NL2025333B1 - Hydraulic fracturing fluid, gas extraction system and gas extraction method - Google Patents
Hydraulic fracturing fluid, gas extraction system and gas extraction method Download PDFInfo
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- NL2025333B1 NL2025333B1 NL2025333A NL2025333A NL2025333B1 NL 2025333 B1 NL2025333 B1 NL 2025333B1 NL 2025333 A NL2025333 A NL 2025333A NL 2025333 A NL2025333 A NL 2025333A NL 2025333 B1 NL2025333 B1 NL 2025333B1
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- 238000000605 extraction Methods 0.000 title claims abstract description 160
- 239000012530 fluid Substances 0.000 title claims abstract description 43
- 239000003245 coal Substances 0.000 claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000035699 permeability Effects 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 28
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 97
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 43
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 17
- -1 transition metal salt Chemical class 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 238000005553 drilling Methods 0.000 claims description 7
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 235000000396 iron Nutrition 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims 22
- 229960004365 benzoic acid Drugs 0.000 claims 2
- 235000010233 benzoic acid Nutrition 0.000 claims 2
- 239000004160 Ammonium persulphate Substances 0.000 claims 1
- 235000019395 ammonium persulphate Nutrition 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000006011 modification reaction Methods 0.000 abstract description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/665—Compositions based on water or polar solvents containing inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
-
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
-
- 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
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/006—Production of coal-bed methane
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/2607—Surface equipment specially adapted for fracturing operations
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/261—Separate steps of (1) cementing, plugging or consolidating and (2) fracturing or attacking the formation
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F7/00—Methods or devices for drawing- off gases with or without subsequent use of the gas for any purpose
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/10—Geothermal energy
Abstract
The invention provides a hydraulic fracturing fluid for fracturing and enhancing permeability for coal seams, including a first component and a second component. The first component is an aqueous solution of persulfate. The second component is a mixture of water and porous carbon containing transition metal ions. The invention further discloses a gas extraction system and a gas extraction method. During hydraulic fracturing, the hydraulic fracturing fluid and the organic matters with different molecular weights in coal seams continuously perform oxidation and in-situ modification reactions in a wide temperature range, thereby partially dissolving organic matters with low molecular weight, dredging the fractures and pores in coal seams, and reducing methane adsorbability of the coal seams. Therefore, the gas absorbed in coal seams is converted to free gas, greatly improving the permeability enhancement effect of coal seams compared with the simple hydraulic fracturing in the prior art.
Description
EXTRACTION METHOD CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority from Chinese Patent Application No. 201910621623.3, filed on July 10, 2019. The content of the aforementioned application, including any intervening amendments thereto, is incorporated herein by reference in its entirety.
TECHNICAL FIELD This application relates to coal mining technique, and more particularly to the permeability enhancement and gas extraction in coal reservoirs.
BACKGROUND OF THE INVENTION Coal mine gas is the main factor that causes coal mine disasters, but it is a non- renewable clean energy. The simultaneous extraction of coal and gas is the basic technique to prevent gas outbursts and achieve resource utilization.
In China, coal seams generally have large gas contents, strong adsorption and low permeability. Most coal seam gas is stored in an adsorbed state on the inner surface of pores in coal matrices, and only a small amount of the coal seam gas dissociates in cleats and fractures. The coal mine gas is mainly extracted by means of borehole extraction, and the extraction efficiency thereof mainly depends on the permeability of the coal. Therefore, it is effective to increase the permeability of coal reservoirs to realize the simultaneous extraction of coal and gas.
As the mine depth continues to increase, the permeability of the coal increasingly limits the gas extraction. Efficient techniques for enhancing the permeability of coal reservoirs are essential for the safe production of coal mine and gas extraction in coal seams. In order to enhance the permeability of coal reservoirs, many studies have been carried out, such as hydraulic fracturing, high-pressure gas fracturing, microwave fracturing and chemical permeability enhancement. However,
existing physical permeability enhancements such as hydraulic fracturing, high- pressure gas fracturing and microwave fracturing are mainly applied to coal seams which are harder and have better air permeability; and existing chemical permeability enhancements have problems such as low efficiency, serious environmental pollution, poor stability of permeability enhancement agents and strong toxicity.
