CN103193689B - Hexadecyl toluene sulfonate for flooding and preparation method thereof, surfactant and application thereof - Google Patents
Hexadecyl toluene sulfonate for flooding and preparation method thereof, surfactant and application thereof Download PDFInfo
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- CN103193689B CN103193689B CN201310133246.1A CN201310133246A CN103193689B CN 103193689 B CN103193689 B CN 103193689B CN 201310133246 A CN201310133246 A CN 201310133246A CN 103193689 B CN103193689 B CN 103193689B
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Abstract
The invention discloses hexadecyl toluene sulfonate for flooding and a preparation method thereof, a surfactant and application thereof. The surfactant prepared from the hexadecyl toluene sulfonate or an industrial product thereof and alcohol has good interfacial activity, strong capacity of resisting dilution and low use concentration (0.05-0.3wt%), can enable the oil-water interfacial tension to be ultralow (order of magnitude of 10<-3>mN/m) in wider or narrower alkali concentration ranges (0.4-1.2wt%) and under the strong and weak alkali conditions and has good composite system stability and high flooding efficiency. The recovery ratio of core flooding experiments is enhanced by more than 20% than that of water flooding. The surfactant which is single in composition, definite in structure and excellent in properties and is stable is provided for popularization and application of tertiary oil recovery, not only can oil recovery be substantially enhanced but also the domestic formula of the surfactant is achieved and the cost of ASP (alkaline-surfactant-polymer) flooding is greatly reduced.
Description
Technical field
The present invention relates to oil field displacement of reservoir oil heavy alkylbenzene sulfonate class tensio-active agent, particularly relate to a kind of form single, structure is known, excellent property, stable the hexadecyl tosylate, tensio-active agent and preparation method thereof that are applicable to oilfield chemistry complex oil displacing.
Background technology
Oil is a kind of non-renewable resource, and along with the fast development of China's economy, the demand of oil increases day by day.The exploitation of oil is related to the overall situation of national economy, plays vital effect to the Sustainable development of China's economy and energy security.
The exploitation of oil is divided into three phases: be rely on the natural energy on stratum to exploit at first, be called primary oil recovery, general recovery ratio is 5%-10%; After natural energy exhaustion, can continue exploitation by man-made injection or gas injection, be called secondary oil recovery, recovery ratio can bring up to 30%-40%; After secondary oil recovery, still have the surplus oil of 60%-70% to remain in underground, the method for physics and chemistry can only be relied on to exploit, be called tertiary oil recovery.
At present, the main oilfield (grand celebration, triumph etc.) in east China area has entered the later stage of secondary oil recovery, and principal feature is High water cut and ultra-high water-containing, and crude production rate successively decreases, and economic benefit declines.In order to improve the recovery ratio in existing oil field, develop remaining reserves to greatest extent, the development research of tertiary oil recovery technology is imperative.Generally believe at present, adopting chemical combined flooding to carry out tertiary oil recovery is comparatively effective means, and oil recovery factor generally can be made to improve more than 15%.Ternary composite driving refers to that alkali and tensio-active agent and high molecular polymer (ASP system) organically carry out the displacement of reservoir oil after compound.It is the viscosity being increased the aqueous solution by high molecular polymer on the one hand, improve water drive sweep efficiency, be the interfacial tension being reduced profit by alkali and tensio-active agent on the other hand, overcome the constraint of capillary force to irreducible oil, thus can oil recovery factor be increased substantially.Alkali and tensio-active agent (AS system) drive mainly by reducing the interfacial tension of profit, improve displacement efficiency.
In ternary composite driving, the chemical agent of most critical is tensio-active agent, and the basic demand being applicable to the tensio-active agent making ternary composite driving is: oil water interfacial tension can be made to reach ultralow (10
-3the mN/m order of magnitude); The working concentration <0.6% (wt) of tensio-active agent, and all can ultra low interfacial tension be formed within the scope of wider surfactant concentration, the composition of tensio-active agent is relatively single, ensures, in displacement process, serious chromatographic separation does not occur; Good compatibleness can be had with alkali and polymkeric substance; The oil displacement efficiency of ternary composite driving on rock core improves more than 20% than water drive; Require that the production technique of tensio-active agent is simple and reliable, constant product quality, reasonable price simultaneously.
