CN104418984A - High-temperature resistant clay stabilizer and preparation method thereof - Google Patents
High-temperature resistant clay stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN104418984A CN104418984A CN201310397434.5A CN201310397434A CN104418984A CN 104418984 A CN104418984 A CN 104418984A CN 201310397434 A CN201310397434 A CN 201310397434A CN 104418984 A CN104418984 A CN 104418984A
- Authority
- CN
- China
- Prior art keywords
- clay stabilizer
- preparation
- temperature resistant
- high temperature
- monomer
- 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 87
- 239000003381 stabilizer Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 4
- 230000000977 initiatory effect Effects 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- QIBPEYMJKPVNHE-UHFFFAOYSA-N butane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCCS(O)(=O)=O QIBPEYMJKPVNHE-UHFFFAOYSA-N 0.000 claims description 3
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 230000002579 anti-swelling effect Effects 0.000 abstract 1
- 238000009991 scouring Methods 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 5
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 0 CC(*)C(C)(C)N=* Chemical compound CC(*)C(C)(C)N=* 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UJGOCJFDDHOGRX-UHFFFAOYSA-M [Fe]O Chemical compound [Fe]O UJGOCJFDDHOGRX-UHFFFAOYSA-M 0.000 description 1
- -1 acrylamide butyl sulfonic acid potassium Chemical compound 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product 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
- 239000002734 clay mineral Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 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
- 230000000694 effects Effects 0.000 description 1
- NTXJYWXCKBIGFH-UHFFFAOYSA-N ethenesulfonic acid;potassium Chemical compound [K].OS(=O)(=O)C=C NTXJYWXCKBIGFH-UHFFFAOYSA-N 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 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
- 150000002892 organic cations Chemical group 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a high-temperature resistant clay stabilizer and a preparation method thereof. The preparation method comprises the following steps: carrying out initiation reaction on epoxy chloropropane, dimethylamine and unsaturated quaternary ammonium salt with a sulfonate-containing anionic monomer under a certain condition; and then adding a chain transfer agent in the reaction process to control the molecular weight and after reaction, obtaining the clay stabilizer, wherein both the main and side chains contain cations and the side chain further contains anions. The clay stabilizer has the abilities of resisting temperature, preventing salt and resisting pollution; the clay stabilizer is small in use level, scouring resistant and good in anti-swelling effect; and the molecular weight is ranged from 1500 to 6000, so that the high-temperature resistant clay stabilizer is suitable for a low permeability reservoir.
Description
Technical field
The present invention relates to a kind of high temperature resistant clay stabilizer and preparation method thereof.
Background technology
Containing a certain amount of clay mineral in stratum, mainly contain kaolinite, montmorillonite, illite and chlorite etc., will expand when these clays run into extraneous water or water-based material at oilfield development process (water filling, acidifying, pressure break), disperse, migrate, block hole throat, cause zone permeability to reduce, destroy even more serious for hypotonic rate oil reservoir.In order to alleviate reservoir damage, often add clay stabilizer in oil field to improve hydration swelling, the dispersion migration of clay.
Different clay stabilizers according to chemical structure can be divided into: inorganic salts, inorganic multinuclear polymer class, organic polymer class.
Inorganic salts clay stabilizer has cheap, and short-term preventive effect of expansion is good; Shortcoming to form multipoint adsorption, and timeliness is short.
Inorganic multinuclear polymer class mainly contains oxyaluminum, zirconyl hydroxy, iron carbonyl etc.This kind of clay stabilizer can effectively prevent clay swelling and migration, but acid resistance is poor, can not be used for the sandstone formation that carbonate content is high.
