally do not meet the requirement of treating the oily sewage containing polymer. At present, most of the cationic polymers are cationic polymers, such as acrylamide copolymers, diallyl dimethyl ammonium chloride homopolymers and the like, aiming at demulsification of O/W emulsion and oil removal of oily sewage, and the cationic polymers are relatively complex in preparation method, expensive in raw materials and not suitable for industrial application.
Disclosure of Invention
The invention aims to provide a multi-branched cationic polyether reverse demulsifier, a preparation method and application thereof.
The method for preparing the cation modified polyether reverse demulsifier comprises the following steps:
1) carrying out polymerization reaction on BPA phenolic amine resin, alkali and ethylene oxide to obtain a polyether reverse demulsifier;
2) carrying out cation modification on the polyether reverse-phase demulsifier in a solvent by using quaternary ammonium salt to obtain the cation-modified polyether reverse-phase demulsifier; in the cation modified polyether reverse-phase demulsifier, the solid content is 45-55%; the number of grafted quaternary ammonium salt accounts for 20-60% of the total number of hydroxyl groups.
In step 1) of the above method, the alkali is at least one selected from potassium hydroxide, sodium hydroxide and sodium carbonate;
the mass ratio of the BPA phenolic amine resin to the ethylene oxide is 1: 1-100;
the mass ratio of the alkali to the BPA phenol amine resin is 0.3-0.9: 100;
in the step of polymerization reaction, the reaction temperature is 105-130 ℃; in particular to 120 ℃; the reaction pressure is 0.2MPa to 0.4MPa, and the reaction time is 4 to 30 hours.
In the step 2), the quaternary ammonium salt is prepared by the following steps: the tertiary amine reacts with bromoalkane, methyl iodide or benzyl chloride in equal molar ratio, and then reacts with isocyanate compounds to obtain the product with hydroxyl and-NCO groups.
Specifically, the tertiary amine is OH (CH)2)nN(CH3)2(ii) a n is 3 to 10;
the solvent is at least one selected from acetone, anhydrous ether, methanol, ethanol, dichloromethane and chloroform;
the brominated alkane is selected from at least one of 1-bromobutane, 1-bromohexane, 1-bromododecane and 1-bromohexadecane;
the isocyanate compound is IPDI (isophorone diisocyanate);
the feeding molar ratio of the tertiary amine to the isocyanate compound is 1: 0.5-1.5;
in the step of reacting the hydroxyl with the-NCO group, the reaction temperature is 20-30 ℃; the reaction time is 3-8 h;
the reaction is carried out in the presence of a catalyst; the catalyst is dibutyltin Dilaurate (DBLT); the mass ratio of the catalyst to the isocyanate compound is 1: 100-255.
The method further comprises the following steps: before the step 2) of cation modification, the obtained polyether reverse phase demulsifier, alkali and ethylene oxide are subjected to ring-opening polymerization reaction under the ring-opening polymerization condition.
In the step 2), in the cation modification step, the temperature is 40-80 ℃; specifically 50-65 ℃; the time is 1-7 h; in particular for 2-5 h.
In the step, under the condition that the addition amount of the polyether reverse-phase demulsifier is fixed, the addition amount of the quaternary ammonium salt can be determined, and then the addition amount of a solvent can be determined according to the solid content, so that the solid content of the obtained cation modified polyether reverse-phase demulsifier is 45-55%; the number of grafted quaternary ammonium salt accounts for 20-60% of the total number of hydroxyl groups. The determination of the chloride ion content can be carried out by the Mohr method.
The invention also claims BPA phenolic amine resins, made according to a process comprising the steps of:
after the Mannich reaction of BPA and formaldehyde aqueous solution, adding polyene amine for branching reaction, and obtaining the BPA phenolic amine resin after the reaction is finished.
The BPA is 2, 2-bis (4-hydroxyphenyl) propane, which is bisphenol-Based Propane (BPA) for short and is called bisphenol A in English;
specifically, the polyene amine is selected from at least one of diethylenetriamine, propylene diamine, triethylene tetramine and tetraethylene pentamine;
the mass percentage concentration of the formaldehyde aqueous solution is 35-37%; in particular to 36 percent;
the feeding molar ratio of the BPA to the formaldehyde to the polyene amine is 1: 2-16: 2-8; specifically, 1: 4-10: 4-6.
