CN110343545B - Body type crude oil demulsifier and preparation method and application thereof - Google Patents
Body type crude oil demulsifier and preparation method and application thereof Download PDFInfo
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- 239000010779 crude oil Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title description 12
- -1 polyethylene Polymers 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000004698 Polyethylene Substances 0.000 claims abstract description 14
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 229920000573 polyethylene Polymers 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims description 24
- 238000006297 dehydration reaction Methods 0.000 claims description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 22
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 7
- 239000012467 final product Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101000803530 Loxosceles intermedia Astacin-like metalloprotease toxin 1 Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
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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
The invention provides a body-type crude oil demulsifier, which is prepared by the following method: (1) preparing an initiator: mixing polyethylene polyamine, phenol and formaldehyde, sequentially heating, refluxing, dehydrating and desolventizing, and cooling to obtain an initiator; (2) preparing an intermediate: adding alkali powder into an initiator, sequentially adding propylene oxide and ethylene oxide under a vacuum condition, reacting for 4-6h at 120-140 ℃, and cooling to obtain an intermediate; (3) preparing a demulsifier: and adding bisphenol A epoxy resin into the intermediate, reacting for 4-6h at 75-90 ℃, and cooling to obtain the demulsifier. The demulsifier provided by the invention can obtain a final product with a body structure, so that the molecular weight of the final demulsifier product is increased, and meanwhile, the permeation and diffusion of demulsifier molecules in thick oil can be enhanced, the diffusion time of the demulsifier is shortened, and the demulsification performance of the demulsifier product is improved.
Description
Technical Field
The application relates to the technical field of petrochemical industry, in particular to a body-type crude oil demulsifier and a preparation method thereof.
Background
In recent years, with the continuous development of oil fields, the oil fields are gradually aged, the water content of produced crude oil is higher and higher, and even some crude oil is converted to heavy oil. In order to improve the oil recovery rate, different enhanced oil recovery technologies such as alkali flooding, acid fracturing operation, foam flooding, polymer flooding, steam flooding, surfactant-polymer binary flooding, alkali-surfactant-polymer ternary combination flooding and the like are adopted in each oil zone according to the formation characteristics. However, due to the implementation of these measures, a large amount of chemical substances are injected into the oil layer, which not only significantly increases the mineralization of the water quality of the formation, but also greatly changes the crude oil properties of a plurality of oil zones. The emulsification degree of the produced crude oil is further enhanced, high-alkalinity crude oil, high-acid value crude oil, thick oil, extra thick oil, high-condensation-point crude oil, tertiary oil recovery crude oil, high-salinity water crude oil and the like appear, even the produced crude oil and water form oil-in-water (O/W) and multiple (O/W/O, W/O/W) emulsions, the crude oil state difference is caused, and the problems of high demulsification dehydration temperature, large addition amount, unsatisfactory sewage separation and the like exist in the oil field at present, so that the huge waste of energy is caused.
The demulsifier is a surfactant which can stabilize the membrane by partially replacing the crude oil emulsion, thus destroying the stability of the crude oil emulsion and separating crude oil from water in the crude oil emulsion. At present, the demulsifier with better using effect in oil fields in China uses polyether as a main body, particularly uses phenolic resin as an initiator, and has the advantages of stronger surface activity, strong adaptability, better wetting property, enough flocculation capability, higher coalescence efficiency and the like.
However, the currently researched polyether demulsifiers often have the defects of small molecular weight, difficult demulsification of thickened oil, uneven diffusion, slow demulsification speed, low dehydration rate and the like. For example, the demulsifiers provided by CN103146418A and CN102746470A are subjected to end-capping modification by using unsaturated acids such as acrylic acid and the like, and the molecular weight is small; CN1537924A adopts a water-soluble cross-linking agent to synthesize a demulsifier, and the prepared product cannot be oil-soluble and has a better demulsification effect than an oil-soluble demulsifier; CN102676209A adopts dicarboxylic acid to carry out crosslinking modification on the demulsifier intermediate molecules, but the permeation and diffusion properties of the demulsifier intermediate molecules in the thick oil are general, so that the demulsification efficiency is reduced.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a crude oil demulsifier which has higher molecular weight, high dehydration speed and higher absolute dehydration rate and can effectively treat a thick oil emulsion and a preparation method thereof.
In one aspect, the present invention provides a bulk crude oil demulsifier having a polymer comprising structural units represented by formulae (I) and (II) linked according to (I) - (II) - (I):
(I)：
(II)：
wherein,
r': removing active hydrogen from R; n is11 to 30, n2Taking 1-5; the molecular weight of the polymer is 8000-10000.
