CN105198757A - Small cationic bisquaternary ammonium salt clay stabilizer and preparation method thereof - Google Patents
Small cationic bisquaternary ammonium salt clay stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN105198757A CN105198757A CN201510671867.4A CN201510671867A CN105198757A CN 105198757 A CN105198757 A CN 105198757A CN 201510671867 A CN201510671867 A CN 201510671867A CN 105198757 A CN105198757 A CN 105198757A
- Authority
- CN
- China
- Prior art keywords
- tertiary amine
- small molecules
- amine hydrochloride
- ammonium salt
- amine
- 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.)
- Granted
Links
- 239000004927 clay Substances 0.000 title claims abstract description 58
- 239000003381 stabilizer Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000003863 ammonium salts Chemical group 0.000 title abstract 2
- 125000002091 cationic group Chemical group 0.000 title abstract 2
- -1 tertiary amine hydrochloride Chemical class 0.000 claims abstract description 174
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 150000001768 cations Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000013459 approach Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003512 tertiary amines Chemical class 0.000 abstract 3
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000003449 preventive effect Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010010214 Compression fracture Diseases 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000009096 changqing Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention provides a small cationic bisquaternary ammonium salt clay stabilizer and a preparation method thereof. According to a formula I, original materials comprise epichlorohydrin, micromolecular tertiary amine and hydrochloric acid, wherein the mole ratio of epichlorohydrin to micromolecular tertiary amine is 1.0: (1.0-1.2); the mole ratio of hydrochloric acid to micromolecule tertiary amine is (1:1.8)-(1:2.2); the quantity of solvents used for a reaction accounts for 1/3-2/3 of the total mass of the original materials. According to a formula II, original materials comprise micromolecular tertiary amine hydrochloride I, epichlorohydrin and micromolecular tertiary amine hydrochloride II, wherein the molecular formulas of micromolecular tertiary amine hydrochloride I and micromolecular tertiary amine hydrochloride II are different; the mole ratio of micromolecular tertiary amine hydrochloride I to epichlorohydrin to micromolecular tertiary amine hydrochloride II is (0.8-1.0) : 1.0: (1.0-1.2), and the quantity of the solvents accounts for 1/3-2/3 of the total mass of the original materials. The clay stabilizer has high positive charge density, excellent stability and clay expansion inhibition capability.
Description
Technical field
The present invention relates to a kind of Oilfield Chemicals for oil-gas field fracturing, particularly relate to the preparation of pressure break clay stabilizer small cation bi-quaternary ammonium salt, specifically a kind of small cation bi-quaternary ammonium salt clay stabilizer and preparation method thereof.
Background technology
Containing a certain amount of clay mineral in oilfield reservoir, these clays in the performance history of the reservoirs such as water filling, acidifying, pressure break, run into water or water-based material is easy to produce hydration swelling, migration, and blocking reservoir passage, causes formation damage.The clay mineral of reservoir damage is caused to mainly contain montmorillonite, illite, kaolinite and chlorite etc.In fracturing liquid, add clay stabilizer, effectively can be adsorbed on surface of clay, to prevent in reservoir water sensitivity mineral hydration swelling and dispersion migration and hydrocarbon zone is damaged, affect Development Response of Oilfield.
Clay stabilizer, according to structure and different in kind, is mainly divided into inorganic salts, inorganic polymer class, organic cationic polymer etc.More with organic cationic polymer research, and based on quaternary, the research of polyquarternium-type clay stabilizer.Comprise low polyquarternium-type expansion-resisting agent, terpolymer expansion-resisting agent, tetrapolymer phosphoric acid salt expansion-resisting agent etc.Small molecule quaternary ammonium salt form clay stabilizer positive charge density is higher, can adsorb multiple clay particle simultaneously, forms multipoint adsorption.Containing two quaternary nitrogen atoms in bi-quaternary ammonium salt (Gemini type) compound, have low toxicity, widely biological activity and the good feature such as water-soluble than general quaternary ammonium salt, its exploitation and application are the focuses of research both at home and abroad now.Become the host of disinfecting medicament in oil field flood pattern because having excellent sterilization effect, but for its application in clay stabilization field, in domestic and foreign literature, then report is few.
The research of current bi-quaternary ammonium salt clay stabilizer mainly contains the Gemini quaternary ammonium salt that trimethylamine hydrochloride, Trimethylamine 99 and epichlorohydrin reaction generate; The Gemini quaternary ammonium salt anti-clayswelling agent etc. that triethylamine hydrochloride, triethylamine and epichlorohydrin reaction generate.Current bi-quaternary ammonium salt clay stabilizer research kind is less, and therefore research and development have many adsorption centers, good water-soluble, and the novel bi-quaternary ammonium salt clay stabilizer with satisfactory stability Property of Clay is significant.
