CN111088065A - Crude oil demulsifier and preparation method thereof - Google Patents
Crude oil demulsifier and preparation method thereof Download PDFInfo
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- CN111088065A CN111088065A CN201811233863.8A CN201811233863A CN111088065A CN 111088065 A CN111088065 A CN 111088065A CN 201811233863 A CN201811233863 A CN 201811233863A CN 111088065 A CN111088065 A CN 111088065A
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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Abstract
The invention belongs to the technical field of chemicals for the petroleum industry, and particularly relates to a thick oil demulsifier and a preparation method thereof. The invention utilizes the synergistic action of polyether and non-polyether demulsifier to compound several demulsifiers of different types, so as to obtain the high-efficiency demulsifier suitable for thick oil produced fluid. The thick oil demulsifier provided by the invention has the advantages of small using amount, high dehydration rate, lasting dehydration property, clear water color, quick oil-water separation in the demulsification process, clear oil-water interface and few emulsification intermediate layers, and can be used for demulsifying thick oil quickly and efficiently at low temperature.
Description
Technical Field
The invention belongs to the technical field of chemicals for the petroleum industry, and particularly relates to a crude oil demulsifier and a preparation method thereof.
Background
With the rapid development of the petroleum industry and the continuous reinforcement of the oil extraction technology, the structure of the crude oil composition is changed, and particularly, the demulsification and dehydration difficulty of the crude oil is increased by the implementation of the three-extraction technology and the extraction of heavy oil at the end of the twentieth century. In order to solve the problem of low demulsification and dehydration efficiency, the oil field needs to perform thermochemical dehydration on crude oil emulsion, the temperature is raised, the molecular motion is intensified, the crude oil viscosity is reduced, the oil-water density difference is increased, droplets after chemical demulsification are easier to settle and separate, the emulsion stability is reduced, and the crude oil dehydration is facilitated; but fuel is consumed by heating, the steam pressure of the crude oil is increased by heating, the evaporation loss of the crude oil in the gathering and transportation process is increased, the common thermochemical demulsification temperature is generally 70-95 ℃, and the reduction of the demulsification temperature of the thickened oil has important significance for saving energy, reducing consumption, protecting the environment and improving the development benefit of the oil field.
At present, most of crude oil demulsifiers used in oil fields in China are ethylene oxide and propylene oxide block polyether demulsifiers. The main types of the demulsifier can be summarized as block polyether using alcohols as an initiator, block polyether using amines as an initiator, alkyl phenolic resin block polyether, phenolic amine aldehyde resin block polyether, silicon-containing demulsifier, ultrahigh relative molecular weight demulsifier, polyphosphate ester and modified products of block polyether. The emulsion breaking effect is poor due to large consumption when the emulsion breaking is carried out at low temperature. From the research and development trends of domestic and foreign crude oil demulsifiers, the non-polyether demulsifiers are demulsifiers which have relatively fast development in recent ten years. The Chinese patent CN105504143B develops that acrylic acid and acrylic ester are used as monomers, an emulsion polymerization mode is adopted to synthesize an acrylic acid-acrylic ester polymer with better emulsion breaking performance, and the acrylic acid-acrylic ester polymer has the characteristics of clear water color, small dosage and durable medicament dehydration performance on the emulsion breaking of crude oil emulsion, particularly heavy oil emulsion, but the emulsion breaking effect under the low temperature condition is not ideal.
Therefore, the development of a high-efficiency thick oil demulsifier which is low in dosage, high in dehydration rate and has a demulsification effect reaching the industrial standard of petroleum and natural gas at low temperature is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problem that a block polyether demulsifier and a non-polyether demulsifier in the prior art have poor demulsification effect at low temperature, and provides a high-efficiency crude oil demulsifier which has the advantages of low consumption, high dehydration rate, lasting dehydration property, clear water color and demulsification effect reaching the industrial standard of petroleum and natural gas at low temperature.
To this end, the invention provides, in a first aspect, a crude oil demulsifier comprising a non-polyether demulsifier and a polyether selected from at least one of a block polyether using an alcohol as an initiator, an alkylphenol aldehyde resin block polyether and a phenol amine aldehyde resin block polyether.
