CN108165252A - It is a kind of for the modifying agent and its preparation process of fracturing propping agents and the modified technique of fracturing propping agents - Google Patents
It is a kind of for the modifying agent and its preparation process of fracturing propping agents and the modified technique of fracturing propping agents Download PDFInfo
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- CN108165252A CN108165252A CN201711354900.6A CN201711354900A CN108165252A CN 108165252 A CN108165252 A CN 108165252A CN 201711354900 A CN201711354900 A CN 201711354900A CN 108165252 A CN108165252 A CN 108165252A
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- propping agents
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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
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
Abstract
The fracturing propping agents used in oil-gas mining can be carried out effectively to be modified the present invention relates to a kind of, very big amplitude promotes the fracturing propping agents modifying agent of its oil ability that blocks water and its preparation process and method of modifying, fracturing propping agents modifying agent is prepared using graphite, fracturing propping agents are modified, adhere to one layer of aluminum oxide/graphite layer on fracturing propping agents surface and pass through reduction method and be reduced into single-layer graphene film, the hydrophobicity of fracturing propping agents is strengthened, the modification fracturing propping agents with the excellent oiliness energy that blocks water are made.
Description
Technical field
The present invention relates to a kind of proppant field more particularly to it is a kind of can to the fracturing propping agents used in oil-gas mining into
Row is effectively modified, and very big amplitude promotes the modifying agent and its preparation process for fracturing propping agents of its oily ability that blocks water, with
And the modified technique of fracturing propping agents.
Background technology
Hydraulic fracturing technology and fracturing propping agents have wide market in natural petroleum gas field, especially in hyposmosis
With very important effect is played in middle and later periods oil-gas field development.Proppant performance indicator and its synthesis technology directly affect
Cost, effect and the environment of hydraulic fracture mining.Especially in the high water-cut stage of oil field development, moisture content is up to 95%, after pressure break easily
Lead to water logging, cause to rise containing water speed, mainly be enhanced at present using the fracturing propping agents such as haydite and quartz sand, resin burnt-in sand
Flow conductivity.But to grease without selectivity, the two all can be penetrated largely, cannot not only improved in this way these common proppants
The recovery ratio of crude oil can also generate a series of side effect.Therefore urgent need, which develops one kind, can realize permselective branch
Agent is supportted, i.e., has smaller resistance to the seepage flow of oil, the proppant for having larger resistance to water seepage flow, so as to improve field output, into
And it is badly in need of a kind of can be effectively modified to the progress of conventional fracturing propping agents and obtains the modifying agent of required performance.
The invention that Patent Office of the People's Republic of China disclosed a kind of hydrophobically modified proppant and preparation method thereof on June 23rd, 2017 is special
Profit application, application publication number CN106883837A, the patent of invention are shaken using a small amount of hydrophobic resin glue is added in into proppant
Or stirring makes hydrophobic glue body wetting proppant surface, then curing obtains hydrophobically modified proppant, has centainly hydrophobic
The performance to block water, but in its raw material, hydrophobic resin glue selects fluorinated acrylamide acid resin glue and the fluorination hydrophobic glue of Dopaminergics
Fluorochemicals are waited, larger adverse effect will be generated to environment, do not meet environmental requirement, and resin gel coating is oxidizable old
Change, stability is insufficient, can not meet the needs of long-time service.
Patent Office of the People's Republic of China also disclosed a kind of functional resin tectorial membrane proppant and preparation method thereof on June 5th, 2013
Invention patent mandate, which uses during resin coating is cured, is added to active group and hydrophobic
The silanes of group are reacted with resin, and organo-silicon compound molecule is connected on resin film cross-linked network, due to having
Organic silicon compound belongs to low-surface energy substance, and the hydrophobic grouping carried is coated on the outer surface of resin, forms hydrophobic structure, but
The contact angle that solid liquid phase is in contact on its outer surface is more than 120 °, and its outer surface is smooth, and water contact angle maximum is also only
120 °, and when being used in the environment of bore oil-reservior or high displacement pressure, its contact angle is likely larger than 120 °, limits it in depth
The effect used in the environment of well oil reservoir or high displacement pressure.
