CN112694911A - Method for treating crude oil containing petroleum sulfonate - Google Patents
Method for treating crude oil containing petroleum sulfonate Download PDFInfo
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- CN112694911A CN112694911A CN201911012587.7A CN201911012587A CN112694911A CN 112694911 A CN112694911 A CN 112694911A CN 201911012587 A CN201911012587 A CN 201911012587A CN 112694911 A CN112694911 A CN 112694911A
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- C—CHEMISTRY; METALLURGY
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- 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
- C10G33/02—Dewatering or demulsification of hydrocarbon oils with electrical or magnetic means
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention relates to the field of crude oil pretreatment, and discloses a treatment method of crude oil containing petroleum sulfonate, which comprises the following steps: contacting crude oil containing petroleum sulfonate with strong-base anion exchange resin at 60-100 ℃ for anion exchange, mixing the mixture of the crude oil and the resin with water injection and a demulsifier, performing electric desalting and demulsification and performing oil-water separation; what is needed isThe crude oil containing petroleum sulfonate has viscosity of not higher than 30mm at 50 deg.C2(ii)/s, the loss rate of exchange capacity of said strongly basic anion exchange resin after heating at 100 ℃ for 140 hours is not higher than 20%. The treatment method has good effect of removing petroleum sulfonate in the crude oil, and can reduce the sodium content of the crude oil.
Description
Technical Field
The invention relates to crude oil pretreatment, in particular to a treatment method of crude oil containing petroleum sulfonate.
Background
With the development of tertiary oil recovery technology, chemical recovery aids are used in oil fields to improve the recovery ratio of crude oil, and with the development of old oil fields, the dosage of the chemical recovery aids used in chemical enhanced oil recovery is gradually increased, and the commonly used chemical enhanced oil recovery technology comprises binary compound flooding, ternary compound flooding and other oil recovery technologies. Taking binary composite flooding as an example, the polymer, petroleum sulfonate and surfactant are used to form O/W emulsion, so as to achieve the purpose of enhanced oil recovery. The petroleum sulfonate is a surfactant which is prepared by using petroleum fractions as raw materials and performing sulfonation treatment, has good compatibility with crude oil and strong emulsification effect, and the usage amount of the petroleum sulfonate in an oil field is gradually increased.
The petroleum sulfonate has certain oil solubility, and a large amount of petroleum sulfonate added in oil extraction is remained in crude oil and can influence the subsequent processing of the crude oil, on one hand, the petroleum sulfonate is an emulsifier and can cause the increase of an oil-water emulsion layer in electric desalting and the increase of oil content in water, and on the other hand, the petroleum sulfonate is remained in the crude oil and can cause the increase of Na content of the crude oil and the poisoning of a catalytic cracking catalyst in a subsequent process adopting the crude oil.
Aiming at the problems caused by petroleum sulfonate, no particularly good treatment method exists at present, and a treatment method of oil field produced liquid containing a tertiary recovery auxiliary agent is generally adopted, and a demulsifier or a flocculating agent is added for treatment. For example: non-ionic demulsifiers such as a dehydration demulsifier for a three-element combination flooding produced fluid disclosed in CN101029253A and a cross-linking type non-ionic reverse demulsifier disclosed in CN1570034A are adopted; or employing quaternary ammonium bromides disclosed by Nguen et al (chemical interactions and devilsifier chemistry for enhanced oil recovery applications, energy & fuels 2012(26) 2742) 2750); or quaternary phosphonium salt ionic liquids disclosed by Xiaohua Li et al (influence and mechanism of destruction of oil-in-water emulsions using ionic liquids, energy & fuels 2016,30, 7622-); or the demulsifier with nuclear membrane structure disclosed in CN1621123A for demulsifier of tertiary oil recovery polymer injection produced liquid in oil field; or a dendritic reverse demulsifier for demulsifying the crude oil as disclosed in CN102233249A and a reverse demulsifier for super heavy crude oil as disclosed in CN104479731A, and a composite demulsifier containing polyquaternary ammonium salt, dendritic polyamidoamine cationic compound and polyaluminium chloride. However, these methods only adopt corresponding demulsification methods for the emulsification problem caused by petroleum sulfonate, and for petroleum sulfonate with certain oil solubility, these methods cannot solve the problem of catalytic cracking catalyst poisoning in the subsequent process due to the residue of petroleum sulfonate in crude oil.
In addition, CN106336891A discloses a composition for reducing the metal content of hydrocarbon oil, its application and a method for reducing the metal content of hydrocarbon oil, which comprises mixing hydrocarbon oil with the composition for reducing the metal content of hydrocarbon oil and water, and subjecting the obtained mixture to oil-water separation to obtain an oil phase and a water phase. The method can effectively reduce the metal content of the hydrocarbon oil, and particularly remove calcium and iron in the residual oil. CN1191326C discloses a hydrocarbon oil demetallization agent and a using method thereof, wherein the method is to fully mix hydrocarbon oil with the demetallization agent, water injection and a demulsifier to ensure that metals in the hydrocarbon oil generate water-soluble complexes, and the water-soluble complexes are dissolved in water and removed through oil-water separation. The method for demetallizing crude oil disclosed above has a good effect of removing oil-soluble metals such as calcium and iron in crude oil, but cannot solve the problem of the increase of the sodium content in crude oil caused by oil-soluble petroleum sodium sulfonate.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for treating crude oil containing petroleum sulfonate, which can effectively remove the petroleum sulfonate in the crude oil.
