阅读说明：本技术 一种新型破乳剂 (Novel demulsifier ) 是由 何林 马俊 李鑫钢 隋红 于 2019-09-24 设计创作，主要内容包括：本发明涉及一种新型破乳剂,制备方法是将脂肪醇聚醚溶于溶剂中,配制成一定浓度的脂肪醇聚醚溶液；将有机催化剂和烯烃酸加入到脂肪醇聚醚溶液中,于一定温度及转速下,进行一定时间的酯化反应；待酯化反应完成后,于一定温度及转速下,加入引发剂进行一定时间的聚合反应；待聚合反应完成后,用旋转蒸发仪将反应容器中的溶剂蒸干后置于真空干燥箱中干燥一定时间得到新型破乳剂。本发明破乳剂具有破乳速度快、效率高的特点,并且制备方法简单,成本低。(The invention relates to a novel demulsifier, which is prepared by dissolving fatty alcohol polyether in a solvent to prepare a fatty alcohol polyether solution with a certain concentration; adding an organic catalyst and an olefin acid into a fatty alcohol polyether solution, and carrying out esterification reaction for a certain time at a certain temperature and a certain rotating speed; after the esterification reaction is finished, adding an initiator at a certain temperature and a certain rotating speed to carry out polymerization reaction for a certain time; and after the polymerization reaction is finished, evaporating the solvent in the reaction container to dryness by using a rotary evaporator, and then placing the solvent in a vacuum drying oven for drying for a certain time to obtain the novel demulsifier. The demulsifier has the characteristics of high demulsification speed and high efficiency, and the preparation method is simple and has low cost.)

1. The preparation method of the novel demulsifier comprises the following steps:

1) dissolving fatty alcohol polyether in an organic solvent to prepare a fatty alcohol polyether solution with a certain concentration;

2) adding an organic catalyst into the fatty alcohol polyether solution obtained in the step 1);

3) adding alkene acid into the solution obtained in the step 2) for esterification reaction;

4) after the esterification reaction in the step 3) is finished, adding an initiator to carry out polymerization reaction;

5) after the polymerization reaction in the step 4) is finished, evaporating the solvent in the product to dryness, and drying the product to obtain the novel demulsifier.

2. The demulsifier of claim 1, wherein: the fatty alcohol polyether is straight-chain type, the initiator is propylene glycol, and the monomer is polyether of ethylene oxide and propylene oxide.

3. The demulsifier of claim 1, wherein: the solvent is an aromatic hydrocarbon solvent.

4. The demulsifier of claim 3, wherein: the aromatic hydrocarbon solvent is one or a mixture of more than two of dimethylbenzene, ethylbenzene, methylbenzene and trimethylbenzene.

5. The demulsifier of any one of claims 1-4, wherein: the ratio of the fatty alcohol polyether monomer to the solvent is 1-15g:100 mL.

6. The demulsifier of claim 1, wherein: the organic catalyst is sulfonic acid or organic acid salt.

7. The demulsifier of claim 6, wherein: the sulfonic acid is aryl sulfonic acid; the organic acid salt is acetate.

8. The demulsifier of claim 7, wherein: the aryl sulfonic acid is one or a mixture of more than two of benzene sulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid and m-toluenesulfonic acid; the acetate is one or a mixture of more than two of zinc acetate, cobalt acetate, manganese acetate and iron acetate.

9. The demulsifier of claim 1, 6, 7 or 8, wherein: the proportion of the added organic catalyst in the reaction accounts for 0.01-10% of the mass fraction of the fatty alcohol polyether.

10. The demulsifier of claim 1, wherein: the alkene acid is alkene acid with 3-20 carbon atoms.

11. The demulsifier of claim 10, wherein: the alkene acid is alkene acid which at least contains one carboxyl and has molecular weight of 72-300 g/mol.

12. The demulsifier of claim 11, wherein: the alkene acid is one or a mixture of more than two of 2-butenoic acid, oleic acid, acrylic acid and undecylenic acid.

13. The demulsifier of claim 1 or 10 or 11 or 12, wherein: the proportion of the alkene acid added in the reaction accounts for 1 to 30 percent of the mass fraction of the fatty alcohol polyether.

