CN107474873B - Super heavy oil demulsifier and preparation method thereof - Google Patents
Super heavy oil demulsifier and preparation method thereof Download PDFInfo
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- 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
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- 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
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- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
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- 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
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- 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
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Abstract
The invention discloses a super heavy oil demulsifier, which comprises the following components in percentage by mass: 40-65% of reverse oil head DP type crude oil demulsifier, 10-40% of mixed oil head MU type crude oil demulsifier, 20-45% of forward oil head PFA type rosin modified phenolic amine crude oil demulsifier, 1-5% of functional anionic biosurfactant rhamnolipid, and a preparation method thereof. The three demulsifiers and the biosurfactant are uniformly mixed according to a certain proportion to obtain the demulsifier. The demulsifier has various structures and extremely strong compatibility and cooperativity among components, and has the characteristics of high demulsification efficiency, good stability, clean water and clean oil after demulsification, clear and smooth oil-water interface and the like aiming at the ultra-thick oil of a Liaohe oil field light oil production plant.
Description
Technical Field
The invention relates to the technical field of oilfield chemical preparations, in particular to a super heavy oil demulsifier and a preparation method thereof.
Background
CRUDE OIL (CRUDE OIL) is the major energy source in the world today and it plays a very important role in national economy and is therefore also called "black gold". According to different standards, crude oil classification is different, wherein one type of heavy oil with high viscosity and high density exists, and according to the classification standard of the Chinese heavy oil proposed by the general engineer of Liu articles in China, the heavy oil (natural asphalt) with dynamic viscosity (50 ℃) being more than or equal to 50000mPa.s and density (20 ℃) being more than 0.98g/cm exists3。
Stausz and other researches show that asphaltene molecules contain 4-10 condensed aromatic systems, aromatic rings are linked with abundant fatty structure units, branched chain structures forming the asphaltene molecules are likely to be curled and coiled to form a three-dimensional space structure of the asphaltene molecules in an oil reservoir system, for the diffusion of the demulsifier to form serious barrier, and simultaneously, between unit sheets which take condensed rings as cores in asphalt molecules, because the pi electron clouds of the intramolecular or intermolecular aromatic rings are overlapped and complexed to form a partially ordered similar crystal structure, the directional arrangement of the demulsifier molecules on an oil-water interface is hindered, the super-thick oil belongs to a stable colloid dispersion system thereof, the dispersed phase is particles formed by taking asphaltene as a core and taking colloid attached to the asphaltene as a solvation layer, and the particles prevent further flocculation and coalescence among asphalt molecules, so that the factors become key factors for effectively demulsifying ultra-thick oil.
The Liaohe oil field eosin oil extraction plant is the best known super-thick oil production area in China, the consistency of crude oil is rare in the world, the dynamic viscosity (50 ℃) of the crude oil is as high as 59989mPa.s, and the density (20 ℃) of the crude oil is as high as 59989mPa.s1.0572g/cm3. The demulsification of the ultra-thick oil always troubles all oil production plants, so that special research and development are carried out at home and abroad aiming at the demulsifier of the ultra-thick oil, and certain achievements are obtained. Patent CN102373077A discloses a functional demulsifier for extra-thick oil, which effectively improves the dehydration effect of extra-thick oil and is only suitable for oil-water separation of sand-containing extra-thick oil with the viscosity of 10000 mPa.s; patent CN 102746470A discloses a naphthenic extra-thick oil demulsifier, which is suitable for demulsification of naphthenic extra-thick oil in Clamayi area, and in 2005, 12 discloses a clear water type extra-thick demulsifier which has a good demulsification effect on oil products of Liaohe cold houses and special oil companies, but is not ideal for demulsification of extra-thick oil in eosine oil production plants.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the super-heavy oil demulsifier which can effectively demulsify super-heavy oil in a Liaohe oil field light oil extraction plant, has the characteristics of high demulsification efficiency, good stability, clear water and clean oil after demulsification, clear and smooth oil-water interface and the like, and also provides the preparation method of the super-heavy oil demulsifier. In order to achieve the above object, the present invention provides the following technical solutions:
the super heavy oil demulsifier comprises the following components in percentage by weight: 40-65% of reverse oil head DP type crude oil demulsifier, 10-40% of mixed oil head MU type crude oil demulsifier, 20-45% of forward oil head PFA type rosin modified phenamine type crude oil demulsifier and 1-5% of rhamnosyl ester.
