CN112680209B - Proppant and preparation method thereof - Google Patents

Proppant and preparation method thereof Download PDF

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Publication number
CN112680209B
CN112680209B CN201910986884.5A CN201910986884A CN112680209B CN 112680209 B CN112680209 B CN 112680209B CN 201910986884 A CN201910986884 A CN 201910986884A CN 112680209 B CN112680209 B CN 112680209B
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proppant
content
coating
coating treatment
cosolvent
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CN112680209A (en
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沈少春
李应成
沙鸥
张卫东
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention discloses a proppant and a preparation method thereof. The proppant comprises proppant particles and a coating coated on the proppant particles; the coating is prepared by spraying and soaking a coating treatment liquid on proppant particles; the coating treatment liquid consists of an organic silicon compound, a silane coupling agent, a cosolvent and a solvent, wherein the content of the organic silicon compound is 0.1-50%, the content of the silane coupling agent is 0.1-30% and the content of the cosolvent is 0.1-10% by weight of the solvent of 100%. The proppant disclosed by the invention can reduce the adsorption of the surface of the proppant on substances such as fracturing fluid, crude oil and the like, improves the flow conductivity of cracks, and has the advantages of simple formula, low field application condition and low construction cost.

Description

Proppant and preparation method thereof
Technical Field
The invention relates to the technical field of oil and gas field exploitation, in particular to a proppant and a preparation method thereof.
Background
Petroleum and natural gas are important natural resources and national strategic materials. With the development of socio-economic, the demand for oil and gas is increasing. In order to improve the oil and gas recovery efficiency, various oil displacement technologies are developed, wherein the hydraulic fracturing technology plays an important role in the development of compact oil and gas reservoirs and is one of the main means.
The proppant used in hydraulic fracturing is supported in an artificial fracture after completion construction, the conductivity of the fracture is maintained, and due to the hydrophilic characteristic and roughness of the surface of the proppant, polymers in fracturing fluid and crude oil in a stratum are easily adsorbed in the actual production process, so that the conductivity of the fracture is influenced, particularly the proppant such as quartz sand, ceramsite and the like used in shale gas exploitation is obvious, and the fracture loses gas production capacity even if the proppant is serious.
The Chinese patent CN109943316A mainly solves the problems that the existing tectorial membrane proppant is not alkali-resistant, and the fracture crack is closed and the fracturing measure is invalid due to the migration of the proppant in the ternary combination flooding process. The invention comprises the following components in percentage by weight: 90-93% of quartz sand, 2.5-5% of alkali-resistant resin, 1.3-3.6% of curing agent, 0.07% of silane coupling agent, 1.5% of diluent and 0.5% of lubricant. The invention improves the alkali resistance of the coated proppant, ensures that the coated proppant still has higher compressive strength under a strong alkali system of the ternary combination flooding, and meets the requirement of fracturing measures of the ternary combination flooding water well.
Chinese patent CN110055048A discloses a coated proppant with slow-release gel breaking effect on fracturing fluid and a preparation method thereof, belonging to the technical field of oil exploitation. The outer layer of the propping agent is sequentially coated with a gel breaking layer and a slow release layer, and is directly bonded, placed and cured by a resin adhesive curing agent. The fracturing fluid gel breaker is suitable for oil well reservoir transformation, can be contacted with reservoir rock for a long time, gradually releases the gel breaker, and can reduce the damage of the retained fracturing fluid by being comprehensively contacted with the fracturing fluid under the condition of restoring the ground temperature, so that the purpose of improving the yield of an oil well is achieved. The labor intensity can be reduced, and meanwhile, the gel breaker is not added manually or by a control machine, and the filling by a special process is not needed. The method can avoid uneven filling of the gel breaker and avoid sand blockage caused by too large dosage of the gel breaker.
The two patents are preparation methods of the film-coated propping agent, and the purpose is to increase the strength of the propping agent; the problem of easy adsorption of the proppant is not improved.
