CN115058261A - Novel modified efficient compound crude oil demulsifier - Google Patents
Novel modified efficient compound crude oil demulsifier Download PDFInfo
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- CN115058261A CN115058261A CN202210864721.1A CN202210864721A CN115058261A CN 115058261 A CN115058261 A CN 115058261A CN 202210864721 A CN202210864721 A CN 202210864721A CN 115058261 A CN115058261 A CN 115058261A
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- demulsifier
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- crude oil
- polyether
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- 239000010779 crude oil Substances 0.000 title claims abstract description 62
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 85
- 229920000570 polyether Polymers 0.000 claims abstract description 85
- 239000003921 oil Substances 0.000 claims abstract description 81
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 50
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 45
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 polyethylene Polymers 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004698 Polyethylene Substances 0.000 claims abstract description 25
- 230000032050 esterification Effects 0.000 claims abstract description 25
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- 229920000768 polyamine Polymers 0.000 claims abstract description 25
- 229920000573 polyethylene Polymers 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000008096 xylene Substances 0.000 claims abstract description 20
- 150000004715 keto acids Chemical class 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 17
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012530 fluid Substances 0.000 claims abstract description 10
- 239000002585 base Substances 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 9
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 40
- 239000004094 surface-active agent Substances 0.000 claims description 33
- 239000004593 Epoxy Substances 0.000 claims description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 27
- 239000003381 stabilizer Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 17
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 16
- 239000013067 intermediate product Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- 239000008098 formaldehyde solution Substances 0.000 claims description 8
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 8
- 229940107700 pyruvic acid Drugs 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000011033 desalting Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011964 heteropoly acid Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 150000004716 alpha keto acids Chemical class 0.000 claims description 4
- 150000004718 beta keto acids Chemical class 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- 150000004721 gamma keto acids Chemical class 0.000 claims description 4
- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 claims description 4
- VTESCYNPUGSWKG-UHFFFAOYSA-N (4-tert-butylphenyl)hydrazine;hydrochloride Chemical compound [Cl-].CC(C)(C)C1=CC=C(N[NH3+])C=C1 VTESCYNPUGSWKG-UHFFFAOYSA-N 0.000 claims description 2
- QARDSQYLYGISQN-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole;hydrochloride Chemical compound [Cl-].CN1C[NH+](C=C)C=C1 QARDSQYLYGISQN-UHFFFAOYSA-N 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001903 2-oxo-3-phenylpropanoic acid Substances 0.000 claims description 2
- TYEYBOSBBBHJIV-UHFFFAOYSA-N 2-oxobutanoic acid Chemical compound CCC(=O)C(O)=O TYEYBOSBBBHJIV-UHFFFAOYSA-N 0.000 claims description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- DEDGUGJNLNLJSR-UHFFFAOYSA-N alpha-hydroxycinnamic acid Natural products OC(=O)C(O)=CC1=CC=CC=C1 DEDGUGJNLNLJSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229950008882 polysorbate Drugs 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 208000005156 Dehydration Diseases 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 6
- 229920000053 polysorbate 80 Polymers 0.000 description 6
- 229940068968 polysorbate 80 Drugs 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of demulsifiers, and provides a novel modified efficient compound type crude oil demulsifier, which comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier; the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst; the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin; the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol; the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 1-2: 1-4 to obtain the modified high-efficiency compounded crude oil demulsifier.
Description
Technical Field
The invention relates to the field of demulsifiers, in particular to a novel modified efficient compound type crude oil demulsifier.
Background
The demulsifier is one of the most used oil field chemicals in the petroleum industry, and is mainly used in the processes of crude oil gathering, transportation and refining. At the end of the nineties, all large oil fields in China have entered the late stage of secondary oil recovery and the tertiary oil recovery stage. In order to maintain the yield of crude oil, measures for increasing water injection and improving the liquid production capacity of an oil well are adopted in each oil field in a large area, and the water content of the crude oil produced liquid and the proportion of thick oil are rapidly increased.