The tensio-active agent used in tertiary oil recovery mainly contains sulfonated petro-leum, heavy alkylbenzene sulfonate, sulfonated lignin and petroleum carboxylate.At present, Daqing oil field adopts heavy alkylbenzene sulfonate tensio-active agent, and alkyl carbon number is 12-24, effective permeability 100 μm
-2, the oil reservoir of more than net thickness 5m carries out the applied research of ternary composite driving technology, achieve good oil displacement efficiency (improve recovery ratio and can reach more than 20%) and economic benefit, but due to heavy alkylbenzene sulfonate feed composition wider distribution, composition is complicated, it is large that component ratio controls difficulty, the change of composition can cause surfactant interface tension range to narrow, alkali span reduces to 0.4wt% by 0.6wt%, the interfacial activity of tensio-active agent is deteriorated, and compound system bad stability (interfacial tension reduced to 60 days by 90 days steady time), have a strong impact on the oil displacement efficiency of ternary composite driving.Other alkyl benzene sulfonate surfactant existing, although have the performance of good reduction interfacial tension and higher oil displacement efficiency, but have that component is many, the shortcoming of complex manufacturing, be therefore necessary to seek that performance is more excellent, component is single, the simple surfactant oil displacement of production technique.
Summary of the invention
An object of the present invention is to provide and a kind ofly forms the hexadecyl tosylate that single, structure is clear and definite, be applicable to prepare oilfield chemistry complex oil displacing tensio-active agent.
Hexadecyl tosylate provided by the present invention, molecular weight is 418, and for structural formula is such as formula the compound shown in I, formula I is:
Another object of the present invention is to provide a kind of hexadecyl tosylate Industrial products be directly used in flooding system.
These hexadecyl tosylate Industrial products, are obtained through continuous sulfonation, hydrolysis and neutralization by hexadecyl toluene, and wherein containing described hexadecyl tosylate 70wt%, surplus is the inorganic salt generated in reaction, unreacted raw material and water.
Another object of the present invention is to provide that a kind of technique is simple, practical, cost is low, the method for hexadecyl tosylate Industrial products described in continuous seepage.Comprise: be hexadecyl toluenesulphonic acids head product by continuous for hexadecyl toluene sulfonation in film sulfonation reactor, hexadecyl toluenesulphonic acids head product is hydrolyzed to stable hexadecyl toluenesulphonic acids intermediate product, and the neutralization of hexadecyl toluenesulphonic acids sodium hydroxide obtains hexadecyl tosylate Industrial products;
The present invention further provides the method for hexadecyl tosylate Industrial products purification hexadecyl tosylate.Comprise, hexadecyl tosylate Industrial products are dried removing moisture, then replace cleaning products with sherwood oil and ethanol to cross and filter inorganic salt, add isopropyl alcohol extraction after oven dry again and go out unsulfonated oil (unreacted raw material), purer hexadecyl tosylate after product is dried again, can be obtained.
In described method, hexadecyl toluene is C by carbon number
16normal olefine and toluene be that raw material prepares, hexadecyl toluene main chain is C
16straight chained alkyl, phenyl ring be toluene, structure is such as formula shown in II:
Described production or preparation method specifically comprise the following steps:
1) hexadecyl toluene is prepared: under 3000L industrial scale, secondary to 1300Kg toluene, 38Kg Primary Catalysts (aluminum chloride) and 4L catalyzer (Tripyrophosphoric acid) is added reactor (5000L), stir 10min, the system that is slowly warming up to has white gas to produce, stop heating, then 640Kg hexadecylene (alpha-olefin) is added reactor, open cycle water cooling during temperature to 40 DEG C, control temperature of reaction and be no more than 60 DEG C, insulation 2h; Insulation terminates rear stopping and stirring sedimentation 10min, releases lower catalyst agent; Add hot water and stir 10min to expiring still, stop stirring 10min, removing lower layer of water, repeating to wash 4-5 time to pH value is 7; Cotton-shaped organic layer is squeezed into still kettle and carries out air distillation, control still temperature and be no more than 155 DEG C, to gas phase temperature falling and without going out to heat up in a steamer thing; Start vacuum pump and carry out underpressure distillation, slowly rise to 140 DEG C to gas phase temperature and terminate to without when going out to heat up in a steamer thing; In still kettle, residuum is hexadecyl toluene;
2) sulfonation hexadecyl toluene: sulfonation reaction is carried out in film sulfonation reactor, sulfonation temperature 45-55 DEG C, the inlet amount of hexadecyl toluene be 1.4-2.1 ton/hour, pass into SO
3the air input of gas is 150-170 kg/hr, i.e. control SO
3be 1.29-1.46:1 with the mol ratio of hexadecyl toluene, obtain hexadecyl toluenesulphonic acids head product; Keep SO
3air input and hexadecyl toluene feed amount are stablized, continuous production;
3) be hydrolyzed: the water adding its total amount 2-4wt% at 45-55 DEG C in hexadecyl toluenesulphonic acids head product, obtains stable hexadecyl toluenesulphonic acids intermediate product;
4) neutralize: dropped in digestion tank by hexadecyl toluenesulphonic acids intermediate product, at temperature 45-55 DEG C, being neutralized to pH value with the sodium hydroxide solution of 20wt% is 8-10, obtains product hexadecyl toluenesulfonic acid sodium salt industrial goods.
