阅读说明：本技术 一种复配型聚醚类破乳剂及其制备方法 (Compound polyether demulsifier and preparation method thereof ) 是由 张进 凌坤华 范阳海 凌功明 于 2020-06-17 设计创作，主要内容包括：本发明公开了一种高效环保的复配型聚醚类破乳剂及其制备方法；首先通过双酚A与二乙烯三胺、甲醛反应制得多胺化合物；接着将其与环氧乙烷和环氧丙烷聚合,阳离子改性得到多支化阳离子聚醚反相破乳剂；最后将制得的多支化阳离子聚醚反相破乳剂与生物破乳剂、絮凝剂、交联剂按一定比例复配,用溶剂溶解后均匀混合后即得复配型聚醚类破乳剂。本发明制备得到的高效环保的复配型聚醚类破乳剂,破乳速度快,破乳效果好,并且可以减少破乳剂的用量,降低对环境的破坏,达到了环保节能的效果。(The invention discloses a high-efficiency environment-friendly compound polyether demulsifier and a preparation method thereof; firstly, reacting bisphenol A, diethylenetriamine and formaldehyde to prepare a polyamine compound; polymerizing the poly-branched cationic polyether with ethylene oxide and propylene oxide, and performing cationic modification to obtain a multi-branched cationic polyether reverse demulsifier; and finally, compounding the prepared multi-branched cationic polyether reverse-phase demulsifier with a biological demulsifier, a flocculant and a cross-linking agent according to a certain proportion, dissolving the mixture by using a solvent, and uniformly mixing the dissolved mixture to obtain the compound polyether demulsifier. The high-efficiency environment-friendly compound polyether demulsifier prepared by the invention has the advantages of high demulsification speed and good demulsification effect, can reduce the using amount of the demulsifier, reduces the damage to the environment and achieves the effects of environmental protection and energy conservation.)

1. The compound polyether demulsifier is characterized by comprising the following substances in percentage by mass: 35-45% of multi-branched cationic polyether reverse-phase demulsifier, 25-30% of biological demulsifier, 15-20% of flocculant and 10-15% of cross-linking agent.

2. The compound polyether demulsifier of claim 1, which is characterized by comprising the following components in percentage by mass: 40% of multi-branched cationic polyether reverse demulsifier, 30% of biological demulsifier, 15% of flocculant and 15% of cross-linking agent.

3. A method for preparing the compounded polyether demulsifier of claim 1, comprising the steps of:

(1) placing an initiator and a bimetallic catalyst in a reactor for reflux reaction to obtain mixed liquor of a branched polyamine compound and the bimetallic catalyst;

(2) transferring the mixed solution obtained in the step (1) into a high-voltage covering type, heating and vacuumizing after sealing;

(3) adding ethylene oxide and propylene oxide into the high-voltage covering type, and continuously reacting after the addition is finished to obtain a multi-branched polyether compound;

(4) reacting the multi-branched polyether compound obtained in the step (3) with halogenated hydrocarbon to obtain a multi-branched cationic polyether reverse demulsifier;

(5) and (4) dissolving the multi-branched cationic polyether reverse demulsifier obtained in the step (4) with a biological demulsifier, a flocculant and a cross-linking agent by using a solvent, and then uniformly stirring to obtain the compound polyether demulsifier.

4. The method for preparing the compound polyether demulsifier according to claim 3, wherein the method comprises the following steps: the biological demulsifier is PRJ-1 demulsifying bacteria; the flocculating agent is polyaluminium chloride and FeCl₃∙6H₂O or AlCl₃∙6H₂One or more of O; the cross-linking agent is one or two of diisocyanate and toluene diisocyanate.

5. The method for preparing the compound polyether demulsifier according to claim 3, wherein the method comprises the following steps: in the step (1), the initiator is bisphenol A, diethylenetriamine or formaldehyde; the double metal catalyst is double metal cyanide; the molar ratio of the bisphenol A to the bimetallic catalyst is (20-35): (1-4).

6. The method for preparing the compound polyether demulsifier according to claim 3, wherein the method comprises the following steps: in the step (2), the temperature of the high-voltage covering after temperature rise is 100-150 ℃.

7. The method for preparing the compound polyether demulsifier according to claim 3, wherein the method comprises the following steps: in the step (3), the pressure of the reaction cover is 0.1-0.7 MPa, and the reaction pressure is-0.2 MPa.

8. The method for preparing the compound polyether demulsifier according to claim 3, wherein the method comprises the following steps: in the step (3), the molar ratio of the branched polyamine compound to the double metal cyanide to the ethylene oxide to the propylene oxide is (6-10): (1-4): (40-60): (40-60).

9. The method for preparing the compound polyether demulsifier according to claim 3, wherein the method comprises the following steps: in the step (4), the molar ratio of the multi-branched polyether compound to the halogenated hydrocarbon is 1: (3-10).

