WO2020258358A1 - Désemulsifiant de pétrole brut tridimensionnel, son procédé de préparation , et son utilisation - Google Patents

Désemulsifiant de pétrole brut tridimensionnel, son procédé de préparation , et son utilisation Download PDF

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Publication number
WO2020258358A1
WO2020258358A1 PCT/CN2019/094657 CN2019094657W WO2020258358A1 WO 2020258358 A1 WO2020258358 A1 WO 2020258358A1 CN 2019094657 W CN2019094657 W CN 2019094657W WO 2020258358 A1 WO2020258358 A1 WO 2020258358A1
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WO
WIPO (PCT)
Prior art keywords
demulsifier
crude oil
preparation
epoxy resin
dehydration
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PCT/CN2019/094657
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English (en)
Chinese (zh)
Inventor
崔学章
崔仕章
王黎明
于长禄
谷之辉
徐丽君
吴丽丽
刘骁
Original Assignee
德仕能源科技集团股份有限公司
山东德仕化工有限公司
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Application filed by 德仕能源科技集团股份有限公司, 山东德仕化工有限公司 filed Critical 德仕能源科技集团股份有限公司
Publication of WO2020258358A1 publication Critical patent/WO2020258358A1/fr

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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G65/2618—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
    • C08G65/2624—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 containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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

