CN105085809B - A kind of polystyrene butene dioic acid ethylhexyl and preparation method and application - Google Patents
A kind of polystyrene butene dioic acid ethylhexyl and preparation method and application Download PDFInfo
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- CN105085809B CN105085809B CN201510423151.2A CN201510423151A CN105085809B CN 105085809 B CN105085809 B CN 105085809B CN 201510423151 A CN201510423151 A CN 201510423151A CN 105085809 B CN105085809 B CN 105085809B
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Abstract
The invention provides a kind of polystyrene butene dioic acid ethylhexyl and preparation method and application.The preparation method is included using styrene and butene dioic acid ethylhexyl as reaction monomers, in the presence of zinc stearate and cyclohexanone peroxide, carries out polymerisation by decentralized medium of water, obtains the polystyrene butene dioic acid ethylhexyl.Present invention also offers the polystyrene butene dioic acid ethylhexyl being prepared by above-mentioned preparation method, the polystyrene butene dioic acid ethylhexyl to prepare horizontal well oil-producing profile monitoring tracer of the horizontal well oil-producing profile monitoring with the application of tracer and containing the polystyrene butene dioic acid ethylhexyl.The polystyrene butene dioic acid ethylhexyl of the present invention can be dissolved completely in crude oil, use it for each section of oil-producing situation after level monitoring well multistage fracturing, can be reached every section of oil-producing situation of analysis and be drawn the purpose of every section of oil-producing liquid section.
Description
Technical field
The present invention relates to a kind of polystyrene butene dioic acid ethylhexyl and preparation method and application, belong to oil and survey
Visit development technique field.
Background technology
At present during In Oil Field Exploration And Development, prospect pit uses horizontal well more, and multi-layer multi-stage pressure break is stratum transformation
Preferred technique, but during being selected in layer position, all it is to select to be layered by experience without specific aim, therefore for pressure break
Data acquisition and issuance fracturing effect afterwards is just particularly important.In the prior art, micro seismic method, potentiometry etc. can be passed through
Method monitor and analysis pressure break after fracture intensity, then whether have a commercial oil by the row's of returning situation awareness reservoir, but for
Each section of oil-producing situation is still without effective monitoring method after staged fracturing.
Therefore, a kind of process of each section of oil-producing situation after level monitoring well multistage fracturing is developed to fracturing effect
Evaluation and the deployment of next step well location have great importance.
Multistage fracturing technique building technology and its related corollary equipment oneself through maturation, oneself realizes 30 grades of pressure breaks, state in the world
Interior maximum pressure break series oneself more than 15 grades.Because pressure break series is more, had differences in addition in long horizontal sections, physical property, every grade of pressure
Evaluation and next step well site deployment of the rear discharge opeing situation for fracturing effect is split to have great importance, but for staged fracturing after
Each section of oil-producing situation does not have effective monitoring method.Due to current largest domestic pressure break series oneself more than 15 grades, correspondingly need
Want more than 15 kinds of horizontal well oil-producing profile monitoring tracer.Existing oil field is water-soluble tracer with tracer, and
And the species of tracer is few, dosage is big, the monitoring of each section of oil-producing situation after horizontal well multi-layer multi-stage pressure break is not suitable for.
Therefore, developing a kind of suitable horizontal well oil-producing profile monitoring tracer, oneself turns into this area urgent need to resolve
Technical problem.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of polystyrene butene dioic acid ethylhexyl
Preparation method.
The present invention also aims to provide a kind of preparation method by above-mentioned polystyrene butene dioic acid ethylhexyl
The polystyrene butene dioic acid ethylhexyl being prepared.
The present invention also aims to provide a kind of above-mentioned polystyrene butene dioic acid ethylhexyl to prepare horizontal well
The application of oil-producing profile monitoring tracer.
The present invention also aims to provide a kind of horizontal well for including above-mentioned polystyrene butene dioic acid ethylhexyl
Oil-producing profile monitoring tracer.