10. The method of claim 3, wherein: in the step (5), the solvent is one or more of ethanol, propanol, isopropanol and terpene; the adding amount of the solvent is 20-60% of the total weight of the compound demulsifier.

Technical Field

The invention belongs to the technical field of oil exploitation, and particularly relates to a high-efficiency environment-friendly compound polyether demulsifier and a preparation method thereof.

Background

Crude oil demulsification refers to separating oil and water in emulsified oil-water mixed liquid by using the chemical action of a demulsifier to realize crude oil dehydration so as to meet the water content standard of crude oil output. Crude oil is complex in composition and contains not only hydrocarbons having different molecular weights and structures but also non-hydrocarbon impurities such as clay, sand, hydrogen sulfide in a free state, inorganic salts dissolved in water, and the like, which are present in crude oil in different forms. In particular, the crude oil in China has low hydrogen-carbon atomic ratio, less light fraction and more heavy fraction. Heavy oil fractions in crude oil contain more colloids and asphaltenes, which can generate soap substances with stable interfaces in an alkaline environment, and the stability of the emulsion is improved. This also adds difficulty to the petroleum exploitation project in our country.

The crude oil is not in the form of an emulsion before being produced, and the crude oil is mixed with water and gas on the way of production and transportation to the ground, and the emulsion is formed by the continuous stirring of a production mechanical probe. The water content of the crude oil can also increase the load of pumps, pipelines and crude oil storage tanks, so that the pipelines and equipment are scaled, corroded and blocked, and the quality and the exploitation efficiency of the crude oil are greatly reduced in the past, so that the environmental pollution is caused. The demulsifier is added into the emulsion system, so that the structure of the stable emulsion can be promoted to be destroyed, when the liquid is dispersed into a plurality of small drops, the interface between oil and water becomes large, the Gibbs function of the interface is increased, the state is a thermodynamically unstable state, and the Gibbs function inevitably tends to be reduced spontaneously, namely the small drops are converged into a large drop, and finally the large drop is divided into two layers. The chemical demulsifier realizes the demulsification function in this way. In recent years, with the continuous progress of crude oil extraction technology, the use of a large amount of various oil extraction aids makes the components of the extracted crude oil become more and more complex, so that the requirements on the performance of the demulsifier are higher and higher.

Compared with the prior art, the method for synthesizing the demulsifier with the new structure has the advantages that the cost is high, the requirement of breaking the emulsion of all crude oil in the industry at present cannot be met, and the active search and exploration of a compounding process based on the prior demulsifier is a good choice. Chinese patent CN 104673358A provides a complex system of polyether demulsifier, alcohol diblock, triblock, multiblock polyether demulsifier synthesized in laboratory is used to complex with traditional anionic demulsifier, and the experiment shows that compared with the traditional demulsifier, the complex system has improved demulsification efficiency and better demulsification effect. For example, the inventor of the compound demulsifier for oil fields provided in chinese patent CN 105524647 a firstly prepares the conventional polyether demulsifiers with different molecular weights, and then compounds the polyether demulsifiers with different molecular weights according to different proportions to obtain the high-performance demulsifier. The two complex demulsifiers have good demulsification effect, but have the disadvantages of large using amount of the demulsifier in the using process and environmental pollution.

The invention content is as follows:

in order to solve the problems, the invention provides a high-efficiency environment-friendly compound polyether demulsifier and a preparation method thereof. The composite polyether demulsifier comprises a biological demulsifier, a flocculating agent and a cross-linking agent, and the demulsifier can fully exert the characteristics of respective single agents and improve the efficacy of synergistic action and the dehydration efficiency. The addition of the biological demulsifier can reduce the dosage of the traditional chemical demulsifier and reduce the harm to the environment; the cross-linking agent and the flocculating agent in the compound system can improve the effect of the demulsifier, reduce the dosage of the demulsifier and achieve the effects of environmental protection and energy saving.

The technical scheme provided by the invention is as follows:

the compound polyether demulsifier comprises the following substances in percentage by mass: 35-45% of multi-branched cationic polyether reverse-phase demulsifier, 25-30% of biological demulsifier, 15-20% of flocculant and 10-15% of cross-linking agent.

Preferably, 40% of multi-branched cationic polyether reverse demulsifier, 30% of biological demulsifier, 15% of flocculant and 15% of cross-linking agent.