Summary of the invention
The object of the present invention is to provide a kind of oil field compression fracture small molecules positively charged ion bi-quaternary ammonium salt clay stabilizer and preparation method thereof, this clay stabilizer has excellent preventive effect of expansion, and good with fracturing liquid compatibleness.
Technical scheme of the present invention is: small cation bi-quaternary ammonium salt clay stabilizer, and its formula one is made up of following initial material: epoxy chloropropane, small molecules tertiary amine and hydrochloric acid; Epoxy chloropropane and small molecules tertiary amine mol ratio are 1.0:(1.0-1.2); The mol ratio of hydrochloric acid and small molecules tertiary amine meets 1:1.8-1:2.2; The amount of the solvent that initial material is used when hybrid reaction is the 1/3-2/3 of initial material total mass;
Or its formula two is made up of following initial material: small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules tertiary ammonium salt two, its small molecular Amine from Tertiary Amine Hydrochloride one is not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two; The mol ratio of small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules tertiary ammonium salt two is (0.8-1.0): 1.0:(1.0-1.2), the amount of the solvent that initial material is used when hybrid reaction is the 1/3-2/3 of initial material total mass.
The molecular formula of above-mentioned small molecules tertiary amine is as follows:
wherein R is CH
3, CH
3cH
2, CH
3cH
2cH
2, (CH
3)
2cH or HOCH
2cH
2.
Above-mentioned small molecules Amine from Tertiary Amine Hydrochloride one R that refer in small molecules Amine from Tertiary Amine Hydrochloride one and small molecules Amine from Tertiary Amine Hydrochloride two both molecular formula not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two
1, R
2and R
3incomplete same; The molecular formula of described small molecules Amine from Tertiary Amine Hydrochloride one or small molecules Amine from Tertiary Amine Hydrochloride two is as follows:
wherein R
1, R
2, R
3be respectively CH
3, CH
3cH
2, CH
3cH
2cH
2, (CH
3)
2cH, CH
3cHOHCH
2or HOCH
2cH
2; R
1, R
2, R
3can be identical, also can not be identical.
Above-mentioned solvent is ethanol, Virahol or water.
Above-mentioned solvent is water.
A preparation method for small cation bi-quaternary ammonium salt clay stabilizer, according to the difference of initial material, by single stage method or two-step approach preparation;
When initial material is for filling a prescription for the moment, adopt single stage method preparation, its preparation process is: be 1.0:(1.0-1.2 in molar ratio) prepare epoxy chloropropane and small molecules tertiary amine; The small molecules tertiary amine of formula ratio, the solvent of formula ratio is added in the there-necked flask that agitator, reflux exchanger, thermometer be housed, stir, adding mass concentration ratio is 30%-33% concentrated hydrochloric acid, and the mol ratio of hydrochloric acid and small molecules tertiary amine meets 1:1.8-1:2.2, after 0.5h, adding the epoxy chloropropane of formula ratio, is 40-80 DEG C in temperature, stirring reaction 4-10h, obtains described small cation bi-quaternary ammonium salt clay stabilizer;
When initial material is formula two, prepared by employing two-step approach, its preparation process is: step 1, is (0.8-1.0): 1.0:(1.0-1.2 in molar ratio) prepare small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules Amine from Tertiary Amine Hydrochloride two; In the there-necked flask that agitator, reflux exchanger, thermometer be housed, add the small molecules Amine from Tertiary Amine Hydrochloride one of formula ratio, the solvent of formula ratio, stir, adding the epoxy chloropropane of formula ratio, is 40-80 DEG C in temperature, stirs 2-6h; Step 2, adds the small molecules Amine from Tertiary Amine Hydrochloride two of formula ratio, is 40-80 DEG C in temperature, and stir 4-8h, naturally cooling, obtains described small cation bi-quaternary ammonium salt clay stabilizer.
Beneficial effect of the present invention:
1, have the advantages that positive charge density is large, molecular weight is little by the bis-quaternary ammonium salt cationic of radical reaction mechanism gained.
2, preventive effect of expansion is good, and 0.5% (W/W) clay stabilizer anti-dilative reaches more than 85%;
3 and other additive compatibleness of fracturing liquid good, do not produce precipitation, residue;
4, good water solubility, complete dissolution time < 10s;
5, there is good thermostability;
6, water-fastness stable period > 300PV.
Accompanying drawing explanation
Fig. 1: the experiment of the fracturing fluid viscosity versus temperature variation relation figure that gets;
Fig. 2: experiment of the fracturing fluid viscosity versus temperature of getting-shear time variation relation figure;
Below with reference to embodiment, the present invention is described in further details.
