CN106675534B - A kind of heat-resistant salt-resistant type prevents swollen clay stabilizer and its synthetic method - Google Patents

A kind of heat-resistant salt-resistant type prevents swollen clay stabilizer and its synthetic method Download PDF

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CN106675534B
CN106675534B CN201710072443.5A CN201710072443A CN106675534B CN 106675534 B CN106675534 B CN 106675534B CN 201710072443 A CN201710072443 A CN 201710072443A CN 106675534 B CN106675534 B CN 106675534B
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clay stabilizer
phthalic anhydride
resistant
heat
synthetic method
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CN106675534A (en
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张松亭
王志坚
荣雁
杨胜利
白昕
杜春安
陈晓春
马天态
孙立柱
陶建强
杨再新
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

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Abstract

The invention belongs to oil field development technical fields, swollen clay stabilizer and its synthetic method are prevented more particularly to a kind of heat-resistant salt-resistant type, the clay stabilizer is to be reacted to generate normal octane base phthalic anhydride half ester with n-octyl alcohol by phthalic anhydride, intermediate is then generated by solution polymerization with 2- (dimethylamino) chloromethanes hydrochloride, generation is finally reacted with cylite again, wherein phthalic anhydride, n-octyl alcohol, the molar ratio of 2- (dimethylamino) chloromethanes hydrochloride and cylite is 1:0.9~1.2:1.1~1.5:1.3~1.8, preferably 1:1.1:1.3:1.6.The feature that the raw material sources of clay stabilizer of the invention are extensive, synthesis technology is simple, dosage is few, oil reservoir conformability is strong；Clay stabilizer heat-resistant salt-resistant performance of the invention is good, and energy heatproof reaches 250 DEG C, and resistance to salinity reaches 200000mg/L, and has good compatibility；Clay stabilizer of the invention can be adsorbed onto surface of clay strongly, be not easily decomposed, and clay stabilizer validity period is long, and anti-dilative is high, and anti-dilative reaches 98% or more.

Description

A kind of heat-resistant salt-resistant type prevents swollen clay stabilizer and its synthetic method
Technical field
The invention belongs to oil field development technical fields, and in particular to a kind of heat-resistant salt-resistant type prevents swollen clay stabilizer and its conjunction At method.
Background technique
Contain a certain amount of clay mineral in stratum, mainly there is kaolinite, montmorillonite, illite and chlorite etc..These Clay encounters water or water-based material in water filling, acidification, fracturing process will generate expansion, and then further (such as you are de- for dispersion Stone, chlorite) or direct fine particle for dispersing (such as kaolinite, illite) at diameter less than 10 μm.Under normal circumstances, from Upper layer is to lower layer, and smectite content is reduced in oil-bearing reservoir, and illite content increases, and kaolinite disappears in certain depth, green mud Stone is mainly distributed on deep layer.These clay minerals mostly form layer structure by oxygen-octahedron and alumina octahedral, wherein covering de- Stone presss from both sides one layer of alumina octahedral by two layers of oxygen-octahedron and forms, and interlayer surface is oxygen layer, and connecting forces are weak, is contacted when with water When, water can enter between crystal layer, and the exchangeable cations on face crystal layer surface dissociates diffusion in water, form diffusion electric double layer, make Laminated structure surface is negatively charged, mutually exclusive between crystal layer, and electronegative laminated structure voluntarily separates, and generates expansion, therefore covers de- Stone category expanded clay mineral, clay swell can cause in-place permeability to reduce.Kaolinite, illite and chlorite or because of interlayer It easily forms hydrogen bond, be coupled closely, water is not easily accessible interlayer, or because of cation exchange capacity very little, water will not cause to expand, generally Ground category non-expansion type clay mineral.In the case where formation fluid washes away, non-swelling clay is dispersed into flaky particles and migrates, into ground Layer hole, blocks venturi, reduces in-place permeability.
In order to protect the permeability of hydrocarbon formations, it is necessary to using clay stabilizer i.e.: anti-soil adhesion swelling agent (expansion-resisting agent) and Anti-soil adhesion fine migration agent (anti-migration agent).