In order to achieve the above object, the present invention provides a method for treating crude oil containing petroleum sulfonate, wherein the method comprises: contacting crude oil containing petroleum sulfonate with strong-base anion exchange resin at 60-100 ℃ for anion exchange, mixing the mixture of the crude oil and the resin with water injection and a demulsifier, performing electric desalting and demulsification and performing oil-water separation; the crude oil containing petroleum sulfonate has viscosity of not higher than 30mm at 50 DEG C2(ii)/s, the loss rate of exchange capacity of said strongly basic anion exchange resin after heating at 100 ℃ for 140 hours is not higher than 20%.
Preferably, the strongly basic anion exchange resin is a styrene macroporous strongly basic anion exchange resin, the functional group of which is
Wherein R is
m is an integer of 1 to 8; r1、R2、R3Each independently is a C1-C8 alkyl group and/or a C1-C8 alkanol group; x-Represents OH coordinated to ammonium-Or Cl-(ii) a The strongly basic anion exchange resin has a working exchange capacity of from 3.6 to 4.8 mmoles/g dry resin, more preferably from 3.9 to 4.5 mmoles/g dry resin.
Preferably, the demulsifier is a cationic demulsifier, more preferably, the demulsifier is a cationized polyoxyethylene polyoxypropylene ether, and the preparation method of the cationized polyoxyethylene polyoxypropylene ether comprises the following steps:
(1) in the presence of an etherification catalyst, the block polyether is obtained by the reaction of an initiator, ethylene oxide and propylene oxide; wherein the block polyether comprises a polyether chain segment combined with an initiator, and the polyether chain segment is a block copolymer formed by the reaction of ethylene oxide and propylene oxide; the initiator is an organic compound with one or more of hydroxyl, carboxyl and amido;
(2) in the presence of an esterification catalyst and a polymerization inhibitor, carrying out ester exchange reaction on the block polyether and unsaturated carboxylic ester to enable the tail end of the block polyether to have the unsaturated carboxylic ester, and then carrying out reduced pressure distillation to remove alcohol to obtain an esterification product;
(3) in the presence of a free radical initiator and a polymerization assistant, carrying out polymerization reaction on the esterification product and a cationic unsaturated monomer to connect a polymerization chain segment formed by the cationic unsaturated monomer at the tail end of unsaturated carboxylic ester of block polyether, thereby obtaining the demulsifier; the weight ratio of the use amount of the esterification product to the use amount of the cationic unsaturated monomer is 1: 1-10;
the addition amount of the demulsifier is 10-20ppm based on 100g of crude oil containing petroleum sulfonate.
According to the treatment method of the crude oil containing the petroleum sulfonate, the treatment method combining the strong-base anion resin with the cationic demulsifier, in particular the preferred cationic demulsifier of the invention, is adopted, on one hand, the petroleum sulfonate in the crude oil can be transferred to a water phase, the sodium content of the crude oil is reduced, the problem that a catalytic cracking catalyst is easy to be poisoned in a subsequent process is solved, the adverse effect of the petroleum sulfonate on the subsequent process is effectively avoided, on the other hand, the emulsification tendency of the crude oil is weakened, and the content of water and oil can be greatly reduced after electric desalting demulsification and oil-water separation are carried out.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to the present invention, the method for treating crude oil containing petroleum sulfonate comprises: at 60-100 deg.C, the crude oil containing petroleum sulfonate is contacted with strong base anion exchange resin to make anion exchange, then the mixture of crude oil and resin is mixed with water injection and demulsifier to make electric desalting demulsification and oil-water separation.
The strong-base anion exchange resin is a high molecular material showing anion exchange function, a plurality of quaternary amine exchange groups are bonded on a high molecular substrate with a cross-linked structure by chemical bonds, the alkalinity of the resin is strong, the resin is equivalent to that of common quaternary amine base, and the resin can show the ion exchange function in acidic, neutral or even basic media.
The method can effectively remove petroleum sulfonate anions with surface activity in the crude oil by contacting the crude oil containing petroleum sulfonate with the strongly basic anion exchange resin at a certain temperature, thereby effectively avoiding the adverse effect of the petroleum sulfonate on the subsequent process.
According to the present invention, the temperature at which petroleum sulfonate-containing crude oil is contacted with strongly basic anion exchange resin has a significant influence on the removal effect of petroleum sulfonate, and therefore, it is required to contact petroleum sulfonate-containing crude oil with strongly basic anion exchange resin at a temperature of 60 to 100 ℃, preferably 80 to 90 ℃, and also that strongly basic anion exchange resin has good heat resistance. The change of the strong base anion exchange resin after being heated is mainly the shedding of the group and the degradation of the strong base. Practical measurement shows that under certain heating condition, part of strong base is changed into weak base and part falls off, so that exchange capacity and alkalinity are reduced simultaneously. In order to ensure more effective removal of petroleum sulfonate, it is necessary to ensure that the loss rate of exchange capacity of the strongly basic anion exchange resin after being heated at 100 ℃ for 140 hours is not higher than 20%, and more preferably, the loss rate of exchange capacity of the strongly basic anion exchange resin after being heated at 100 ℃ for 140 hours is not higher than 10%, so as to ensure that the strongly basic anion exchange resin has certain heat resistance, namely, the capability of keeping the physical and chemical properties thereof when being heated.
