CN107699212A - A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method - Google Patents

A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method Download PDF

Info

Publication number
CN107699212A
CN107699212A CN201710952167.1A CN201710952167A CN107699212A CN 107699212 A CN107699212 A CN 107699212A CN 201710952167 A CN201710952167 A CN 201710952167A CN 107699212 A CN107699212 A CN 107699212A
Authority
CN
China
Prior art keywords
clay stabilizer
clay
oil well
long
dimethylamino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201710952167.1A
Other languages
Chinese (zh)
Inventor
郝晓燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai Zhiben Intellectual Property Operation and Management Co Ltd
Original Assignee
Yantai Zhiben Intellectual Property Operation and Management Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai Zhiben Intellectual Property Operation and Management Co Ltd filed Critical Yantai Zhiben Intellectual Property Operation and Management Co Ltd
Priority to CN201710952167.1A priority Critical patent/CN107699212A/en
Publication of CN107699212A publication Critical patent/CN107699212A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/14—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Lubricants (AREA)

Abstract

The invention belongs to oil field development technical field, more particularly to a kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method, the clay stabilizer is by 2, 3 naphthalic anhydrides and n-dodecanol reaction generation dodecyl neighbour's naphthalic anhydride half ester, intermediate is then generated by solution polymerization with 2 (dimethylamino) chloromethanes hydrochlorides, finally react and generate with 1 bromomethyl naphthalene again, wherein 2, 3 naphthalic anhydrides, n-dodecanol, the mol ratio of 2 (dimethylamino) chloromethanes hydrochlorides and 1 bromomethyl naphthalene is 1: 0.8~1.4: 1.2~1.6: 1.1~1.8, preferably 1: 1: 1.4: 1.2.The raw material sources of the clay stabilizer of the present invention are extensive, the characteristics of synthesis technique is simple, dosage is few, oil reservoir conformability is strong；The clay stabilizer heat-resistant salt-resistant performance of the present invention is good, and energy heatproof reaches 250 DEG C, and resistance to salinity reaches 220000mg/L, and has good compatibility；The clay stabilizer of the present invention can be adsorbed onto surface of clay strongly, be not easily decomposed, and clay stabilizer term of validity length, anti-dilative is high, and anti-dilative reaches more than 98%.