The heavy crude oil and the light crude oil are generally divided into heavy crude oil with the density of more than 0.934g/cm3 according to the density. With the annual reduction of the recoverable reserves of common crude oil, the heavy oil becomes the main energy source in the 21 st century, but the heavy oil is difficult to recover, so the difficulty of the utilization of the heavy oil is increased. At the end of the 90 s in the 20 th century, the yield of oil fields gradually decreases, and in order to maintain the yield of crude oil, each oil field adopts a method of increasing water injection to improve the yield of crude oil, so that the water content of produced liquid of an oil well rapidly rises, and many oil fields are in development stages of medium and high water content periods. Meanwhile, the application of a large amount of oil extraction additives in various adoption processes also makes the composition of crude oil, especially the produced fluid of thick oil more complex, so that the efficient and rapid demulsification of the thick oil and the extra thick oil becomes a key technology which influences the oil extraction cost, the quality and the yield of the crude oil and controls the environmental pollution of an oil field. The thick oil is characterized by containing more asphaltene and colloid, and the colloid and the asphalt can be adsorbed on an oil-water interface to reduce the interfacial tension and ensure that a crude oil emulsion becomes very stable, so that the dehydration of the thick oil is more difficult than the dehydration of common crude oil.
As in application No.: CN88107715.1 discloses a high-efficiency thick oil demulsifier and a preparation method thereof, the invention sulfats multi-branched ethylene oxide (Eo) and propylene oxide (Po) block copolyether, and then adds special synergistic additives and solvents to obtain the high-efficiency thick oil demulsifier.
As in application No.: CN98113742.3 discloses a crude oil demulsifier for oil field crude oil gathering, transportation and dehydration treatment and a preparation method thereof. The crude oil demulsifier uses ethylene glycol or propylene glycol as an initiator, and a mixture of alkaline earth metal compounds and alkali metal hydroxides as a catalyst to initiate copolymerization of ethylene oxide and propylene oxide to obtain linear polyether, and the linear polyether reacts with polyisocyanate in an aromatic solvent to obtain the crude oil demulsifier.
However, the demulsifier has poor water solubility, and because the molecular structure of the demulsifier only contains nonionic functional groups, strong interaction does not exist on some electronegative surfaces of crude oil, so that the defects of poor demulsification effect or poor adaptability are caused; the dewatering performance is poor and the speed is slow.
Disclosure of Invention
In order to solve the problem that the demulsifier has poor water solubility, the demulsifier has the defects of poor demulsification effect or poor adaptability due to the fact that the molecular structure of the demulsifier only contains nonionic functional groups, and strong interaction does not exist on some electronegative surfaces of crude oil; the invention provides a novel modified efficient compound type crude oil demulsifier, which solves the problems of poor dehydration performance and low speed.
In order to achieve the purpose, the invention provides the following technical scheme:
a novel modified efficient compound crude oil demulsifier comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 1-2: 1-4 to obtain the modified high-efficiency compounded crude oil demulsifier.
Preferably, the preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 80-90 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 1.5-2.5 h;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 1-2 h;
s4: adding an esterification catalyst, heating to 110-150 ℃, continuing stirring for 3-5 h, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
Preferably, the esterification catalyst is concentrated sulfuric acid, toluenesulfonic acid, trifluoromethanesulfonic acid, heteropolyacids and organic sulfonic acids.
Preferably, the vinyl imidazole ionic liquid is 1-allyl-3-methylimidazole chloride or 1-vinyl-3-methylimidazole chloride.
Preferably, the preparation of the high-water emulsion breaker comprises the following steps:
s1: dripping formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at the temperature of 30-60 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1-2:1-2:3-5, then heating to 100 ℃ and reacting at the temperature of 150 ℃ for 1-5h, and cooling to obtain an initiator;
s2: under the conditions of 115-145 ℃ and 0.25-0.5MPa, the initiator, ethylene oxide and propylene oxide are polymerized under the catalysis of KOH, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1-2:5-6, and the polyether is obtained by neutralizing with acetic acid, filtering and desalting;
s3: diluting polyether with xylene solution at the temperature of 100-150 ℃ and under the pressure of 0.1-0.6MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of the polyether to the epoxy chloropropane is 1-1.5: 3-5;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3-5: 0.5-1, stirring for reaction for 0.5-1.5h, heating to 70-110 ℃, reacting for 12-30h, and reacting with epichlorohydrin to obtain epoxy polyether B;
s5: epoxy polyether A and epoxy polyether B are mixed in a molar ratio of 1-1.1: dissolving in xylene at a ratio of 0.9-1.2 to obtain the high-water-content demulsifier.