14. The demulsifier of claim 1, wherein: the temperature of the esterification reaction is 80-170 ℃.

15. The demulsifier of claim 1, wherein: the initiator is one or a mixture of more than two of azodiisobutyronitrile, azodiisoheptanitrile, benzoyl peroxide, di-tert-butyl peroxide and peroxydicarbonate.

16. The demulsifier of claim 1 or 15, wherein: the mass fraction of the initiator added in the reaction accounts for 0.01-10% of that of the fatty alcohol polyether.

17. The demulsifier of claim 1, wherein: the temperature of the polymerization reaction is 70-130 ℃.

18. The demulsifier of claim 1, wherein: the temperature of the dried product is 80-130 ℃, the pressure is-0.1 Mpa to-0.5 Mpa, and the time is 20-60 min.

19. Use of the demulsifier of claim 1 in the separation of water-in-oil and heavy water-in-oil emulsion systems.

Technical Field

The invention belongs to the field of demulsifiers, relates to a demulsification technology for emulsions of water-in-oil, heavy water-in-oil and the like, and particularly relates to a novel demulsifier.

Background

With the development of the world oil industry, the oil exploitation amount is increased day by day, and the world oil demand is also increased year by year. The gap of China's oil supply and demand is also increased year by year, and heavy oil resources such as oil sand, oil shale, oil sludge and the like are developed and utilized, so that part of conventional oil is replaced, the pressure of China's energy sources can be relieved, and the resources can be effectively utilized to the maximum extent.

However, in the process of heavy oil extraction, a key problem to be solved is to perform demulsification of oil-water emulsion, because the heavy oil contains natural interface active substances capable of stabilizing the oil-water emulsion, such as colloid, asphaltene, naphthenic acid and microcrystalline paraffin, which are natural emulsifiers and can stabilize an oil-water two-phase system, especially high-content colloid in the heavy oil, and the asphaltene can form an interface film with certain viscoelasticity, and the interface film can be strongly adsorbed on the surface of water molecules so as to stabilize the oil-water emulsion. In addition, surface active substances or other chemical additives brought in the process of mining and processing can be adsorbed on an oil-water interface, so that the emulsification degree of oil and water phases is increased, the oil-water two-phase system is more stable, and a highly stable oil-water emulsion is formed. The formed oil-water emulsion not only brings great difficulty to the subsequent processing process (corrosion of equipment, poisoning of catalyst and increase of transportation of finished products), but also seriously affects the quality of oil products, so that demulsification and dehydration of the oil-water emulsion are required to improve the quality of oil and reduce the loss of oil.

In order to break a stable oil-water two-phase system formed in the process of processing heavy oil, namely, break emulsion, different methods can be adopted, but the most common and effective method in industry is to add a chemical agent to break emulsion, wherein molecules of the added emulsion breaker penetrate and adhere to the interface of emulsified water drops to replace a natural emulsifier and destroy an oil-water interface film, so that the water drops are gathered, enlarged and settled, and then the oil phase and the water phase are separated.

Disclosure of Invention

The invention aims to provide a demulsifier for separating a heavy oil-water emulsion system and a preparation method thereof aiming at the defects of the prior art, the prepared demulsifier can quickly and effectively realize demulsification and separation of the heavy oil-water emulsion system, and has the characteristics of high demulsification speed and high dehydration rate.

The technical scheme for realizing the purpose of the invention is as follows:

the preparation method of the novel demulsifier comprises the following steps:

1) dissolving fatty alcohol polyether in an organic solvent to prepare a fatty alcohol polyether solution with a certain concentration;

2) adding an organic catalyst into the fatty alcohol polyether solution obtained in the step 1);

3) adding alkene acid into the solution obtained in the step 2) for esterification reaction;

4) after the esterification reaction in the step 3) is finished, adding an initiator to carry out polymerization reaction;

5) after the polymerization reaction in the step 4) is finished, evaporating the solvent in the product to dryness, and drying the product to obtain the novel demulsifier.

The fatty alcohol polyether is straight-chain polyether, specifically is polyether with propylene glycol as an initiator and ethylene oxide and propylene oxide as reaction monomers.