Organic polymer class studies a class clay stabilizer the most widely.At present, what this kind of clay stabilizer use was maximum is organic cation type polymkeric substance.This kind of clay stabilizer again based on polyquarternium-type, as Poly Dimethyl Diallyl Ammonium Chloride, poly-trimethylallylammonium chloride, cationic polyacrylamide etc.Such clay stabilizer has the advantages such as heatproof, acidproof, validity period is long.The organic clay stabilizers majority of current use is straight chain type, and when molecular weight is large, easy centering low permeability formation hole throat results in blockage, and molecular weight hour preventive effect of expansion difference, validity period is short.
Although existing clay stabilizer has the ability of heatproof, clay stabilization to a certain extent, at high temperature resistant, anti-salt, long-lasting and at middle LOW PERMEABILITY RESERVOIR use Shortcomings.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of high temperature resistant clay stabilizer and preparation technology thereof.
The technical solution used in the present invention is: high temperature resistant clay stabilizer, it is characterized in that this stablizer is by epoxy chloropropane, dimethylamine, unsaturated quaternary ammonium salt and form containing sulfonic monomer polymerization, its main chain contains azonia, and its side chain is simultaneously containing azonia and azochlorosulfonate acid anion.
Described clay stabilizer, is characterized in that its molecular structural formula is as follows:
In formula, x:y:z=(1-42): (1-14): (1-10);
Or its molecular structural formula is as follows:
In formula, x:y:z=(1-42): (1-12): (1-12);
Or its molecular structural formula is as follows:
In formula, x:y:z=(1-42): (1-10): (1-18).
Clay stabilizer preparation method that one of the present invention is high temperature resistant, comprises the following steps:
1) by a certain amount of soluble in water containing sulfonic monomer, with KOH adjust ph to 6 ~ 8;
2) in reactor, add epoxy chloropropane, temperature of reactor controls at 10 ~ 30 DEG C;
3) add in above-mentioned reactor in dimethylamine agueous solution, unsaturated quaternary ammonium salt and step 1 containing sulfonic monomer solution.Finally being made into monomer total mass percentage concentration is 30 ~ 55%;
4) in above-mentioned reactor, lead to nitrogen and add initiator, temperature of reaction is 40 ~ 90 DEG C, and the reaction times is 2 ~ 8h;
5) when the molecular weight of the reaction product of step 4 is 1500 ~ 6000 time, add chain-transfer agent, react complete and namely obtain clay stabilizer.
Wherein, the raw materials used proportioning of described high temperature resistant clay stabilizer: with monomer total amount for 1, the mass percent of each monomer is: epoxy chloropropane 30 ~ 60%; Dimethylamine 11 ~ 19%, unsaturated quaternary ammonium salt 2 ~ 20%, containing sulfonic group monomer 2 ~ 20%, sodium formiate 0.5% ~ 5%; Finally being made into monomer total mass percentage concentration is the aqueous solution of 30% ~ 55%.
Described unsaturated quaternary ammonium salt can be one or several the mixture in allyl group trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride.
Described can be one or several mixture in 2-acrylamide-2-methylpro panesulfonic acid, vinyl sulfonic acid, acrylamide butyl sulfonic acid containing sulfonic monomer.
Described initiator can be water miscible azo-initiator, hydrogen peroxide and ammonium persulfate-sodium bisulfite redox system, also can choose Potassium Persulphate-sodium bisulfite redox system, and initiator add-on is 0.1 ~ 4.0% of monomer total mass; Initiator initiator system of ammonium persulfate-sodium bisulfite redox system, sodium bisulfite and ammonium persulphate mol ratio are 1:1.0 ~ 1.3, preferred 1:1.2.
Beneficial effect of the present invention and feature:
(1) clay stabilizer main chain of the present invention and the equal cation of side chain.The positive charge that main chain contains is more, can adsorb simultaneously, form multipoint adsorption, suppress the hydration swelling of clay with multiple clay particle; The azonia simultaneously contained in side chain, freedom of movement is larger, and the dispersion migration for clay particle has strong control action kou, has very strong water-wash resistance.
