CN105754579A - Clay anti-swelling and swelling shrinkage agent and preparation method thereof - Google Patents
Clay anti-swelling and swelling shrinkage agent and preparation method thereof Download PDFInfo
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- CN105754579A CN105754579A CN201610242846.5A CN201610242846A CN105754579A CN 105754579 A CN105754579 A CN 105754579A CN 201610242846 A CN201610242846 A CN 201610242846A CN 105754579 A CN105754579 A CN 105754579A
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- 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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- 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
- C09K8/608—Polymer compositions
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- 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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- 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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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Abstract
The invention provides a clay anti-swelling and swelling shrinkage agent and a preparation method thereof.The clay anti-swelling and swelling shrinkage agent is used for oilfield acidification and water injection.The anti-swelling and swelling shrinkage agent consists of the following components in percentages by mass: 20%-30% of alkylated polyether amine, 2%-5% of polyethylenimine, 20-35% of acid and the balance of water, and the sum of mass percentages of the components is 100%.The anti-swelling rate of the anti-swelling and swelling shrinkage agent can reach 92.8%, and the swelling shrinkage rate of the anti-swelling and swelling shrinkage agent can reach 46.1%.The clay anti-swelling and swelling shrinkage agent is good in temperature resistance and excellent in anti-swelling endurance property, is suitable to be used in acidification and water injection, and is used for protecting permeability of a reservoir.
Description
Technical field:
The present invention relates to a kind of anti-clayswelling and contract swollen dose and preparation method thereof, it is adaptable to acidifying the injecting process.
Background technology:
Acidifying is Oil/gas Well stable yields, volume increase, water injection well blood pressure lowering, augmented injection one of main technique measure, purpose is by acid solution flowing in the intergranular of formation pore, hole and microcrack and reaction, dissolve the near wellbore stratum various solid phase particles in the processes such as drilling well, completion, well workover and water filling, impurity, release its injury to in-place permeability, dredging fluid neuron network passage, thus recovering and improving well capacity.But the clay mineral that in stratum, ubiquitous clay mineral especially water sensitivity is strong (such as montmorillonite, illite/smectite mixed layer mineral etc.) can cause the secondary injury on stratum in acidization, reduce in-place permeability.In order to protect the permeability of oil and gas reservoir, it is necessary to use clay stabilizer to process the clay in stratum, to reduce the phenomenons such as the hydration swelling of clay mineral, particle migration, protect reservoir permeability.The inorganic agent that can prevent swelling clay mineral is anti-soil adhesion extender (expansion-resisting agent), can prevent the inorganic agent that small bits of clay is migrated is anti-soil adhesion fine migration agent (anti-migration agent), the clay mineral intergranular expanded can be made from the shrinkage agent for swelled clay reducing, reducing swell increment, belong to clay stabilizer.
Clay stabilizer can be divided into three major types according to the difference of chemical composition: (1) inorganic salts clay stabilizer；(2) organic cation class clay stabilizer；(3) organic polymer class clay stabilizer.Wherein the resistance to erosion ability of inorganic salts clay stabilizer is weak, organic cation class clay stabilizer resistance to erosion but stratum wettability can be changed, the use scope of organic polymer class clay stabilizer is wide, and stablizing effect is good, long action time, and the ability of antiscour is stronger.Organic polymeric clay stabilizer conventional both at home and abroad is mainly organic cation type polymer, can be divided into polyquaternary ammonium salt, poly-quaternary phosphonium salt and poly-tertiary sulfosalt three class by contained cationic difference.The wide variety of cationic clay stabilizer in domestic scene has polyepichlorohydrin-dimethylamine, poly-trimethylallylammonium chloride, PDDA and acrylamide, dimethyl diallyl ammonium chloride, acrylamide oxy-ethyl-trimethyl salmiac copolymer etc..But the heat resistance of these clay stabilizers is general, temperature higher than 100 DEG C after effect substantially reduce, simultaneously conventional clay stabilizer does not possess the swollen performance of contracting, improves effect for the permeability of low permeability reservoir not notable.Therefore developing one not only high temperature resistant but also resistance to erosion, the anti-clayswelling that the clay particle expanded also can have swollen effect of substantially contracting simultaneously contracts swollen dose, and to reducing, reservoir damage in operation process is significant.