Therefore, it is necessary to develop a high-efficient, safe and stable chemical permeability enhancement method to improve the permeability of coal seams to promote gas extraction.
SUMMARY OF THE INVENTION An object of the invention is to provide a hydraulic fracturing fluid for improving gas extraction efficiency.
To achieve the above-mentioned object, the invention provides a hydraulic fracturing fluid for fracturing and enhancing permeability of a coal seam, which comprises a first component and a second component, wherein the first component is an aqueous solution of persulfate; the second component is a mixture of water and porous carbon containing transition metal ions; and based on the hydraulic fracturing fluid, the first component is 0.9-1.1 parts by volume, and the second component is
0.9-1.1 parts by volume.
In some embodiments, based on the hydraulic fracturing fluid, the first component is 1 part by volume, and the second component is 1 part by volume.
In some embodiments, the persulfate in the first component is ammonium persulfate and/or sodium persulfate and/or calcium persulfate and/or potassium persulfate; and the first component comprises 1-25 parts by weight of persulfate and 100 parts by weight of water.
In some embodiments, the porous carbon containing transition metal ions in the second component is prepared by a method comprising steps of: mixing transition metal salt with aromatic carboxylic acid in a ball mill to obtain a mixture, and calcining the mixture in an inert atmosphere at high temperature to obtain the porous carbon containing transition metal ions;
wherein the transition metal salt is nickel nitrate and/or manganese chloride and/or cobalt nitrate and/or copper sulfate and/or zinc nitrate; the aromatic carboxylic acid is benzenetricarboxylic acid and/or terephthalic acid and derivatives thereof and/or p-hydroxybenzoic acid and/or p-aminobenzoic acid; the inert atmosphere is nitrogen or argon, and a calcining temperature is 500-1000 °C; the transition metal salt is 0.8-1.2 parts by weight, and the aromatic carboxylic acid is 0.8-1.2 parts by weight; and the second component comprises not more than 25 parts by weight of the porous carbon containing transition metal ions and 100 parts by weight of water.
The invention further discloses a gas extraction system using the hydraulic fracturing fluid, which comprises a fracturing borehole and a plurality of extraction boreholes provided between a roof and a floor of the coal seam; wherein the fracturing borehole has a fractured area in the coal seam, and the extraction boreholes are provided in the fractured area at left and right sides of the fracturing borehole, respectively; a fracturing pipe is inserted in the fracturing borehole, and an extraction pipe is inserted in each of the extraction boreholes; a fluid inlet is provided on the fracturing pipe, and a gas outlet is provided on the extraction pipe; the fracturing pipe reaches downward out of the floor of the coal seam and is connected to a mixer; the mixer is provided with a first inlet, a second inlet and an outlet; the outlet of the mixer is connected to the fracturing pipe, the first inlet of the mixer is connected to a first component feeder, and the second inlet of the mixer is connected to a second component feeder; the fracturing pipe between the mixer and the fracturing borehole is connected with a pressure gauge and a discharge pipe provided with a discharge valve; and the extraction pipe reaches downward out of the floor of the coal seam and is connected to a main extraction pipe which is connected to a gas extractor and provided with a main extraction valve, and an extraction valve is provided on the extraction pipe.
In some embodiments, the first component feeder comprises a first component feed tank which is connected to a first component feed pump via a first outlet pipe; an outlet of the first component feed pump is connected to the first inlet of the mixer via a first component feed pipe, and a first component feed valve is provided on the first component feed pipe; and the second component feeder comprises a second component feed tank which is connected to a second component feed pump via a second outlet pipe; an outlet of the second component feed pump is connected to the second inlet of the mixer via a second component feed pipe, and a second component feed valve is provided on the second component feed pipe.
In some embodiments, an ultrasonic vibration plate is provided on a bottom of the second component feed tank, and an ultrasonic generator is provided on the ultrasonic vibration plate.
