CN109575280B - Method for demulsifying oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine - Google Patents

Method for demulsifying oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine Download PDF

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CN109575280B
CN109575280B CN201811425377.6A CN201811425377A CN109575280B CN 109575280 B CN109575280 B CN 109575280B CN 201811425377 A CN201811425377 A CN 201811425377A CN 109575280 B CN109575280 B CN 109575280B
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hyperbranched polyamidoamine
amphiphilic
demulsifying
polyamidoamine
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CN109575280A (en
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闫澍
何桂金
方文军
郭永胜
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • 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

Abstract

The invention relates to a method for demulsifying an oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine, which comprises the following steps: 1) c is to be10～C18Carrying out amidation reaction on the saturated fatty acid and the hyperbranched polyamidoamine to obtain amphiphilic hyperbranched polyamidoamine; the mass ratio of the saturated fatty acid to the hyperbranched polyamidoamine is 0.4-2.5; 2) and dispersing the amphiphilic hyperbranched polyamidoamine into an oil-in-water type emulsion for demulsification. The method realizes that the deoiling rate of the lower water phase of the oil-in-water type emulsion reaches 97 percent in a short time, and realizes the purpose of efficient and rapid demulsification.

Description

Method for demulsifying oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine
Technical Field
The invention relates to the field of petroleum additives, in particular to a method for demulsifying an oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine.
Background
Crude oil is a multicomponent mixture containing water in an emulsified state, and a stable emulsion is formed between water and oil, wherein the water is difficult to automatically settle down. In order to break down their stable emulsified state, methods of adding crude oil demulsifiers are employed in the dehydration process.
With the continuous deepening of oil field exploitation technology, each large oil field enters a tertiary oil recovery stage successively, oil resources are reduced day by day, crude oil extracted from an oil well is converted into oil-in-water (O/W) type emulsion from water-in-oil (W/O) type emulsion at the initial development stage, the stability of the crude oil emulsion is gradually enhanced due to the wide application of a chemical oil displacement method, the produced liquid treatment becomes a technical problem in the production of a plurality of oil fields, the demulsification difficulty is increased more and more, and the requirement on the performance of a demulsifier is highest.
The hyperbranched polymer has an irregular dendritic divergent structure, molecules are in a spreading divergent shape when not becoming compact spheres within a certain molecular weight range, the divergent structure can be rapidly dispersed in a solution and is not easy to tangle, the intrinsic viscosity of the hyperbranched polymer is far less than that of a conventional demulsifier, the hyperbranched polymer is favorable for diffusion and adsorption to an interface, a highly branched unstable adsorption film is rapidly generated while a stable interface film is formed by weakening a natural emulsifier, and a good demulsification effect is further obtained.
Wherein, Hyperbranched Polyamidoamine (HPAMAM) is a mature hyperbranched polymer, and Tomalia et al synthesizes polymers in 2001The amide amine dendritic polymer (marked as PAMAM) usually takes ammonia or ethylenediamine as a core, has the molecular weight of more than 930,000g/mol at most, has the polydispersity of less than 1.8, is a colorless to light yellow liquid on a macroscopic view, has low volatility, and has the kinematic viscosity of 10-10000 mm at the temperature of 25 DEG C2And s. The hyperbranched polyamidoamine end group is amino, the skeleton contains a large number of hyperbranched structures, the hydrophilic property is good, and the tail end of the branched chain is provided with a large number of amino groups for modification. However, there is no report that the amino group at the terminal of the hyperbranched polyamidoamine is modified and then used in an oil-in-water emulsion for demulsification.
Disclosure of Invention
The invention aims to provide a method for demulsifying an oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine, aiming at the defects of the prior art and achieving the purpose of quickly and efficiently demulsifying the oil-in-water type emulsion in a short time.
The technical scheme provided by the invention is as follows:
a method for demulsifying an oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine comprises the following steps:
1) c is to be10～C18Carrying out amidation reaction on the saturated fatty acid and the hyperbranched polyamidoamine to obtain amphiphilic hyperbranched polyamidoamine; the mass ratio of the saturated fatty acid to the hyperbranched polyamidoamine is 0.4-2.5;
2) and dispersing the amphiphilic hyperbranched polyamidoamine into an oil-in-water type emulsion for demulsification.
In the present invention, the compound C10～C18The saturated fatty acid carries out graft modification on the hyperbranched polyamidoamine, so that the terminal group of the hyperbranched polyamidoamine is grafted with long-chain alkyl. HPAMAM in the modified hyperbranched polymer is a hydrophilic compact core, and the shell consists of lipophilic long-chain alkyl and hydrophilic amino to form amphiphilic polymers with different degrees of substitution and a core-shell structure, wherein the number average molecular weight distribution of the amphiphilic polymers is 8000-20000.
Secondly, by controlling the mass ratio of saturated fatty acid to hyperbranched polyamidoamine, the modified hyperbranched polymer has higher interfacial activity because the end group is partially substituted by lipophilic group long-chain alkyl, so that the modified hyperbranched polymer can be more quickly dispersed in oil-water emulsion to quickly reach an oil-water interface while ensuring good water solubility, and an oil-water interface membrane is damaged.
Preferably, the mass ratio of the saturated fatty acid to the hyperbranched polyamidoamine is 1.6-1.7.
In the invention C10～C18The saturated fatty acids of (b) are a class of fatty acids having no unsaturated bonds (double bonds) in the carbon chain. Preferably, the saturated fatty acid is selected from one or more of n-capric acid, lauric acid, myristic acid, palmitic acid and stearic acid. Further preferred is palmitic acid.
The amidation reaction of the present invention includes:
1.1) dissolving saturated fatty acid in an organic solvent, adding a catalyst N, N' -carbonyldiimidazole, then dropwise adding hyperbranched polyamidoamine dissolved in the same organic solvent, and performing amidation reaction at 40-100 ℃ for 3-24 h to obtain a crude product;
1.2) concentrating the crude product obtained in the step 1.1), separating acetone, and performing rotary evaporation to obtain the amphiphilic hyperbranched polyamidoamine.
Preferably, the mass ratio of the saturated fatty acid to the hyperbranched polyamidoamine is 0.4-2.5.
Preferably, the temperature of the amidation reaction is 50-70 ℃, and the reaction time is 6-12 h.
The mass ratio of the hyperbranched N, N' -carbonyldiimidazole to the hyperbranched polyamidoamine is 0.2-1.5. More preferably 0.9 to 1.1.
The organic solvent is trichloromethane or methanol.
The addition amount of the amphiphilic hyperbranched polyamidoamine in the oil-in-water emulsion is 10-80 mg/L. The addition amount is less than 10mg/L, and the demulsification effect is poor; the addition amount is more than 80mg/L, the demulsification effect is not changed greatly, but the economic cost is increased greatly.
The temperature of demulsification is 25-65 ℃, and the settling time is 0.5-2 h. Preferably, the demulsification temperature is 30-60 ℃, and the settling time is 60-90 min.
The oil phase in the oil-in-water emulsion of the present invention is a simulated oil or an actual oil. Preferably, the simulated oil is n-dodecane, n-tridecane, n-tetradecane, or n-hexadecane. Preferably, the actual oil is kerosene, diesel oil or gasoline.
The mineralization degree of a water phase in the oil-in-water type emulsion is 0-20000 mg/L, wherein NaCl and CaCl in the water phase2The mass ratio of (A) to (B) is 0.1 to 1.5.
Compared with the prior art, the invention has the beneficial effects that:
according to the modified amphiphilic hyperbranched polyamidoamine, the end group is partially substituted into the lipophilic group long-chain alkyl group, the shell simultaneously contains the strong hydrophilic group amino group and the hydrophobic group long-chain alkyl group, so that the modified amphiphilic hyperbranched polyamidoamine can quickly reach an oil-water interface to damage an oil-water interface membrane while ensuring good water solubility, and meanwhile, the external long-chain alkyl group has strong adsorption capacity and can adsorb more oil drops to enable the oil drops to coalesce and float upwards to finally achieve oil-water separation, and quick demulsification can be realized under the condition of less addition amount.
Drawings
FIG. 1 is a schematic structural diagram of an amphiphilic hyperbranched polyamide-amine modified with palmitic acid according to the present invention;
FIG. 2 is a schematic structural diagram of the myristic acid modified amphiphilic hyperbranched polyamidoamine of the invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: amphiphilic hyperbranched polyamidoamine (HPAMAM-g-C)n) Preparation of