Embodiment
The invention provides a kind of small cation bi-quaternary ammonium salt clay stabilizer, its formula one is made up of following initial material: epoxy chloropropane, small molecules tertiary amine and hydrochloric acid; Epoxy chloropropane and small molecules tertiary amine mol ratio are 1.0:(1.0-1.2); The mol ratio of hydrochloric acid and small molecules tertiary amine meets 1:1.8-1:2.2; The amount of the solvent that initial material is used when hybrid reaction is the 1/3-2/3 of initial material total mass;
Or its formula two is made up of following initial material: small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules tertiary ammonium salt two, its small molecular Amine from Tertiary Amine Hydrochloride one is not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two; The mol ratio of small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules tertiary ammonium salt two is (0.8-1.0): 1.0:(1.0-1.2), the amount of the solvent that initial material is used when hybrid reaction is the 1/3-2/3 of initial material total mass.
The preparation method of this small cation bi-quaternary ammonium salt clay stabilizer, according to the difference of initial material, by single stage method or two-step approach preparation;
When initial material is for filling a prescription for the moment, adopt single stage method preparation, its preparation process is: be 1.0:(1.0-1.2 in molar ratio) prepare epoxy chloropropane and small molecules tertiary amine; The small molecules tertiary amine of formula ratio, the solvent of formula ratio is added in the there-necked flask that agitator, reflux exchanger, thermometer be housed, stir, adding mass concentration ratio is 30%-33% concentrated hydrochloric acid, and the mol ratio of hydrochloric acid and small molecules tertiary amine meets 1:1.8-1:2.2, after 0.5h, adding the epoxy chloropropane of formula ratio, is 40-80 DEG C in temperature, stirring reaction 4-10h, obtains described small cation bi-quaternary ammonium salt clay stabilizer;
When initial material is formula two, prepared by employing two-step approach, its preparation process is: step 1, is (0.8-1.0): 1.0:(1.0-1.2 in molar ratio) prepare small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules Amine from Tertiary Amine Hydrochloride two; In the there-necked flask that agitator, reflux exchanger, thermometer be housed, add the small molecules Amine from Tertiary Amine Hydrochloride one of formula ratio, the solvent of formula ratio, stir, adding the epoxy chloropropane of formula ratio, is 40-80 DEG C in temperature, stirs 2-6h; Step 2, adds the small molecules Amine from Tertiary Amine Hydrochloride two of formula ratio, is 40-80 DEG C in temperature, and stir 4-8h, naturally cooling, obtains described small cation bi-quaternary ammonium salt clay stabilizer.
On the basis of the total scheme of small cation bi-quaternary ammonium salt clay stabilizer provided above and preparation method thereof, following specific embodiment has prepared plurality of stable agent according to stablizer of the present invention and compound method thereof:
Embodiment 1:
In the 100mL there-necked flask that agitator, reflux exchanger, thermometer are housed, adding 0.22mol small molecules tertiary amine, 30mL ethanol, stirred at ambient temperature, add 0.1mol concentrated hydrochloric acid, after 0.5h, add 0.1mol epoxy chloropropane, is 50 DEG C in temperature, stirs 8h.
The molecular formula of the small molecules tertiary amine in the present embodiment is as follows:
wherein R is CH
3.The present embodiment solvent for use is ethanol.
Embodiment 2:
0.09mol small molecules tertiary amine is added, 25mL water in the 100mL there-necked flask that agitator, reflux exchanger, thermometer are housed.Stirred at ambient temperature, adds 0.09mol concentrated hydrochloric acid, and reaction generates the hydrochloride of trolamine.After 0.5h, adding 0.11mol trolamine, 0.1mol epoxy chloropropane, is 60 DEG C in temperature, stirs 8h.
The molecular formula of the small molecules tertiary amine in the present embodiment is as follows:
wherein R is CH
3cH
2.The present embodiment solvent for use is water.
Embodiment 3:
0.1mol small molecules Amine from Tertiary Amine Hydrochloride one, 35mL Virahol is added in the 100mL there-necked flask that agitator, reflux exchanger, thermometer are housed.Stirred at ambient temperature, adds 0.1mol epoxy chloropropane, is 60 DEG C in temperature, stirs 2h.Continue to stir, adding 0.12mol small molecules Amine from Tertiary Amine Hydrochloride two, is 80 DEG C in temperature, stirs 6h.Naturally cooling, obtains described bi-quaternary ammonium salt clay stabilizer.
The present embodiment solvent for use is Virahol;
The molecular structural formula of the small molecules Amine from Tertiary Amine Hydrochloride one in the present embodiment is as follows:
wherein R
1, R
2, R
3be followed successively by CH in order
3, CH
3cH
2,cH
3cH
2cH
2.
Small molecules Amine from Tertiary Amine Hydrochloride two in the present embodiment is N methyldiethanol amine, and its molecular structural formula is as follows:
Wherein R
1, R
2, R
3be followed successively by CH in order
3, CH
3cH
2,cH
3cH
2oH.