In some preferred embodiments of the present invention, the polyether is a mixture of at least two of a block polyether, an alkyl phenol-formaldehyde resin block polyether and a phenol-amine-aldehyde resin block polyether, which are initiated with alcohols.
In some embodiments of the invention, the mass ratio of the non-polyether demulsifier to the polyether is (0.1-10): 1.
in some preferred embodiments of the present invention, the mass ratio of the non-polyether demulsifier to the polyether is (0.5-7): 1.
in some more preferred embodiments of the present invention, the mass ratio of the non-polyether demulsifier to the polyether is (1-4): 1.
in some preferred embodiments of the present invention, the polyether is a mixture of a block polyether using an alcohol as an initiator, an alkyl phenol resin block polyether and a phenol amine aldehyde resin block polyether, wherein the mass ratio of the block polyether using an alcohol as an initiator, the alkyl phenol resin block polyether and the phenol amine aldehyde resin block polyether is 1: (0.3-7): (0.3-7).
In another preferred embodiment of the present invention, the mass ratio of the block polyether using an alcohol as an initiator, the alkylphenol aldehyde resin block polyether, and the phenol amine aldehyde resin block polyether is 1: (0.5-6): (0.5-6).
In some more preferred embodiments of the present invention, the mass ratio of the block polyether using alcohol as an initiator, the alkylphenol aldehyde resin block polyether and the phenol amine aldehyde resin block polyether is 1: (0.7-4): (0.7-4).
In some most preferred embodiments of the present invention, the mass ratio of the block polyether using alcohol as an initiator, the alkylphenol aldehyde resin block polyether and the phenol amine aldehyde resin block polyether is 1: (0.75-2): (0.75-2).
In some embodiments of the present invention, the block polyether using alcohol as a starter is the starter of the block polyether using alcohol as a starter commonly used in the art, and propylene glycol, glycerol, pentaerythritol or octadecanol are preferred.
In other embodiments of the present invention, the block polyether using an alcohol as a starter is a block polyether using an alcohol as a starter commonly used in the art, such as SP169, BPE2070, BPE2040, BPE22064, BPE2420, BPE2045, or BP 169.
In some embodiments of the present invention, the alkylphenol-phenolic resin block polyether is synthesized with the initiator of alkylphenol-phenolic resin block polyether commonly used in the art, such as nonylphenol or mixed alkylphenol with C9 as main component.
In other embodiments of the present invention, the alkylphenol-formaldehyde resin block polyether is a phenol-formaldehyde 3111, 3105, AF6231, AF3125, AF136, AR16, AR36 or AR48, which are commonly used in the art.
In some embodiments of the present invention, the phenol-amine-aldehyde resin block polyether initiator is a condensation product of an alkylphenol, a vinylamine compound and formaldehyde, and is selected from the group consisting of TA1031, PFA8311, XW-1, DPA2031, XW-4, XW-9, XW-12, BC-26, BC-68, and the like, which are commonly used in the art.
In some embodiments of the invention, the crude oil demulsifier further comprises a fatty alcohol-polyoxyethylene ether and/or an organic alcohol.
In other embodiments of the present invention, the fatty alcohol-polyoxyethylene ether is at least one selected from isooctanol polyoxyethylene ether and decanoyl-octanoyl polyoxyethylene ether.
In some preferred embodiments of the present invention, the fatty alcohol-polyoxyethylene ether is isooctanol polyoxyethylene ether.
In the invention, the non-polyether demulsifier is a solution, the block polyether, the alkyl phenolic resin block polyether, the phenolic amine aldehyde resin block polyether and the fatty alcohol-polyoxyethylene ether which take the alcohol as the initiator can be emulsion, paste or solid powder, but when at least one of the block polyether, the alkyl phenolic resin block polyether and the phenolic amine aldehyde resin block polyether which take the alcohol as the initiator is mixed with the non-polyether demulsifier solution, the state of each polyether demulsifier is required to be kept consistent.
