CN117843943A - Demulsification and clear water integrated supermolecule polyether and preparation method thereof - Google Patents
Demulsification and clear water integrated supermolecule polyether and preparation method thereof Download PDFInfo
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- CN117843943A CN117843943A CN202410024822.7A CN202410024822A CN117843943A CN 117843943 A CN117843943 A CN 117843943A CN 202410024822 A CN202410024822 A CN 202410024822A CN 117843943 A CN117843943 A CN 117843943A
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- 229920000570 polyether Polymers 0.000 title claims abstract description 72
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000412 dendrimer Substances 0.000 claims abstract description 101
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 101
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000000126 substance Substances 0.000 claims abstract description 31
- 239000010779 crude oil Substances 0.000 claims abstract description 29
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000010865 sewage Substances 0.000 claims abstract description 16
- 230000018044 dehydration Effects 0.000 claims abstract description 13
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- 239000000543 intermediate Substances 0.000 claims description 28
- 238000003786 synthesis reaction Methods 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- 229940125904 compound 1 Drugs 0.000 claims description 13
- 238000006845 Michael addition reaction Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 11
- 229940125782 compound 2 Drugs 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000003321 amplification Effects 0.000 claims description 6
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000010802 sludge Substances 0.000 abstract description 5
- 239000013043 chemical agent Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 26
- 229960001124 trientine Drugs 0.000 description 10
- 239000003814 drug Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000053 physical method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241001052560 Thallis Species 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Classifications
-
- 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
- C08G65/2633—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 the other compounds containing amide groups
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a preparation method of demulsification and clear water integrated supermolecular polyether, which comprises the steps of firstly forming polyamide-amine dendrimer through iterative reaction of amine substances and methyl acrylate, then reacting with one or more epoxy compounds to form a supermolecular polyether intermediate, and then adding a cross-linking agent to carry out cross-linking reaction to obtain a final product supermolecular polyether. The demulsification and clean water integrated supermolecular polyether prepared by the method disclosed by the invention has the advantages of high polymerization degree, environment friendliness, capability of effectively treating the generated oily sewage while demulsification and dehydration are performed on the crude oil produced liquid, capability of avoiding the generation of viscous sludge in the clean water process, capability of effectively improving the problems of equipment blockage and pipeline corrosion, great convenience for treating the crude oil produced liquid of an offshore oilfield, capability of greatly simplifying the flow, shortening the operation time, greatly reducing the chemical agent addition amount and reducing the treatment cost.
Description
Technical Field
The invention relates to the technical field of offshore crude oil dehydration and oily sewage treatment, in particular to demulsification and clear water integrated supermolecular polyether and a preparation method thereof.
Background
At present, various large oil fields in China enter a tertiary oil recovery stage, and polymer flooding is widely applied as an effective development technology for improving recovery ratio and increasing crude oil yield. The produced crude oil contains a large amount of water and forms oil-water emulsion with the water, and with the use of polymer flooding technology, the polymer and the crude oil are mixed together, so that the stability of produced liquid is greatly improved, and the subsequent demulsification and dehydration of the crude oil are affected. And a large amount of oily sewage containing crude oil, solid particles, various salts, oil extraction auxiliary agents and other pollution components is generated while the produced liquid is treated, if the oily sewage is untreated or improperly discharged, the environment is seriously damaged, and many damages are irreversible. In recent years, with the follow-up entering of some oil fields in China into a high water content exploitation period and the increase of yield measures such as polymer flooding and water injection, the treatment difficulty of the oil fields is further increased, and because of few offshore oil extraction treatment equipment and short treatment flow, the treatment difficulty is higher than that of land oil fields, and higher requirements are put forward on the medicament performance. The common methods for the dehydration of crude oil and the treatment of oily sewage in offshore oil fields mainly comprise a physical method, a chemical method, a biological method and the like at present.
The physical method mainly utilizes the physical property difference of different substances to carry out treatment, and the treatment process specifically comprises a gravity sedimentation method, a centrifugal separation method, a membrane separation method and the like. The gravity sedimentation method and the centrifugal separation method realize oil-water separation by utilizing the property of oil-water density difference and oil-water incompatibility, and the membrane separation method mainly utilizes the selective permeability of a membrane to separate oil from water. However, the physical method has lower demulsification and dehydration efficiency, higher equipment requirements and easy consumption, and the oily sewage treated by the physical method often cannot meet the standard of safe discharge.
The chemical method is a common method for dewatering crude oil and treating oily sewage in an oil field, and the strength of an interface film is weakened, so that the stability of the interface film is destroyed, the interface film is broken, and oil drops are released, so that the purpose of oil-water separation is achieved.
The biological method is to screen natural microorganism thalli, and destroy an oil-water interface by using metabolites of the natural microorganism thalli, so that oil-water separation is finally realized, but the quantity of microorganisms is not easy to control, the flexibility is poor, and equipment corrosion can be caused after long-term use.