In the Mannich reaction and the branching reaction, the temperature is 45-85 ℃; in particular to 55 ℃; the reaction time of the Mannich reaction is 3-7 h; in particular 5 h; the reaction time of the branching reaction is 4-8 h; in particular 5 h;
the Mannich reaction and the branching reaction are both carried out in a solvent;
the solvent is at least one selected from methanol, ethanol, dichloromethane, trichloromethane, dimethyl sulfoxide and tetrahydrofuran;
the formaldehyde aqueous solution is mixed with BPA in a dropwise manner; the dropping speed of the formaldehyde aqueous solution is 2-20 g/min.
In addition, the cation modified polyether reverse demulsifier prepared by the method and the application of the cation modified polyether reverse demulsifier in demulsification of oily sewage or O/W type oily sewage also belong to the protection scope of the invention. In the cation modified polyether reverse-phase demulsifier, the solid content is 45-55%; in particular to 50 percent; the number of grafted quaternary ammonium salt accounts for 20-60% of the total number of hydroxyl groups, and specifically can be 20%, 40% or 60%. The dosage of the cation modified polyether reverse demulsifier in the demulsification can be 50-300 mg/L; more specifically, it may be 100-200 mg/L.
According to the invention, hydroxymethyl BPA is firstly prepared, and then the hydroxymethyl BPA reacts with polyene amine to prepare the multi-branched BPA type phenol amine resin, the synthesis process of the phenol amine resin effectively avoids the side reaction of formaldehyde and ethylene amine, and the ortho-position of phenolic hydroxyl can be completely reacted. And then the multi-branch BPA type phenol amine resin is taken as a core, the terminal amino group and ethylene oxide are subjected to ring-opening polymerization for grafting, so that the good hydrophilic performance of the multi-branch BPA type phenol amine resin is ensured, and the quaternary ammonium salt is adopted to carry out cation modification on the polyether reverse-phase demulsifier, so that the water solubility of the polyether reverse-phase demulsifier is ensured, and the adsorption capacity of the polyether reverse-phase demulsifier on oil drop anions is also improved through cations, thereby finally realizing the oil removal treatment on the oily sewage, ensuring the requirement of an offshore platform on the oil recovery rate, and solving the problems of difficult recovery and direct discharge of demulsified.
Drawings
FIG. 1 is a graph showing the change in the degree of deoiling according to the graft amount of quaternary ammonium salt;
FIG. 2 is a comparison of the oil removal rates of different samples at different dosages.
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 Synthesis of polyether reverse demulsifier A
(1) And (2) completely dissolving 25g of BPA by adopting 250g of methanol, dropwise adding the BPA into 145g of formaldehyde water solution, reacting for 30min at a constant temperature of 55 ℃, introducing N2, condensing and refluxing for 5h, carrying out vacuum rotary evaporation to remove the methanol and the formaldehyde, and finally placing in a vacuum drying oven for 24h to obtain the BPA with the active hydroxymethyl.
(2) Diluting the product obtained in the step (1) by using methanol, slowly dropwise adding 85g of tetraethylenepentamine solution to react for 1h at 55 ℃, then heating to 70 ℃, condensing and refluxing for 5h to obtain a light yellow transparent liquid, then vacuum-evaporating the methanol solvent and part of water in a rotary manner, and placing in a vacuum drying oven for 24h to obtain the initiator BPA phenolic amine resin.
(3) And (3) synthesizing polyether by using the product obtained in the step (2) and ethylene oxide through a high-pressure reaction kettle, sequentially adding 92g of initiator and 0.4g of KOH into the high-pressure kettle, heating while vacuumizing to-0.1 MPa after sealing, continuously vacuumizing, and heating to 100 ℃. When the temperature is close to 120 ℃, 365g of EO is slowly introduced, the pressure is controlled to be 0.2-0.4MPa, the temperature is lower than 120 ℃, when the reaction pressure is reduced to-0.1 MPa, the reaction is completed, and 456g of the reverse demulsifier A is prepared.
Example 2 Synthesis of polyether reverse demulsifier B
Polyether synthesis is carried out through a high-pressure reaction kettle, 125g of reverse demulsifier A and 0.4g of KOH are sequentially added into the high-pressure kettle, the temperature is raised while vacuumizing to-0.1 MPa after sealing, and the vacuum is continuously pumped to 100 ℃. When the temperature is close to 120 ℃, slowly introducing 150gEO, controlling the pressure at 0.2-0.4MPa and the temperature below 120 ℃, and when the reaction pressure is reduced to-0.1 MPa, indicating that the reaction is complete, preparing 275g of reverse demulsifier B.
