CN107556995B - Petroleum sulfonic acid sodium salt composition and preparation method and application thereof - Google Patents
Petroleum sulfonic acid sodium salt composition and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a petroleum sulfonic acid sodium salt composition, a preparation method and application thereof. Said systemThe preparation method comprises the steps of uniformly mixing 5 wt% -95 wt% of fraction 1 with the average molecular weight of 252-312, 5 wt% -95 wt% of fraction 2 with the average molecular weight of 313-395 and 0-50 wt% of fraction 3 with the average molecular weight of 396-490 by taking the total weight of the mixture as 100% to obtain the mixture; adding a diluent into the mixture to obtain a diluted product, and then adopting SO3The diluted product is sulfonated by gas to obtain a sulfonated product; wherein, the diluent comprises one or a combination of a plurality of alcohols with carbon chain length of C3-C10, and the dosage of the diluent is 0.1-10 percent of the weight of the mixture; and neutralizing petroleum sulfonic acid in the sulfonated product by using a sodium hydroxide aqueous solution until the pH value of the system is 7-10 to obtain the petroleum sulfonic acid sodium salt composition.
Description
Technical Field
The invention relates to a petroleum sulfonic acid sodium salt composition and a preparation method and application thereof, belonging to the technical field of petroleum exploitation.
Background
The tertiary oil recovery (EOR) technology is an important oilfield development technology capable of improving the crude oil recovery rate by using new technologies such as physical, chemical and biological technologies. The chemical compound flooding is an effective method capable of greatly improving the crude oil recovery rate of an oil field in a tertiary oil recovery technology, and generally can improve the crude oil recovery rate by more than 15%. The strong base (NaOH) ternary complex flooding adopting the alkylbenzene sulfonate as the surfactant is applied to site tests of Daqing oil fields, and test results show that the ternary complex flooding can improve the recovery ratio by more than 20 percent. However, the strong base ASP flooding field test reveals some problems: firstly, because high-concentration strong base is used in the composite system, the oil well has serious scaling, the pump detection period is shortened, the equipment is seriously corroded, and the productivity of the oil well is reduced; secondly, the produced fluid is seriously emulsified in a strong alkali composite system, so that the demulsification and dehydration are difficult, and the water treatment difficulty of the produced fluid is increased, so that the technical difficulty and the additional cost of oil extraction are increased; in addition, since the alkali concentration has a large influence on the viscosity of the ternary system, the concentration of the polymer in the formulation system has to be increased in order to achieve the designed flow control capability, thereby increasing the cost of the oil-displacing agent. Therefore, the development direction of the chemical combination flooding is changed from strong-base ternary combination flooding to weak-base and alkali-free combination flooding systems, and the development of a high-efficiency and cheap surfactant product for oil displacement, which is suitable for the weak-base and alkali-free systems, is one of the major problems in the popularization and application of the chemical combination flooding.
The surfactant for chemical composite flooding has the advantages of wide raw material source, simple production process, low production cost and good product performance, can enable oil and water to reach ultra-low interfacial tension under the condition of a weak-base composite system, thereby improving the oil displacement efficiency, and particularly, can enable the oil and water to reach the ultra-low interfacial tension by the composite system under the alkali-free condition, thereby completely eliminating the adverse factors brought by alkali to on-site oil extraction production. Chinese patent CN 1782019A adopts the combination of different carbon chain alkylbenzene sulfonates to obtain the heavy alkylbenzene sulfonate product suitable for weak base composite flooding, but because the heavy alkylbenzene raw materials in China are limited, the number of synthesized products can not meet the requirements of composite flooding field tests, and in addition, the heavy alkylbenzene sulfonate product can not reach ultra-low interfacial tension under the alkali-free condition. Therefore, other kinds of surfactants for oil displacement need to be synthesized. The Chinese patent CN 1458220A adopts a raw material which is vacuum second-line distillate oil, but because the molecular weight of the raw material is low, the raw material is often required to be compounded with other types of surfactants to have good adaptability, and an alkali-free system described in the patent needs to be added with salt to replace alkali. Meanwhile, the technical scheme disclosed in the chinese patent CN1275431A also has the problems of narrow molecular weight range of raw materials, poor product adaptability and the like, and the unreacted oil needs to be extracted and separated in the synthesis process due to the low content of the aromatic hydrocarbon of the selected raw material.