The chemical agent method is the most commonly used method in crude oil demulsification and sewage treatment of oil fields, and mainly comprises the steps of adding corresponding demulsifiers and water-clearing agents into crude oil produced liquid and oily sewage to carry out corresponding demulsification and dehydration and flocculation of clear water. Because the offshore treatment process is shorter, the treatment place is limited, and the corrosion protection requirements on the dosing equipment and pipelines are higher, so that the input cost is increased, and the water treatment requirements are difficult to meet. At present, the offshore platform generally adopts a two-section or three-section treatment mode for treating produced liquid, and demulsifier and water scavenger are respectively added in each section treatment process, so that the problems of large dosage, complex medicament type, complex operation and the like can be generated, the exploitation treatment cost is greatly increased, and a large amount of viscous sludge can be generated to block equipment and pipelines in the clear water process by the conventional cationic water scavenger in the oily sewage treatment, so that the subsequent treatment cost is increased. The demulsification and clean water integrated medicament is researched and developed aiming at the problems, the flow can be simplified to a great extent, and the chemical medicament addition amount is greatly reduced, so that the treatment cost is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the primary aim of the invention is to provide a demulsification and clean water integrated supermolecule polyether. The demulsification and clear water integrated supermolecular polyether has high polymerization degree, is environment-friendly, can effectively treat the generated oily sewage while demulsification and dehydration are carried out on the crude oil produced liquid, can avoid producing viscous sludge in the clear water process, effectively improves the problems of equipment blockage and pipeline corrosion, brings great convenience for treating the crude oil produced liquid of the offshore oilfield, can greatly simplify the flow, shortens the operation time, greatly reduces the chemical agent addition amount and reduces the treatment cost.
The invention further aims at providing a preparation method of the demulsification and clean water integrated supermolecule polyether.
Another object of the invention is to provide the use of the demulsification and clean water integrated supramolecular polyether in the treatment of crude oil production fluids, in particular crude oil production fluids of offshore oil fields.
The above object of the present invention is achieved by the following technical solutions:
a demulsification and clean water integrated supermolecule polyether preparation method comprises the following steps:
(1) Synthesis of 0.5-generation Polyamide-amine dendrimers: the preparation method comprises the steps of adopting amine substances and methyl acrylate as raw materials, wherein the mass ratio of the amine substances to the methyl acrylate is 1:4-1:64, adding the amine substances to an alcohol solvent into a reactor, slowly dropwise adding the methyl acrylate under the ice water bath condition, uniformly mixing, heating to 15-50 ℃, carrying out Michael addition reaction for 1-48 h at the constant temperature to obtain a 0.5-generation polyamide-amine dendrimer, and carrying out reduced pressure distillation at the temperature of 50-70 ℃ and the pressure of 133Pa to remove the methanol solvent and excessive methyl acrylate;
(2) 1.0 Synthesis of Polyamide-amine dendrimers: dissolving the 0.5-generation polyamide-amine dendrimer obtained in the step (1) by using an alcohol solvent, adding the solution into a reactor, slowly dropwise adding excessive amine substances under the ice water bath condition, wherein the mass ratio of the amine substances of the 0.5-generation polyamide-amine dendrimer is 1:4-1:64, uniformly mixing, heating to 15-50 ℃ for reacting for 1-48 h to obtain the 1.0-generation polyamide-amine dendrimer, and carrying out reduced pressure distillation at the temperature of 60-80 ℃ and the pressure of 133Pa to remove the methanol solvent and the excessive amine substances;
(3) Synthesis of supramolecular polyether intermediates
Adding polyamide-amine dendrimer obtained through the steps into a high-temperature high-pressure reaction kettle as an initiator and a catalyst, blowing out air in the reaction kettle for 15min by using nitrogen, vacuumizing the reaction kettle, heating to a preset temperature, slowly adding an epoxy compound 1 into the reaction kettle to react to negative pressure, slowly adding an epoxy compound 2 into the reaction kettle to react to negative pressure, finally cooling, opening the kettle, discharging, and adding glacial acetic acid to regulate the PH of a product to obtain a supermolecule polyether intermediate; in the whole reaction process, the pressure in the reaction kettle is controlled to be not higher than 0.4MPa, the reaction temperature is controlled to be 120-150 ℃ when the reaction kettle reacts with the epoxy compound 1, the reaction temperature is controlled to be 100-130 ℃ when the reaction kettle reacts with the epoxy compound 2, the mass ratio of the initiator to the epoxy compound 1 is 1:9-1:199, and the mass ratio of the epoxy compound 1 to the epoxy compound 2 is 1:1-4:1;
(4) Synthesis of supermolecular polyether by crosslinking reaction
Adding the supermolecular polyether intermediate obtained in the step (3) into a reactor, dropwise adding a cross-linking agent under stirring at the temperature of 15-50 ℃, and reacting for 0.5-5 h to obtain the supermolecular polyether, wherein the mass ratio of the supermolecular polyether intermediate to the cross-linking agent is 5:1-30:1.
Preferably, the amine substances in the steps (1) and (2) are selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine, preferably ethylenediamine.
Preferably, the alcoholic solvent of step (1) and (2) is selected from methanol, ethanol, butanol, propylene glycol and ethylene glycol, preferably methanol.
Preferably, the product obtained in the step (2) is reacted with methyl acrylate again (without adding amine substances) in the same manner as in the step (1) to obtain polyamide-amine dendrimers with half generations, such as 1.5 generation, 2.5 generation, 3.5 generation and 4.5 generation … …, and the dosage of the methyl acrylate is gradually increased in proportion during each amplification; similarly, the polyamide-amine dendrimer which is reacted with methyl acrylate to obtain half-generation increase is reacted with amine substances again in the same way as the step (2), so that the polyamide-amine dendrimer which is further half-generation increase is obtained, for example, the polyamide-amine dendrimer is 2.0 generation, 3.0 generation, 4.0 generation and 5.0 generation of … …, and the dosage of the amine substances is gradually increased in proportion during each amplification.
