CN115595173B - Method for demulsifying emulsion by using amphiphilic hyperbranched polyglycidyl ether - Google Patents
Method for demulsifying emulsion by using amphiphilic hyperbranched polyglycidyl ether Download PDFInfo
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- CN115595173B CN115595173B CN202211184513.3A CN202211184513A CN115595173B CN 115595173 B CN115595173 B CN 115595173B CN 202211184513 A CN202211184513 A CN 202211184513A CN 115595173 B CN115595173 B CN 115595173B
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000000839 emulsion Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 100
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004185 ester group Chemical group 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 40
- 239000007764 o/w emulsion Substances 0.000 claims description 26
- 230000033558 biomineral tissue development Effects 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 20
- 239000011780 sodium chloride Substances 0.000 claims description 20
- 238000004062 sedimentation Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 110
- 239000012071 phase Substances 0.000 description 66
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010779 crude oil Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229920000587 hyperbranched polymer Polymers 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 229940008099 dimethicone Drugs 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229940083037 simethicone Drugs 0.000 description 3
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001788 irregular Effects 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
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 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
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a method for demulsifying a thickened oil-in-water type emulsion by utilizing amphiphilic hyperbranched polyglycidyl ether, which comprises the following steps: 1) Esterification reaction is carried out on palmitoyl chloride and hyperbranched polyglycidyl ether to obtain amphiphilic hyperbranched polyglycidyl ether; the hydrophilic compact inner core of the amphiphilic hyperbranched polyglycidyl ether is hyperbranched polyglycidyl ether, and the outer shell consists of a lipophilic long-chain alkyl group and an ester group; the mass ratio of the palmitoyl chloride to the hyperbranched polyglycidyl ether is 0.8-2.0; 2) And dispersing the amphiphilic hyperbranched polyglycidyl ether into a thick oil-in-water type emulsion for demulsification. The method realizes that the oil content of the water phase of the thick oil-in-water type emulsion is lower than 10% in a short time, and meanwhile, the water content of the oil phase of the thick oil-in-water type emulsion can be as low as below 1.5%, so that a clear oil-water interface is formed.
Description
Technical Field
The invention relates to the field of petroleum additives, in particular to a method for demulsifying a thickened oil-in-water emulsion by utilizing amphiphilic hyperbranched polyglycidyl ether.
Background
In the petroleum and petrochemical industries, methods of breaking emulsions in various forms are receiving increasing attention. During transportation, the presence of large amounts of emulsion can promote corrosion of the piping leading to catalyst poisoning during oil refining. The rising of thick oil exploitation causes the increase of asphaltene, colloid and solid fine powder content in the produced liquid, and the increase of emulsion viscosity, thereby increasing the demulsification difficulty. Physical and chemical methods are two commonly used demulsification techniques. The physical demulsification method is gradually decreasing in application range due to the high technical cost. The chemical demulsification is a demulsification method with the widest application range and the most obvious effect, and the efficient separation of oil and water is realized mainly by adding the demulsifier. The principle is that a chemical reagent with higher interfacial activity is added into the emulsion to replace natural surfactant and other emulsifying agents which are originally adsorbed on the oil-water interfacial film, and the interfacial property is changed to realize demulsification. The chemical demulsifiers are various and mainly comprise nonionic demulsifiers, cationic demulsifiers, ionic liquids and the like.
The thick oil is a heavy crude oil with high density and high viscosity, and refers to the viscosity of stratum of more than 50mPa.s (oil layer temperatureA crude oil having a viscosity of greater than 1000 mPa.s) and a relative density of greater than 0.934g/cm 3 . The emulsion formed between the thick oil and the water is more stable, and oil-water separation is difficult to realize through automatic sedimentation. In order to destroy the stable emulsified state, a method of adding a crude oil demulsifier is adopted in a dehydration process to realize crude oil dehydration. Demulsifiers break down the stability of the interfacial layer primarily by competitively adsorbing at the interface, displacing asphaltene-colloid agglomerates, breaking down the asphaltene-colloid interfacial film, and simultaneously reducing the interfacial tension between the hydrocarbons and the aqueous phase, thereby enhancing the coalescence kinetics of the droplets. The goal of the breaker system is to weaken or disperse the asphaltene/resin layer by counteracting the stabilization mechanism through competitive adsorption at the interface region. However, due to the complexity and uncertainty of the crude oil components, it is necessary to screen or design suitable demulsifiers for the nature of the crude oil production fluids in combination with on-site practical situations and economic costs.
