CN101717625A - Clay stabilizing agent suitable for low-permeability oil pool - Google Patents
Clay stabilizing agent suitable for low-permeability oil pool Download PDFInfo
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- CN101717625A CN101717625A CN200910223281A CN200910223281A CN101717625A CN 101717625 A CN101717625 A CN 101717625A CN 200910223281 A CN200910223281 A CN 200910223281A CN 200910223281 A CN200910223281 A CN 200910223281A CN 101717625 A CN101717625 A CN 101717625A
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- oil field
- clay stabilizer
- ammonium chloride
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Abstract
The invention discloses a clay stabilizing agent suitable for low-permeability oil pool, which comprises the following materials in percentage by weight: 0.8-98% of (2-hydroxyethyl)trimethylammonium chloride, 0-20% of inorganic salt containing ammonium or potassium ions, and the balance of tap water or oil field return water. The clay stabilizing agent effectively prevents the clay from swelling, can achieve the anti-swelling rate more than 90 percent, has good compatibility with HPAM-containing oil field return water without generating floccules and low damage rate of an oil field and is suitable for the low-permeability oil pool developed by infusing the HPAM-containing oil field return water.
Description
Technical field:
The present invention relates to a kind of clay stabilizer that low-permeability oil pool argillaceous uses.
Background technology:
Low-permeability oil pool in the oilfield development process contains clay mineral usually, has water sensitivity.Its CLAY MINERALS AND THEIR SIGNIFICANCE is because of expanding, disperse, migration, stopping up pore constriction, makes originally that lower rate of permeation descends significantly, and this not only influences the production capacity of oil well but also the exploitation in oil field later stage is caused extremely bad irreversible influence.
Injecting clay stabilizer is the effective ways of protection water-sensitive oil reservoir.The widely used cationic polymers type clay stabilizer in the oil field in recent years, its positive charge density height, consumption is few, and effect is lasting.But this class clay stabilizer molecular weight is big, though can reach anti-swollen stable purpose, LOW PERMEABILITY RESERVOIR is produced very big injury, stops up pore constriction.In addition, when the clay stabilizer that molecular weight is bigger mixed with the oil field return water that contains HPAM (polyacrylamide), the HPAM in the return water of oil field separated out, and causes and injects the water muddiness, make the injection deteriorating water quality, can occur problems such as water injection pressure raises, well is shorted equally.Therefore contain the hyposmosis water-sensitive oil reservoir of HPAM oil field return water exploitation for notes, need a kind ofly can effectively prevent clay swelling and contain the good clay stabilizer of HPAM oilfield sewage compatibleness.
Summary of the invention:
Technical problem to be solved by this invention is at ubiquitous problem in the prior art, provide a kind of and can effectively prevent clay swelling, and and to contain HPAM oil field return water compatibleness good, be applicable to the clay stabilizer of annotating the low-permeability oil pool that contains the return water exploitation of HPAM oil field.
For achieving the above object, technical scheme of the present invention is:
A kind of clay stabilizer that is applicable to low-permeability oil pool, make by following component raw material by mass percentage:
2-hydroxyethyl trimethyl ammonium chloride 0.8～98%
The inorganic salt 0～20% that contain ammonium or potassium ion
Surplus is tap water or oil field return water
Ammonium ion wherein or potassium ion inorganic salt are a kind of of Repone K, ammonium chloride, potassium formiate, ammonium formiate, potassium acetate, ammonium acetate, saltpetre.
Preferred ammonium ion or potassium ion inorganic salt wherein are a kind of in Repone K or the potassium formiate.
Preferably be applicable to the clay stabilizer of low-permeability oil pool, its composition and mass percent are as follows:
2-hydroxyethyl trimethyl ammonium chloride 30～40%
The inorganic salt 5～15% that contain ammonium or potassium ion
Surplus is tap water or oil field return water
More preferably the composition of this clay stabilizer and mass percent are as follows:
2-hydroxyethyl trimethyl ammonium chloride 30%
Repone K 10%
Tap water or oil field return water 60%
Clay stabilizer of the present invention, when being applied to the water drive operation of hyposmosis water-sensitive oil reservoir, only need clay stabilizer of the present invention and oil field return water are mixed by a certain percentage, the 2-hydroxyethyl trimethyl ammonium chloride in the typical oilfield return water and the mass percent concentration of sylvite or ammonium salt are 0.8～2.5%.