Preferably, the polyamide-amine dendrimer used as the initiator in step (3) is a 1.0 to 5.0 generation polyamide-amine dendrimer, more preferably, the polyamide-amine dendrimer used as the initiator is a 2.0 to 4.0 generation polyamide-amine dendrimer.
Preferably, the epoxy compound 1 in step (3) is ethylene oxide, propylene oxide or butylene oxide, preferably propylene oxide.
Preferably, the epoxy compound 2 of step (3) is ethylene oxide, propylene oxide or butylene oxide, preferably ethylene oxide.
Preferably, the epoxy compound 1 and the epoxy compound 2 in the step (3) are not the same.
Preferably, the base in step (3) is sodium hydroxide, potassium hydroxide or lithium hydroxide, preferably potassium hydroxide.
Preferably, the crosslinking agent in the step (4) is toluene diisocyanate, epichlorohydrin, epoxy resin oligomer (theoretical molecular weight 500-2000), preferably epichlorohydrin.
According to another aspect of the invention, the invention provides a demulsification clear water integrated supermolecule polyether, which is prepared by the preparation method according to the invention.
According to another aspect of the invention, the invention also provides the application of the demulsification and clean water integrated supermolecular polyether in the demulsification and dehydration of crude oil and the treatment of oily sewage, particularly crude oil produced liquid of offshore oil fields and oily sewage.
The beneficial effects of the invention are as follows:
1. the preparation method of the demulsification and clear water integrated supermolecule polyether is simple to operate, low in material cost and environment-friendly.
2. The synthesized demulsification and clear water integrated supermolecular polyether can effectively treat the generated oily sewage while demulsification and dehydration are carried out on the crude oil produced liquid, and can effectively improve the problems of equipment blockage and pipeline corrosion and viscous sludge in the clear water process, thereby bringing great convenience to the treatment of the crude oil produced liquid of an offshore oilfield, greatly simplifying the flow, shortening the operation time, greatly reducing the chemical agent addition and reducing the treatment cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 shows the dehydration rate of crude oil produced from the demulsified clear water integrated supramolecular polyethers synthesized in examples 1 to 5.
Fig. 2 shows the oil removal rate of the demulsified clear water integrated supramolecular polyethers synthesized in examples 1 to 5.
FIG. 3 is an infrared spectrum of a 3-substituted polyamide-amine dendrimer prepared in the step (2) of example 1.
FIG. 4 is an infrared spectrum of the supramolecular polyether prepared in step (4) of example 1.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
"comprising," "having," "containing," or any other similar language, are open ended terms that are intended to cover a non-exclusive inclusion. For example, a composition or article comprising a plurality of elements is not limited to only those elements listed herein, but may include other elements not explicitly listed but typically inherent to such composition or article. In addition, unless explicitly stated to the contrary, the term "or" refers to an inclusive "or" and not to an exclusive "or". For example, any one of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent), a is false (or absent) and B is true (or present), a and B are both true (or present). Furthermore, the terms "comprising," "including," "having," "containing," and their derivatives, as used herein, are intended to be open ended terms that have been specifically disclosed and encompass both the closed and semi-closed terms, consisting of …, and consisting essentially of ….
All features or conditions defined herein in terms of numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values within the range, particularly integer values. For example, a range description of "1 to 8" should be taken as having specifically disclosed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly sub-ranges defined by all integer values, and should be taken as having specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, etc. within the range. The foregoing explanation applies to all matters of the invention throughout its entirety unless indicated otherwise, whether or not the scope is broad.
If an amount or other numerical value or parameter is expressed as a range, preferred range, or a series of upper and lower limits, then it is understood that any range, whether or not separately disclosed, from any pair of the upper or preferred value for that range and the lower or preferred value for that range is specifically disclosed herein. Furthermore, where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the accuracy of the numerical significance of the numerical values provided that the objectives of the present invention are achieved. For example, the number 40.0 is understood to cover a range from 39.50 to 40.49.
In the preparation method according to the present invention, the step (1) and the step (2) are preparation steps for preparing a polyamide-amine dendrimer as a subsequent initiator, wherein first a 0.5-generation polyamide-amine dendrimer is obtained by a reaction of an amine substance and methyl acrylate, then methyl acrylate and an amine substance are alternately added, and the amount of methyl acrylate or amine substance added each time is proportionally increased, so that the polyamide-amine dendrimer is gradually grown into a dendrimer containing a plurality of branches.
Wherein, the product obtained in the step (2) is reacted with methyl acrylate (without adding amine substances) again according to the same mode of the step (1) to obtain polyamide-amine dendrimer which is increased by half, for example, 1.5 generation, 2.5 generation, 3.5 generation and 4.5 generation … …, and the dosage of the methyl acrylate is gradually increased in proportion during each amplification; similarly, the polyamide-amine dendrimer which is reacted with methyl acrylate to obtain half-generation increase is reacted with amine substances again in the same way as the step (2), so that the polyamide-amine dendrimer which is further half-generation increase is obtained, for example, the polyamide-amine dendrimer is 2.0 generation, 3.0 generation, 4.0 generation and 5.0 generation of … …, and the dosage of the amine substances is gradually increased in proportion during each amplification. In this way dendrimers with the desired structure and molecular weight can be obtained.