Dissolving 5g of palmitic acid in 30mL of chloroform, weighing 3.17g of CDI, adding the CDI into the reaction system, and stirring until the CDI is dissolved to obtain a palmitic acid mixed solution. Dissolving 3g of HPAMAM in 10mL of chloroform, then dropwise adding the solution into a palmitic acid mixed solution, and carrying out amidation reaction at 55 ℃ for 9 hours to obtain a crude product with high polymerization degree;
then, the crude product is cooled to room temperature and poured into 250mL of acetone to be stirred for 60min, yellow transparent viscous liquid can be observed to be precipitated at the lower layer, the upper layer of acetone is discarded, the precipitation is repeated for 2 times, and the HPAMAM-g-C can be obtained by rotary evaporation at 50 ℃ in vacuum16。
Amphiphilic hyperbranched polyamidoamine (HPAMAM-g-C)16) The schematic structural diagram of (a) is shown in fig. 1, it should be noted that, since the hyperbranched structure is variable and complex, the structure shown is only an example.
Examples 2 to 7
The amphiphilic hyperbranched polyamidoamine (HPAMAM-g-C) can be obtained by preparing the amphiphilic hyperbranched polyamidoamine according to the example 1, wherein the specific process parameters are shown in the table 1n)。
Table 1: comparison of preparation Process parameters for examples 1 to 7
Figure BDA0001881485940000051
Among them, the amphiphilic hyperbranched polyamidoamine (HPAMAM-g-C) prepared in example 214) The schematic structural diagram of (a) is shown in fig. 2, it should be noted that, since the hyperbranched structure is variable and complex, the structure shown is only an example.
Application examples 1 to 7
HPAMAM-g-C prepared in examples 1 to 7 was weighed separatelyn(number average molecular weight distribution: 10000 to 20000) and dissolved in 80mg/L of n-hexadecane as an oil phase with a degree of mineralization of 5000mg/L by stirring. The results of measuring the oil removal rate w of the lower aqueous phase at a settling time of 60min at 60 ℃ and a concentration of 80mg/L are shown in Table 2.
Table 2: application examples 1 to 7 dehydration ratio comparison
Figure BDA0001881485940000052
Figure BDA0001881485940000061
Analysis shows that the demulsifier prepared in example 1 has the best performance, and HPAMAM-g-C obtained by the reaction of the mass ratio of palmitic acid to hyperbranched polyamidoamine is mainly regulated and controlled16The degree of reducing interfacial tension is higher, the breaking rate of emulsion liquid drops is obviously improved, the liquid discharge time is shorter, and the purpose of the efficient demulsifier can be achieved.
Application example 8
Weighing HPAMAM-g-C in example 116(number average molecular weight distribution: 10000 to 20000) and dissolved in an oil-in-water emulsion containing n-hexadecane as an oil phase and having a degree of mineralization of 7500mg/L, with stirring at a concentration of 60 mg/L. The oil removal efficiency was measured at 45 ℃ for settling times of 1min, 10min, 20min and 30min, respectively. The results show that HPAMAM-g-C16The deoiling efficiency at these settling times increased from 7% to 50%, 73%, 86% and 95%, respectively.
Application examples 9 to 17
The test was conducted with reference to application example 8, and the specific process parameters and the results of the oil removal efficiency of the aqueous phase are shown in table 3.
Table 3: comparison of Process parameters and Water phase oil removal efficiency in application examples 9-17
Figure BDA0001881485940000062
Figure BDA0001881485940000071
Application example 18
Weighing HPAMAM-g-C in example 214(number average molecular weight distribution: 10000 to 20000) and dissolved in an oil-in-water emulsion containing n-hexadecane as an oil phase and having a degree of mineralization of 7500mg/L, with stirring at a concentration of 40 mg/L. The oil removal efficiency was measured at 45 ℃ for settling times of 1min, 10min, 20min and 30min, respectively. The results show that HPAMAM-g-C14The deoiling efficiency at these settling times was 7%Increased to 56%, 71%, 86% and 93%, respectively.
Application example 19
Weighing HPAMAM-g-C in example 312(number average molecular weight distribution: 10000 to 20000) and dissolved in an oil-in-water emulsion containing n-hexadecane as an oil phase and having a degree of mineralization of 10000mg/L, with stirring at a concentration of 40 mg/L. The oil removal efficiency was measured at 60 ℃ for settling times of 1min, 10min, 20min and 30min, respectively. The results show that HPAMAM-g-C12The deoiling efficiency at these settling times increased from 7% to 53%, 68%, 80% and 87%, respectively.
Application example 20
Weighing HPAMAM-g-C in example 418(number average molecular weight distribution: 10000 to 20000) and dissolved in 80mg/L of n-hexadecane as an oil phase with a degree of mineralization of 5000mg/L by stirring. The oil removal efficiency was measured at 60 ℃ for settling times of 1min, 10min, 20min and 30min, respectively. The results show that HPAMAM-g-C18The deoiling efficiency at these settling times increased from 7% to 43%, 61%, 73% and 80%, respectively.