Therefore, how to reduce the adsorption of the propping agent on fracturing fluid and crude oil so as to improve the fracture conductivity of the oil-gas well after fracturing is of great significance to the development of oil-gas fields.
Disclosure of Invention
The proppant can reduce the adsorption of the surface of the proppant on substances such as fracturing fluid, crude oil and the like, improve the fracture conductivity, and has the advantages of simple formula, low field application condition and low construction cost.
It is an object of the present invention to provide a proppant.
The proppant comprises proppant particles and a coating coated on the proppant particles;
the coating thickness is preferably 0.1 to 50 μm.
The coating is prepared by spraying and soaking a coating treatment liquid on proppant particles;
the coating treatment liquid consists of an organic silicon compound, a silane coupling agent, a cosolvent and a solvent;
wherein, based on the weight of the solvent as 100 percent,
the content of the organic silicon compound is 0.1 to 50 percent, preferably 5 to 35 percent;
the content of the silane coupling agent is 0.1-30%, preferably 3-15%;
the content of the cosolvent is 0.1-10%, preferably 2-8%;
the organic silicon compound is one or a combination of hydroxyl silicone oil, hydrogen-containing silicone oil, hydroxyl fluorine-containing polysiloxane, fluorine-containing alkyl trialkoxysilane and alkyl trialkoxysilane.
The content of hydroxyl in the selected hydroxyl silicone oil is preferably 0.5-5%; the hydrogen content in the hydrogen-containing silicone oil is preferably 0.1-3%.
The fluorine-containing alkyl of the fluorine-containing alkyl trialkoxysilane is preferably partially fluorinated or perfluorinated alkyl or cycloalkyl with the carbon number of 1-18; the alkoxy group is selected from methoxy or ethoxy.
The alkyl of the alkyl trialkoxysilane is preferably alkyl or cycloalkyl with the carbon number of 1-18, and the alkoxy is selected from methoxy or ethoxy.
The silane coupling agent is selected from one of aminoethyl methyldimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethyl aminopropylmethyldimethoxysilane and aminopropylmethyldimethoxysilane.
The cosolvent is selected from one or a combination of methanol, ethanol, isopropanol, propanol, acetone, diethyl ether and acetonitrile;
the solvent is one or a combination of alkane, cyclane, benzene, toluene and ethylbenzene with 5-8 carbon atoms.
The proppant particles in the invention are conventional proppant particles in the prior art, such as ceramsite, quartz sand and the like.
The invention also aims to provide a preparation method of the proppant.
The method comprises the following steps:
1) Dissolving an organic silicon compound, a silane coupling agent and a cosolvent in a solvent according to the dosage, and stirring and mixing to prepare a coating treatment solution; preferably, the mixture is stirred for 2 hours at room temperature;
2) And spraying the coating treatment liquid on the surfaces of the proppant particles, or soaking the proppant particles in the coating treatment liquid, and drying at room temperature or heating for curing to obtain the proppant.
Among them, the curing temperature is preferably 50 to 120 ℃.
In particular, the amount of the solvent to be used,
the proppant particles are subjected to soaking and spraying to construct a surface coating, and after the surface coating is dried at room temperature or heated and cured at a high temperature of 50-120 ℃, the treated proppant is injected into a stratum through normal fracturing construction.
According to the invention, the organic silicon compound and the silane coupling agent are adopted to act together, so that a coating is formed on the surface of the fracturing propping agent for modification, the adsorption of the surface of the propping agent on substances such as fracturing fluid, crude oil and the like is reduced in a stratum, and the flow conductivity of cracks is improved, thereby increasing the oil gas yield and improving the economic benefit. The technology has the outstanding advantages of simple selected formula, less chemical agent consumption, simple application conditions, no change of the original fracturing construction technical parameters, effective control of process cost and improvement of economic benefits.
By adopting the technical scheme of the invention, the long-term fracture conductivity of the proppant filling is improved by more than 20%, and a better technical effect is achieved.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples are all commercially available;
example 1
100g of methyltriethoxysilicone oil, 35g of aminopropylmethyldimethoxysilane and 1g of ethanol were added to 1kg of cyclohexane and mixed uniformly to prepare a coating treatment liquid 1a.
Soaking 500g of 20/40-mesh ceramsite proppant in 300mL of the treatment solution 1a for 8 hours, filtering, draining, and curing in an oven at 80 ℃ for 5 hours to obtain the treated proppant, wherein the thickness of the coating is 15 microns.
Example 2