(2) clay stabilizer side chain of the present invention containing azochlorosulfonate acid anion is strong aquation group, fine and close hydration shell can be formed in clay particle surface, can stop and delay water molecules and contact with surface of clay, play and prevent hydration and expansion of clay object, also there is high temperature resistance, anti-salt, resistant to pollution effect simultaneously.
(3) clay stabilizer molecular weight of the present invention is low, can be applicable to low-permeability oil pool, and consumption is few, effective.
Embodiment
For a better understanding of the present invention, illustrate the content of invention further below in conjunction with embodiment, but content of the present invention is not limited only to the following examples.
Embodiment 1
Getting 42g 2-acrylamide-2-methylpro panesulfonic acid is dissolved in 58g water, regulates about pH to 7 with KOH, for subsequent use.69.4g epoxy chloropropane is added in reactor, temperature of reactor controls at 20 DEG C, add dimethylamine agueous solution and the above-mentioned 2-acrylamide-2-methylpro panesulfonic acid potassium solution prepared of 50g that 56.3g massfraction is 40%, then 13.5g allyl group trimethyl ammonium chloride is added, 60g water, the sodium bisulfite of 1.1g is added pass into nitrogen 30min in reactor after, 2.7g ammonium persulphate is added after 3min, 2 ~ 8h is reacted at temperature is 40 DEG C, the molecular weight of resultant is detected in reaction process, when molecular weight is 4216 time, add 4.1g sodium formiate, react complete and obtain a kind of clay stabilizer, as follows through its structural formula of infrared analysis:
In formula, x:y:z=5:1:1.
Embodiment 2
Getting 40g acrylamide butyl sulfonic acid is dissolved in 60g water, regulates about pH to 7 with KOH, for subsequent use.69.4g epoxy chloropropane is added in reactor, temperature of reactor controls at 20 DEG C, add dimethylamine agueous solution and the above-mentioned acrylamide butyl sulfonic acid potassium solution prepared of 50g that 56.3g massfraction is 40%, then the dimethyl diallyl ammonium chloride aqueous solution that 23.4g massfraction is 70% is added, 65g water, the sodium bisulfite of 1.1g is added pass into nitrogen 30min in reactor after, 2.7g ammonium persulphate is added after 3min, 2 ~ 8h is reacted at temperature is 40 DEG C, the molecular weight of resultant is detected in reaction process, when molecular weight is 4330 time, add 3.3g sodium formiate, react complete and obtain a kind of clay stabilizer, as follows through its structural formula of infrared analysis:
In formula, x:y:z=25:5:6.
Embodiment 3
Getting 22g vinyl sulfonic acid is dissolved in 40g water, regulates about pH to 7 with KOH, for subsequent use.34.7g epoxy chloropropane is added in reactor, temperature of reactor controls at 20 DEG C, add dimethylamine agueous solution and the above-mentioned vinyl sulfonic acid potassium solution prepared of 31g that 28.2g massfraction is 40%, then the diethyl diallyl ammonium chloride aqueous solution that 31.5g massfraction is 60% is added, 24 g water, the sodium bisulfite of 0.5g is added pass into nitrogen 30min in reactor after, 1.3g ammonium persulphate is added after 3min, 2 ~ 8h is reacted at temperature is 40 DEG C, the molecular weight of resultant is detected in reaction process, when molecular weight is 5517 time, add 2.5g sodium formiate, react complete and obtain a kind of clay stabilizer, as follows through its structural formula of infrared analysis:
In formula, x:y:z=25:9:10.
Embodiment 4
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=5:1:1.
According to China National Petroleum industry standard " water filling clay stabilizer method of evaluating performance SY/T1994 (2002) ", under test room temperature and roll the preventive effect of expansion of the sample after 24h through 250 DEG C of heat.
Embodiment 5
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=25:5:6.
According to China National Petroleum industry standard " water filling clay stabilizer method of evaluating performance SY/T1994 (2002) ", under test room temperature and roll the preventive effect of expansion of the sample after 24h through 250 DEG C of heat.