Preferably, the preparation of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 30-60 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 30-60 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
Preferably, in S2, the keto acid is one or more of an α -keto acid, a β -keto acid, and a γ -keto acid, and the alkynol is one or more of propiolic alcohol and 3-methylbutynol.
Preferably, the alpha-ketoacid is one or more of pyruvic acid, 2-ketobutyric acid, phenylpyruvic acid and benzoylformic acid; the beta-keto acid is acetoacetic acid; the gamma-keto acid is 4-pentanoic acid.
Preferably, the compounding of the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier comprises the following steps:
s1: adding the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier in a weight ratio of 1-2: 1-4 into a reaction kettle, stirring for 0.5-1h, and heating to 50-80 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 50-80 ℃, and continuously stirring for 1-2 hours, wherein the mass part of the surfactant is 8% -12%; the mass portion of the stabilizer is 4.5-8%.
Preferably, the surfactant is a polysorbate or a polyoxyethylene fatty acid ester; the stabilizer is one of ammonium sulfate, ammonium carbonate or sodium sulfate.
The invention has the advantages that: in the demulsifier, the modified demulsifier is obtained by the chain extension action of vinyl imidazole ionic liquid monomer and acrylic acid copolymerization on polyether molecules, and the molecular chain of the modified demulsifier contains cationic and nonionic functional groups at the same time, so that the modified demulsifier can have strong action with some electronegative surfaces of crude oil, and is converted into a thermodynamically unstable system to realize oil-water separation; in the thick oil demulsifier, the raw materials comprise polyether, keto acid, alkynol and water, can be rapidly dispersed into an oil-water emulsion, and has good demulsification performance on a crude oil emulsion. The component keto acid has weaker acidity and low corrosivity, and the alkynol has the functions of a solvent on one hand and the functions of rust prevention and corrosion prevention on the other hand, so that the corrosivity problem of the conventional demulsifier product is well solved; the high-water-content demulsifier has good dehydration effect and high dehydration rate; the novel modified efficient compound crude oil demulsifier is prepared by compounding the modified demulsifier, the thickened oil demulsifier and the high-water-content demulsifier as raw materials and adding the solubilizer and the stabilizer, has high stability, good demulsification effect, good dehydration effect, short dehydration time and strong adaptability, and can be used for demulsifying oil products such as thickened oil.
Detailed Description
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the drawings, which are based on the orientations and positional relationships indicated in the drawings, and are used for convenience in describing the present invention and for simplicity in description, but do not indicate or imply that the device or element so referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The first embodiment is as follows:
a novel modified efficient compound crude oil demulsifier comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 1:1 to obtain the modified high-efficiency compounded crude oil demulsifier.
The preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 85 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 2 hours;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 2 h;
s4: adding an esterification catalyst, heating to 140 ℃, continuously stirring for 4 hours, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
The esterification catalyst is heteropoly acid.
The vinyl imidazole ionic liquid is chlorinated 1-allyl-3-methylimidazole.
The preparation method of the high-water-content demulsifier comprises the following steps:
s1: dropwise adding a formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at 50 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1:1:3, heating to 140 ℃, reacting for 3 hours, and cooling to obtain an initiator;
s2: at the temperature of 140 ℃ and under the pressure of 0.5MPa, the initiator, ethylene oxide and propylene oxide are polymerized under the catalysis of KOH, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1:5, and the polyether is obtained by neutralizing with acetic acid, filtering and desalting;
s3: diluting polyether with xylene solution at 140 ℃ and 0.5MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of polyether to epoxy chloropropane is 1: 3;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3: 1, stirring and reacting for 1h, heating to 100 ℃, reacting for 24h, and reacting with epoxy chloropropane to obtain epoxy polyether B;
s5: epoxy polyether A and epoxy polyether B are mixed in a molar ratio of 1: dissolving the mixture in dimethylbenzene according to the proportion of 1 to obtain the high-water-content demulsifier.
The preparation of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 50 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 50 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
In the S2, the keto acid is pyruvic acid, and the alkynol is propargyl alcohol.
The compounding of the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier comprises the following steps:
s1: adding a modified demulsifier, a high-water-content demulsifier and a thick oil demulsifier in a weight ratio of 1:1 into a reaction kettle, stirring for 1h, and heating to 60 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 60 ℃, and continuing stirring for 2 hours, wherein the mass part of the surfactant is 10%; the mass portion of the stabilizer is 6%.