Definitions

  • This application relates to the field of petrochemical technology, in particular to a bulk crude oil demulsifier and a preparation method thereof.
  • each oil area adopts different enhanced oil recovery technologies according to the formation characteristics, such as alkaline flooding, acid fracturing operations, foam flooding, polymer flooding, steam flooding, surfactant flooding, surfactant-polymer two
  • the application of these technologies such as yuan flooding and alkali-surfactant-polymer ternary combination flooding, provides effective measures for stabilizing and increasing oilfield production, and has achieved huge economic benefits.
  • Demulsifier is a surface active agent that partially replaces the crude oil emulsion stabilizing film, thereby destroying the stability of the crude oil emulsion and separating the crude oil and water in the crude oil emulsion.
  • demulsifiers used in my country’s oilfields are demulsifiers with polyether as the main body, especially polyether demulsifiers with phenolic resin as the initiator. They have strong surface activity, strong adaptability, and better lubrication. Wet performance, sufficient flocculation capacity and high coalescence efficiency.
  • the polyether demulsifiers currently studied often have shortcomings such as small molecular weight, difficult to demulsify heavy oil, uneven diffusion, slow demulsification speed, and low dehydration rate.
  • the demulsifiers provided by CN103146418A and CN102746470A are end-blocked and modified by unsaturated acids such as acrylic acid and have a small molecular weight;
  • CN1537924A uses water-soluble crosslinking agents to synthesize demulsifiers, and the products made are not oil-soluble, and the demulsification effect is not as good as oil-soluble ones.
  • the emulsion is good;
  • CN102676209A uses dicarboxylic acid to cross-link and modify the demulsifier intermediate molecules, but its penetration and diffusion properties in heavy oil are average, which reduces the demulsification efficiency.
  • the present invention aims to provide a crude oil demulsifier with higher molecular weight, fast dehydration speed, higher absolute dehydration rate, and capable of effectively processing heavy oil emulsions and a preparation method thereof.
  • the present invention provides a bulk crude oil demulsifier, which has a polymer composed of structural units represented by formula (I) and formula (II) connected by (I)-(II)-(I):
  • R' removes active hydrogen; n 1 is 1-30, n 2 is 1-5; the molecular weight of the polymer is 8000-10000.
  • the active hydrogen on R includes hydrogen on the phenyl hydroxyl group and amino hydrogen on the polyvinyl polyamine structure in the formula.
  • the polymer has a density of 1.00-1.02 g/cm 3 , a pH value of 7-9, and a flash point ⁇ 50°C; the appearance is a dark yellow viscous uniform liquid with a solid content ⁇ 95%.
  • the viscosity of the polymer is less than 300 mPa.s, and the freezing point is less than or equal to -35°C.
  • the absolute dehydration rate of the polymer is ⁇ 93%.
  • the structure with subscripts x and y is derived from the raw material polyethylene polyamine, and the structure with subscript n is derived from bisphenol A epoxy resin.
  • the crude oil demulsifier provided in this application utilizes the characteristics of the two epoxy groups in the bisphenol A epoxy resin to effectively cross-link the two demulsifier intermediate molecules together to obtain the final product of the body structure and make the final product
  • the molecular weight of the demulsifier product increases, and it also has more benzene ring structures.
  • the benzene ring structure can enhance the penetration and diffusion of the demulsifier molecules in the heavy oil, and can achieve a uniform distribution in the heavy oil in a short time. To shorten the demulsifier diffusion time, make the demulsifier molecules act as soon as possible, improve the demulsification efficiency, shorten the demulsification time, and thus improve the demulsification performance of the demulsifier product.
  • the present invention also provides a method for preparing the above-mentioned bulk crude oil demulsifier, including:
  • the bisphenol A epoxy resin is selected from one or more of epoxy resin 828 and epoxy resin E-51, preferably epoxy resin 828.
  • the added mass ratio of the bisphenol A epoxy resin and the intermediate is 3 to 5:50.
  • the reaction molar ratio of phenol, formaldehyde and polyethylene polyamine is 1:3:3.
  • the formaldehyde in the step (1) is 37% formaldehyde solution or paraformaldehyde.
  • the addition mass ratio of the initiator, propylene oxide, and ethylene oxide in the step (2) is 1:(15 ⁇ 35):(4 ⁇ 6), preferably 1:(20 ⁇ 30): (4.5-5.5), more preferably 1:29:5.
  • the solvent in the step (1) and/or step (2) is xylene.
  • the polyvinyl polyamine and molten phenol are dissolved in xylene, and then formaldehyde is added dropwise to it; in step (2), the intermediate and bisphenol A epoxy resin are separately dissolved in two Remix in toluene, where the mass ratio of bisphenol A epoxy resin to xylene is 1:4.
  • an electric heating reactor and/or polymerization reactor is used.
  • the above preparation method specifically includes the following steps:
  • the present invention also provides a crude oil demulsifier prepared by the above method.
  • R' R removes the active hydrogen on the phenyl hydroxyl group.
  • the present invention also provides the above crude oil demulsifier and/or the application of the crude oil demulsifier prepared by the above method to increase the dehydration rate of crude oil.
  • the water content of the crude oil is less than or equal to 30%.
  • the crude oil demulsifier provided by the present invention has fast dehydration speed, clear water quality and uniform oil-water interface, exhibits significant demulsification and dehydration performance, and has a dehydration and demulsification effect higher than that of existing demulsifiers.
  • the crude oil demulsifier provided by the present invention treats crude oil with a water content of 30% at 70°C for 90 minutes, the absolute dehydration rate at a concentration of 50 ppm is as high as 95.8%, and the absolute dehydration rate at a concentration of 100 ppm is 100%.
  • the crude oil demulsifier provided by the present invention utilizes the characteristics of the two epoxy groups in the bisphenol A epoxy resin to effectively cross-link the two demulsifier intermediate molecules together to obtain the final product of the body structure.
  • the molecular weight of the final demulsifier product is increased, thereby improving the demulsification performance of the demulsifier product.
  • the absolute dehydration rate of the crude oil demulsifier provided by the present invention is ⁇ 93%
  • the crude oil demulsifier provided by the present invention also has more benzene ring structures, and the benzene ring structure can enhance the penetration and diffusion of the demulsifier molecules in the heavy oil, and can achieve a uniform distribution in the heavy oil in a short time. In this way, the diffusion time of the demulsifier is shortened, the molecules of the demulsifier can act as soon as possible, the efficiency of demulsification is improved, and the demulsification time is shortened;
  • the crude oil demulsifier provided by the present invention can be water-soluble or oil-soluble, and can be adjusted for different site conditions, so that it can exert its best performance on site and stabilize the site;
  • the preparation method of the bulk crude oil demulsifier provided by the invention is simple, and the raw materials are easily available, so that the bulk crude oil demulsifier is easy to industrially produce.
  • the reagents in the following examples are all commercially available.
  • polyethylene polyamine is provided by Shanghai Aladdin Biochemical Technology Co., Ltd. CAS: 29320-38-5; xylene, phenol and formaldehyde are all purchased from Yantai Far East Fine Chemical Co., Ltd.; epoxy resin 828 is provided by Hexion HEXION Provided by the company; both ethylene oxide and propylene oxide are taken from industrial samples.
  • the purity of the above reagents is analytical grade.
  • Example 1 provides a method for preparing a bulk crude oil demulsifier, including the following steps:
  • Example 2 provides a bulk crude oil demulsifier prepared in Example 1.
  • the bulk crude oil demulsifier is a polymer having the following structural formula:
  • R' is the R in the following formula to remove active hydrogen:
  • n 1 is 1 to 30, n 2 is 1 to 5; wherein, the active hydrogen on R includes hydrogen on the phenyl hydroxyl group in the formula and amino hydrogen on the polyvinyl polyamine structure.
  • the obtained polymer has a molecular weight of 8000-10000, a density of 1.00-1.02g/cm 3 , a pH value of 7-9, and a flash point ⁇ 50°C; its appearance is a dark yellow viscous uniform liquid, no mechanical impurities, and solid content ⁇ 95%; viscosity ⁇ 300mPa.s, freezing point ⁇ -35°C, absolute dehydration rate ⁇ 93%.
  • the structure with subscripts x and y is derived from the raw material polyethylene polyamine, and the structure with subscript n is derived from bisphenol A epoxy resin.
  • the above-mentioned crude oil demulsifier is denoted by the code name DST, and the demulsification performance test is performed on it.
  • Six kinds of agents with good indoor evaluation effects and on-site agents are selected, and the experiments are carried out at the same temperature and different dosages.
  • the crude oil sample comes from Le'an Joint Station, the water content of the oil sample is 30%, the dehydration temperature is 75°C, and the test results obtained are Table 1:
  • LALP LALP
  • the bulk crude oil demulsifier provided by the present invention has a fast dehydration speed, has an even oil-water interface, and has clear water quality, and has significant demulsification dehydration performance.
  • the dehydration rate of DST demulsifier reaches 95.8% at a concentration of 50ppm, which is much higher than the on-site dehydration rate of 79.2% at the same concentration, and the effect is the same as that under the condition of 100ppm.
  • the dehydration rate under the condition of the drug concentration of 100ppm is as high as 100%, and the dehydration and demulsification effect of DST demulsifier is higher than other demulsifiers under the same concentration of drug dosage.
  • the crude oil demulsifier provided by the present invention has a body structure and a larger molecular weight, and exhibits significant demulsification performance. At the same time, it has good penetration and diffusibility in heavy oil, and can be used in heavy oil in a short time. Achieve uniform distribution, shorten the diffusion time of the demulsifier, and can be adjusted according to different site conditions, so that it can exert the best performance on the site, and the preparation method is simple, the raw materials are easy to obtain, and the industrial production is easy.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)