Embodiment 6
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=25:9:10.
According to China National Petroleum industry standard " water filling clay stabilizer method of evaluating performance SY/T1994 (2002) ", under test room temperature and roll the preventive effect of expansion of the sample after 24h through 250 DEG C of heat.
Embodiment 4-6 test-results is as shown in table 1.
The anti-swollen result of table 1 clay stabilizer
Embodiment 7
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=5:1:1.
The swelling property test of sample is carried out according to China National Petroleum industry standard " shale-control agent for drilling fluid evaluation method SY/T6335-1997 ".Instrument is NP-3 shale expansion tester.
Embodiment 8
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=25:5:6.
The swelling property test of sample is carried out according to China National Petroleum industry standard " shale-control agent for drilling fluid evaluation method SY/T6335-1997 ".Instrument is NP-3 shale expansion tester.
Embodiment 9
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=25:9:10.
The swelling property test of sample is carried out according to China National Petroleum industry standard " shale-control agent for drilling fluid evaluation method SY/T6335-1997 ".Instrument is NP-3 shale expansion tester.
Embodiment 7-9 test-results is as shown in table 2.
Table 2 embodiment 7-9 test-results
| Sample ID | 8h linear expansion rate/% | 16h linear expansion rate/% |
| Embodiment 7 | 51.42 | 68.96 |
| Embodiment 8 | 53.75 | 70.29 |
| Embodiment 9 | 49.31 | 66.38 |
Embodiment 10
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=5:1:1.
At room temperature water-fastness rate performance test is carried out to sample according to company standard " technical requirements of Q/SH 0053-2010 clay stabilizer ".
Embodiment 11
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=25:5:6.
At room temperature water-fastness rate performance test is carried out to sample according to company standard " technical requirements of Q/SH 0053-2010 clay stabilizer ".
Embodiment 12
Take 0.5g clay stabilizer sample, add water to 100g, being made into concentration is 0.5% clay stabilization agent solution, and wherein clay stabilizer structure is
In formula, x:y:z=25:9:10.
At room temperature water-fastness rate performance test is carried out to sample according to company standard " technical requirements of Q/SH 0053-2010 clay stabilizer ".
Embodiment 10-12 test-results is as shown in table 3
The water-fastness rate of table 3 clay stabilizer
| Sample ID | First time bentonite inflated volume (mL) | Second time expansion wilkinite volume (mL) | Third time bentonite inflated volume (mL) | Water-fastness rate (%) |
| Embodiment 10 | 0.89 | 0.90 | 0.90 | 98.89 |
| Embodiment 11 | 0.97 | 0.97 | 0.98 | 98.97 |
| Embodiment 12 | 1.00 | 1.02 | 1.05 | 95.24 |
The above results shows, clay stabilizer prepared by the present invention has the ability of good heatproof, water-fastness and good suppression clay swelling.
Claims (10)
1. a high temperature resistant clay stabilizer, it is characterized in that this stablizer is by epoxy chloropropane, dimethylamine, unsaturated quaternary ammonium salt and form containing sulfonic monomer polymerization, its main chain contains azonia, and its side chain is simultaneously containing azonia and azochlorosulfonate acid anion.
2. clay stabilizer as claimed in claim 1, is characterized in that its molecular structural formula is as follows:
In formula, x:y:z=(1-42): (1-14): (1-10); Or its molecular structural formula is as follows:
In formula, x:y:z=(1-42): (1-12): (1-12); Or its molecular structural formula is as follows:
In formula, x:y:z=(1-42): (1-10): (1-18).
3. the preparation method of a high temperature high efficiency clay stabilizer, it is characterized in that by epoxy chloropropane, dimethylamine, unsaturated quaternary ammonium salt and obtained by the initiation reaction of initiator containing sulfonic monomer, and control its molecular weight by adding chain-transfer agent sodium formiate in reaction process.