Wherein the reverse oil head DP type crude oil demulsifier has the following structure:
in the above formula, EO is- -CH2-CH2O- - -, PO is
m is an integer of 1 to 5, n is an integer of 1 to 8, p is an integer of 1 to 7, k is an integer of 1 to 3, and z is an integer of 1 to 3.
The mixed oil head MU type crude oil demulsifier has the following structure:
in the above formula, EO is- -CH2-CH2O- - -, PO is
MO is a PO and EO random mixed polymerization unit, m is an integer of 1-10, n is an integer of 1-8, and p is an integer of 1-9. The PFA type crude oil demulsifier has the following structure:
in the above formula, EO is- -CH2-CH2O- - -, PO is
m is an integer of 1 to 11, and n is an integer of 1 to 6.
The structure of rhamnose ester is complex and various, and is mainly characterized by the following four structures:
the preparation method of the super heavy oil demulsifier preferably comprises the following steps:
1. preparing a reverse oil head DP type crude oil demulsifier:
1.1 accurately weighing 1 part of bisphenol fluorene and 0.1-0.3% of alkaline catalyst in total parts, transferring the bisphenol fluorene into a reaction kettle, heating and stirring, keeping the temperature for 30-45 minutes when the temperature reaches 225-230 ℃, then starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration, controlling the temperature to be 225-230 ℃, the dehydration time to be 35-40 minutes, continuously introducing 13-25 parts of ethylene oxide after the dehydration is finished, controlling the reaction temperature to be 225-230 ℃ and the reaction pressure to be 0.15-0.4 MPa; and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain a demulsifier intermediate DPA.
Preferably, the basic catalyst includes potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium alkoxide, sodium alkoxide, etc., and is preferably applied as the catalyst for polymerization as follows.
Preferably, the proportion of parts in the formula is as follows: bisphenol fluorene and ethylene oxide in the ratio of 1 to 15-21
1.2 accurately weighing 1 part of DPA and 0.1-0.25% of basic catalyst in total, transferring the DPA and the basic catalyst into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-120 ℃, the dehydration time is 35-40 minutes, the dehydration final temperature is 120-130 ℃, continuously introducing 6-10 parts of propylene oxide after the dehydration is finished, the reaction temperature is 130-135 ℃, the reaction pressure is 0.15-0.4 MPa, after the propylene oxide is completely introduced, continuously keeping the reaction temperature, introducing 0.1-0.7 part of ethylene oxide when the pressure is reduced to be below 0.02MPa, wherein the reaction temperature is 120-130 ℃, the reaction pressure is 0.15-0.4 MPa, and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to be below 0.02MPa, neutralizing the material with acetic acid until the PH value is 6-7, cooling to 90-100 ℃, and discharging to obtain the demulsifier intermediate DPB.
Preferably, the parts ratio in the formula is as follows: DPA, propylene oxide and ethylene oxide are 1: 7-9: 0.5-0.6
1.3 accurately weighing 1 part of demulsifier intermediate DPB, transferring the demulsifier intermediate DPB into a reaction kettle, heating and stirring, dripping 3-6% of phosphorus oxychloride in total parts when the temperature reaches 90-115 ℃, starting vacuum (the vacuum pressure is kept at-0.03 to-0.02 MPa), heating to 120-130 ℃ after the dripping is finished, preserving the heat for 30-40 minutes, sampling to determine the pH value of the material, cooling to 90-100 ℃ when the pH value is not less than 4, discharging, continuing preserving the heat for 120-130 ℃ when the pH value is not more than 4, cooling to 90-100 ℃ until the pH value is not less than 4, and discharging.
Preferably, the chain extender is phosphorus oxychloride, dichloromethyldimethylsilane, dichloroacetic acid, dichlorophen, phosphorus phenyloxychloride, phosphorus oxychloride, 1, 3-dichloro-2-propanediol, or the like.
Preferably, the dosage of the phosphorus oxychloride is 3.5-5% of the total parts.
Preferably, the method for determining the pH value of the material by end-point sampling comprises the following steps: sampling and preparing 5% solution (the mass part of isopropanol and water is 3: 1), and selecting precision test paper with the measuring range of 2.7-4.7 for determination.
