CN102653674B - A kind of preparation method of surfactant oil displacement and product - Google Patents
A kind of preparation method of surfactant oil displacement and product Download PDFInfo
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- CN102653674B CN102653674B CN201110050901.8A CN201110050901A CN102653674B CN 102653674 B CN102653674 B CN 102653674B CN 201110050901 A CN201110050901 A CN 201110050901A CN 102653674 B CN102653674 B CN 102653674B
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Abstract
The present invention relates to a kind of preparation method and product of surfactant oil displacement.Method wherein comprises, and is mixed by coking distillate with fraction oil of petroleum, first carries out alkylated reaction, then carries out sulfonation reaction, then uses alkali neutralization reaction product, finally obtains product.The surfactant oil displacement adopting the inventive method to prepare, can form ultralow oil-water interfacial tension, and stronger to the adaptability of different oilfield conditions.
Description
Technical field
The present invention relates to a kind of preparation method and product of surfactant oil displacement.
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.
Tertiary oil recovery method mainly contains that heating power drives, mixed phase drives, chemical flooding and microorganism drive.The reserves that China oil field is applicable to chemical flooding account for major portion, so chemical flooding is the main development direction of China's tertiary oil recovery.In chemical flooding, surfactant flooding is one of most effective means.Due to the complicacy of oil properties and formation condition, need during option table surface-active agent to consider numerous factors, wherein oil-water interfacial tension is the most basic factor.
The tensio-active agent used in tertiary oil recovery mainly contains sulfonated petro-leum, heavy alkylbenzene sulfonate, sulfonated lignin and petroleum carboxylate, and the price of sulfonated petro-leum is wherein low, efficiency is high, is most widely used surfactant oil displacement.
Sulfonated petro-leum, usually to be rich in the fraction oil of petroleum of aromatic hydrocarbons for raw material, after sulfonation process, obtains with alkali neutralization.What be sulfonated is fragrance ingredient in raw material, and therefore sulfonated petro-leum is the dope containing sulfonate, unsulfonated oil and inorganic salt.The adaptability of the different oilfield conditions of conventional mahogany acid salt pair is also undesirable.
Summary of the invention
The invention provides a kind of preparation method and product of surfactant oil displacement, oil-water interfacial tension can be down to lower and stronger to the adaptability of different oilfield conditions by this tensio-active agent.
A preparation method for surfactant oil displacement, comprising:
(1) coking distillate of boiling range between 50 DEG C ~ 500 DEG C is mixed with fraction oil of petroleum, react under alkylation reaction condition, olefin(e) centent >=10 quality the % of described coking distillate, aromaticity content >=40 quality % in described fraction oil of petroleum, in the mixture of coking distillate and fraction oil of petroleum, the mass ratio of alkene and aromatic hydrocarbons is 1: 5 ~ 1: 15;
(2) react under sulfonation reaction condition with the product that step (1) obtains;
(3) with the product that alkali neutralization procedure (2) obtains, product is obtained.
The boiling range of coking distillate is preferably 90 DEG C ~ 460 DEG C, is more preferably 120 DEG C ~ 380 DEG C.
Described coking distillate is the distillate of delayed coking, flexicoking or fluid coking.
Described coking distillate is preferably one or more in coker gas oil, wax tailings or coking fractional distillation column turning oil.
Olefin(e) centent in described coking distillate is preferably 15 ~ 40 quality %.
Aromaticity content in described coking tower distillate is preferably 20 ~ 40 quality %.
In the mixture of coking distillate and fraction oil of petroleum, the mass ratio of alkene and aromatic hydrocarbons is preferably 1: 8 ~ 1: 12.
Described fraction oil of petroleum can be vacuum distillate, oil is extracted in solvent treatment out or the pressed oil of solvent treatment extraction oil, and preferred solvent refines extraction oil or oily pressed oil is extracted in solvent treatment out.Aromaticity content in described fraction oil of petroleum preferably >=50 quality %, more preferably >=60 quality %.
Described solvent treatment is extracted oil out and is referred to the extraction oil that solvent refining processes obtains.
The pressed oil that oil is extracted in described solvent treatment out refers to that first obtaining solvent treatment through solvent refining processes extracts oil out, then solvent treatment extraction oil is carried out the pressed oil that solvent dewaxing process obtains.