Example 3 Synthesis of polyether reverse demulsifier C
Polyether synthesis is carried out through a high-pressure reaction kettle, 100g of reverse demulsifier A and 0.82g of KOH are sequentially added into the high-pressure kettle, the temperature is raised while vacuumizing to-0.1 MPa after sealing, and the vacuum is continuously pumped to 100 ℃. When the temperature is close to 120 ℃, 373g of EO is slowly added, the pressure is controlled to be 0.2-0.4MPa, the temperature is lower than 120 ℃, when the reaction pressure is reduced to-0.1 MPa, the reaction is completed, and 348g of reverse demulsifier C is prepared.
Example 4 Synthesis of cation-modified polyether reverse demulsifier B-1
(1) 2.06g of tertiary amine OH (CH)2)3N(CH3)2Condensing and refluxing 2.83g of methyl iodide at 55 ℃ for 24h under the condition of taking 30ml of acetone as a solvent, dripping the product into an anhydrous ether solvent, and separating out white solid powder to finally obtain 4.65g of methyl iodide quaternary ammonium salt;
(2) 1.10g of the product obtained in step (1) was weighed out and dissolved in 8.16g of solvent DMSO, and reacted with 2.065g of IPDI at 25 ℃ for 5 hours in the presence of 0.0081g of DBLT as a catalyst, in an amount which was 60% of the amount of hydroxyl groups of the polyether.
(3) And (3) weighing 5g of reverse demulsifier A, adding the reverse demulsifier A into the product obtained in the step (2), and carrying out condensation reflux for 3h at 60 ℃ to obtain a final product, namely the cation modified polyether reverse demulsifier B-1, wherein the solid content is 50%, and the number of grafted quaternary ammonium salts accounts for 60% of the total number of hydroxyl groups.
Example 5 Synthesis of cation-modified polyether reverse demulsifier B-4
(1) 2.06g of tertiary amine OH (CH)2)3N(CH3)2Condensing and refluxing 2.74g of 1-bromo-n-butane alkyl at 55 ℃ for 24h under the condition of taking 30ml of acetone as a solvent, dropwise adding the product into an anhydrous ether solvent, and separating out white solid powder to finally obtain 4.56g of bromo-n-butane quaternary ammonium salt;
(2) 1.49g of the product obtained in step (1) was weighed out and dissolved in 8.56g of solvent DMSO, and reacted with 2.067g of IPDI at 25 ℃ for 5 hours in the presence of 0.0086g of DBLT as a catalyst, in an amount which was 60% of the amount of hydroxyl groups of the polyether.
(3) And (3) weighing 5g of reverse demulsifier B, adding the reverse demulsifier B into the product obtained in the step (2), and carrying out condensation reflux for 3h at 60 ℃ to obtain a final product, namely the cation modified polyether reverse demulsifier B-4, wherein the solid content is 50%, and the number of grafted quaternary ammonium salts accounts for 60% of the total number of hydroxyl groups.
Example 6 Synthesis of cation-modified polyether reverse demulsifier B-6
(1) 2.06g of tertiary amine OH (CH)2)3N(CH3)2Condensing and refluxing 3.30g of 1-bromohexane at 55 ℃ for 24h under the condition of taking 30ml of acetone as a solvent, dropwise adding the product into an anhydrous ether solvent, and separating out white solid powder to finally obtain 5.092g of bromohexane quaternary ammonium salt;
(2) 1.74g of the product of step (1) was weighed out and dissolved in 11.97g of solvent DMSO, and reacted with 2.067g of IPDI at 25 ℃ for 5 hours in the presence of 0.0119g of DBLT as a catalyst, in an amount which reacted to 60% of the amount of hydroxyl groups in the polyether.
(3) And (3) weighing 5g of reverse demulsifier C, adding the reverse demulsifier C into the product obtained in the step (2), and carrying out condensation reflux for 3h at 60 ℃ to obtain a final product, namely the cation modified polyether reverse demulsifier B-6, wherein the solid content is 50%, and the number of grafted quaternary ammonium salts accounts for 60% of the total number of hydroxyl groups.
Example 7 Synthesis of cation-modified polyether reverse demulsifier B-7
(1) 2.06g of tertiary amine OH (CH)2)3N(CH3)2Condensing and refluxing 2.53g of benzyl chloride at 55 ℃ for 24h under the condition of taking 30ml of acetone as a solvent, dropwise adding the product into an anhydrous ether solvent, and separating out white solid powder to finally obtain 4.36g of benzyl chloride quaternary ammonium salt;
(2) 1.80g of the product of step (1) was weighed and dissolved in 12.43g of solvent DMSO, and reacted with 2.067g of IPDI at 25 ℃ for 5 hours in the presence of 0.0124g of DBLT as a catalyst, in an amount which is 60% of the amount of hydroxyl groups of the polyether.