2. Preparing a mixing head MU type crude oil demulsifier:
2.1 accurately weighing 1 part of N-methyldiethanolamine and 0.1-0.3% of basic catalyst in total, transferring the N-methyldiethanolamine and the basic catalyst into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature to be 100-110 ℃, the dehydration time to be 35-40 minutes, continuously introducing 15-25 parts of a mixture of propylene oxide and ethylene oxide (the mass ratio of PO to EO is 2: 1) after the dehydration is finished, controlling the reaction temperature to be 120-130 ℃, and controlling the reaction pressure to be 0.15-0.4 MPa; and after the propylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain a demulsifier intermediate MUA.
Preferably, the proportion of parts in the formula is as follows: the mass ratio of the N-methyldiethanolamine to the mixture of the propylene oxide and the ethylene oxide (PO: EO: 2: 1) is 1: 20-23.
2.2 accurately weighing 1 part of intermediate MUA and 0.1-0.2% of basic catalyst in total parts, transferring into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature at 100-110 ℃ for 35-40 minutes, continuously introducing 5-8 parts of ethylene oxide after dehydration is finished, wherein the reaction temperature is 125-140 ℃, and the reaction pressure is 0.15-0.4 MPa; and when the ethylene oxide is completely introduced, continuously keeping the reaction temperature, when the pressure is reduced to below 0.02MPa, then introducing 8-12 parts of propylene oxide, when the reaction temperature is 120-130 ℃, the reaction pressure is 0.15-0.4 MPa, when the propylene oxide is completely introduced, continuously keeping the reaction temperature, when the pressure is reduced to below 0.02MPa, curing for 30-45 minutes, neutralizing the material with acetic acid until the pH value is 6-7, then cooling to 90-100 ℃, and discharging to obtain the demulsifier MU.
Preferably, the proportion of parts in the formula is as follows: the intermediate MUA, the ethylene oxide and the propylene oxide are 1: 5.5-7: 9-10.
3. Preparing a PFA type rosin esterified crude oil demulsifier:
3.1 preparation of PFA type resin: accurately weighing 1 part of phenol, 6-8 parts of pentaethylenehexamine and 10-15 parts of dimethylbenzene, transferring the mixture into a kettle, heating and stirring, keeping the temperature at 45-55 ℃ for 30-45 minutes, then dropwise adding 3-8 parts of industrial formaldehyde with the content of 35-37%, keeping the temperature of materials in the kettle at 45-55 ℃ in the process of dropwise adding formaldehyde, keeping the temperature at 30-45 minutes after dropwise adding, then starting to slowly heat the materials until reflux is generated, stopping heating when the temperature is constant for more than half an hour at 140-145 ℃, cooling to 90-100 ℃ and discharging to obtain the PFA resin.
Preferably, the proportion of parts in the formula is as follows: phenol, pentaethylenehexamine, formaldehyde (35-37%) and xylene (1: 6.5-7.5: 4.5-6: 12-14).
Preferably, the phenols in the formulation are phenol, nonylphenol, octylphenol, p-tert-butylphenol, naphthol, bisphenol S, bisphenol F, and the like.
Preferably, the amine is ethylenediamine, diethanolamine, triethanolamine, isopropanolamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, or the like.
Preferably, the aldehydes are formaldehyde, acetaldehyde, paraformaldehyde.
3.2 PFA demulsifier preparation:
accurately weighing 3-7 parts of PFA type resin in 3.2 and 0.1-0.3% of alkaline catalyst in total, transferring the PFA type resin and the alkaline catalyst into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature at 100-110 ℃, the dehydration time at 35-40 minutes, and continuously introducing: 0.5-3 parts of ethylene oxide, wherein the reaction temperature is 120-130 ℃, and the reaction pressure is 0.15-0.4 MPa; and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain the PFA demulsifier.
Preferably, the proportion of parts in the formula is as follows: PFA type resin and ethylene oxide are 4.5-5.5: 0.8-1.5.
3.3 esterification of PFA-type demulsifiers
Accurately weighing 8-11 parts of PFA demulsifier, 3-5 parts of hydrogenated rosin and 0.1-0.3% concentrated sulfuric acid (with the concentration of 98%) in the total parts in 3.2, transferring into a kettle, stirring and heating to 220-230 ℃, starting vacuum (the vacuum pressure is-0.03-0.05 MPa) for dehydration, sampling and measuring the viscosity after 5-8 hours, continuing vacuum dehydration when the viscosity is less than 35000mPa.s, cooling to 90-100 ℃ until the viscosity is more than or equal to 35000mPa.s, and discharging to obtain the PFA esterified rosin crude oil demulsifier.
