CN111717960B - Oily sewage compound type reverse demulsifier and application thereof - Google Patents
Oily sewage compound type reverse demulsifier and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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Abstract
The invention provides a compound reverse demulsifier for treating oil-bearing sewage from oil sand washing. Synthesizing a cation reverse demulsifier A by adopting a method of quaternizing chlorinated ether and dimethylamine; synthesizing a cationic polymer B by using formaldehyde, acetone, PAM and polyamine as raw materials; c is a polyquaternium surfactant. A, B, C are mixed in different proportions to form a mixed reverse demulsifier for carrying out sewage demulsification and separation. The mixed reverse demulsifier can adjust the content of A, B, C three surfactants to treat oily sewage with various characteristics, particularly the oily sewage of oil sand washing, can reduce the oil content in the treated water to 20mg/L or lower, and has the advantages of high dehydration speed, mild reaction conditions and wide adaptability.
Description
Technical Field
The invention relates to a chemical auxiliary agent for petroleum industry, belongs to the technical field of oilfield chemistry, and particularly relates to a compound reverse demulsifier for treating oilfield oil extraction sewage and oil sand washing oil-containing sewage.
Background
Currently, oil sand bitumen is being noted and developed with the decrease in conventional petroleum resources. A commonly used method for oil sand bitumen recovery is the hot water caustic wash technique. Because a large amount of emulsifying agents and alkalis are applied in the oil sand washing process, the properties of a large amount of oily sewage generated in the washing process are more complex, the oil content is high, the silt content is high, the emulsion type is complex, and all the properties cause that the treatment of the oil-containing sewage generated in the oil sand washing process is more difficult. At present, the reverse demulsifiers used for O/W type oily sewage demulsification at home and abroad mainly comprise three categories of low molecular electrolytes, alcohols, surfactants and high molecular polymers. The demulsification effect of the electrolyte and the alcohol is limited, the addition amount is large, secondary pollution is easy to form, and the electrolyte and the alcohol are eliminated. The surfactant demulsifiers mainly include cationic, anionic and nonionic demulsifiers. The cationic surfactant is mainly quaternary ammonium salt, the anionic surfactant is mainly dithiocarbamate, and the nonionic surfactant is mainly polyamine. The high molecular polymer reverse demulsifier comprises polyether type, polyquaternary ammonium salt, polysiloxane and the like. However, the currently published reverse demulsifier for oily sewage is intensively applied to oily sewage in oil fields, and the treatment effect is to be improved.
CN102559245A discloses a reverse demulsifier and a preparation method thereof, wherein the reverse demulsifier is obtained by the reaction of polyamide-amine, epichlorohydrin and acryloyloxyethyl trimethyl ammonium chloride, and has a good demulsification effect on oil-in-water type emulsion of oil field produced fluid.
CN104291412A discloses a preparation method of a reverse demulsifier for polymer-containing oil extraction wastewater treatment, wherein the reverse demulsifier is obtained by reacting epichlorohydrin, dimethylamine and carbon disulfide, and has a good demulsification effect on polymer-containing wastewater in an oil field. Because the two reverse demulsifiers have single composition, the treatment effect on the complex oily sewage of the oil field can not meet the production requirement of the oil field.
CN105523606A provides a composite reverse demulsifier, a preparation method and a use method thereof. The composite reverse demulsifier comprises two cationic surfactants, namely dimethyl diallyl ammonium chloride and octadecyl ammonium chloride, two demulsifiers SP169 and AE121, polymeric aluminum and the like. The reverse demulsifier has reasonable component compounding, good synergistic effect, and obviously better treatment effect on oily sewage in an oil field than that of a single reverse demulsifier, but the demulsifier has poorer treatment effect on sewage with high silt content.
The literature, "the number of micelle aggregation of the trimeric quaternary ammonium salt surfactant is determined by a steady-state fluorescence probe method" (physical and chemical reports, 2005, 21 (12): 1403-1406) describes the synthesis and the study of the properties of the trimeric ammonium salt surfactant, and the trimeric ammonium salt surfactant is mainly used in the fields of wetting agents of cosmetics and the like.