The hyperbranched polymer has an irregular branch-shaped divergent structure, molecules are spread and diverged when not formed into compact spheres in a certain molecular weight range, the divergent structure can be rapidly dispersed in a solution, entanglement is not easy to occur, the intrinsic viscosity of the hyperbranched polymer is far smaller than that of a conventional demulsifier, the hyperbranched polymer is favorable for diffusing and adsorbing to an interface, and a highly branched unstable adsorption film is rapidly generated while a natural emulsifier is weakened to form a stable interfacial film, so that a good demulsification effect is obtained. Among them, hyperbranched polyglycidyl ethers (HPGs) are a class of hyperbranched polymers which are well-studied and environmentally friendly and have been used in various fields at present. HPG is a highly branched polymer with low viscosity in solvents and good flowability. Meanwhile, compared with other demulsifier molecules, the demulsifier has good temperature resistance and salt resistance, and thermogravimetric analysis shows that the demulsifier is not decomposed in the air below 300 ℃; the pH is kept stable in a system with a pH of 3 to 12. The large number of hydroxyl groups on the periphery of the emulsion breaker is favorable for modification, and can be used for designing and developing novel demulsifiers with special hyperbranched structures.
Disclosure of Invention
The invention aims to provide a method for demulsifying a thick oil-in-water type emulsion by using amphiphilic hyperbranched polyglycidyl ether, which can realize the oil-water separation of the stable thick oil emulsion in a short time by the thick oil-in-water type emulsion, has the demulsifying efficiency of up to 90 percent, has the water content of an oil phase of less than 1.5 percent and forms a clear oil-water interface.
The technical scheme provided by the invention is as follows:
a method for demulsifying a thick oil-in-water emulsion by using amphiphilic hyperbranched polyglycidyl ether comprises the following steps:
(1) Esterification reaction is carried out on palmitoyl chloride and hyperbranched polyglycidyl ether to obtain amphiphilic hyperbranched polyglycidyl ether; the hydrophilic compact inner core of the amphiphilic hyperbranched polyglycidyl ether is hyperbranched polyglycidyl ether, and the outer shell consists of a lipophilic long-chain alkyl group and an ester group;
(2) And dispersing the amphiphilic hyperbranched polyglycidyl ether into a thick oil-in-water type emulsion for demulsification.
In the invention, palmitoyl chloride is adopted to graft and modify the hyperbranched polyglycidyl ether, so that the terminal group of the hyperbranched polyglycidyl ether is grafted with long-chain alkyl. HPG in the modified hyperbranched polymer is a hydrophilic porous core, and the shell consists of lipophilic long-chain alkyl and ester groups, so that the amphiphilic polymer with different substitution degrees and a core-shell structure is formed, and the number average molecular weight distribution of the amphiphilic polymer is 40000-150000.
The esterification reaction of the invention specifically comprises the following steps:
(1) Dropwise adding palmitoyl chloride into an organic solvent in which hyperbranched polyglycidyl ether is dissolved, and carrying out esterification reaction for 3-24 hours at the temperature of 40-110 ℃ to obtain a crude product;
(2) Concentrating the crude product obtained in the step (1), cooling to room temperature, precipitating in acetone, dissolving the precipitate in water, extracting with water-saturated n-butanol solution, concentrating and drying to obtain the amphiphilic hyperbranched polyglycidyl ether.
Preferably, the mass ratio of the palmitoyl chloride to the hyperbranched polyglycidyl ether is 0.8 to 2.0.
Preferably, the mass ratio of the palmitoyl chloride to the hyperbranched polyglycidyl ether is 1.1 to 2.0.
The serial amphiphilic hyperbranched polyglycidyl ether demulsifier is prepared by controlling the mass ratio of palmitoyl chloride to hyperbranched polyglycidyl ether. The modified hyperbranched polyglycidyl ether has higher interfacial activity due to the fact that the end group is partially replaced by lipophilic group long-chain alkyl, the good water solubility of the modified hyperbranched polyglycidyl ether is ensured, the external long-chain alkyl can be dispersed in the oil-water emulsion more quickly to reach the oil-water interface to destroy the oil-water interface film, meanwhile, the long-chain alkyl has stronger adsorption capacity, more oil drops can be adsorbed to be gathered and float upwards, the oil-water separation is finally achieved, the stable oil-water separation of the thick oil emulsion can be realized under the condition of less additive amount by the HPG type demulsifier, the demulsification efficiency is up to 90%, the water content of the oil phase is lower than 1.5%, and meanwhile, a clear oil-water interface is formed.