SO wherein: described step 2)
3gas is generated by combustion of sulfur.
A present invention also object is the tensio-active agent providing a kind of good fluidity, excellent property, stable be directly used in oilfield chemistry complex oil displacing.
This tensio-active agent main component is above-described hexadecyl tosylate or hexadecyl tosylate Industrial products and solubility promoter, and solubility promoter is alcohol, and alcohol content is the 15-20wt% of tensio-active agent; Described alcohol is C
1-C
4alcohol, specifically can be ethanol, propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol, be preferably propyl carbinol.
Described tensio-active agent, it mainly consists of the water of 50-55wt% hexadecyl tosylate, the alcohol of 15-20wt%, unsulfonated oil (unreacted alkylbenzene) about 3wt%, inorganic salt 7wt% and surplus.
A present invention also object is to provide a kind of low cost and effective ternary built flooding system.
In this ternary built flooding system, NaOH or Na
2cO
30.4-1.2wt%, the above tensio-active agent 0.05-0.3wt%, polymer poly acrylamide 1200mg/L, surplus is water; System viscosity 40mPa.s.
Described ternary built flooding system, preferably wherein NaOH or Na
2cO
31.0-1.2wt%, tensio-active agent 0.2-0.3wt%.
The present invention can provide that composition is single, hexadecyl tosylate that structure is clear and definite, and its Industrial products preparation cost is low, can directly (without the need to separation) in flooding system.Good with the surfactant interface activity that hexadecyl tosylate or its Industrial products are prepared for main component, anti-dilution capacity is strong, working concentration low (concentration is 0.05-0.3wt%), can make oil water interfacial tension reach ultralow (10 wider alkali concn span (concentration is 0.4-1.2wt%)
-3the mN/m order of magnitude), the displacement of reservoir oil is carried out with the ternary composite oil-displacing system of its preparation, dosage of surfactant (consumption is low to moderate 0.2wt%) can be reduced and inject alkali concn (being low to moderate 1.0wt%), compound system good stability (can keep ultra low interfacial tension in 90 days), oil displacement efficiency is high.The experiment proved that, tensio-active agent of the present invention, under highly basic, weak base condition, all can produce stable ultra low interfacial tension with crude oil, and core oil-displacement test improves recovery ratio more than 20% than water drive.Its major advantage is:
1, the present invention adopts single hexadecyl toluene as raw material, and raw material sources are wide, cost is low, and forms with crude oil and match, and the interfacial activity of product is strong, good stability.
2, S0 is adopted
3membrane-type sulfonation method prepares hexadecyl tosylate, and process for sulfonation is simple, and sulfonation process side reaction is few, no coupling product, and sulfonation transformation efficiency is high, the Industrial products obtained without the need to aftertreatment, easy heavy industrialization.
3, tensio-active agent of the present invention adopts single, that structure the is clear and definite hexadecyl tosylate of composition to be main component, the molecular-weight average of its average equivalent and crude oil matches, thus ternary composite oil-displacing system and crude oil can be made to form ultra low interfacial tension, and in application, comparatively water drive can improve recovery ratio and reaches more than 20%.
4, add mobility, homogeneity that alcohol is conducive to improving product in tensio-active agent of the present invention, improve the stability of product, be conducive to the use of product.
5, hexadecyl toluenesulphonic acids salt surfactant of the present invention is good in low alkaline concentration lower range bound face activity, drives in note to reduce and injects alkali concn (being down to 1.0wt%), thus reduce the injury to oil reservoir.
In sum, the present invention is applying to provide and a kind ofly forming that single, structure is clear and definite, excellent property, stable surfactant oil displacement of tertiary oil recovery technology, not only oil recovery factor can be increased substantially, simultaneously, achieve the production domesticization formula of tensio-active agent, greatly reduce ternary composite driving cost, the spread for ternary composite driving has established theory and practice basis, has a extensive future.