Obvious small molecules Amine from Tertiary Amine Hydrochloride one is not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two, and not identical reason is because the R of small molecules Amine from Tertiary Amine Hydrochloride one and small molecules Amine from Tertiary Amine Hydrochloride two
1, R
2, R
3not identical.
Embodiment 4:
In the four-hole boiling flask that agitator, thermometer, dropping funnel and reflux exchanger are housed, add 0.1mol epoxy chloropropane, stir, dripping 0.1mol small molecules Amine from Tertiary Amine Hydrochloride one aqueous solution (33%), is 52 DEG C in temperature, stirs 6h.Continue to stir, adding 0.1mol small molecules Amine from Tertiary Amine Hydrochloride two, is 70 DEG C in temperature, stirs 6h.Naturally cooling, obtains described bi-quaternary ammonium salt clay stabilizer.
The present embodiment solvent for use is water (forming the aqueous solution with small molecules Amine from Tertiary Amine Hydrochloride one).
Its molecular structural formula of small molecules Amine from Tertiary Amine Hydrochloride one in the present embodiment is:
wherein R
1, R
2, R
3be followed successively by CH in order
3cH
2, CH
3, CH
3cH
2cH
2.
Small molecules Amine from Tertiary Amine Hydrochloride two in the present embodiment specifically tri-isopropanolamine hydrochloride, its molecular structural formula is:
Wherein R
1, R
2, R
3be followed successively by CH in order
3cHOHCH
2.
Obvious small molecules Amine from Tertiary Amine Hydrochloride one is not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two, and not identical reason is because the R of small molecules Amine from Tertiary Amine Hydrochloride one and small molecules Amine from Tertiary Amine Hydrochloride two
1, R
2, R
3not identical.
Embodiment 5:
In the 100mL there-necked flask that agitator, reflux exchanger, thermometer are housed, adding 0.18mol small molecules tertiary amine, 30mL ethanol, stirred at ambient temperature, add 0.1mol concentrated hydrochloric acid, after 0.5h, add 0.1mol epoxy chloropropane, is 50 DEG C in temperature, stirs 8h.
The molecular formula of the small molecules tertiary amine in the present embodiment is as follows:
wherein R is CH
3.The present embodiment solvent for use is ethanol.
Embodiment 6:
In the four-hole boiling flask that agitator, thermometer, dropping funnel and reflux exchanger are housed, add 0.08mol epoxy chloropropane, stir, dripping 0.1mol small molecules Amine from Tertiary Amine Hydrochloride one aqueous solution (33%), is 52 DEG C in temperature, stirs 6h.Continue to stir, adding 0.1mol small molecules Amine from Tertiary Amine Hydrochloride two, is 70 DEG C in temperature, stirs 6h.Naturally cooling, obtains described bi-quaternary ammonium salt clay stabilizer.
The present embodiment solvent for use is water (forming the aqueous solution with small molecules Amine from Tertiary Amine Hydrochloride one).
Its molecular structural formula of small molecules Amine from Tertiary Amine Hydrochloride one in the present embodiment is:
wherein R
1, R
2, R
3be followed successively by CH in order
3cH
2, CH
3, CH
3cH
2cH
2.
Small molecules Amine from Tertiary Amine Hydrochloride two in the present embodiment specifically tri-isopropanolamine hydrochloride, its molecular structural formula is:
Wherein R
1, R
2, R
3be CH
3cHOHCH
2.
Obvious small molecules Amine from Tertiary Amine Hydrochloride one is not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two, and not identical reason is because the R of small molecules Amine from Tertiary Amine Hydrochloride one and small molecules Amine from Tertiary Amine Hydrochloride two
1, R
2, R
3not identical.
It is a certain that the molecular formula of small molecules tertiary amine used in the various embodiments described above belongs in following biomolecule expressions:
wherein R is CH
3, CH
3cH
2, CH
3cH
2cH
2, (CH
3)
2cH or HOCH
2cH
2.
Small molecules Amine from Tertiary Amine Hydrochloride one R that refer in small molecules Amine from Tertiary Amine Hydrochloride one and small molecules Amine from Tertiary Amine Hydrochloride two both molecular formula not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two used in the various embodiments described above
1, R
2and R
3incomplete same; The molecular formula of small molecules Amine from Tertiary Amine Hydrochloride one or small molecules Amine from Tertiary Amine Hydrochloride two belongs to the one in following expression:
wherein R
1, R
2, R
3be respectively CH
3, CH
3cH
2, CH
3cH
2cH
2, (CH
3)
2cH, CH
3cHOHCH
2or HOCH
2cH
2; R
1, R
2, R
3can be identical, also can not be identical.