Preferably, the temperature of the esterification reaction is 60-100 ℃ and the reaction time is 8-18 h.
The organic solvent is pyridine or dimethylformamide.
The addition amount of the amphiphilic hyperbranched polyglycidyl ether in the thickened oil-in-water type emulsion is 40-200 mg/L. The addition amount is less than 40mg/L, and the demulsification effect is poor; the addition amount is more than 200mg/L, the demulsification effect is not changed greatly or even is poor, and the economic cost is increased greatly.
The demulsification temperature is 25-65 ℃, and the sedimentation time is 0.5-3 h. Preferably, the demulsification temperature is 45-60 ℃ and the sedimentation time is 1-1.5 h.
The oil phase in the thick oil-in-water type emulsion is simulated oil or crude oil. Preferably, the simulated oil is simethicone (1000 mPa.s,30000mPa.s,60000 mPa.s) with different viscosities, and the crude oil is high-rise thick oil, liaoyang thick oil, island thick oil, single temple thick oil and Xinjiang thick oil.
The mineralization degree of the water phase in the thick oil-in-water type emulsion is 0-20000 mg/L, wherein NaCl and CaCl are in the water phase 2 The mass ratio of (2) is 0.1-1.5.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the modified amphiphilic hyperbranched polyglycidyl ether disclosed by the invention, as the end group is partially substituted into the lipophilic group long-chain alkyl, the shell simultaneously contains the strong hydrophilic group hydroxyl and the hydrophobic group long-chain alkyl, so that the modified amphiphilic hyperbranched polyglycidyl ether can reach an oil-water interface rapidly to damage an oil-water interface film while ensuring good water solubility, and meanwhile, the external long-chain alkyl has stronger adsorption capacity, can adsorb more oil drops, so that the oil drops are gathered and float upwards, and finally the oil-water separation is achieved.
(2) The modified amphiphilic hyperbranched polyglycidyl ether is adopted in the invention, so that emulsion can reach demulsification balance rapidly, high demulsification efficiency is obtained, and the limitation of unclear oil-water interface after demulsification is broken through. The demulsifier can ensure that the water content of the oil phase is lower than 1.5 percent on the premise of ensuring that the oil content of the water phase is lower than 10 percent, and meanwhile, a clear oil-water interface is formed.
Drawings
FIG. 1 is a schematic structural diagram of an amphiphilic hyperbranched polyglycidyl ether modified by palmitoyl chloride;
FIG. 2 is a graph showing the comparative demulsification effects of application example 1 and application comparative examples 1 to 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: preparation of amphiphilic hyperbranched polyglycidyl ether (PHPG-1)
3g of HPG is dissolved in 100mL of pyridine, 3.7mL of palmitoyl chloride is dripped into the reaction system, and esterification reaction is carried out for 12 hours at 85 ℃ to obtain a highly branched crude product; concentrating the crude product, cooling to room temperature, precipitating in acetone, dissolving the precipitate in water, extracting with water saturated n-butanol solution, concentrating, and oven drying to obtain yellow transparent viscous PHPG-1.
The structural schematic diagram of the amphiphilic hyperbranched polyglycidyl ether (PHPG-1) is shown in FIG. 1, and it should be noted that the structure is merely an example because the hyperbranched structure is changeable and complex.
Example 2: preparation of amphiphilic hyperbranched polyglycidyl ether (PHPG-2)
1g of HPG is dissolved in 50mL of DMF, 1.8mL of palmitoyl chloride is dripped into the reaction system, and esterification reaction is carried out at 90 ℃ for 8 hours, thus obtaining a highly branched crude product; concentrating the crude product, cooling to room temperature, precipitating in acetone, dissolving the precipitate in water, extracting with water saturated n-butanol solution, concentrating, and oven drying to obtain yellow transparent viscous PHPG-2.