Description

A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method
Technical field
The invention belongs to oilfield exploitation technical field, and in particular to a kind of long-acting oil well anti-swollen clay stabilizer and its conjunction Into method.
Background technology
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, acidifying, fracturing process will produce expansion, and then further scattered (such as you are de- Stone, chlorite) or direct fine particle for disperseing (such as kaolinite, illite) and being less than 10 μm into diameter.Under normal circumstances, from Upper strata is to lower floor, and smectite content is reduced in oil-bearing reservoir, and illite content increase, kaolinite disappears in certain depth, green mud Stone is mainly distributed on deep layer.These clay minerals form layer structure by silicon-oxy tetrahedron and alumina octahedral more, wherein covering de- Stone presss from both sides one layer of alumina octahedral by two layers of silicon-oxy tetrahedron and formed, 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, forms diffusion electric double layer, makes Laminated structure surface is negatively charged, mutually exclusive between crystal layer, and electronegative laminated structure voluntarily separates, and produces 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 Easily forming hydrogen bond, be coupled closely, water is not easily accessible interlayer, or because cation exchange capacity very little, water will not cause expansion, typically Ground category non-expansion type clay mineral.In the case where formation fluid washes away, non-swelling clay is dispersed into flaky particles and migrated, into ground Layer hole, blocks venturi, reduces in-place permeability.
In order to protect the permeability of hydrocarbon formations, it is necessary to be using clay stabilizer：Anti-soil adhesion swelling agent (expansion-resisting agent) and Anti-soil adhesion fine migration agent (anti-migration agent).
With the exploitation in oil field, the application of clay stabilizer is more and more extensive, and species 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) it is the 0-60 later stages in age, main Stablize clay with inorganic salts；(2) seventies stablizes clay with inorganic more nuclear polymers and cationic surfactant； (3) research and experiment with the stable clay of 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 in clay particle The negative electrical charge of surface of clay is neutralized on surface, so expansion-resisting agent can be used as.But when cationic active agent makees anti-clayswelling agent easily with Several anion chemical agent reactions produce precipitation, such as petroleum sulfonate or to improve the partial hydrolysis polypropylene that recovery ratio uses Acid amides and some biopolymers.The shortcomings that its is maximum is that the wettability that can make reservoir is changed into oil-wet, can make the phase of water To permeability decrease.
Patent ZL201310118314.7 " a kind of low molecule amount clay stabilizer preparation method " is with the ammonium salt containing carbon carbon It polymerize in aqueous for raw material with 2- acrylamide-2-methylpro panesulfonic acids and is prepared, polymer number-average molecular weight is less than 5 Ten thousand.Sulfonic acid group is introduced in the polymer stabilizer, adds the water solubility and heat-resisting property of polymer.It can be same in water When with multiple clay particles formed multiple spot absorption, after absorption, clay particle surface formed one layer absorption diaphragm, 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 temperature salt resistant character of the clay stabilizer is poor, limits its application.
The content 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, completion, production, Play a part of preventing the clay stabilizer of clay swell protection reservoir in exploitation, pressure break and water filling, be in 250 DEG C and salinity Can keep stable under the conditions of 200000mg/L will not decompose, and be applicable to oil reservoir in oil field development and prevent the swollen clay used Stabilizer, the stabilizer have that preparation technology is simple, cost is cheap, compatibility is good, strong adaptability and anti-dilative of oil reservoir are high Feature；The second purpose provides the synthetic method of the clay stabilizer.
An object of the present invention is to provide a kind of long-acting oil well with preventing swollen clay stabilizer, the clay stabilizer be by 2,3- naphthalic anhydrides and n-dodecanol reaction generation dodecyl neighbour's naphthalic anhydride half ester, then with 2- (dimethylamino) chlorine Methane hydrochloride salt generates intermediate by solution polymerization, finally reacts and generates with 1- bromomethyls naphthalene again, its molecular formula is as follows：
Described 2,3- naphthalic anhydrides, n-dodecanol, 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromomethyl naphthalenes Mol ratio is 1: 0.8~1.4: 1.2~1.6: 1.1~1.8, preferably 1: 1: 1.4: 1.2.
It is another object of the present invention to provide a kind of long-acting oil well synthetic method for preventing swollen clay stabilizer, this is viscous The preparation method of soil stabilizer specifically includes following steps：