Preferably, the active hydrogen on R comprises hydrogen on a benzene hydroxyl group in the formula and amino hydrogen on a polyethylene polyamine structure.
Further, the polymer has a density of 1.00 to 1.02g/cm3The pH value is 7-9, and the flash point is more than or equal to 50 ℃; the appearance character is deep yellow viscous uniform liquid, and the solid content is more than or equal to 95 percent.
Further, the viscosity of the polymer is less than 300mPa.s, and the freezing point is less than or equal to-35 ℃.
Further, the absolute dehydration rate of the polymer is more than or equal to 93 percent.
In the polymer represented by the above formula, the structure with subscripts x and y is derived from the raw material polyethylene polyamine, and the structure with subscript n is derived from the bisphenol a type epoxy resin.
The application provides a crude oil demulsifier, utilize the characteristic of two epoxy groups in the bisphenol A type epoxy resin, can be effectively in the same place two demulsifier intermediate molecule cross-links, obtain the final product of size structure, make final demulsifier product molecular weight increase, still have more benzene ring structure simultaneously, and benzene ring structure can strengthen the infiltration of demulsifier molecule in the viscous crude, the diffusion, can reach evenly distributed in the viscous crude in short time, shorten demulsifier diffusion time with this, make the demulsifier molecule take effect as early as possible, improve demulsification efficiency, shorten demulsification time, thereby improve the demulsification performance of demulsifier product.
On the other hand, the invention also provides a preparation method of the body-type crude oil demulsifier, which comprises the following steps:
(1) preparing an initiator: mixing polyethylene polyamine, phenol and formaldehyde, sequentially heating, refluxing, dehydrating and desolventizing, and cooling to obtain an initiator;
(2) preparing an intermediate: adding alkali powder into an initiator, sequentially adding propylene oxide and ethylene oxide under a vacuum condition, reacting for 4-6h at 120-140 ℃, and cooling to obtain an intermediate;
(3) preparing a demulsifier: and adding bisphenol A epoxy resin into the intermediate, reacting for 4-6h at 75-90 ℃, and cooling to obtain the demulsifier.
Further, the bisphenol A epoxy resin is selected from one or more of epoxy resin 828 and epoxy resin E-51, and epoxy resin 828 is preferred.
Further, the addition mass ratio of the bisphenol A type epoxy resin to the intermediate is 3-5: 50.
Further, the reaction molar ratio of the phenol, the formaldehyde and the polyethylene polyamine in the step (1) is 1:3: 3.
Further, the formaldehyde in the step (1) is 37% formaldehyde solution or paraformaldehyde.
Furthermore, the mass ratio of the initiator, the propylene oxide and the ethylene oxide in the step (2) is 1 (15-35) to (4-6), preferably 1 (20-30) to (4.5-5.5), and more preferably 1:29: 5.
Further, the solvent in the step (1) and/or the step (2) is xylene. Preferably, in the step (1), the polyethylene polyamine and the molten phenol are dissolved in xylene, and then formaldehyde is added dropwise thereto; and (2) respectively dissolving the intermediate and the bisphenol A epoxy resin in dimethylbenzene and then mixing, wherein the mass ratio of the bisphenol A epoxy resin to the dimethylbenzene is 1: 4.
Further, the above method uses an electrically heated reaction vessel and/or polymerization vessel.
In a preferred embodiment, the above preparation method specifically comprises the steps of:
(1) sequentially adding dimethylbenzene, polyethylene polyamine and molten phenol into an electric heating reaction kettle, uniformly stirring at 50-60 ℃, dropwise adding 37% formaldehyde solution at constant temperature, and reacting for 2 hours; then reacting for 2h at 120-130 ℃, refluxing and dehydrating for 6h at 150-160 ℃, desolventizing for 4h at 220-240 ℃, and cooling to 100-110 ℃ to obtain an initiator;
(2) adding alkali powder into an initiator, dehydrating for 1h under vacuum at 140 ℃, introducing propylene oxide, and reacting for 2h under the conditions that the temperature is 130 ℃ and the pressure is-0.1 Mpa to-0.05 Mpa; introducing ethylene oxide, and reacting for 2h under the conditions of 125 ℃ and-0.1 to-0.05 Mpa; after the reaction is finished, cooling to 65-70 ℃ to obtain an intermediate;
(3) and uniformly stirring the intermediate and xylene at 80 ℃, dissolving bisphenol A epoxy resin in the xylene, dropwise adding the mixture into a xylene solution of the intermediate for 1.5-2h, reacting at 85 ℃ for 3h, and cooling to 65-70 ℃ to obtain the demulsifier.
