阅读说明：本技术 一种高分子原油破乳剂 (Macromolecule crude oil demulsifier ) 是由 鄢靖峰 张世春 赵琴 何五星 张莹 于 2020-06-30 设计创作，主要内容包括：本发明提供了一种高分子原油破乳剂,其通式为[A-(EO)<Sub>a</Sub>-(EO)<Sub>a</Sub>-]<Sub>x</Sub>B,其中EO为-(O-CH<Sub>2</Sub>CH<Sub>2</Sub>)-,PO为-(CH<Sub>2</Sub>-O-CH<Sub>2</Sub>CH<Sub>2</Sub>)-,A为酚醛胺树脂,B为环戊二异氰酸酯,其中x为2～4的整数,A中包含-(CH<Sub>2</Sub>CH<Sub>2</Sub>NH)<Sub>n</Sub>-基团,其中n为3～18的整数,通式的均分子量为3000～8000,中a与b的比值为(1：10)～(2:1)；本发明将酚醛胺聚氧乙烯聚氧丙烯醚进一步反应,通过环氧氯丙烷在醚键上添加2,3-环氧丙基,然后用环戊二异氰酸酯取代2,3-环氧丙基扩链得到新的大分子,因环戊二异氰酸酯具有多个可取代基团,因此可以连接多个酚醛胺聚氧乙烯聚氧丙烯酯,从而形成复杂的空间网状结构,使得分子量变大,活泼官能团增多,对原油乳液有较好的破乳作用,同时能够提高脱水的效率和效果。(The invention provides a polymer crude oil demulsifier with a general formula of [ A- (EO) a ‑(EO) a ‑] x B, where EO is- (O-CH) 2 CH 2 ) -, PO is- (CH) 2 ‑O‑CH 2 CH 2 ) -, A is phenolic aldehyde amine resin, B is cyclopentane diisocyanate, x is an integer of 2-4, A contains- (CH) 2 CH 2 NH) n -a group, wherein n is an integer from 3 to 18, the average molecular weight of the general formula is from 3000 to 8000, and the ratio of a to b is (1: 10) to (2: 1); according to the invention, the phenolic aldehyde amine polyoxyethylene polyoxypropylene ether is further reacted, 2, 3-epoxypropyl is added on an ether bond through epoxy chloropropane, and then 2, 3-epoxypropyl is replaced by cyclopentanediisocyanate for chain extension to obtain a new macromolecule, and because the cyclopentanediisocyanate has a plurality of substitutable groups, a plurality of phenolic aldehyde amine polyoxyethylene polyoxypropylene esters can be connected, so that a complex space network structure is formed, the molecular weight is increased, active functional groups are increased, a better demulsification effect on crude oil emulsion is achieved, and the dehydration efficiency can be improved at the same timeAnd an effect.)

1. A macromolecule crude oil demulsifier is characterized in that: the general formula is [ A- (EO)_a-(PO)_b-]_xB, where EO is- (O-CH)₂CH₂) -, PO is- (CH)₂-O-CH₂CH₂) -, A is phenolic aldehyde amine resin, B is cyclopentane diisocyanate, wherein x is an integer of 2-4.

2. The polymeric crude oil demulsifier of claim 1, wherein: wherein A comprises- (CH)₂CH₂NH)_n-a group, wherein n is an integer from 3 to 18.

3. The polymeric crude oil demulsifier of claim 1 or 2, wherein: the average molecular weight of the general formula is 6000 to 15000.

4. The polymeric crude oil demulsifier of claim 1 or 2, wherein: the ratio of a to b in the general formula is (1: 10) - (2: 1).

5. A method for preparing the polymer crude demulsifier of any one of claims 1-4, wherein: the method comprises the following steps (the parts are the parts of materials):

(1) adding 6.5-8 parts of polyethylene polyamine into a stirring reaction kettle, then adding 1-1.5 parts of phenol in a molten state, starting stirring, controlling the temperature of materials in the kettle to be 25-45 ℃, stirring for 0.5-2 hours to uniformly mix the materials, then slowly dropwise adding 2-3 parts of formaldehyde, controlling the temperature to be 35 +/-10 ℃, and maintaining the temperature to continuously react to generate phenol-aldehyde amine resin after dropwise adding;

(2) heating to 160 ℃ of temperature of 120-;

(3) putting the phenolic aldehyde amine polyoxyethylene polyoxypropylene ether product obtained in the step (2) into a new reaction kettle, adding a catalyst, controlling the temperature to be 30-50 ℃, slowly dropwise adding 1-8% of epoxy chloropropane by mass fraction, stirring for 5-10 min after dropwise adding is finished, heating to 75-90 ℃, carrying out heat preservation reaction for 1.5-2.5h, finally cooling to below 60 ℃, adding low molecular alcohol to terminate the reaction, and stirring for 15-30 min to obtain phenolic aldehyde amine polyoxyethylene polyoxypropylene ester with an epoxypropylene group;

(4) and (3) dehydrating and desalting the phenol aldehyde amine polyoxyethylene polyoxypropylene ester product with the epoxy propylene group obtained in the step (3), adding 0.8-1.2% of cyclopentane diisocyanate in mass fraction, and mixing and stirring at 80 ℃ for 60-80min to obtain the final product.

6. The method for demulsifying polymeric crude oil of claim 5, wherein the step of: in the step (1), the formaldehyde is a solution with the mass fraction of 30-45%.