With the exploitation in oil field, clay stabilizer using more and more extensive, type is more and more, according to different structures And the different developments in this respect of used chemicals can substantially be divided into 3 stages: (1) 50-60 later period in age, it is main Stablize clay with inorganic salts；(2) seventies stablizes clay with inorganic multicore polymer and cationic surfactant； (3) research and experiment for stablizing clay with cationic organic polymer have mainly been carried out after the eighties.
Cation of the cationic active agent due to that can dissociate surface-active in water, can be adsorbed on clay particle The negative electrical charge that surface of clay is neutralized on surface, so can be used as expansion-resisting agent.But cationic active agent makees anti-clayswelling agent Shi Yiyu Several anion chemical agent reactions generate precipitating, such as petroleum sulfonate or to improve the partial hydrolysis polypropylene that recovery ratio uses Amide and some biopolymers.Its is maximum the disadvantage is that can make the wettability of reservoir becomes oil-wet, can make the phase of water To permeability decrease.
Patent ZL201310118314.7 " a kind of low molecular weight clay stabilizer preparation method " is with the ammonium salt containing carbon carbon It polymerize in aqueous solution with 2- acrylamide-2-methylpro panesulfonic acid for raw material and is prepared, polymer number-average molecular weight is lower than 5 Ten thousand.Sulfonic acid group is introduced in the polymer stabilizer, increases the water solubility and heat-resisting property of polymer.It in water can be same When with multiple clay particles formed multiple spot absorption, after absorption, clay particle surface formed one layer of absorption protective film, prevent from gluing The expansion and migration of soil particle.But the stabilizer is easy to be adsorbed onto rock surface, reduces in-place permeability, or directly by stratum The shortcomings that blocking, while the heat-resistant salt-resistant performance of the clay stabilizer is poor, limits its scope of application.
Summary of the invention
The present invention is directed to the deficiency of currently available technology, the first purpose be to provide it is a kind of oil drilling, complete well, production, The heat-resistant salt-resistant type clay stabilizer for playing the role of preventing clay swell protection reservoir in exploitation, pressure break and water filling, at 250 DEG C Stabilization can be kept not decompose under the conditions of being 200000mg/L with salinity, it is with high salt to be applicable to oil field development high temperature Oil reservoir prevents the swollen high temperature resistant type clay stabilizer used, the stabilizer have preparation process is simple, low in cost, compatibility is good, The high feature of the adaptable and anti-dilative of oil reservoir；The second purpose provides the synthetic method of the clay stabilizer.
One of the objects of the present invention is to provide a kind of heat-resistant salt-resistant types to prevent swollen clay stabilizer, the clay stabilizer be by Phthalic anhydride is reacted with n-octyl alcohol generates normal octane base phthalic anhydride half ester, then passes through with dimethylamino chloromethanes Solution polymerization generates intermediate, finally reacts generation with cylite again, molecular formula is as follows:
The phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite molar ratio be 1:0.9~1.2: 1.1~1.5:1.3~1.8, preferably 1:1.1:1.3:1.6.
It is another object of the present invention to provide the synthetic method that a kind of heat-resistant salt-resistant type prevents swollen clay stabilizer, the conjunctions At method specifically includes the following steps:
(1) phthalic anhydride of aforementioned proportion and n-octyl alcohol are added to four-hole boiling flask, are heated to 60~80 DEG C, stirring Rate is 200~250rpm, and the reaction time is 1~2h, and normal heptane is then added, and the reaction time is 2~6h, is then cooled to room Temperature stirs 15~30min, obtains half ester solution of normal octane base phthalic anhydride；
(2) the dimethylamino chloromethanes of aforementioned proportion is added in above-mentioned half ester solution of normal octane base phthalic anhydride, It reacts while stirring, stirring rate is 300~350rpm, and the reaction time is 5~10h, is then heated to 70~80 DEG C, side stirring Side reaction, stirring rate are 400~500rpm, and the reaction time is 10~15h, are filtered immediately after the reaction time, with heat Ethyl alcohol filter wash slag collects filtrate, with the dry 24~48h of anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains brown yellow oil liquid Body；
(3) cylite of above-mentioned oily liquids and aforementioned proportion is added in the flask equipped with blender and condenser pipe, Butanone is added thereto again, under the protection of nitrogen at 50~80 DEG C reaction 10~for 24 hours, stirring rate be 400~500rpm, After to the reaction time, it is cooled to room temperature, obtains crude product；
(4) above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtained yellow and stick shape liquid, crossed silica gel column chromatography, point Eluant, eluent is not made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, and as of the invention is viscous Soil stabilizer.