The surfactant is polysorbate-80; the stabilizer is sodium sulfate.
The second embodiment:
a novel modified efficient compound crude oil demulsifier comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 1: 2:1 to obtain the modified high-efficiency compounded crude oil demulsifier.
The preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 85 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 2 hours;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 2 h;
s4: adding an esterification catalyst, heating to 140 ℃, continuously stirring for 4 hours, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
The esterification catalyst is heteropoly acid.
The vinyl imidazole ionic liquid is chlorinated 1-allyl-3-methylimidazole.
The preparation method of the high-water-content demulsifier comprises the following steps:
s1: dropwise adding a formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at 50 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1:1:3, heating to 140 ℃, reacting for 3 hours, and cooling to obtain an initiator;
s2: at the temperature of 140 ℃ and under the pressure of 0.5MPa, the initiator, ethylene oxide and propylene oxide are polymerized under the catalysis of KOH, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1:5, and the polyether is obtained by neutralizing with acetic acid, filtering and desalting;
s3: diluting polyether with xylene solution at 140 ℃ and 0.5MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of polyether to epoxy chloropropane is 1: 3;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3: 1, stirring and reacting for 1h, heating to 100 ℃, reacting for 24h, and reacting with epoxy chloropropane to obtain epoxy polyether B;
s5: epoxy polyether A and epoxy polyether B are mixed in a molar ratio of 1: dissolving the mixture in dimethylbenzene according to the proportion of 1 to obtain the high-water-content demulsifier.
The preparation of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 50 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 50 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
In the S2, the keto acid is pyruvic acid, and the alkynol is propargyl alcohol.
The compounding of the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier comprises the following steps:
s1: adding a modified demulsifier, a high-water-content demulsifier and a thick oil demulsifier in a weight ratio of 1: 2:1 into a reaction kettle, stirring for 1h, and heating to 60 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 60 ℃, and continuing stirring for 2 hours, wherein the mass part of the surfactant is 10%; the mass portion of the stabilizer is 6%.
The surfactant is polysorbate-80; the stabilizer is sodium sulfate.
Example three:
a novel modified efficient compound crude oil demulsifier comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 1: 2: 4 to obtain the modified high-efficiency compounded crude oil demulsifier.
The preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 85 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 2 hours;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 2 h;
s4: adding an esterification catalyst, heating to 140 ℃, continuously stirring for 4 hours, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
The esterification catalyst is heteropoly acid.
The vinyl imidazole ionic liquid is chlorinated 1-allyl-3-methylimidazole.
The preparation method of the high-water-content demulsifier comprises the following steps:
s1: dropwise adding a formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at 50 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1:1:3, heating to 140 ℃, reacting for 3 hours, and cooling to obtain an initiator;
s2: at the temperature of 140 ℃ and under the pressure of 0.5MPa, the initiator, ethylene oxide and propylene oxide are polymerized under the catalysis of KOH, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1:5, and the polyether is obtained by neutralizing with acetic acid, filtering and desalting;
s3: diluting polyether with xylene solution at 140 ℃ and 0.5MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of polyether to epoxy chloropropane is 1: 3;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3: 1, stirring and reacting for 1h, heating to 100 ℃, reacting for 24h, and reacting with epoxy chloropropane to obtain epoxy polyether B;
s5: epoxy polyether a and epoxy polyether B are mixed in a molar ratio of 1: dissolving the mixture in dimethylbenzene according to the proportion of 1 to obtain the high-water-content demulsifier.
The preparation of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 50 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 50 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
In the S2, the keto acid is pyruvic acid, and the alkynol is propargyl alcohol.
The compounding of the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier comprises the following steps:
s1: adding a modified demulsifier, a high-water-content demulsifier and a thick oil demulsifier in a weight ratio of 1: 2: 4 into a reaction kettle, stirring for 1h, and heating to 60 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 60 ℃, and continuing stirring for 2 hours, wherein the mass part of the surfactant is 10%; the mass portion of the stabilizer is 6%.
The surfactant is polysorbate-80; the stabilizer is sodium sulfate.
Example four:
a novel modified efficient compound crude oil demulsifier comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 1: 4 to obtain the modified high-efficiency compounded crude oil demulsifier.
The preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 85 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 2 hours;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 2 h;
s4: adding an esterification catalyst, heating to 140 ℃, continuously stirring for 4 hours, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
The esterification catalyst is heteropoly acid.
The vinyl imidazole ionic liquid is chlorinated 1-allyl-3-methylimidazole.
The preparation method of the high-water-content demulsifier comprises the following steps:
s1: dropwise adding a formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at 50 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1:1:3, heating to 140 ℃, reacting for 3 hours, and cooling to obtain an initiator;
s2: at the temperature of 140 ℃ and under the pressure of 0.5MPa, the initiator, ethylene oxide and propylene oxide are polymerized under the catalysis of KOH, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1:5, and the polyether is obtained by neutralizing with acetic acid, filtering and desalting;
s3: diluting polyether with xylene solution at 140 ℃ and 0.5MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of polyether to epoxy chloropropane is 1: 3;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3: 1, stirring and reacting for 1h, heating to 100 ℃, reacting for 24h, and reacting with epoxy chloropropane to obtain epoxy polyether B;
s5: epoxy polyether A and epoxy polyether B are mixed in a molar ratio of 1: dissolving the mixture in dimethylbenzene according to the proportion of 1 to obtain the high-water-content demulsifier.
The preparation of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 50 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 50 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
In the S2, the keto acid is pyruvic acid, and the alkynol is propargyl alcohol.
The compounding of the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier comprises the following steps:
s1: adding a modified demulsifier, a high-water-content demulsifier and a thick oil demulsifier in a weight ratio of 1: 4 into a reaction kettle, stirring for 1h, and heating to 60 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 60 ℃, and continuing stirring for 2 hours, wherein the mass part of the surfactant is 10%; the mass portion of the stabilizer is 6%.
The surfactant is polysorbate-80; the stabilizer is sodium sulfate.
Example five:
a novel modified efficient compound crude oil demulsifier comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the modified demulsifier is prepared from ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 2:1 to obtain the modified high-efficiency compounded crude oil demulsifier.
The preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 85 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 2 hours;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 2 h;
s4: adding an esterification catalyst, heating to 140 ℃, continuously stirring for 4 hours, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
The esterification catalyst is heteropoly acid.
The vinyl imidazole ionic liquid is chlorinated 1-allyl-3-methylimidazole.
The preparation method of the high-water-content demulsifier comprises the following steps:
s1: dropwise adding a formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at 50 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1:1:3, heating to 140 ℃, reacting for 3 hours, and cooling to obtain an initiator;
s2: at the temperature of 140 ℃ and under the pressure of 0.5MPa, the initiator, ethylene oxide and propylene oxide are polymerized under the catalysis of KOH, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1:5, and the polyether is obtained by neutralizing with acetic acid, filtering and desalting;
s3: diluting polyether with xylene solution at 140 ℃ and 0.5MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of polyether to epoxy chloropropane is 1: 3;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3: 1, stirring and reacting for 1h, heating to 100 ℃, reacting for 24h, and reacting with epoxy chloropropane to obtain epoxy polyether B;
s5: epoxy polyether A and epoxy polyether B are mixed in a molar ratio of 1: dissolving the mixture in dimethylbenzene according to the proportion of 1 to obtain the high-water-content demulsifier.
The preparation method of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 50 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 50 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
In the S2, the keto acid is pyruvic acid, and the alkynol is propargyl alcohol.
The compounding of the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier comprises the following steps:
s1: adding a modified demulsifier, a high-water-content demulsifier and a thick oil demulsifier in a weight ratio of 2:1 into a reaction kettle, stirring for 1h, and heating to 60 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 60 ℃, and continuing stirring for 2 hours, wherein the mass part of the surfactant is 10%; the mass portion of the stabilizer is 6%.
The surfactant is polysorbate-80; the stabilizer is sodium sulfate.
Example six:
a novel modified efficient compound crude oil demulsifier comprises: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, propylene oxide, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 2: 1: 4 to obtain the modified high-efficiency compounded crude oil demulsifier.
The preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 85 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 2 hours;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 2 h;
s4: adding an esterification catalyst, heating to 140 ℃, continuously stirring for 4 hours, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
The esterification catalyst is heteropoly acid.
The vinyl imidazole ionic liquid is chlorinated 1-allyl-3-methylimidazole.
