CN107057661A - Completion fluid environment-friendly type clay expansion-resisting agent and preparation method thereof - Google Patents
Completion fluid environment-friendly type clay expansion-resisting agent and preparation method thereof Download PDFInfo
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- CN107057661A CN107057661A CN201710406233.5A CN201710406233A CN107057661A CN 107057661 A CN107057661 A CN 107057661A CN 201710406233 A CN201710406233 A CN 201710406233A CN 107057661 A CN107057661 A CN 107057661A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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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
- 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 discloses a kind of environment-friendly type clay expansion-resisting agent, include the polymerization species clay expansion-resisting agent of the little molecular cation peptides bioactivator ammonium salts of 35~50 parts by weight, the screener of 5~20 parts by weight and 50~75 parts by weight；Wherein, little molecular cation peptides bioactivator ammonium salt uses relative molecular mass≤200 that carbon number is made for the organic amine neutralization reaction that C1~C6 organic acid and carbon number is C2~C6；The screener is from the long-chain fat amine that carbon number is C12~C18；The polymerization species clay expansion-resisting agent is polyethylene polyamines, polyaminoacid or modified starch；And formed by reacting to be mixed with successively；The completion fluid environment-friendly type clay expansion-resisting agent heatproof temperature is 100~140 DEG C, can significantly improve the system clay such as well killing fluid, workover fluid, acidifying solution, fracturing fluid and prevent swollen performance, while good with the other additive compatibilities of system；When addition is 1wt% in system, anti-dilative is more than 90%, shows that good clay prevents swollen performance, and half lethal concentration LC50 is more than 10000mg/L, and good environmental-protecting performance is shown to ecological environment.
Description
Technical field
The present invention relates to Well Completion Engineering of Oil Reservoirs technical field, more particularly to a kind of completion fluid environment-friendly type clay expansion-resisting agent and its system
Preparation Method.
Background technology
The working solution used in completion practice referred to as completion fluid.Such as well killing fluid, fills for balancing formation fluid pressure
The working solution filled out in pit shaft；Such as workover fluid, the operation liquid safeguarded with recompletion is repaired for underground equipment；Such as pressure break
Liquid, for pressing off reservoir rock crack with reach volume increase purpose liquid；Such as acidifying solution, working solution during for being acidified.
According to the selection and design of completion fluid set type, our general requirements are the infringements reduced to oil-gas Layer and ensure underground equipment
With the safety of job execution.In above-mentioned several completion fluid systems, clay expansion-resisting agent can be all used, its effect is mainly control
The expansion of clay particle and scattered.
The clay expansion-resisting agent commonly used in current completion fluid system, which includes quaternary ammonium salt expansion-resisting agent, potassium chloride-poly- ammonium salt class, to be prevented
Swollen dose, ammonium chloride-quaternary ammonium salt expansion-resisting agent etc., they achieve good preventive effect of expansion in system, but there is also certain
The problem of.Being introduced into for such as potassium chloride, ammonium chloride inorganic salts result in the normal chlorion containing higher concentration in completion fluid system
Concentration, the chlorion of high concentration can be combined chloro chemical combination of the generation with the effect such as mutagenesis, carcinogenic with the organic matter in environment
Thing, has a strong impact on ecological environment, although and inorganic salts can temporarily suppress clay swelling, clay salination, secondary dirt can be made
Contaminate environment.In addition, the bio-toxicity of the quaternary ammonium salt expansion-resisting agent of poly- ammonium salt class clay expansion-resisting agent and macromolecule is higher, in environmental protection
The application in future for being increasingly subject to pay attention to can be also restricted.Therefore, urgent need exploitation biological degradability is good, prevent that swollen performance is stable, resistance to
The permanent completion fluid system of warm nature with environment-friendly type clay expansion-resisting agent to solve environmental pollution the problems such as.
The content of the invention
It is an object of the invention to provide a kind of completion fluid that biological degradability is good, anti-swollen performance is stable, temperature tolerance is permanent use
Environment-friendly type clay expansion-resisting agent.