Preferably, the percentage in the formula is as follows: PFA demulsifier and hydrogenated rosin are 9.5-10: 3.5-4.
Preferably, the hydrogenated rosin is a first grade product.
Preferably, the viscosity is more than or equal to 42000mPa.s, and the viscosity measurement standard is GB/T12008.8-1992.
4. Rhamnolide (RHAMNOLIPID) is obtained from commercial sources.
Preferably, compared with the prior art, the purity is 75-80%, the PH is 7-8, and the HLB is 20-25, the invention has the following advantages:
1. the main structure and the side chain of the two components in the demulsifier have structural units similar to colloid asphaltene molecules, which is beneficial to the diffusion behavior of the demulsifier molecules;
2. one component of the demulsifier takes a reverse oil head as an initiator and the other component takes a mixed oil head as an initiator, thereby solving the defect of uneven oil-water interface caused by the curling and the escape of demulsifier molecules when the demulsifier molecules are directionally arranged at the oil-water interface due to insufficient hydrophilicity at one end of the demulsifier molecules.
3. One component structure of the demulsifier is a multi-branch structure, which is beneficial to coalescence and flocculation of a water phase.
4. One component of the demulsifier is an anionic biosurfactant with amphipathy and specific chemical structure functionality, can neutralize the positive charge of water drops, reduce electrostatic repulsion, destroy an interface film protected by isotropic electricity, has outstanding penetration wettability and has excellent cooperativity with the demulsifier.
5. Therefore, the demulsifier has the characteristics of high demulsification efficiency, good stability, clean water and clean oil after demulsification, clear and smooth oil-water interface and the like.
Detailed Description
The present invention is described in detail below with reference to examples, and the description in this section is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
Example 1
The preparation of the demulsifier DMPRA comprises the following steps
1. Preparing a reverse oil head DP type crude oil demulsifier:
1.1 accurately weighing 1 part of bisphenol fluorene and 0.25% of potassium hydroxide in total parts, transferring the mixture into a reaction kettle, heating and stirring the mixture, keeping the temperature for 30 to 45 minutes when the temperature reaches 225 to 230 ℃, then starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration, controlling the temperature to 225 to 230 ℃, the dehydration time to 35 to 40 minutes, continuously introducing 16 parts of ethylene oxide after the dehydration is finished, and controlling the reaction temperature to 225 to 230 ℃ and the reaction pressure to 0.15 to 0.4 MPa; and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain a demulsifier intermediate DP 01.
1.2 accurately weighing 1 part of DP-1 and 0.2 percent of potassium hydroxide in total, transferring the weighed materials into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration for 35-40 minutes when the temperature reaches 100-120 ℃, keeping the final dehydration temperature at 120-130 ℃, continuously introducing 8.5 parts of propylene oxide after the dehydration is finished, keeping the reaction temperature at 130-135 ℃, keeping the reaction pressure at 0.15-0.4 MPa, after the propylene oxide is completely introduced, continuously keeping the reaction temperature, introducing 0.55 part of ethylene oxide when the pressure is reduced to be below 0.02MPa, wherein the reaction temperature is 120-130 ℃, the reaction pressure is 0.15-0.4 MPa, and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to be below 0.02MPa, neutralizing the material with acetic acid until the PH is 6-7, cooling to 90-100 ℃, and discharging to obtain a demulsifier intermediate DP 02.
1.3 accurately weighing 1 part of demulsifier intermediate DPB, transferring the demulsifier intermediate DPB into a reaction kettle, heating and stirring, starting to dropwise add 4.5% of phosphorus oxychloride when the temperature reaches 90-115 ℃, starting vacuum (the vacuum pressure is kept at-0.03 to-0.02 MPa), heating to 120-130 ℃ after the dropwise addition is finished, preserving heat for 30-40 minutes, sampling to determine the pH value of the material, cooling to 90-100 ℃ when the pH value is not less than 4, discharging, continuing to preserve heat for 120-130 ℃ when the pH value is not more than 4, cooling to 90-100 ℃ until the pH value is not less than 4, and discharging to obtain the demulsifier DPA.