The preparation method of the high-water-content demulsifier comprises the following steps:
s1: dropwise adding a formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at 50 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1:1:3, heating to 140 ℃, reacting for 3 hours, and cooling to obtain an initiator;
s2: under the conditions of 140 ℃ and 0.5MPa, an initiator, ethylene oxide and propylene oxide are subjected to KOH catalytic polymerization, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1:5, acetic acid is used for neutralization, and the polyether is obtained through suction filtration and desalination;
s3: diluting polyether with xylene solution at 140 ℃ and 0.5MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of polyether to epoxy chloropropane is 1: 3;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3: 1, stirring and reacting for 1h, heating to 100 ℃, reacting for 24h, and reacting with epoxy chloropropane to obtain epoxy polyether B;
s5: epoxy polyether A and epoxy polyether B are mixed in a molar ratio of 1:1 in the ratio of the obtained product to xylene to obtain the high-water-content demulsifier.
The preparation of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 50 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 50 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
In the S2, the keto acid is pyruvic acid, and the alkynol is propargyl alcohol.
The compounding of the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier comprises the following steps:
s1: adding the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier in a weight ratio of 2: 1: 4 into a reaction kettle, stirring for 1h, and heating to 60 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 60 ℃, and continuing stirring for 2 hours, wherein the mass part of the surfactant is 10%; the mass portion of the stabilizer is 6%.
The surfactant is polysorbate-80; the stabilizer is sodium sulfate.
This embodiment has the raw materials easily get, low cost, the breakdown of emulsion is effectual, through dropwise add surfactant active and stabilizer to three kinds of mixed demulsifier solvents, can increase its surface activity, and make its solubility of dissolving in the viscous crude show and improve, accelerate dehydration effect, the stabilizer is convenient for increase the stability ability after the mixture of three kinds of demulsifiers, it is better to make mixed effect, be convenient for through reducing the quantity in order to reach the same effect, this reagent preparation method is simple, and the simple operation, gained demulsifier has the quantity less, the dehydration volume is big with dehydration rate fast wait positive effect, the water layer parallel and level is convenient for extract.
Through the embodiment, the obtained novel modified efficient compound crude oil demulsifier is shown in the following table:
it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof; the present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any minor modifications, equivalent replacements and improvements made to the above embodiment according to the technical spirit of the present invention should be included in the protection scope of the technical solution of the present invention.
Claims (10)
1. The utility model provides a novel modified high-efficient compound type crude oil demulsifier which characterized in that includes: modified demulsifier, high water-containing demulsifier and thick oil demulsifier;
the synthetic raw materials of the modified demulsifier are ethanol, toluene, dibenzoyl peroxide, vinyl imidazole ionic liquid, acrylic acid, ethylene oxide, propylene oxide and an esterification catalyst;
the synthetic raw materials of the high-water-content demulsifier are polyethylene polyamine, bisphenol S, formaldehyde, a KOH catalyst, ethylene oxide, epoxypropane, acetic acid, xylene, triethylene diamine, methyl 2-butenoate and epichlorohydrin;
the thick oil demulsifier is prepared by taking a modified demulsifier as a base fluid and adding polyether, keto acid and alkynol;
the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier are compounded according to the weight ratio of 1-2: 1-4 to obtain the modified high-efficiency compounded crude oil demulsifier.
2. The novel modified high-efficiency compound crude oil demulsifier according to claim 1, wherein the preparation method of the modified demulsifier comprises the following steps:
s1: adding 95% ethanol into a reaction kettle, controlling the temperature to be 80-90 ℃, adding vinyl imidazole ionic liquid, acrylic acid and dibenzoyl peroxide, and stirring for 1.5-2.5 h;
s2: after the reaction is finished, carrying out reduced pressure distillation to remove ethanol to obtain an intermediate product;
s3: adding ethylene oxide, propylene oxide and toluene into the intermediate product, and stirring for 1-2 h;
s4: adding an esterification catalyst, heating to 110-150 ℃, continuing stirring for 3-5 h, and removing toluene by reduced pressure distillation to obtain the modified crude oil demulsifier.
3. The novel modified high-efficiency compound crude oil demulsifier according to claim 2, wherein the esterification catalyst is concentrated sulfuric acid, toluenesulfonic acid, trifluoromethanesulfonic acid, heteropoly acid and organic sulfonic acid.