Below in conjunction with specific embodiment, the present invention is described in further details.
Accompanying drawing explanation
Fig. 1 is the mass spectrum of hexadecyl tosylate (sodium) prepared by the present invention
Fig. 2 A is hexadecyl benzene toluene sulfonate (sodium) strong base ternary compound system interfacial activity detected result of the present invention
Fig. 2 B is hexadecyl benzene toluene sulfonate (sodium) weak base three-component compound system interfacial activity detected result of the present invention
Fig. 3 is the Detection of Stability result of the ternary composite oil-displacing system containing hexadecyl tosylate (sodium) tensio-active agent of the present invention
Embodiment
First the present invention provides that a kind of composition is single, structure is known, can form the hexadecyl tosylate with ultra low interfacial tension oilfield chemistry complex oil displacing tensio-active agent.Molecular weight is 418, and for structural formula is such as formula the compound shown in I, formula I is:
This hexadecyl tosylate is C by carbon number
16normal olefine and toluene be that the hexadecyl toluene for preparing of raw material obtains through continuous sulfonation, hydrolysis, neutralization again, hexadecyl toluene main chain is C
16straight chained alkyl, aryl is toluene, and structure is such as formula shown in II:
The production method of hexadecyl tosylate Industrial products comprises: be hexadecyl toluenesulphonic acids head product by continuous for hexadecyl toluene sulfonation in film sulfonation reactor, hexadecyl toluenesulphonic acids head product is hydrolyzed to stable hexadecyl toluenesulphonic acids intermediate product, and the neutralization of hexadecyl toluenesulphonic acids sodium hydroxide obtains hexadecyl tosylate Industrial products.Containing hexadecyl tosylate 70wt% in these Industrial products, surplus is the inorganic salt of generation in reaction, the raw material of unsulfonated and water.Hexadecyl tosylate Industrial products are dried at 120 DEG C, removing moisture, then replace cleaning products with sherwood oil and ethanol and cross and filter inorganic salt, dry again, add Virahol to dissolve, extract unsulfonated oil (unreacted raw material), purer hexadecyl tosylate after product is dried again, can be obtained.
The present invention also provides with tensio-active agent, and its main component is hexadecyl tosylate or its Industrial products and solubility promoter, and solubility promoter is alcohol, and its content is the 15-20wt% of tensio-active agent; Alcohol can be C
1-C
4alcohol, as ethanol, propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
Concrete, this tensio-active agent its mainly consist of the water of 50-55wt% hexadecyl tosylate, the alcohol of 15-20wt%, unsulfonated oil (unreacted alkylbenzene) about 3wt%, inorganic salt 7wt% and surplus.
Present invention also offers above-mentioned hexadecyl toluenesulphonic acids salt surfactant in highly basic, weak base oil-displacing agent or the application in highly basic, weak base chemical combined flooding oil systems or ternary composite oil-displacing system.
Ternary built flooding system provided by the invention, wherein alkali is highly basic or weak base, and its concentration range can at 0.4-1.2wt%, the concentration 0.05-0.3wt% of tensio-active agent, polymer poly acrylamide 1200mg/L, and surplus is water; System viscosity 40mPa.s.Particularly, use and also can reach effective oil displacement efficiency compared with low alkaline concentration 1.0wt% and/or compared with the system of low surfactant concentration 0.2wt%, displacement of reservoir oil cost can be reduced, reduce the injury to oil reservoir.
Further illustrate the present invention with specific embodiment below, but protection scope of the present invention is not limited to following embodiment.
In following embodiment, method therefor is ordinary method if no special instructions.
The production of the preparation of embodiment 1, hexadecyl toluenesulfonate (sodium) and Industrial products thereof
Describe it in detail obtain process to prepare hexadecyl Sodium Toluene Sulphonate below.Be understandable that, the preparation of hexadecyl toluene is dispensable, and this raw material also can be purchased.