The invention further discloses a gas extraction method using the gas extraction system, which comprises: (1) preparation (1.1) drilling and preparing the hydraulic fracturing fluid drilling one fracturing borehole and two extraction boreholes by a drilling rig from the floor to the roof of the coal seam, so that the two extraction boreholes are located in the fractured area at two sides of the fracturing borehole, respectively; preparing the first component: dissolving 1-25 parts by weight of persulfate in 100 parts by weight of water to obtain the first component and storing the first component in the first component feed tank; and preparing the second component: mixing transition metal salt with aromatic carboxylic acid to obtain a mixture, calcining the mixture in an inert atmosphere at high temperature to obtain the porous carbon containing transition metal ions; placing the porous carbon containing transition metal ions in water to obtain the second component and storing the second component in the second component feed tank; and turning on the ultrasonic generator on the ultrasonic vibration plate, so that the porous carbon containing transition metal ions evenly disperses in water inthe second component feed tank;
(1.2) arranging fracturing equipment and extraction equipment pre-installing the pressure gauge and the discharge pipe on a part of the fracturing pipe out of the fracturing borehole, and pre-installing the discharge valve on the discharge pipe; and pre-installing the main extraction valve on the main
5 extraction pipe, and pre-installing the extraction valve on the extraction pipe;
placing the fracturing pipe in the fracturing borehole, such that one end of the fracturing pipe reaches the roof of the coal seam, and the other end of the fracturing pipe, out of the fracturing borehole, is connected to the outlet of the mixer;
connecting individual parts of the first component feeder, and connecting the first component feed pipe to the first inlet of the mixer;
connecting individual parts of the second component feeder, and connecting the second component feed pipe to the second inlet of the mixer; and arranging the extraction equipment: placing the extraction pipe in each of the extraction boreholes, such that one end of the extraction pipe reaches the roof of the coal seam, and the other end of the extraction pipe, out of each of the extraction boreholes, is connected to the main extraction pipe; connecting the main extraction pipe to the gas extractor;
(2) hole sealing sealing openings of the fracturing and extraction boreholes by a hole packer; (3) hydraulic fracturing closing the discharge valve; opening the first and second component feed valves, and the first and second component feed pumps; pumping the first and second components to the fracturing borehole at the same time to fracture the coal seam to enhance permeability thereof;
recording an initial pressure in the fracturing pipe by reading the pressure gauge within 5 min after the first and second component feed pumps are turned on, wherein the initial pressure is 25-30 MPa;
continuously observing the pressure gauge; when a pressure in the fracturing pipe drops to 15+3 MPa and remains not more than 18 MPa for 5 min, closing the first and second component feed valves, and the first and second component feed pumps; and opening the discharge valve to release the pressure in the fracturing pipe; when the pressure reading on the pressure gauge returns to atmospheric pressure, closing the discharge valve; and (4) gas extracting opening the main extraction valve and extraction valves, starting the gas extractor to extract gas in the extraction boreholes and storing the gas; observing the gas extraction volume per unit time via the gas extractor, and when the gas extraction volume per unit time is not more than 10 L/min, ending step (4).
In some embodiments, the persulfate in the first component is ammonium persulfate; the porous carbon containing transition metal ions in the second component is porous carbon containing copper irons which is prepared by mixing copper sulfate and benzenetricarboxylic acid at a weight ratio of 6:4 in a ball mill and calcining the resulting mixture under a nitrogen atmosphere at 600 °C.
In some embodiments, the first component is an aqueous solution of ammonium persulfate having a percent concentration by weight of 5%-10%; and the second component is a mixture of water and the porous carbon containing copper ions having a percent concentration by weight of 6%. The present invention has the following beneficial effects: In the present invention, during the hydraulic fracturing of coal seams, the hydraulic fracturing fluid and organic matter with different molecular weights in the coal seam continuously perform oxidation and in-situ modification reactions in a wide temperature range, thereby partially dissolving organic matters with a low molecular weight, dredging fractures and pores in the coal seam, and reducing the methane adsorbability of the coal seam. Therefore, compared with the simple hydraulic fracturing in the prior art, in the present invention, gas absorbed by the coal seam is converted to free gas, which greatly improves the permeability enhancement effect of the coal seam.