4. The novel modified high-efficiency compound crude oil demulsifier according to claim 2, wherein the vinyl imidazole ionic liquid is 1-allyl-3-methylimidazole chloride or 1-vinyl-3-methylimidazole chloride.
5. The novel modified high-efficiency compound crude oil demulsifier according to claim 2, wherein the preparation of the high-water-content demulsifier comprises the following steps:
s1: dripping formaldehyde solution into a reaction kettle filled with polyethylene polyamine and bisphenol S at the temperature of 30-60 ℃, wherein the molar ratio of the polyethylene polyamine to the bisphenol S to the formaldehyde is 1-2:1-2:3-5, then heating to 100 ℃ and reacting at the temperature of 150 ℃ for 1-5h, and cooling to obtain an initiator;
s2: under the conditions of 115-145 ℃ and 0.25-0.5MPa, the initiator, ethylene oxide and propylene oxide are polymerized under the catalysis of KOH, wherein the molar ratio of the ethylene oxide to the propylene oxide is 1-2:5-6, and the polyether is obtained by neutralizing with acetic acid, filtering and desalting;
s3: diluting polyether with xylene solution at the temperature of 100-150 ℃ and under the pressure of 0.1-0.6MPa, and reacting the diluted polyether with epoxy chloropropane to obtain epoxy polyether A, wherein the molar ratio of the polyether to the epoxy chloropropane is 1-1.5: 3-5;
s4: dropwise adding 2-methyl crotonate into triethylene diamine, wherein the molar ratio of the triethylene diamine to the 2-methyl crotonate is 3-5: 0.5-1, stirring for reaction for 0.5-1.5h, heating to 70-110 ℃, reacting for 12-30h, and reacting with epichlorohydrin to obtain epoxy polyether B;
s5: epoxy polyether A and epoxy polyether B are mixed in a molar ratio of 1-1.1: dissolving in xylene at a ratio of 0.9-1.2 to obtain the high-water-content demulsifier.
6. The novel modified efficient compound type crude oil demulsifier according to claim 1, wherein the preparation of the thick oil demulsifier comprises the following steps:
s1: adding polyether with required amount into a reaction kettle filled with the modified demulsifier, and heating to 30-60 ℃;
s2: adding a required amount of ketonic acid, alkynol and the balance of water into a reactor to obtain a mixed material;
s3: and (3) preserving the temperature of the mixed material at 30-60 ℃, and stirring until the material is completely dissolved to form uniform liquid, thereby obtaining the thick oil demulsifier.
7. The novel modified high-efficiency compounded crude oil demulsifier according to claim 6, wherein in S2, the keto acid is one or more of an α -keto acid, a β -keto acid and a γ -keto acid, and the alkynol is one or more of propiolic alcohol and 3-methylbutynol.
8. The novel modified high-efficiency compound crude oil demulsifier according to claim 7, wherein the α -ketoacid is one or more of pyruvic acid, 2-ketobutyric acid, phenylpyruvic acid and benzoylformic acid; the beta-keto acid is acetoacetic acid; the gamma-keto acid is 4-pentanoic acid.
9. The novel modified efficient compound type crude oil demulsifier according to claim 1, wherein the compounding of the modified demulsifier, the high-water-content demulsifier and the heavy oil demulsifier comprises the following steps:
s1: adding the modified demulsifier, the high-water-content demulsifier and the thick oil demulsifier in a weight ratio of 1-2: 1-4 into a reaction kettle, stirring for 0.5-1h, and heating to 50-80 ℃ to obtain a mixed solution;
s2: adding a surfactant into the mixed solution, adding a stabilizer after the surfactant is completely dissolved, maintaining the temperature at 50-80 ℃, and continuously stirring for 1-2 hours, wherein the mass part of the surfactant is 8% -12%; the mass portion of the stabilizer is 4.5-8%.
10. The novel modified high-efficiency compound crude oil demulsifier according to claim 9, wherein the surfactant is a polysorbate or a polyoxyethylene fatty acid ester; the stabilizer is one of ammonium sulfate, ammonium carbonate or sodium sulfate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115536213A (en) * | 2022-09-27 | 2022-12-30 | 广州思伊特环保科技有限公司 | Oily wastewater treatment method |
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| US4341716A (en) * | 1979-09-25 | 1982-07-27 | Hoechst Aktiengesellschaft | Polyether polyamines, the salts thereof, process for their manufacture and their use |
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