Claims (8)

1. A method for demulsifying an oil-in-water type emulsion by using amphiphilic hyperbranched polyamidoamine is characterized by comprising the following steps:
1) c is to be10～C18Carrying out amidation reaction on the saturated fatty acid and the hyperbranched polyamidoamine to obtain amphiphilic hyperbranched polyamidoamine, wherein the number average molecular weight distribution of the amphiphilic hyperbranched polyamidoamine is 8000-20000; the mass ratio of the saturated fatty acid to the hyperbranched polyamidoamine is 0.4-2.5;
2) and dispersing the amphiphilic hyperbranched polyamidoamine into an oil-in-water type emulsion for demulsification.
2. The method for demulsifying an oil-in-water emulsion using amphiphilic hyperbranched polyamidoamine according to claim 1, wherein the saturated fatty acid is selected from one or more of n-decanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid.
3. The method of demulsifying an oil-in-water emulsion using amphiphilic hyperbranched polyamidoamine according to claim 1, wherein the amidation reaction comprises:
1.1) dissolving saturated fatty acid in an organic solvent, adding a catalyst N, N' -carbonyldiimidazole, then dropwise adding hyperbranched polyamidoamine dissolved in the same organic solvent, and performing amidation reaction at 40-100 ℃ for 3-24 h to obtain a crude product;
1.2) concentrating the crude product obtained in the step 1.1), separating acetone, and performing rotary evaporation to obtain the amphiphilic hyperbranched polyamidoamine.
4. The method for demulsifying an oil-in-water emulsion by using amphiphilic hyperbranched polyamidoamine as claimed in claim 3, wherein the mass ratio of the N, N' -carbonyldiimidazole to the hyperbranched polyamidoamine is 0.2-1.5.
5. The method of demulsifying an oil-in-water emulsion using amphiphilic hyperbranched polyamidoamine according to claim 3, wherein the organic solvent is chloroform or methanol.
6. The method for demulsifying an oil-in-water emulsion by using amphiphilic hyperbranched polyamidoamine according to claim 1, wherein the addition amount of the amphiphilic hyperbranched polyamidoamine in the oil-in-water emulsion is 10-80 mg/L.
7. The method for demulsifying an oil-in-water emulsion by using amphiphilic hyperbranched polyamidoamine according to claim 1, wherein the temperature for demulsification is 25-65 ℃ and the settling time is 0.5-2 h.
8. The method for demulsifying an oil-in-water emulsion according to claim 1, wherein the degree of mineralization of the water phase in the oil-in-water emulsion is 0 to 20000 mg/L.
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