2-hydroxyethyl trimethyl ammonium chloride in the present invention's prescription, contain strong polar group (hydroxyl) in its structure, its handling characteristics is can arbitrary proportion miscible with water, good with the compatibleness of the oil field return water that contains HPAM, after HPAM in the sewage and 2-hydroxyethyl trimethyl ammonium chloride electrically neutralize, still can be dissolved in the water, not occur floss in the water; Again because the molecular weight (139.5) of 2-hydroxyethyl trimethyl ammonium chloride is very little, the 2-hydroxyethyl trimethyl ammonium chloride of unit mass contains more positive charge, under the unit mass concentration, it has charge neutrality ability preferably, thereby have and prevent the clay swelling ability preferably, 2-hydroxyethyl trimethyl ammonium chloride is a strong polar molecule positively charged, that contain hydroxyl, has the effect of bond clay particulate, can prevent the migration of clay particle.So when containing the oil field return water of clay stabilizer of the present invention and entering the oil reservoir that contains clay, can suppress clay swelling, the protection oil reservoir.
Technique effect of the present invention is:
1, clay stabilizer involved in the present invention is anti-swollen effective, and anti-swollen rate can reach more than 90%.
2, clay stabilizer involved in the present invention and to contain HPAM oil field return water compatibleness good does not produce floss.
3, clay stabilizer involved in the present invention is low to the injury rate of oil reservoir, is applicable to LOW PERMEABILITY RESERVOIR.
4, clay stabilizer colorless and odorless involved in the present invention, nontoxic, stable in properties.
5, clay stabilizer good weatherability involved in the present invention, acid and alkali-resistance, good water solubility is convenient to rig-site utilization.
Embodiment:
Embodiment 1
At 10m
3The liquid 2-hydroxyethyl trimethyl ammonium chloride that adds 5.7 ton 70% in the mixing tank adds 4.3 tons of tap water again, mixes, and filtering and obtaining solid content is 10 tons of 40% clay stabilizer products.
Wherein 2-hydroxyethyl trimethyl ammonium chloride is commonly called as and is choline chloride 60, and 70% liquid 2-hydroxyethyl trimethyl ammonium chloride is that commercially available technical grade product gets final product.
During use, be mixed with and contain the clay stabilization agent solution that above-mentioned clay stabilizer product is respectively 2%, 3%, 4%, 5%, 6% (mass percent) with containing HPAM oil field return water, its anti-swollen rate sees Table 1.
Anti-swollen rate is measured with reference to SY/T 5971-94 water filling and is measured with the clay stabilizer evaluation method.
Table 1 embodiment 1 clay stabilization agent solution is prevented swollen rate
| Mass concentration/% | ??2 | ??3 | ??4 | ??5 | ??6 |
| Anti-swollen rate/% | ??63.7 | ??75.1 | ??84.9 | ??88.7 | ??90.3 |
The anti-swollen rate of regulation clay stabilizer was considered as reaching requirement greater than 60% o'clock, by table 1 as seen, used 2-hydroxyethyl trimethyl ammonium chloride can satisfy anti-swollen requirement separately.
Especially when above-mentioned clay stabilization agent solution was 6%, anti-swollen rate reached 90.3%.
Embodiment 2
At 10m
3The Klorvess Liquid that adds 5 ton 20% in the mixing tank; The liquid 2-hydroxyethyl trimethyl ammonium chloride that adds 4.3 ton 70% again adds 0.7 ton of tap water again, mixes, and filtering and obtaining solid content is 10 tons of 40% clay stabilizers.
20% Klorvess Liquid: it is formulated that commercially available technical grade solid Repone K adds tap water.
With reference to the using method of embodiment 1, preparation contains the clay stabilization agent solution that above-mentioned clay stabilizer is respectively 2%, 3%, 4%, 5%, 6% (mass percent) respectively, and its anti-swollen rate sees Table 2.
Table 2 embodiment 2 clay stabilization agent solutions are prevented swollen rate
| Mass concentration/% | ??2 | ??3 | ??4 | ??5 | ??6 |
| Anti-swollen rate/% | ??67.9 | ??80.6 | ??88.6 | ??91.4 | ??92.5 |
As can be seen from Table 2, the composite clay stabilization agent solution of inorganic salt Repone K, its anti-swollen rate is better than embodiment 1 product.