Example 3: preparation of amphiphilic hyperbranched polyglycidyl ether (PHPG-3)
0.5g of HPG is dissolved in 50mL of pyridine, 1.1mL of palmitoyl chloride is dripped into the reaction system, and esterification reaction is carried out at 80 ℃ for 18 hours to obtain a highly branched crude product; concentrating the crude product, cooling to room temperature, precipitating in acetone, dissolving the precipitate in water, extracting with water saturated n-butanol solution, concentrating, and oven drying to obtain yellow transparent viscous PHPG-3.
Comparative example 1: preparation of amphiphilic hyperbranched polyglycidyl ether (PHPG-4)
1.5g of HPG is dissolved in 50mL of DMF, 0.4mL of palmitoyl chloride is dripped into the reaction system, and esterification reaction is carried out for 8 hours at 65 ℃ to obtain a highly branched crude product; concentrating the crude product, cooling to room temperature, precipitating in acetone, dissolving the precipitate in water, extracting with water saturated n-butanol solution, concentrating, and oven drying to obtain yellow transparent viscous PHPG-4.
Comparative example 2: preparation of amphiphilic hyperbranched polyglycidyl ether (PHPG-5)
2.4g of HPG is dissolved in 100mL of pyridine, 1.8mL of palmitoyl chloride is dripped into the reaction system, and esterification reaction is carried out at 95 ℃ for 10 hours, thus obtaining a highly branched crude product; concentrating the crude product, cooling to room temperature, precipitating in acetone, dissolving the precipitate in water, extracting with water saturated n-butanol solution, concentrating, and oven drying to obtain yellow transparent viscous PHPG-5.
Comparative example 3: preparation of amphiphilic hyperbranched polyglycidyl ether (PHPG-6)
2.7g of HPG is dissolved in 150mL of pyridine, 6.8mL of palmitoyl chloride is dripped into the reaction system, and esterification reaction is carried out at 85 ℃ for 14 hours, thus obtaining a highly branched crude product; concentrating the crude product, cooling to room temperature, precipitating in acetone, dissolving the precipitate in water, extracting with water saturated n-butanol solution, concentrating, and oven drying to obtain yellow transparent viscous PHPG-6.
Application example 1
PHPG-1 (number average molecular weight distribution of 40000-60000) prepared in example 1 was weighed and dissolved in an oil-in-water emulsion with simethicone (1000 mPa.s) as oil phase, pH 10 and mineralization of 4500mg/L with stirring at a concentration of 80mg/L, wherein NaCl and CaCl were contained in the water phase 2 The mass ratio of (2) was 0.7. At 45 ℃, the oil removal efficiency is 98.5% and the water content of the oil phase is 0.2% when the sedimentation time is 40min.
Application example 2
PHPG-2 (number average molecular weight distribution: 60000-110000) prepared in example 2 was weighed and dissolved in an oil-in-water emulsion with dimethicone (30000 mPa.s) as oil phase, pH 11 and mineralization of 20000mg/L with stirring at a concentration of 100mg/L, wherein NaCl and CaCl were contained in the water phase 2 The mass ratio of (2) was 1.2. At 30 ℃, the oil removal efficiency is 95.2% and the water content of the oil phase is 0.4% when the sedimentation time is 120 min.
Application example 3
PHPG-3 (number average molecular weight distribution 110000 ～ 150000) prepared in example 3 was weighed and dissolved in an oil-in-water emulsion with dimethicone (60000 mPa.s) as oil phase, pH 12 and mineralization of 15000mg/L with stirring at a concentration of 200mg/L, wherein NaCl and CaCl were added to the water phase 2 The mass ratio of (2) was 0.2. At 60 ℃, the oil removal efficiency is 98.3% and the water content of the oil phase is 0.2% when the sedimentation time is 40min.
Analysis shows that the demulsifiers prepared in the examples 1-3 are good in performance, the feeding mass ratio of the palmitoyl chloride to the hyperbranched polyglycidyl ether is mainly regulated and controlled, and the PHPG obtained by a certain feeding mass ratio reaction is high in interfacial tension reduction degree, so that the emulsion droplet breaking rate is remarkably improved, the liquid discharge time is shorter, and the purpose of the efficient demulsifier can be achieved.