On the other hand, the invention also provides a crude oil demulsifier prepared by the method.
The synthetic route for preparing the crude oil demulsifier by adopting the method is as follows:
synthesis of three-dimensional resin initiator R:
synthesis of body type demulsifier intermediate Y:
wherein:
r' is: and removing active hydrogen on the benzene hydroxyl group by using the R.
Wherein, letting the intermediate be Y:
synthesizing a body type crude oil demulsifier:
on the other hand, the invention also provides the crude oil demulsifier and/or the application of the crude oil demulsifier prepared by the method in improving the dehydration rate of crude oil, preferably, the water content of the crude oil is less than or equal to 30 percent.
The crude oil demulsifier provided by the invention has the advantages of high dehydration speed, clear dehydrated water and uniform oil-water interface, shows remarkable demulsification and dehydration performances, and has a dehydration demulsification effect higher than that of the conventional demulsifier. Experiments show that the crude oil demulsifier provided by the invention can treat crude oil with the water content of 30% for 90min at 70 ℃, the absolute dehydration rate at 50ppm concentration is as high as 95.8%, and the absolute dehydration rate at 100ppm concentration is 100%.
The following beneficial effects can be brought through the application:
1. the crude oil demulsifier provided by the invention utilizes the characteristics of two epoxy groups in bisphenol A epoxy resin, can effectively crosslink two demulsifier intermediate molecules together to obtain a final product with a body structure, and increases the molecular weight of the final demulsifier product, so that the demulsification performance of the demulsifier product is improved, and experiments show that the absolute dehydration rate of the crude oil demulsifier provided by the invention is more than or equal to 93%;
2. the crude oil demulsifier provided by the invention also has more benzene ring structures, and the benzene ring structures can enhance the permeation and diffusion of demulsifier molecules in the thickened oil and can achieve uniform distribution in the thickened oil in a short time, so that the diffusion time of the demulsifier is shortened, the demulsifier molecules can act as soon as possible, the demulsification efficiency is improved, and the demulsification time is shortened;
3. the crude oil demulsifier provided by the invention can be dissolved in water and oil, and can be adjusted according to different field conditions, so that the crude oil demulsifier can exert the optimal performance on the field and stabilize the field;
4. the preparation method of the body-type crude oil demulsifier provided by the invention is simple, and raw materials are easily available, so that the body-type crude oil demulsifier is easy for industrial production.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. It will be apparent, however, to one skilled in the art, that the present application may be practiced without one or more of these specific details. In other instances, well-known features of the art have not been described in order to avoid obscuring the present application.
Unless otherwise specified, the reagents in the following examples are commercially available. Wherein the polyethylene polyamine is provided by Shanghai Allantin Biotechnology Co., Ltd, CAS: 29320-38-5; xylene, phenol and formaldehyde were purchased from cigarette ends, far east, fine chemical, ltd; epoxy 828 is supplied by hansen HEXION corporation, usa; both ethylene oxide and propylene oxide were taken from commercial samples. The purity of the reagents is analytical purity.
Example 1
Embodiment 1 provides a preparation method of a body-type crude oil demulsifier, comprising the following steps:
(1) preparation of the Starter R
Sequentially pumping 300kg of dimethylbenzene, 700kg of polyethylene polyamine and 90kg of molten phenol into a dry and clean electric heating reaction kettle, heating to 50-60 ℃, and stirring until the mixture is uniform; then, under the condition of constant temperature, pumping 240kg of formaldehyde solution with the content of 37 percent into a dripping tank, controlling the dripping time to be 0.5 h-1 h, and carrying out heat preservation reaction for 2h after finishing dripping; and then heating to 120-130 ℃, continuing to perform constant-temperature reaction for 2h, continuing to heat to 150-160 ℃, performing reflux dehydration for 6h until no water is removed, continuing to heat to 220-240 ℃, performing dehydration and desolventizing for 4h until no liquid is removed, cooling to 100-110 ℃ to obtain the body-type resin initiator R, and transferring to a kettle for later use.