In some preferred embodiments of the present invention, the organic alcohol is selected from C1-C20 organic alcohols, preferably at least one of methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, tert-butanol, n-octanol, n-dodecanol.
In some embodiments of the invention, the non-polyether demulsifier solution comprises, by mass, 20-70% of block polyether using alcohol as an initiator, 5-20% of alkyl phenolic resin block polyether, 5-20% of phenolic amine aldehyde resin block polyether, 0-2% of isooctanol polyoxyethylene ether, and 10-40% of organic alcohol.
In some embodiments of the present invention, in the crude oil demulsifier system, the mass ratio of the non-polyether demulsifier solution, fatty alcohol-polyoxyethylene ether, and organic alcohol is 100: (0-10): (20-100).
In some preferred embodiments of the present invention, in the crude oil demulsifier system, the mass ratio of the non-polyether demulsifier solution, fatty alcohol-polyoxyethylene ether, and organic alcohol is 100: (0-4): (20-100).
In a second aspect, the present invention provides a method of preparing the crude oil demulsifier provided in the first aspect of the present invention, which comprises:
step S1, mixing polyether or a mixture of polyether and organic alcohol with a non-polyether demulsifier to obtain a first mixture.
In some preferred embodiments of the present invention, the method further comprises a step S2 of mixing the fatty alcohol-polyoxyethylene ether with the first mixture obtained in the step S1.
In some embodiments of the present invention, step S1 is performed at a temperature of 50 to 80 ℃.
In some preferred embodiments of the present invention, step S1 is performed at a temperature of 60 to 70 ℃.
In other embodiments of the present invention, the time for performing step S1 is 20-100 min.
In other preferred embodiments of the present invention, the time for performing step S1 is 30-60 min.
In some embodiments of the present invention, step S2 is performed at a temperature of 50 to 80 ℃.
In some preferred embodiments of the present invention, step S2 is performed at a temperature of 60 to 70 ℃.
In other embodiments of the present invention, the time for performing step S2 is 20-100 min.
In other preferred embodiments of the present invention, the time for performing step S2 is 30-60 min.
The third aspect of the invention provides the use of the crude oil demulsifier provided by the first aspect of the invention or the crude oil demulsifier prepared by the method provided by the second aspect of the invention in demulsification of crude oil, preferably in demulsification of thick oil.
At present, most of crude oil demulsifiers used in oil fields in China are block polyether demulsifiers. In the prior art, some initiators and emulsifiers are added to modify the block polyether demulsifier, but the problems of large dosage and poor demulsification effect when crude oil demulsification is carried out still cannot be solved. In view of the current state of research and development of demulsifiers, non-polyether demulsifiers have become a class of demulsifiers that have developed faster in the last decade. Although the non-polyether demulsifier is chemically modified, the high-efficiency thick oil demulsifier with clear water color, low dosage and lasting medicament dehydration property is obtained. However, the demulsifying effect of the conventional demulsifier under low-temperature conditions is still not ideal. And because of the complexity of the crude oil composition, coupled with numerous factors that affect the formation of emulsified crude oil, many difficulties are presented to the research efforts of crude oil demulsifiers. And with the implementation of the three-extraction technology and the extraction of heavy oil, the demulsification and dehydration difficulty of the crude oil is increased.
The complex formulation of the demulsifier is an economic, rapid and effective technical approach for improving the performance of the demulsifier. Based on the above, the inventor of the present application has conducted a great deal of research on demulsifiers for crude oil, and creatively found that, since a non-polyether demulsifier and a polyether demulsifier have respective demulsification characteristics, the non-polyether demulsifier and the polyether demulsifier are compounded, and a small amount of an auxiliary agent is added thereto, the demulsifier has an obvious effect on improving the dehydration efficiency of thick oil and improving the water color of dehydrated water.