(1) 2, the 3- naphthalic anhydrides and n-dodecanol of aforementioned proportion are added to four-hole boiling flask, heat while stirring, add Hot temperature is 75~85 DEG C, and stir speed (S.S.) is 300~400rpm, and the reaction time is 0.5~1.5h, is subsequently added into normal heptane, instead It is 3~8h between seasonable, is then cooled to room temperature, stirs 10~25min, it is molten to obtain dodecyl -2,3- naphthalic anhydride half ester Liquid；
(2) 2- (dimethylamino) of aforementioned proportion is added in the above-mentioned ester solution of dodecyl -2,3- naphthalic anhydride half Chloromethanes hydrochloride, reacts while stirring, and stir speed (S.S.) is 200~300rpm, and the reaction time is 5~8h, is then heated to 75 ~85 DEG C, react while stirring, stir speed (S.S.) is 400~500rpm, and the reaction time is 10~15h, mistake immediately after the completion of reaction Filter, with the petroleum ether filter wash slag of heat, collects filtrate, dries 15~30h with anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains palm fibre Yellow oily liquid；
(3) the 1- bromomethyl naphthalenes of above-mentioned brown yellow oil liquid and aforementioned proportion are added to equipped with agitator and condenser pipe Flask in, then add butanone thereto, react 10~24h, stir speed (S.S.) 400 at 50~80 DEG C under the protection of nitrogen ~500rpm, after the question response time terminates, room temperature is cooled to, 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 not being made with petroleum ether and ether and washing impurity off, again with methanol elutes to obtain faint yellow viscous shape liquid, that is, obtains the present invention's Clay stabilizer.
The dosage of described normal heptane is 10~20 times of 2,3- naphthalic anhydride quality, and the dosage of described butanone is 2, 25~30 times of 3- naphthalic anhydride quality.
Described reaction equation is as follows：
Provided by the invention to prevent swollen clay stabilizer, it belongs to cationic surface active agent, contains two naphthylene groups and N Element, the cation of the high positive electricity price of dissociation generation, can form multiple spot absorption with multiple clay particles in water, after absorption, The surface of clay particle forms one layer of adsorbed film, prevents the expansion and migration of clay particle.Anti-clayswelling provided by the invention is steady Agent is determined because molecular weight is moderate, and molecule, which need not crimp, to be combined closely with clay, and anti-salt property is excellent, effectively raises Service efficiency；And there are two benzene radicals on molecule, there is certain rigid structure, effectively increase the temperature resistance of molecule Energy.In addition, the present invention is because with Long carbon chain hydrophobic grouping, freedom of movement is bigger, thus the aquation to controlling clay is swollen The swollen and scattered migration significant effect of mineral microparticle.
The present invention has the following advantages that compared with prior art and beneficial effect：
The present invention has the following advantages that compared with prior art and beneficial effect：
(1) raw material sources of clay stabilizer of the invention are extensive, and synthesis technique is simple, and cost is cheap；
(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 220000mg/L, and there is good compatibility；
(4) clay stabilizer of the invention can be adsorbed onto surface of clay strongly, be not easily decomposed, the clay stabilizer term of validity Long, anti-dilative is high, and anti-dilative reaches more than 98%.
Embodiment
The present invention is described in further detail with reference to specific embodiment, and with reference to data.It should be understood that these embodiments It is of the invention solely for the purpose of illustration, rather than the scope limiting the invention in any way.
Embodiment 1：Clay stabilizer B1And preparation method thereof
(1) clay stabilizer B1Composition, component and molecular formula it is as follows：
Clay stabilizer B1By 2,3- naphthalic anhydrides, n-dodecanol, 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromines The mol ratio of methyl naphthalene is 1: 0.8: 1.2: 1.1, and its molecular formula is as follows：
(2) clay stabilizer B1Synthetic method it is as follows：
1. 1mol 2,3- naphthalic anhydrides and 0.8mol n-dodecanols are added into four-hole boiling flask, heat while stirring, Heating-up temperature is 75 DEG C, stir speed (S.S.) 350rpm, reaction time 0.8h, is subsequently added into 1981.8g normal heptanes, reaction time For 6h, room temperature is then cooled to, 10min is stirred, obtains the ester solution of dodecyl -2,3- naphthalic anhydride half；
2. 1.2mol 2- (dimethylamino) chloromethane is added in the above-mentioned ester solution of dodecyl -2,3- naphthalic anhydride half Heptane hydrochloride salt, reacts while stirring, stir speed (S.S.) 200rpm, reaction time 5h, is then heated to 83 DEG C, while stirring instead Should, stir speed (S.S.) 400rpm, reaction time 10h, filter after the completion of reaction, with the petroleum ether filter wash slag of heat, collect immediately Filtrate, 15h is dried with anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the 1- bromomethyl naphthalenes of above-mentioned brown yellow oil liquid and 1.1mol are added to equipped with agitator and condenser pipe In flask, then 4954.5g butanone is added thereto, react 10h at 50 DEG C under the protection of nitrogen, stir speed (S.S.) is 400rpm, after the question response time terminates, room temperature is cooled to, 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 impurity off, and again with methanol elutes to obtain faint yellow viscous shape liquid, that is, obtains the viscous of the present invention Soil stabilizer B1。