According to the present invention, from the viewpoint of satisfying both the ion exchange effect of petroleum sulfonate anions and the heat resistance of the strongly basic anion exchange resin, the strongly basic anion exchange resin is preferably a styrene-based macroporous-type strongly basic anion exchange resin, the skeleton of the styrene-based macroporous-type strongly basic anion exchange resin is a styrene-divinylbenzene copolymer structure, and resins having functional groups of different structures also have significantly different heat resistance, and preferably, the functional group of the styrene-based macroporous-type strongly basic anion exchange resin is a functional group of
The functional group refers to a functional group bonded to a skeleton resin of an anion exchange resin.
According to one embodiment of the invention, R is
m is an integer of 1 to 8. The preparation method of the resin can be carried out by referring to the known technology in the field, for example, the specific method comprises the following steps:
(1) using styrene-divinyl copolymerized spherule and acylating reagent to make acylation reaction, introducing-SO on benzene ring of styrene2A Cl functional group; wherein the acylating agent is preferably sulfuryl chloride;
(2) carrying out amination reaction on the product obtained in the step (1) and N, N-dialkyl long-carbon-chain diamine, wherein the carbon number of the carbon chain of the N, N-dialkyl long-carbon-chain diamine can be an integer of 1-8;
(3) and (3) carrying out quaternization on the product of the step (2) to obtain the strongly-alkaline anion exchange resin, wherein the reagent for quaternization is preferably chlorohydrocarbon.
For a specific preparation method, reference is made to patent application with publication number CN 101481466A.
More preferably, the exchange groups of the styrenic strongly basic anion exchange resin obtained according to the above embodiment have a structure of
m is an integer of 1 to 8, R1、R2、R3Each independently is methyl, ethyl, n-propyl or isopropyl, more preferably R1、R2、R3Both methyl groups or both ethyl groups.
According to the invention, the strongly basic anion exchange resin has a working exchange capacity of 3.6 to 4.8 mmoles/g dry resin, more preferably 3.9 to 4.5 mmoles/g dry resin.
According to the present invention, in order to ensure the petroleum sulfonate removal effect, the petroleum sulfonate-containing crude oil, the viscosity of which at 50 ℃ is not higher than 30mm, needs to be in sufficient contact with the strongly basic anion exchange resin, thereby effectively ensuring that the petroleum sulfonate-containing crude oil needs to be in sufficient contact with the strongly basic anion exchange resin to ensure the petroleum sulfonate removal effect2/s, preferably, the viscosity of the petroleum sulfonate containing crude oil is 5 to 30mm at 50 DEG C2/s。
The manner of contacting the petroleum sulfonate containing crude oil with the strongly basic anion exchange resin according to the present invention may employ various conventional contacting means in the art, for example, directly mixing the petroleum sulfonate containing crude oil with the strongly basic anion exchange resin, the mixing preferably being performed under agitation to sufficiently contact.
According to the invention, in order to further improve the removal effect of the petroleum sulfonate, the amount of the strongly basic anion exchange resin is 2-30 wt% of the weight of the crude oil containing the petroleum sulfonate, preferably, the amount of the strongly basic anion exchange resin is 6-10 wt% of the weight of the crude oil containing the petroleum sulfonate; the petroleum sulfonate-containing crude oil generally has a petroleum sulfonate content of 50 to 1000 mg/kg.
According to the present invention, in order to effectively remove petroleum sulfonate from crude oil, it is necessary to contact crude oil containing petroleum sulfonate with a strongly basic anion exchange resin at a temperature of 60 to 100 ℃, preferably 80 to 90 ℃, and the time for contacting crude oil containing petroleum sulfonate with a strongly basic anion exchange resin may be appropriately selected depending on the contact temperature, for example, the contact time may be 0.5 to 60 minutes.
According to the present invention, in order to effectively remove petroleum sulfonate from crude oil and facilitate the operation, the method further comprises: the petroleum sulfonate containing crude oil is preheated to 60-100 deg.c, preferably 80-90 deg.c, before contacting the petroleum sulfonate containing crude oil with the strongly basic anion exchange resin.
According to the invention, in order to further reduce the emulsification tendency of the crude oil on the basis of reducing the sodium content of the desalted crude oil, after the crude oil containing petroleum sulfonate is contacted with the strongly basic anion exchange resin for anion exchange, the method also comprises the step of mixing the mixture of the crude oil and the resin after the ion exchange with water injection and a demulsifier for electric desalting and demulsification, and after the electric desalting and demulsification and oil-water separation are carried out, the content of oil in water can be greatly reduced. The demulsifier is preferably a cationic demulsifier, such as the cationic demulsifiers disclosed in CN103922438, CN102233249, and the like. Further preferably, the cationic demulsifier is a cationized polyoxyethylene polyoxypropylene ether.