For the above-mentioned purpose, should the invention provides a kind of preparation method of polystyrene butene dioic acid ethylhexyl
Method is included using styrene and butene dioic acid ethylhexyl as reaction monomers, in the presence of zinc stearate and cyclohexanone peroxide
Under, polymerisation is carried out by decentralized medium of water, obtains the polystyrene butene dioic acid ethylhexyl；
Wherein, zinc stearate is dispersant, and cyclohexanone peroxide is initiator.
According to preparation method of the present invention, it is preferable that the butene dioic acid ethylhexyl includes maleic acid
Ethylhexyl or fumaric acid ethylhexyl；
It is also preferred that maleic acid ethylhexyl includes maleic acid two (2- ethyl hexyls) ester, maleic acid
Two (3- ethyl hexyls) esters or maleic acid two (4- ethyl hexyls) ester；
The fumaric acid ethylhexyl includes fumaric acid two (2- ethyl hexyls) ester, (3- of fumaric acid two
Ethyl hexyl) ester or fumaric acid two (4- ethyl hexyls) ester.
Wherein described butene dioic acid ethylhexyl (C20H36O4), zinc stearate (C36H70O4Zn), styrene (C8H8) and
Cyclohexanone peroxide (C12H22O5) be this area conventional reagent, any commercially available butene dioic acid diethyl commonly used in the art oneself
Ester, zinc stearate, styrene and cyclohexanone peroxide may be used to the present invention.
According to preparation method of the present invention, it is preferable that to react the whole material gross weights added as 100%
Meter, adding each weight of material percentage is respectively：Butene dioic acid ethylhexyl is 35wt%-45wt%, styrene is
2.5wt%-5wt%, zinc stearate 1wt%-2wt%, cyclohexanone peroxide 0.2wt%-1wt%, surplus are water.
According to preparation method of the present invention, it is preferable that the reaction temperature of the polymerisation is 80 DEG C -90 DEG C, more
It is preferred that the reaction temperature is 85 DEG C.
According to preparation method of the present invention, it is preferable that the reaction time of the polymerisation is 8-10h, more preferably
The reaction time is 10h.
In the preparation process of polystyrene butene dioic acid ethylhexyl of the present invention, the reaction temperature of polymerisation is timely
Between change it is influenceed less, as long as by reaction temperature control at 80 DEG C -90 DEG C, the reaction time is controlled in 8-10h.
According to preparation method of the present invention, it is preferable that methods described includes：Zinc stearate is dissolved into water first
In, the mixed solution of butene dioic acid ethylhexyl, styrene and cyclohexanone peroxide is added, is reacted after the completion of addition and obtains institute
State polystyrene butene dioic acid ethylhexyl.
According to preparation method of the present invention, it is preferable that methods described includes：Zinc stearate is dissolved into 80 first
In DEG C -90 DEG C of hot water, the mixed solution of butene dioic acid ethylhexyl, styrene and cyclohexanone peroxide is added.
According to preparation method of the present invention, it is preferable that methods described includes：Zinc stearate is dissolved into water first
In, 80 DEG C of -90 DEG C of constant temperature 20-30min are warming up to, add butene dioic acid ethylhexyl, styrene and cyclohexanone peroxide
Mixed solution.
According to preparation method of the present invention, it is preferable that described to be incorporated as being added dropwise；It is highly preferred that the speed being added dropwise is
5-10 drops/min, rate of addition is too fast to easily cause viscous kettle.
It is prepared present invention also offers the preparation method by above-mentioned polystyrene butene dioic acid ethylhexyl poly-
Butylene styrene diacid ethylhexyl.
Present invention also offers above-mentioned polystyrene butene dioic acid ethylhexyl to prepare horizontal well oil-producing section prison
The application of survey tracer.
According to application of the present invention, during multistage fracturing, variety classes is mixed into every section of fracturing propping agents
Solid oil-soluble tracer particles, with the output of crude oil, solid oil-soluble tracer particles constantly can be dissolved in crude oil, lead to
The concentration of tracer in undue analysis production fluid, it is possible to reach every section of oil-producing situation of analysis and draw the mesh of every section of oil-producing liquid section
's.