The dosage of the normal heptane is 10~15 times of phthalic anhydride quality, and the dosage of the butanone is adjacent benzene 20~30 times of dicarboxylic acid anhydride quality.
The reaction equation is as follows:
It is provided by the invention to prevent swollen clay stabilizer, belong to cationic surface active agent, contains phenyl group and N member Element, dissociation generates the cation of high positive electricity price in water, multiple spot absorption can be formed with multiple clay particles, after absorption, viscous The surface of soil particle forms one layer of adsorbed film, prevents the expansion and migration of clay particle.Anti-clayswelling provided by the invention is stablized Agent is since molecular weight is moderate, and molecule, which does not need curling, to combine closely with clay, and anti-salt property is excellent, and effectively raising makes Use efficiency；And there are two benzene radicals for tool on molecule, have certain rigid structure, effectively increase the temperature resistance of molecule Energy.In addition, the present invention is since with Long carbon chain hydrophobic grouping, freedom of movement is bigger, thus it is swollen to the aquation of control clay Swollen and mineral microparticle dispersion migration significant effect.
The present invention is had the following advantages and beneficial effects: compared with prior art
(1) raw material sources of clay stabilizer of the invention are extensive, and synthesis technology is simple, low in cost；
(2) dosage of clay stabilizer of the invention is few, and oil reservoir conformability is strong, can meet the needs of oil field development；
(3) clay stabilizer heat-resistant salt-resistant performance of the invention is good, and energy heatproof reaches 250 DEG C, and resistance to salinity reaches 200000mg/L, and there is good compatibility；
(4) what clay stabilizer of the invention can be strong is adsorbed onto surface of clay, is not easily decomposed, clay stabilizer validity period Long, anti-dilative is high, and anti-dilative reaches 98% or more.
Specific embodiment
The present invention is described in further detail below with reference to specific embodiment, and referring to data.It should be understood that these embodiments It is of the invention solely for the purpose of illustration, rather than limit the scope of the invention in any way.
Embodiment 1: clay stabilizer A1And preparation method thereof
(1) clay stabilizer A1Composition, component and molecular formula it is as follows:
Clay stabilizer A1It is according to molar ratio by phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite 1:0.9:1.1:1.3 ratio reacts to obtain, and molecular formula is as follows:
(2) clay stabilizer A1Synthetic method it is as follows:
1. the phthalic anhydride of 1mol and 0.9mol n-octyl alcohol are added to four-hole boiling flask, 60 DEG C are heated to, stirring speed Rate is 200rpm, reaction time 1h, and 1481.1g normal heptane is then added, and reaction time 2h is then cooled to room temperature, stirs 15min is mixed, half ester solution of normal octane base phthalic anhydride is obtained；
2. the dimethylamino chloromethanes of 1.1mol is added in above-mentioned half ester solution of normal octane base phthalic anhydride, while stirring Side reaction is mixed, stirring rate 330rpm, reaction time 5h are then heated to 75 DEG C, react while stirring, and stirring rate is 400rpm, reaction time 10h, is filtered immediately after the reaction time, with the ethyl alcohol filter wash slag of heat, collects filtrate, use is anhydrous Magnesium sulfate is dry for 24 hours, and normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the cylite of above-mentioned oily liquids and 1.3mol is added in the flask equipped with blender and condenser pipe, then to 2962.2g butanone is wherein added, reacts 10h, stirring rate 400rpm, to the reaction time at 50 DEG C under the protection of nitrogen After, it is cooled to room temperature, obtains crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention Stabilizer A1。
Clay stabilizer A1Reaction equation it is as follows:
Embodiment 2: clay stabilizer A2And preparation method thereof
(1) clay stabilizer A2Composition, component and molecular formula it is as follows:
Clay stabilizer A2It is according to molar ratio by phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite 1:1.1:1.3:1.6 ratio reacts to obtain, and molecular formula is as follows:
(2) clay stabilizer A2Synthetic method it is as follows:
1. the phthalic anhydride of 1mol and 1.1mol n-octyl alcohol are added to four-hole boiling flask, 70 DEG C are heated to, stirring speed Rate is 220rpm, reaction time 1.5h, and 1856.3g normal heptane is then added, and reaction time 4h is then cooled to room temperature, 20min is stirred, half ester solution of normal octane base phthalic anhydride is obtained；
2. the dimethylamino chloromethanes of 1.3mol is added in above-mentioned half ester solution of normal octane base phthalic anhydride, while stirring Side reaction is mixed, stirring rate 300rpm, reaction time 10h are then heated to 70 DEG C, react while stirring, stirring rate It is filtered immediately after the reaction time for 500rpm, reaction time 12h, with the ethyl alcohol filter wash slag of heat, filtrate is collected, with nothing Water magnesium sulfate dries 36h, and normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the cylite of above-mentioned oily liquids and 1.6mol is added in the flask equipped with blender and condenser pipe, then to 3156.5g butanone is wherein added, is reacted for 24 hours at 70 DEG C under the protection of nitrogen, stirring rate 450rpm, to the reaction time After, it is cooled to room temperature, obtains crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention Stabilizer A2。
Clay stabilizer A2Reaction equation it is as follows:
Embodiment 3: clay stabilizer A3And preparation method thereof
(1) clay stabilizer A3Composition, component and molecular formula it is as follows:
Clay stabilizer A3It is according to molar ratio by phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite 1:1.2:1.5:1.8 ratio reacts to obtain, and molecular formula is as follows:
(2) clay stabilizer A3Synthetic method it is as follows:
1. the phthalic anhydride of 1mol and 1.2mol n-octyl alcohol are added to four-hole boiling flask, 80 DEG C are heated to, stirring speed Rate is 250rpm, reaction time 2h, and 2221.6g normal heptane is then added, and reaction time 6h is then cooled to room temperature, stirs 30min is mixed, half ester solution of normal octane base phthalic anhydride is obtained；
2. the dimethylamino chloromethanes of 1.5mol is added in above-mentioned half ester solution of normal octane base phthalic anhydride, while stirring Side reaction is mixed, stirring rate 350rpm, reaction time 8h are then heated to 80 DEG C, react while stirring, and stirring rate is 450rpm, reaction time 15h, is filtered immediately after the reaction time, with the ethyl alcohol filter wash slag of heat, collects filtrate, use is anhydrous Magnesium sulfate dries 48h, and normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the cylite of above-mentioned oily liquids and 1.8mol is added in the flask equipped with blender and condenser pipe, then to 4443.3g butanone is wherein added, reacts 16h, stirring rate 500rpm, to the reaction time at 80 DEG C under the protection of nitrogen After, it is cooled to room temperature, obtains crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention Stabilizer A3。
Clay stabilizer A3Reaction equation it is as follows:
Embodiment 4: clay stabilizer A4And preparation method thereof
(1) clay stabilizer A4Composition, component and molecular formula it is as follows:
Clay stabilizer A4It is according to molar ratio by phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite 1:1.0:1.2:1.5 ratio reacts to obtain, and molecular formula is as follows:
(2) clay stabilizer A4Synthetic method it is as follows:
1. the phthalic anhydride of 1mol and 1.0mol n-octyl alcohol are added to four-hole boiling flask, 65 DEG C are heated to, stirring speed Rate is 210rpm, reaction time 2h, and 1632.4g normal heptane is then added, and reaction time 3h is then cooled to room temperature, stirs 18min is mixed, half ester solution of normal octane base phthalic anhydride is obtained；
2. the dimethylamino chloromethanes of 1.2mol is added in above-mentioned half ester solution of normal octane base phthalic anhydride, while stirring Side reaction is mixed, stirring rate 320rpm, reaction time 6h are then heated to 72 DEG C, react while stirring, and stirring rate is 420rpm, reaction time 13h, is filtered immediately after the reaction time, with the ethyl alcohol filter wash slag of heat, collects filtrate, use is anhydrous Magnesium sulfate dries 42h, and normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the cylite of above-mentioned oily liquids and 1.5mol is added in the flask equipped with blender and condenser pipe, then to 3562.3g butanone is wherein added, reacts 20h, stirring rate 430rpm, to the reaction time at 55 DEG C under the protection of nitrogen After, it is cooled to room temperature, obtains crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention Stabilizer A4。
Clay stabilizer A4Reaction equation it is as follows:
Embodiment 5: clay stabilizer A5And preparation method thereof
(1) clay stabilizer A5Composition, component and molecular formula it is as follows:
Clay stabilizer A5It is according to molar ratio by phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite 1:1.0:1.4:1.7 ratio reacts to obtain, and molecular formula is as follows:
(2) clay stabilizer A5Synthetic method it is as follows:
1. the phthalic anhydride of 1mol and 1.0mol n-octyl alcohol are added to four-hole boiling flask, 75 DEG C are heated to, stirring speed Rate is 240rpm, reaction time 1h, and 1853.8g normal heptane is then added, and reaction time 5h is then cooled to room temperature, stirs 25min is mixed, half ester solution of normal octane base phthalic anhydride is obtained；
2. the dimethylamino chloromethanes of 1.4mol is added in above-mentioned half ester solution of normal octane base phthalic anhydride, while stirring Side reaction is mixed, stirring rate 340rpm, reaction time 7h are then heated to 78 DEG C, react while stirring, and stirring rate is 460rpm, reaction time 14h, is filtered immediately after the reaction time, with the ethyl alcohol filter wash slag of heat, collects filtrate, use is anhydrous Magnesium sulfate dries 30h, and normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the cylite of above-mentioned oily liquids and 1.7mol is added in the flask equipped with blender and condenser pipe, then to 4125.3g butanone is wherein added, reacts 12h, stirring rate 470rpm, to the reaction time at 70 DEG C under the protection of nitrogen After, it is cooled to room temperature, obtains crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention Stabilizer A5。
Clay stabilizer A5Reaction equation it is as follows:
Embodiment 6
The above-mentioned A of 5.0g is accurately weighed respectively1~A5Clay stabilizer sample is dissolved in 995.0g distilled water, stirring 30min forms homogeneous solution, for use.
Embodiment 7
Having rated product in temperature according to " SY/T5971-94 fills the water clay stabilizer method of evaluating performance " is 250 DEG C Anti-dilative and validity period under the conditions of being 200000mg/L with salinity.Clay stabilization agent solution used in this experiment is embodiment 6 Middle matched solution, test result are shown in Table 1.
1 clay stabilizer A of table1~A5Evaluation result
As it can be seen from table 1 clay stabilizer A1~A5Anti-dilative be all larger than 98.0%, wherein clay stabilizer A2's Anti-dilative highest, reaches 99.2%.Illustrate that the clay stabilizer of the invention developed is 250 DEG C in temperature and salinity is There is the good ability for preventing bentonite hydration swelling under the conditions of 200000mg/L.
Embodiment 8
Reference standard " SY-T 5613-2000 mud shale physicochemical property test method " evaluates sample and inhibits Shale Hydration point Scattered ability.Rock sample used is Gudao area of Shengli Oilfield landwaste, washes 10min with 3% dioxygen, then dries.200mL is being taken respectively 20-30 mesh landwaste 50g is added in the prepared clay stabilization agent solution of embodiment 6, and clear water is used in heat rolling afterwards for 24 hours at a temperature of 250 DEG C It cleans, sieves with 100 mesh sieve, 6h is dried at a temperature of 250 DEG C, weighing calculates primary recovery, the results are shown in Table 2.
2 landwaste rolling rate of recovery test result of table
As can be seen from Table 2, clay stabilizer A1~A5A rolling rate of recovery be all larger than 97.0%, wherein clay stabilizer A2A rolling rate of recovery highest, reach 98.5%.Test result shows clay stabilizer product prepared by the present invention 250 DEG C heat rolling after still with it is very strong inhibition Shale Hydration dispersion ability.
Embodiment 9
The linear dilatancy experiment of sample is carried out according to China National Petroleum professional standard evaluation SY/T6335-1997.Institute It is NP-3 shale expansion tester with instrument.Weigh second level bentonite (the diameter 0.01- that 5.00g dries 10h at 250 DEG C 0.05mm), tabletting (pressure 10MPa, time 5min) is made on press machine.Tabletting is put into shale expansion instrument, addition is matched The certain density stabiliser solution (matched solution in embodiment 6) made, the expansion of mud shale tabletting after measurement test solution impregnates Rate.The expansion rate of mud shale tabletting is smaller, illustrates that the ability of the inhibition hydration and expansion of clay of product is stronger；It is on the contrary then poorer.It is real Test that the results are shown in Table 3.