In the preparation method according to the present invention, the polyamide-amine dendrimer obtained by alternately performing the step (1) and the step (2) is further polymerized with an epoxy compound as an initiator to further form a polymerized long chain structure. And the polymerization may be carried out using one or more epoxy compounds, preferably using two or more different epoxy compound monomers, to form different blocks. Taking Propylene Oxide (PO) and Ethylene Oxide (EO) as examples, in the method of the invention, firstly preparing a polyamide-amine dendrimer as a core structure, then adding propylene oxide (PO, epoxy compound 1) for first polymerization to form a propoxy block, connecting the propoxy block with the polyamide-amine dendrimer through a large amount of amino groups in the polyamide-amine dendrimer, and then adding ethylene oxide (EO, epoxy compound 2) for second polymerization to form an ethoxy block at the periphery of the propoxy block.
Preferably, the polyamide-amine dendrimer used as the initiator in step (3) is a 1.0 to 5.0 generation polyamide-amine dendrimer, more preferably, the polyamide-amine dendrimer used as the initiator is a 2.0 to 4.0 generation polyamide-amine dendrimer.
Example 1
(1) Synthesis of 0.5-generation Polyamide-amine dendrimers:
the ethylene diamine and the methyl acrylate are used as raw materials, and the mass ratio of the ethylene diamine to the methyl acrylate is 1:8. 9g (0.15 mol) of ethylenediamine and 32g (1.0 mol) of methyl acrylate are added into a three-necked flask, 103.2g (1.2 mol) of methyl acrylate is slowly dripped under the ice water bath condition, michael addition reaction is carried out at the constant temperature of 25 ℃ for 24 hours after the dripping is finished, the product is distilled under reduced pressure at 50 ℃ and 133Pa to remove the methanol solvent and excessive methyl acrylate, and the obtained light yellow liquid is 0.5-generation polyamide-amine dendrimer.
(2) 1.0 Synthesis of Polyamide-amine dendrimers:
the 0.5-generation polyamide-amine dendrimer and ethylenediamine prepared in the step (1) are adopted as raw materials, and the mass ratio of the 0.5-generation polyamide-amine dendrimer to the ethylenediamine is 1:24. 20.2g (0.05 mol) of 0.5-substituted polyamide-amine dendrimer and 64g (2.0 mol) of methanol are added into a three-neck flask, 72g (1.2 mol) of ethylenediamine is slowly added dropwise under the ice water bath condition, michael addition reaction is carried out for 24 hours at the constant temperature of 25 ℃ after the dropwise addition is finished, and the product is distilled under reduced pressure at 72 ℃ and 133Pa to remove the methanol solvent and excessive ethylenediamine, so that the light yellow viscous liquid is 1.0-substituted polyamide-amine dendrimer.
And repeating the step (1) on the basis, but only adding methyl acrylate, and not adding ethylenediamine, so as to obtain a 1.5-generation polyamide-amine dendrimer, then adding ethylenediamine in the mode of the step (2) again to react so as to obtain a 2.0-generation polyamide-amine dendrimer, and alternately repeating the steps for 48 hours to obtain a 3-generation polyamide-amine dendrimer, wherein the figure 3 is an infrared spectrogram of the prepared 3-generation polyamide-amine dendrimer.
(3) Synthesis of supramolecular polyether intermediates
Adding 5g of the 3-generation polyamide-amine dendrimer obtained by the steps into a high-temperature high-pressure reaction kettle as an initiator and 0.7g of potassium hydroxide catalyst, blowing out air in the kettle for 15min by using nitrogen, vacuumizing the kettle, heating the reaction kettle to 130 ℃, slowly feeding 495g of Propylene Oxide (PO) into a feed inlet, controlling the pressure of the reaction kettle to be about 0.2MPa, and ending the first-step reaction when the pressure is negative pressure; 0.7g of potassium hydroxide and 183.3g of Ethylene Oxide (EO) were added to the reaction vessel in the same manner, and the reaction was completed when the reaction vessel was heated to 120℃and the pressure was negative, to obtain a supermolecular polyether intermediate. Wherein the mass ratio of the initiator to the Propylene Oxide (PO) is 1:99, and the mass ratio of the Propylene Oxide (PO) to the Ethylene Oxide (EO) is 2.7:1.
(4) Synthesis of supermolecular polyether by crosslinking reaction
Adding the intermediate obtained in the step (3) into a three-neck flask, dropwise adding epichlorohydrin at a speed of 0.5mL/min under stirring at a water bath temperature of 30 ℃, and reacting for 3 hours to obtain the supermolecular polyether. Wherein the mass ratio of the supermolecule polyether intermediate to the epichlorohydrin is 30:1, and FIG. 4 is an infrared spectrogram of the supermolecule polyether prepared in the step (4).
Example 2
(1) Synthesis of 0.5-generation Polyamide-amine dendrimers:
the material ratio of diethylenetriamine to methyl acrylate is 1:24. 15.5g (0.15 mol) of diethylenetriamine and 46g (1.0 mol) of ethanol are added into a three-neck flask, 310g (3.6 mol) of methyl acrylate is slowly dripped under the ice water bath condition, michael addition reaction is carried out at the constant temperature of 30 ℃ for 20 hours after the dripping is finished, the product is distilled under reduced pressure at 55 ℃ and the pressure of 133Pa to remove the ethanol solvent and excessive methyl acrylate, and the obtained light yellow liquid is the 0.5-generation polyamide-amine dendrimer.