This small molecules Amine from Tertiary Amine Hydrochloride can adopt Cnpc Changqing Drilling Engineering Co., Ltd. Changqing Downhole Technology Operating Company to produce and the FPZJ product sold, production address: Xianyang, Shanxi province city is exposed to the sun four tunnels.
Its structural formula of small cation bi-quaternary ammonium salt clay stabilizer of final generation is as follows,
In formula, R
1, R
2, R
3, R
4, R
5, R
6be respectively CH
3, CH
3cH
2, CH
3cH
2cH
2, (CH
3)
2cH, HOCH
2cH
2and CH
3cH (OH) CH
2in any one, but R
1, R
2, R
3, R
4, R
5, R
6be asynchronously CH
3or CH
3cH
2.
To above each embodiment, accurately take the sample in each embodiment of 5.0g respectively, embodiment is corresponding in turn in 1-6 clay stabilizer sample by its sequence number (SN), be accurate to 0.1g, be dissolved in 995.0g distilled water, be accurate to 0.1g, stir 30min, form homogeneous solution, put on 1#-4# respectively, stand-by.Evaluate the anti-dilative of product by " SY/T5762-1995 fracture acidizing clay stabilizer performance measurement method ", test-results is in table 1.
Table 1 product anti-dilative is tested
As can be seen from anti-swollen data, the clay stabilizer of the present invention's development has the good ability preventing wilkinite hydration swelling, best with 3# preventive effect of expansion.
Clay stabilizer of the present invention and of the fracturing fluid compatibleness are analyzed, fracturing liquid base fluid consists of clear water+0.25% viscosifying agent+0.5% cleanup additive+0.1% sterilant+0.3%pH conditioning agent+0.5% bi-quaternary ammonium salt clay stabilizer, apparent viscosity is surveyed after crosslinked, observe compatibleness after its broken glue, test-results is in table 2.
Table 2 clay stabilizer of the present invention and fracturing liquid compatibleness are tested
As can be seen from fracturing liquid compatibleness, the clay stabilizer of the present invention's development on of the fracturing fluid apparent viscosity without impact, and good with other additive compatiblenesies of the fracturing fluid, show clay stabilizer of the present invention and fracturing liquid compatibleness good.
Above-mentioned obtained bi-quaternary ammonium salt clay stabilizer is mixed with fracturing fluid gel by 0.5% dosage.Ratio is: clear water+0.25% thickening material+0.5% cleanup additive+0.1% sterilant+0.3%pH conditioning agent+0.5% bi-quaternary ammonium salt clay stabilizer, adds linking agent configuration frozen glue, at 170s
-1under shearing rate, raised temperature gradually, measure of the fracturing fluid viscosity B coefficent situation, data as shown in Figure 1.Can find from Fig. 1: along with temperature rise, fracturing liquid viscosity reduces gradually, and when temperature is elevated to 90 DEG C time, viscosity reaches 113mPas, when temperature rise to be elevated to 125 DEG C time, viscosity is 50mPas, shows that resistance to warm spot is 125 DEG C.
Above-mentioned obtained bi-quaternary ammonium salt clay stabilizer is mixed with fracturing fluid gel by 0.5% dosage.Ratio is: clear water+0.25% thickening material+0.5% cleanup additive+0.1% sterilant+0.3%pH conditioning agent+0.5% bi-quaternary ammonium salt clay stabilizer, adds linking agent configuration frozen glue, at 170s
-1under shearing rate, raised temperature gradually, when temperature reaches 85 DEG C, at shearing rate 170s
-1under, continue to shear 60min, measure of the fracturing fluid viscosity B coefficent situation, data are as shown in Figure 2.Can find from Fig. 2: along with temperature rises, fracturing liquid viscosity reduces gradually, and when temperature is elevated to 85 DEG C time, viscosity is 220mPas, and in 85 DEG C of continuous shear stress 60min processes, viscosity remains on more than 110mPas always, is greater than 50mPas requirement.Result shows, clay stabilizer of the present invention is applied in fracturing liquid, and fracturing liquid meets anti-shear ability requirement.
Above result shows, clay stabilizer provided by the invention has the ability of good suppression hydration and expansion of clay, good with fracturing liquid compatibleness.
To sum up, the present invention possesses following advantage:
1, have the advantages that positive charge density is large, molecular weight is little by the bis-quaternary ammonium salt cationic of radical reaction mechanism gained.
2, preventive effect of expansion is good, and 0.5% (W/W) clay stabilizer anti-dilative reaches more than 85%;
3 and other additive compatibleness of fracturing liquid good, do not produce precipitation, residue;
4, good water solubility, complete dissolution time < 10s;
5, there is good thermostability;
6, water-fastness stable period > 300PV.