1) hexadecyl toluene is prepared: take carbon number as C
16normal olefine and toluene be that hexadecyl toluene prepared by raw material, process is: amplify application test for 3000L, by 1300Kg toluene, 38Kg Primary Catalysts (aluminum chloride) and the secondary catalyzer (Tripyrophosphoric acid) of 4L add 5000L reactor, stir 10min, the system that is slowly warming up to has white gas to produce, stop heating, again 640Kg hexadecylene (alpha-olefin) is added reactor, open cycle water cooling during temperature to 40 DEG C, control temperature of reaction and be no more than 60 DEG C, insulation 2h, insulation terminates rear stopping and stirring, sedimentation 10min, system is divided into two-layer up and down, catalyzer is precipitated to lower floor, separate whole lower floor, then add hot water and stir 10min to expiring still, stop stirring 10min, divide water outlet and floss, except anhydrating.Repeating to wash 4-5 time to pH value is 7, this floss (organic layer) is squeezed into still kettle, is warming up to 90-100 DEG C, gas phase temperature 70 DEG C starts to heat up in a steamer (going out to heat up in a steamer thing is water and unreacted toluene), control still temperature and be no more than 155 DEG C, fall after rise when gas phase temperature and terminate without air distillation when going out to heat up in a steamer thing.Start vacuum pump, start to carry out underpressure distillation (going out to heat up in a steamer thing is unreacted alkene), gas phase temperature slowly rises to 140 DEG C extremely without when going out to heat up in a steamer thing, and underpressure distillation terminates, and in still kettle, residuum is hexadecyl toluene, and its purity can reach more than 90%.
This step chemical reaction formula is as follows:
Wherein alkene is carbon number is C
16normal olefine, m+n=15
2) sulfonation hexadecyl toluene: sulfonation reaction is carried out in film sulfonation reactor, the inlet amount of hexadecyl toluene be 1.4-2.1 ton/hour, use SO
3gas sulfonation hexadecyl toluene, SO
3air input controls at 150-170 kg/hr, i.e. SO
3be 1.29-1.46:1 with the mol ratio of hexadecyl toluene, sulfonation temperature controls at 45-55 DEG C, obtains hexadecyl toluenesulphonic acids head product, keeps SO
3air input and hexadecyl toluene feed amount are stablized, and continuous production, the conversion ratio of hexadecyl toluene and hexadecyl toluenesulphonic acids head product is 1:1.3.This step chemical reaction formula is as follows:
In preparation, SO
3gas is generated by combustion of sulfur, and concrete grammar is: melted by solid sulfur as liquid at 150 DEG C, the SO generated after burning
2gas is through converter (SO
2-SO
3converter, Fujian builds Machinery Co., Ltd.) generate SO
3gas, chemical equation is as follows:
SO
2+O
2→SO
3
3) be hydrolyzed: the water adding its total amount 2-4wt% at 45-55 DEG C in hexadecyl toluenesulphonic acids head product, hydrolysis hexadecyl toluenesulphonic acids head product, obtains stable hexadecyl toluenesulphonic acids intermediate product.SO unnecessary in system
3react with water and produce acid, chemical equation is as follows:
SO
3+H
2O→H
2SO
4
4) neutralize: dropped in digestion tank by intermediate product hexadecyl toluenesulphonic acids, at temperature 45-55 DEG C, being neutralized to pH value with the alkali lye (sodium hydroxide) of 20wt% is 8-10, and obtain hexadecyl toluenesulfonic acid sodium salt, chemical equation is as follows:
Wherein m+n=15
Sulfuric acid (the H of the production in hexadecyl toluenesulphonic acids hydrolytic process
2sO
4) also produce neutralization reaction with alkali, inorganic salt sodium sulfate (Na can be produced in acid-base neutralisation process
2sO
4) and water.Chemical equation is as follows:
H
2SO
4+NaOH→Na
2SO
4+H
2O
First hexadecyl toluenesulfonic acid sodium salt Industrial products are obtained by above process.
Be further purified and can obtain hexadecyl toluenesulfonic acid sodium salt.
Purification process is: dried at 120 DEG C by hexadecyl tosylate Industrial products, removing moisture, then replace cleaning products with sherwood oil and ethanol and cross and filter inorganic salt, dry again, add Virahol to dissolve, extract unsulfonated oil (unreacted raw material alkylbenzene), after product is dried again, purer synthetic product can be obtained.
Detect synthetic product by mass spectroscopy, detecting instrument is gas (liquid) phase chromatograph-mass spectrometer (purchased from Hewlett-Packard).(X-coordinate is mass-to-charge ratio to detected result as shown in Figure 1, ordinate zou is abundance), can find out that synthetic product has the structure determined, on spectrogram, peak value display is comparatively single, show that its ratio of components is more single, made the hexadecyl toluenesulfonic acid sodium salt synthetic product that purity is higher.