(2) 1.0 Synthesis of Polyamide-amine dendrimers:
the 0.5 generation polyamide-amine dendrimer and the diethylenetriamine prepared in the step (1) are adopted as raw materials, and the mass ratio of the 0.5 generation polyamide-amine dendrimer to the diethylenetriamine is 1:16. 20.2g (0.05 mol) of 0.5-generation polyamide-amine dendrimer and 92g (2.0 mol) of ethanol are added into a three-neck flask, 82.4g (0.8 mol) of diethylenetriamine is slowly dripped under the ice water bath condition, michael addition reaction is carried out for 20h at the constant temperature of 30 ℃ after the dripping is finished, the product is subjected to reduced pressure distillation at 65 ℃ and the pressure of 133Pa to remove the ethanol solvent and the excessive diethylenetriamine, and the obtained light yellow sticky liquid is 1.0-generation polyamide-amine dendrimer.
And (2) repeating the step (1) on the basis, but only adding methyl acrylate, and not adding diethylenetriamine any more to obtain a 1.5-generation polyamide-amine dendrimer, and then adding diethylenetriamine again in the mode of the step (2) to react for 32 hours to obtain the 2.0-generation polyamide-amine dendrimer.
(3) Synthesis of supramolecular polyether intermediates
Adding 5g of the 2-generation polyamide-amine dendrimer obtained by the steps into a high-temperature high-pressure reaction kettle as an initiator and 0.7g of potassium hydroxide catalyst, blowing out air in the kettle for 15min by using nitrogen, vacuumizing the kettle, heating the reaction kettle to 125 ℃, slowly feeding 95g of Propylene Oxide (PO) into a feed inlet, controlling the pressure of the reaction kettle to be about 0.3MPa, and ending the first-step reaction when the pressure is negative pressure; 0.7g of potassium hydroxide and 47.5g of Ethylene Oxide (EO) were added to the reaction vessel in the same manner, and the reaction was completed when the reaction vessel was heated to 115℃and the pressure was negative, to obtain a supermolecular polyether intermediate. Wherein the mass ratio of the initiator to the Propylene Oxide (PO) is 1:19 and the mass ratio of the Propylene Oxide (PO) to the Ethylene Oxide (EO) is 2.0:1.
(4) Synthesis of supermolecular polyether by crosslinking reaction
Adding the intermediate obtained in the step (3) into a three-neck flask, dropwise adding epichlorohydrin at a speed of 0.5mL/min under stirring at a water bath temperature of 20 ℃, and reacting for 2.5h to obtain the supermolecular polyether. Wherein the mass ratio of the supermolecule polyether intermediate to the epichlorohydrin is 25:1.
Example 3
(1) Synthesis of 0.5-generation Polyamide-amine dendrimers:
triethylene tetramine and methyl acrylate are used as raw materials, and the mass ratio of the Triethylene tetramine to the methyl acrylate is 1:32. 22g (0.15 mol) triethylene tetramine and 74g (1.0 mol) butanol are added into a three-neck flask, 413g (4.8 mol) methyl acrylate is slowly dripped under the ice water bath condition, michael addition reaction is carried out at the constant temperature of 35 ℃ for 18 hours after the dripping is finished, the butanol solvent and excessive methyl acrylate are removed by reduced pressure distillation at 60 ℃ and 133Pa pressure, and the obtained light yellow liquid is 0.5-generation polyamide-amine dendrimer.
(2) 1.0 Synthesis of Polyamide-amine dendrimers:
the 0.5 generation polyamide-amine dendrimer and triethylene tetramine prepared in the step (1) are adopted as raw materials, and the mass ratio of the 0.5 generation polyamide-amine dendrimer to the triethylene tetramine is 1:8. 20.2g (0.05 mol) of 0.5-generation polyamide-amine dendrimer and 148g (2.0 mol) of ethanol are added into a three-neck flask, 58.4g (0.4 mol) of triethylene tetramine is slowly dripped under the ice water bath condition, michael addition reaction is carried out for 18h at the constant temperature of 35 ℃ after the dripping is finished, the product is subjected to reduced pressure distillation at 65 ℃ and the pressure of 133Pa to remove butanol solvent and excess triethylene tetramine, and the obtained light yellow viscous liquid is 1.0-generation polyamide-amine dendrimer.
And repeating the step (1) on the basis, but only adding methyl acrylate, and not adding triethylene tetramine, so as to obtain a 1.5-generation polyamide-amine dendrimer, and then adding triethylene tetramine again in the step (2) for reacting for 28 hours, so as to obtain the 3-generation polyamide-amine dendrimer.