It is a further object of the present invention to provide a kind of preparation method for preparing above-mentioned completion fluid environment-friendly type clay expansion-resisting agent.
Therefore, technical solution of the present invention is as follows：
A kind of completion fluid environment-friendly type clay expansion-resisting agent, including 35~50 parts by weight little molecular cation peptides bioactivator ammonium salt, 5~20
The polymerization species clay expansion-resisting agent of the screener of parts by weight and 50~75 parts by weight；Wherein, the little molecular cation peptides bioactivator ammonium salt is adopted
It is C with carbon number1~C6Organic acid and carbon number be C2~C6Organic amine neutralization reaction be made, and the little molecular cation peptides bioactivator ammonium
Relative molecular mass≤200 of salt；The screener is C from carbon number12~C18Long-chain fat amine；The polymerization species are sticked
Native expansion-resisting agent is polyethylene polyamines, polyaminoacid or modified starch.
It is preferred that, in the organic acid formic acid, acetic acid, ethanedioic acid, maleic acid, tartaric acid, caproic acid and acrylic acid at least
It is a kind of；The organic amine is fatty amine, aliphatic cyclic amine or hydramine；Wherein, fatty amine selects dimethylamine, trimethylamine, diethylamine, three
At least one of ethamine, ethylenediamine, isopropylamine and 2- allylamines；Aliphatic cyclic amine selects diethylenetriamines, triethylenediamine, ring
At least one of aziridine and hexa；Hydramine selects diethanol amine, triethanolamine, 3- Propanolamines, three isopropanols
At least one of amine.
Carbon number is used for C1~C6Organic acid and carbon number be C2~C6Organic amine made from molecular weight no more than 200
Little molecular cation peptides bioactivator ammonium salt, it is compared with clay expansion-resisting agent of the prior art, and the completion fluid is with environment-friendly type clay expansion-resisting agent
Most of cation groups can enter between clay layer, thus with the stronger work for suppressing clay fine migration and expanding
With.
It is preferred that, the screener is lauryl amine, cetylamine, octadecylamine or 20 amine.
It is preferred that, the polyethylene polyamines are ethylenediamine, diethylenetriamines, trien, tetren
Co-product；The polyaminoacid is the one or more in poly-aspartate, polyglutamic acid, polylysine；The modified starch
For hydroxyethyl modified starch or carboxymethyl modified starch.
A kind of preparation method of completion fluid environment-friendly type clay expansion-resisting agent, step is as follows：
S1, little molecular cation peptides bioactivator ammonium salt preparation：In the aqueous solvent that organic amine is dissolved into 2~3 times of organic amine weight
It is diluted, adds 1~2h of stirring under the organic acid of 1.8~3.5 times of organic amine weight, normal temperature, obtain containing small molecule
The mixed solution I of cation ammonium salt；
Wherein, the addition of organic acid is 1.8~3.5 times of organic amine, makes organic amine completely complete with organic acid reaction,
Subsequent processes are not only convenient for simple, while it also avoid the smell that the amine remained occurs in job site.
S2, add into mixed solution I screener and and be added dropwise a small amount of ethanol, continue agitating solution to well mixed, obtain
To mixed solution I I；Wherein, the addition of ethanol is 0.1~0.5wt.% of added aqueous solvent weight in step S1；
S3, add polymerization species clay expansion-resisting agent into mixed solution I I and stir well mixed to solution, obtain sticky
Solid-liquid phase mixture；Solvent in sticky solid-liquid phase mixture is evaporated, that is, obtains the production of environment-friendly type clay expansion-resisting agent solid
Product.