Abstract

L'invention concerne un désémulsifiant de pétrole brut, son procédé de préparation et son utilisation. Le désémulsifiant est un polymère formé par liaison de deux unités structurales, et est préparé par le procédé comprenant les étapes suivants : (1) la préparation d'un initiateur : après le mélange de polyéthylène polyamine, de phénol et de formaldéhyde, l'exécution séquentielle d'un chauffage, d'un reflux, d'une déshydratation et d'une élimination de solvant, et le refroidissement sur le mélange, de manière à obtenir un initiateur ; (2) la préparation d'un intermédiaire : l'ajout d'une poudre alcaline à l'initiateur, l'ajout séquentiel de l'oxyde de propylène et de l'oxyde d'éthylène dans des conditions de vide et la réaction de ceux-ci à 120 °C à 140 °C pendant 4 à 6 h, puis le refroidissement pour obtenir un intermédiaire ; et (3) la préparation de désémulsifiant : l'ajout d'une résine époxy de bisphénol A à l'intermédiaire et la réaction à 75°C à 90 °C pendant 4 à 6 h, puis le refroidissement pour obtenir un désémulsifiant. Le désémulsifiant est utilisé pour la déshydratation de pétrole brut, et peut améliorer la pénétration et la diffusion de molécules désémulsifiantes dans de l'huile lourde, raccourcir le temps de diffusion du désémulsifiant, et améliorer les performances de désémulsification du produit désémulsifiant.
PCT/CN2019/094657 2019-06-28 2019-07-04 Désemulsifiant de pétrole brut tridimensionnel, son procédé de préparation , et son utilisation WO2020258358A1 (fr)

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CN201910573789.2 2019-06-28
CN201910573789.2A CN110343545B (zh) 2019-06-28 2019-06-28 一种体型原油破乳剂及其制备方法和应用

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CN111676053B (zh) * 2020-06-19 2021-03-30 西北大学 油田破乳剂的制备方法
CN114621105A (zh) * 2020-12-10 2022-06-14 中国石油化工股份有限公司 一种含聚合物原油破乳剂及其制备方法
CN113372246B (zh) * 2021-06-02 2023-08-15 德仕能源科技集团股份有限公司 一种针对高含蜡原油驱油用表面活性剂的生产及应用

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