4. the preparation method of high temperature resistant clay stabilizer as claimed in claim 3, epoxy chloropropane is it is characterized in that to join in reactor, temperature controls at 10 ~ 30 DEG C, then dimethylamine is added, unsaturated quaternary ammonium salt, containing sulfonic group monomer, wherein soluble in water in advance containing sulfonic group monomer, pH to 6 ~ 8 are regulated with KOH, logical nitrogen in reactor also adds initiator, 2 ~ 8h is reacted at temperature is 40 ~ 90 DEG C, when molecular weight is 1500 ~ 6000 time, add chain-transfer agent sodium formiate, its add-on is 0.5% ~ 5% of monomer total mass, react complete and obtain clay stabilizer.
5. the preparation method of the high temperature resistant clay stabilizer as described in claim 3 or 4, is characterized in that with monomer total amount for 1, and the mass percent of each monomer is: epoxy chloropropane 30 ~ 60%; Dimethylamine 11 ~ 19%, unsaturated quaternary ammonium salt 2 ~ 20%, containing sulfonic group monomer 2 ~ 20%, sodium formiate 0.5% ~ 5%; Finally being made into monomer total mass percentage concentration is the aqueous solution of 30% ~ 55%.
6. the preparation method of the high temperature resistant clay stabilizer as described in claim 3 or 4, is characterized in that: unsaturated quaternary ammonium salt is one or several the mixture in allyl group trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride.
7. the preparation method of the high temperature resistant clay stabilizer as described in claim 3 or 4, is characterized in that: the monomer containing azochlorosulfonate acid anion is one or several the mixture in 2-acrylamide-2-methylpro panesulfonic acid, vinyl sulfonic acid, acrylamide butyl sulfonic acid.
8. the preparation method of high temperature resistant clay stabilizer as claimed in claim 3, it is characterized in that: initiator is water miscible azo-initiator, hydrogen peroxide, ammonium persulfate-sodium bisulfite redox system or Potassium Persulphate-sodium bisulfite redox system, and initiator add-on is 0.1 ~ 4.0% of monomer total mass.
9. the preparation method of high temperature resistant clay stabilizer as claimed in claim 8, it is characterized in that initiator is ammonium persulfate-sodium bisulfite redox system, sodium bisulfite and ammonium persulphate mol ratio are 1:1.0 ~ 1.3.
10. the preparation method of high temperature resistant clay stabilizer as claimed in claim 9, is characterized in that sodium bisulfite and ammonium persulphate mol ratio are 1:1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310397434.5A CN104418984B (en) | 2013-09-04 | 2013-09-04 | High-temperature resistant clay stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310397434.5A CN104418984B (en) | 2013-09-04 | 2013-09-04 | High-temperature resistant clay stabilizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104418984A true CN104418984A (en) | 2015-03-18 |
| CN104418984B CN104418984B (en) | 2017-02-22 |
Family
ID=52969166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310397434.5A Active CN104418984B (en) | 2013-09-04 | 2013-09-04 | High-temperature resistant clay stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104418984B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647509A (en) * | 2016-01-21 | 2016-06-08 | 西安石油大学 | Active anti-swelling and swelling-shrinkage agent and preparation method and application thereof |
| CN106279661A (en) * | 2015-05-28 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of Cationic Polymers Containing Quaternary Ammonium Salts |
| CN106608949A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Clay stabilizer and preparation method thereof |
| CN106753316A (en) * | 2017-02-07 | 2017-05-31 | 西安石油大学 | A kind of multi-functional clay stabilizer |