The ultrasonic vibration plate promotes the uniform and thorough mixing of water and the porous carbon containing transition metal ions by transmitting ultrasonic waves to water, which improves the reaction efficiency between the hydraulic fracturing fluid and the organic matter in the coal seam.
The gas extraction system in the present invention has a simple structure, is convenient for operation, and is capable of conveniently performing hydraulic fracturing in the coal seam using the hydraulic fracturing fluid. It is possible to enhance the permeability by employing water or only a persulfate solution as the hydraulic fracturing fluid, but it causes a poor effect. However, the permeability is obviously enhanced when the hydraulic fracturing fluid is obtained by mixing a solution of persulfate and a mixture of water and the porous carbon containing transition metal ions.
Compared with existing gas extraction methods, the gas extraction method in the present invention uses the hydraulic fracturing fluid and the gas extraction system to greatly improve the gas extraction efficiency, which not only solves safety problems caused by coal seam gas, but also improves the gas extraction efficiency and the gas production.
In conclusion, the hydraulic fracturing fluid, the gas extraction system and the gas extraction method in the present invention are safe, stable and high-efficient.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 schematically shows a gas extraction system according to an embodiment of the present invention.
Fig. 2 schematically shows gas extraction rates of a single extraction borehole using different hydraulic fracturing solutions according to an embodiment of the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS The present invention provides a hydraulic fracturing fluid for fracturing and increasing permeability of a coal seam, which includes a first component and a second component, wherein the first component is an aqueous solution of persulfate;
the second component is a mixture of water and porous carbon containing transition metal ions; and based on the hydraulic fracturing fluid, the first component is 0.9-1.1 parts by volume, and the second component is 0.9-1.1 parts by volume; preferably, based on the hydraulic fracturing fluid, the first component is 1 part by volume, and the second component is 1 part by volume.
In some embodiments, the persulfate in the first component is ammonium persulfate and/or sodium persulfate and/or calcium persulfate and/or potassium persulfate, i.e., persulfate is one or combinations of ammonium persulfate, sodium persulfate, calcium persulfate and potassium persulfate; and the first component includes 1-25 parts by weight of persulfate and 100 parts by weight of water.
The porous carbon containing transition metal ions in the second component is prepared by the following steps.
Transition metal salt is mixed with aromatic carboxylic acid in a ball mill to obtain a mixture, and the mixture is calcined in an inert atmosphere at high temperature to obtain porous carbon containing transition metal ions; where the ball mill is a conventional device, so the specific structure thereof is not described herein.
The transition metal salt is nickel nitrate and/or manganese chloride and/or cobalt nitrate and/or copper sulfate and/or zinc nitrate, i.e., the transition metal salt is one or combinations of nickel nitrate, manganese chloride, cobalt nitrate, copper sulfate and zinc nitrate; the aromatic carboxylic acid is benzenetricarboxylic acid and/or terephthalic acid and derivatives thereof and/or p-hydroxybenzoic acid and/or p-aminobenzoic acid, i.e., the aromatic carboxylic acid is one or combinations of benzenetricarboxylic acid, terephthalic acid and derivatives thereof, p- hydroxybenzoic acid and p-hydroxybenzoic acid; the inert atmosphere is nitrogen or argon, and a calcining temperature is 500-1000 °C; the transition metal salt is 0.8-
1.2 parts by weight, preferably 1.2 parts, and the aromatic carboxylic acid is 0.8-1.2 parts by weight, preferably 0.8 part.
The second component comprises not more than 25 parts by weight of porous carbon containing transition metal ions and 100 parts by weight of water.
As shown in Fig. 1, the invention further discloses a gas extraction system using the hydraulic fracturing fluid, which includes a fracturing borehole 3 and a plurality of extraction boreholes 4 provided between a roof 1 and a floor 2 of the coal seam. The fracturing borehole 3 is provided with a fractured area, where the coal in the fractured area is fractured and permeability thereof is enhanced. The extraction boreholes 4 are provided in the fractured area at the left and right sides of the fracturing borehole 3, respectively.