Summary of the invention:
For the deficiencies in the prior art, the invention aims to provide a kind of anti-clayswelling to contract swollen dose, be mainly used in acidifying water filling, reduce reservoir damage.
The purpose of the present invention realizes by techniques below scheme:
Described Swelling-resistant shrinking and swelling agent, includes following component according to mass percent:
Alkylation polyetheramine 20%～30%；
Polyethyene diamine 2%～5%；
Acid 20%～35%；
Water surplus,
The mass percentage content sum of above-mentioned each component is 100%.
Wherein, the structure of described alkylation polyetheramine is
In formula, R is C2H4, R1C for straight or branched1To C4Alkyl, x=1～6.
Described acid includes but not limited to: at least one in hydrochloric acid, formic acid and acetic acid, is used for neutralizing organic diamine, makes the pH of Swelling-resistant shrinking and swelling agent system in 4～8 scopes.
The Swelling-resistant shrinking and swelling agent system of present invention performance when pH value is 4 is more excellent.
The contract preparation method of swollen dose of above-mentioned anti-clayswelling realizes as follows:
1, mass concentration alkylation polyetheramine in 20%～30% scope is prepared with deionized water, adding acid for adjusting pH value on request, this is exothermic reaction, needs to control system temperature at 45 DEG C～50 DEG C in acid adding process, regulating pH value is 4～8, continues stirring system 0.5～1h.
2, polyethyene diamine is added in above-mentioned joined alkylation polyether amine solution to fully dissolving, wherein polyethyene diamine is 1 6～1 10 with the mass ratio of alkylation polyetheramine, continues stirring system 1h, makes temperature control at 40 DEG C～45 DEG C, obtain light yellow transparent liquid, be the target product of the present invention.
The invention has the beneficial effects as follows:
1, the alkyl, polyether amine used due to the present invention is used in conjunction with producing synergism with polyethyene diamine, little compared with alkyl, polyether amine of the molecular weight of polyethyene diamine and molecular size, can enter between the crystal layer of clay mineral, form monolayer adsorption and can discharge part intermediary water, there is the swollen effect of contracting；Both can pass through hydrogen bond action adsorbing clays crystal layer surface simultaneously, and the negative charge in electrostatic interaction and clay crystal layer surface can be passed through in the ammonium cation of dissociation in water, reduce clay aquation repulsion, decrease the formation of surface of clay hydration shell, it is prevented that clay continues hydration swelling；The combined effect of alkylation polyetheramine and polyethyene diamine make between clay crystal layer discharge absorption water will more than being used alone one of which material, it is more tight that the two combined effect arranges between clay crystal layer surface and crystal layer, add the hydrophobicity of surface of clay, prevent the further aquation of clay, simultaneously work as the not only anti-swollen but also swollen effect that contracts.
2, compared with domestic widely used cationic clay stabilizer, the molecular weight of the Swelling-resistant shrinking and swelling agent used by the present invention is little, it is possible to effectively reduce the risk of the low permeability reservoir hole throat blocking that high molecular clay stabilizer causes；Clay stabilizer preparation used by the present invention is simple simultaneously, good with formation water compatibility, and the pH scope being suitable for is wide, also has good compatibility with fracturing fluid, and relatively low working concentration can reach the good swollen effect of anti-swollen contracting.
Detailed description of the invention:
The present invention is further illustrated below by detailed description of the invention.
In order to be more clearly understood from the present invention, now specific embodiments of the present invention are explained in detail, but institute of the present invention protection domain is not limited only to this.
Below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1:
A kind of anti-clayswelling contracts swollen dose, and the weight/mass percentage composition of its component is:
Alkylation polyetheramine 20%, structure is
Polyethyene diamine 2%；
Acid 20%；
Water 58%.