Wherein, the addition weight of the screener and the polymerization species clay expansion-resisting agent is with reference to organic amine weight in step S1
The weight that amount conversion obtains little molecular cation peptides bioactivator ammonium salt is obtained, and makes little molecular cation peptides bioactivator ammonium salt:Screener:It polymerize species clay to prevent
Swollen dose of weight ratio is 35~50:5~20:50~75；And little molecular cation peptides bioactivator ammonium salt, screener, polymerization species clay prevent swollen
The specific composition of agent specific material selected in being formulated with above-mentioned completion fluid with environment-friendly type clay expansion-resisting agent is consistent.
The completion fluid is sticked with environment-friendly type clay expansion-resisting agent using small molecule organic cation ammonium salt, screener and polymerization species
Native expansion-resisting agent is composited；It is free of inorganic salt compound and chlorion in being formulated, it is to avoid three cause effect or clay salination；Together
When, compared with prior art, the environment-friendly type clay expansion-resisting agent product heatproof temperature is 100~140 DEG C, can significantly improve kill-job
The system clay such as liquid, workover fluid, acidifying solution, fracturing fluid prevents swollen performance, while good with the other additive compatibilities of system；When
When addition is 1wt% in system, anti-dilative is more than 90%, shows that good clay prevents swollen performance, and half lethal concentration
LC50 is more than 10000mg/L, and good environmental-protecting performance is shown to ecological environment.
Embodiment
With reference to specific embodiment, the present invention is described further, but following embodiments absolutely not to the present invention have appoint
What is limited.
Embodiment 1
20g ethylenediamines are dissolved in 40g water, adds under 70g acrylic acid, normal temperature and stirs 1h, obtain cation organic ammonium
The mixed solution I of salt；Then 15g cetylamines and 0.2g ethanol are added into mixed solution I, continues agitating solution 30min to mixed
Close uniform, obtain mixed solution I I；The 62g polyethylene polyamines that are added into mixed solution I I simultaneously stir 30min and mixed to solution
Uniformly, sticky solid-liquid phase mixture is obtained；Solvent in sticky solid-liquid phase mixture is evaporated, that is, obtains environment-friendly type clay
Expansion-resisting agent solid product.
Embodiment 2
30g triethylamines are dissolved in 65g water, adds under 60g acetic acid, normal temperature and stirs 2h, obtain cation organic ammonium salt
Mixed solution I；Then the amine of 20g 20 and 0.25g ethanol are added into mixed solution I, continues agitating solution 30min to mixing
Uniformly, mixed solution I I is obtained；The 75g hydroxyethyl modified starch that is added into mixed solution I I and to stir 30min mixed to solution
Close uniform, obtain sticky solid-liquid phase mixture；Solvent in sticky solid-liquid phase mixture is evaporated, that is, obtains environment-friendly type and sticks
Native expansion-resisting agent solid product.
Embodiment 3
18g trimethylamines are dissolved in 65g water, adds under 60g maleic acids, normal temperature and stirs 1h, obtain cation organic ammonium
The mixed solution I of salt；Then 5g octadecylamines and 0.3g ethanol are added into mixed solution I, continues agitating solution 30min to mixing
Uniformly, mixed solution I I is obtained；The 55g poly-aspartates that are added into mixed solution I I and to stir 30min equal to solution mixing
It is even, obtain sticky solid-liquid phase mixture；Solvent in sticky solid-liquid phase mixture is evaporated, that is, obtains environment-friendly type clay and prevents
Swollen dose of solid product.
Embodiment 4
30g triethylenediamines are dissolved in 90g water, 80g ethanedioic acids are added, 1.5h are stirred under normal temperature, obtain sun from
The mixed solution I of sub- organic ammonium salt；Then 10g cetylamines and 0.1g ethanol are added into mixed solution I, continues agitating solution
30min obtains mixed solution I I to well mixed；The 65g polyethylene polyamines that are added into mixed solution I I simultaneously stir 30min extremely
Solution is well mixed, and obtains sticky solid-liquid phase mixture；Solvent in sticky solid-liquid phase mixture is evaporated, that is, obtains ring
Guarantor's type clay expansion-resisting agent solid product.