According to the present invention, the method for preparing the cationized polyoxyethylene polyoxypropylene ether comprises:
(1) in the presence of an etherification catalyst, the block polyether is obtained by the reaction of an initiator, ethylene oxide and propylene oxide; wherein the block polyether comprises a polyether chain segment combined with an initiator, and the polyether chain segment is a block copolymer formed by the reaction of ethylene oxide and propylene oxide; the initiator is an organic compound with one or more of hydroxyl, carboxyl and amido;
(2) in the presence of an esterification catalyst and a polymerization inhibitor, carrying out ester exchange reaction on the block polyether and unsaturated carboxylic ester to enable the tail end of the block polyether to have the unsaturated carboxylic ester, and then carrying out reduced pressure distillation to remove alcohol to obtain an esterification product;
(3) in the presence of a free radical initiator and a polymerization assistant, carrying out polymerization reaction on the esterification product and a cationic unsaturated monomer to connect a polymerization chain segment formed by the cationic unsaturated monomer at the tail end of unsaturated carboxylic ester of block polyether, thereby obtaining the demulsifier; the weight ratio of the esterification product to the cationic unsaturated monomer is 1: 1-10.
According to the invention, in step (1), the initiator is polymerized with ethylene oxide or propylene oxide so that a polymerized block of ethylene oxide or propylene oxide is linked to the initiator, and then ethylene oxide or propylene oxide is added stepwise, continuing to form a new block on the basis of the previous block. Such blocks may be diblock or multiblock. Multiple such block structures may be bonded per molecule of initiator.
In a preferred embodiment of the present invention, the initiator is first linked to a polymerized block of propylene oxide, which is then linked to a polymerized block of ethylene oxide, which is then linked to a new polymerized block of propylene oxide, forming a triblock structure of polymerized block of initiator-propylene oxide-polymerized block of ethylene oxide-polymerized block of propylene oxide.
In another preferred embodiment of the present invention, the initiator is first linked to a polymeric block of propylene oxide, which is then linked to a polymeric block of ethylene oxide to form a diblock structure of a polymeric block of initiator-propylene oxide-a polymeric block of ethylene oxide.
According to the invention, the initiator is preferably one or more of monohydric alcohol, dihydric alcohol, alkyl phenolic resin, alkyl phenolic amine resin and polyethylene polyamine, more preferably alkyl phenolic resin and/or polyethylene polyamine; the alkyl phenol-formaldehyde resin can be one or more of nonyl phenol-formaldehyde resin, octyl phenol-formaldehyde resin and the like. The polyethylene polyamine may be, for example, one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.
Preferably, the weight ratio of the starter to the total amount of ethylene oxide and propylene oxide used is from 1:10 to 700; the ethylene oxide and propylene oxide are used in a weight ratio of 0.1 to 10:1, more preferably 0.25 to 2.5: 1.
According to the invention, the etherification catalyst is polyether obtained by catalyzing polymerization of ethylene oxide and/or propylene oxideCatalysts like polymers, such catalysts may be basic catalysts or Lewis acids, e.g. BF3、AlCl3Etc.; the catalyst may be a complex cationic polymerization catalyst, for example, a compound having a metal-oxygen bond, an alkaline earth metal compound, or the like. Preferably, the etherification catalyst is a base catalyst, and specifically may be selected from one or more of sodium hydroxide, potassium hydroxide, metallic sodium, metallic lithium, and metallic potassium. The etherification catalyst is used in an amount of 0.1 to 2% by weight, based on the total amount of ethylene oxide and propylene oxide used.
According to the present invention, in step (1), the conditions for preparing the block polyether may be those conventional in the art for polymerization of ethylene oxide and propylene oxide, for example, at 100 ℃ and 150 ℃, and in order to prepare the block polymer, the next monomer may be added after the reaction of each monomer is substantially completed.
According to the present invention, in step (2), hydroxyl groups of the block polyether can be reacted with an unsaturated carboxylic acid ester by means of transesterification to form an alcohol as a by-product, and the unsaturated carboxylic acid ester is connected to the terminal of the block polyether by an ester bond to obtain the block polyether having an unsaturated carboxylic acid ester at the terminal, which is required in the present invention, and the alcohol can be easily removed by means of reduced pressure distillation to obtain an esterified product.
According to the invention, in the step (2), the block polyether is a combination of a block polyether A obtained by taking alkyl phenolic resin as an initiator and a block polyether B obtained by taking polyethylene polyamine as an initiator; preferably, the weight ratio of block polyether A to block polyether B is from 1:0.2 to 5, more preferably from 1:0.5 to 1.
Preferably, the unsaturated carboxylic acid ester is one or more of methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, monomethyl fumarate, dimethyl itaconate and monomethyl itaconate.
The ratio of the block polyether to the unsaturated carboxylic ester can vary within a wide range, and the weight ratio of the block polyether to the unsaturated carboxylic ester is preferably 100:0.5-100, more preferably 100:0.8-50, and even more preferably 100: 1-10.
According to the present invention, the esterification catalyst is a catalyst that can catalyze the above-mentioned transesterification reaction, and preferably, the esterification catalyst is one or more of sulfuric acid, phosphoric acid, and p-toluenesulfonic acid. Preferably, the esterification catalyst is used in an amount of 0.1 to 8% by weight, more preferably 0.4 to 1.5% by weight, based on the total weight of the block polyether and the unsaturated carboxylic acid ester.
According to the invention, the polymerization inhibitor can prevent the polymerization reaction between unsaturated carboxylic acid esters, and preferably, the polymerization inhibitor is hydroquinone and/or p-hydroxyanisole. Preferably, the polymerization inhibitor is used in an amount of 0.1 to 1% by weight, more preferably 0.2 to 0.6% by weight, based on the total weight of the block polyether and the unsaturated carboxylic acid ester.