It is mutually collaborative that its principle is that Repone K and 2-hydroxyethyl trimethyl ammonium chloride have, the effect that complements each other.Potassium ion enters and plays antiexpanding action between clay seam, and 2-hydroxyethyl trimethyl ammonium chloride plays the effect of charge neutralization in the clay particle periphery, thereby reaches anti-swollen purpose, and under two kinds of composition synergies, product has higher anti-swollen rate.
Embodiment 3
At 10m
3The ammonium chloride solution that adds 7.0 ton 27% in the mixing tank; The liquid 2-hydroxyethyl trimethyl ammonium chloride that adds 3.0 ton 70% again mixes, and filtering and obtaining solid content is 10 tons of 40% clay stabilizers.
27% ammonium chloride solution: it is formulated that commercially available technical grade solid ammonium chloride adds tap water.
With reference to the using method of embodiment 1, preparation contains the clay stabilization agent solution that above-mentioned clay stabilizer is respectively 2%, 3%, 4%, 5%, 6% (mass percent) respectively, and its anti-swollen rate sees Table 3.
Table 3 embodiment 3 clay stabilization agent solutions are prevented swollen rate
| Mass concentration/% | ??2 | ??3 | ??4 | ??5 | ??6 |
| Anti-swollen rate/% | ??60.7 | ??74.6 | ??80.7 | ??85.1 | ??88.0 |
As can be seen from Table 3, composite embodiment 3 products of ammonium chloride, its anti-swollen rate also can satisfy anti-swollen requirement.Also there are synergy in ammonium chloride and 2-hydroxyethyl trimethyl ammonium chloride.
Embodiment 4
Clay stabilizer is formed and proportioning: 0.16 ton 50% 2-hydroxyethyl trimethyl ammonium chloride, 9.84 tons of oil field return waters.
This clay stabilizer is directly applied to the water drive operation of hypotonic water-sensitive oil reservoir, and measuring anti-swollen rate is 63.7%, satisfies anti-swollen requirement.
Embodiment 5
Clay stabilizer is formed and proportioning: the solid 2-hydroxyethyl trimethyl ammonium chloride of mass percent concentration 98%.
With reference to the using method of embodiment 1, be mixed with and contain the clay stabilization agent solution that above-mentioned clay stabilizer is 0.8% (mass percent).
Measuring anti-swollen rate is 63.0%.
Embodiment 6
The anti-swollen rate contrast of the clay stabilizer that table 4 different quality constitutes
| Clay stabilizer is formed and proportioning | 5 ton 70% 2-hydroxyethyl trimethyl ammonium chloride; 2.5 the Klorvess Liquid of ton 20%; 2.5 ton tap water. | 5 ton 70% 2-hydroxyethyl trimethyl ammonium chloride; 2.5 the Klorvess Liquid of ton 20%; 2.5 ton oil field return water. |
| Clay stabilizer strength of solution/% | 2 | 2 |
| Anti-swollen rate/% | 66.7 | 67.1 |
As can be known from the above table, use the clay stabilizer of oil field return water preparation, because it is the salinity of oil field return water is higher, favourable to improving anti-swollen effect.
Embodiment 7
The clay stabilizer that different inorganic salt constitute with reference to the using method of embodiment 1, is mixed with and contains the clay stabilization agent solution that following clay stabilizer is 5.0% (mass percent), and its anti-swollen rate sees Table 5.
The anti-swollen rate of the clay stabilizer that the different inorganic salt of table 5 constitute
| Clay stabilizer | The potassium formiate of 30% A 10%; Surplus is a tap water. | 30% A; 10% ammonium formiate; Surplus is a tap water. | 30%A; 10% potassium acetate; Surplus is a tap water. | 30% A; 10% ammonium acetate; Surplus is a tap water. | 30% A; 10% saltpetre; Surplus is a tap water. |
| Anti-swollen rate % | 90.6 | 84.3 | 87.5 | 81.9 | 87.1 |
Annotate: the A in the table 5 represents 2-hydroxyethyl trimethyl ammonium chloride.
As can be seen from Table 5, potassium formiate, ammonium formiate, potassium acetate, ammonium acetate, saltpetre all can with the compound use of 2-hydroxyethyl trimethyl ammonium chloride.Wherein the effect of sylvite is better than ammonium salt.