(3) And (3) weighing 5g of reverse demulsifier A, adding the reverse demulsifier A into the product obtained in the step (2), and carrying out condensation reflux for 3h at 60 ℃ to obtain a final product, namely the cation modified polyether reverse demulsifier B-7, wherein the solid content is 50%, and the number of grafted quaternary ammonium salts accounts for 60% of the total number of hydroxyl groups.
Example 8 Synthesis of cation-modified polyether reverse demulsifier B-12
(1) 2.06g of tertiary amine OH (CH)2)3N(CH3)2Condensing and refluxing 4.985g of 1-bromododecane at 55 ℃ for 24h under the condition of taking 30ml of acetone as a solvent, dropwise adding the product into an anhydrous ether solvent, and separating out white solid powder to finally obtain 6.69g of bromododecane quaternary ammonium salt;
(2) 2.47g of the product from step (1) was weighed out and dissolved in 16.52g of solvent DMSO, and reacted with 2.067g of IPDI at 25 ℃ for 5h in the presence of 0.0165g of DBLT as a catalyst, in an amount which reacted 60% of the amount of hydroxyl groups in the polyether.
(3) And (3) weighing 5g of reverse demulsifier B, adding the reverse demulsifier B into the product obtained in the step (2), and carrying out condensation reflux for 3h at 60 ℃ to obtain a final product, namely the cation modified polyether reverse demulsifier B-12, wherein the solid content is 50%, and the number of grafted quaternary ammonium salts accounts for 60% of the total number of hydroxyl groups.
Example 9 Synthesis of cation-modified polyether reverse demulsifier B-16
(1) 2.06g of tertiary amine OH (CH)2)3N(CH3)2Condensing and refluxing 6.10g of 1-bromohexadecane at 55 ℃ for 24h under the condition of taking 30ml of acetone as a solvent, dripping the product into an anhydrous ether solvent, and separating out white solid powder to finally obtain 7.76g of bromohexadecane quaternary ammonium salt;
(2) 3.05g of the product from step (1) was weighed out and dissolved in 17.54g of DMSO solvent, and reacted with 2.067g of IPDI at 25 ℃ for 5h in the presence of 0.0175g of DBLT as a catalyst, in an amount which reacted 60% of the amount of hydroxyl groups in the polyether.
(3) And (3) weighing 5g of reverse demulsifier C, adding the reverse demulsifier C into the product obtained in the step (2), and carrying out condensation reflux for 3h at 60 ℃ to obtain a final product, namely the cation modified polyether reverse demulsifier B-16, wherein the solid content is 50%, and the number of grafted quaternary ammonium salts accounts for 60% of the total number of hydroxyl groups.
Example 10 reverse demulsifier clean water test
The invention provides a demulsification and dehydration method of O/W type crude oil emulsion, which uses the cation modified polyether reverse demulsifier provided by the invention;
the conditions for demulsification and dehydration are generally as follows: diluting the reverse demulsifier stock solution with methanol, adding into O/W crude oil emulsion, and mixing completely and uniformly, wherein the demulsification temperature is 30-80 ℃, and preferably 60-70 ℃;
and D-500D instrument is adopted to measure the oil content of the sewage.
The reverse demulsifier of the invention is a synthetic medicament, can reduce the oil content of 9227.3mg/L of high oil-containing sewage to about 202.7mg/L under the conditions of 65 ℃ and dosage of 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L and 300mg/L and the dosage of 200mg/L, and the evaluation result is shown in figure 1 and figure 2. The figure shows that the evaluation and characterization of the cation modified polyether reverse demulsifier obtained by the invention have good effect. The reverse demulsifiers used in examples 4 to 9 were optionally replaced with the reverse demulsifiers A to C obtained in examples 1 to 3, and the demulsification effect of the obtained cation-modified polyether reverse demulsifier was not substantially different and will not be described again.