However, the above-mentioned prior art reverse demulsifier does not consider the surface modifier component for silt, and still has a technical problem in that it is only applicable to the treatment of oily sewage under the condition of low silt content. For oil sand washing oil-containing sewage and oil field oil-containing sewage with high silt content, the stability of sewage emulsion is obviously enhanced due to the dispersion effect of silt, so that the sewage treatment effect is poor.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides the following technical solutions.
The invention provides a compound reverse demulsifier for oily sewage, which comprises the following components in percentage by mass:
5% -98% of a cation reverse demulsifier A;
1-90% of cationic polymer B;
polyquaternium surfactant C1-20%;
wherein the polyquaternium surfactant C is a main agent; the A is a cation reverse demulsifier synthesized by a method of quaternizing chlorinated ether and dimethylamine; and B is formaldehyde, acetone, PAM and polyamine which are used as raw materials to synthesize the cationic polymer.
The invention provides a compound reverse demulsifier for oily sewage, which comprises the following components in percentage by mass: 5-15% of polyquaternium surfactant C, 30-90% of cationic reverse demulsifier A and 5-70% of cationic polymer B.
The invention provides a compound reverse demulsifier for oily sewage, which comprises the following components in percentage by mass: 5-10% of polyquaternium surfactant C, 40-90% of cationic reverse demulsifier A and 5-60% of cationic polymer B.
The invention provides a compound reverse demulsifier for oily sewage, which comprises the following components in percentage by total mass: 5-20% of polyquaternary ammonium salt surfactant C and 80-95% of cation reverse demulsifier A.
The oil-containing sewage compound reverse demulsifier provided by the invention can be diluted to a certain mass concentration by water and is used for treating oil-containing sewage washed by oil sand water.
The present invention can be described in detail as follows:
the invention relates to a compound reverse demulsifier for oil-containing sewage in oil sand washing, which is obtained by mixing at least two cationic surfactants and has excellent demulsification effect on O/W and O/W/O mixed emulsions of sewage with high sediment content in oil sand washing.
Therefore, the invention provides a compound reverse demulsifier for oil sand washing oily sewage, wherein: the oil sand washing oily sewage reverse demulsifier is compounded with a polyquaternary ammonium surfactant C as a main agent and a cation reverse demulsifier A or a cation reverse demulsifier A and a cation polymer B; diluting the components to obtain a final oil sand water-washing oily sewage reverse-phase demulsifier; the composite material comprises the following components in percentage by mass: a: 5 to 98 percent; b: 1-90%; c: 1 to 20 percent; wherein A is a cation reverse demulsifier synthesized by a method of quaternizing chlorinated ether and dimethylamine; b is formaldehyde, acetone, PAM and polyamine which are used as raw materials to synthesize a cationic polymer; c is polyquaternium surfactant.
In the invention, when the oil sand washing oily sewage compound reverse demulsifier only contains polyquaternium surfactant and cation reverse demulsifier A, the preferable oil-containing sewage compound reverse demulsifier comprises the following components (by mass percent): 5-20% of polyquaternary ammonium salt surfactant C and 80-95% of cation reverse demulsifier A.
The more preferable oil sand washing oily sewage compound reverse demulsifier comprises the following components in percentage by mass: 5-15% of polyquaternium surfactant C, 30-90% of cationic reverse demulsifier A and 5-70% of cationic polymer B.
The more preferable oil sand washing oily sewage compound reverse demulsifier comprises the following components in percentage by mass: 1-10% of polyquaternium surfactant C, 40-90% of cationic reverse demulsifier A and 5-60% of cationic polymer B.
The invention A is a method for synthesizing a cation reverse demulsifier by quaternizing chloro-and dimethylamine, which is an auxiliary agent in the prior art, and the invention does not particularly limit the preparation method of the composition, and the preparation method is a method in the prior art, such as the preparation method of the cation polyether reverse demulsifier of CN1059669A, the synthesis and performance evaluation of the emulsion demulsifier of O/W type (proceedings of petroleum university, 1997,21 (6): 82-84). The cation reverse demulsifier has high positive charge density and obvious demulsification effect on oil-in-water type emulsion.