2. Preparing a mixing head MU type crude oil demulsifier:
2.1 accurately weighing 1 part of N-methyldiethanolamine and 0.25 percent of potassium hydroxide in total parts, transferring the N-methyldiethanolamine and the potassium hydroxide into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature to be 100-110 ℃, the dehydration time to be 35-40 minutes, continuously introducing 22 parts of a mixture of propylene oxide and ethylene oxide (the mass ratio of PO to EO is 2: 1) after the dehydration is finished, controlling the reaction temperature to be 120-130 ℃ and controlling the reaction pressure to be 0.15-0.4 MPa; and after the propylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain a demulsifier intermediate MU 01.
2.2 accurately weighing 1 part of intermediate MUA01 and 0.1-0.2% of potassium hydroxide in total parts, transferring into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature at 100-110 ℃ for 35-40 minutes, continuously introducing 6.5 parts of ethylene oxide after dehydration is finished, and controlling the reaction temperature at 125-140 ℃ and the reaction pressure at 0.15-0.4 MPa; and when the ethylene oxide is completely introduced, continuously maintaining the reaction temperature, when the pressure is reduced to below 0.02MPa, introducing 9 parts of propylene oxide, when the reaction temperature is 120-130 ℃, the reaction pressure is 0.15-0.4 MPa, when the propylene oxide is completely introduced, continuously maintaining the reaction temperature, when the pressure is reduced to below 0.02MPa, curing for 30-45 minutes, neutralizing the material with acetic acid until the pH value is 6-7, cooling to 90-100 ℃, and discharging to obtain the demulsifier MUA.
3. Preparing a PFA type rosin esterified crude oil demulsifier:
3.1 preparation of PFA type resin:
accurately weighing 1 part of phenol, 6.8 parts of pentaethylenehexamine and 12.3 parts of dimethylbenzene, transferring the weighed materials into a kettle, heating and stirring the materials, keeping the temperature at 45-55 ℃ for 30-45 minutes, then dropwise adding 5 parts of industrial formaldehyde with the content of 35-37%, keeping the materials in the kettle at 45-55 ℃ in the process of dropwise adding the formaldehyde, keeping the temperature for 30-45 minutes after the dropwise adding is finished, then slowly heating the materials until reflux is generated, stopping heating when the temperature is constant for more than half an hour at 140-145 ℃, cooling the materials to 90-100 ℃ and discharging the materials to obtain the PFA resin.
3.2 PFA demulsifier preparation:
accurately weighing 6 parts of PFA resin in 3.1 and 0.3 percent of alkaline catalyst in total, transferring the PFA resin and the alkaline catalyst into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature to be 100-110 ℃, the dehydration time to be 35-40 minutes, continuously introducing 1.2 parts of ethylene oxide after the dehydration is finished, controlling the reaction temperature to be 120-130 ℃ and controlling the reaction pressure to be 0.15-0.4 MPa; and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain the PFA01 demulsifier.
3.3 demulsifier PFA01 esterification
Accurately weighing 9.7 parts of demulsifier PFA01, 3.7 parts of hydrogenated rosin and 0.3% concentrated sulfuric acid in the total parts in 3.2, transferring into a kettle, stirring and heating to 220-230 ℃, starting vacuum (vacuum pressure is-0.03-0.05 MPa) for dehydration, sampling after 5-8 hours, measuring viscosity, cooling to 90-100 ℃ when the viscosity is more than or equal to 35000mPa.s, and discharging to obtain the rosin esterified crude oil demulsifier PFA 23.
4. The components are mixed evenly according to the weight percentage (DPA: MUA: PFA 23: RHAMINOLIPID: 52%: 16%: 30%: 2%) at normal temperature to obtain the demulsifier DMPRA of the invention
The physical and chemical indexes of the demulsifier DMPRA are respectively as follows:
1. appearance: reddish brown transparent viscous liquid
2. Solid content: 97.1 percent
3. Density (20 ℃): 0.91g/cm3
4. pH value: 7.5
5. Flash point (closed cup): higher than 40 DEG C
6. Freezing point: less than-35 deg.C
7. Viscosity: (50 ℃ C.): 42150mPa.s
The indexes all meet the requirements of general technical conditions of a crude oil demulsifier of the China oil and gas industry standard SY/T5280-2000 on the use specification of the water-soluble demulsifier.