Embodiment 8
PDMDAAC (Poly Dimethyl Diallyl Ammonium Chloride) is the widely used a kind of polyquaternium type clay stabilizer in oil field.Get PDMDAAC (solid content 37% respectively; Intrinsic viscosity 145mL/g), each 10.0g of clay stabilizer of making of embodiment 1 and embodiment 2, take again that six dark sewage plants contain HPAM oil field return water 190g in the Daqing oil field oil extraction No.1 Factory, being mixed with the argillaceous stablizer is the clay stabilization agent solution of 5% (mass percent), and the anti-swollen rate of PDMDAAC clay stabilization agent solution at this moment is 84.7%; After stirring 30min, with 0.45 μ m membrane filtration, the oven dry constant weight, the suspension content of its appearance sees Table 6.Suspension content is measured with reference to SY/T 5329-94.
Suspension content after the adding clay stabilizer in table 6 sewage
| The clay stabilizer kind | ??PDMDAAC | Embodiment 1 product | Embodiment 2 products |
| Suspension content/mgL -1 | ??101.4 | ??7.5 | ??9.6 |
As can be seen from Table 6, clay stabilizer of the present invention and contain HPAM oil field return water good compatibleness is arranged.Though charge neutralization exists, and can not cause separating out of HPAM.
Embodiment 9
Investigate clay stabilizer of the present invention to the core damage situation with reference to SY/T 5358-2002 reservoir flowrate test evaluation method.
With extracting, survey air K
gRock core pack in the flooding test device, 45 ℃ of simulated formation temperature are injected the smart filter of 2PV salt solution, treat pressure-stabilisation after, measure flow, record pressure reduction calculates rate of permeation K
1Change and annotate mass concentration 5.0% clay stabilization agent solution, behind the injection 5PV, change and inject water, behind the injection 5PV, measurement of discharge and pressure reduction calculate rate of permeation K
2
Core damage rate D
kCalculation formula: D
k=(1-K
2/ K
1) * 100%
Select PDMDAAC, embodiment 1 product and embodiment 2 products for use, be made into the oil field return water respectively that to contain the clay stabilizer mass concentration be 5% solution; Use grand celebration Sa zero group rock core, inject smart filter salt solution, clay stabilization agent solution and oil field return water successively,, investigate 3 kinds of clay stabilizers low permeability cores adaptability according to the variation of core permeability.Test-results sees Table 7.
3 kinds of clay stabilizer core flow tests of table 7 result
As can be seen from Table 7, not with clay stabilizer, directly oiling field return water exploitation, the core damage rate is very big, reaches 82.63%; Static anti-swollen test effect is PDMDAAC preferably, and in core flow test, the injury that low permeability cores is caused is bigger.This is because PDMDAAC has very big hydrodynamic volume, has stopped up pore throat; On the other hand, its molecular diffusion speed of PDMDAAC is slower, and preferential the contact with clay mineral of water molecules causes hydration swelling, causes core permeability to descend.And less embodiment 1 and embodiment 2 products of molecular weight are less to the injury of low permeability cores, and the injury rate only is 17.85% and 16.45%, illustrates that clay stabilizer of the present invention has adaptability preferably for LOW PERMEABILITY RESERVOIR.
By above embodiment and description of test clay stabilizer of the present invention have and prevent the clay swelling ability preferably, the oilfield sewage that less and grand celebration contains HPAM to the injury rate of the lower grand celebration Sa zero group rock core of rate of permeation has compatibleness preferably.The present invention provides a kind of clay stabilizer product of excellent property for developing low-permeability oil deposit argillaceous.
Claims (4)
1. clay stabilizer that is applicable to low-permeability oil pool, make by following component raw material by mass percentage:
2-hydroxyethyl trimethyl ammonium chloride 0.8～98%
The inorganic salt 0～20% that contain ammonium or potassium ion
Surplus is tap water or oil field return water
The inorganic salt that wherein contain ammonium or potassium ion are a kind of of Repone K, ammonium chloride, potassium formiate, ammonium formiate, potassium acetate, ammonium acetate or saltpetre.
2. according to the described clay stabilizer that is applicable to low-permeability oil pool of claim 1, the inorganic salt that contain ammonium or potassium ion wherein are a kind of in Repone K or the potassium formiate.