(3) Synthesis of supramolecular polyether intermediates
5g of the 3-generation polyamide-amine dendrimer obtained through the steps is taken as an initiator and added into a high-temperature high-pressure reaction kettle with 0.7g of sodium hydroxide catalyst, the air in the kettle is blown out by nitrogen for 15min, the interior of the kettle is pumped into a vacuum state, the reaction kettle is heated to 135 ℃, 245g of butylene oxide (PO) is slowly fed into a feed inlet, the pressure of the reaction kettle is controlled to be about 0.2MPa, and the first-step reaction is finished when the pressure is negative pressure; 0.7g of sodium hydroxide and 163.3g of Ethylene Oxide (EO) were added to the reaction vessel in the same manner, and the reaction was completed when the reaction vessel was heated to 110℃and the pressure was negative, to obtain a supermolecular polyether intermediate. Wherein the mass ratio of the initiator to the butylene oxide (PO) is 1:49 and the mass ratio of the butylene oxide (PO) to the Ethylene Oxide (EO) is 1.5:1.
(4) Synthesis of supermolecular polyether by crosslinking reaction
Adding the intermediate obtained in the step (3) into a three-neck flask, dropwise adding epichlorohydrin at a speed of 0.5mL/min under stirring at a water bath temperature of 35 ℃, and reacting for 3 hours to obtain the supermolecular polyether. Wherein the mass ratio of the supermolecule polyether intermediate to the epichlorohydrin is 20:1.
Example 4
(1) Synthesis of 0.5-generation Polyamide-amine dendrimers:
the tetraethylenepentamine and methyl acrylate are used as raw materials, and the mass ratio of the tetraethylenepentamine to the methyl acrylate is 1:48. 28g (0.15 mol) of tetraethylenepentamine and 76g (1.0 mol) of propylene glycol are added into a three-neck flask, 619g (7.2 mol) of methyl acrylate is slowly dripped under the ice water bath condition, michael addition reaction is carried out at the constant temperature of 40 ℃ for 28h after the dripping is finished, the product is distilled under reduced pressure at 65 ℃ and 133Pa to remove the propylene glycol solvent and excessive methyl acrylate, and the obtained light yellow liquid is the 0.5-generation polyamide-amine dendrimer.
(2) 1.0 Synthesis of Polyamide-amine dendrimers:
the 0.5 generation polyamide-amine dendrimer and tetraethylenepentamine prepared in the step (1) are adopted as raw materials, and the mass ratio of the 0.5 generation polyamide-amine dendrimer to the tetraethylenepentamine is 1:32. 20.2g (0.05 mol) of 0.5-generation polyamide-amine dendrimer and 152g (2.0 mol) of propylene glycol are added into a three-neck flask, 121.6g (1.6 mol) of tetraethylenepentamine is slowly dripped under the ice water bath condition, michael addition reaction is carried out at the constant temperature of 40 ℃ for 28h after dripping is finished, and the product is distilled under reduced pressure at 70 ℃ and 133Pa to remove the propylene glycol solvent and excessive tetraethylenepentamine, so that the light yellow sticky liquid is 1.0-generation polyamide-amine dendrimer.
And (3) repeating the step (1) on the basis, but only adding methyl acrylate, and not adding tetraethylenepentamine to obtain a 1.5-generation polyamide-amine dendrimer, and then adding tetraethylenepentamine to react for 36 hours according to the mode of the step (2) to obtain the 4-generation polyamide-amine dendrimer.
(3) Synthesis of supramolecular polyether intermediates
5g of the 4-generation polyamide-amine dendrimer obtained by the steps is taken as an initiator and added into a high-temperature high-pressure reaction kettle with 0.7g of lithium hydroxide catalyst, the air in the kettle is blown out by nitrogen for 15min, the kettle is pumped into a vacuum state, the reaction kettle is heated to 140 ℃, 345g of Propylene Oxide (PO) is slowly fed into a feed inlet, the pressure of the reaction kettle is controlled to be about 0.3MPa, and the first-step reaction is finished when the pressure is negative pressure; 0.7g of lithium hydroxide and 115g of Ethylene Oxide (EO) were added to a reaction vessel in the same manner, and the reaction was completed when the reaction vessel was heated to 125℃and the pressure was negative, to obtain a supermolecular polyether intermediate. Wherein the mass ratio of the initiator to Propylene Oxide (PO) is 1:69 and the mass ratio of Propylene Oxide (PO) to Ethylene Oxide (EO) is 3.0:1.
(4) Synthesis of supermolecular polyether by crosslinking reaction
Adding the intermediate obtained in the step (3) into a three-neck flask, dropwise adding epichlorohydrin at a speed of 0.5mL/min under stirring at a water bath temperature of 40 ℃, and reacting for 3.5h to obtain the supermolecular polyether. Wherein the mass ratio of the supermolecule polyether intermediate to the epichlorohydrin is 15:1.
Example 5
(1) Synthesis of 0.5-generation Polyamide-amine dendrimers:
polyethylene polyamine and methyl acrylate are used as raw materials, and the mass ratio of the polyethylene polyamine to the methyl acrylate is 1:16. Adding 0.15mol of polyethylene polyamine and 62g (1.0 mol) of ethylene glycol into a three-neck flask, slowly dropwise adding 206.4g (2.4 mol) of methyl acrylate under the ice water bath condition, carrying out Michael addition reaction for 30h at the constant temperature of 45 ℃ after the dropwise adding, and carrying out reduced pressure distillation on the product at the temperature of 55 ℃ and the pressure of 133Pa to remove the ethylene glycol solvent and excessive methyl acrylate, wherein the obtained light yellow liquid is the 0.5-generation polyamide-amine dendrimer.