A fracturing pipe 5 is inserted in the fracturing borehole 3, and an extraction pipe 6 is inserted in each of the extraction boreholes 4. A fluid inlet is provided on the fracturing pipe 5, so that the fluid flows from the fracturing pipe 5 to the coal seam through the fracturing borehole 3; and a gas outlet is provided on the extraction pipe 6, so that the gas flows from the coal seam to the extraction pipe 6 through the extraction boreholes 4; it is a conventional technique to provide openings on pipes, so the inlet on the fracturing pipe 5 and the outlets on the extraction pipe 6 are not shown in the drawings.
The fracturing pipe 5 extends out of the floor 2 of the coal seam and is connected to a mixer 7; the mixer 7 is provided with a first inlet 8, a second inlet 9 and an outlet 10; the outlet 10 of the mixer is connected to the fracturing pipe 5; the first inlet 8 of the mixer is connected to a first component feeder, and the second inlet 9 of the mixer is connected to a second component feeder.
The fracturing pipe 5 between the mixer 7 and the fracturing borehole 3 is connected with a pressure gauge 11 and a discharge pipe 12 which is provided with a discharge valve 13.
The extraction pipe 6 extends out of the floor 2 of the coal seam and is connected to a main extraction pipe 14; the main extraction pipe 14 is connected to a gas extractor 15 and provided with a main extraction valve 16, and an extraction valve 17 is provided on the extraction pipe 6.
The gas extractor 15 is existing and is able to generate a negative pressure (containing a negative pressure generator such as an exhaust fan), which is not further described herein.
In some embodiments, the first component feeder includes a first component feed tank 18 which is connected to a first component feed pump 20 via a first outlet pipe 19; an outlet of the first component feed pump 20 is connected to the first inlet 8 of the mixer 7 via a first component feed pipe 21, and a first component feed valve 22 is provided on the first component feed pipe 21; and the second component feeder includes a second component feed tank 23 which is connected to a second component feed pump 25 via a second outlet pipe 24; an outlet of the second component feed pump 25 is connected to the second inlet 9 of the mixer 7 via a second component feed pipe 26, and a second component feed valve 27 is provided on the second component feed pipe 26.
The first component feed pump 20 and the second component feed pump 25 are the same type, so they have the same feed volume, which ensures that a volume ratio of the first component to the second component is approximately 1:1.
The gas extraction system in the present invention has a simple structure, is convenient for operation, and is able to pump the mixture of the first and second components to the fracturing borehole 3, thereby fracturing the coal seams around the fracturing boreholes. The gas extractor 15 generates a negative pressure to extract the gas in the fractured area via the extraction boreholes 4, the extraction pipe 6 and the main extraction pipe 14. The hydraulic fracturing fluid in the invention is employed to achieve a complex operation of fracturing and extraction, which obviously improves the gas extraction efficiency compared with ordinary gas extraction systems.
In some embodiments, an ultrasonic vibration plate 28 is provided on a bottom of the second component feed tank 23, and an ultrasonic generator is provided on the ultrasonic vibration plate 28. The ultrasonic generator is a conventional device and is not shown in the drawings.
The ultrasonic vibration plate 28 promotes an even mixing of water and porous carbon containing transition metal ions by transmitting ultrasonic waves to water.
The invention further discloses a gas extraction method using the gas extraction system, which includes the following steps.
(1) Preparation
(1.1) Boreholes are drilled and the hydraulic fracturing fluid is prepared.
A fracturing borehole 3 and two extraction boreholes 4 are drilled by a drilling rig from the floor 2 to the roof 1 of the coal seam, and the two extraction boreholes 4 are located in the fractured area at two sides of the fracturing borehole 3, respectively.
The hydraulic fracturing fluid is prepared by preparing the first component and the second component, respectively.