R in abovementioned alkyl polyetheramine is C2H4, R1For C2Alkyl, x=2；Acid is the hydrochloric acid of 37% for mass concentration.First 116g deionized water is added in three mouthfuls of beakers, being warmed up to 45 DEG C, be subsequently adding 40g alkylation polyetheramine, stirring is to fully dissolving, it is subsequently adding 40g hydrochloric acid, continue stirring 0.5h, the pH of solution in 6～7 scopes (because acid has loss in the process weighed and drip, preparation solution ph is not fixed every time), add 4g polyethyene diamine, stirring, to fully dissolving, is stirred 1h at 45 DEG C, is obtained light yellow transparent liquid.
Testing room temperature with through 130 DEG C according to oil and gas industry standard SY/T5971-94, the swollen effect of anti-swollen contracting of sample after 36h heat treatment, and anti-swollen persistency (the water-fast brush performance) effect under room temperature, result of the test is in Table 1, table 2.
Embodiment 2:
A kind of anti-clayswelling contracts swollen dose, its constituent content mass percent:
Alkylation polyetheramine 25%, structural formula is
Polyethyene diamine 3%；
Acid 25%；
Water 47%.
R in abovementioned alkyl polyetheramine is C2H4, R1For C3Straight chained alkyl, x=3；Acid is the hydrochloric acid of 37% for mass concentration.First 94g deionized water is added in three mouthfuls of beakers, it is warmed up to 45 DEG C, being subsequently adding 50g alkylation polyetheramine, stirring, to fully dissolving, is subsequently adding 50g hydrochloric acid, continue stirring 0.5h, the pH of solution, in 5～6 scopes, adds 6g polyethyene diamine, and stirring is to fully dissolving, at 40 DEG C, stir 1h, obtain light yellow transparent liquid.
Testing room temperature with through 130 DEG C according to oil and gas industry standard SY/T5971-94, the swollen effect of anti-swollen contracting of sample after 36h heat treatment, and anti-swollen persistency (the water-fast brush performance) effect under room temperature, result of the test is in Table 1, table 2.
Embodiment 3:
A kind of anti-clayswelling contracts swollen dose, its constituent content mass percent:
Alkylation polyetheramine 30%, structural formula is
Polyethyene diamine 5%；
Acid 33%；
Water 32%.
R in abovementioned alkyl polyetheramine is C2H4, R1For C4Straight chained alkyl, x=4；Acid is the hydrochloric acid of 37% for mass concentration.First 64g deionized water is added in three mouthfuls of beakers, it is warmed up to 50 DEG C, being subsequently adding 60g alkylation polyetheramine, stirring, to fully dissolving, is subsequently adding 66g hydrochloric acid, continue stirring 0.5h, the pH of solution, in 4～5 scopes, adds 10g polyethyene diamine, and stirring is to fully dissolving, at 45 DEG C, stir 1h, obtain light yellow transparent liquid.
Testing room temperature with through 130 DEG C according to oil and gas industry standard SY/T5971-94, the swollen effect of anti-swollen contracting of sample after 36h heat treatment, and anti-swollen persistency (the water-fast brush performance) effect under room temperature, result of the test is in Table 1, table 2.
The swollen performance evaluation of swollen contracting prevented by table 1
| Swelling-resistant shrinking and swelling agent | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Anti-dilative/% | 91.3 | 92.4 | 92.8 |
| Contract swollen rate/% | 45.2 | 45.7 | 46.1 |
| 130 DEG C, the anti-dilative/% after 36h process | 90.8 | 91.2 | 91.5 |
The above results shows, clay stabilizer provided by the invention has the good anti-swollen and swollen effect that contracts, and heat resistance is good simultaneously.
Table 2 acidifying water filling Swelling-resistant shrinking and swelling agent flushing resistance is evaluated
In table, KBL-1 is the Cationic Polymers Containing Quaternary Ammonium Salts that the triumphant Bora Environmental Protection Technology Co., Ltd in Zhangjiagang produces.D230 is polyetheramine D230.