Present invention also offers a kind of horizontal well oil-producing profile monitoring tracer, the tracer includes above-mentioned polyphenyl second
Alkene butene dioic acid ethylhexyl.
The horizontal well oil-producing profile monitoring that is prepared of polystyrene butene dioic acid ethylhexyl by the present invention is with showing
Track agent is oil-soluble tracer, and it can be dissolved completely in crude oil, and when concentration is low, accuracy of detection is high, and dosage is low.Pressed in multistage
During splitting, every section is mixed into different types of solid oil-soluble tracer particles in fracturing propping agents, with the output of crude oil,
Solid oil-soluble tracer particles are constantly dissolved in crude oil, by analyzing polystyrene butene dioic acid ethylhexyl in production fluid
The concentration of tracer, every section of oil-producing situation of analysis can be reached and draw the purpose of every section of oil-producing liquid section.
Embodiment
The implementation process of the present invention and caused beneficial effect will be explained by specific embodiment below, it is intended to
Help reader more fully understand the present invention essence and feature, but not as to this case can practical range restriction.
Embodiment 1
Present embodiments provide a kind of preparation method of polystyrene maleic acid two (2- ethyl hexyls) ester, it include with
Lower step：
A, 1g zinc stearates are dissolved into 50g hot water, are warming up to 85 DEG C of constant temperature 30min, obtain the water of zinc stearate
Solution；
B, 45g maleic acids two are slowly added dropwise into the aqueous solution of above-mentioned zinc stearate with 5-10 drops/min speed again
The mixed solution of (2- ethyl hexyls) ester, 4.5g styrene and 0.8g cyclohexanone peroxides, reacts 10h after being added dropwise to complete, is cooled to
Room temperature discharges, and obtains polystyrene maleic acid two (2- ethyl hexyls) ester, its particle diameter is 0.300mm-0.600mm (30 mesh -50
Mesh).
Embodiment 2
Present embodiments provide a kind of preparation method of polystyrene maleic acid two (2- ethyl hexyls) ester, it include with
Lower step：
A, 1.5g zinc stearates are dissolved into 55g hot water, are warming up to 85 DEG C of constant temperature 30min, obtain zinc stearate
The aqueous solution；
B, 40g maleic acids two are slowly added dropwise into the aqueous solution of above-mentioned zinc stearate with 5-10 drops/min speed again
The mixed solution of (2- ethyl hexyls) ester, 4g styrene and 0.6g cyclohexanone peroxides, reacts 10h after being added dropwise to complete, is cooled to room
Temperature discharging, obtains polystyrene maleic acid two (2- ethyl hexyls) ester, its particle diameter is 0.250mm-0.425mm (40 mesh -60
Mesh).
Embodiment 3
Present embodiments provide a kind of preparation method of polystyrene maleic acid two (2- ethyl hexyls) ester, it include with
Lower step：
A, 2g zinc stearates are dissolved into 60g hot water, are warming up to 85 DEG C of constant temperature 30min, obtain the water of zinc stearate
Solution；
B, 35g maleic acids two are slowly added dropwise into the aqueous solution of above-mentioned zinc stearate with 5-10 drops/min speed again
The mixed solution of (2- ethyl hexyls) ester, 3.5g styrene and 0.4g cyclohexanone peroxides, reacts 10h after being added dropwise to complete, is cooled to
Room temperature discharges, and obtains polystyrene maleic acid two (2- ethyl hexyls) ester, its particle diameter is 0.180mm-0.300mm (50 mesh -80
Mesh).