Comparative examples 1 to 3 were used
Application pairRatio 1-3 experiments were conducted with reference to application example 1, in which the kind of demulsifier was changed, and simethicone (1000 mPa.s) was used as the oil phase, and an oil-in-water emulsion having a pH of 10 and a mineralization of 4500mg/L was used, wherein NaCl and CaCl were contained in the water phase 2 The mass ratio of (2) was 0.7.
The demulsification temperature is 45 ℃ and the sedimentation time is 40min. Comparative example 1 is a blank test. The demulsifier of comparative example 2 was A (LSY-502, tian Xin chemical Co., ltd.). The demulsifier in comparative example 3 was HPG.
As shown in FIG. 2, the demulsification effect of application examples 1 to 3 and application example 1 is compared, and it can be seen that application example 1 has an excellent demulsification effect.
Application example 4
PHPG-1 (number average molecular weight distribution of 40000-60000) in example 1 was weighed and dissolved in a thick oil-in-water emulsion with an oil content of 10% in which the high-rise thick oil was used as an oil phase, pH 3 and mineralization of 2000mg/L, with stirring at a concentration of 150mg/L, wherein NaCl and CaCl were contained in the water phase 2 The mass ratio of (2) is 1.2. The oil removal rate of the emulsion and the water content of the upper oil phase were measured at 45℃for 60 min. The results show that the demulsification efficiency of PHPG-1 is as high as 95.3%, and the water content of the upper oil phase is only 0.4%.
Application example 5
PHPG-1 (number average molecular weight distribution of 40000-60000) in example 1 was weighed and dissolved in a thick oil-in-water emulsion with Liaoyang thick oil as oil phase, pH 5, mineralization 8000mg/L and oil content of 30%, wherein NaCl and CaCl were contained in the water phase 2 The mass ratio of (2) was 1.2.. The oil removal rate of the emulsion and the water content of the upper oil phase were measured at 45℃for 60 min. The results show that the demulsification efficiency of PHPG-1 is as high as 91.3%, and the water content of the upper oil phase is only 1.4%.
Application example 6
PHPG-1 (number average molecular weight distribution of 40000-60000) in example 1 was weighed and dissolved in a thick oil-in-water emulsion with a concentration of 100mg/L, wherein the thick oil-in-water emulsion had an oil content of 40% and a pH of 7 and a mineralization of 10000mg/L, and was obtained by stirring the thick oil-in-water emulsion with a concentration of 100mg/L 2 The mass ratio of (2) was 1.5.. Measuring the sedimentation time at 60 ℃ for 120minIs used for the oil removal rate of the emulsion and the water content of the upper oil phase. The results show that the demulsification efficiency of PHPG-1 is as high as 96.5%, and the water content of the upper oil phase is only 0.3%.
Application example 7
PHPG-1 (number average molecular weight distribution of 40000-60000) in example 1 was weighed and dissolved in an oil phase of island heavy oil with stirring at a concentration of 200mg/L, pH 10, mineralization 20000mg/L and oil content of 20% of heavy oil-in-water emulsion, wherein NaCl and CaCl were contained in the water phase 2 The mass ratio of (2) was 0.9. At 60 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 60min of sedimentation time are measured. The results show that the demulsification efficiency of PHPG-1 is as high as 92.4%, and the water content of the upper oil phase is only 1.2%.
Application example 8
PHPG-2 (number average molecular weight distribution: 60000-110000) in example 2 was weighed and dissolved in a thick oil-in-water emulsion with a concentration of 200mg/L and a water content of 40% and with a pH of 11 and a mineralization of 10000mg/L, in which the aqueous phase was stirred and dissolved in a concentration of 200mg/L and with dimethicone (60000 mPa.s) as the oil phase, wherein NaCl and CaCl were present in the aqueous phase 2 The mass ratio of (2) was 1.1. At 60 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 60min of sedimentation time are measured. The results showed that HPG-g-C 16 The demulsification efficiency of the-2 is up to 96.3%, and the water content of the upper oil phase is only 0.5%.
Application example 9
PHPG-2 (number average molecular weight distribution of 60000-110000) in example 2 was weighed and dissolved in an oil phase of island heavy oil with 200mg/L concentration with stirring, pH 10, mineralization 20000mg/L oil content of 20% heavy oil-in-water emulsion, wherein NaCl and CaCl were in the water phase 2 The mass ratio of (2) was 1.2. At 60 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 60min of sedimentation time are measured. The results show that the demulsification efficiency of PHPG-2 is as high as 97.9%, and the water content of the upper oil phase is only 0.4%.