Specifically, 1-25 parts by weight of persulfate is dissolved in 100 parts by weight of water to obtain the first component, and the first component is stored in the first component feed tank 18; transition metal salt is mixed with aromatic carboxylic acid to obtain a mixture, and the mixture is calcined in an inert atmosphere at high temperature to obtain porous carbon containing transition metal ions. The porous carbon containing transition metal ions is placed in water to obtain the second component, and the second component is stored in the second component feed tank
23. The ultrasonic generator on the ultrasonic vibration plate 28 is turned on, so that the porous carbon containing transition metal ions evenly disperses in water in the second component feed tank 23.
(1.2) Fracturing equipment and extraction equipment are arranged.
The pressure gauge 11 and the discharge pipe 12 are pre-installed on a part of the fracturing pipe 5 out of the fracturing borehole 3, and the discharge valve 13 is pre-installed on the discharge pipe 12. The main extraction valve 16 is pre-installed on the main extraction pipe 14, and the extraction valve 17 is pre-installed on the extraction pipe 6.
The arrangement of the fracturing equipment is described as follows. The fracturing pipe 5 is placed in the fracturing borehole 3, such that one end of the fracturing pipe 5 reaches the roof 1 of the coal seam, and the other end of the fracturing pipe 5, out of the fracturing borehole 3, is connected to the outlet 10 of the mixer 7.
Individual parts of the first component feeder are connected, and the first component feed pipe 21 is connected to the first inlet 8 of the mixer 7.
Individual parts of the second component feeder are connected, and the second component feed pipe 26 is connected to the second inlet 9 of the mixer 7.
The arrangement of the extraction equipment is described as follows. The extraction pipe 6 is placed in each of the extraction boreholes 4, such that one end of the extraction pipe 6 reaches the roof 1 of the coal seam, and the other end of the extraction pipe 6, out of each of the extraction boreholes 4, is connected to the main extraction pipe 14; and the main extraction pipe 14 is connected to the gas extractor
15. (2) Sealing boreholes The fracturing borehole 3 and the extraction boreholes 4 are sealed by a hole packer.
(3) Hydraulic fracturing The discharge valve 13 is closed. The first component feed valve 22, the second component feed valve 27, the first component feed pump 20 and the second component feed pump 25 are opened. The first and the second components are pumped to the fracturing borehole 3 at the same time to fracture the coal seam to increase the permeability thereof.
An initial pressure in the fracturing pipe 5 is recorded within 5 min by reading the pressure gauge 11 after the first component feed pump 20 and the second component feed pump 25 are turned on, where the initial pressure is 25-30 MPa.
The pressure gauge 11 is continuously observed; when a pressure in the fracturing pipe drops to 1513 MPa and remains not more than 18 MPa for 5 min, the first component feed valve 22, the second component feed valve 27, the first component feed pump 20 and the second component feed pump 25 are closed; and the discharge valve 13 is opened to release the pressure in the fracturing pipe 5; when the pressure reading on the pressure gauge 11 returns to the atmospheric pressure, the discharge valve 13 is closed.
(4) Gas extraction The main extraction valve 16 and extraction valves 17 are opened, the gas extractor 15 is started to extract gas in the extraction boreholes 4 and the gas is stored.
A gas extraction volume per unit time is observed via the gas extractor 15. When the gas extraction volume per unit time is not more than 10 L/min, step (4) is ended.
In some embodiments, the persulfate in the first component is ammonium persulfate.
In some embodiments, porous carbon containing transition metal ions in the second component is porous carbon containing copper irons. Copper sulfate and benzenetricarboxylic acid are mixed at a weight ratio of 6:4 in a ball mill and the resulting mixture is calcined under a nitrogen atmosphere at 600 °C to obtain the porous carbon containing copper ions.