Described solvent dewaxing adopts organic solvent, filters the high condensation point component removed in crude oil fractions oil at low temperatures.
Described alkylated reaction refers to the alkylated reaction of alkene and aromatic hydrocarbons.Conventional catalyzer is aluminum chloride, HF, H
2sO
4, molecular sieve, phosphate diatomite, modification sial, heteropolyacid, oxonium ion exchange resin, ionic liquid etc.Preferred employing aluminum chloride is catalyzer, temperature of reaction 50 ~ 80 DEG C, and the reaction times is 1 ~ 10 hour.
Described sulfonation reaction can adopt the popular response condition preparing sulfonated petro-leum.Sulphonating agent can adopt oleum, sulphur trioxide or chlorsulfonic acid.When adopting oleum to be sulphonating agent, temperature of reaction 26 ~ 120 DEG C, is preferably 37 ~ 93 DEG C, is more preferably 54 ~ 82 DEG C, 1 ~ 8 hour reaction times, is preferably 2 ~ 6 hours, oleic acid mass ratio 1: 1 ~ 5: 1, is preferably 1.25: 1 ~ 3.75: 1.
The alkylated reaction of alkene and aromatic hydrocarbons and the sulfonation reaction of aromatic hydrocarbons all belong to prior art, and the present invention repeats no more.
Those skilled in the art know the product how used with sulfonation reaction in alkali, and the present invention preferably adopts the aqueous solution of alkali metal hydroxide or ammoniacal liquor to carry out the product of neutralization procedure (2) sulfonation reaction.
Present invention also offers the product that aforesaid method obtains.
Prior art is usually to be rich in the fraction oil of petroleum of aromatic hydrocarbons for raw material, sulfonated petro-leum is prepared by sulfonation reaction, the ability that sulfonated petro-leum prepared by the method reduces oil-water interfacial tension needs to be improved further, also undesirable to the adaptability of different oilfield conditions.The present invention by being mixed with fraction oil of petroleum by coking distillate, and before sulfonation reaction, first carries out alkylation process to mixing raw material, makes the surfactant oil displacement of preparation have better performance.Oil-water interfacial tension can be down to lower by the surfactant oil displacement prepared by the present invention, and stronger to the adaptability of different oilfield conditions.
Embodiment
Embodiment 1
The present embodiment is for illustration of the preparation method of surfactant oil displacement of the present invention.
By furfural extract oil (aromaticity content 75 quality %) and delayed coking distillate (boiling range 180 ~ 380 DEG C, olefin(e) centent 27 quality %, aromaticity content 23 quality %) mixing, the mass ratio of alkene and aromatic hydrocarbons in mixture is made to be 1: 5, add aluminum chloride (consumption is 1/15 of raw material total mass), react after 2 hours at 60 DEG C, go out catalyzer with filtered on buchner funnel; Filtrate is transferred in container, oleum is dripped while stirring in container, oleic acid ratio is 1.25: 1 (stock oil total mass and oleum mass ratios), react at 50 DEG C after 4 hours, be added dropwise to the NaOH solution that mass concentration is 20%, the pH value of fluid is adjusted to 7 ~ 8, product is transferred to separate aqueous layer in separating funnel and namely obtain product, product composition is in table 1.
Comparative example 1
This comparative example is for illustration of the preparation of conventional oil sulfonate.Except not adding delayed coking distillate and not carrying out except alkylated reaction, all the other conditions are all identical with embodiment 1, and product composition is in table 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of surfactant oil displacement of the present invention.
By the pressed oil (aromaticity content 50 quality %) of furfural extract oil and delayed coking diesel oil distillate (olefin(e) centent 12 quality %, aromaticity content 37 quality %) mixing, the mass ratio of alkene and aromatic hydrocarbons in mixture is made to be 1: 8, add aluminum chloride (consumption is 1/15 of raw material total mass), react after 2 hours at 50 DEG C, go out catalyzer with filtered on buchner funnel; Filtrate is transferred in container, oleum is dripped while stirring in container, oleic acid ratio is 1.25: 1 (stock oil total mass and oleum mass ratios), react at 70 DEG C after 4 hours, be added dropwise to the ammonia soln that mass concentration is 25%, the pH value of fluid is adjusted to 7 ~ 8, the product after neutralization is transferred to static separatory in separating funnel, obtains product.