Application example 10
PHPG-2 (number average molecular weight distribution of 60000-110000) in example 2 was weighed and dissolved in 200mg/L under stirring in a single temple of thick oil as an oil phase, pH 7, mineralization of 4000mg/L and oil content of 10%Thickened oil-in-water emulsions wherein NaCl and CaCl are present in the aqueous phase 2 The mass ratio of (2) was 0.5. At 30 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 180min of sedimentation time are measured. The results show that the demulsification efficiency of PHPG-2 is as high as 91.2%, and the water content of the upper oil phase is only 1.4%.
Application example 11
PHPG-2 (number average molecular weight distribution of 60000-110000) in example 2 was weighed and dissolved in a thick oil-in-water emulsion with an oil content of 40% and a pH of 10 and a mineralization of 18000mg/L, in which NaCl and CaCl were added to the aqueous phase, with stirring at a concentration of 200mg/L 2 The mass ratio of (2) was 0.2. The oil removal rate of the emulsion and the water content of the upper oil phase were measured at 45℃for 60 min. The results show that the demulsification efficiency of PHPG-2 is as high as 92.3%, and the water content of the upper oil phase is only 1.2%.
Application example 12
PHPG-3 (number average molecular weight distribution 110000 ～ 150000) of example 3 was weighed and dissolved in a thick oil-in-water emulsion with an oil content of 40% and a pH of 9 and a mineralization of 20000mg/L, wherein NaCl and CaCl were added to the aqueous phase 2 The mass ratio of (2) was 0.2. At 60 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 60min of sedimentation time are measured. The results show that the demulsification efficiency of PHPG-3 is as high as 98.3%, and the water content of the upper oil phase is only 0.2%.
Application example 13
PHPG-3 (number average molecular weight distribution 110000 ～ 150000) of example 3 was weighed and dissolved in a thick oil-in-water emulsion with an oil content of 40% and a pH of 10 and a mineralization of 10000mg/L, in which NaCl and CaCl were added to the aqueous phase, with stirring at a concentration of 160mg/L 2 The mass ratio of (2) was 0.4. At 60 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 60min of sedimentation time are measured. The results show that the demulsification efficiency of PHPG-3 is as high as 97.4%, and the water content of the upper oil phase is only 0.3%.
Application example 14
PHPG-3 (number average molecular weight distribution of 110000 ～ 150000) in example 3 was weighed out at 200mg/LStirring to dissolve in a thick oil-in-water type emulsion with Liaoyang thick oil as oil phase, pH of 11, mineralization degree of 8000mg/L and oil content of 40%, wherein NaCl and CaCl are contained in water phase 2 The mass ratio of (2) was 0.9. The oil removal rate of the emulsion and the water content of the upper oil phase were measured at 45℃for 120 min. The results show that the demulsification efficiency of PHPG-3 is as high as 96.6%, and the water content of the upper oil phase is only 0.8%.
Application example 15
PHPG-3 (number average molecular weight distribution 110000 ～ 150000) of example 3 was weighed and dissolved in 160mg/L thick oil phase of single temple with stirring, pH 12, mineralization 4000mg/L thick oil-in-water emulsion with 40% oil content, wherein NaCl and CaCl were contained in the aqueous phase 2 The mass ratio of (2) was 0.3. At 30 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 180min of sedimentation time are measured. The results show that the demulsification efficiency of PHPG-3 is as high as 94.7%, and the water content of the upper oil phase is only 1.1%.
Comparative example 4 was used
PHPG-4 (number average molecular weight distribution of 10000-20000) in example 4 was weighed and dissolved in a thick oil-in-water emulsion with an oil content of 20% in which the concentration of 200mg/L was stirred and dissolved in a thick oil phase of Xinjiang, pH 12, mineralization 5000mg/L, wherein NaCl and CaCl were contained in the aqueous phase 2 The mass ratio of (2) was 1.1. The oil removal rate of the emulsion and the water content of the upper oil phase were measured at 60℃for a settling time of 150 min. The result shows that the demulsification efficiency of PHPG-4 is only 65.2%, and the water content of the upper oil phase is as high as 15.4%.