In some embodiments, the first component is an aqueous solution of ammonium persulfate having a percent concentration by weight of 2%-10%; preferably 5%-10%; and the second component is a mixture of water and the porous carbon containing copper ions having a percent concentration by weight of 1%-6%, preferably 6%. The present invention provides the hydraulic fracturing fluid, the gas extraction method and the gas extraction system, such that organic matter with low molecular weight is dissolved, fractures and pores in the coal seam are enlarged, increased and dredged, resulting in a smoother channel for gas extraction to improve the gas extraction efficiency. Moreover, the aromatic flakes in the coal are oxidized in-situ, and the methane adsorbability of the coal seam is reduced, so that the adsorbed gas is transferred to free gas, providing gas supply for the continuous and high-efficient gas extraction.
Experiments for hydraulic fracturing and gas extraction respectively using only water and the hydraulic fracturing fluid in the present invention were carried out herein. The first component was an aqueous solution of ammonium persulfate.
Experiments for hydraulic fracturing and gas extraction using the first component with different weight concentrations of ammonium persulfate were carried out and the results thereof were shown in Fig. 2. In Fig. 2, group A represented that only water was used for the hydraulic fracturing and gas extraction; group B represented that the first component was an aqueous solution of 2% by weight of ammonium persulfate; group C represented that the first component was an aqueous solution of
5% by weight of ammonium persulfate; group D represented that the first component was an aqueous solution of 10% by weight of ammonium persulfate; group E represented that the first component was an aqueous solution of 2% by weight of ammonium persulfate and simultaneously the second component was a mixture of water and 1% by weight of porous carbon containing copper ions; group F represented that the first component was an aqueous solution of 5% by weight of ammonium persulfate and simultaneously the second component was a mixture of water and 2% by weight of porous carbon containing copper ions; and group G represented that the first component was an aqueous solution of 10% by weight of ammonium persulfate and simultaneously the second component was a mixture of water and 6% by weight of porous carbon containing copper ions.
It was concluded from Fig. 2 that group G had the optimal extraction effect, that is, when the first component was an aqueous solution of 10% by weight of ammonium persulfate and simultaneously the second component was a mixture of water and 6% by weight of porous carbon containing copper ions, the gas extraction rate was 95 L/min. Compared with group G, group F had a lower gas extraction rate, but the gas extraction rate thereof is 78 L/min, which was still tar higher than other groups. Moreover, group F only used half of ammonium persulfate and two thirds of porous carbon of group G, resulting in lower cost. Therefore, in the present invention, the optimal dosage range of ammonium persulfate is between dosages of ammonium persulfate in groups G and F, i.e., 5%-10%.
It was also seen from Fig. 2 that as long as the hydraulic fracturing fluid in the present invention was employed, the gas extraction rate was increased. When the permeability of the coal seam was enhanced by adopting an aqueous solution of persulfate to corrode and modify the coal in the coal reservoirs during the hydraulic fracturing, average gas extraction rate of every borehole was increased obviously, and the permeability enhancement effect was greatly improved. The permeability enhancement effect was poor when only water or the aqueous solution of persulfate is used as the hydraulic fracturing fluid, and the permeability enhancement effect was greatly improved by using a mixed solution of persulfate and porous carbon containing copper ions.
There are differences between the present invention and the methods using acids for permeability enhancement. Hydrochloric acid, hydrofluoric acid and acetic acid dissolve carbonate minerals and sulfides in coal. Although the number of pores in the coal can be increased, it is not effective to enhance the connectivity of the pores and fractures. The hydraulic fracturing fluid of the invention can dissolve organic matters with low molecular weights in the coal, which not only increases the number of pores in the coal, but also greatly improves the connectivity of pores and fractures in the coal, thereby providing more favorable conditions for gas extraction.
There are differences between the present invention and methods using chlorine dioxide for permeability enhancement. Chlorine dioxide has strong oxidizing properties, but is extremely unstable and highly chemically corrosive. In addition, it is very sensitive to heat, vibration, impact and friction, easy to decompose to cause explosions, and inconvenient to be transported. Only on-site preparation is reliable, and it is difficult for on-site application on a large scale. However, respective components of the hydraulic fracturing fluid in the present invention are safe and stable during the whole process of transportation, storage and use.