Embodiment 2：Clay stabilizer B2And preparation method thereof
(1) clay stabilizer B2Composition, component and molecular formula it is as follows：
Clay stabilizer B2By 2,3- naphthalic anhydrides, n-dodecanol, 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromines The mol ratio of methyl naphthalene is 1: 1.0: 1.4: 1.2, and its molecular formula is as follows：
(2) clay stabilizer B2Synthetic method it is as follows：
1. 1mol 2,3- naphthalic anhydrides and 1.0mol n-dodecanols are added into four-hole boiling flask, heat while stirring, Heating-up temperature is 78 DEG C, stir speed (S.S.) 380rpm, reaction time 1.0h, is subsequently added into 2352.3g normal heptanes, reaction time For 5h, room temperature is then cooled to, 15min is stirred, obtains the ester solution of dodecyl -2,3- naphthalic anhydride half；
2. 1.4mol 2- (dimethylamino) chloromethane is added in the above-mentioned ester solution of dodecyl -2,3- naphthalic anhydride half Heptane hydrochloride salt, reacts while stirring, stir speed (S.S.) 220rpm, reaction time 6h, is then heated to 80 DEG C, while stirring instead Should, stir speed (S.S.) 420rpm, reaction time 11h, filter after the completion of reaction, with the petroleum ether filter wash slag of heat, collect immediately Filtrate, 20h is dried with anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the 1- bromomethyl naphthalenes of above-mentioned brown yellow oil liquid and 1.2mol are added to equipped with agitator and condenser pipe In flask, then 5125.3g butanone is added thereto, react 16h at 55 DEG C under the protection of nitrogen, stir speed (S.S.) is 500rpm, after the question response time terminates, room temperature is cooled to, 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 impurity off, and again with methanol elutes to obtain faint yellow viscous shape liquid, that is, obtains the viscous of the present invention Soil stabilizer B2。
Embodiment 3：Clay stabilizer B3And preparation method thereof
(1) clay stabilizer B3Composition, component and molecular formula it is as follows：
Clay stabilizer B3By 2,3- naphthalic anhydrides, n-dodecanol, 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromines The mol ratio of methyl naphthalene is 1: 1.1: 1.3: 1.4, and its molecular formula is as follows：
(2) clay stabilizer B3Synthetic method it is as follows：
1. 1mol 2,3- naphthalic anhydrides and 1.1mol n-dodecanols are added into four-hole boiling flask, heat while stirring, Heating-up temperature is 85 DEG C, stir speed (S.S.) 300rpm, reaction time 1.2h, is subsequently added into 2932.5,3345.8g normal heptanes, Reaction time is 4h, is then cooled to room temperature, stirs 20min, obtains the ester solution of dodecyl -2,3- naphthalic anhydride half；
2. 1.3mol 2- (dimethylamino) chloromethane is added in the above-mentioned ester solution of dodecyl -2,3- naphthalic anhydride half Heptane hydrochloride salt, reacts while stirring, stir speed (S.S.) 250rpm, reaction time 7h, is then heated to 78 DEG C, while stirring instead Should, stir speed (S.S.) 450rpm, reaction time 12h, filter after the completion of reaction, with the petroleum ether filter wash slag of heat, collect immediately Filtrate, 25h is dried with anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the 1- bromomethyl naphthalenes of above-mentioned brown yellow oil liquid and 1.4mol are added to equipped with agitator and condenser pipe In flask, then 5364.5g butanone is added thereto, react 18h at 60 DEG C under the protection of nitrogen, stir speed (S.S.) is 430rpm, after the question response time terminates, room temperature is cooled to, 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 impurity off, and again with methanol elutes to obtain faint yellow viscous shape liquid, that is, obtains the viscous of the present invention Soil stabilizer B3。
Embodiment 4：Clay stabilizer B4And preparation method thereof
(1) clay stabilizer B4Composition, component and molecular formula it is as follows：
Clay stabilizer B4By 2,3- naphthalic anhydrides, n-dodecanol, 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromines The mol ratio of methyl naphthalene is 1: 1.2: 1.5: 1.4, and its molecular formula is as follows：
(2) clay stabilizer B4Synthetic method it is as follows：
1. 1mol 2,3- naphthalic anhydrides and 1.2mol n-dodecanols are added into four-hole boiling flask, heat while stirring, Heating-up temperature is 80 DEG C, stir speed (S.S.) 320rpm, reaction time 0.5h, is subsequently added into 3345.8g normal heptanes, reaction time For 3h, room temperature is then cooled to, 18min is stirred, obtains the ester solution of dodecyl -2,3- naphthalic anhydride half；
2. 1.5mol 2- (dimethylamino) chloromethane is added in the above-mentioned ester solution of dodecyl -2,3- naphthalic anhydride half Heptane hydrochloride salt, reacts while stirring, stir speed (S.S.) 280rpm, reaction time 6h, is then heated to 75 DEG C, while stirring instead Should, stir speed (S.S.) 480rpm, reaction time 13h, filter after the completion of reaction, with the petroleum ether filter wash slag of heat, collect immediately Filtrate, 25h is dried with anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the 1- bromomethyl naphthalenes of above-mentioned brown yellow oil liquid and 1.6mol are added to equipped with agitator and condenser pipe In flask, then 5635.8g butanone is added thereto, react 20h at 70 DEG C under the protection of nitrogen, stir speed (S.S.) is 450rpm, after the question response time terminates, room temperature is cooled to, 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 impurity off, and again with methanol elutes to obtain faint yellow viscous shape liquid, that is, obtains the viscous of the present invention Soil stabilizer B4。