The invention also provides a preparation method of the cation reverse demulsifier A, which comprises the following steps: adding polyalcohol and a catalyst into a reactor, controlling the temperature within the range of 40-60 ℃, and dropwise adding epoxy chloropropane. And after the dropwise addition is finished, heating to 70-90 ℃ to obtain the chlorinated polyether. Weighing a chlorinated polyether and a dimethylamine aqueous solution, adding the chlorinated polyether and the dimethylamine aqueous solution into a high-pressure reaction kettle, heating the mixture, controlling the temperature in the kettle to be within the range of 60-80 ℃, stirring the mixture for reaction for 3-5 hours, then gradually heating the mixture to 100-120 ℃, and continuing the reaction to obtain the cation reverse-phase demulsifier A.
The polyhydric fatty alcohol may be any polyhydric fatty alcohol commonly used in the art, and the present invention is not particularly limited thereto, and may be ethylene glycol, glycerol, or pentaerythritol.
The structure of the chlorinated polyether varies depending on the polyhydric aliphatic alcohol.
The catalyst may be any one commonly used in the art, and the present invention is not particularly limited, and may be triethylboron trifluoride or trimethylboron trifluoride.
In the invention, B is formaldehyde, acetone, PAM and polyamine which are used as raw materials to synthesize the cationic polymer, and is also an auxiliary agent in the prior art, the preparation method of the composition is not particularly limited, and the preparation method is a method in the prior art, such as synthesis and application of cationic polyacrylamide, (fine petrochemical, 2004, 6: 54-57). The cationic polymer has strong bridging effect in aqueous solution and has good synergistic effect with A.
The invention also provides a preparation method of the cationic polymer B, which comprises the following steps: adding a certain amount of formaldehyde, acetone and PAM (polyacrylamide) into a reactor, reacting for 2-3 hours at the temperature of 20-30 ℃, dropwise adding polyamine, controlling the temperature not to exceed 55 ℃, heating to 60-80 ℃ after adding, and reacting for a period of time to obtain the cationic polymer B. The polyamine may be a polyamine commonly used in the art, and the present invention is not particularly limited, and may be ethylenediamine, diethylenetriamine, or triethylenetetramine.
The C is polyquaternium surfactant and is also an auxiliary agent in the prior art, the preparation method of the composition is not particularly limited, and the preparation method is only the method in the prior art. C is a dendritic surfactant, has strong modification and flocculation effects on sewage with high silt content, is particularly suitable for demulsification of oil in silt when being compounded with A, and has good separation effect.
A method for synthesizing the trimeric ammonium salt surfactant is also described in the section of the number of micelle aggregations of the trimeric ammonium salt surfactant by the steady-state fluorescence probe method (physical chemistry report, 2005, 21 (12): 1403-1406)).
The invention also provides a preparation method of the quaternary ammonium salt poly surfactant C, which comprises the following steps: adding 0.5-4.5 half-generation polyamide-amine into a reactor, dissolving with methanol, dropwise adding N, N-dimethylethylenediamine at a system temperature of less than 10 ℃, adjusting the reaction temperature to 25-35 ℃ after dropwise adding, and reacting for 48-72 hours. After the reaction is finished, performing vacuum rotary evaporation to obtain an intermediate. And adding the intermediate into a reactor, then dropwise adding bromoalkane, raising the reaction temperature to 40-60 ℃, removing the solvent after the reaction is finished, and drying to obtain a white solid compound, namely C.
The compound reverse demulsifier for treating the oil sand washing oily sewage obtained by the method disclosed by the invention has the advantages that the oil content in the treated water is reduced to 100mg/L, and the oil content in the water can be reduced to below 20mg/L under the optimal condition, so that the compound reverse demulsifier has the advantages of high dehydration speed, mild treatment condition and wide adaptability.
Detailed Description
The characterization and calculation method comprises the following steps: the oil content in the sewage is measured by using an ultraviolet spectrophotometer, and the reference is made to the oil and gas industry standard SY/T0530-2011 of the people's republic of China.