Therefore, it is a technical problem to be solved in the art to provide a cheap sodium petroleum sulfonate composition capable of reducing oil-water interfacial tension to an ultra-low level under weak base and no base conditions, and to provide a preparation method and a three-time application method thereof.
Disclosure of Invention
In order to solve the above disadvantages and shortcomings, the present invention aims to provide a method for preparing a petroleum sulfonic acid sodium salt composition.
The invention also aims to provide a petroleum sodium sulfonate composition prepared by the preparation method of the petroleum sodium sulfonate composition.
The invention also aims to provide a composite flooding composition which contains the petroleum sodium sulfonate composition.
The invention also aims to provide the application of the compound flooding composition in the enhanced recovery ratio of the tertiary oil recovery chemical compound flooding.
In order to achieve the above object, the present invention provides a method for preparing a petroleum sulfonic acid sodium salt composition, comprising the steps of:
(1) selecting and matching raw materials: uniformly mixing fraction 1 with the average molecular weight of 252-312, fraction 2 with the average molecular weight of 313-395-490 and fraction 3 with the average molecular weight of 396-490 to obtain a mixture;
based on the total weight of the mixture as 100%, the mixture comprises 5 wt% -95 wt% of fraction 1, 5 wt% -95 wt% of fraction 2 and 0-50 wt% of fraction 3, and the sum of the weight percentages of fraction 1, fraction 2 and fraction 3 is 100%;
wherein, the fraction 1 with the average molecular weight of 252-312 comprises one or a combination of a plurality of types of vacuum second-line reverse dewaxed oil (the distillation range is 350-475 ℃), vacuum second-line distillate oil and vacuum second-line furfural extract oil;
the fraction 2 with the average molecular weight of 313-;
the fraction 3 with the average molecular weight of 396-490 comprises reverse-order dewaxed oil of a vacuum four-line (the distillation range is 410-550 ℃), distillate oil of the vacuum four-line and furfural extract oil of the vacuum four-line;
(2)SO3gas film sulfonation: adding a diluent into the mixture to obtain a diluted product, and then adopting SO3The diluted product is sulfonated by gas to obtain a sulfonated product;
wherein the diluent comprises one or a combination of more of alcohols with carbon chain length of C3-C10, and the dosage of the diluent is 0.1-10% of the weight of the mixture;
(3) alkali treatment: and then neutralizing petroleum sulfonic acid in the sulfonated product by using a sodium hydroxide aqueous solution until the pH value of the system is 7-10 to obtain the petroleum sulfonic acid sodium salt composition.
According to a specific embodiment of the present invention, in the preparation method, preferably, the aromatic hydrocarbon content in the mixed material is 25 wt% to 65 wt%;
more preferably from 30 wt% to 45 wt%.
According to a specific embodiment of the invention, in the preparation method, the fraction 1 with the average molecular weight of 252-312-fluid is vacuum-two-line reverse-order dewaxed oil;
the fraction 2 with the average molecular weight of 313-;
the fraction 3 with an average molecular weight of 396-490 was a vacuum four-line reverse dewaxed oil.
According to a particular embodiment of the invention, in the preparation process, preferably, the SO used for the sulfonation treatment3The volume concentration of the gas is 5-10%, and the temperature of the sulfonation treatment is 50-80 ℃. Wherein the diluting gas used in the sulfonation treatment is air.
According to a specific embodiment of the present invention, in the preparation method, the step (2) is SO3The viscosity of the intermediate product sulfonic acid can be reduced by adding the diluent in the gas sulfonation treatment process, so that the sulfonation reaction can be smoothly carried out; in addition, the alcohol diluent used in the sulfonation process may be sulfonated to an alkyl sulfate, which is a surfactant that may be used as an active component of the sulfonated synthetic product.
According to a particular embodiment of the invention, in said preparation process, SO3Gas membrane sulfonation is carried out in a membrane sulfonation reactor, which is a conventional apparatus used in the art.