(2) Preparation of intermediate Y-OH
Adding 100kg of a body-type resin initiator R and 17kg of potassium hydroxide powder into a dry and clean polymerization kettle, stirring and heating to 140 ℃, starting to perform vacuum dehydration for 1h, then cooling to 130 ℃, introducing 2900kg of propylene oxide, controlling the temperature to be 130 +/-5 ℃ and the reaction pressure to be less than or equal to 0.5Mpa in the reaction process, and after the material introduction is finished, performing heat preservation reaction for 2h at the temperature of 130 ℃ and reducing the pressure to be between-0.1 Mpa and-0.05 Mpa; and continuously introducing 500kg of ethylene oxide, slowly reducing the temperature after the reaction, controlling the temperature to be 125 +/-5 ℃ and the reaction pressure to be less than or equal to 0.5Mpa in the reaction process, and after the material introduction is finished, carrying out heat preservation reaction for 2 hours at the temperature of 125 ℃ and reducing the pressure to be between-0.1 Mpa and-0.05 Mpa to finish the reaction. And (3) reducing the temperature in the reaction kettle to 65-70 ℃, and discharging to obtain the body type demulsifier intermediate Y-OH.
(3) Preparation of body type demulsifier
Adding 500kg of body type demulsifier intermediate Y-OH and 300kg of dimethylbenzene into a dry and clean reaction kettle, heating to 80 ℃, and stirring until the state is uniform; according to the epoxy resin 828: xylene 50 kg: preparing an epoxy resin 828 solution according to a proportion of 200kg, pumping the epoxy resin 828 solution into a dripping tank, slowly dripping the epoxy resin 828 solution at 80 +/-2 ℃, controlling the temperature in the dripping process, controlling the dripping time for 1.5-2h, heating to 85 ℃ after the dripping is finished, carrying out heat preservation reaction for 3h, cooling to 65-70 ℃, and discharging to obtain the body type demulsifier.
Example 2
Example 2 provides a bulk crude oil demulsifier prepared from example 1, wherein the bulk crude oil demulsifier is a polymer having the following structural formula:
wherein Y has the following structural formula:
wherein R' is R in the following formula for removing active hydrogen:
in the formula: n is11 to 30, n2Taking 1-5; wherein, the active hydrogen on R comprises hydrogen on a benzene hydroxyl group in the formula and amino hydrogen on a polyethylene polyamine structure.
The molecular weight of the obtained polymer is 8000-10000, and the density of the polymer is 1.00-1.02g/cm3The pH value is 7-9, and the flash point is more than or equal to 50 ℃; the appearance character of the liquid is dark yellow viscous uniform liquid, no mechanical impurities exist, and the solid content is more than or equal to 95 percent; the viscosity is less than 300mPa.s, the solidifying point is less than or equal to minus 35 ℃, and the absolute dehydration rate is more than or equal to 93 percent.
In the polymer represented by the above formula, the structure with subscripts x and y is derived from the raw material polyethylene polyamine, and the structure with subscript n is derived from the bisphenol a type epoxy resin.
Example 3 crude oil demulsification experiment
The body type crude oil demulsifier is expressed by a code DST, and is subjected to demulsification performance test, six agents with better indoor evaluation effect and six on-site agents are selected and respectively subjected to experiments under the conditions of the same temperature and different dosage. Wherein, the crude oil sample comes from the joint station of le' an, and the water content of the oil sample is 30%, and dehydration temperature 75 ℃, and the test result piece table 1 is obtained:
TABLE 1 comparison of demulsification effects of the body-type crude oil demulsifier provided by the invention and other demulsifiers at different dosages
Note: the on-site agent is LALP.
As can be seen from the table 1, the body-type crude oil demulsifier provided by the invention has the advantages of high dehydration speed, uniform oil-water interface, clear dehydrated water and remarkable demulsification and dehydration performances. Meanwhile, the dehydration rate of the DST demulsifier under the condition of adding medicine concentration of 50ppm reaches 95.8 percent, is much higher than the dehydration rate of 79.2 percent on site under the same concentration, and has the same effect as that of the DST demulsifier under the condition of adding medicine amount of 100ppm on site; the dehydration rate of the DST demulsifier under the condition of adding the chemical concentration of 100ppm is more up to 100 percent, and the dehydration demulsification effect of the DST demulsifier is higher than that of other demulsifiers under the condition of using the chemical agent with the same concentration.
The crude oil demulsifier provided by the invention has a body structure and a larger molecular weight, shows remarkable demulsification performance, has good permeation and diffusion in thick oil, can achieve uniform distribution in the thick oil in a short time, shortens the diffusion time of the demulsifier, can be adjusted according to different field conditions, can exert the optimal performance on the field, and has the advantages of simple preparation method, easily obtained raw materials and easy industrial production.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (9)
1. A body-type crude oil demulsifier comprising a polymer having structural units represented by the formulae (I) and (II) linked by the formulae (I) to (II) to (I):
(I):
(II):
wherein,
r': removing active hydrogen from R; wherein, the active hydrogen on R comprises hydrogen on a benzene hydroxyl group in the formula and amino hydrogen on a polyethylene polyamine structure;
n11 to 30, n2Taking 1-5; the molecular weight of the polymer is 8000-10000.