Patent Office of the People's Republic of China is also in the patent of invention for disclosing a kind of hydrophobic proppant and preparation method thereof on the 3rd of August in 2016
It authorizes, Authorization Notice No. CN102443387B is used and added nanoparticle to being coated in the film covered resin of particles of aggregates outer layer
Son, and nano-particle is made to be uniformly distributed in film covered resin so that its contact angle with water is 120~180 °, improve its
The effect used in the environment of bore oil-reservior or high displacement pressure, but there are still fluorine compounds in its raw material, and environment will be generated
Larger adverse effect, the problem of not meeting environmental requirement.
Invention content
To solve in the prior art, there has been no can prepare high-performance, applied widely and with permselective pressure break
The problem of technique of proppant, can effectively change the fracturing propping agents used in oil-gas mining the present invention provides a kind of
Property, very big amplitude promoted its oily ability that blocks water for the modifying agent and its preparation process of fracturing propping agents and pressure break branch
Support the modified technique of agent, by the modifying agent for fracturing propping agents and its corresponding modified technique can to proppant into
Row is effectively modified.
To achieve the above object, the present invention uses following technical scheme：
A kind of modifying agent for fracturing propping agents, the modifying agent for fracturing propping agents prepare raw material and include following weight
The substance of number：15~30 parts of native graphite, 6~15 parts of sodium nitrate, 40~80 parts of potassium permanganate, hydrogenperoxide steam generator 18.5~
26.5 parts.
Preferably, the modifying agent for fracturing propping agents prepares the substance that raw material includes following parts by weight：My god
Right 18~22.5 parts of graphite, 9~11.5 parts of sodium nitrate, 48~62 parts of potassium permanganate, 20.5~21.5 parts of hydrogenperoxide steam generator.
Preferably, the modifying agent for fracturing propping agents prepares the substance that raw material includes following parts by weight：My god
Right 20 parts of graphite, 10 parts of sodium nitrate, 60 parts of potassium permanganate, 21.4 parts of hydrogenperoxide steam generator.
Preferably, the hydrogenperoxide steam generator is the aqueous hydrogen peroxide solution of 18~22% concentration.
Preparing for the modifying agent for fracturing propping agents does not contain pollutant in raw material, environment will not be caused bad
It influences.
A kind of preparation process of modifying agent for fracturing propping agents, the preparation process include following preparation process：
1）Native graphite and sodium nitrate are added in the concentrated sulfuric acid of 70~80 parts by weight, are stirred in ice-water bath to completely mixed
It closes, obtains mixed liquor；
2）Potassium permanganate is divided into 2~50 parts by weight, to step 1）Obtained mixed liquor adds in one every 2~5min
It is secondary, it is added completely into, and mixeding liquid temperature in adition process is controlled to be no more than 20 DEG C, is stirred after potassium permanganate is added completely by several times
2~3h is reacted, obtains oxidation mixed liquor；
3）By step 2）Obtained oxidation mixed liquor is warming up to 33~37 DEG C, continues 30~45min of stirring, it is slowly added to 900~
The deionized water of 1100 parts by weight is warming up to 90~92 DEG C, continues 20~25min of stirring, adds in 3800~4100 parts by weight
Deionized water, and hydrogenperoxide steam generator is added dropwise, solution is in glassy yellow, obtains glassy yellow mixed liquor；
4）To step 3）Obtained bright yellow solution is filtered to obtain reaction product, and with the hydrogen chloride solution pair of 10% concentration
Reaction product is washed, and the reaction product after hydrogen chloride solution washs is centrifuged repeatedly and is washed using deionized water, until
Its last time cleaning solution pH value is 6.8~7.2, obtains graphite oxide, graphite oxide is scattered in deionized water, be made into matter
Measure the graphite oxide dispersion of a concentration of 2mg/mL, be placed in deionized water after the 7d that dialyses filter drying obtain it is described for pressure break
The modifying agent of proppant.
Preferably, step 4）Described in centrifugal rotational speed be 8000~11000rpm.
The preparation process is succinctly efficient, not can cause environmental pollution, and is suitble to industrialized production.
A kind of modified technique of fracturing propping agents, the modified technique of the fracturing propping agents include the following steps：
a）The modifier solution that mass concentration is 2mg/mL is made into deionized water by being dissolved in for the modifying agent of fracturing propping agents,
Proppant aggregate is placed in 30~35min of dipping in modifier solution by 30~35min of ultrasonic disperse, and taking-up is placed on vacuum ring
In border, dry 24~30h, obtains tentatively being modified proppant under the conditions of 40~45 DEG C；
b）By step a）Obtained preliminary modified proppant is placed in hydrazine hydrate steam, under the conditions of 78~82 DEG C reductase 12 4~
26h, taking-up are placed in vacuum environment, are dried under the conditions of 80 DEG C to constant weight, obtain modified fracturing propping agents.