The part do not described in detail in present embodiment belongs to the known conventional means of the industry, does not describe one by one here.More than exemplifying is only illustrate of the present invention, does not form the restriction to protection scope of the present invention, everyly all belongs within protection scope of the present invention with the same or analogous design of the present invention.
Claims (6)
1. small cation bi-quaternary ammonium salt clay stabilizer, is characterized in that, its formula one is made up of following initial material: epoxy chloropropane, small molecules tertiary amine and hydrochloric acid; Epoxy chloropropane and small molecules tertiary amine mol ratio are 1.0:(1.0-1.2); The mol ratio of hydrochloric acid and small molecules tertiary amine meets 1:1.8-1:2.2; The amount of the solvent that initial material is used when hybrid reaction is the 1/3-2/3 of initial material total mass;
Or its formula two is made up of following initial material: small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules tertiary ammonium salt two, its small molecular Amine from Tertiary Amine Hydrochloride one is not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two; The mol ratio of small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules tertiary ammonium salt two is (0.8-1.0): 1.0:(1.0-1.2), the amount of the solvent that initial material is used when hybrid reaction is the 1/3-2/3 of initial material total mass.
2. small cation bi-quaternary ammonium salt clay stabilizer as claimed in claim 1, it is characterized in that, the molecular formula of described small molecules tertiary amine is as follows:
wherein R is CH
3, CH
3cH
2, CH
3cH
2cH
2, (CH
3)
2cH or HOCH
2cH
2.
3. small cation bi-quaternary ammonium salt clay stabilizer as claimed in claim 1, it is characterized in that, described small molecules Amine from Tertiary Amine Hydrochloride one R that refer in small molecules Amine from Tertiary Amine Hydrochloride one and small molecules Amine from Tertiary Amine Hydrochloride two both molecular formula not identical with the molecular formula of small molecules Amine from Tertiary Amine Hydrochloride two
1, R
2and R
3incomplete same; The molecular formula of described small molecules Amine from Tertiary Amine Hydrochloride one or small molecules Amine from Tertiary Amine Hydrochloride two is as follows:
wherein R
1, R
2, R
3be respectively CH
3, CH
3cH
2, CH
3cH
2cH
2, (CH
3)
2cH, HOCH
2cH
2or CH
3cHOHCH
2; R
1, R
2, R
3can be identical, also can not be identical.
4. small cation bi-quaternary ammonium salt clay stabilizer as claimed in claim 1, it is characterized in that, described solvent is ethanol, Virahol or water.
5. small cation bi-quaternary ammonium salt clay stabilizer as claimed in claim 4, it is characterized in that, described solvent is water.
6. a preparation method for small cation bi-quaternary ammonium salt clay stabilizer as claimed in claim 1, is characterized in that, according to the difference of initial material, by single stage method or two-step approach preparation;
When initial material is for filling a prescription for the moment, adopt single stage method preparation, its preparation process is: be 1.0:(1.0-1.2 in molar ratio) prepare epoxy chloropropane and small molecules tertiary amine; The small molecules tertiary amine of formula ratio, the solvent of formula ratio is added in the there-necked flask that agitator, reflux exchanger, thermometer be housed, stir, adding mass concentration ratio is 30%-33% concentrated hydrochloric acid, and the mol ratio of hydrochloric acid and small molecules tertiary amine meets 1:1.8-1:2.2, after 0.5h, adding the epoxy chloropropane of formula ratio, is 40-80 DEG C in temperature, stirring reaction 4-10h, obtains described small cation bi-quaternary ammonium salt clay stabilizer;
When initial material is formula two, prepared by employing two-step approach, its preparation process is: step 1, is (0.8-1.0): 1.0:(1.0-1.2 in molar ratio) prepare small molecules Amine from Tertiary Amine Hydrochloride one, epoxy chloropropane and small molecules Amine from Tertiary Amine Hydrochloride two; In the there-necked flask that agitator, reflux exchanger, thermometer be housed, add the small molecules Amine from Tertiary Amine Hydrochloride one of formula ratio, the solvent of formula ratio, stir, adding the epoxy chloropropane of formula ratio, is 40-80 DEG C in temperature, stirs 2-6h; Step 2, adds the small molecules Amine from Tertiary Amine Hydrochloride two of formula ratio, is 40-80 DEG C in temperature, and stir 4-8h, naturally cooling, obtains described small cation bi-quaternary ammonium salt clay stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671867.4A CN105198757B (en) | 2015-10-15 | 2015-10-15 | Small cation bi-quaternary ammonium salt clay stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671867.4A CN105198757B (en) | 2015-10-15 | 2015-10-15 | Small cation bi-quaternary ammonium salt clay stabilizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105198757A true CN105198757A (en) | 2015-12-30 |