Through actual production metering, be raw material with 10 tons of hexadecyl toluene, 13 tons of hexadecyl toluenesulphonic acidss can be obtained, after neutralization, generate 26 tons of hexadecyl tosylate Industrial products.The hexadecyl toluenesulfonic acid sodium salt mixing solutions of hexadecyl tosylate Industrial products to be content be about 70wt%, surplus is the inorganic salt, the raw material of unsulfonated and the water that generate in reaction.This mixing solutions be used for the displacement of reservoir oil time without the need to carrying out Component seperation.In addition, the mobility of hexadecyl tosylate Industrial products is not good, need add solubility promoter and improve its mobility when directly using in flooding system.
Embodiment 2, prepare hexadecyl toluene sulfonic acide salt surfactant
In displacement of reservoir oil application process, require that surfactant has good mobility, therefore produce in embodiment 1 in the hexadecyl toluenesulfonic acid sodium salt Industrial products (mixing solutions) obtained and add solubility promoter dilution, namely obtain the hexadecyl toluene sulfonic acide salt surfactant that can be directly used in displacement of reservoir oil compound system.The optional ethanol of solubility promoter, propyl alcohol, Virahol or isopropylcarbinol, add-on is the 15-20wt% of tensio-active agent total amount, and solubility promoter add-on should not have ceiling restriction technically, but considers cost, the most economical to be no more than 20%.
The present invention finally obtains can the surfactant-hexadecyl toluenesulphonic acids salt surfactant of filed application, it mainly consists of 50-55wt% hexadecyl tosylate synthetic product, the alcohol of 15-20wt%, unsulfonated oil (unreacted alkylbenzene) are about 3wt%, and inorganic salt and water (neutralization reaction gained) are respectively 7wt% and 20wt%.
The Performance Detection of embodiment 3, hexadecyl toluenesulphonic acids salt surfactant
Two kinds of (highly basic NaOH, weak base Na are become with hexadecyl tosylate surfactant formulatory prepared by embodiment 2
2cO
3) ternary chemistry composite oil-displacing system, measure interfacial tension between composite oil-displacing system and Daqing crude oil.During mensuration, crude oil is well head gas-free oil, and water is for injecting water; Experimental temperature 45 DEG C; Testing tool: tensiometer is dripped in the rotation of Texas, USA university, model 500.
System 1: alkali system, the interfacial activity of mensuration is shown in Fig. 2 A.
Tensio-active agent: hexadecyl toluenesulphonic acids salt surfactant (be the surfactant of 15% for propyl carbinol add-on), implantation concentration 0.05wt%-0.3wt% in three-component compound system;
Alkali: highly basic sodium hydroxide, implantation concentration 0.2wt%-1.2wt% in three-component compound system;
Polymkeric substance: Daqing Refinery company high molecular polymer partially hydrolyzed polyacrylamide (molecular weight is 1,900 ten thousand), implantation concentration is 1200mg/L in three-component compound system.
System 2: alkalescent system, the interfacial activity of mensuration is shown in Fig. 2 B.
Tensio-active agent: hexadecyl toluenesulphonic acids salt surfactant, implantation concentration 0.05wt%-0.3wt% in three-component compound system;
Alkali: weak base sodium carbonate, implantation concentration 0.2wt%-1.2wt% in three-component compound system;
Polymkeric substance: Daqing Refinery company high score polymer moieties hydro-polyacrylamide (molecular weight is 1,900 ten thousand), implantation concentration is 1200mg/L in three-component compound system.
Detected result is as Fig. 2 A(alkali system, system 1) and Fig. 2 B(alkalescent system, system 2) shown in, show the ternary composite oil-displacing system with highly basic and weak base and hexadecyl tosylate surfactant formulatory of the present invention, at alkali concn 0.4-1.2wt%, can ultra low interfacial tension be obtained in the scope of surfactant concentration 0.05-0.3wt% and between Daqing crude oil, reach 10
-3the mN/m order of magnitude.
The stability of embodiment 4, the ternary composite oil-displacing system of detection containing hexadecyl toluenesulphonic acids salt surfactant
In the ternary composite oil-displacing process of reality, ternary composite oil-displacing system needs the time of periods of months under oil reservoir physicochemical condition, so require that it has good stability.