According to a specific embodiment of the present invention, in the preparation method, preferably, the mass concentration of the sodium hydroxide aqueous solution is 20% to 40%.
The invention also provides a petroleum sulfonic acid sodium salt composition prepared by the preparation method of the petroleum sulfonic acid sodium salt composition.
According to an embodiment of the present invention, in the petroleum sulfonic acid sodium salt composition, preferably, it contains 20% to 45% of petroleum sulfonic acid sodium salt based on 100% of the total weight of the petroleum sulfonic acid sodium salt compositionAcid sodium salt active. The petroleum sulfonic acid sodium salt composition meets the requirements of compound flooding on the surfactant by various indexes in performance tests, and the petroleum sulfonic acid sodium salt composition surfactant has good interfacial activity under a lower concentration (0.05-0.3 wt%), and enables the oil-water interfacial tension to be ultralow (10) within a wider and lower weak base concentration range-3Lower than mN/m magnitude order), the dosage of the surfactant and the concentration of injected alkali can be reduced, and even for some oil water, the ultra-low interfacial tension can be achieved under the condition of not adding alkali.
The invention also provides a composite flooding composition which contains the petroleum sodium sulfonate composition, wherein the composite flooding composition comprises the following components in percentage by weight based on 100 percent of the total weight of the composite flooding composition:
0.05 to 0.3 weight percent of petroleum sulfonic acid sodium salt composition,
0 to 1.4 weight percent of alkali,
0.1 wt% to 0.25 wt% of polymer,
the balance being water.
According to a specific embodiment of the present invention, in the composite flooding composition, preferably, the polymer includes one or a combination of several of polyacrylamide and salt-resistant polymer.
In the composite flooding composition according to the embodiment of the present invention, the average molecular weight of the polymer is preferably 500-3000 ten thousand.
In the present combination flooding composition, preferably, the alkali comprises Na according to a specific embodiment of the present invention2CO3、NaHCO3、K2CO3And Na2B4O7One or a combination of several of them.
According to a specific embodiment of the present invention, in the composite flooding composition, preferably, the alkali is Na2CO3More preferably, it is contained in an amount of 0.2 wt% to 1.4 wt%.
According to a specific embodiment of the present invention, in the composite flooding composition, the water is oilfield injection water.
The method for preparing the composite flooding composition is not particularly required according to the specific embodiment of the invention, and the composite flooding composition can be prepared by a person skilled in the art according to the field operation requirement and by adopting the conventional technical means in the field.
The invention also provides application of the compound flooding composition in improving the recovery ratio of tertiary oil recovery chemical compound flooding.
According to a specific embodiment of the invention, in the application, preferably, the chemical combination flooding for tertiary oil recovery comprises alkali-free binary chemical combination flooding or weak alkali ternary chemical combination flooding.
The preparation of the petroleum sodium sulfonate composition provided by the invention adopts various petroleum fractions of refineries as raw materials, and the raw materials have wide sources and low cost; the method adopts at least two raw materials, the molecular weight range is wide, and the method of homologous compound combination can improve the interfacial activity and the adaptability of the product (crude oil is a composition of alkane, aromatic hydrocarbon and the like with different molecular weights, therefore, the molecular weight distribution of the petroleum sodium sulfonate composition surfactant product synthesized by adopting the combined raw materials is better matched with the crude oil, generally, according to the similar intermiscibility theory, the hydrophobic group of the petroleum sodium sulfonate composition is matched with the crude oil, and the petroleum sodium sulfonate composition is easier to enrich at an oil-water interface, so that the oil-water interfacial tension is easier to reduce); the preparation method selects various distillate oil raw materials with high aromatic hydrocarbon content (25 wt% -65 wt%), does not need an extraction separation process in the synthesis process, simplifies the synthesis reaction process, reduces the production cost, and is easy for large-scale industrial production; in addition, because the preparation process selects the petroleum fraction raw material with high molecular weight and contains a large amount of colloid, especially the raw materials of three-way decompression, four-way decompression and oil extraction, the intermediate product of the sulfonation process has high viscosity and is easy to coke, and the addition of alcohol as a diluent can reduce the viscosity of the intermediate product, improve the sulfonation efficiency and the product quality, and is beneficial to industrial continuous production.