2. The crude oil demulsifier of claim 1, wherein the polymer has a density of 1.00-1.02g/cm3The pH value is 7-9, and the flash point is more than or equal to 50 ℃; the appearance of the polymer is dark yellow viscous uniform liquid, and the solid content is more than or equal to 95 percent.
3. The method for preparing the body-type crude oil demulsifier according to claim 1 or 2, comprising the steps of:
(1) sequentially adding dimethylbenzene, polyethylene polyamine and molten phenol into an electric heating reaction kettle, uniformly stirring at 50-60 ℃, dropwise adding 37% formaldehyde solution at constant temperature, and reacting for 2 hours; then reacting for 2h at 120-130 ℃, refluxing and dehydrating for 6h at 150-160 ℃, desolventizing for 4h at 220-240 ℃, and cooling to 100-110 ℃ to obtain an initiator;
(2) adding alkali powder into an initiator, dehydrating for 1h under vacuum at 140 ℃, introducing propylene oxide, and reacting for 2h under the conditions that the temperature is 130 ℃ and the pressure is-0.1 Mpa to-0.05 Mpa; introducing ethylene oxide, and reacting for 2h under the conditions of 125 ℃ and-0.1 to-0.05 Mpa; after the reaction is finished, cooling to 65-70 ℃ to obtain an intermediate;
(3) and uniformly stirring the intermediate and xylene at 80 ℃, dissolving bisphenol A epoxy resin in the xylene, dropwise adding the mixture into a xylene solution of the intermediate for 1.5-2h, reacting at 85 ℃ for 3h, and cooling to 65-70 ℃ to obtain the demulsifier.
4. The method according to claim 3, wherein the bisphenol A epoxy resin is selected from one or more of epoxy resin 828 and epoxy resin E-51.
5. The method according to claim 3, wherein the addition mass ratio of the bisphenol A epoxy resin to the intermediate is 3-5: 50.
6. The method of claim 3, wherein the reaction molar ratio of the phenol, the formaldehyde and the polyethylene polyamine in step (1) is 1:3: 3.
7. The method as claimed in claim 3, wherein the addition mass ratio of the initiator, the propylene oxide and the ethylene oxide in the step (2) is 1 (15-35) to (4-6).
8. Use of the crude oil demulsifier of any one of claims 1 to 2 and/or the crude oil demulsifier produced by the process of any one of claims 3 to 7 for increasing the rate of dehydration of crude oil.
9. The use according to claim 8, wherein the crude oil has a water content of 30% or less.
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| CN201910573789.2A CN110343545B (en) | 2019-06-28 | 2019-06-28 | Body type crude oil demulsifier and preparation method and application thereof |
| PCT/CN2019/094657 WO2020258358A1 (en) | 2019-06-28 | 2019-07-04 | Three-dimensional crude oil demulsifier, preparation method therefor, and application thereof |
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| CN1317363C (en) * | 2003-10-22 | 2007-05-23 | 山东大学 | Low-temperature quick deemulsifying agent for water-containing wax-containing erude oil and its preparation method |
| CN101100615B (en) * | 2007-07-31 | 2010-06-30 | 中国石油天然气股份有限公司 | Low-temperature demulsifier and preparation method thereof |
| BR112013012214A2 (en) * | 2010-11-17 | 2019-09-24 | Dow Brasil Sudeste Ind | method for destabilizing a crude oil / water emulsion |
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| CN102993434B (en) * | 2012-12-28 | 2014-10-22 | 山东大学 | Preparation method of crude oil rapid demulsifying agent |
| US10202551B2 (en) * | 2013-03-15 | 2019-02-12 | Dober Chemical Corp | Dewatering compositions and methods |
| CN103450467B (en) * | 2013-08-09 | 2016-01-20 | 新疆天普石油天然气工程技术有限公司 | A kind of multiple-branching construction emulsion splitter of aromatic ring core |
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| CN107557055A (en) * | 2017-10-23 | 2018-01-09 | 天津正达科技有限责任公司 | A kind of preparation method of modified polyether crude oil rapid demulsifier |
| CN109734876A (en) * | 2018-12-03 | 2019-05-10 | 中国海洋石油集团有限公司 | A kind of polymer-bearing produced fluid reverse-phase emulsifier and preparation method thereof |
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