Preferably, the proppant aggregate includes but not limited to quartz sand and ceramic particle.
Preferably, the grain diameter of the quartz sand and ceramic particle is 10~60 mesh.
Single-layer graphene institute structure can be covered in proppant aggregate outer surface by the modified technique of the fracturing propping agents
Into clad, single-layer graphene is a kind of nonpolar molecule, have extremely strong hydrophobicity, and to oil have extremely strong transmission
Property, therefore obtained modification fracturing propping agents have the very strong oily ability that blocks water.
The beneficial effects of the invention are as follows：
1）The present invention provides a kind of modifying agent for fracturing propping agents, can be used for most of proppant in the prior art
Aggregate, it is applied widely；
2）Being modified rear obtained modification fracturing propping agents by the modifying agent for being used for fracturing propping agents has extremely strong resistance
The saturating oiliness energy of water has extremely strong selection permeability；
3）It is longer that rear obtained modification fracturing propping agents service life is modified by the modifying agent for being used for fracturing propping agents,
Non-aging, damage；
4）The preparation process of the modifying agent for fracturing propping agents is succinctly efficient, can industrialized production.
Specific embodiment
The technical solution in the embodiment of the present invention is clearly and completely described with reference to the present invention, it is clear that retouched
It is only part of the embodiment rather than whole embodiments of the present invention to state embodiment.Based on the embodiments of the present invention, this field is general
Logical technical staff all other embodiments obtained without making creative work belong to the protection of the present invention
Range.
Embodiment 1
A kind of preparation process of modifying agent for fracturing propping agents, the preparation process include following preparation process：
1）Native graphite and sodium nitrate are added in the concentrated sulfuric acid of 70 parts by weight, are stirred in ice-water bath to being thoroughly mixed, obtained
To mixed liquor；
2）Potassium permanganate is divided into 2 parts by weight, to step 1）Obtained mixed liquor adds in once every 5min, complete by several times
It is complete to add in, and mixeding liquid temperature in adition process is controlled to be no more than 20 DEG C, 2h is stirred to react after potassium permanganate is added completely into, is obtained
To oxidation mixed liquor；
3）By step 2）Obtained oxidation mixed liquor is warming up to 33 DEG C, continues to stir 30min, is slowly added to going for 900 parts by weight
Ionized water is warming up to 90 DEG C, continues to stir 20min, adds in the deionized water of 3800 parts by weight, and hydrogenperoxide steam generator is added dropwise,
Solution is in glassy yellow, obtains glassy yellow mixed liquor；
4）To step 3）Obtained bright yellow solution is filtered to obtain reaction product, and with the hydrogen chloride solution pair of 10% concentration
Reaction product is washed, and the reaction product after hydrogen chloride solution washs is centrifuged repeatedly and is washed using deionized water, is centrifuged
Rotating speed is 8000rpm, until its last time cleaning solution pH value be 6.8, obtain graphite oxide, by graphite oxide be scattered in from
In sub- water, the graphite oxide dispersion that mass concentration is 2mg/mL is made into, is placed in filter after dialysis 7d in deionized water and dry
To the modifying agent for fracturing propping agents.
The modifying agent for fracturing propping agents prepares the substance that raw material includes following parts by weight：Native graphite 15
Part, 6 parts of sodium nitrate, 40 parts of potassium permanganate, 18.5 parts of hydrogenperoxide steam generator.