There are differences between the present invention and the methods using Fenton reagent (a strong oxidation system containing hydrogen peroxide and ferrous ions) for permeability enhancement. Hydrogen peroxide decomposes quickly, especially at high concentrations, so that the Fenton reagent has strong oxidizing properties only in the first few minutes after preparation, so it is difficult to store, and must be prepared on site, and works only within few minutes after entering the coal seam. However, the hydraulic fracturing fluid of the present invention does not need to be prepared on site, and can continuously react with organic matters in the coal seam after entering the coal seam.
The above-mentioned embodiments are merely an illustration of the invention and are not intended to limit the scope of the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood that any modifications or equivalent replacements obtained by those skilled in the art without departing from the spirit of the invention shall fall within the scope of the appended claims.
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| CN111075496B (en) * | 2020-03-09 | 2021-04-02 | 河南理工大学 | Device for comprehensively eliminating and suppressing outburst and dust of coal bed by injecting flue gas absorption liquid at low pressure and outburst-eliminating and dust-suppressing method |
| CN113236217A (en) * | 2021-05-31 | 2021-08-10 | 中煤科工集团沈阳研究院有限公司 | Device and method for permeability increasing of low-permeability coal seam by using high-power ultrasonic waves |
| CN114737938A (en) * | 2022-03-21 | 2022-07-12 | 重庆大学 | Coal seam ultrasonic activation staged fracturing device |
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| US5967233A (en) * | 1996-01-31 | 1999-10-19 | Vastar Resources, Inc. | Chemically induced stimulation of subterranean carbonaceous formations with aqueous oxidizing solutions |
| US5964290A (en) * | 1996-01-31 | 1999-10-12 | Vastar Resources, Inc. | Chemically induced stimulation of cleat formation in a subterranean coal formation |
| US7541312B2 (en) * | 2004-03-18 | 2009-06-02 | Tda Research, Inc. | Porous carbons from carbohydrates |
| US9029300B2 (en) * | 2011-04-26 | 2015-05-12 | Baker Hughes Incorporated | Composites for controlled release of well treatment agents |
| CN102516957A (en) * | 2011-12-06 | 2012-06-27 | 中国地质大学（武汉） | Degradable drilling fluid used for drilling in soft coal seam |
| EP2935359A4 (en) * | 2012-12-21 | 2016-06-15 | Rhodia Operations | Compositions with ph responsive copolymer containing maep and/or mahp and methods for using same |
| JP2015059376A (en) * | 2013-09-20 | 2015-03-30 | 東レ株式会社 | Method for collection of gaseous hydrocarbon and/or liquid hydrocarbon from underground |
| CN103821554B (en) * | 2014-03-07 | 2016-03-30 | 重庆大学 | Based on the boring method for arranging without coal pillar mining Y type ventilation goaf |
| CA2944508C (en) * | 2014-04-03 | 2022-06-21 | Orin Technologies, Llc. | Method of chemically increasing the efficiency of peroxygen based viscosity reduction reactions |
| CN105822341B (en) * | 2016-06-12 | 2018-03-13 | 河南理工大学 | A kind of hypotonic anti-reflection system and method for coal seam supercritical carbon dioxide |
| CN106433599A (en) * | 2016-08-17 | 2017-02-22 | 富象油气技术服务有限公司 | Weakly-acidic copolymer fracturing fluid system and preparation method therefor |
| CN107282102B (en) * | 2017-06-22 | 2020-02-28 | 中国天辰工程有限公司 | Preparation method of metal-loaded molecular sieve catalyst |
| CN109519209A (en) * | 2018-10-25 | 2019-03-26 | 平顶山天安煤业股份有限公司 | A kind of fracturing process and device improving coal mine gas drainage effect |
| CN109681262B (en) * | 2018-12-10 | 2020-08-07 | 中国矿业大学 | Method for improving gas drilling extraction concentration in broken coal body |
| CN109794246B (en) * | 2019-01-11 | 2021-08-24 | 江苏理工学院 | Integrated honeycomb Ni @ C/C catalyst and preparation method and application thereof |
| CN210483691U (en) * | 2019-07-10 | 2020-05-08 | 河南理工大学 | Gas extraction system |
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