The non-polyether demulsifier is prepared by copolymerizing butyl acrylate and acrylic acid solution, wherein the butyl acrylate monomer is fed once, the acrylic acid monomer is added by 20-50% of the total amount of acrylic acid, and the rest acrylic acid monomer is added continuously or in batches in the polymerization process. The monomer composition in the system can be kept unchanged, and the copolymer with more uniform composition distribution of acrylic ester and acrylic acid, namely hydrophobic group and hydrophilic group, is obtained, so that the copolymer is favorable for entering the interface of the crude oil emulsion to carry out demulsification. The copolymer has high surface activity and can be well adsorbed on an oil-water interface to achieve a demulsification effect. The polyether demulsifier in the invention is at least one selected from block polyether, alkyl phenolic resin block polyether and phenolic amine aldehyde resin block polyether which take alcohols as initiators. The high-efficiency demulsifier suitable for the thick oil produced liquid is obtained by compounding several demulsifiers of different types by utilizing the synergistic action of a polyether demulsifier and a non-polyether demulsifier. The thick oil demulsifier provided by the invention has the advantages of small using amount, high dehydration rate, lasting dehydration property, clear water color, quick oil-water separation in the demulsification process, clear oil-water interface and few emulsification intermediate layers, and can be used for demulsifying thick oil quickly and efficiently at low temperature. And by utilizing the synergistic action of the polyether demulsifier and the non-polyether demulsifier in the thick oil demulsifier, the proportion of the polyether demulsifier and the non-polyether demulsifier, the composition of the polyether demulsifier and the proportion of the components are properly adjusted according to crude oil with different water contents, so as to obtain different compound systems for guiding the field application.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention is provided below. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, to the extent that there is no stated or intervening value in that stated range, to the extent that there is no such intervening value, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where a specified range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
The invention aims to solve the problems of low dehydration rate, slow oil-water separation and poor demulsification effect of the demulsifier in the prior art during low-temperature demulsification.
To this end, the invention provides, in a first aspect, a crude oil demulsifier comprising a non-polyether demulsifier and a polyether selected from at least one of a block polyether using an alcohol as an initiator, an alkylphenol aldehyde resin block polyether and a phenol amine aldehyde resin block polyether.
In some preferred embodiments of the present invention, the polyether is a mixture of at least two of a block polyether, an alkyl phenol-formaldehyde resin block polyether and a phenol-amine-aldehyde resin block polyether, which are initiated with alcohols.
In some embodiments of the invention, the mass ratio of the non-polyether demulsifier to the polyether is (0.1-10): 1.
in some preferred embodiments of the present invention, the mass ratio of the non-polyether demulsifier to the polyether is (0.5-7): 1.
in some more preferred embodiments of the present invention, the mass ratio of the non-polyether demulsifier to the polyether is (1-4): 1.
in some preferred embodiments of the present invention, the polyether is a mixture of a block polyether using an alcohol as an initiator, an alkyl phenol resin block polyether and a phenol amine aldehyde resin block polyether, wherein the mass ratio of the block polyether using an alcohol as an initiator, the alkyl phenol resin block polyether and the phenol amine aldehyde resin block polyether is 1: (0.3-7): (0.3-7).
In another preferred embodiment of the present invention, the mass ratio of the block polyether using an alcohol as an initiator, the alkylphenol aldehyde resin block polyether, and the phenol amine aldehyde resin block polyether is 1: (0.5-6): (0.5-6).
In some more preferred embodiments of the present invention, the mass ratio of the block polyether using alcohol as an initiator, the alkylphenol aldehyde resin block polyether and the phenol amine aldehyde resin block polyether is 1: (0.7-4): (0.7-4).
In some most preferred embodiments of the present invention, the mass ratio of the block polyether using alcohol as an initiator, the alkylphenol aldehyde resin block polyether and the phenol amine aldehyde resin block polyether is 1: (0.75-2): (0.75-2).
The non-polyether type thick oil demulsifier is prepared by copolymerizing butyl acrylate and acrylic acid, the number average molecular weight is 5,000-200,000, and the molecular formula is as follows:
wherein R is3Representing butyl, a ═ 70% to 99%, b ═ 1% to 30%.
Preferably, the non-polyether demulsifier is prepared by a solution copolymerization method, wherein the butyl acrylate monomer is fed in one time, the acrylic acid monomer is added into the solution at first by 20-50 percent, more preferably by 30-40 percent, of the total amount of acrylic acid, and the rest acrylic acid monomer is continuously or in batches added in the polymerization process.