The raw material sources are as follows:
1. oil sand water oil-containing sewage in Xinjiang
2. Inner Mongolia oil sand water oil-containing sewage
Example 1
Preparation of surfactant a in this example: 10.36g of isoamyl tetrol and 0.052g of catalyst triethylboron trifluoride are added into a four-mouth bottle provided with an electric stirrer, a dropping liquid pipe, a thermometer and a serpentine condenser pipe, and 42.03 epichlorohydrin is added while stirring at the temperature of 55 ℃. After the dropwise addition, the temperature is raised to 80 ℃, and the stirring is continued until the materials are uniform and transparent, thus obtaining the chlorinated polyether. Weighing 37.25g of chlorinated polyether and 36.81g of dimethylamine aqueous solution, adding the chlorinated polyether and the dimethylamine aqueous solution into a high-pressure reaction kettle, sealing the kettle to 70 ℃, reacting for 5 hours, gradually heating to 110 ℃, continuously stirring and reacting for 4 hours, stopping the reaction, and taking out the reactant when the reaction temperature is reduced to 40 ℃ to obtain the cationic surfactant A.
Preparation of surfactant B in this example: adding 2mol of formaldehyde and 1.5mol of acetone into a three-necked bottle provided with a thermometer and a stirrer, reacting for 2.5 hours at the temperature of 30 ℃, then dropwise adding 1mol of triethylene tetramine and PAM at the temperature of 40 ℃, controlling the temperature to be not more than 50 ℃, heating to 65 ℃ after finishing adding, and reacting for 3 hours to obtain the cationic polymer B.
Preparation of surfactant C in this example: 20 g of 2.5-half generation polyamide-amine is added into a reactor, 100 g of methanol is added for dissolution, 30 g of N, N-dimethylethylenediamine is dripped, the temperature of the system is lower than 10 ℃, after the dripping is finished, the reaction temperature is adjusted to 30 ℃, and the reaction is carried out for 60 hours. After the reaction is finished, performing vacuum rotary evaporation to obtain an intermediate. Adding the intermediate into a reactor, then dropwise adding bromoalkane, raising the reaction temperature to 55 ℃, removing the solvent after the reaction is finished, and drying to obtain a white solid compound, namely C.
In this example, the preparation of the complex reverse demulsifier for oily wastewater from oil sand washing: A. b, C the three surfactants are all solid, and the oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 85% by mass of A, 10% by mass of B and 5% by mass of C, and is diluted by water to have a mass concentration of 20% and used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 2
Preparation of surfactant a in this example: 10.36g of isoamyl tetrol and 0.052g of catalyst triethylboron trifluoride are put into a four-mouth bottle provided with an electric stirrer, a dropping liquid pipe, a thermometer and a serpentine condenser, and 42.52g of epichlorohydrin is added while stirring at the temperature of 50 ℃. After the dropwise addition, the temperature is raised to 90 ℃, and the stirring is continued until the materials are uniform and transparent, thus obtaining the chlorinated polyether. 39.35g of chlorinated polyether and 37.93g of dimethylamine aqueous solution are weighed and added into a high-pressure reaction kettle, the kettle is sealed to 70 ℃, the temperature is gradually increased to 120 ℃ after the reaction is carried out for 5 hours, the stirring reaction is continued for 4 hours, and the reaction is stopped until the reaction temperature is reduced to 40 ℃, and the reactant is taken out, thus obtaining the cationic surfactant A.
Preparation of surfactant B in this example: adding 2mol of formaldehyde and 1.5mol of acetone into a three-necked bottle provided with a thermometer and a stirrer, reacting for 3 hours at the temperature of 20 ℃, then dropwise adding 1mol of triethylene tetramine and PAM at the temperature of 40 ℃, controlling the temperature to be not more than 50 ℃, heating to 80 ℃ after adding, and reacting for 4 hours to obtain the cationic polymer B.
Preparation of surfactant C in this example: adding 20 g of 3.5-half generation polyamide-amine into a reactor, adding 100 g of methanol for dissolving, dropwise adding 20 g of N, N-dimethylethylenediamine, wherein the system temperature is lower than 5 ℃, adjusting the reaction temperature to 30 ℃ after dropwise adding, and reacting for 70 hours. After the reaction is finished, performing vacuum rotary evaporation to obtain an intermediate. Adding the intermediate into a reactor, then dropwise adding bromoalkane, raising the reaction temperature to 55 ℃, removing the solvent after the reaction is finished, and drying to obtain a white solid compound, namely C.