The solvent is an aromatic hydrocarbon solvent, and further the aromatic hydrocarbon solvent is one or a mixture of more than two of dimethylbenzene, ethylbenzene, toluene and trimethylbenzene.

The ratio of the fatty alcohol polyether single agent to the solvent is 1-15g:100 mL.

In the proportion, the mass fraction of the fatty alcohol polyether single agent in the aromatic hydrocarbon solvent is 1-15%; the volume ratio of the two aromatic hydrocarbon mixed solvents is 1: 1; specifically, the volume ratio of xylene to toluene is 1:1, and the volume ratio of the three aromatic hydrocarbon mixed solvents is 1:2: 1; specifically, the volume ratio of toluene, trimethylbenzene and ethylbenzene is 1:2:1, the volume ratio of the four aromatic hydrocarbon mixed solvents is 1:2:1:1, and specifically, the volume ratio of xylene, ethylbenzene, toluene and trimethylbenzene is 1:2:1: 1.

The organic catalyst is sulfonic acid or acetate, the sulfonic acid is aryl sulfonic acid, the organic acid salt is acetate, and the aryl sulfonic acid is benzene sulfonic acid, specifically one or a mixture of more than two of benzene sulfonic acid, p-toluene sulfonic acid, o-toluene sulfonic acid and m-toluene sulfonic acid. The acetate is one or more of zinc acetate, cobalt acetate, manganese acetate and iron acetate.

The proportion of the added organic catalyst in the reaction accounts for 0.01-10% of the mass fraction of the fatty alcohol polyether.

In the proportion, the mass fraction of a single benzene sulfonic acid substance is 0.01-10%; the mass ratio of the two benzene sulfonic acid substances is 1: 1; specifically, the mass ratio of p-toluenesulfonic acid to o-toluenesulfonic acid is 1: 1; the mass ratio of the three benzene sulfonic acid substances is 1:2: 1; specifically, the mass ratio of p-toluenesulfonic acid, m-toluenesulfonic acid and benzenesulfonic acid is 1:2: 1; the mass fraction of the single acetate is 0.01-10%; the mass ratio of the two acetates is 1: 1; specifically, the mass ratio of zinc acetate to cobalt acetate is 1: 1; the mass ratio of manganese acetate to iron acetate is 1: 1; the mass ratio of the three acetates is 1:1: 1; the mass ratio of zinc acetate to cobalt acetate to manganese acetate is 1:1: 1; the mass ratio of the cobalt acetate to the manganese acetate to the iron acetate is 1:1: 1.

The alkene acid is alkene acid with 3-20 carbon atoms.

Furthermore, the alkene acid is alkene acid with the carbon atom number of 3-20 and the molecular weight of 72-283 g/mol.

Furthermore, the alkene acid has 3-20 carbon atoms, molecular weight of 72-283g/mol, and at least one carboxyl.

The alkene acid is 2-butenoic acid, oleic acid, acrylic acid, undecylenic acid, or their mixture.

The proportion of the alkene acid added in the reaction accounts for 1 to 30 percent of the mass fraction of the fatty alcohol polyether.

In the proportion, the mass fraction of a single alkene acid is 1-30%; the mass ratio of the two olefin acids is 1:1, specifically, the mass ratio of acrylic acid to 2-butenoic acid is 1: 1; the mass ratio of the oleic acid to the undecylenic acid is 1: 1; the mass ratio of the three olefin acids is 1:2: 1; specifically, the mass ratio of acrylic acid, 2-butenoic acid and oleic acid is 1:2: 1; the mass ratio of the 2-butenoic acid to the oleic acid to the undecylenic acid is 1:2: 1.

The temperature of the esterification reaction is 80-170 ℃.

In the temperature, when single aromatic hydrocarbon in a reaction system is used as a solvent, the esterification reaction temperature is 80-170 ℃, and particularly when dimethylbenzene is used as a solvent, the temperature is 130 ℃; when ethylbenzene is used as a solvent, the temperature is 136 ℃; when toluene is used as a solvent, the temperature is 80 ℃; when xylene is used as solvent, the temperature is 170 ℃.