According to the present invention, preferably, in the step (2), the transesterification reaction conditions include: the temperature is 80-120 ℃, and the time is 1-10 h.
According to the invention, in the step (3), the added cationic unsaturated monomer and the unsaturated bond of the unsaturated carboxylic ester connected to the esterification product are subjected to free radical polymerization reaction, so that a polymerization chain segment formed by the cationic unsaturated monomer is connected behind the unsaturated carboxylic ester, thereby obtaining the demulsifier.
According to the present invention, the ratio by weight of the amount of the esterification product and the cationic unsaturated monomer is preferably 1:2 to 4. The cation unsaturated monomer is one or more of allyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, 2- (methacrylamide) ethyl trimethyl ammonium chloride and (3-acrylamidopropyl) trimethyl ammonium chloride.
According to the present invention, the radical initiator is preferably one or more of potassium persulfate, ammonium persulfate, dicumyl peroxide and dibenzoyl peroxide. Preferably, the free radical initiator is used in an amount of 1 to 10% by weight, more preferably 6 to 8% by weight, based on the total weight of the esterification product and the cationic unsaturated monomer.
According to the invention, the polymerization auxiliary is preferably Na4EDTA、Na2One or more of EDTA, EDTA and DTPA. Preferably, the polymerization aid is used in an amount of 0.5 to 5% by weight, more preferably 0.8 to 1.2% by weight, based on the total weight of the esterification product and the cationic unsaturated monomer.
According to the present invention, the polymerization is preferably carried out in the presence of water, preferably in an amount of 30 to 80% by weight, preferably 40 to 70% by weight, based on the total weight of the esterification product and the cationic unsaturated monomer. The polymerization reaction comprises: firstly reacting for 1-10h at 40-60 ℃, and then reacting for 1-10h at 60-90 ℃; preferably, the polymerization reaction comprises: firstly reacting for 2-5h at 45-55 ℃, and then reacting for 2-5h at 65-80 ℃.
According to the invention, the dosage of the demulsifier can be properly selected according to the emulsification condition of crude oil, and the dosage of the demulsifier is preferably 10-20ppm based on 100g of crude oil containing petroleum sulfonate.
According to the invention, the demulsification is a mode of electric desalting demulsification, and the conditions of the electric desalting demulsification comprise: the temperature is 60-150 ℃, the time is 10-100min, and the electric field intensity is 100-. Preferably, the conditions for demulsification by electric desalting comprise: the temperature is 80-120 ℃, the time is 20-60min, and the electric field intensity is 200-. After the electric desalting, the oil can be separated by oil-water separation, and the resin can be discharged together with water. Further preferably, the temperature of the electric desalting demulsification is 80-90 ℃ in order to recover and regenerate the strong-base anion resin better.
According to the invention, the petroleum sulfonate containing crude oil may be derived from crude oil obtained from tertiary oil recovery in an oil field.
By adopting the method for treating the crude oil containing the petroleum sulfonate, the sodium content of the desalted crude oil is reduced, the petroleum sulfonate in the crude oil can be transferred to a water phase, the sodium content of the crude oil is reduced, the problem that a catalytic cracking catalyst in a subsequent process is easy to be poisoned is solved, the adverse effect of the petroleum sulfonate on the subsequent process is effectively avoided, the emulsification tendency of the crude oil is weakened, and the content of the petroleum in the water can be greatly reduced after electric desalting demulsification and oil-water separation.
The present invention will be described in detail below by way of examples.
In the following preparation examples, the loss rate of exchange capacity of the high temperature resistant resin after heating at 100 ℃ for 140 hours was measured by DL/T77L-2001.
In the following examples, properties of the crude oils for experiments are shown in table 1.
In the following examples, the method for measuring the content of oil salt after oil-water separation is SY0536-94, the method for measuring the content of iron, nickel, sodium and vanadium in crude oil is GB/T18608-2001, and the method for measuring the content of calcium in crude oil and lubricating oil fractions is Q/SYLS 0206-2002; the method for measuring the oil content of the sewage obtained by separation is GB/T16488-1996 petroleum and animal and vegetable oil measurement and an infrared photometry.
Preparation example 1
This preparation is illustrative of the preparation of high temperature resistant strong base anion exchange resin.
(1) Acylation reaction
Suspending and polymerizing to obtain styrene-divinylbenzene crosslinked polymeric microspheres (white spheres) 150g, swelling in dichloroethane, swelling for 2 hr, and adding sulfuryl chloride (SO)2CL2) Performing acylation reaction, wherein the molar ratio of the white spheres to the sulfuryl chloride is 1:2, heating to 60 ℃, keeping the temperature for 6h, cooling, repeatedly washing with dichloroethane for 3 times, and filtering to obtain a product P2.
(2) Amination reaction
Swelling 100g of the product P2 with dichloroethane, adding 5g of N, N-dimethyl-1, 6-hexanediamine, carrying out amination reaction at 60 ℃, filtering after 40h of reaction, washing and drying to obtain the product P3.
(3) Quaternization reaction
Swelling 80g of the product P3 in 200ml of absolute ethyl alcohol, adding 40g of bromoethane, reacting for 40h at 60 ℃, cooling to room temperature, taking out the resin, filling the resin into a column, and washing with distilled water until no free halide ions exist to obtain a product P4, namely the high-temperature resistant strong-base anion exchange resin R1.