Embodiment 2
A kind of preparation process of modifying agent for fracturing propping agents, the preparation process include following preparation process：
1）Native graphite and sodium nitrate are added in the concentrated sulfuric acid of 80 parts by weight, are stirred in ice-water bath to being thoroughly mixed, obtained
To mixed liquor；
2）Potassium permanganate is divided into 50 parts by weight, to step 1）Obtained mixed liquor adds in primary, gradation every 2min
It is added completely into, and mixeding liquid temperature in adition process is controlled to be no more than 20 DEG C, 3h is stirred to react after potassium permanganate is added completely into,
Obtain oxidation mixed liquor；
3）By step 2）Obtained oxidation mixed liquor is warming up to 37 DEG C, continues to stir 45min, is slowly added to going for 1100 parts by weight
Ionized water is warming up to 92 DEG C, continues to stir 25min, adds in the deionized water of 4100 parts by weight, and hydrogenperoxide steam generator is added dropwise,
Solution is in glassy yellow, obtains glassy yellow mixed liquor；
4）To step 3）Obtained bright yellow solution is filtered to obtain reaction product, and with the hydrogen chloride solution pair of 10% concentration
Reaction product is washed, and the reaction product after hydrogen chloride solution washs is centrifuged repeatedly and is washed using deionized water, is centrifuged
Rotating speed is 11000rpm, until its last time cleaning solution pH value is 7.2, obtains graphite oxide, graphite oxide is scattered in
In ionized water, the graphite oxide dispersion that mass concentration is 2mg/mL is made into, drying is filtered after being placed in deionized water the 7d that dialyses
Obtain the modifying agent for being used for fracturing propping agents.
The modifying agent for fracturing propping agents prepares the substance that raw material includes following parts by weight：Native graphite 30
Part, 15 parts of sodium nitrate, 80 parts of potassium permanganate, 26.5 parts of hydrogenperoxide steam generator.
Embodiment 3
A kind of preparation process of modifying agent for fracturing propping agents, the preparation process include following preparation process：
1）Native graphite and sodium nitrate are added in the concentrated sulfuric acid of 75 parts by weight, are stirred in ice-water bath to being thoroughly mixed, obtained
To mixed liquor；
2）Potassium permanganate is divided into 30 parts by weight, to step 1）Obtained mixed liquor adds in primary, gradation every 3min
It is added completely into, and mixeding liquid temperature is controlled in adition process to be no more than 20 DEG C, it is stirred to react 2 after potassium permanganate is added completely into~
3h obtains oxidation mixed liquor；
3）By step 2）Obtained oxidation mixed liquor is warming up to 35 DEG C, continues to stir 30min, is slowly added to going for 1000 parts by weight
Ionized water is warming up to 90 DEG C, continues to stir 20min, adds in the deionized water of 4000 parts by weight, and hydrogenperoxide steam generator is added dropwise,
Solution is in glassy yellow, obtains glassy yellow mixed liquor；
4）To step 3）Obtained bright yellow solution is filtered to obtain reaction product, and with the hydrogen chloride solution pair of 10% concentration
Reaction product is washed, and the reaction product after hydrogen chloride solution washs is centrifuged repeatedly and is washed using deionized water, is centrifuged
Rotating speed is 10000rpm, until its last time cleaning solution pH value is 7.0, obtains graphite oxide, graphite oxide is scattered in
In ionized water, the graphite oxide dispersion that mass concentration is 2mg/mL is made into, drying is filtered after being placed in deionized water the 7d that dialyses
Obtain the modifying agent for being used for fracturing propping agents.
The modifying agent for fracturing propping agents prepares the substance that raw material includes following parts by weight：Native graphite 18
Part, 9 parts of sodium nitrate, 48 parts of potassium permanganate, 20.5 parts of hydrogenperoxide steam generator.
Embodiment 4
A kind of preparation process of modifying agent for fracturing propping agents, the preparation process include following preparation process：
1）Native graphite and sodium nitrate are added in the concentrated sulfuric acid of 75 parts by weight, are stirred in ice-water bath to being thoroughly mixed, obtained
To mixed liquor；
2）Potassium permanganate is divided into 40 parts by weight, to step 1）Obtained mixed liquor adds in primary, gradation every 2min
It is added completely into, and mixeding liquid temperature in adition process is controlled to be no more than 20 DEG C, 2h is stirred to react after potassium permanganate is added completely into,
Obtain oxidation mixed liquor；
3）By step 2）Obtained oxidation mixed liquor is warming up to 35 DEG C, continues to stir 30min, is slowly added to going for 1000 parts by weight
Ionized water is warming up to 90 DEG C, continues to stir 20min, adds in the deionized water of 4000 parts by weight, and hydrogenperoxide steam generator is added dropwise,
Solution is in glassy yellow, obtains glassy yellow mixed liquor；
4）To step 3）Obtained bright yellow solution is filtered to obtain reaction product, and with the hydrogen chloride solution pair of 10% concentration
Reaction product is washed, and the reaction product after hydrogen chloride solution washs is centrifuged repeatedly and is washed using deionized water, is centrifuged
Rotating speed is 10000rpm, until its last time cleaning solution pH value is 7.0, obtains graphite oxide, graphite oxide is scattered in
In ionized water, the graphite oxide dispersion that mass concentration is 2mg/mL is made into, drying is filtered after being placed in deionized water the 7d that dialyses
Obtain the modifying agent for being used for fracturing propping agents.