3 linear expansion rate experimental test result of table
Product Reduced rate of the 16h with respect to clear water, %
A1 23.5
A2 21.2
A3 22.3
A4 23.0
A5 24.6
Seen from table 3, clay stabilizer A1~A516h is below 25% with respect to the reduced rate of clear water, wherein clay stabilization Agent A216h is minimum with respect to the reduced rate of clear water, reaches 21.2%, illustrates that clay stabilizer product prepared by the present invention can be effective The hydration swelling of ground inhibition clay.

Claims (6)

1. the synthetic method that a kind of heat-resistant salt-resistant type prevents swollen clay stabilizer, which is characterized in that the synthetic method specifically include with Lower step:
1. phthalic anhydride and n-octyl alcohol are added to four-hole boiling flask, it being heated to 60~80 DEG C, stirring rate is 200~ 250rpm, reaction time are 1~2h, are then added normal heptane, and the reaction time is 2~6h, are then cooled to room temperature, stirring 15~ 30min obtains half ester solution of normal octane base phthalic anhydride；
2. dimethylamino chloromethanes is added in above-mentioned half ester solution of normal octane base phthalic anhydride, reacts, stir while stirring Mixing rate is 300~350rpm, and the reaction time is 5~10h, is then heated to 70~80 DEG C, reacts while stirring, stirring rate For 400~500rpm, the reaction time is 10~15h, is filtered immediately after the reaction time, with the ethyl alcohol filter wash slag of heat, is collected Filtrate is removed under reduced pressure normal heptane, is obtained brown yellow oil liquid with the dry 24~48h of anhydrous magnesium sulfate；
3. being added to above-mentioned oily liquids and cylite in the flask equipped with blender and condenser pipe, then fourth is added thereto Ketone, under the protection of nitrogen at 50~80 DEG C reaction 10~for 24 hours, stirring rate be 400~500rpm, to the end of the reaction time Afterwards, it is cooled to room temperature, obtains crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, use stone respectively Oily ether and ether make eluant, eluent and wash off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, as clay stabilizer.
2. the synthetic method that heat-resistant salt-resistant type according to claim 1 prevents swollen clay stabilizer, which is characterized in that described Clay stabilizer, molecular formula are as follows:
3. the synthetic method that heat-resistant salt-resistant type according to claim 1 prevents swollen clay stabilizer, which is characterized in that described Phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite molar ratio be 1:0.9~1.2:1.1~1.5:1.3~ 1.8。
4. the synthetic method that heat-resistant salt-resistant type according to claim 3 prevents swollen clay stabilizer, which is characterized in that described Phthalic anhydride, n-octyl alcohol, dimethylamino chloromethanes and cylite molar ratio be 1:1.1:1.3:1.6.
5. the synthetic method that heat-resistant salt-resistant type according to claim 1 prevents swollen clay stabilizer, which is characterized in that described The dosage of normal heptane is 10~15 times of phthalic anhydride quality.
6. the synthetic method that heat-resistant salt-resistant type according to claim 1 prevents swollen clay stabilizer, which is characterized in that described The dosage of butanone is 20~30 times of phthalic anhydride quality.
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CN101157755A (en) * 2007-08-22 2008-04-09 东营华锐石油技术应用有限责任公司 Production technique of quaternary ammonium salt cationic polymer HMAT
CN101585775A (en) * 2009-05-11 2009-11-25 中国海洋石油总公司 Clay stabilizer, preparing method and application thereof
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CN1556169A (en) * 2004-01-12 2004-12-22 高芒来 Use of single moleule quarternary ammonium salt compound as clay stabilizing, antiexpanding and deblocking extender
CN101157755A (en) * 2007-08-22 2008-04-09 东营华锐石油技术应用有限责任公司 Production technique of quaternary ammonium salt cationic polymer HMAT
CN101585775A (en) * 2009-05-11 2009-11-25 中国海洋石油总公司 Clay stabilizer, preparing method and application thereof
CN102816461A (en) * 2012-08-27 2012-12-12 暨南大学 Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application

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