The loss rate of the exchange capacity of the high-temperature resistant resin R1 after being heated at 100 ℃ for 140 hours is 9.8 percent, and the working exchange capacity is 4.0 millimole/g dry resin.
Preparation example 2
This preparation is illustrative of the preparation of high temperature resistant strong base anion exchange resin.
A high-temperature resistant strong base anion exchange resin was prepared by following the procedure of preparation example 1 except that N, N-dimethyl-1, 3-propanediamine was used in place of N, N-dimethyl-1, 6-hexanediamine to obtain a high-temperature resistant strong base anion exchange resin R2.
The loss rate of the exchange capacity of the high-temperature resistant resin R2 after being heated at 100 ℃ for 140 hours is 20 percent, and the working exchange capacity is 4.0 millimole/g of dry resin.
Preparation example 3
This preparation is illustrative of the preparation of high temperature resistant strong base anion exchange resin.
A high-temperature resistant strong base anion exchange resin was prepared by following the procedure of preparation example 1 except that N, N-dimethyl-1, 4-butanediamine was used in place of N, N-dimethyl-1, 6-hexanediamine to obtain a high-temperature resistant strong base anion exchange resin R3.
The loss rate of the exchange capacity of the high-temperature resistant resin R3 after being heated at 100 ℃ for 140 hours was 17%, and the working exchange capacity was 4.0 mmol/g of dry resin.
Preparation example 4
This preparation is illustrative of the preparation of high temperature resistant strong base anion exchange resin.
A high-temperature resistant strong base anion exchange resin was prepared by following the procedure of preparation example 1 except that N, N-dimethyl-1, 8-octanediamine was used in place of N, N-dimethyl-1, 6-hexanediamine to obtain a high-temperature resistant strong base anion exchange resin R4.
The loss rate of the exchange capacity of the high-temperature resistant resin R4 after being heated at 100 ℃ for 140 hours is 13 percent, and the working exchange capacity is 4.0 millimole/g of dry resin.
Preparation example 5
This preparation is illustrative of the preparation of the demulsifier.
(1) Preparation of Block polyether A1
Adding 15g of nonyl phenol-formaldehyde resin (the relative molecular mass is 1090) and 0.9g of potassium hydroxide into an autoclave, dropwise adding 36.2g of propylene oxide, controlling the reaction temperature to be 130 ℃, and stopping the reaction until the reaction pressure is not reduced any moreWhen the reaction is low (the reaction is considered to be complete), 65.8g of ethylene oxide is added dropwise, the temperature is controlled at 130 ℃, and the pressure is controlled at 2.3kg/cm2When the ethylene oxide is completely reacted, 72.5g of propylene oxide is added at the temperature, the reaction is continued for 0.5h, and when the pressure drop of the kettle is 0kg/m2And cooling and discharging to obtain the block polyether A1.
(2) Preparation of Block polyether A2
Adding 5g of tetraethylenepentamine, 2.4g of potassium hydroxide and 400g of propylene oxide into an autoclave, replacing 3 times with nitrogen, heating to 115 ℃, keeping the temperature until the pressure is 0, continuing to react for 0.5h, heating to 130 ℃, and dropwise adding 200g of ethylene oxide until the pressure is not reduced any more to obtain the block polyether A2.
(3) Esterification product B1 preparation
Adding 50g of block polyether A1, 50g of block polyether A2, 0.9g of p-toluenesulfonic acid and 0.34g of hydroquinone into a reaction vessel, stirring, heating to 105 ℃, dropwise adding 1.18g of methyl methacrylate, after dropwise adding, carrying out heat preservation reaction at 105 ℃ for 4 hours, and carrying out reduced pressure distillation to remove methanol to obtain an esterified product B1.
(4) Preparation of polymer demulsifier containing cation
6.5g of esterified product B1, 13.1g of cationic monomer methacryloyloxyethyl trimethylammonium chloride, 8.4g of deionized water, 1.5g of ammonium persulfate and 0.2g of Na4EDTA were added to a reaction vessel, and mixed with stirring, and N was introduced into the reaction system2Deoxidizing for 20min, heating to 50 ℃ for reaction for 3h, then heating to 70 ℃ for reaction for 3h, cooling and discharging to obtain a polymerization product, namely the demulsifier C1.
TABLE 1
| Item | Numerical value |
| Density (20 ℃ C.)/(kg. m)-3) | 868.4 |
| Kinematic viscosity (50 ℃ C.)/(mm)2.s-1) | 27.5 |
| Salt content/mgNaCL.L-1 | 10 |
| Total acid value/mgKOH. g-1 | 0.06 |
| Na content/(μ g/g) | 14.4 |
(Note: the petroleum sulfonate in the crude oil was 193mg/kg in terms of average molecular weight of 450.)
Example 1
This example illustrates the treatment of crude oil containing petroleum sulfonate.
(1) 100g of crude oil was preheated at 80 ℃ and then mixed with 10g of strongly basic anion exchange resin R1 prepared in preparation example 1 in a 250ml Erlenmeyer flask by magnetic stirring for 60 minutes.