The non-polyether type thick oil demulsifier can be prepared by the following preparation method:
adding butyl acrylate and a solvent into a reactor, replacing with nitrogen and keeping nitrogen atmosphere, uniformly stirring at 30-90 ℃, adding a polymerization initiator, uniformly stirring, adding 20-50% of acrylic acid, continuously adding the rest acrylic acid or adding the rest acrylic acid in batches every 0.5-3 hours, continuously reacting for 2-6 hours after all the acrylic acid is added, then adding a polymerization terminator, and reacting for 0.5-1 hour to obtain the non-polyether thick oil demulsifier; wherein, based on the total mass of the butyl acrylate and the acrylic acid, the addition amount of the butyl acrylate is 70-99 percent, and the addition amount of the acrylic acid is 1-30 percent.
In the polymerization reaction, the kind and the amount of the polymerization initiator and the polymerization terminator to be added are not particularly limited, and those skilled in the art can select them based on the common knowledge. For example, the polymerization initiator is preferably added in an amount of 0.1% to 2% and the polymerization terminator is preferably added in an amount of 0.1% to 2%, based on the total weight of butyl acrylate and acrylic acid. The polymerization initiator is preferably an azo type initiator or an organic peroxy type initiator, such as azobisisobutyronitrile. The polymerization terminator is preferably hydroquinone.
In the preparation method of the present invention, the solvent used in the solution polymerization reaction of the present invention may be arbitrarily selected within a range that does not affect the demulsifier of the present invention, and for example, the solvent is an aromatic hydrocarbon, alcohol, ketone or ester organic solvent such as benzene, xylene, or the like.
The polymerization reaction of the present invention is preferably carried out at 50 to 90 ℃.
Preferably, the amount of the acrylic monomer added at the initial stage of the polymerization is 20% to 50% of the total amount of acrylic acid, and the remaining acrylic monomer may be added in a continuous dropwise or batchwise manner, the number of times of batchwise addition being 2 to 6, more preferably 3. The time intervals for adding the acrylic monomers can be equal or different and can be selected according to the requirements of the polymerization process.
In some embodiments of the invention, the crude oil demulsifier further comprises a fatty alcohol-polyoxyethylene ether and/or an organic alcohol.
In other embodiments of the present invention, the fatty alcohol-polyoxyethylene ether is at least one selected from isooctanol polyoxyethylene ether JFC-E, capryl-decyl alcohol polyoxyethylene ether JFC-C, and isooctanol polyoxyethylene ether OE 35.
In some embodiments of the present invention, the organic alcohol is selected from C1-C20 organic alcohols, preferably at least one of methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, tert-butanol, n-octanol, n-dodecanol.
In some embodiments of the invention, the non-polyether demulsifier solution comprises, by mass, 20-70% of block polyether using alcohol as an initiator, 5-20% of alkyl phenolic resin block polyether, 5-20% of phenolic amine aldehyde resin block polyether, 0-2% of isooctanol polyoxyethylene ether, and 10-40% of organic alcohol.
In some embodiments of the present invention, in the crude oil demulsifier system, the mass ratio of the non-polyether demulsifier solution, fatty alcohol-polyoxyethylene ether, and organic alcohol is 100: (0-10): (20-100).
In some preferred embodiments of the present invention, in the crude oil demulsifier system, the mass ratio of the non-polyether demulsifier solution, fatty alcohol-polyoxyethylene ether, and organic alcohol is 100: (0-4): (20-100).
In a second aspect, the present invention provides a method of preparing the crude oil demulsifier provided in the first aspect of the present invention, which comprises:
step S1, mixing polyether or a mixture of polyether and organic alcohol with a non-polyether demulsifier to obtain a first mixture.
In some preferred embodiments of the present invention, the method further comprises a step S2 of mixing the fatty alcohol-polyoxyethylene ether with the first mixture obtained in the step S1.
In some embodiments of the present invention, step S1 is performed at a temperature of 50 to 80 ℃.