The petroleum sodium sulfonate composition prepared by the method is used for tertiary oil recovery, and can enable the oil-water interfacial tension to reach ultralow interfacial tension in weak-base ternary (alkali + petroleum sodium sulfonate composition surfactant + polymer) compound flooding and alkali-free binary (petroleum sodium sulfonate composition surfactant + polymer) compound flooding; and simultaneously, the crude oil recovery rate can be obviously improved.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, the pressure-reducing second-line and pressure-reducing third-line reverse-order dewaxed oil of the large continuous petrochemical plant is used as a raw material, the total weight of the mixture is 100%, the mixture comprises 65 wt% of pressure-reducing second-line reverse-order dewaxed oil and 35 wt% of pressure-reducing third-line reverse-order dewaxed oil, and the aromatic hydrocarbon content in the mixture is 30 wt% -32 wt%;
SO3the membrane sulfonation reaction (carried out in a membrane sulfonation reactor) is carried out at 50-60 ℃ and SO3The volume concentration of the gas is 5-6%, and the n-butyl alcohol is a diluent, and the using amount is 1 wt%;
neutralizing with 25 wt% NaOH solution to make pH value of the product reach 8-9, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content is about 30 wt%), and recording as PS-1.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as above, sodium carbonate, polymer and water, and the weight contents of the components are shown in table 1.
The results of the interfacial tension test of the composite flooding composition prepared in this example on oil and water in daqing four factories are shown in table 1. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 1 influence of PS-1 on interfacial tension (mN/m) of crude oil/reinjection wastewater from four plants in Daqing
(Polymer HPAM, molecular weight 2500 ten thousand, concentration 0.13 wt%)
As can be seen from Table 1, at concentrations of 0.05 wt% to 0.3 wt% of the petroleum sulfonic acid sodium salt composition, Na2CO3The concentration is in the range of 0.2 wt% to 1.4 wt%, and the composite flooding composition can enable the interfacial tension of oil/water to be ultra-low (<1×10- 2mN/m) can meet the requirement of a weak base composite system on interfacial tension.
Example 2
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, pressure-reducing second-line, three-line and reverse-order dewaxed oil and pressure-reducing second-line furfural extract oil of a large continuous petrochemical plant are used as raw materials, and the mixture comprises 50 wt% of pressure-reducing second-line and reverse-order dewaxed oil, 30 wt% of pressure-reducing third-line and reverse-order dewaxed oil and 20 wt% of pressure-reducing second-line furfural extract oil by taking the total weight of the mixture as 100%, and the content of aromatic hydrocarbon in the mixture is 38-42 wt%;
SO3the sulfonation reaction temperature is 65-70 ℃, and SO3The volume concentration of the gas is 7-9 percent, the n-butyl alcohol is used as a diluent, the dosage is 2 weight percent,
neutralizing with 20 wt% NaOH solution to make pH value of the product reach 9-10, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content about 40 wt%), and recording as PS-2.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as above, sodium carbonate, polymer and water, and the weight contents of the components are shown in table 2.
The results of the interfacial tension test of the composite flooding composition prepared in this example on oil and water in daqing four factories are shown in table 2. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 2 influence of PS-2 on interfacial tension (mN/m) of crude oil/reinjection wastewater from four plants in Daqing
(Polymer HPAM, molecular weight 2500 ten thousand, concentration 0.13 wt%)
As can be seen from Table 2, at concentrations of 0.05 wt% to 0.3 wt% of the petroleum sulfonic acid sodium salt composition, Na2CO3The concentration is in the range of 0.2 wt% to 1.4 wt%, and the composite flooding composition can enable the interfacial tension of oil/water to be ultra-low (<1×10- 2mN/m) can meet the requirement of a weak base composite system on interfacial tension.