| CN105198757B CN105198757B (en) | 2017-08-25 |
Family
ID=54946760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510671867.4A Active CN105198757B (en) | 2015-10-15 | 2015-10-15 | Small cation bi-quaternary ammonium salt clay stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105198757B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675531A (en) * | 2016-10-20 | 2017-05-17 | 天津民旌科技发展有限公司 | Efficient anti-swelling swelled shrinkage agent for stratum treatment |
| CN108329902A (en) * | 2018-01-23 | 2018-07-27 | 中国石油天然气股份有限公司 | Salt-tolerant clay stabilizer for preparing fracturing fluid from oilfield effluent and preparation method thereof |
| CN109054798A (en) * | 2018-07-13 | 2018-12-21 | 中国石油大学(华东) | A kind of preparation method of oil field high temperature clay stabilizer |
| CN110885293A (en) * | 2019-12-12 | 2020-03-17 | 东营市泽澳化工有限责任公司 | Synthesis method of biquaternary ammonium salt |
| CN110964493A (en) * | 2019-12-16 | 2020-04-07 | 成都碧隆双田化工科技有限公司 | Clay stabilizer for oil field |
| CN111732946A (en) * | 2020-06-29 | 2020-10-02 | 中国石油天然气集团有限公司 | Anti-swelling cleanup additive for fracturing and preparation method thereof |
| CN111808598A (en) * | 2020-08-26 | 2020-10-23 | 肯特催化材料股份有限公司 | Clay anti-swelling agent |
| CN112745233A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Small-molecule clay stabilizer suitable for low-permeability oil reservoir and preparation method thereof |
| CN113403046A (en) * | 2021-05-12 | 2021-09-17 | 中国石油大学(华东) | Shrinkage-expansion agent for preventing borehole wall instability in oil extraction and drilling processes of high-argillaceous oil reservoirs and preparation method thereof |
| CN114854390A (en) * | 2022-04-14 | 2022-08-05 | 西南石油大学 | Polyhydroxy super-large hydrophilic head-based viscoelastic surfactant and synthesis method thereof |
| CN114989801A (en) * | 2022-06-15 | 2022-09-02 | 胜利油田华滨化工有限责任公司 | Small cation clay stabilizer and preparation method thereof |
| CN115028541A (en) * | 2021-03-08 | 2022-09-09 | 中国石油化工股份有限公司 | Long-chain small-molecule polyamine, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329602A (en) * | 2011-08-03 | 2012-01-25 | 西安长庆化工集团有限公司 | Ultralow-concentration fracturing fluid and preparation method thereof |
| CN102329603A (en) * | 2011-08-03 | 2012-01-25 | 西安长庆化工集团有限公司 | Low-concentration carboxymethyl fracturing fluid and preparation method thereof |
-
2015
- 2015-10-15 CN CN201510671867.4A patent/CN105198757B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329602A (en) * | 2011-08-03 | 2012-01-25 | 西安长庆化工集团有限公司 | Ultralow-concentration fracturing fluid and preparation method thereof |
| CN102329603A (en) * | 2011-08-03 | 2012-01-25 | 西安长庆化工集团有限公司 | Low-concentration carboxymethyl fracturing fluid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 尚蕴果: "季铵盐型粘土稳定剂的合成研究及防膨胀性能评价", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675531A (en) * | 2016-10-20 | 2017-05-17 | 天津民旌科技发展有限公司 | Efficient anti-swelling swelled shrinkage agent for stratum treatment |
| CN108329902A (en) * | 2018-01-23 | 2018-07-27 | 中国石油天然气股份有限公司 | Salt-tolerant clay stabilizer for preparing fracturing fluid from oilfield effluent and preparation method thereof |
| CN109054798B (en) * | 2018-07-13 | 2020-10-16 | 中国石油大学(华东) | Preparation method of high-temperature clay stabilizer for oil field |
| CN109054798A (en) * | 2018-07-13 | 2018-12-21 | 中国石油大学(华东) | A kind of preparation method of oil field high temperature clay stabilizer |
| CN112745233A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Small-molecule clay stabilizer suitable for low-permeability oil reservoir and preparation method thereof |
| CN110885293A (en) * | 2019-12-12 | 2020-03-17 | 东营市泽澳化工有限责任公司 | Synthesis method of biquaternary ammonium salt |
| CN110964493A (en) * | 2019-12-16 | 2020-04-07 | 成都碧隆双田化工科技有限公司 | Clay stabilizer for oil field |
| CN111732946A (en) * | 2020-06-29 | 2020-10-02 | 中国石油天然气集团有限公司 | Anti-swelling cleanup additive for fracturing and preparation method thereof |
| CN111808598A (en) * | 2020-08-26 | 2020-10-23 | 肯特催化材料股份有限公司 | Clay anti-swelling agent |
| CN111808598B (en) * | 2020-08-26 | 2022-05-20 | 肯特催化材料股份有限公司 | Clay anti-swelling agent |