(2) The mixture of the crude oil and the resin after the contact with the strong basic anion exchange resin is fully mixed with 10g of deionized water at 90 ℃, 10mg/kg of the demulsifier C1 prepared in the preparation example 5 is added, the mixture is poured into a conical glass desalting tank after mixing, and oil-water separation is carried out by adopting a DPY-2 demulsifier evaluation instrument (Jiangsu ginger weir analytical instrument factory), wherein the electric field gradient is 400v/cm, the temperature is 90 ℃, and the time is 60 minutes. Separating oil from water, separating oil to obtain salt content and metal content, and analyzing oil content in separated sewage. The desalting and sodium removing effects and the oil content of the wastewater are shown in Table 2.
Comparative example 1
Crude oil containing petroleum sulfonate was treated in the same manner as in example 1, except that, in step (2), a commercially available demulsifier SP169 was used. The desalting and sodium removing effects and the oil content of the wastewater are shown in Table 2.
Comparative example 2
Crude oil containing petroleum sulfonate was treated in the same manner as in example 1, except that in step (2), no demulsifier was added, and the effects of desalting and sodium removal and the oil content of wastewater were as shown in Table 2.
Comparative example 3
Crude oil containing petroleum sulfonate was treated in accordance with the method of example 1 except that in step (1), the acidic demetallizing agent disclosed in example 1 of CN1982413 was used in place of the strongly basic anion exchange resin, and the amount of the demetallizing agent added was 100mg/kg based on 100g of crude oil having a sodium content of 14 mg/kg. The desalting and sodium removing effects and the oil content of the wastewater are shown in Table 2.
Comparative example 4
Crude oil containing petroleum sulfonate was treated in the same manner as in example 1, except that the crude oil was not subjected to the treatment of the strongly basic anion exchange resin of step (1), but was subjected directly to the demulsification by electric desalting in step (2) by mixing with a demulsifier C1. The desalting and sodium removing effects and the oil content of the wastewater are shown in Table 2.
Examples 2 to 4
Crude oil containing petroleum sulfonate was treated in the same manner as in example 1 except that R1 was replaced with strongly basic anion exchange resins R2 to R4 prepared in preparation examples 2 to 4, respectively. The desalting and sodium removing effects and the oil content of the wastewater are shown in Table 2.
Example 5
Crude oil containing petroleum sulfonate was treated according to the method of example 1 except that in step (2), the demulsifier C1 was replaced with the cationic demulsifier obtained by the method disclosed in example CN 102233249. The desalting and sodium removing effects and the oil content of the wastewater are shown in Table 2.
TABLE 2
As can be seen from the results in Table 1, the sodium content of the desalted crude oil can be greatly reduced by the treatment method of crude oil containing petroleum sulfonate according to the present invention, and preferably, the salt content after deoiling can be less than 1.0 mgNaCl/kg. Further preferably, a treatment method combining strong-base anion resin with a cationic demulsifier is adopted, and particularly the preferred cationized polyoxyethylene polyoxypropylene ether demulsifier disclosed by the invention reduces the sodium content of desalted crude oil, solves the problem that a catalytic cracking catalyst is easy to poison in a subsequent process, weakens the emulsification tendency of the crude oil, and can greatly reduce the content of oil in water after electric desalting demulsification and oil-water separation.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A method of treating petroleum sulfonate-containing crude oil, said method comprising: contacting crude oil containing petroleum sulfonate with strong-base anion exchange resin at 60-100 ℃ for anion exchange, mixing the mixture of the crude oil and the resin with water injection and a demulsifier, performing electric desalting and demulsification and performing oil-water separation;
the crude oil containing petroleum sulfonate has viscosity of not higher than 30mm at 50 DEG C2(ii)/s, the loss rate of exchange capacity of said strongly basic anion exchange resin after heating at 100 ℃ for 140 hours is not higher than 20%.
2. The process of claim 1 wherein the petroleum sulfonate containing crude oil has a viscosity of 5 to 30mm at 50 ℃2(ii)/s, the loss rate of exchange capacity of said strongly basic anion exchange resin after heating at 100 ℃ for 140 hours is not higher than 10%.
3. A process according to claim 1 or 2, whereinThe strong base anion exchange resin is styrene series macroporous type strong base anion exchange resin, and the functional group of the styrene series macroporous type strong base anion exchange resin is
Wherein R is
m is an integer of 1 to 8;
R1、R2、R3each independently is a C1-C8 alkyl group and/or a C1-C8 alkanol group;
X-represents OH coordinated to ammonium-Or Cl-；
The strongly basic anion exchange resin has a working exchange capacity of from 3.6 to 4.8 mmoles/g dry resin, preferably from 3.9 to 4.5 mmoles/g dry resin.
4. The process of claim 3, wherein R1、R2、R3Each independently being methyl, ethyl, n-propyl or isopropyl, preferably R1、R2、R3Both methyl groups or both ethyl groups.
5. The treatment method according to any one of claims 1 to 4, wherein the strongly basic anion exchange resin is used in an amount of 2 to 30 wt% based on the weight of the petroleum sulfonate containing crude oil, and the petroleum sulfonate containing crude oil has a petroleum sulfonate content of 50 to 1000 mg/kg.
6. The process of claim 5 wherein the strongly basic anion exchange resin is used in an amount of 6 to 10 wt% based on the weight of the petroleum sulfonate containing crude oil.
7. The process according to any one of claims 1 to 6, wherein the crude oil containing petroleum sulfonate is contacted with the strongly basic anion exchange resin at a temperature of 80 to 90 ℃ for a time of 0.5 to 60 minutes.