In some preferred embodiments of the present invention, step S1 is performed at a temperature of 60 to 70 ℃.
In other embodiments of the present invention, the time for performing step S1 is 20-100 min.
In other preferred embodiments of the present invention, the time for performing step S1 is 30-60 min.
In some embodiments of the present invention, step S2 is performed at a temperature of 50 to 80 ℃.
In some preferred embodiments of the present invention, step S2 is performed at a temperature of 60 to 70 ℃.
In other embodiments of the present invention, the time for performing step S2 is 20-100 min.
In other preferred embodiments of the present invention, the time for performing step S2 is 30-60 min.
The third aspect of the invention provides the use of the crude oil demulsifier provided by the first aspect of the invention or the crude oil demulsifier prepared by the method provided by the second aspect of the invention in demulsification of crude oil, preferably in demulsification of thick oil.
The preparation method of the non-polyether demulsifier is obtained according to the preparation method in patent CN101255354B, the block polyether, alkyl phenolic resin block polyether, phenolic amine aldehyde resin block polyether and isooctanol polyoxyethylene ether which take alcohols as initiators in the invention can be obtained by market, and other chemicals which are not specially indicated are all commercially available analytically pure.
The inventor of the application creatively discovers that the demulsifier which is low in dosage, high in dehydration rate, lasting in dehydration property, clear in water color, fast in oil-water separation in the demulsification process, clear in oil-water interface, few in emulsification intermediate layer, and capable of demulsifying the thick oil at low temperature, fast and efficiently can be obtained by compounding the non-polyether demulsifier and the polyether demulsifier and adding a small amount of auxiliary agent.
Examples
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Preparation of non-polyether demulsifier solution:
adding 41.4 g of butyl acrylate and 55 g of toluene into a reactor, heating to 60 ℃, uniformly stirring, replacing by nitrogen, continuously introducing nitrogen, adding 0.25 g of initiator azobisisobutyronitrile, uniformly stirring, adding 1.1 g of acrylic acid every 1.5 hours, adding three times of acrylic acid, wherein the total amount is 3.3 g, and continuously reacting for 4 hours at 60 ℃. Then, 0.3 g of hydroquinone is added as a terminator, the mixture reacts for 0.5 hour at constant temperature, and then the temperature is reduced to obtain white solution, namely non-polyether demulsifier solution.
Example 1:
adding three raw materials, namely block polyether BPE 204010 g taking alcohols as an initiator, alkyl phenolic resin block polyether 310520g and phenolic amine resin block polyether drying agent DPA 203120 g, into a reaction kettle in proportion, adding 4g of n-dodecanol and 46g of methanol into the reaction kettle under the condition of continuous stirring, raising the temperature of the reaction kettle to 60 ℃, continuing stirring for 30min, adding 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 354 g into the mixture, stirring for 30min, stopping heating, cooling while stirring, cooling to normal temperature, and obtaining the low-temperature demulsifier.
Example 2:
adding three raw materials of block polyether BPE 20405 g, alkyl phenolic resin block polyether 310510 g and phenolic amine resin block polyether drier DPA 203110 g which take alcohols as initiators into a reaction kettle according to a proportion, adding 4g of n-octanol and 20g of methanol into the reaction kettle under the condition of continuous stirring, raising the temperature of the reaction kettle to 60 ℃, continuing stirring for 30min, adding 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 351 g into the mixture, stirring for 30min, stopping heating, cooling while stirring, and cooling to normal temperature to obtain the low-temperature demulsifier.
Example 3:
adding three raw materials, namely block polyether BPE 204040 g taking alcohols as an initiator, alkyl phenolic resin block polyether 310530g and phenolic amine resin block polyether drying agent DPA 203130 g, into a reaction kettle in proportion, adding 20g of isopropanol, 10g of n-octanol and 70g of methanol into the reaction kettle under continuous stirring, raising the temperature of the reaction kettle to 60 ℃, continuing stirring for 30min, adding 100g of non-polyether demulsifier solution into the mixture, stirring for 30min, stopping heating, cooling while stirring, and cooling to normal temperature to obtain the low-temperature demulsifier.