Embodiment 5：Clay stabilizer B5And preparation method thereof
(1) clay stabilizer B5Composition, component and molecular formula it is as follows：
Clay stabilizer B5By 2,3- naphthalic anhydrides, n-dodecanol, 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromines The mol ratio of methyl naphthalene is 1: 1.4: 1.6: 1.8, and its molecular formula is as follows：
(2) clay stabilizer B5Synthetic method it is as follows：
1. 1mol 2,3- naphthalic anhydrides and 1.4mol n-dodecanols are added into four-hole boiling flask, heat while stirring, Heating-up temperature is 82 DEG C, stir speed (S.S.) 400rpm, reaction time 1.5h, is subsequently added into 3963.6g normal heptanes, reaction time For 8h, room temperature is then cooled to, 25min is stirred, obtains the ester solution of dodecyl -2,3- naphthalic anhydride half；
2. 1.6mol 2- (dimethylamino) chloromethane is added in the above-mentioned ester solution of dodecyl -2,3- naphthalic anhydride half Heptane hydrochloride salt, reacts while stirring, stir speed (S.S.) 300rpm, reaction time 8h, is then heated to 85 DEG C, while stirring instead Should, stir speed (S.S.) 500rpm, reaction time 15h, filter after the completion of reaction, with the petroleum ether filter wash slag of heat, collect immediately Filtrate, 30h is dried with anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. the 1- bromomethyl naphthalenes of above-mentioned brown yellow oil liquid and 1.8mol are added to equipped with agitator and condenser pipe In flask, then 5945.4g butanone is added thereto, react 24h at 80 DEG C under the protection of nitrogen, stir speed (S.S.) is 480rpm, after the question response time terminates, room temperature is cooled to, 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 impurity off, and again with methanol elutes to obtain faint yellow viscous shape liquid, that is, obtains the viscous of the present invention Soil stabilizer B5。
Embodiment 6
The above-mentioned B of 5.0g are accurately weighed respectively1~B5Clay stabilizer sample, it is dissolved in 995.0g distilled water, stirs 30min, homogeneous solution is formed, it is stand-by.
Embodiment 7
According to《SY/T5971-94 water fillings clay stabilizer method of evaluating performance》Product be have rated in 250 DEG C and mineralising Anti-dilative under the conditions of spending for 220000mg/L.Clay stabilization agent solution used in this experiment is tested by matching somebody with somebody solution in embodiment 6 It the results are shown in Table 1.
The clay stabilizer B of table 11~B5Evaluation result
Product Anti-dilative, %
B1 98.5
B2 99.5
B3 98.7
B4 98.3
B5 98.2
As it can be seen from table 1 clay stabilizer B1~B5Anti-dilative be all higher than 98.0%, wherein, clay stabilizer B2's Anti-dilative highest, reaches 99.2%.Illustrate that the clay stabilizer developed of the present invention in 250 DEG C and salinity is 220000mg/L bars There is the good ability for preventing bentonite hydration swelling under part.
Embodiment 8
Reference standard《SY-T 5613-2000 mud shale physicochemical property test methods》Evaluate sample and suppress 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 The clay stabilization agent solution that embodiment 6 is prepared, 20-30 mesh landwaste 50g are added, clear water is used after heat rolling 24h at a temperature of 250 DEG C Clean, cross 100 mesh sieves, dry 6h at a temperature of 250 DEG C, weigh and calculate primary recovery, the results are shown in Table 2.
The landwaste rolling rate of recovery result of the test of table 2
From table 2, clay stabilizer B1~B5A rolling rate of recovery be all higher than 97.0%, wherein, clay stabilizer B2A rolling rate of recovery highest, reach 98.8%.Result of the test shows the clay stabilizer product of the invention prepared 250 Still have after DEG C heat rolling and very strong suppress the scattered ability of Shale Hydration.
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 testers with instrument.Weigh two level bentonite (a diameter of 0.01- that 5.00g dries 10h at 250 DEG C 0.05mm), tabletting (pressure 10MPa, time 5min) is made on forcing press.Tabletting is put into shale expansion instrument, addition is matched somebody with somebody The certain density stabiliser solution (matching somebody with somebody solution in embodiment 6) made, the expansion of mud shale tabletting after measure test solution immersion Rate.The expansion rate of mud shale tabletting is smaller, illustrates that the ability of the suppression hydration and expansion of clay of product is stronger；It is on the contrary then poorer.It is real It is as shown in table 3 to test result.
The linear expansion rate experimental test result of table 3
From table 3, clay stabilizer B1~B516h is below 23% with respect to the reduced rate of clear water, wherein, clay stabilization Agent B216h is minimum with respect to the reduced rate of clear water, reaches 20.6%, illustrates that clay stabilizer product prepared by the present invention can be effectively Suppress the hydration swelling of clay.