8. The processing method according to any one of claims 1 to 7, wherein the method further comprises: the petroleum sulfonate containing crude oil is preheated to 60-100 deg.c, preferably 80-90 deg.c, before contacting the petroleum sulfonate containing crude oil with the strongly basic anion exchange resin.
9. The treatment method of claim 1, wherein the demulsifier is a cationic demulsifier, preferably the demulsifier is a cationized polyoxyethylene polyoxypropylene ether prepared by a method comprising:
(1) in the presence of an etherification catalyst, the block polyether is obtained by the reaction of an initiator, ethylene oxide and propylene oxide; wherein the block polyether comprises a polyether chain segment combined with an initiator, and the polyether chain segment is a block copolymer formed by the reaction of ethylene oxide and propylene oxide; the initiator is an organic compound with one or more of hydroxyl, carboxyl and amido;
(2) in the presence of an esterification catalyst and a polymerization inhibitor, carrying out ester exchange reaction on the block polyether and unsaturated carboxylic ester to enable the tail end of the block polyether to have the unsaturated carboxylic ester, and then carrying out reduced pressure distillation to remove alcohol to obtain an esterification product;
(3) in the presence of a free radical initiator and a polymerization assistant, carrying out polymerization reaction on the esterification product and a cationic unsaturated monomer to connect a polymerization chain segment formed by the cationic unsaturated monomer at the tail end of unsaturated carboxylic ester of block polyether, thereby obtaining the demulsifier; the weight ratio of the use amount of the esterification product to the use amount of the cationic unsaturated monomer is 1: 1-10;
the addition amount of the demulsifier is 10-20ppm based on 100g of crude oil containing petroleum sulfonate.
10. The treatment method according to claim 9, wherein in the step (1), the initiator is one or more of monohydric alcohol, dihydric alcohol, alkyl phenolic resin, alkyl phenolic amine resin and polyethylene polyamine, preferably alkyl phenolic resin and/or polyethylene polyamine;
the weight ratio of the initiator to the total amount of the ethylene oxide and the propylene oxide is 1: 10-700; the weight ratio of the used amount of ethylene oxide and propylene oxide is 0.1-10:1, preferably 0.25-2.5: 1;
the etherification catalyst is an alkali catalyst, preferably one or more of sodium hydroxide, potassium hydroxide, metallic sodium, metallic lithium and metallic potassium; the total dosage of the ethylene oxide and the propylene oxide is taken as a reference, and the dosage of the etherification catalyst is 0.1 to 2 weight percent;
the temperature for preparing the block polyether is 100-150 ℃.
11. The treatment method according to claim 9, wherein in the step (2), the block polyether used is a combination of a block polyether A obtained by using an alkylphenol aldehyde resin as an initiator and a block polyether B obtained by using polyethylene polyamine as an initiator; preferably, the weight ratio of block polyether A to block polyether B is 1:0.2-5, more preferably 1: 0.5-1;
the unsaturated carboxylic acid ester is one or more of methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, monomethyl fumarate, dimethyl itaconate and monomethyl itaconate;
preferably, the weight ratio of the block polyether to the unsaturated carboxylic acid ester is 100:0.5-100, more preferably 100:0.8-50, and further preferably 100: 1-10;
the esterification catalyst is one or more of sulfuric acid, phosphoric acid and p-toluenesulfonic acid; the esterification catalyst is used in an amount of 0.1 to 8 wt%, preferably 0.4 to 1.5 wt%, based on the total weight of the block polyether and the unsaturated carboxylic acid ester;
the polymerization inhibitor is hydroquinone and/or p-hydroxyanisole; the amount of the polymerization inhibitor is 0.1-1 wt%, preferably 0.2-0.6 wt%, based on the total weight of the block polyether and the unsaturated carboxylic ester;
the conditions of the transesterification reaction include: the temperature is 80-120 ℃, and the time is 1-10 h.
12. The treatment process according to claim 9, wherein in the step (3), the esterification product and the cationic unsaturated monomer are used in a weight ratio of 1:2 to 4; the cation unsaturated monomer is one or more of allyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, 2- (methacrylamide) ethyl trimethyl ammonium chloride and (3-acrylamidopropyl) trimethyl ammonium chloride;
the free radical initiator is one or more of potassium persulfate, ammonium persulfate, dicumyl peroxide and dibenzoyl peroxide; the amount of the radical initiator is 1 to 10% by weight, preferably 6 to 8% by weight, based on the total weight of the esterification product and the cationic unsaturated monomer;
the polymerization assistant is Na4EDTA、Na2One or more of EDTA, EDTA and DTPA; the amount of the polymerization assistant is 0.5 to 5 wt%, preferably 0.8 to 1.2 wt%, based on the total weight of the esterification product and the cationic unsaturated monomer;
the polymerization reaction comprises: firstly reacting for 1-10h at 40-60 ℃, and then reacting for 1-10h at 60-90 ℃; preferably, the polymerization reaction comprises: firstly reacting for 2-5h at 45-55 ℃, and then reacting for 2-5h at 65-80 ℃.
13. The processing method according to any one of claims 1 and 9 to 12,
the conditions for the electric desalting and demulsifying comprise: the temperature is 60-150 ℃, the time is 10-100min, and the electric field strength is 100-;
preferably, the conditions for demulsification of electric desalting comprise: the temperature is 80-120 ℃, the time is 20-60min, and the electric field intensity is 200-.
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