Embodiment 5
25g diethylamine is dissolved in 60g water, adds under 65g acetic acid, normal temperature and stirs 1h, obtain cation organic ammonium salt
Mixed solution I；Then 15g octadecylamines and 0.2g ethanol are added into mixed solution I, continues agitating solution 30min to mixing
Uniformly, mixed solution I I is obtained；The 50g polyethylene polyamines that are added into mixed solution I I and to stir 30min equal to solution mixing
It is even, obtain sticky solid-liquid phase mixture；Solvent in sticky solid-liquid phase mixture is evaporated, that is, obtains environment-friendly type clay and prevents
Swollen dose of solid product.
Performance test：
Respectively environment-friendly type clay expansion-resisting agent solid product prepared by embodiment 1~5 is carried out putting swollen test and bio-compatible
Property test.
According to SY5971-94, the anti-dilative of sand expansion-resisting agent is pressed down with centrifugal determination above each group.Mainly by measuring swelling
Swelling volume of the soil in acidifying liquid system calculates anti-dilative.
Wherein, the formula of fracturing fluid system is：The row of helping of+0.35% crosslinking agent of+0.5% guar gum of 0.5% expansion-resisting agent+0.5%
The foaming agent of agent+0.5%+1%KCl+0.02%NaOH.
Anti-dilative calculation formula is：B=(V2-V1)/(V2-V0) × 100%
In formula：B- anti-dilatives, %；
V1Swelling volume of-the bentonite in suppression sand expansion-resisting agent solution, mL；
V2Swelling volume of-the bentonite in distilled water, mL；
V0Swelling volume of-the bentonite in kerosene, mL.
The anti-dilative of each environment-friendly type clay expansion-resisting agent solid product see the table below 1 in practical measuring examples 1~5.Wherein, environment-friendly type is sticked
The addition of native expansion-resisting agent is 1wt.%.
Table 1：
As can be seen from Table 1, the environment-friendly type clay expansion-resisting agent is applied to 100~140 DEG C of temperature, can significantly improve pressure
The system clay such as well liquid, workover fluid, acidifying solution, fracturing fluid prevents swollen performance, and its dosage is measured in 1wt.% under relevant temperature
Expansion rate is all higher than 90%, illustrates that it can be efficiently applied to, and shows that good clay prevents swollen performance.
Further, biocompatibility test is carried out to environment-friendly type clay expansion-resisting agent solid product prepared by embodiment 1~5.
By test, the half lethal concentration LC50 of product prepared by embodiment 1~5 is all higher than 10000mg/L, it is seen that it is to ecological environment
Show good environmental-protecting performance.
Claims (6)
1. a kind of completion fluid environment-friendly type clay expansion-resisting agent, it is characterised in that include the little molecular cation peptides bioactivator of 35~50 parts by weight
The polymerization species clay expansion-resisting agent of ammonium salt, the screener of 5~20 parts by weight and 50~75 parts by weight；Wherein, the small molecule sun
Ion ammonium salt uses carbon number for C1~C6Organic acid and carbon number be C2~C6Organic amine neutralization reaction be made, and described small point
Relative molecular mass≤200 of sub- cation ammonium salt；The screener is C from carbon number12~C18Long-chain fat amine；It is described
It is polyethylene polyamines, polyaminoacid or modified starch to polymerize species clay expansion-resisting agent.
2. completion fluid according to claim 1 environment-friendly type clay expansion-resisting agent, it is characterised in that the organic acid selects first
At least one of acid, acetic acid, ethanedioic acid, maleic acid, tartaric acid, caproic acid and acrylic acid；The organic amine is fatty amine, aliphatic cyclic amine
Or hydramine；Wherein, fatty amine is selected in dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine, isopropylamine and 2- allylamines
It is at least one；Aliphatic cyclic amine is selected at least one in diethylenetriamines, triethylenediamine, cyclic ethylene imines and hexa
Kind；Hydramine is from least one of diethanol amine, triethanolamine, 3- Propanolamines, triisopropanolamine.