The modifying agent for fracturing propping agents prepares the substance that raw material includes following parts by weight：Native graphite 22.5
Part, 11.5 parts of sodium nitrate, 62 parts of potassium permanganate, 21.5 parts of hydrogenperoxide steam generator.
Embodiment 5
A kind of preparation process of modifying agent for fracturing propping agents, the preparation process include following preparation process：
1）Native graphite and sodium nitrate are added in the concentrated sulfuric acid of 70 parts by weight, are stirred in ice-water bath to being thoroughly mixed, obtained
To mixed liquor；
2）Potassium permanganate is divided into 20 parts by weight, to step 1）Obtained mixed liquor adds in primary, gradation every 5min
It is added completely into, and mixeding liquid temperature in adition process is controlled to be no more than 20 DEG C, 2h is stirred to react after potassium permanganate is added completely into,
Obtain oxidation mixed liquor；
3）By step 2）Obtained oxidation mixed liquor is warming up to 35 DEG C, continues to stir 30min, is slowly added to going for 1000 parts by weight
Ionized water is warming up to 90 DEG C, continues to stir 20min, adds in the deionized water of 4000 parts by weight, and hydrogenperoxide steam generator is added dropwise,
Solution is in glassy yellow, obtains glassy yellow mixed liquor；
4）To step 3）Obtained bright yellow solution is filtered to obtain reaction product, and with the hydrogen chloride solution pair of 10% concentration
Reaction product is washed, and the reaction product after hydrogen chloride solution washs is centrifuged repeatedly and is washed using deionized water, is centrifuged
Rotating speed is 10000rpm, until its last time cleaning solution pH value is 7.0, obtains graphite oxide, graphite oxide is scattered in
In ionized water, the graphite oxide dispersion that mass concentration is 2mg/mL is made into, drying is filtered after being placed in deionized water the 7d that dialyses
Obtain the modifying agent for being used for fracturing propping agents.
The modifying agent for fracturing propping agents prepares the substance that raw material includes following parts by weight：Native graphite 20
Part, 10 parts of sodium nitrate, 60 parts of potassium permanganate, 21.4 parts of hydrogenperoxide steam generator.
Embodiment 6
A kind of modified technique of fracturing propping agents, the modified technique include the following steps：
a）The modifier solution that mass concentration is 2mg/mL is made into deionized water by being dissolved in for the modifying agent of fracturing propping agents,
Proppant aggregate is placed in modifier solution and impregnates 30min by ultrasonic disperse 30min, and taking-up is placed in vacuum environment, 40
Drying for 24 hours, obtains tentatively being modified proppant under the conditions of DEG C；
b）By step a）Obtained preliminary modified proppant is placed in hydrazine hydrate steam, the reductase 12 4h under the conditions of 78 DEG C, after taking-up
It is placed in vacuum environment, is dried under the conditions of 80 DEG C to constant weight, obtain modified fracturing propping agents.
The proppant aggregate is the quartz sand of 10 mesh, and the modifying agent for fracturing propping agents is made for embodiment 1
.
Embodiment 7
A kind of modified technique of fracturing propping agents, the modified technique include the following steps：
a）The modifier solution that mass concentration is 2mg/mL is made into deionized water by being dissolved in for the modifying agent of fracturing propping agents,
Proppant aggregate is placed in modifier solution and impregnates 35min by ultrasonic disperse 35min, and taking-up is placed in vacuum environment, 45
Dry 30h, obtains tentatively being modified proppant under the conditions of DEG C；
b）By step a）Obtained preliminary modified proppant is placed in hydrazine hydrate steam, the reductase 12 6h under the conditions of 82 DEG C, after taking-up
It is placed in vacuum environment, is dried under the conditions of 80 DEG C to constant weight, obtain modified fracturing propping agents.
The proppant aggregate is the quartz sand of 60 mesh, and the modifying agent for fracturing propping agents is made for embodiment 2
.