| CN115028541A (en) * | 2021-03-08 | 2022-09-09 | 中国石油化工股份有限公司 | Long-chain small-molecule polyamine, and preparation method and application thereof |
| CN113403046A (en) * | 2021-05-12 | 2021-09-17 | 中国石油大学(华东) | Shrinkage-expansion agent for preventing borehole wall instability in oil extraction and drilling processes of high-argillaceous oil reservoirs and preparation method thereof |
| CN113403046B (en) * | 2021-05-12 | 2023-01-06 | 中国石油大学(华东) | Shrinkage-expansion agent for preventing borehole wall instability in oil production and drilling processes of high-argillaceous oil reservoirs and preparation method of shrinkage-expansion agent |
| CN114854390A (en) * | 2022-04-14 | 2022-08-05 | 西南石油大学 | Polyhydroxy super-large hydrophilic head-based viscoelastic surfactant and synthesis method thereof |
| CN114854390B (en) * | 2022-04-14 | 2023-06-09 | 西南石油大学 | Polyhydroxy super-hydrophilic head-based viscoelastic surfactant and synthesis method thereof |
| CN114989801A (en) * | 2022-06-15 | 2022-09-02 | 胜利油田华滨化工有限责任公司 | Small cation clay stabilizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105198757B (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105198757A (en) | Small cationic bisquaternary ammonium salt clay stabilizer and preparation method thereof | |
| US7879769B2 (en) | Polycationic viscoelastic compositions | |
| US7867951B2 (en) | Viscoelastic cationic carbohydrate ether compositions | |
| CN102021583B (en) | Corrosion inhibitor for oil well and preparation method thereof | |
| WO2014144387A1 (en) | Environmentally friendly permanent quaternaries of polyamines and their use as clay stabilizers and methods for making and using same | |
| CN106519254B (en) | A kind of dendroid quaternary ammonium salt shale control agent and preparation method and application | |
| CN104232033B (en) | Multifunctional type high-temperature-resistant composite well control fluid and preparation method and applications thereof | |
| CN110665431A (en) | Preparation of sulfonic acid amphoteric gemini viscoelastic surfactant and application of surfactant in fracturing fluid | |
| Zhang et al. | Development of a stimuli‐responsive gemini zwitterionic viscoelastic surfactant for self‐diverting acid | |
| CN106008255A (en) | Quaternary ammonium salt type Gemini surface active agent and preparation, product and application thereof | |
| CN104592955A (en) | Polyamine shale inhibitor and preparation method thereof | |
| CN103396782B (en) | Anti-swelling agent for acidification and preparation method thereof | |
| Mao et al. | Molecular simulation of polyether amines intercalation into Na-montmorillonite interlayer as clay-swelling inhibitors | |
| Azmi et al. | Adsorption of the xanthan gum polymer and sodium dodecylbenzenesulfonate surfactant in sandstone reservoirs: Experimental and density function theory studies | |
| WO2006013596A1 (en) | Shale inhibitors for the petroleum industry | |
| Cetin et al. | Rheological study of a novel sulfobetaine surfactant-based acid system | |
| CN105623636B (en) | Anti-swelling and anti-shrinking agent, preparation method and application thereof | |
| CN111662194B (en) | Environment-friendly ether amine shale inhibitor and water-based drilling fluid thereof | |
| CN104419400A (en) | Fracturing fluid and application thereof | |
| Ao et al. | Deep Eutectic Solvents with Different Alkyl Chain Lengths as Inhibitors for Shale in Water-Based Drilling Fluids | |
| Wang et al. | Insight into functional groups of salt compounds on the performance of viscoelastic surfactant-based fluids | |
| US10889742B1 (en) | Modified polyhistidine suitable for being used as a supramolecular shale inhibitor, method of preparing the same and its application in water-based drilling fluids | |
| CN116622361B (en) | Clean fracturing fluid composition, clean fracturing fluid, and preparation method and application thereof | |
| CN113105874B (en) | Double-inorganic-acid-salt clay stabilizer for shale fracturing and preparation method thereof | |
| Daneshfar et al. | Shale Hydration Inhibitive Materials as a Solution for the Formation Damage: a Review |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201102 Address after: 100007 Dongcheng District, Dongzhimen, China, North Street, No. 9 Oil Mansion, No. Patentee after: CHINA NATIONAL PETROLEUM Corp. Patentee after: CNPC CHUANQING DRILLING ENGINEERING Co.,Ltd. Address before: 710018 Shaanxi province Xi'an Weiyang Changqing Changqing prosperous Park District Building Room 1207 Patentee before: CHINA NATIONAL PETROLEUM CORPORATION CHUANQING DRILLING ENGINEERING COMPANY LIMITED CHANGQING DOWNHOLE TECHNOLOGY Co. |