Example 3
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, pressure-reducing second-line, three-line and reverse-order dewaxed oil and pressure-reducing second-line furfural extract oil of a large continuous petrochemical plant are used as raw materials, and the mixture comprises 45 wt% of pressure-reducing second-line and reverse-order dewaxed oil, 45 wt% of pressure-reducing third-line and reverse-order dewaxed oil and 10 wt% of pressure-reducing second-line furfural extract oil, wherein the content of aromatic hydrocarbon in the mixture is 34-37 wt%;
SO3the sulfonation reaction temperature is 65-70 ℃, and SO3The volume concentration of the gas is 6-7 percent, n-octanol is used as a diluent, the dosage is 1.2 weight percent,
neutralizing with 25 wt% NaOH solution to make pH value of the product reach 8-9, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content about 35 wt%), and recording as PS-3.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as above, sodium carbonate, polymer and water, and the weight content of each component is shown in table 3.
The results of the interfacial tension test of the composite flooding composition prepared in this example on oil and water in daqing four factories are shown in table 3. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 3 influence of PS-3 on interfacial tension (mN/m) of crude oil/reinjection wastewater from four plants in Daqing
(Polymer HPAM, molecular weight 2500 ten thousand, concentration 0.13 wt%)
As can be seen from Table 3, at concentrations of 0.05 wt% to 0.3 wt% of the petroleum sulfonic acid sodium salt composition, Na2CO3The concentration is in the range of 0.2 wt% to 1.4 wt%, and the composite flooding composition can enable the interfacial tension of oil/water to be ultra-low (<1×10- 2mN/m) can meet the requirement of a weak base composite system on interfacial tension.
Example 4
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, a vacuum second-line, a vacuum third-line reverse-order dewaxed oil and a vacuum third-line furfural extract oil of a large continuous petrochemical plant are used as raw materials, and the mixture comprises 60 wt% of the vacuum second-line reverse-order dewaxed oil, 33 wt% of the vacuum third-line reverse-order dewaxed oil and 7 wt% of the vacuum second-line furfural extract oil by taking the total weight of the mixture as 100%, and the content of aromatic hydrocarbon in the mixture is 32-35 wt%;
SO3the sulfonation reaction temperature is 65-70 ℃, and SO3The volume concentration of the gas is 6-7 percent, the amyl alcohol is taken as a diluent, the dosage is 2 weight percent,
neutralizing with 20 wt% NaOH solution to make pH value of the product reach 8-9, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content is about 33 wt%), and recording as PS-4.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as above, sodium carbonate, polymer and water, and the weight content of each component is shown in table 4.
The results of the interfacial tension test of the composite flooding composition prepared in this example on oil and water in daqing four factories are shown in table 4. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 4 influence of PS-4 on interfacial tension (mN/m) of crude oil/reinjection wastewater from four plants in Daqing
(Polymer HPAM, molecular weight 2500 ten thousand, concentration 0.14 wt%)
As can be seen from Table 4, at concentrations of 0.05 wt% to 0.3 wt% of the petroleum sulfonic acid sodium salt composition, Na2CO3The concentration is in the range of 0.2 wt% to 1.4 wt%, and the composite flooding composition can enable the interfacial tension of oil/water to be ultra-low (<1×10- 2mN/m) can meet the requirement of a weak base composite system on interfacial tension.
Example 5
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, pressure-reducing second-line, three-line and reverse-order dewaxed oil and pressure-reducing second-line furfural extract oil in Daqing refinery are used as raw materials, and the raw materials comprise 60 wt% of pressure-reducing second-line and reverse-order dewaxed oil, 30 wt% of pressure-reducing third-line and reverse-order dewaxed oil and 10 wt% of pressure-reducing second-line furfural extract oil, wherein the content of aromatic hydrocarbon in the mixture is 32-35 wt%;
SO3the sulfonation reaction temperature is 65-75 ℃, and SO3The volume concentration of the gas is 7-8 percent, n-octanol is used as a diluent, the dosage is 2.0 weight percent,
neutralizing with 30 wt% NaOH solution to make pH value of the product reach 9-10, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content is about 33%), and recording as PS-5.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as above, sodium carbonate, polymer and water, and the weight content of each component is shown in table 5.