Comparative example 5 was used
PHPG-5 (number average molecular weight distribution of 20000-40000) in example 5 was weighed and dissolved in a thick oil-in-water emulsion having an oil content of 10% in which the high-rise thick oil was used as an oil phase, pH was 7, mineralization was 2000mg/L, with stirring at a concentration of 200mg/L, wherein NaCl and CaCl were contained in the water phase 2 The mass ratio of (2) was 1.0. At 65 ℃, the oil removal rate of the emulsion and the water content of the upper oil phase at 180min of sedimentation time are measured. The result shows that the demulsification efficiency of PHPG-5 is only 71.2%, and the water content of the upper oil phase is as high as 11.8%.
Comparative example 6 was used
PHPG-6 (number average molecular weight distribution 200000 ～ 250000) of example 6 was weighed and dissolved in 160mg/L thick oil phase of single temple with stirring, pH 5, mineralization 8000mg/L thick oil-in-water emulsion with 30% oil content, wherein NaCl and CaCl were contained in the aqueous phase 2 The mass ratio of (2) was 1.5. The oil removal rate of the emulsion and the water content of the upper oil phase were measured at 65℃for 120min of sedimentation time. The result shows that the demulsification efficiency of PHPG-6 is only 59.7%, and the water content of the upper oil phase is up to 22.4%.
The demulsification efficiency of comparative examples 4-6 shows that the PHPG synthesized based on the esterification reaction has the demulsification performance, but the demulsifier capable of realizing the complete separation of oil and water two phases of the thick oil emulsion system can be prepared by adjusting the mass ratio of palmitoyl chloride to HPG reaction substances.
Claims (3)
1. A method for demulsifying a thick oil-in-water emulsion using amphiphilic hyperbranched polyglycidyl ether, comprising the steps of:
1.1 Esterification reaction is carried out on palmitoyl chloride and hyperbranched polyglycidyl ether to obtain amphiphilic hyperbranched polyglycidyl ether; the hydrophilic porous inner core of the amphiphilic hyperbranched polyglycidyl ether is hyperbranched polyglycidyl ether, and the outer shell consists of a lipophilic long-chain alkyl group and an ester group;
1.2 Dispersing the amphiphilic hyperbranched polyglycidyl ether into a thick oil-in-water type emulsion for demulsification;
the esterification reaction specifically comprises the following steps:
2.1 Dropwise adding palmitoyl chloride into an organic solvent in which hyperbranched polyglycidyl ether is dissolved, and carrying out esterification reaction for 3-18 hours at the temperature of 40-100 ℃ to obtain a crude product;
2.2 Concentrating the crude product obtained in the step 2.1), cooling to room temperature, precipitating in acetone, dissolving the precipitate into water, extracting with water-saturated n-butanol solution, concentrating and drying to obtain the amphiphilic hyperbranched polyglycidyl ether;
the mass ratio of the palmitoyl chloride to the hyperbranched polyglycidyl ether is 0.8-2.0;
the number average molecular weight distribution of the amphiphilic hyperbranched polyglycidyl ether is 40000-150000;
the organic solvent is pyridine or dimethylformamide;
the addition amount of the amphiphilic hyperbranched polyglycidyl ether in the thick oil-in-water type emulsion is 40-200 mg/L;
the demulsification temperature is 25-65 ℃ and the sedimentation time is 0.5-3 h.
2. The method for breaking thick oil-in-water emulsion using amphiphilic hyperbranched polyglycidyl ether according to claim 1, wherein the mineralization degree of the aqueous phase in the thick oil-in-water emulsion is 0-20000 mg/L, wherein NaCl and CaCl are contained in the aqueous phase 2 The mass ratio of (2) is 0.1-1.5.
3. The method of breaking thick oil-in-water emulsion using amphiphilic hyperbranched polyglycidyl ether according to claim 1 wherein the pH of the thick oil-in-water emulsion is from 3 to 12.
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| CN109370635A (en) * | 2018-10-19 | 2019-02-22 | 浙江大学 | The method that a kind of pair of oil-in-water emulsion is demulsified |
| CN109575280A (en) * | 2018-11-27 | 2019-04-05 | 浙江大学 | The method being demulsified using Ambident hyperbranched daiamid to oil-in-water emulsion |
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| CN109370635A (en) * | 2018-10-19 | 2019-02-22 | 浙江大学 | The method that a kind of pair of oil-in-water emulsion is demulsified |
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