Comparative example 1:
200g of non-polyether demulsifier solution is used as a demulsifier to directly demulsify.
Comparative example 2:
adding block polyether BPE 2040100 g using alcohols as initiator into a reaction kettle, adding 100g of methanol into the reaction kettle, heating the reaction kettle to 60 ℃, stirring for 30min, stopping heating, stirring while cooling, and cooling to normal temperature to obtain the demulsifier.
Comparative example 3:
adding 3105100 g of alkyl phenolic resin block polyether into a reaction kettle, adding 100g of methanol into the reaction kettle, heating the kettle to 60 ℃, stirring for 30min, stopping heating, cooling while stirring, and cooling to normal temperature to obtain the demulsifier.
Comparative example 4:
adding the phenolic aldehyde resin block polyether drier DPA 2031100 g into a reaction kettle, adding 100g of methanol into the reaction kettle, heating the reaction kettle to 60 ℃, stirring for 30min, stopping heating, stirring while cooling, and cooling to normal temperature to obtain the demulsifier.
Example 4:
adding block polyether BPE 204050 g using alcohols as initiator into a reaction kettle, adding 4g of n-dodecanol and 46g of methanol into the reaction kettle under continuous stirring, heating the kettle to 60 ℃, continuing stirring for 30min, adding 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 354 g into the mixture, stirring for 30min, stopping heating, cooling while stirring, and cooling to normal temperature to obtain the low-temperature demulsifier.
Example 5:
adding 310550 g of alkyl phenolic resin block polyether into a reaction kettle, adding 4g of n-dodecanol and 46g of methanol into the reaction kettle under the condition of continuous stirring, heating the reaction kettle to 60 ℃, continuously stirring for 30min, adding 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 354 g into the mixture, stirring for 30min, stopping heating, stirring while cooling, and cooling to normal temperature to obtain the low-temperature demulsifier.
Example 6:
adding phenolic aldehyde resin block polyether drier DPA 203150 g into a reaction kettle, adding 4g of n-dodecanol and 46g of methanol into the reaction kettle under the condition of continuous stirring, heating the kettle to 60 ℃, continuously stirring for 30min, adding 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 354 g into the mixture, stirring for 30min, stopping heating, cooling while stirring, and cooling to normal temperature to obtain the low-temperature demulsifier.
Example 7:
adding block polyether BPE 204025 g and alkyl phenolic resin block polyether 310525g which take alcohols as initiators into a reaction kettle according to a proportion, adding 4g of n-dodecanol and 46g of methanol into the reaction kettle under the condition of continuous stirring, raising the temperature of the reaction kettle to 60 ℃, continuing stirring for 30min, adding 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 354 g into the mixture, stirring for 30min, stopping heating, stirring while cooling, and cooling to the normal temperature to obtain the low-temperature demulsifier.
Example 8:
adding block polyether BPE 204025 g taking alcohols as an initiator and 25g of phenolic aldehyde resin block polyether dry agent into a reaction kettle according to a proportion, adding 4g of n-dodecanol and 46g of methanol into the reaction kettle under the condition of continuous stirring, raising the temperature of the reaction kettle to 60 ℃, continuously stirring for 30min, adding 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 354 g into the mixture, stirring for 30min, stopping heating, stirring while cooling, and cooling to normal temperature to obtain the low-temperature demulsifier.
Example 9:
310525g of alkyl phenolic resin block polyether and DPA203125g g of phenolic resin block polyether drier are added into a reaction kettle in proportion, 4g of n-dodecanol and 46g of methanol are added into the reaction kettle under the condition of continuous stirring, the temperature of the reaction kettle is raised to 60 ℃, after stirring is continued for 30min, 100g of non-polyether demulsifier solution and isooctanol polyoxyethylene ether OE 354 g are added into the mixture, after stirring for 30min, heating is stopped, stirring is carried out while cooling is carried out, and cooling is carried out to normal temperature, so that the low-temperature demulsifier is obtained.