At 45 DEG C of temperature, with the ternary composite oil-displacing system of actual re-injection oil reservoir production water preparation containing hexadecyl toluenesulphonic acids salt surfactant of the present invention, moiety: with the polymkeric substance (molecular weight is the polyacrylamide of 1,900 ten thousand) of the alkali (sodium hydroxide and sodium carbonate) of the hexadecyl toluenesulphonic acids salt surfactant (propyl carbinol, 15%) of 0.3wt%, 1.2wt% and 1200mg/L for example.During experiment, in ternary system solution, pass to nitrogen, removing oxygen wherein, is sealed in color-comparison tube, the state of routine observation solution the interfacial tension measured between ternary composite oil-displacing system and crude oil.
As shown in Figure 3, within 90 days, interface stress does not change detected result substantially, shows that the ternary composite oil-displacing system containing hexadecyl toluenesulphonic acids salt surfactant of the present invention has good interfacial tension stability.
The indoor Berea core oil displacement experiment of embodiment 5, ternary composite oil-displacing system containing hexadecyl toluenesulphonic acids salt surfactant
Adopt Berea core; carried out the Oil Displacing Capacity evaluation of the ternary composite oil-displacing system containing hexadecyl toluenesulphonic acids salt surfactant of the present invention according to People's Republic of China (PRC) oil and gas industry standard SY/T6424-2000: when water drive to moisture 100% time inject the chemical combined flooding oil systems (see following system) of 0.3 times of volume of voids (PV); and then (molecular weight is the polyacrylamide of 1,900 ten thousand to inject the polymkeric substance of 0.2PV; viscosity 40mPa.s) protect slug, last water drive to moisture 100% time terminate.
In oil displacement experiment, to migrate longer distance when ensureing ultra low interfacial tension to make ternary oil displacement system, guarantee the oil displacement efficiency of compound system, consider economic benefit simultaneously, in ternary oil displacement system, alkali concn selects 1.0-1.2wt%, and surfactant concentration (adding 15% propyl carbinol) selects 0.2-0.3%wt, polymkeric substance to be molecular weight be 1,900 ten thousand polyacrylamide, the viscosity 40mPa.s of concentration compound system determines, investigates the oil displacement efficiency of ternary oil displacement system.
Experimental result is as shown in table 1.
Table 1 oil displacement experiment result
Alkali system 1:NaOH1.2wt%, hexadecyl toluenesulphonic acids salt surfactant (propyl carbinol, 15%) 0.3wt%, compound system viscosity 40mPa.s;
Alkali system 2:NaOH1.0wt%, hexadecyl toluenesulphonic acids salt surfactant (propyl carbinol, 15%) 0.3wt%, compound system viscosity 40mPa.s;
Alkali system 3:NaOH1.0wt%, hexadecyl toluenesulphonic acids salt surfactant (propyl carbinol, 15%) 0.2wt%, compound system viscosity 40mPa.s;
Alkalescent system 1:Na
2cO
31.2wt%, hexadecyl toluenesulphonic acids salt surfactant (propyl carbinol, 15%) 0.3wt%, compound system viscosity 40mPa.s;
Alkalescent system 2:Na
2cO
31.0wt%, hexadecyl toluenesulphonic acids salt surfactant (propyl carbinol, 15%) 0.3wt%, compound system viscosity 40mPa.s;
Alkalescent system 3:Na
2cO
31.0wt%, hexadecyl toluenesulphonic acids salt surfactant (propyl carbinol, 15%) 0.2wt%, compound system viscosity 40mPa.s.
Table 1 result shows, two kinds of (highly basic, weak base) systems all improve recovery ratio and all reach more than 20%OOIP, show hexadecyl toluenesulphonic acids salt surfactant that the present invention obtains under the condition of highly basic and weak base all can and Daqing crude oil between form ultra low interfacial tension, and with crude oil forms ultra low interfacial tension in lower surfactant concentration (0.2wt%) with comparatively under low alkaline concentration (1.0wt%) by the ternary built system of its preparation, core oil-displacement test is than water drive raising recovery ratio more than 20%.
Above embodiment and experiment, be what determine for illustration of hexadecyl tosylate structure provided by the invention, with the alkyl benzene sulfonate surfactant of its assembly, form simple and ultra low interfacial tension can be formed with crude oil within the scope of wider surfactant concentration and alkali concn, by the ternary composite oil-displacing system of this surfactant compound, lower surfactant concentration and alkali concn can be used, reach core oil-displacement test improves recovery ratio more than 20% oil displacement efficiency than water drive equally.The present invention is applying to provide and a kind ofly forming that single, structure is definite, the surfactant oil displacement of excellent property of tertiary oil recovery technology.Compared with former alkylbenzene sulfonate (its contrast as shown in table 2) in displacement system, hexadecyl tosylate of the present invention achieves continuous print industrial production, and Industrial products can directly use, the surfactant component used in displacement system is single, good stability (can reach 90 days).