| CN107325795A (en) * | 2017-07-28 | 2017-11-07 | 克拉玛依市正诚有限公司 | Water-fastness swollen clay stabilizer of contracting and preparation method thereof |
| 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 |
| CN110317586A (en) * | 2018-03-29 | 2019-10-11 | 晋州市茂源钻采技术开发有限公司 | A kind of formula and preparation method thereof of drilling fluid shale potent inhibitor |
| CN111607375A (en) * | 2020-06-16 | 2020-09-01 | 胜利油田凯渡石油技术开发有限公司 | Anti-swelling shrinkage expansion agent for low-permeability sensitive oil reservoir and preparation method thereof |
| 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 |
| CN114478275A (en) * | 2020-10-27 | 2022-05-13 | 中石化南京化工研究院有限公司 | High-temperature-resistant clay stabilizer and preparation method thereof |
| CN114989799A (en) * | 2022-07-18 | 2022-09-02 | 华巍博大(北京)科技有限公司 | Oligomeric cationic type shrinkage-swelling agent composition, oligomeric cationic type shrinkage-swelling agent, and preparation method and application thereof |
| CN117285429A (en) * | 2022-06-17 | 2023-12-26 | 中国石油化工股份有限公司 | Compound and preparation method and application thereof |
| CN119060342A (en) * | 2024-11-06 | 2024-12-03 | 克拉玛依市华油精细化工有限责任公司 | A kind of polymer clay stabilizer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966605A (en) * | 2006-10-13 | 2007-05-23 | 冀东石油勘探开发公司 | Amphoteric ion polymeric alcohol for drilling fluid and its preparation method |
-
2013
- 2013-09-04 CN CN201310397434.5A patent/CN104418984B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966605A (en) * | 2006-10-13 | 2007-05-23 | 冀东石油勘探开发公司 | Amphoteric ion polymeric alcohol for drilling fluid and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 刘燕等: "新型两性离子粘土稳定剂的合成与性能评价", 《化学与生物工程》 * |
| 彭刚: "耐高温两性离子粘土稳定剂TTA的制备及性能评价", 《石油与天然气化工》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279661A (en) * | 2015-05-28 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of Cationic Polymers Containing Quaternary Ammonium Salts |
| CN106279661B (en) * | 2015-05-28 | 2018-10-02 | 中国石油化工股份有限公司 | A kind of Cationic Polymers Containing Quaternary Ammonium Salts |
| CN106608949A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Clay stabilizer and preparation method thereof |
| CN106608949B (en) * | 2015-10-26 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of clay stabilizer and preparation method thereof |
| CN105647509A (en) * | 2016-01-21 | 2016-06-08 | 西安石油大学 | Active anti-swelling and swelling-shrinkage agent and preparation method and application thereof |
| CN106753316A (en) * | 2017-02-07 | 2017-05-31 | 西安石油大学 | A kind of multi-functional clay stabilizer |
| CN106753316B (en) * | 2017-02-07 | 2019-10-01 | 西安石油大学 | A kind of multi-functional clay stabilizer |
| CN115404054A (en) * | 2017-07-28 | 2022-11-29 | 克拉玛依市正诚有限公司 | Washing-resistant shrinkage-expansion clay stabilizer and preparation method and application thereof |
| CN107325795A (en) * | 2017-07-28 | 2017-11-07 | 克拉玛依市正诚有限公司 | Water-fastness swollen clay stabilizer of contracting and preparation method thereof |
| 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 |
| CN110317586A (en) * | 2018-03-29 | 2019-10-11 | 晋州市茂源钻采技术开发有限公司 | A kind of formula and preparation method thereof of drilling fluid shale potent inhibitor |
| CN111607375A (en) * | 2020-06-16 | 2020-09-01 | 胜利油田凯渡石油技术开发有限公司 | Anti-swelling shrinkage expansion agent for low-permeability sensitive oil reservoir and preparation method thereof |
| CN111607375B (en) * | 2020-06-16 | 2022-09-23 | 胜利油田凯渡石油技术开发有限公司 | Anti-swelling shrinkage and expansion-shrinkage agent for low-permeability sensitive oil reservoir and preparation method thereof |
| 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 |
| CN114478275A (en) * | 2020-10-27 | 2022-05-13 | 中石化南京化工研究院有限公司 | High-temperature-resistant clay stabilizer and preparation method thereof |