Embodiment 8
A kind of modified technique of fracturing propping agents, the modified technique include the following steps：
a）The modifier solution that mass concentration is 2mg/mL is made into deionized water by being dissolved in for the modifying agent of fracturing propping agents,
Proppant aggregate is placed in modifier solution and impregnates 30min by ultrasonic disperse 30min, and taking-up is placed in vacuum environment, 40
Drying for 24 hours, obtains tentatively being modified proppant under the conditions of DEG C；
b）By step a）Obtained preliminary modified proppant is placed in hydrazine hydrate steam, the reductase 12 4h under the conditions of 80 DEG C, after taking-up
It is placed in vacuum environment, is dried under the conditions of 80 DEG C to constant weight, obtain modified fracturing propping agents.
The proppant aggregate is the ceramic particle of 10 mesh, and the modifying agent for fracturing propping agents is 3 institute of embodiment
It is made.
Embodiment 9
A kind of modified technique of fracturing propping agents, the modified technique include the following steps：
a）The modifier solution that mass concentration is 2mg/mL is made into deionized water by being dissolved in for the modifying agent of fracturing propping agents,
Proppant aggregate is placed in modifier solution and impregnates 30min by ultrasonic disperse 30min, and taking-up is placed in vacuum environment, 40
Drying for 24 hours, obtains tentatively being modified proppant under the conditions of DEG C；
b）By step a）Obtained preliminary modified proppant is placed in hydrazine hydrate steam, the reductase 12 4h under the conditions of 80 DEG C, after taking-up
It is placed in vacuum environment, is dried under the conditions of 80 DEG C to constant weight, obtain modified fracturing propping agents.
The proppant aggregate is the ceramic particle of 60 mesh, and the modifying agent for fracturing propping agents is 4 institute of embodiment
It is made.
Embodiment 10
A kind of modified technique of fracturing propping agents, the modified technique include the following steps：
a）The modifier solution that mass concentration is 2mg/mL is made into deionized water by being dissolved in for the modifying agent of fracturing propping agents,
Proppant aggregate is placed in modifier solution and impregnates 30min by ultrasonic disperse 30min, and taking-up is placed in vacuum environment, 40
Drying for 24 hours, obtains tentatively being modified proppant under the conditions of DEG C；
b）By step a）Obtained preliminary modified proppant is placed in hydrazine hydrate steam, the reductase 12 4h under the conditions of 80 DEG C, after taking-up
It is placed in vacuum environment, is dried under the conditions of 80 DEG C to constant weight, obtain modified fracturing propping agents.
The proppant aggregate is the ceramic particle of 30 mesh, and the modifying agent for fracturing propping agents is 5 institute of embodiment
It is made.
Embodiment 6~10 is detected：
1）Normal atmospheric is tested
The modification fracturing propping agents prepared by quartz sand, ceramic particle and the embodiment of the present invention 6~10 is taken to take two parts of each 40ml
In test tube, 20ml water and 20ml kerosene are separately added into, water is colourless liquid, and kerosene is yellow liquid, is oozed by observing liquid
Saturating situation determines its grease permeability, the experimental results showed that, oil, water are permeated in quartz sand and ceramic particle and are all exceedingly fast, but water
Seepage flow is extremely slow and few in the modification fracturing propping agents obtained by embodiment 6~10, and oily seepage velocity is exceedingly fast, water level without
Remaining average water is 14.6ml after being decreased obviously, it can be seen that the modifying agent pair provided by the present invention for fracturing propping agents
The modifying function of fracturing propping agents is fabulous, significantly enhances it and selects permeability；
2）Applied voltage test
The modification fracturing propping agents obtained by 50g embodiments 6~10 are weighed, pours into respectively in core holding unit packing element, adds confining pressure
4.0MPa in lower difference displacement clear water different in flow rate, the same drive of grease and kerosene, records displacement pressure, as a result as follows：Clear water flow velocity
During for 5mL/min, displacement pressure 0.042MPa, when clear water flow velocity is 10mL/min, displacement pressure 0.061MPa；Grease is same
When driving flow velocity as 5mL/min, displacement pressure 0.031MPa, when grease is with flow velocity is driven as 10mL/min, displacement pressure is
0.050MPa；When kerosene flow velocity is 5mL/min, displacement pressure 0.011MPa, when kerosene flow velocity is 10mL/min, displacement pressure
For 0.016MPa, it can be seen that the modifying agent provided by the present invention for fracturing propping agents is to the modifying function of fracturing propping agents
It is fabulous, it significantly enhances it and selects permeability.