The results of the interfacial tension test of the composite flooding composition prepared in this example on oil and water in Daqing three factories are shown in Table 5. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 5 influence of PS-5 on interfacial tension (mN/m) of crude oil/reinjection wastewater from Daqing three plants
(salt-resistant polymer KYPAM with molecular weight of 2500 ten thousand and concentration of 0.13 wt%)
As can be seen from Table 5, at concentrations of 0.05 wt% to 0.3 wt% of the petroleum sulfonic acid sodium salt composition, Na2CO3The concentration is in the range of 0.2 wt% to 1.4 wt%, and the composite flooding composition can enable the interfacial tension of oil/water to be ultra-low (<1×10- 2mN/m) can meet the requirement of a weak base composite system on interfacial tension.
Example 6
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, the vacuum second-line distillate oil and the vacuum third-line distillate oil of a Xinjiang refinery are used as raw materials, the total weight of the mixture is 100%, the mixture comprises 30 wt% of the vacuum second-line distillate oil and 70 wt% of the vacuum third-line distillate oil, and the content of aromatic hydrocarbon in the mixture is 32 wt% -35 wt%;
SO3the sulfonation reaction temperature is 60-65 ℃, and SO3The volume concentration of the gas is 5-6 percent, the n-butyl alcohol is used as a diluent, the dosage is 3 weight percent,
neutralizing with 30 wt% NaOH solution to make pH value of the product reach 8-9, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content is about 33 wt%), and recording as PS-6.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as above, sodium carbonate, polymer and water, and the weight content of each component is shown in table 6.
The results of interfacial tension testing of the composite flooding composition prepared in this example on oil and water in a krameri oilfield in Xinjiang are shown in Table 6. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 6 influence of PS-6 on interfacial tension (mN/m) of Sinkiang crude oil/reinjection Sewage
(salt-resistant polymer KYPAM with molecular weight of 2500 ten thousand and concentration of 0.13 wt%)
As can be seen from Table 6, at concentrations of 0.05 wt% to 0.3 wt% of the petroleum sulfonic acid sodium salt composition, Na2CO3The concentration is in the range of 0.2 wt% to 1.4 wt%, and the composite flooding composition can enable the interfacial tension of oil/water to be ultra-low (<1×10- 2mN/m) can meet the requirement of a weak base composite system on interfacial tension.
Example 7
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, the vacuum second-line distillate oil and the vacuum third-line distillate oil of a Xinjiang refinery are used as raw materials, the total weight of the mixture is 100%, the mixture comprises 40 wt% of the vacuum second-line distillate oil and 60 wt% of the vacuum third-line distillate oil, and the content of aromatic hydrocarbon in the mixture is 30 wt% -33 wt%;
SO3the sulfonation reaction temperature is 65 ℃, SO3The volume concentration of the gas is 5-7 percent, the n-butyl alcohol is used as a diluent, the dosage is 0.7 weight percent,
neutralizing with 35 wt% NaOH solution to make pH value of the product reach 9-10, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content about 31 wt%), and recording as PS-7.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as above, sodium carbonate, polymer and water, and the weight content of each component is shown in table 7.
The interfacial tension test results of the composite flooding composition prepared in this example on oil and water in a krameri oilfield in Xinjiang are shown in Table 7. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 7 influence of PS-7 on interfacial tension (mN/m) of Sinkiang crude oil/reinjection Sewage
(salt-resistant polymer KYPAM with molecular weight of 2500 ten thousand and concentration of 0.12 wt%)
As can be seen from Table 7, at concentrations of 0.05 wt% to 0.3 wt% of the petroleum sulfonic acid sodium salt composition, Na2CO3The concentration is in the range of 0.2 wt% to 1.4 wt%, and the composite flooding composition can enable the interfacial tension of oil/water to be ultra-low (<1×10- 2mN/m) can meet the requirement of a weak base composite system on interfacial tension.