| CN114478275B (en) * | 2020-10-27 | 2024-01-16 | 中石化南京化工研究院有限公司 | High-temperature-resistant clay stabilizer and preparation method thereof |
| CN117285429A (en) * | 2022-06-17 | 2023-12-26 | 中国石油化工股份有限公司 | Compound and preparation method and application thereof |
| CN114989799A (en) * | 2022-07-18 | 2022-09-02 | 华巍博大(北京)科技有限公司 | Oligomeric cationic type shrinkage-swelling agent composition, oligomeric cationic type shrinkage-swelling agent, and preparation method and application thereof |
| CN114989799B (en) * | 2022-07-18 | 2022-10-25 | 华巍博大(北京)科技有限公司 | Oligomeric cationic shrinking and swelling agent composition, oligomeric cationic shrinking and swelling agent, and preparation method and application thereof |
| CN119060342A (en) * | 2024-11-06 | 2024-12-03 | 克拉玛依市华油精细化工有限责任公司 | A kind of polymer clay stabilizer and preparation method thereof |
| CN119060342B (en) * | 2024-11-06 | 2025-04-22 | 克拉玛依市华油精细化工有限责任公司 | A kind of polymer clay stabilizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104418984B (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104418984A (en) | High-temperature resistant clay stabilizer and preparation method thereof | |
| CN104098738B (en) | A kind of low-molecular-weight clay stabilizer preparation method | |
| CN101798503B (en) | A polymer oil displacement agent for enhanced oil recovery and its application | |
| CN103539902B (en) | Preparation method of high temperature resistant contraction-expansion system for promoting stratum clay modification | |
| CN104087271A (en) | Compound polyamine shale inhibitor for drilling fluid and preparation method thereof | |
| CN102899006A (en) | Phosphonic acid group-containing polymer drilling fluid viscosity reducer and preparation method thereof | |
| CN106866506B (en) | N-heterocyclic quaternary ammonium salt cationic anti-swelling clay stabilizer and synthesis method thereof | |
| CN103421137B (en) | The preparation method of high temperature resistance polyacrylamide for oil displacement | |
| CN113896831B (en) | A double-effect inhibitor for natural gas hydrate drilling fluid and its preparation method and application | |
| CN103554357A (en) | Polymer-ionic liquid compounded clay stabilizer and synthesis method thereof | |
| CN105505341A (en) | Clay anti-swelling agent | |
| CN104059625A (en) | Method for preparing high-stability heat-resistance and salt-tolerance air foam oil displacing agent | |
| CN104371687A (en) | Clay stabilizer for oil fields | |
| CN106608949B (en) | A kind of clay stabilizer and preparation method thereof | |
| CN104449599A (en) | Anti-swelling agent for clay | |
| CN103396782A (en) | anti-swelling agent for acidification and preparation method thereof | |
| CN103497288B (en) | A kind of AM/AA/HMDAAC/A-β-CD multipolymer and preparation method thereof | |
| CN101892041A (en) | A ASP flooding system based on hydrophobic association polymer | |
| CN109554170B (en) | Calcium-resistant high-temperature-resistant drilling fluid filtrate reducer and preparation method thereof | |
| CN104140801B (en) | A kind of alumina gel profile control agent and preparation method thereof | |
| CN108192584A (en) | A kind of preparation method of temperature resistance salt tolerant displacement of reservoir oil foaming agent | |
| CN111925477B (en) | Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution | |
| CN108117861A (en) | A kind of anticalcium salt drilling fluid fluid loss additive and preparation method | |
| CN103541701B (en) | For improving the flooding method of high-temperature oil reservoir tertiary oil recovery rate | |
| CN114644914B (en) | Oilfield depressurization injection increasing agent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
|
| CP01 | Change in the name or title of a patent holder |