The invention also discloses a method for preparing the compound polyether demulsifier, which comprises the following steps:

(1) placing an initiator and a bimetallic catalyst in a reactor for reflux reaction to obtain mixed liquor of a branched polyamine compound and the bimetallic catalyst;

(2) transferring the mixed solution obtained in the step (1) into a high-voltage covering type, heating and vacuumizing after sealing;

(3) adding ethylene oxide and propylene oxide into the high-voltage covering type, and continuously reacting after the addition is finished to obtain a multi-branched polyether compound;

(4) reacting the multi-branched polyether compound obtained in the step (3) with halogenated hydrocarbon to obtain a multi-branched cationic polyether reverse demulsifier;

(5) and (4) dissolving the multi-branched cationic polyether reverse demulsifier obtained in the step (4) with a biological demulsifier, a flocculant and a cross-linking agent by using a solvent, and then uniformly stirring to obtain the compound polyether demulsifier.

Preferably, the biological breakingThe emulsion is PRJ-1 demulsifying bacteria; the flocculating agent is polyaluminium chloride and FeCl₃·6H₂O or AlCl₃·6H₂One or more of O; the cross-linking agent is one or two of diisocyanate and toluene diisocyanate.

Preferably, in step (1), the initiator is bisphenol a, diethylenetriamine or formaldehyde; the double metal catalyst is double metal cyanide; the molar ratio of the bisphenol A to the bimetallic catalyst is (20-35): (1-4).

Preferably, in the step (2), the temperature of the high-voltage covering after temperature rise is 100-150 ℃.

Preferably, in the step (3), the pressure of the reaction cover is 0.1-0.7 MPa, and the reaction pressure is-0.2 MPa. Preferably, in the step (3), the molar ratio of the branched polyamine compound, the double metal cyanide, the ethylene oxide and the propylene oxide is (6-10): (1-4): (40-60): (40-60).

Preferably, in the step (4), the molar ratio of the multi-branched polyether compound to the halogenated hydrocarbon is 1: (3-10).

Preferably, in the step (5), the solvent is one or more of ethanol, propanol, isopropanol and terpene; the adding amount of the solvent is 20-60% of the total weight of the compound demulsifier.

Compared with the prior art, the invention has the following technical advantages:

(1) the composite polyether demulsifier prepared by the invention contains the biological demulsifier, the biological demulsifier is easy to degrade, has low toxicity and small pollution to the environment, can exert respective dehydration characteristics with a chemical demulsifier as a composite monomer, and after the demulsifying bacteria in the biological demulsifier are compounded with the cation multi-branched polyether, the volume of the whole demulsifier monomer molecule is increased, the branching degree is enriched, the amount of emulsion which can be contacted with one monomer is more, and a synergistic effect is generated. Not only can accelerate the dehydration speed, promote the emulsion breaking effect, but also can reduce the dosage of a chemical emulsion breaker, lighten the corrosion to pipeline equipment and reduce the pollution to the environment.

(2) The terpene solvent adopted in the invention is derived from natural plants, has an unsaturated cyclic structure, abundant double bonds in the structure are easy to convert more aromatic rings through dehydrogenation reaction, the lipophilicity is excellent, and the adsorption capacity to aromatic hydrocarbons and heterocyclic substances is strong, so that the solubility to oil sludge on an asphaltene and water-oil interface is good, the aromaticity of the environment where the asphaltene is located is increased, the viscosity of the water-oil interface is reduced, the stability of a crude oil emulsion is weakened to a certain extent, the application range of the compound system is expanded, the demulsification effect of the compound polyether demulsifier is increased, and the use amount and the cost of the demulsifier are reduced.

(3) The invention adds polyaluminium chloride (PAC) and FeCl in the preparation of the complex polyether demulsifier₃·6H₂O as a flocculant component, FeCl when the pH of the emulsion is around 7₃·6H₂Conversion of O to Fe (OH) in aqueous solution₂ ⁺The colloid is in a colloid form, so that the formation of the colloid can neutralize the negative charges on the surfaces of the small droplets, reduce the repulsion between the small droplets, promote the aggregation of the small droplets and accelerate the separation of oil and water phases; similarly, under the action of electrostatic attraction and dispersion force, polyaluminium chloride (PAC) attracts a large number of small droplets with negative charges to form floccules, and the floccules are settled, so that the separation of oil phase and water phase is accelerated. Therefore, the addition of the two substances can improve the demulsification efficiency of the demulsifier.

(4) According to the invention, when the compound polyether demulsifier is prepared, the toluene diisocyanate is added as a cross-linking agent, after chain extension by the cross-linking agent, branched chains are increased, the molecular weight is obviously increased, the contact area with crude oil is increased, the demulsification performance of the demulsifier can be improved, and the dehydration interface is regular.

(5) The invention uses double metal cyanide complex catalyst to replace the traditional alkali catalyst, has high activity and less dosage, can realize the recovery of the catalyst by means of centrifugation and filtration operation, saves the use cost and greatly reduces the damage to the environment.

Drawings

FIG. 1 is a schematic diagram of a production process of the complex polyether demulsifier of the present invention.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.