Example 2
The preparation of the demulsifier DMPRB comprises the following steps
1. Preparing a reverse oil head DP type crude oil demulsifier:
1.1 accurately weighing 1 part of bisphenol fluorene and 0.2% of potassium hydroxide in total parts, transferring the mixture into a reaction kettle, heating and stirring the mixture, preserving the heat for 30 to 45 minutes when the temperature reaches 225 to 230 ℃, then starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) to dehydrate the mixture, controlling the temperature to 225 to 230 ℃, the dehydration time to 35 to 40 minutes, continuously introducing 18 parts of ethylene oxide after the dehydration is finished, and controlling the reaction temperature to 225 to 230 ℃ and the reaction pressure to 0.15 to 0.4 MPa; and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain a demulsifier intermediate DP 03.
1.2 accurately weighing 1 part of DP03 and 0.25% of potassium hydroxide in total, transferring the weighed materials into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration for 35-40 minutes when the temperature reaches 100-120 ℃, keeping the dehydration time at 120-130 ℃, continuously introducing 10 parts of propylene oxide after the dehydration is finished, keeping the reaction temperature at 130-135 ℃, keeping the reaction pressure at 0.15-0.4 MPa after the propylene oxide is completely introduced, continuously introducing 0.7 part of ethylene oxide when the pressure is reduced to below 0.02MPa, keeping the reaction temperature at 120-130 ℃, keeping the reaction pressure at 0.15-0.4 MPa after the ethylene oxide is completely introduced, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, neutralizing the pH with oxalic acid to 6-7, and then reducing the pH to 90-100 ℃ to obtain an intermediate DP04 demulsifier.
1.3 accurately weighing 1 part of demulsifier intermediate DP04 and 7% of sodium hydroxide in total, transferring the weighed materials into a reaction kettle, heating and stirring, dripping 6% of 1, 3-dichloro-2-propylene glycol in total when the temperature reaches 90-115 ℃, heating to 120-130 ℃ after the dripping is finished, preserving the heat for 30-40 minutes, sampling, measuring the pH value of the material, and neutralizing with citric acid to 6-7 to obtain the demulsifier DPB.
2. Preparing a reverse head MU type crude oil demulsifier:
2.1 accurately weighing 1 part of N-methyldiethanolamine and 0.25 percent of potassium hydroxide in total parts, transferring the N-methyldiethanolamine and the potassium hydroxide into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature to be 100-110 ℃, controlling the dehydration time to be 35-40 minutes, continuously introducing 25 parts of a mixture of propylene oxide and ethylene oxide (the mass ratio of PO to EO is 2: 1) after the dehydration is finished, controlling the reaction temperature to be 120-130 ℃, and controlling the reaction pressure to be 0.15-0.4 MPa; and after the propylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain a demulsifier intermediate MU 02.
2.2 accurately weighing 1 part of intermediate MU01 and 0.2% of potassium hydroxide in total, transferring the mixture into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature at 100-110 ℃, the dehydration time at 35-40 minutes, continuously introducing 7.2 parts of ethylene oxide after the dehydration is finished, and controlling the reaction temperature at 125-140 ℃ and the reaction pressure at 0.15-0.4 MPa; and when the ethylene oxide is completely introduced, continuously maintaining the reaction temperature, when the pressure is reduced to below 0.02MPa, introducing 10.3 parts of propylene oxide, when the reaction temperature is 120-130 ℃, the reaction pressure is 0.15-0.4 MPa, when the propylene oxide is completely introduced, continuously maintaining the reaction temperature, when the pressure is reduced to below 0.02MPa, curing for 30-45 minutes, neutralizing the material with acetic acid until the pH value is 6-7, then cooling to 90-100 ℃, and discharging to obtain the demulsifier MUB.
3. Preparing a PFA type rosin esterified crude oil demulsifier:
3.1 preparation of PFA type resin:
accurately weighing 1 part of phenol, 6.8 parts of pentaethylenehexamine and 12.3 parts of dimethylbenzene, transferring the weighed materials into a kettle, heating and stirring the materials, keeping the temperature at 45-55 ℃ for 30-45 minutes, then dropwise adding 5 parts of industrial formaldehyde with the content of 35-37%, keeping the materials in the kettle at 45-55 ℃ in the process of dropwise adding the formaldehyde, keeping the temperature for 30-45 minutes after the dropwise adding is finished, then slowly heating the materials until reflux is generated, stopping heating when the temperature is constant for more than half an hour at 140-145 ℃, cooling the materials to 90-100 ℃ and discharging the materials to obtain the PFA resin.