340g of methylhydroxysilicone oil (hydroxyl group content: 5%), 35g of aminoethyl aminopropyl methyldimethoxysilane and 11g of methanol were added to 1kg of octane and mixed uniformly to prepare a coating treatment liquid 2a.
300mL of the treating fluid 2a is sprayed on the surface of 500g of 20/40-mesh ceramsite proppant, and the surface is cured for 4 hours in an oven at 120 ℃ to obtain the treated proppant, wherein the thickness of the coating is 45 mu m.
Example 3
350g of methylhydroxy silicone oil (hydroxyl content: 1.5%), 45g of aminopropyltriethoxysilane, and 10g of methanol were added to 1kg of n-hexane and mixed uniformly to prepare a coating treatment liquid 3a.
400g of 20/40 mesh ceramsite proppant is soaked in 300mL of treatment liquid 3a for 6 hours, filtered, drained and cured in an oven at 60 ℃ for 5 hours to obtain the treated proppant, and the thickness of the coating is 50 microns.
Example 4
200g of hydrogen-containing silicone oil (hydrogen content: 3%), 15g of aminoethyl methyldimethoxysilane, and 20g of ethanol were added to 1kg of pentane, and the mixture was mixed uniformly to prepare a coating treatment liquid 4a.
300mL of the treatment solution 4a is sprayed on the surface of 500g of 20/40-mesh ceramsite proppant and dried for 2 days at room temperature to obtain the treated proppant, wherein the thickness of the coating is 26 microns.
Example 5
1g of methylhydroxysilicone oil (hydroxyl group content: 5%), 1g of aminopropyltrimethoxysilane and 100g of acetone were added to 1kg of toluene and mixed uniformly to prepare a coating treatment liquid 5a.
And spraying 300mL of treatment solution 5a on the surface of 800g of 50/70-mesh quartz sand proppant, and curing for 5 hours in an oven at 100 ℃ to obtain the treated proppant, wherein the thickness of the coating is 0.1 mu m.
Example 6
500g of fluorinated pentyltriethoxysilane, 300g of aminoethylaminopropylmethyldimethoxysilane and 100g of ethanol were added to 1kg of pentane, and the mixture was uniformly mixed to prepare a coating treatment liquid 6a.
Spraying 200mL of treatment solution 6a on the surface of 500g of 20/40-mesh ceramsite proppant, and curing for 8 hours in an oven at 100 ℃ to obtain the treated proppant, wherein the thickness of the coating is 40 mu m.
Example 7
380g of hydrogen-containing silicone oil (hydrogen content: 0.1%), 24g of aminoethyl aminopropyl methyldimethoxysilane and 10g of propanol were added to 1kg of n-hexane and mixed uniformly to prepare a coating treatment liquid 7a.
And (3) spraying 100mL of treatment liquid 7a on the surface of 500g of 20/40-mesh ceramsite proppant, and curing for 6 hours in an oven at 60 ℃ to obtain the treated proppant, wherein the thickness of the coating is 15 microns.
Example 8
To 1kg of n-hexane, 260g of methylhydroxy silicone oil (hydroxyl content: 0.5%), 16g of aminopropyltrimethoxysilane and 12g of acetonitrile were added and mixed uniformly to prepare a coating treatment liquid 8a.
400g of 50/70 mesh quartz sand proppant is soaked in 250mL of treatment liquid 8a for 6 hours, filtered and drained, and cured in an oven at 60 ℃ for 5 hours to obtain the treated proppant, wherein the thickness of the coating is 24 microns.
Example 9
200g of hydrogen-containing silicone oil (hydrogen content: 0.16%), 20g of aminoethyl methyldimethoxysilane, and 12g of ethanol were added to 1kg of ethylbenzene, and the mixture was mixed uniformly to prepare a coating treatment liquid 9a.
Spraying 200mL of treatment solution 9a on the surface of a 600g 20/40-mesh ceramsite proppant, and curing for 6 hours in an oven at 120 ℃ to obtain the treated proppant, wherein the thickness of the coating is 18 microns.
Example 10
460g of hydroxyl fluorine-containing polysiloxane, 46g of aminopropyltrimethoxysilane and 20g of isopropanol were added to 1kg of pentane and mixed uniformly to prepare a coating treatment liquid 10a.
250mL of the treatment solution 10a is sprayed on the surface of 750g of 20/40-mesh ceramsite proppant, and the treated proppant is obtained after being cured for 5 hours in an oven at 120 ℃ and the thickness of the coating is 20 microns.
Indoor long-term conductivity test and comparison: the proppant product is filled into the indoor sand filling pipe, the fracturing fluid is injected at a constant speed, the injection experiment is maintained for 7 days, the flow conductivity of the proppant which is not subjected to coating treatment and the flow conductivity of the proppant which is subjected to coating treatment are respectively measured, and the experimental results are shown in table 1:
TABLE 1
Examples The flow conductivity is improved in proportion after the coating treatment
1 11%
2 15%
3 30%
4 20%
5 10%
6 16%
7 21%
8 31%
9 16%
10 23%
As can be seen from the data in Table 1, the flow conductivity of the proppant prepared in the example and treated by the coating treatment fluid is obviously improved, and the improvement amplitude can reach 31% at most.
The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention will be covered within the protection scope of the present invention.