Example 8
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, pressure-reducing second-line distillate oil and pressure-reducing third-line distillate oil of a Xinjiang refinery are used as raw materials, the total weight of the mixture is 100%, the mixture comprises 15 wt% of pressure-reducing second-line distillate oil and 85 wt% of pressure-reducing third-line distillate oil, and the content of aromatic hydrocarbon in the mixture is 32 wt% -35 wt%;
SO3the sulfonation reaction temperature is 65 ℃, SO3The volume concentration of the gas is 5-7 percent, n-octanol is used as a diluent, the dosage is 0.5 weight percent,
neutralizing with 30 wt% NaOH solution to make pH value of the product reach 9-10, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content is about 33 wt%), and recording as PS-8.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as described above, sodium carbonate (optional component), polymer and water, wherein the weight content of each component is shown in table 8.
The interfacial tension test results of the composite flooding composition prepared in this example on oil and water in a krameri oilfield in Xinjiang are shown in Table 8. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 8 influence of PS-8 on interfacial tension (mN/m) of Sinkiang crude oil/reinjection Sewage
(salt-resistant polymer KYPAM with molecular weight of 2500 ten thousand and concentration of 0.12 wt%)
As can be seen from Table 8, the combination flooding composition can make the interfacial tension of oil/water ultra low and meet the requirement of alkali-free binary composite system on the interfacial tension in the range of 0.05 wt% -0.3 wt% of petroleum sulfonate composition under the condition of no alkali or low alkali concentration.
Example 9
The embodiment provides a preparation method of a petroleum sodium sulfonate composition, which comprises the following steps:
in the embodiment, the vacuum second-line distillate oil and the vacuum fourth-line distillate oil of a Xinjiang refinery are used as raw materials, the total weight of the mixture is 100%, the mixture comprises 30 wt% of the vacuum second-line distillate oil and 70 wt% of the vacuum fourth-line distillate oil, and the content of aromatic hydrocarbon in the mixture is 30 wt% -33 wt%;
SO3the sulfonation reaction temperature is 65 ℃, SO3The volume concentration of the gas is 6-7 percent, n-octanol is used as a diluent, the dosage is 1.0 weight percent,
neutralizing with 30% NaOH solution to make pH value of the product reach 9-10, and obtaining uniform product, i.e. petroleum sodium sulfonate surfactant (active matter effective content about 32 wt%), and recording as PS-9.
The embodiment also provides a composite flooding composition, which comprises the petroleum sodium sulfonate composition prepared as described above, sodium carbonate (optional component), polymer and water, wherein the weight content of each component is shown in table 9.
The results of interfacial tension testing of the flooding composition prepared in this example on oil and water in a krameri oilfield in Xinjiang are shown in Table 9. Wherein, the interfacial tension tester adopts a TEXAS-500C rotary drop interfacial tension tester, the surfactant is prepared by using the formation water reinjection sewage of an oil field oil extraction plant to have the use concentration of 0.05-0.3 wt%, and the interfacial tension is a stable balance value for testing for 2 hours.
TABLE 9 influence of PS-9 on interfacial tension (mN/m) of Sinkiang crude oil/reinjection Sewage
(salt-resistant polymer KYPAM with molecular weight of 2500 ten thousand and concentration of 0.12 wt%)
As can be seen from Table 9, the combination flooding composition can make the interfacial tension of oil/water ultra low and meet the requirement of alkali-free binary composite system on the interfacial tension in the range of 0.05 wt% -0.3 wt% of petroleum sulfonate composition under the condition of no alkali or low alkali concentration.
Example 10 core flooding efficiency of composite flooding system
A natural outcrop core with the length of 30cm and the diameter of 3.8cm is selected indoors to be used for the oil displacement efficiency research of weak-alkali ternary and alkali-free binary compound flooding formulas. The weak base ternary composite system surfactant is a PS-2 sample prepared in example 2, the polymer is polyacrylamide HPAM, the molecular weight is 2500 ten thousand, and the crude oil sample is dehydrated crude oil in Daqing four factories; the alkali-free composite flooding surfactant adopts a PS-8 sample in example 8, the polymer adopts salt-resistant polymer KYPAM, the molecular weight is 2500 ten thousand, and the crude oil sample is dehydrated crude oil in Xinjiang oil fields.