3. according to the described clay stabilizer that is applicable to low-permeability oil pool of claim 1, its composition and mass percent are as follows:
2-hydroxyethyl trimethyl ammonium chloride 30～40%
The inorganic salt 5～15% that contain ammonium or potassium ion
Surplus is tap water or oil field return water
4. according to the described clay stabilizer that is applicable to low-permeability oil pool of claim 1, its composition and mass percent are as follows:
2-hydroxyethyl trimethyl ammonium chloride 30%
Repone K 10%
Tap water or oil field return water 60%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910223281A CN101717625A (en) | 2009-11-23 | 2009-11-23 | Clay stabilizing agent suitable for low-permeability oil pool |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910223281A CN101717625A (en) | 2009-11-23 | 2009-11-23 | Clay stabilizing agent suitable for low-permeability oil pool |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643634A (en) * | 2012-04-24 | 2012-08-22 | 段华生 | Dual-core copolymerized clay stabilizer and preparation method thereof |
| CN102838972A (en) * | 2012-08-17 | 2012-12-26 | 中国石油天然气股份有限公司 | Clay stabilizer special for huff and puff of rocket power compound heat carrier |
| CN104531127A (en) * | 2014-12-23 | 2015-04-22 | 克拉玛依新科澳石油天然气技术股份有限公司 | Scale inhibition clay stabilizer |
| CN105925251A (en) * | 2016-05-10 | 2016-09-07 | 重庆鼎顺隆能源技术有限责任公司 | Environment-friendly clay stabilizer |
| CN106202695A (en) * | 2016-07-07 | 2016-12-07 | 龙威 | A kind of method using digital cores simulation to calculate core permeability |
| CN108977190A (en) * | 2017-06-05 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of small molecule liquid expansion-resisting agent, pressure break anti-clayswelling agent and preparation method |
| CN109735313A (en) * | 2019-02-28 | 2019-05-10 | 青岛海石元创石油技术有限公司 | Petroleum drilling and mining for clay interface is stabilizing agent specially used and preparation method thereof |
| CN110105928A (en) * | 2019-05-08 | 2019-08-09 | 成都碧隆双田化工科技有限公司 | A kind of environment-friendlysticky sticky soil stabilizer of oil field low molecular weight and preparation method thereof |
| 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 |
-
2009
- 2009-11-23 CN CN200910223281A patent/CN101717625A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643634A (en) * | 2012-04-24 | 2012-08-22 | 段华生 | Dual-core copolymerized clay stabilizer and preparation method thereof |
| CN102643634B (en) * | 2012-04-24 | 2014-12-10 | 段华生 | Dual-core copolymerized clay stabilizer and preparation method thereof |
| CN102838972A (en) * | 2012-08-17 | 2012-12-26 | 中国石油天然气股份有限公司 | Clay stabilizer special for huff and puff of rocket power compound heat carrier |
| CN104531127A (en) * | 2014-12-23 | 2015-04-22 | 克拉玛依新科澳石油天然气技术股份有限公司 | Scale inhibition clay stabilizer |
| CN105925251A (en) * | 2016-05-10 | 2016-09-07 | 重庆鼎顺隆能源技术有限责任公司 | Environment-friendly clay stabilizer |
| CN106202695A (en) * | 2016-07-07 | 2016-12-07 | 龙威 | A kind of method using digital cores simulation to calculate core permeability |
| CN108977190A (en) * | 2017-06-05 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of small molecule liquid expansion-resisting agent, pressure break anti-clayswelling agent and preparation method |
| CN108977190B (en) * | 2017-06-05 | 2020-12-25 | 中国石油化工股份有限公司 | Small-molecular liquid anti-swelling agent, clay anti-swelling agent for fracturing and preparation method of clay anti-swelling agent |
| CN109735313A (en) * | 2019-02-28 | 2019-05-10 | 青岛海石元创石油技术有限公司 | Petroleum drilling and mining for clay interface is stabilizing agent specially used and preparation method thereof |
| CN110105928A (en) * | 2019-05-08 | 2019-08-09 | 成都碧隆双田化工科技有限公司 | A kind of environment-friendlysticky sticky soil stabilizer of oil field low molecular weight and preparation method thereof |
| 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 |
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Application publication date: 20100602 |