Claims (8)

1. A proppant, characterized by:
the proppant comprises proppant particles and a coating coated on the proppant particles;
the coating is prepared by spraying and soaking a coating treatment liquid on proppant particles;
the coating treatment liquid consists of an organic silicon compound, a silane coupling agent, a cosolvent and a solvent, wherein the content of the organic silicon compound is 0.1-50%, the content of the silane coupling agent is 0.1-30% and the content of the cosolvent is 0.1-10% by weight of the solvent of 100%;
the organic silicon compound is one or a combination of hydroxyl silicone oil, hydrogen-containing silicone oil, hydroxyl fluorine-containing polysiloxane, fluorine-containing alkyl trialkoxysilane and alkyl trialkoxysilane;
the silane coupling agent is selected from one of aminoethyl methyldimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethyl aminopropylmethyldimethoxysilane and aminopropylmethyldimethoxysilane;
the cosolvent is selected from one or a combination of methanol, ethanol, isopropanol, propanol, acetone, diethyl ether and acetonitrile;
the solvent is one or a combination of alkane, cyclane, benzene, toluene and ethylbenzene with 5-8 carbon atoms.
2. The proppant of claim 1, wherein:
in the coating treatment fluid, the weight of a solvent is 100%, the content of an organic silicon compound is 5% -35%, the content of a silane coupling agent is 3% -15%, and the content of a cosolvent is 2% -8%.
3. The proppant of claim 1, wherein:
the thickness of the coating is 0.1-50 μm.
4. The proppant of claim 1, wherein:
the hydroxyl content in the selected hydroxyl silicone oil is 0.5-5 percent; the hydrogen content in the hydrogen-containing silicone oil is 0.1-3%.
5. The proppant of claim 4, wherein:
the fluorine-containing alkyl of the fluorine-containing alkyl trialkoxysilane is partially fluorinated or perfluorinated alkyl or cycloalkyl with the carbon number of 1-18;
the alkoxy group is selected from methoxy or ethoxy.
6. The proppant of claim 4, wherein:
the alkyl of the alkyl trialkoxysilane is alkyl or cycloalkyl with 1-18 carbon atoms;
the alkoxy group is selected from methoxy or ethoxy.
7. A method of making the proppant of any one of claims 1-6, wherein the method comprises:
1) Dissolving an organic silicon compound, a silane coupling agent and a cosolvent in a solvent according to the using amounts, and stirring and mixing to prepare a coating treatment solution;
2) And spraying the coating treatment liquid on the surface of the proppant particles, or soaking the proppant particles in the coating treatment liquid, and drying at room temperature or heating for curing to obtain the proppant.
8. The method of claim 7, wherein:
the curing temperature is 50-120 ℃.
CN201910986884.5A 2019-10-17 2019-10-17 Proppant and preparation method thereof Active CN112680209B (en)

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CN115612480A (en) * 2021-07-16 2023-01-17 中国石油化工股份有限公司 Carbon nano tube/perfluorosilane composite sol material and synthesis method and application thereof
CN114774104A (en) * 2022-05-20 2022-07-22 西南石油大学 High-efficiency conveying filling proppant based on bionics and preparation method

Citations (6)

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US20100276142A1 (en) * 2007-12-05 2010-11-04 Skildum John D Method of treating proppants and fractures in-situ with fluorinated silane
CN103275694A (en) * 2013-05-21 2013-09-04 中国地质大学(武汉) Clean-water-carrying petroleum proppant for petroleum production of low-permeability petroleum reservoir and preparation method thereof
CN103849371A (en) * 2012-11-30 2014-06-11 亿利资源集团有限公司 Fracturing propping agent and its preparation method
CN106634939A (en) * 2016-11-30 2017-05-10 王展旭 Preparation method for self-suspension propping agent in laboratory
CN107201221A (en) * 2017-05-26 2017-09-26 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 A kind of CO2The method that dry method pressure break functional material coats proppant
CN110079295A (en) * 2019-04-19 2019-08-02 北京奇想达新材料有限公司 Curable proppant and its preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100276142A1 (en) * 2007-12-05 2010-11-04 Skildum John D Method of treating proppants and fractures in-situ with fluorinated silane
CN103849371A (en) * 2012-11-30 2014-06-11 亿利资源集团有限公司 Fracturing propping agent and its preparation method
CN103275694A (en) * 2013-05-21 2013-09-04 中国地质大学(武汉) Clean-water-carrying petroleum proppant for petroleum production of low-permeability petroleum reservoir and preparation method thereof
CN106634939A (en) * 2016-11-30 2017-05-10 王展旭 Preparation method for self-suspension propping agent in laboratory
CN107201221A (en) * 2017-05-26 2017-09-26 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 A kind of CO2The method that dry method pressure break functional material coats proppant
CN110079295A (en) * 2019-04-19 2019-08-02 北京奇想达新材料有限公司 Curable proppant and its preparation method and application

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