(2) 1.0 Synthesis of Polyamide-amine dendrimers:
the 0.5 generation polyamide-amine dendrimer and polyethylene polyamine prepared in the step (1) are adopted as raw materials, and the mass ratio of the 0.5 generation polyamide-amine dendrimer to the tetraethylenepentamine is 1:4. 20.2g (0.05 mol) of 0.5-generation polyamide-amine dendrimer and 124g (2.0 mol) of ethylene glycol are added into a three-neck flask, 0.2mol of polyethylene polyamine is slowly dripped under the ice water bath condition, michael addition reaction is carried out at the constant temperature of 45 ℃ for 30 hours after the dripping is finished, and the product is distilled under reduced pressure at 75 ℃ and 133Pa to remove the propylene glycol solvent and excessive polyethylene polyamine, so that the light yellow sticky liquid is 1.0-generation polyamide-amine dendrimer.
And repeating the step (1) on the basis, but only adding methyl acrylate, and not adding tetraethylenepentamine to obtain a 1.5-generation polyamide-amine dendrimer, and then adding tetraethylenepentamine to react for 48 hours according to the mode of the step (2) to obtain the 2-generation polyamide-amine dendrimer.
(3) Synthesis of supramolecular polyether intermediates
Adding 5g of the 2-generation polyamide-amine dendrimer obtained by the steps into a high-temperature high-pressure reaction kettle as an initiator and 0.7g of lithium hydroxide catalyst, blowing out air in the kettle for 15min by using nitrogen, vacuumizing the kettle, heating the reaction kettle to 145 ℃, slowly feeding 795g of butylene oxide (PO) into a feed inlet, controlling the pressure of the reaction kettle to be about 0.3MPa, and ending the first-step reaction when the pressure is negative pressure; 0.7g of lithium hydroxide and 214.9g of Ethylene Oxide (EO) were added to a reaction vessel in the same manner, and the reaction was completed when the reaction vessel was heated to 130℃and the pressure was negative, to obtain a supermolecular polyether intermediate. Wherein the mass ratio of initiator to butylene oxide (PO) is 1:159 and the mass ratio of butylene oxide (PO) to Ethylene Oxide (EO) is 3.7:1.
(4) Synthesis of supermolecular polyether by crosslinking reaction
Adding the intermediate obtained in the step (3) into a three-neck flask, dropwise adding epichlorohydrin at a speed of 0.5mL/min under stirring at a water bath temperature of 45 ℃, and reacting for 4.5h to obtain the supermolecular polyether. Wherein the mass ratio of the supermolecule polyether intermediate to the epichlorohydrin is 10:1.
Test examples
The measurement of the indoor performance of the crude oil demulsifier is carried out according to the SY/T5281-2000 crude oil demulsifier using performance detection method (bottle test method).
The step of measuring the oil removal rate is carried out according to a spectrophotometry method for measuring the oil content in the produced water of a SY/T0530-2011 oil field.
Table 1 shows the results of the demulsification performance evaluation experiment of the demulsification clear water integrated supermolecular polyether prepared in examples 1 to 5, wherein the demulsification clear water integrated supermolecular polyether prepared in examples 1 to 5 is added to the crude oil produced liquid (the water content is 45%) of a certain offshore oil field for treatment, the treatment temperature is 65 ℃, the effect is good, and the results are shown in the attached table 1. The on-site agent in table 1 is an SP polyether crude oil demulsifier synthesized from an alcohol compound as an initiator (Tianjin metallocene chemical reagent plant 20200907).
Crude oil dehydration rate = volume of dehydrated water/crude oil original volume x 100%
Table 2 shows the results of the evaluation experiments of the clear water properties of 5 demulsified clear water integrated supramolecular polyethers prepared according to examples 1 to 5.
Wherein a certain offshore oily wastewater (oil content 4724 mg/L) is added with the demulsified clear water integrated supermolecular polyether prepared in the examples 1 to 5 for treatment, the treatment temperature is 60 ℃, the effect is good, and the result is shown in the attached table 2. The site agent in table 2 is a polyacrylamide water scavenger and the comparative agent is a polydimethyldiallyl ammonium chloride cationic water scavenger (national drug group chemical reagent company 20200109, national drug group chemical reagent company 20200803).
Oil removal rate = (oil content in initial produced water-oil content in current produced water)/oil content in initial produced water×100%
Fig. 1 is a graph showing the dehydration rate of the demulsified clear water integrated supramolecular polyethers prepared according to examples 1 to 5.