In this example, the preparation of the complex reverse demulsifier for oily wastewater from oil sand washing: A. b, C the three surfactants are all solid, and the oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 85% by mass of A, 10% by mass of B and 5% by mass of C, and is diluted by water to have a mass concentration of 20% and used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 3
Preparation of surfactant a in this example: 10.36g of glycerol and 0.052g of triethylboron trifluoride as a catalyst are placed in a four-neck flask equipped with an electric stirrer, a dropping tube, a thermometer and a serpentine condenser, and 38.75g of epichlorohydrin is added while stirring at a controlled temperature of 40 ℃. After the dropwise addition, the temperature is raised to 70 ℃, and the stirring is continued until the materials are uniform and transparent, thus obtaining the chlorinated polyether. 39.01g of chlorinated polyether and 37.93g of dimethylamine aqueous solution are weighed and added into a high-pressure reaction kettle, the kettle is sealed to 70 ℃, the temperature is gradually increased to 100 ℃ after 5 hours of reaction, the reaction is continuously stirred for 6 hours, and the reaction is stopped until the reaction temperature is reduced to 40 ℃, and then the reactant is taken out to obtain the cationic surfactant A.
Preparation of surfactant B in this example: adding 2mol of formaldehyde and 1.5mol of acetone into a three-necked bottle provided with a thermometer and a stirrer, reacting for 2 hours at the temperature of 20 ℃, then dropwise adding 1mol of triethylene tetramine and PAM at the temperature of 40 ℃, controlling the temperature to be not more than 50 ℃, heating to 60 ℃ after adding, and reacting for 4 hours to obtain the cationic polymer B.
Preparation of surfactant C in this example: 20 g of 1.5-half generation polyamide-amine is added into a reactor, 100 g of methanol is added for dissolution, 35g of N, N-dimethylethylenediamine is dripped, the temperature of the system is lower than 5 ℃, after the dripping is finished, the reaction temperature is adjusted to 30 ℃, and the reaction is carried out for 50 hours. After the reaction is finished, performing vacuum rotary evaporation to obtain an intermediate. Adding the intermediate into a reactor, then dropwise adding bromoalkane, raising the reaction temperature to 55 ℃, removing the solvent after the reaction is finished, and drying to obtain a white solid compound, namely C.
In this embodiment, the preparation of the oil sand washing oil-containing sewage compound reverse demulsifier: A. b, C the three surfactants are all solid, and the oil sand washing oily sewage reverse phase demulsifier is formed by mixing the oil sand washing oily sewage reverse phase demulsifier with the mass ratio of 85% of A, 10% of B and 5% of C, and is diluted to the mass concentration of 20% by water for treating the Xinjiang oil sand washing sewage. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 4
A, B, C in this example is identical to example 1. The oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 70% of A, 10% of B and 20% of C in different mass ratios, and is diluted to 20% in mass concentration by water and used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 5
A, B, C in this example is identical to example 1. The oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 70% of A, 10% of B and 10% of C according to different mass ratios, is diluted to 20% of mass concentration by water and is used for treating inner oil sand washing sewage. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 6
A, B, C in this example is identical to example 1. The oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 75% of A, 20% of B and 5% of C in different mass ratios, and is diluted to 20% in mass concentration by water and used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Comparative example 1
A, B in this example is identical to example 1. The oil sand washing oily sewage reverse-phase demulsifier is formed by mixing oil sand washing oily sewage with different mass ratios, and comprises 75% of A and 25% of B, wherein the oil sand washing oily sewage reverse-phase demulsifier is obtained by compounding, is diluted by water to have a mass concentration of 20%, and is used for treating Xinjiang oil sand washing sewage. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 7
A, B, C in this example is identical to example 1. The oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 75% of A, 15% of B and 10% of C, is diluted to 20% of mass concentration by water and is used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 8
Preparation of surfactant a in this example: 10.36g of isoamyl tetrol and 0.061g of catalyst triethylboron trifluoride are added into a four-mouth bottle provided with an electric stirrer, a dropping tube, a thermometer and a serpentine condenser, and 42.03 epichlorohydrin is added while stirring at the temperature of 45 ℃. After the dropwise addition, the temperature is raised to 90 ℃, and the stirring is continued until the materials are uniform and transparent, thus obtaining the chlorinated polyether. Weighing 37.25g of chlorinated polyether and 36.81g of dimethylamine aqueous solution, adding the chlorinated polyether and the dimethylamine aqueous solution into a high-pressure reaction kettle, sealing the kettle to 80 ℃, reacting for 3 hours, gradually heating the kettle to 100 ℃, continuously stirring the kettle for reaction for 4 hours, stopping the reaction, and taking out the reactant when the reaction temperature is reduced to 30 ℃ to obtain the cationic surfactant A.