Claims (9)
1. a kind of modifying agent for fracturing propping agents, which is characterized in that the modifying agent for fracturing propping agents prepares former
Material includes the substance of following parts by weight：15~30 parts of native graphite, 6~15 parts of sodium nitrate, 40~80 parts of potassium permanganate, peroxide
Change 18.5~26.5 parts of hydrogen solution.
2. a kind of modifying agent for fracturing propping agents according to claim 1, which is characterized in that described to be used for pressure break branch
The modifying agent of support agent prepares the substance that raw material includes following parts by weight：18~22.5 parts of native graphite, sodium nitrate 9~11.5
Part, 48~62 parts of potassium permanganate, 20.5~21.5 parts of hydrogenperoxide steam generator.
3. a kind of modifying agent for fracturing propping agents according to claim 1, which is characterized in that described to be used for pressure break branch
The modifying agent of support agent prepares the substance that raw material includes following parts by weight：20 parts of native graphite, 10 parts of sodium nitrate, 60 parts of permanganic acid
Potassium, 21.4 parts of hydrogenperoxide steam generator.
4. according to a kind of modifying agent for fracturing propping agents described in claim 1,2 or 3, which is characterized in that the peroxide
Change the aqueous hydrogen peroxide solution that hydrogen solution is 18~22% concentration.
A kind of 5. preparation process of the modifying agent as claimed in claim 4 for fracturing propping agents, which is characterized in that the system
Standby technique includes following preparation process：
1）Native graphite and sodium nitrate are added in the concentrated sulfuric acid of 70~80 parts by weight, are stirred in ice-water bath to completely mixed
It closes, obtains mixed liquor；
2）Potassium permanganate is divided into 2~50 parts by weight, to step 1）Obtained mixed liquor adds in one every 2~5min
It is secondary, it is added completely into, and mixeding liquid temperature in adition process is controlled to be no more than 20 DEG C, is stirred after potassium permanganate is added completely by several times
2~3h is reacted, obtains oxidation mixed liquor；
3）By step 2）Obtained oxidation mixed liquor is warming up to 33~37 DEG C, continues 30~45min of stirring, it is slowly added to 900~
The deionized water of 1100 parts by weight is warming up to 90~92 DEG C, continues 20~25min of stirring, adds in 3800~4100 parts by weight
Deionized water, and hydrogenperoxide steam generator is added dropwise, solution is in glassy yellow, obtains glassy yellow mixed liquor；
4）To step 3）Obtained bright yellow solution is filtered to obtain reaction product, and with the hydrogen chloride solution pair of 10% concentration
Reaction product is washed, and the reaction product after hydrogen chloride solution washs is centrifuged repeatedly and is washed using deionized water, until
Its last time cleaning solution pH value is 6.8~7.2, obtains graphite oxide, graphite oxide is scattered in deionized water, be made into matter
Measure the graphite oxide dispersion of a concentration of 2mg/mL, be placed in deionized water after the 7d that dialyses filter drying obtain it is described for pressure break
The modifying agent of proppant.
A kind of 6. preparation process of modifying agent for fracturing propping agents according to claim 5, which is characterized in that step
4）Described in centrifugal rotational speed be 8000~11000rpm.
7. the modified technique of a kind of fracturing propping agents using described in claim 4, which is characterized in that the modified technique includes
Following steps：
a）The modifier solution that mass concentration is 2mg/mL is made into deionized water by being dissolved in for the modifying agent of fracturing propping agents,
Proppant aggregate is placed in 30~35min of dipping in modifier solution by 30~35min of ultrasonic disperse, and taking-up is placed on vacuum ring
In border, dry 24~30h, obtains tentatively being modified proppant under the conditions of 40~45 DEG C；
b）By step a）Obtained preliminary modified proppant is placed in hydrazine hydrate steam, under the conditions of 78~82 DEG C reductase 12 4~
26h, taking-up are placed in vacuum environment, are dried under the conditions of 80 DEG C to constant weight, obtain modified fracturing propping agents.
A kind of 8. modified technique of fracturing propping agents according to claim 7, which is characterized in that the proppant aggregate packet
It includes but is not limited to quartz sand and ceramic particle.
9. the modified technique of a kind of fracturing propping agents according to claim 8, which is characterized in that the quartz sand and ceramics
The grain diameter of particle is 10~60 mesh.
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