FIG. 2 shows the oil removal rate of the demulsified clear water-integrated supramolecular polyethers prepared according to examples 1 to 5
TABLE 1
TABLE 2
| Medicament name | Dosage (mg/L) | Oil content (mg/L) | Whether or not there is wall-sticking sludge | Water colour |
| On-site medicament | 100 | 724 | Has (relatively serious) | Cleaner (cleaner) |
| Contrast agent | 100 | 865 | Has (relatively serious) | Cleaner (cleaner) |
| Example 1 | 100 | 136 | Without any means for | Clearing heat |
| Example 2 | 100 | 23 | Without any means for | Clearing heat |
| Example 3 | 100 | 358 | Without any means for | Clearing heat |
| Example 4 | 100 | 190 | Without any means for | Clearing heat |
| Example 5 | 100 | 534 | Without any means for | Clearing heat |
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A demulsification and clean water integrated supermolecule polyether preparation method comprises the following steps:
(1) Synthesis of 0.5-generation Polyamide-amine dendrimers: the preparation method comprises the steps of adopting amine substances and methyl acrylate as raw materials, wherein the mass ratio of the amine substances to the methyl acrylate is 1:4-1:64, adding the amine substances to an alcohol solvent into a reactor, slowly dropwise adding the methyl acrylate under the ice water bath condition, uniformly mixing, heating to 15-50 ℃, carrying out Michael addition reaction for 1-48 h at the constant temperature to obtain a 0.5-generation polyamide-amine dendrimer, and carrying out reduced pressure distillation at the temperature of 50-70 ℃ and the pressure of 133Pa to remove the methanol solvent and excessive methyl acrylate;
(2) 1.0 Synthesis of Polyamide-amine dendrimers: dissolving the 0.5-generation polyamide-amine dendrimer obtained in the step (1) by using an alcohol solvent, adding the solution into a reactor, slowly dropwise adding excessive amine substances under the ice water bath condition, wherein the mass ratio of the amine substances of the 0.5-generation polyamide-amine dendrimer is 1:4-1:64, uniformly mixing, heating to 15-50 ℃ for reacting for 1-48 h to obtain the 1.0-generation polyamide-amine dendrimer, and carrying out reduced pressure distillation at the temperature of 60-80 ℃ and the pressure of 133Pa to remove the methanol solvent and the excessive amine substances;
(3) Synthesis of supramolecular polyether intermediates
Adding polyamide-amine dendrimer obtained through the steps into a high-temperature high-pressure reaction kettle as an initiator and a catalyst, blowing out air in the reaction kettle for 15min by using nitrogen, vacuumizing the reaction kettle, heating to a preset temperature, slowly adding an epoxy compound 1 into the reaction kettle to react to negative pressure, slowly adding an epoxy compound 2 into the reaction kettle to react to negative pressure, finally cooling, opening the kettle, discharging, and adding glacial acetic acid to regulate the PH of a product to obtain a supermolecule polyether intermediate; in the whole reaction process, the pressure in the reaction kettle is controlled to be not higher than 0.4MPa, the reaction temperature is controlled to be 120-150 ℃ when the reaction kettle reacts with the epoxy compound 1, the reaction temperature is controlled to be 100-130 ℃ when the reaction kettle reacts with the epoxy compound 2, the mass ratio of the initiator to the epoxy compound 1 is 1:9-1:199, and the mass ratio of the epoxy compound 1 to the epoxy compound 2 is 1:1-4:1;
(4) Synthesis of supermolecular polyether by crosslinking reaction
Adding the supermolecular polyether intermediate obtained in the step (3) into a reactor, dropwise adding a cross-linking agent under stirring at the temperature of 15-50 ℃, and reacting for 0.5-5 h to obtain the supermolecular polyether, wherein the mass ratio of the supermolecular polyether intermediate to the cross-linking agent is 5:1-30:1.
2. The method for preparing supermolecular polyether according to claim 1, wherein the amine substances in step (1) and (2) are selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylenepolyamine, preferably ethylenediamine.
3. The method for preparing supermolecular polyether according to claim 1, wherein the alcoholic solvent in step (1) and (2) is selected from methanol, ethanol, butanol, propylene glycol and ethylene glycol, preferably methanol.
4. The method for preparing supermolecular polyether according to claim 1, wherein the product obtained in step (2) is reacted with methyl acrylate (without amine substances) again in the same manner as in step (1) to obtain polyamide-amine dendrimer with half generation added, such as generation 1.5, generation 2.5, generation 3.5 and generation 4.5 of … …, and the amount of methyl acrylate is gradually increased in proportion during each amplification; similarly, the polyamide-amine dendrimer which is reacted with methyl acrylate to obtain half-generation increase is reacted with amine substances again in the same way as the step (2), so that the polyamide-amine dendrimer which is further half-generation increase is obtained, for example, the polyamide-amine dendrimer is 2.0 generation, 3.0 generation, 4.0 generation and 5.0 generation of … …, and the dosage of the amine substances is gradually increased in proportion during each amplification.
5. The method for producing the supramolecular polyether according to claim 1, wherein the polyamide-amine dendrimer as initiator in step (3) is 1.0 to 5.0 generation polyamide-amine dendrimer, more preferably the polyamide-amine dendrimer as initiator is 2.0 to 4.0 generation polyamide-amine dendrimer;
preferably, the epoxy compound 1 of step (3) is ethylene oxide, propylene oxide or butylene oxide, preferably propylene oxide;
preferably, the epoxy compound 2 of step (3) is ethylene oxide, propylene oxide or butylene oxide, preferably ethylene oxide;
preferably, the epoxy compound 1 and the epoxy compound 2 of the step (3) are not the same;
preferably, the base in step (3) is sodium hydroxide, potassium hydroxide or lithium hydroxide, preferably potassium hydroxide.
6. The method for preparing supermolecular polyether according to claim 1, wherein the crosslinking agent in the step (4) is toluene diisocyanate, epichlorohydrin, epoxy resin oligomer (theoretical molecular weight 500-2000), preferably epichlorohydrin.
7. A demulsification clean water integrated supramolecular polyether prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the demulsified and clear water integrated supermolecular polyether according to claim 7 for demulsification and dehydration of crude oil and for treatment of oily sewage, in particular crude oil produced from offshore fields and oily sewage.
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