B, C in this example is identical to example 1.
In this embodiment, the preparation of the oil sand washing oil-containing sewage compound reverse demulsifier: A. b, C the three surfactants are all solid, and the oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 75% of A, 15% of B and 10% of C, and is diluted to 20% of mass concentration by water and used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 9
Preparation of surfactant B in this example: adding 2mol of formaldehyde, 1.5mol of acetone and 50 g of PAM into a three-necked bottle provided with a thermometer and a stirrer, reacting for 3 hours at the temperature of 20 ℃, then dropwise adding 1mol of diethylenetriamine at the temperature of 30 ℃, controlling the temperature to be not more than 40 ℃, heating to 80 ℃ after the addition, and reacting for 3 hours to obtain the cationic polymer B.
A, C in this example is identical to example 1.
In this embodiment, the preparation of the oil sand washing oil-containing sewage compound reverse demulsifier: A. b, C the three surfactants are all solid, and the oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 75% of A, 15% of B and 10% of C, and is diluted to 20% of mass concentration by water and used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 10
Preparation of surfactant C in this example: adding 20 g of 3.5-half generation polyamide-amine into a reactor, adding 100 g of ethanol for dissolving, dropwise adding N, N-dimethyl propane diamine, wherein the system temperature is lower than 15 ℃, adjusting the reaction temperature to 35 ℃ after dropwise adding, and reacting for 72 hours. After the reaction is finished, performing vacuum rotary evaporation to obtain an intermediate. Adding the intermediate into a reactor, then dropwise adding bromoalkane, raising the reaction temperature to 60 ℃, removing the solvent after the reaction is finished, and drying to obtain a white solid compound, namely C.
A, B in this example is identical to example 1.
In this embodiment, the preparation of the oil sand washing oil-containing sewage compound reverse demulsifier: A. b, C the three surfactants are all solid, and the oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 75% of A, 10% of B and 15% of C, and is diluted by water to 20% of mass concentration for treating the inner oil sand washing sewage. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Example 11
Preparation a in this example: the method shown in the document "synthesis and performance evaluation of O/W type emulsion demulsifier" (proceedings of Petroleum university, 1997,21 (6): 82-84) is used, and the specific process is as follows: a mixture of 22.8g of 33% dimethylamine aqueous solution and 1.3g n-butylamine was charged into a three-necked flask, 13.8g of epichlorohydrin was added within 10 to 15min while stirring the mixture, and the temperature of the mixture was maintained at 30 to 35 ℃ by a cooling device. Then, the raw materials in the reactor are heated to 70 ℃, stirred and reacted for 1 hour, and then 9.4g of epoxy chloropropane is added. When the epichlorohydrin is completely added, continuously reacting for a certain time, and adding H in a ratio of 1: 1 when the product reaches a certain viscosity2SO4The product was brought to pH 5 to quench the reaction and the product was dried.
B, preparation: the method shown in the literature, namely the synthesis and application of cationic polyacrylamide (fine petrochemical industry, 2004, 6: 54-57), is used, and the specific process is as follows: adding 100 g of a solution with the w (PAM) of 3 percent to 5 percent into a 250mL three-neck flask, heating to 30 ℃, uniformly stirring, adding a proper amount of formaldehyde and acetone, reacting for about lh completely, adding polyamine, heating to 60 ℃, reacting for 3h, cooling and discharging.
C, preparation: using the literature physical chemistry journal, 2005, 21 (12): 1403-1406) in the step of determining the micelle aggregation number of the trimeric quaternary ammonium salt surfactant by using a steady-state fluorescence probe method, a method for synthesizing the trimeric quaternary ammonium salt surfactant is also described. The specific process is as follows: adding metered citric acid and isopropanol into a four-neck flask, heating and stirring at a proper temperature of 20 ℃ for 30min to completely dissolve the citric acid and the isopropanol, adding dodecyl dimethyl tertiary amine, stirring and reacting at a temperature of 80 ℃ for 1h, then slowly dropwise adding epoxy chloropropane, and reacting at the constant temperature for 12 h. Cooling to room temperature, adding appropriate amount of anhydrous ether, and extracting for multiple times. And obtaining the trimeric quaternary ammonium salt surfactant C.