7. The method for demulsifying polymeric crude oil of claim 5, wherein the step of: the catalyst in the step (3) is 0.8-1.5% of KOH by mass fraction.

8. The method for demulsifying polymeric crude oil of claim 5, wherein the step of: the low molecular alcohol added in the step (3) is 1-5% of methanol by mass fraction.

Technical Field

The invention relates to the technical field of crude oil demulsification, in particular to a high-molecular crude oil demulsifier.

Background

In recent years, the water content of crude oil gradually rises with the successive production of most oil fields in the middle and later stages and the application of yield increasing technologies such as tertiary oil recovery and large pump extract. Natural emulsifiers such as colloid, asphaltene and solid particles existing in crude oil components, and various surfactants, polymers and the like added in the oil displacement process lead to complicated produced liquid components, obviously increased oil-water interface strength and enhanced emulsion stability, seriously affect the processes of crude oil production, field treatment, gathering and transportation and the like, and lead to higher and higher requirements on crude oil demulsification.

Injecting a chemical demulsifier with a certain concentration into the crude oil emulsion is the most common demulsification mode for the oil field at present and is one of the fastest effective demulsification methods. The demulsifier belongs to the type of surfactant, the molecule of the demulsifier consists of oleophylic and hydrophilic groups, and the oleophylic part is a hydrocarbon group, in particular a long-chain hydrocarbon group; and the hydrophilic part is composed of an ionic or nonionic hydrophilic group. The demulsifiers are of various types, and can be classified according to the classification method of the surfactants: cationic, anionic, nonionic and dual-type ionic demulsifiers. The main principle of the commonly used nonionic demulsifiers in oil fields at present mainly comprises that an initiator with a hydrophilic group, resin, polyoxyethylene and polyoxypropylene form long-chain macromolecules, and the hydrophilic group penetrates into emulsion drops to destroy the emulsification interface of the emulsion drops so as to achieve the effect of separating two phases.

However, in the existing demulsifiers, the formed long-chain macromolecules are single-chain linear macromolecules, and although some branched structures exist in the AP and AE demulsifiers, the branched structures are mainly located in polyethylene polyamines at the ends and are hydrophilic branched chains with the chain length less than 20, and active hydrophobic groups which are large enough are not available to effectively achieve the oil-water separation effect, so that the oil-water separation effect is not ideal.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a high-molecular crude oil demulsifier which is used for solving the problems that the existing demulsifier mainly has a straight chain structure, so that the molecular weight of the demulsifier is not large enough, and the oil-water separation capability is not strong enough due to the fact that the existing demulsifier contains few active functional groups.

In order to achieve the purpose, the invention adopts the following technical scheme:

a polymer crude oil demulsifier with a general formula of [ A- (EO)_a-(PO)_b-]_xB, where EO is- (O-CH)₂CH₂) -, PO is- (CH)₂-O-CH₂CH₂) -, A is phenolic aldehyde amine resin, B is cyclopentane diisocyanate, wherein x is an integer of 2-4.

Further, A includes- (CH)₂CH₂NH)_n-a group, wherein n is an integer from 3 to 18.

Further, the average molecular weight of the general formula is 3000-8000.

Further, the ratio of a to b in the general formula is (1: 10) to (2: 1).

A method for preparing a polymer crude oil demulsifier comprises the following steps (the parts are the weight parts of the materials):

(1) adding 6.5-8 parts of polyethylene polyamine into a stirring reaction kettle, then adding 1-1.5 parts of phenol in a molten state, starting stirring, controlling the temperature of materials in the kettle to be 25-45 ℃, stirring for 0.5-2 hours to uniformly mix the materials, then slowly dropwise adding 2-3 parts of formaldehyde, controlling the temperature to be 35 +/-10 ℃, and maintaining the temperature to continuously react to generate phenol-aldehyde amine resin after dropwise adding;

(2) heating to 160 ℃ of temperature of 120-;

(3) putting the phenolic aldehyde amine polyoxyethylene polyoxypropylene ether product obtained in the step (2) into a new reaction kettle, adding a catalyst, controlling the temperature to be 30-50 ℃, slowly dropwise adding 1-8% of epoxy chloropropane by mass fraction, stirring for 5-10 min after dropwise adding is finished, heating to 75-90 ℃, carrying out heat preservation reaction for 1.5-2.5h, finally cooling to below 60 ℃, adding low molecular alcohol to terminate the reaction, and stirring for 15-30 min to obtain phenolic aldehyde amine polyoxyethylene polyoxypropylene ester with an epoxypropylene group;

(4) and (3) dehydrating and desalting the phenol aldehyde amine polyoxyethylene polyoxypropylene ester product with the epoxy propylene group obtained in the step (3), adding 0.8-1.2% of cyclopentane diisocyanate in mass fraction, and mixing and stirring at 80 ℃ for 60-80min to obtain the final product.

Further, in the step (1), the formaldehyde is a solution with the mass fraction of 30-45%.

Further, the catalyst in the step (3) is 0.8-1.5% of KOH by mass fraction.

Further, the low molecular alcohol added in the step (3) is 1-5% of methanol by mass fraction.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, the phenolic amine polyoxyethylene polyoxypropylene ether is further reacted, 2, 3-epoxypropyl is added on an ether bond through epoxy chloropropane, and then 2, 3-epoxypropyl is replaced by cyclopentanediisocyanate for chain extension to obtain a new macromolecule.

Detailed Description

The technical solution of the present invention is further illustrated by the following examples.