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 (5)
1. A method of preparing a cation-modified polyether reverse demulsifier, comprising:
1) carrying out ring-opening polymerization reaction on BPA phenolic amine resin, alkali and ethylene oxide to obtain a polyether reverse demulsifier;
the BPA phenolic amine resin is prepared by the method comprising the following steps:
after carrying out Mannich reaction on BPA and formaldehyde aqueous solution, adding polyene amine for carrying out branching reaction, and obtaining the BPA phenolic amine resin after the reaction is finished;
the polyene amine is selected from at least one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
the mass percentage concentration of the formaldehyde aqueous solution is 35-37%;
the feeding molar ratio of the BPA to the formaldehyde to the polyene amine is 1: 2-16: 2-8;
in the Mannich reaction and the branching reaction, the temperature is 45-85 ℃; the reaction time of the Mannich reaction is 3-7 h; the reaction time of the branching reaction is 4-8 h;
the Mannich reaction and the branching reaction are both carried out in a solvent;
the solvent is at least one selected from methanol, ethanol, dichloromethane, trichloromethane, dimethyl sulfoxide and tetrahydrofuran;
2) carrying out cation modification on the polyether reverse-phase demulsifier in a solvent by using quaternary ammonium salt to obtain the cation-modified polyether reverse-phase demulsifier; in the cation modified polyether reverse-phase demulsifier, the solid content is 45-55%; the number of grafted quaternary ammonium salts accounts for 20-60% of the total number of hydroxyl groups;
in the step 1), alkali is selected from at least one of potassium hydroxide, sodium hydroxide and sodium carbonate;
the mass ratio of the BPA phenolic amine resin to the ethylene oxide is 1: 1-100;
the mass ratio of the alkali to the BPA phenol amine resin is 0.3-0.9: 100;
in the step of ring-opening polymerization, the reaction temperature is 105-130 ℃; the reaction pressure is 0.2 MPa-0.4 MPa, and the reaction time is 4-30 h;
in the step 2), in the cation modification step, the temperature is 40-80 ℃; the time is 1-7 h;
in the step 2), the quaternary ammonium salt is prepared by the following steps: reacting tertiary amine with bromoalkane, methyl iodide or benzyl chloride in equal molar ratio, and then reacting with isocyanate compounds to obtain the product, wherein the product is obtained by reacting hydroxyl and-NCO groups;
the tertiary amine is OH (CH)2)nN(CH3)2(ii) a n is 3 to 10.
2. The method of claim 1, wherein: in the step 2), in the cation modification step, the temperature is 50-65 ℃; the time is 2-5 h.
3. The method of claim 1, wherein: in the step 2), the solvent is at least one selected from acetone, anhydrous ether, methanol, ethanol, dichloromethane and chloroform;
the brominated alkane is selected from at least one of 1-bromobutane, 1-bromohexane, 1-bromododecane and 1-bromohexadecane;
the isocyanate compound is IPDI;
the feeding molar ratio of the tertiary amine to the isocyanate compound is 1: 0.5-1.5;
in the step of reacting the hydroxyl with the-NCO group, the reaction temperature is 20-30 ℃; the reaction time is 3-8 h;
the reaction is carried out in the presence of a catalyst; the mass ratio of the catalyst to the isocyanate compound is 1: 100-255.
4. The method of claim 3, wherein: the catalyst is dibutyltin dilaurate.
5. The method according to any one of claims 1 to 4, wherein: the method further comprises the following steps: before the step 2) of cationic modification, the obtained polyether reverse demulsifier, alkali and ethylene oxide are subjected to ring-opening polymerization under the conditions of claim 1.
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| CN111423902B (en) * | 2020-04-20 | 2022-04-22 | 中国石油化工股份有限公司 | Demulsification synergist for thickened oil and preparation method thereof |
| CN113429955B (en) * | 2021-06-24 | 2022-03-11 | 中国矿业大学 | Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment |
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| CN1537924A (en) * | 2003-10-22 | 2004-10-20 | 山东大学 | Low-temperature quick deemulsifying agent for water-containing wax-containing erude oil and its preparation method |
| CN101376707A (en) * | 2008-10-07 | 2009-03-04 | 青岛科技大学 | Method for synthesizing polyether type high polymer quaternary ammonium salt |
| CN106700059A (en) * | 2016-12-16 | 2017-05-24 | 滨州市丰泰技术开发有限公司 | Preparation method of low-temperature demulsifier and low-temperature demulsifier prepared by means of method |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537924A (en) * | 2003-10-22 | 2004-10-20 | 山东大学 | Low-temperature quick deemulsifying agent for water-containing wax-containing erude oil and its preparation method |
| CN101376707A (en) * | 2008-10-07 | 2009-03-04 | 青岛科技大学 | Method for synthesizing polyether type high polymer quaternary ammonium salt |
| CN106700059A (en) * | 2016-12-16 | 2017-05-24 | 滨州市丰泰技术开发有限公司 | Preparation method of low-temperature demulsifier and low-temperature demulsifier prepared by means of method |
Non-Patent Citations (1)
| Title |
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| 阳离子多枝型聚醚制备及对含油污水处理应用研究;耿宏坤等;《中国化学会第十六届胶体与界面化学会议论文摘要集》;20170724;第30-31页 * |
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