The contrast of table 2 displacement composition
Claims (3)
1. the production method of hexadecyl tosylate Industrial products, it is characterized in that, comprise: be hexadecyl toluenesulphonic acids head product by continuous for hexadecyl toluene sulfonation in film sulfonation reactor, hexadecyl toluenesulphonic acids head product is hydrolyzed to stable hexadecyl toluenesulphonic acids intermediate product, the neutralization of hexadecyl toluenesulphonic acids sodium hydroxide obtains hexadecyl tosylate Industrial products, wherein containing hexadecyl tosylate 70wt%, surplus is the inorganic salt generated in reaction, unreacted raw material and water;
Described hexadecyl toluene is C by carbon number
16normal olefine and toluene be that raw material prepares, hexadecyl toluene main chain is C
16straight chained alkyl, phenyl ring be toluene, structure is such as formula shown in II:
Hexadecyl toluene preparation process is as follows: under 3000L industrial scale, secondary to 1300Kg toluene, 38Kg Primary Catalysts aluminum chloride and 4L catalyzer Tripyrophosphoric acid is added 5000L reactor, stir 10min, the system that is slowly warming up to has white gas to produce, stop heating, then 640Kg hexadecylene is added reactor, open cycle water cooling during temperature to 40 DEG C, control temperature of reaction and be no more than 60 DEG C, insulation 2h; Insulation terminates rear stopping and stirring sedimentation 10min, releases lower catalyst agent; Add hot water and stir 10min to expiring still, stop stirring 10min, removing lower layer of water, repeating to wash 4-5 time to pH value is 7; Cotton-shaped organic layer is squeezed into still kettle and carries out air distillation, control still temperature and be no more than 155 DEG C, to gas phase temperature falling and without going out to heat up in a steamer thing; Start vacuum pump and carry out underpressure distillation, slowly rise to 140 DEG C to gas phase temperature and terminate to without when going out to heat up in a steamer thing; In still kettle, residuum is hexadecyl toluene.
2. production method according to claim 1, is characterized in that: specifically comprise the following steps:
1) hexadecyl toluene is prepared;
2) sulfonation hexadecyl toluene: sulfonation reaction is carried out in film sulfonation reactor, sulfonation temperature 45-55 DEG C, the inlet amount of hexadecyl toluene be 1.4-2.1 ton/hour, pass into SO
3the air input of gas is 150-170 kg/hr, i.e. control SO
3be 1.29-1.46:1 with the mol ratio of hexadecyl toluene, obtain hexadecyl toluenesulphonic acids head product; Keep SO
3air input and hexadecyl toluene feed amount are stablized, continuous production;
3) be hydrolyzed: the water adding its total amount 2-4wt% at 45-55 DEG C in hexadecyl toluenesulphonic acids head product, obtains stable hexadecyl toluenesulphonic acids intermediate product;
4) neutralize: dropped in digestion tank by hexadecyl toluenesulphonic acids intermediate product, at temperature 45-55 DEG C, being neutralized to pH value with the sodium hydroxide solution of 20wt% is 8-10, obtains product hexadecyl toluenesulfonic acid sodium salt industrial goods.
3. the preparation method of hexadecyl tosylate, it is characterized in that: claim 1 or 2 is produced the hexadecyl tosylate Industrial products obtained and dry removing moisture, then replace cleaning products with sherwood oil and ethanol to cross and filter inorganic salt, add isopropyl alcohol extraction after oven dry again and go out unsulfonated oil and unreacted alkylbenzene, purer hexadecyl tosylate after product is dried again, can be obtained.
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| CN112251209B (en) * | 2020-10-29 | 2021-05-28 | 大庆再创科技有限公司 | Surfactant for efficiently improving recovery efficiency and preparation method thereof |
| CN112266776B (en) * | 2020-10-29 | 2021-05-28 | 大庆轩隆化工有限公司 | Surfactant for oil displacement and preparation method thereof |
| CN113666849A (en) * | 2021-07-16 | 2021-11-19 | 中国石油天然气股份有限公司 | Acid sludge treatment method and binary oil-displacing surfactant |
| CN117049985A (en) * | 2023-08-11 | 2023-11-14 | 安徽金桐精细化学有限公司 | High-carbon sodium alkylbenzenesulfonate and preparation method and application thereof |
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