Claims (6)

1. the anti-swollen clay stabilizer of a kind of long-acting oil well, it is characterised in that described clay stabilizer is by 2,3- naphthalene diformazans Acid anhydrides and n-dodecanol reaction generation dodecyl neighbour's naphthalic anhydride half ester, then with 2- (dimethylamino) chloromethanes hydrochloride Intermediate is generated by solution polymerization, finally reacts and generates with 1- bromomethyls naphthalene again, its molecular formula is as follows：
A kind of 2. anti-swollen clay stabilizer of long-acting oil well according to claim 1, it is characterised in that described 2,3- naphthalenes Dicarboxylic acid anhydride, n-dodecanol, the mol ratio of 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromomethyl naphthalenes are 1: 0.8~1.4: 1.2~1.6: 1.1~1.8.
A kind of 3. anti-swollen clay stabilizer of long-acting oil well according to claim 1 or 2, it is characterised in that described 2, 3- naphthalic anhydrides, n-dodecanol, the mol ratio of 2- (dimethylamino) chloromethanes hydrochlorides and 1- bromomethyl naphthalenes are 1: 1：1.4∶ 1.2。
4. a kind of long-acting oil well synthetic method for preventing swollen clay stabilizer, it is characterised in that the synthetic method specifically includes Following steps：
1. 2, the 3- naphthalic anhydrides and n-dodecanol of aforementioned proportion are added into four-hole boiling flask, heat while stirring, heating temperature Spend for 75~85 DEG C, stir speed (S.S.) is 300~400rpm, and the reaction time is 0.5~1.5h, is subsequently added into normal heptane, during reaction Between be 3~8h, be then cooled to room temperature, stir 10~25min, obtain the ester solution of dodecyl -2,3- naphthalic anhydride half；
2. 2- (dimethylamino) chloromethanes of aforementioned proportion is added in the above-mentioned ester solution of dodecyl -2,3- naphthalic anhydride half Hydrochloride, to react while stirring, stir speed (S.S.) is 200~300rpm, and the reaction time is 5~8h, is then heated to 75~85 DEG C, React while stirring, stir speed (S.S.) is 400~500rpm, and the reaction time is 10~15h, is filtered immediately after the completion of reaction, with heat Petroleum ether filter wash slag, collect filtrate, with anhydrous magnesium sulfate dry 15~30h, normal heptane is removed under reduced pressure, obtains brown yellow oil Liquid；
3. the 1- bromomethyl naphthalenes of above-mentioned brown yellow oil liquid and aforementioned proportion are added to the burning equipped with agitator and condenser pipe In bottle, then butanone is added thereto, react 10~24h at 50~80 DEG C under the protection of nitrogen, stir speed (S.S.) is 400~ 500rpm, after the question response time terminates, room temperature is cooled to, 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 impurity off, and again with methanol elutes to obtain faint yellow viscous shape liquid, that is, the clay for obtaining the present invention is steady Determine agent.
A kind of 5. long-acting oil well synthetic method for preventing swollen clay stabilizer according to claim 4, it is characterised in that institute The dosage for the normal heptane stated is 10~20 times of 2,3- naphthalic anhydride quality.
6. a kind of long-acting oil well synthetic method for preventing swollen clay stabilizer according to claim 4 or 5, its feature exist In the dosage of described butanone is 25~30 times of 2,3- naphthalic anhydride quality.
CN201710952167.1A 2017-10-13 2017-10-13 A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method Withdrawn CN107699212A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710952167.1A CN107699212A (en) 2017-10-13 2017-10-13 A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710952167.1A CN107699212A (en) 2017-10-13 2017-10-13 A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method