The oil sand washing oily sewage reverse-phase demulsifier is formed by mixing 75% of A, 20% of B and 5% of C in different mass ratios, and is diluted to 20% in mass concentration by water and used for treating the oil sand washing sewage in Xinjiang. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is increased.
Comparative example 2
The oil sand washing oily sewage reverse-phase demulsifier is formed by mixing different mass ratios, and comprises 80% of B and 20% of C, and is diluted by water to have a mass concentration of 20% for treating Xinjiang oil sand washing sewage. The experimental conditions were: when the temperature is 50 ℃ and the pH value is 7.0-8.0, the oil removal rate of the reverse demulsifier for the oil-containing sewage washed by the oil sand water under the condition of 40mg/L is achieved.
TABLE 1 oil sand washing oily sewage reverse demulsifier effect data for water washing sewage treatment
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (5)
1. The composite reverse demulsifier for oily sewage comprises the following components in percentage by mass:
5% -98% of a cation reverse demulsifier A;
cationic polymer B1-90%;
polyquaternium surfactant C1-20%;
the method is characterized in that the polyquaternium surfactant C is used as a main agent; the cation reverse demulsifier A is a cation reverse demulsifier synthesized by a method of quaternizing chlorinated ether and dimethylamine; the cationic polymer B is synthesized by taking formaldehyde, acetone, PAM and polyamine as raw materials.
2. The oily sewage compound reverse demulsifier according to claim 1, which is characterized in that: the composition of the reverse demulsifier is as follows by the total mass percentage of the demulsifier: 5-15% of polyquaternium surfactant C, 30-90% of cationic reverse demulsifier A and 5-70% of cationic polymer B.
3. The oily sewage compound reverse demulsifier according to claim 1, which is characterized in that: the reverse demulsifier comprises the following components in percentage by mass: 5-10% of polyquaternium surfactant C, 40-90% of cationic reverse demulsifier A and 5-60% of cationic polymer B.
4. The oily sewage compound reverse demulsifier of claim 1, wherein the reverse demulsifier comprises, in terms of the total mass percentage of demulsifiers: 5-20% of polyquaternary ammonium salt surfactant C and 80-95% of cation reverse demulsifier A.
5. The use of the oily sewage compound reverse demulsifier according to any one of claims 1 to 4, wherein the reverse demulsifier is diluted to a certain mass concentration with water for the treatment of oil sand water-washing oily sewage.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059669A (en) * | 1991-07-23 | 1992-03-25 | 中国石油天然气总公司胜利设计院 | The preparation method of antiphase emulsion breaker of cation polyether model |
| CN102399577A (en) * | 2011-09-28 | 2012-04-04 | 中国石油天然气集团公司 | Chemical settling dehydration method for thick oil transition zone ageing oil |
| CN102559245A (en) * | 2012-02-16 | 2012-07-11 | 中国海洋石油总公司 | Reverse demulsifier and preparation method thereof |
| CN105523606A (en) * | 2015-12-30 | 2016-04-27 | 克拉玛依市三达新技术股份有限公司 | A composite reverse demulsifier, a preparing method thereof and a using method of the composite reverse demulsifier |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059669A (en) * | 1991-07-23 | 1992-03-25 | 中国石油天然气总公司胜利设计院 | The preparation method of antiphase emulsion breaker of cation polyether model |
| CN102399577A (en) * | 2011-09-28 | 2012-04-04 | 中国石油天然气集团公司 | Chemical settling dehydration method for thick oil transition zone ageing oil |
| CN102559245A (en) * | 2012-02-16 | 2012-07-11 | 中国海洋石油总公司 | Reverse demulsifier and preparation method thereof |
| CN105523606A (en) * | 2015-12-30 | 2016-04-27 | 克拉玛依市三达新技术股份有限公司 | A composite reverse demulsifier, a preparing method thereof and a using method of the composite reverse demulsifier |
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