3.2 PFA demulsifier preparation:
accurately weighing 6 parts of PFA resin in 3.1 and 0.3 percent of alkaline catalyst in total, transferring the PFA resin and the alkaline catalyst into a reaction kettle, heating and stirring, starting vacuum (the vacuum pressure is less than or equal to-0.09 MPa) for dehydration when the temperature reaches 100-110 ℃, controlling the temperature to be 100-110 ℃, the dehydration time to be 35-40 minutes, continuously introducing 1.2 parts of ethylene oxide after the dehydration is finished, controlling the reaction temperature to be 120-130 ℃ and controlling the reaction pressure to be 0.15-0.4 MPa; and after the ethylene oxide is completely introduced, continuously keeping the reaction temperature, curing for 30-45 minutes when the pressure is reduced to below 0.02MPa, cooling to 90-100 ℃, and discharging to obtain the PFA02 demulsifier.
3.3 esterification of PFA-type demulsifiers
Accurately weighing 10.2 parts of demulsifier PFA02, 4.5 parts of hydrogenated rosin and 0.25% concentrated sulfuric acid in the total parts in 3.2, transferring into a kettle, stirring and heating to 220-230 ℃, starting vacuum (vacuum pressure-0.03-0.05 MPa) for dehydration, sampling after 5-8 hours, measuring viscosity, cooling to 90-100 ℃ when the viscosity is more than or equal to 35000mPa.s, and discharging to obtain the rosin esterified crude oil demulsifier PFA 25.
4. The components are mixed evenly according to the weight percentage (DPB: MUB: PFA 25: RHAMINOLIPID: 48%: 21%: 28%: 3%) at normal temperature to obtain the demulsifier DMPRB of the invention.
The physical and chemical indexes of the demulsifier DMPRB are respectively as follows:
1. appearance: reddish brown transparent viscous liquid
2. Solid content: 96.9 percent
3. Density (20 ℃): 0.90g/cm3
4. pH value: 7.5
5. Flash point (closed cup): higher than 40 DEG C
6. Freezing point: less than-35 deg.C
7. Viscosity: (50 ℃ C.): 43057mPa.s
The indexes all meet the requirements of general technical conditions of a crude oil demulsifier of the China oil and gas industry standard SY/T5280-2000 on the use specification of the water-soluble demulsifier.
The demulsification effect pair of the super heavy oil in the Liaohe oil field eosin oil production plant is shown in the table 1 and the table 2. The evaluation standard adopts a method (bottle test method) for detecting the service performance of the crude oil demulsifier in the China oil and gas industry standard SY/T5281-2000.
TABLE 1 comparison of demulsifying effects of demulsifiers of different models
TABLE 2 comparison of demulsifying effects of demulsifiers of different models
As can be seen from the data in tables 1 and 2, the demulsifier provided by the invention has the advantages of high dehydration speed and strong demulsification capability aiming at the ultra-thick oil in the Liaohe oil field eosin oil production plant.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. The super heavy oil demulsifier is characterized in that: the paint consists of the following components in percentage by weight: 40-65% of reverse oil head DP type crude oil demulsifier, 10-40% of mixed oil head MU type crude oil demulsifier, 20-45% of forward oil head PFA type rosin modified phenol amine type crude oil demulsifier and 1-5% of rhamnolipid; wherein the reverse oil head DP type crude oil demulsifier has the following structure:
in the above formula, EO is- -CH2-CH2O- - -, PO is
m is an integer of 1-5, n is an integer of 1-8, p is an integer of 1-7, k is an integer of 1-3, and z is an integer of 1-3; the mixed oil head MU type crude oil demulsifier has the following structure:
in the above formula, EO is- -CH2-CH2O- - -, PO is
MO is a PO and EO random mixed polymerization unit, m is an integer of 1-10, n is an integer of 1-8, and p is an integer of 1-9; the forward oil head PFA type crude oil demulsifier has the following structure:
in the above formula, EO is- -CH2-CH2O- - -, PO is
m is an integer of 1 to 11, n is an integer of 1 to 6;
rhamnolipids are complex and diverse in structure and are mainly characterized by the following four structures:
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