Table 10 weak base ternary, alkali-free binary composite flooding system core flooding test results
As can be seen from Table 10, the oil displacement efficiency of the weak-base ternary and alkali-free binary composite system is improved by more than 23%, which shows that the petroleum sodium sulfonate surfactant provided by the invention has good performance of improving the oil displacement efficiency. The oil displacement efficiency of the alkali-free binary combination flooding is slightly lower than that of the weak alkali ternary combination flooding, but the alkali is not added, the concentration of the used polymer is low, the cost of the combination flooding can be reduced, adverse factors such as scaling and corrosion caused by alkali can be eliminated, and the method is more favorable for field implementation.
Claims (12)
1. A method for preparing a petroleum sulfonic acid sodium salt composition, comprising the steps of:
(1) selecting and matching raw materials: uniformly mixing fraction 1 with the average molecular weight of 252-312, fraction 2 with the average molecular weight of 313-395-490 and fraction 3 with the average molecular weight of 396-490 to obtain a mixture;
based on the total weight of the mixture as 100%, the mixture comprises 5 wt% -95 wt% of fraction 1, 5 wt% -95 wt% of fraction 2 and 0-50 wt% of fraction 3, and the sum of the weight percentages of fraction 1, fraction 2 and fraction 3 is 100%;
wherein the fraction 1 with the average molecular weight of 252-312 comprises one or more of vacuum second-line reverse dewaxed oil, vacuum second-line distillate oil and vacuum second-line furfural extract oil;
the fraction 2 with the average molecular weight of 313-;
the fraction 3 with the average molecular weight of 396-490 comprises one or a combination of several of vacuum four-line reverse-sequence dewaxed oil, vacuum four-line distillate oil and vacuum four-line furfural extract oil;
the aromatic hydrocarbon weight content in the mixture is 25 wt% -65 wt%;
(2)SO3gas film sulfonation: adding a diluent into the mixture to obtain a diluted product, and then adopting SO3The diluted product is sulfonated by gas to obtain a sulfonated product;
SO for sulphonation3The volume concentration of the gas is 5-10%, and the temperature of the sulfonation treatment is 50-80 ℃;
wherein, the diluent is one or a combination of a plurality of alcohols with carbon chain length of 4-10, and the dosage of the diluent is 0.1-10% of the weight of the mixture;
(3) alkali treatment: neutralizing petroleum sulfonic acid in the sulfonated product by using a sodium hydroxide aqueous solution until the pH value of the system is 7-10 to obtain the petroleum sulfonic acid sodium salt composition;
the mass concentration of the sodium hydroxide aqueous solution is 20-40%.
2. The method of claim 1, wherein the weight content of aromatic hydrocarbons in the blend is 30 wt% to 45 wt%.
3. The sodium petroleum sulfonate composition prepared by the method of claim 1 or 2.
4. The sodium petroleum sulfonate composition of claim 3 which contains from 20% to 45% of the sodium petroleum sulfonate active, based upon the total weight of the sodium petroleum sulfonate composition taken as 100%.
5. A composite flooding composition comprising the sodium petroleum sulfonate salt composition of claim 3 or 4, wherein the composite flooding composition comprises, based on the total weight of the composite flooding composition taken as 100%:
0.05 to 0.3 weight percent of petroleum sulfonic acid sodium salt composition,
0 to 1.4 weight percent of alkali,
0.1 wt% to 0.25 wt% of polymer,
the balance being water.
6. The composite flooding composition as recited in claim 5, wherein said polymer comprises one or a combination of polyacrylamide and salt-resistant polymer.
7. The composite flooding composition as set forth in claim 6, wherein the polymer has an average molecular weight of 500-3000 ten thousand.
8. The composite flooding composition of any one of claims 5-7, wherein the base comprises Na2CO3、NaHCO3、K2CO3And Na2B4O7One or a combination of several of them.
9. The composite flooding composition of claim 8, wherein the base is Na2CO3。
10. The composite flooding composition of claim 9, wherein said base is present in an amount of from 0.2 wt% to 1.4 wt%.
11. Use of a complex flooding composition according to any one of claims 5-10 in enhanced recovery of tertiary oil recovery chemical complex flooding.
12. The use of claim 11 wherein the enhanced oil recovery chemical combination flooding comprises alkali-free binary chemical combination flooding or weak alkali ternary chemical combination flooding.
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