When two kinds of aromatic hydrocarbons are mixed to be used as a solvent, specifically, xylene and toluene are mixed to be used as the solvent, and the temperature is 140 ℃; when three kinds of aromatic hydrocarbons are mixed to be used as a solvent, specifically, toluene, trimethylbenzene and xylene are mixed to be used as the solvent, and the temperature is 110 ℃; when four kinds of aromatic hydrocarbon are mixed as the solvent, the solvent is specifically mixed of dimethylbenzene, ethylbenzene, methylbenzene and trimethylbenzene, and the temperature is 95 ℃.

The initiator is one or a mixture of more than two of azodiisobutyronitrile, azodiisoheptanitrile, benzoyl peroxide, di-tert-butyl peroxide and peroxydicarbonate.

The mass fraction of the initiator added in the reaction accounts for 0.01-10% of that of the fatty alcohol polyether.

In the proportion, when the selected initiator is any one of the initiators, the mass fraction is 0.01-10%; when the selected initiator is any two of the initiators, the ratio is 1:1, and specifically the mass ratio of the azodiisobutyronitrile to the azodiisoheptadecylenide is 1: 1; the mass ratio of the benzoyl peroxide to the di-tert-butyl peroxide is 1: 1; when the selected initiator is any three of the initiators, the ratio is 1:1:1, and specifically, the mass ratio of the benzoyl peroxide, the di-tert-butyl peroxide and the peroxydicarbonate is 1:1: 1; the mass ratio of the azodiisoheptanitrile to the benzoyl peroxide to the di-tert-butyl peroxide is 1:1: 1.

The temperature of the polymerization reaction is 70-130 ℃.

In the temperature, when the selected initiator is any one of the initiators, the polymerization temperature is 70-130 ℃, and specifically the polymerization temperature is corresponding to azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, di-tert-butyl peroxide and peroxydicarbonate; when the selected initiators are any two of the initiators, specifically, when the azodiisobutyronitrile and the azodiisoheptanitrile are used as the initiators, the polymerization temperature is 110 ℃; when benzoyl peroxide and di-tert-butyl peroxide are used as initiators, the polymerization temperature is 120 ℃; when the selected initiators are any three of the initiators, specifically benzoyl peroxide, di-tert-butyl peroxide and peroxydicarbonate are taken as the initiators, the polymerization temperature is 125 ℃; when azodiisoheptanitrile, benzoyl peroxide and di-tert-butyl peroxide are used as initiators, the polymerization temperature is 130 ℃.

The temperature of the dried product is 80-130 ℃, the pressure is-0.1 Mpa to-0.5 Mpa, and the time is 20-60 min.

The invention protects the application of the demulsifier in the separation of emulsion systems such as water-in-oil, heavy water-in-oil and the like.

The specific application method comprises the following steps:

a) dissolving a demulsifier in deionized water to prepare a polyether demulsifier aqueous solution with a certain concentration;

b) adding a certain amount of aqueous solution of the polyether demulsifier into water-in-oil or heavy water-in-oil emulsion for demulsification.

Compared with the prior art, the invention has the beneficial effects that: the condition for preparing the demulsifier is controllable, the preparation process is simple and feasible, the demulsifier can effectively demulsify the heavy oil water emulsion which is stable for up to one year, can completely remove water in the heavy oil water emulsion system in a short time, has good dehydration effect, and plays a great role in promoting the demulsification of the existing heavy oil water emulsion system.

Drawings

In order to more clearly illustrate the embodiments of the present invention, the drawings, which are required to be used in the embodiments, will be briefly described below.

FIG. 1 shows the general chemical reaction formulas of esterification and polymerization reactions in the examples.

Fig. 2 is a photograph of the demulsifier prepared in example 1.

Fig. 3 is a Fourier Transform Infrared (FTIR) spectrum of the demulsifier prepared in example 2.

FIG. 4 is a nuclear magnetic hydrogen spectrum of the demulsifier of example 5: (¹H-NMR)。

FIG. 5 is the nuclear magnetic carbon spectrum of the demulsifier of example 5: (¹³C-NMR)。

FIG. 6 is a Thermogravimetric (TG) plot of the demulsifier prepared in example 4.

Detailed Description

The present invention will be described below by way of examples for facilitating understanding of the present invention, but the present invention is not limited thereto. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.