The amounts of the respective substances added in the preparation of the low temperature demulsifiers provided in examples 1 to 9 and comparative examples 1 to 4 are shown in table 1:
TABLE 1
The demulsifiers prepared in examples 1 to 9 and comparative examples 1 to 4 are respectively adopted to evaluate the demulsification performance of Chengdong thickened oil in the oil extraction plant at the estuary of the Shengli oil field, and the demulsification performance of the Chengdong thickened oil is evaluated by an evaluation method specified by a service performance detection method (bottle test method) of a crude oil demulsifier in a standard SY-T5281-2000 in the petroleum and natural gas industry. The test results of the indoor demulsification performance evaluation experiment of the obtained heavy oil demulsifier are shown in tables 2 and 3.
TABLE 2
TABLE 3
The field demulsification temperature of the Chengdong united station of the oil extraction plant at the estuary of the Shengli oil field is 74 ℃. The high-efficiency demulsifier prepared by the method has the advantages that the dehydration speed of crude oil is greatly improved, the demulsification temperature is reduced to 60 ℃, the addition amount is 50mg/L, and the dehydration rate of the crude oil can still reach over 80 percent, so that the produced fluid of aged thick oil can be demulsified at a lower temperature, and the energy conservation and consumption reduction are realized.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A crude oil demulsifier comprising a non-polyether demulsifier and a polyether, wherein the polyether is selected from at least one of a block polyether using an alcohol as an initiator, an alkylphenol aldehyde resin block polyether and a phenol amine aldehyde resin block polyether.
2. The crude oil demulsifier of claim 1, wherein the mass ratio of the non-polyether demulsifier to the polyether is (0.1-10): 1, preferably (0.5-7): 1, more preferably (1-4): 1.
3. the crude oil demulsifier of claim 1 or 2, wherein the polyether is a mixture of a block polyether using an alcohol as an initiator, an alkylphenol aldehyde resin block polyether and a phenol amine aldehyde resin block polyether, wherein the mass ratio of the block polyether using an alcohol as an initiator, the alkylphenol aldehyde resin block polyether and the phenol amine aldehyde resin block polyether is 1: (0.3-7): (0.3-7), preferably 1: (0.5-6): (0.5-6), more preferably 1: (0.7-4): (0.7-4).
4. The crude oil demulsifier of any one of claims 1-3, wherein the crude oil demulsifier further comprises fatty alcohol-polyoxyethylene ether and/or organic alcohol, preferably wherein the fatty alcohol-polyoxyethylene ether is selected from at least one of isooctanol polyoxyethylene ether and capryl-decyl alcohol polyoxyethylene ether, preferably isooctanol polyoxyethylene ether.
5. The crude oil demulsifier of claim 4, wherein the organic alcohol is selected from the group consisting of C1-C20 organic alcohols, preferably at least one of methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, t-butanol, n-octanol, and n-dodecanol.
6. The crude oil demulsifier of any one of claims 1 to 5, wherein the non-polyether demulsifier comprises, in parts by mass, 20 to 70% of a block polyether comprising an alcohol as an initiator, 5 to 20% of an alkylphenol formaldehyde resin block polyether, 5 to 20% of a phenol amine aldehyde resin block polyether, 0 to 2% of isooctanol polyoxyethylene ether, and 10 to 40% of an organic alcohol.
7. A method of making the crude demulsifier of any one of claims 1-6 comprising:
step S1, mixing polyether or a mixture of polyether and organic alcohol with a non-polyether demulsifier to obtain a first mixture.
8. The method of claim 7, further comprising a step S2 of mixing the fatty alcohol-polyoxyethylene ether with the first mixture obtained in step S1.
9. The method according to claim 7 or 8, wherein step S1 is performed at a temperature of 50-80 ℃, preferably 60-70 ℃, preferably for 20-100min, more preferably for 30-60 min; and/or, step S2 is performed at a temperature of 50-80 ℃, preferably 60-70 ℃, preferably 20-100min, more preferably 30-60 min.
10. Use of the crude oil demulsifier of any one of claims 1 to 6 or the crude oil demulsifier prepared by the method of any one of claims 7 to 9 in the breaking of milk from crude oils, preferably in the breaking of milk from thick oils.
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