Embodiment 4
Present embodiments provide the polystyrene maleic two that above-described embodiment 1, embodiment 2 and embodiment 3 are prepared
Sour two (2- ethyl hexyls) esters prepare the application of horizontal well oil-producing profile monitoring tracer, the application process can be with level monitoring
Each section of oil-producing situation after well multistage fracturing, it comprises the following steps：
Polystyrene maleic acid two (2- ethyl hexyls) ester oil dissolubility that 0.1g embodiments 1-3 is prepared respectively shows
Track agent is dissolved in the emerging buried hill block crude oil of 100g, is warming up to 70 DEG C so that tracer dissolution velocity raising in a solvent, shortens
Evaluation time, after polystyrene maleic acid two (2- ethyl hexyls) ester oil dissolubility tracer is completely dissolved and is well mixed, take
The above-mentioned mixed solution of 1g dilutes 20 times using petroleum ether, with polystyrene maleic acid in gas chromatograph-mass spectrometer determination sample
The content of two (2- ethyl hexyls) ester oil dissolubility tracers, test result are as shown in table 1.
Polystyrene maleic acid two (2- ethyl hexyls) ester measurement result in the sample of table 1
Claims (11)
1. polystyrene butene dioic acid ethylhexyl is preparing the application of horizontal well oil-producing profile monitoring tracer, described poly-
The preparation method of butylene styrene diacid ethylhexyl is included using styrene and butene dioic acid ethylhexyl as reaction monomers,
In the presence of zinc stearate and cyclohexanone peroxide, polymerisation is carried out by decentralized medium of water.
2. application according to claim 1, wherein, counted using reacting the whole material gross weights added as 100%, it is added
Entering each weight of material percentage is respectively：Butene dioic acid ethylhexyl is 35wt%-45wt%, styrene 2.5wt%-
5wt%, zinc stearate 1wt%-2wt%, cyclohexanone peroxide 0.2wt%-1wt%, surplus are water.
3. application according to claim 1 or 2, wherein, the reaction temperature of the polymerisation is 80 DEG C -90 DEG C.
4. application according to claim 1 or 2, wherein, the reaction time of the polymerisation is 8-10h.
5. application according to claim 1 or 2, wherein, methods described includes：Zinc stearate is dissolved into water first,
The mixed solution of butene dioic acid ethylhexyl, styrene and cyclohexanone peroxide is added, is reacted after the completion of addition described in obtaining
Polystyrene butene dioic acid ethylhexyl.
6. application according to claim 5, wherein, it is described to be incorporated as being added dropwise.
7. application according to claim 6, wherein, the speed of the dropwise addition is 5-10 drops/min.
8. application according to claim 5, wherein, methods described includes：Zinc stearate is dissolved into 80 DEG C -90 DEG C first
In hot water, the mixed solution of butene dioic acid ethylhexyl, styrene and cyclohexanone peroxide is added.
9. application according to claim 5, wherein, methods described includes：Zinc stearate is dissolved into water first, heated up
To 80 DEG C of -90 DEG C of constant temperature 20-30min, the mixing for adding butene dioic acid ethylhexyl, styrene and cyclohexanone peroxide is molten
Liquid.
10. application according to claim 1 or 2, wherein, the butene dioic acid ethylhexyl includes maleic acid two
Ethylhexyl or fumaric acid ethylhexyl.
11. application according to claim 10, wherein, the maleic acid ethylhexyl includes maleic acid two
(2- ethyl hexyls) ester, (3- ethyl hexyls) ester of maleic acid two or maleic acid two (4- ethyl hexyls) ester；
The fumaric acid ethylhexyl includes fumaric acid two (2- ethyl hexyls) ester, (the 3- ethyls of fumaric acid two
Oneself) ester or fumaric acid two (4- ethyl hexyls) ester.
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| DE1176871B (en) * | 1963-01-18 | 1964-08-27 | Rheinpreussen Ag | Process for the production of thermoplastic homo- or copolymers using esters ª ‡, ª ‰ -unsaturated dicarboxylic acids |
| US3429858A (en) * | 1965-08-19 | 1969-02-25 | Monsanto Co | Styrene/dialkyl fumarate process using a solubility modifier |
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