Publications (1)

Publication Number Publication Date
CN107699212A true CN107699212A (en) 2018-02-16

Family

ID=61183434

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710952167.1A Withdrawn CN107699212A (en) 2017-10-13 2017-10-13 A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method

Country Status (1)

Country Link
CN (1) CN107699212A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426618A (en) * 2020-10-14 2022-05-03 中国石油化工股份有限公司 Polymer type high-temperature-resistant anti-swelling and anti-shrinking agent and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106675534A (en) * 2017-02-10 2017-05-17 中国石油化工股份有限公司 Temperature-resistant and salt-resistant type anti-swelling clay stabilizer and synthetic method thereof
CN106866506A (en) * 2017-02-10 2017-06-20 中国石油化工股份有限公司 The salt cationic of heterocyclic quaternary ammonium containing N prevents swollen clay stabilizer and its synthetic method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106675534A (en) * 2017-02-10 2017-05-17 中国石油化工股份有限公司 Temperature-resistant and salt-resistant type anti-swelling clay stabilizer and synthetic method thereof
CN106866506A (en) * 2017-02-10 2017-06-20 中国石油化工股份有限公司 The salt cationic of heterocyclic quaternary ammonium containing N prevents swollen clay stabilizer and its synthetic method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426618A (en) * 2020-10-14 2022-05-03 中国石油化工股份有限公司 Polymer type high-temperature-resistant anti-swelling and anti-shrinking agent and preparation method and application thereof
CN114426618B (en) * 2020-10-14 2024-03-22 中国石油化工股份有限公司 Polymer type high-temperature-resistant anti-swelling and shrinking agent and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN106866506B (en) The salt cationic of heterocyclic quaternary ammonium containing N prevents swollen clay stabilizer and its synthetic method
Bai et al. Preformed particle gel for conformance control: factors affecting its properties and applications
CN103539902B (en) Preparation method of high temperature resistant contraction-expansion system for promoting stratum clay modification
CN105198757B (en) Small cation bi-quaternary ammonium salt clay stabilizer and preparation method thereof
CN103328603B (en) For the method with amine fluoride oxide process siliciclastic hydrocarbon containing formation
CN105086989A (en) Shale gas reservoir pre-fracture composite acid solution, preparation method and application thereof
CN103320112B (en) A kind of anti-shearing dendritic polymers oil-displacing agent and synthetic method thereof
CN103409118B (en) A kind of synthetic method of water-base drilling fluid ultrahigh-temperature stablizer
CN108102099B (en) Preparation method of high-temperature clay stabilizer for oil field
CN106281288A (en) A kind of low permeability reservoir pressure reducing and injection increasing agent used for flooding well and preparation method thereof
CN104861110A (en) Anti-swelling and sand-inhibiting agent for high-permeability heavy oil reservoir and preparation method of anti-swelling and sand-inhibiting agent
CN104418984A (en) High-temperature resistant clay stabilizer and preparation method thereof
CN109021159B (en) Oil well water shutoff agent and preparation method and application thereof
CN106336467A (en) Modified chitosan, preparation method thereof, application of chitosan as shale inhibitor, drilling fluid and application thereof
CN102276489B (en) Alkylphenol polyoxyethylene ether carboxylate type betaine and preparation method thereof
CN113896831A (en) Double-effect inhibitor for natural gas hydrate drilling fluid and preparation method and application thereof
CN108456511A (en) A kind of layer is interior to generate CO2System and its application
CN107699212A (en) A kind of long-acting oil well anti-swollen clay stabilizer and its synthetic method
CN106675534B (en) A kind of heat-resistant salt-resistant type prevents swollen clay stabilizer and its synthetic method
CN106367042A (en) Application of modified chitosan as shale inhibitor and application of anti-temperature and environment-friendly water-based drilling fluid
CN104531127A (en) Scale inhibition clay stabilizer
CN109851710A (en) A kind of organic phospho acid polymer fluid loss agent resistant to high temperatures and its preparation method and application
Zhang et al. Self-Generated Organic Acid System for Acid Fracturing in an Ultrahigh-Temperature Carbonate Reservoir
CN104559986B (en) Binary is driven poly- table pack thing and its is applied in intensified oil reduction
CN106987240A (en) Prevent swollen clay stabilizer and preparation method thereof for low-permeability oil deposit water filling

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20180216

WW01 Invention patent application withdrawn after publication