3. completion fluid according to claim 1 environment-friendly type clay expansion-resisting agent, it is characterised in that the screener is 12
Amine, cetylamine, octadecylamine or 20 amine.
4. completion fluid according to claim 1 environment-friendly type clay expansion-resisting agent, it is characterised in that the polyethylene polyamines are
Ethylenediamine, diethylenetriamines, trien, the co-product of tetren；The polyaminoacid is poly- asparagus fern ammonia
One or more in acid, polyglutamic acid, polylysine；The modified starch is that hydroxyethyl modified starch or sodium are carboxymethyl modified
Starch.
5. a kind of completion fluid preparation method of environment-friendly type clay expansion-resisting agent, it is characterised in that step is as follows：
S1, little molecular cation peptides bioactivator ammonium salt preparation：Organic amine is dissolved into the aqueous solvent of 2~3 times of organic amine weight and carried out
Dilution, adds under the organic acid of 1.8~3.5 times of organic amine weight, normal temperature 1~2h of stirring, obtain containing small molecule it is positive from
The mixed solution I of sub- ammonium salt；
S2, add into mixed solution I screener and and be added dropwise a small amount of ethanol, continue agitating solution to well mixed, mixed
Close solution II；Wherein, the addition of ethanol is 0.1~0.5wt.% of added aqueous solvent weight in step S1；
S3, add polymerization species clay expansion-resisting agent into mixed solution I I and stir well mixed to solution, obtain it is sticky it is solid-
Liquid phase mixture；Solvent in sticky solid-liquid phase mixture is evaporated, that is, obtains environment-friendly type clay expansion-resisting agent solid product.
6. completion fluid according to claim 1 environment-friendly type clay expansion-resisting agent, it is characterised in that the screener and described
The addition weight for polymerizeing species clay expansion-resisting agent obtains little molecular cation peptides bioactivator ammonium salt with reference to organic amine weight conversion in step S1
Weight is obtained, and makes little molecular cation peptides bioactivator ammonium salt:Screener:The weight ratio for polymerizeing species clay expansion-resisting agent is 35~50:5~20:
50~75.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109554171A (en) * | 2018-12-21 | 2019-04-02 | 中国石油集团渤海钻探工程有限公司 | Environment-friendlysticky sticky soil stabilizer |
| CN109679642A (en) * | 2018-12-21 | 2019-04-26 | 中国石油集团渤海钻探工程有限公司 | Environmentally friendly clay stabilizer |
| CN110396397A (en) * | 2019-07-23 | 2019-11-01 | 中国石油集团渤海钻探工程有限公司 | Application of the organic amine salt in drilling applications |
| CN113153254A (en) * | 2020-10-16 | 2021-07-23 | 中国石油化工股份有限公司 | Efficient anti-expansion fracturing process for low-porosity low-permeability strong water-sensitive reservoir |
| CN113755146A (en) * | 2021-09-28 | 2021-12-07 | 中国石油化工股份有限公司 | Sand stabilizing 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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| CN109679642A (en) * | 2018-12-21 | 2019-04-26 | 中国石油集团渤海钻探工程有限公司 | Environmentally friendly clay stabilizer |
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| CN113153254A (en) * | 2020-10-16 | 2021-07-23 | 中国石油化工股份有限公司 | Efficient anti-expansion fracturing process for low-porosity low-permeability strong water-sensitive reservoir |
| CN113153254B (en) * | 2020-10-16 | 2022-12-27 | 中国石油化工股份有限公司 | Efficient anti-expansion fracturing process for low-porosity low-permeability strong-water-sensitivity reservoir |
| CN113755146A (en) * | 2021-09-28 | 2021-12-07 | 中国石油化工股份有限公司 | Sand stabilizing agent and preparation method thereof |
| CN113755146B (en) * | 2021-09-28 | 2023-06-23 | 中国石油化工股份有限公司 | Sand stabilizing 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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Application publication date: 20170818 |