The above results shows, Swelling-resistant shrinking and swelling agent provided by the invention has good resistance to erosion and heat resistance, is suitable for 130 DEG C of formation temperatures, and anti-swollen enduring quality is excellent, have great importance for reducing reservoir damage.
Claims (3)
1. an anti-clayswelling contracts swollen dose, it is characterized in that including following component according to mass percent:
Alkylation polyetheramine 20%～30%；
Polyethyene diamine 2%～5%；
Acid 20%～35%；
Water surplus,
The mass percentage content sum of above-mentioned each component is 100%；
Wherein, the structure of described alkylation polyetheramine is
In formula, R is C2H4, R1C for straight or branched1～C4Alkyl, x=1～6；
Described acid is at least one in hydrochloric acid, formic acid and acetic acid.
2. anti-clayswelling according to claim 1 contracts swollen dose, it is characterized in that pH=4～8 of this Swelling-resistant shrinking and swelling agent.
3. anti-clayswelling as claimed in claim 1 is contracted the preparation method of swollen dose, it is characterized in that realizing as follows:
(1) preparing, with deionized water, the alkylation polyetheramine that mass concentration is 20%～30%, adding acid for adjusting pH value is 4～8, needs to control system temperature at 45 DEG C～50 DEG C, stir 0.5～1h in acid adding process；
(2) polyethyene diamine is added in abovementioned alkyl polyether amine solution to fully dissolving, wherein polyethyene diamine is 1 6～1 10 with the mass ratio of alkylation polyetheramine, continues stirring 1h, makes temperature control at 40 DEG C～45 DEG C, obtain light yellow transparent liquid, be the target product of the present invention.
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| CN201610242846.5A CN105754579A (en) | 2016-04-19 | 2016-04-19 | Clay anti-swelling and swelling shrinkage agent and preparation method thereof |
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| CN201610242846.5A CN105754579A (en) | 2016-04-19 | 2016-04-19 | Clay anti-swelling and swelling shrinkage agent and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057672A (en) * | 2017-01-06 | 2017-08-18 | 中国海洋石油总公司 | It is acidified water filling Swelling-resistant shrinking and swelling agent and preparation method thereof |
| CN110105930A (en) * | 2019-04-23 | 2019-08-09 | 上海勃利燃气设备有限公司 | A kind of bentonite drilling fluid and preparation method thereof |
| CN110268034A (en) * | 2016-12-09 | 2019-09-20 | 赢创德固赛有限公司 | Shale hydration inhibitor |
| CN112457838A (en) * | 2020-11-25 | 2021-03-09 | 陕西科技大学 | Novel acid-resistant and salt-resistant shrinking and swelling agent and preparation method thereof |
| CN116376528A (en) * | 2023-03-30 | 2023-07-04 | 天津新翔油气技术有限公司 | Anti-swelling shrinkage sand-inhibiting agent, preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110268034A (en) * | 2016-12-09 | 2019-09-20 | 赢创德固赛有限公司 | Shale hydration inhibitor |
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| CN110105930A (en) * | 2019-04-23 | 2019-08-09 | 上海勃利燃气设备有限公司 | A kind of bentonite drilling fluid and preparation method thereof |
| CN110105930B (en) * | 2019-04-23 | 2021-05-07 | 上海勃利燃气设备有限公司 | Bentonite drilling fluid and preparation method thereof |
| CN112457838A (en) * | 2020-11-25 | 2021-03-09 | 陕西科技大学 | Novel acid-resistant and salt-resistant shrinking and swelling agent and preparation method thereof |
| CN112457838B (en) * | 2020-11-25 | 2022-09-20 | 陕西科技大学 | Novel acid-resistant and salt-resistant shrinking and swelling agent and preparation method thereof |
| CN116376528A (en) * | 2023-03-30 | 2023-07-04 | 天津新翔油气技术有限公司 | Anti-swelling shrinkage sand-inhibiting agent, preparation method and application thereof |
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