Embodiment 3
The present embodiment is for illustration of the preparation method of surfactant oil displacement of the present invention.
By vacuum distillate (aromaticity content 31.68 quality %) and delayed coking distillate (boiling range 90 ~ 220 DEG C, olefin(e) centent 35 quality %, aromaticity content 11 quality %) mixing, the mass ratio of alkene and aromatic hydrocarbons in mixture is made to be 1: 10, add aluminum chloride (consumption is 1/15 of raw material total mass), react after 2 hours at 80 DEG C, go out catalyzer with filtered on buchner funnel; Filtrate is transferred in container, oleum is dripped while stirring in container, oleic acid ratio is 1.5: 1 (stock oil total mass and oleum mass ratios), react at 60 DEG C after 4 hours, be added dropwise to the NaOH solution that mass concentration is 20%, the pH value of fluid is adjusted to 7 ~ 8, the product after neutralization is transferred to static separatory in separating funnel, obtains product.
Embodiment 4
The present embodiment is for illustration of the performance of product of the present invention.
The profit system simulating certain oil field three class domestic five blocks is tested, and the character of profit system is in table 2.Adopting the injection water of corresponding block to prepare mass concentration is the sulfonate solution of 0.3%, under the formation temperature conditions of these blocks of simulation, the sulfonate solution of preparation is injected in rotary test pipe, then crude oil corresponding for each system is injected in rotary test pipe solution, TX500C type gamut interfacial tension survey meter measures oil water interfacial tension, and rotating speed is 5000r/min.Every 1min automatic data collection once, METHOD FOR CONTINUOUS DETERMINATION, until oil water interfacial tension value stabilization or oil droplet chain rupture, test-results is in table 3.
As can be seen from table 1 and table 3, the active matter content of product of the present invention is lower than contrast medium, but oil-water interfacial tension is lower, interfacial tension stationary value and minimum value also closer to, interface performance is better than contrast medium.This illustrates the product that obtained through alkylation, sulfonation by crude oil fractions, and wetting ability and lipophilicity balance more, the easier interfacial layer enrichment in crude oil and water filling, the lower level that oil-water interfacial tension is reached.
Table 1
| Classification | Volatiles/% | Salts contg/% | Active matter content/% | Unsulfonated oil content/% |
| Embodiment 1 | 34.6 | 1.8 | 25.4 | 38.2 |
| Comparative example | 30.2 | 5.5 | 38.4 | 25.9 |
Table 2
Table 3
Claims (4)
1. a surfactant oil displacement, is characterized in that, the preparation method of this tensio-active agent comprises:
(1) coking distillate of boiling range between 120 DEG C ~ 380 DEG C is mixed with fraction oil of petroleum, react under alkylation reaction condition; Described coking distillate is the distillate of delayed coking, and olefin(e) centent is wherein 15 ~ 40 quality %, and aromaticity content is 20 ~ 40 quality %; Described fraction oil of petroleum is that solvent treatment extracts oil out, the aromaticity content >=50 quality % in described fraction oil of petroleum; In the mixture of coking distillate and fraction oil of petroleum, the mass ratio of alkene and aromatic hydrocarbons is 1: 5 ~ 1: 15;
(2) react under sulfonation reaction condition with the product that step (1) obtains;
(3) with the product that alkali neutralization procedure (2) obtains, product is obtained.
2. according to surfactant oil displacement according to claim 1, it is characterized in that, in the mixture of coking distillate and fraction oil of petroleum, the mass ratio of alkene and aromatic hydrocarbons is 1: 8 ~ 1: 12.
3. according to surfactant oil displacement according to claim 1, it is characterized in that, in described alkylated reaction, catalyzer is aluminum chloride, temperature of reaction 50 ~ 80 DEG C, and the reaction times is 1 ~ 10 hour.
4. according to surfactant oil displacement according to claim 1, it is characterized in that, in described sulfonation reaction, sulphonating agent is oleum, temperature of reaction 26 ~ 120 DEG C, 1 ~ 8 hour reaction times, oleic acid mass ratio 1: 1 ~ 5: 1.
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