CN112322271A - Low-temperature gel breaking activator and using method thereof - Google Patents
Low-temperature gel breaking activator and using method thereof Download PDFInfo
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- CN112322271A CN112322271A CN202011247575.5A CN202011247575A CN112322271A CN 112322271 A CN112322271 A CN 112322271A CN 202011247575 A CN202011247575 A CN 202011247575A CN 112322271 A CN112322271 A CN 112322271A
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- 239000012190 activator Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000012530 fluid Substances 0.000 claims abstract description 83
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 24
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims abstract description 22
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 22
- 239000008103 glucose Substances 0.000 claims abstract description 22
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 21
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 21
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 19
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 28
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 16
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 8
- 229920002907 Guar gum Polymers 0.000 claims description 7
- 239000000665 guar gum Substances 0.000 claims description 7
- 229960002154 guar gum Drugs 0.000 claims description 7
- 235000010417 guar gum Nutrition 0.000 claims description 7
- 229920013818 hydroxypropyl guar gum Polymers 0.000 claims description 7
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 6
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000176 sodium gluconate Substances 0.000 claims description 5
- 235000012207 sodium gluconate Nutrition 0.000 claims description 5
- 229940005574 sodium gluconate Drugs 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- -1 hydroxypropyl Chemical group 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000010276 construction Methods 0.000 abstract description 13
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 abstract description 9
- JDXXTKLHHZMVIO-UHFFFAOYSA-N 2-(3-hydroxypropyl)guanidine Chemical compound NC(=N)NCCCO JDXXTKLHHZMVIO-UHFFFAOYSA-N 0.000 abstract description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 abstract 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 244000250129 Trigonella foenum graecum Species 0.000 description 1
- 235000001484 Trigonella foenum graecum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000001019 trigonella foenum-graecum Nutrition 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
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/26—Gel breakers other than bacteria or enzymes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a low-temperature gel breaking activator and a using method thereof, wherein the gel breaking activator comprises 0.2-0.5% of ferrous acetylacetonate; 0.3-0.8% of ferrous sulfate; 0.5-3% of glucose; the balance of water. Under the condition that ammonium persulfate or hydrogen peroxide is taken as a gel breaker in a hydroxypropyl guanidine gum and carboxymethyl guanidine gum system, gel breaking can be completed in 3-4 hours by adding 0.1-0.4% of gel breaking activator at the low temperature of 30 ℃ and 40 ℃, and the viscosity of the fracturing fluid after gel breaking is less than or equal to 5mPa & s. The gel breaking activator reduces the addition amount, enhances the applicability of the gel breaking activator, breaks gel thoroughly, reduces the influence of peroxide on the environment, and meets the requirement of oil field fracturing construction.
Description
Technical Field
The invention relates to the field of oilfield chemicals, in particular to a low-temperature gel breaking activator in a low-permeability oilfield fracturing fluid system and a using method thereof.
Technical Field
Fracturing is one of the main means for increasing oil field production and has been commonly used in various large oil fields. The basic functions of the fracturing fluid in fracturing construction are as follows: (1) forming and extending a crack using hydraulic wedge action; (2) conveying and paving fracturing propping agents along the cracks; (3) after fracturing, the liquid can break gel and flow back to the maximum extent, the damage to cracks and a liquid layer is reduced, and a supporting seam belt with a certain length and high flow conductivity is formed in a reservoir stratum. Conventional fracturing operations typically employ water-based fracturing fluids as the primary. Typically, guar gum, fenugreek gum, polyacrylamide, etc. are used. Water-based fracturing fluids can cause some damage to the formation if not broken, and therefore, a breaker is required to break the polymer.
Common breakers are 1) oxidizing agents such as ammonium persulfate, potassium persulfate, hydrogen peroxide, and the like; 2) releasing the acid; 3) the biological enzyme can play a good role in breaking gel at the temperature lower than 25 ℃, the activity of the enzyme is reduced at the temperature higher than 25 ℃, the cost of the enzyme is higher, and the requirement on the environment is harsh, so an oxidant is generally adopted as a gel breaker at the temperature higher than 25 ℃. The gel breaking performance of oxidants such as ammonium persulfate and hydrogen peroxide is better above 50 ℃ due to the fact that the oxidants release highly reactive oxygen radicals at high temperatures. For low-permeability oilfield wells, the ambient temperature is relatively low, about 25-50 ℃, due to shallow burial depth. When the temperature is lower than 50 ℃, the energy required by the oxidant to generate oxygen free radicals is not enough provided, so that the gel breaking capacity of the oxidant gel breaker is greatly weakened, and the purpose of gel breaking cannot be achieved, therefore, the oxidant is used for reducing the temperature to 25-50 DEG CThe gel breaking system needs to be added with a gel breaking activator, so that the oxidant can release oxygen free radicals at low temperature to break the macromolecular structure of the fracturing fluid, and the purpose of gel breaking is achieved. A common oxide gel breaking activator is FeSO4Etc. but Fe2+After gel breaking, Fe (OH) is generated3Precipitation, which affects the efficiency of construction, simply adding FeSO4The fracturing fluid can break gel rapidly, and the operation purpose can not be achieved. At present, the gel breaking system used at the low temperature of 25-50 ℃ has the defects of large addition amount of an activator, narrow application range, long gel breaking time, large environmental hazard, incomplete gel breaking and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a low-temperature gel breaking activator and a using method thereof, which are used for solving the problem of Fe in the existing low-permeability oil field fracturing fluid system2+Breaking the gel to produce Fe (OH)3Large addition amount of the precipitation and gel breaking activator, narrow application range, short gel breaking time, large harm to the environment, incomplete gel breaking and the like.
In order to achieve the purpose, the invention adopts the technical scheme that: the low-temperature gel breaking activator comprises the following components in percentage by mass:
0.2-0.5% of ferrous acetylacetonate;
0.3-0.8% of ferrous sulfate;
0.5-3% of glucose;
the balance of water; the mass percentage of each component is one hundred percent.
In the scheme, the total effective content of the ferrous acetylacetonate is more than or equal to 98.0 percent, and the iron content is 21.5-22 percent; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg.
The invention also provides a use method of the low-temperature gel breaking activator, which is characterized in that the prepared guanidine gum fracturing fluid is preheated for 15-20min to 30-40 ℃ at the specified temperature, 0.1-0.4% of the low-temperature gel breaking activator is added, and the mixture is stirred for 5-10 min.
In the method, the gel breaking temperature is 30 ℃ or 40 ℃.
In the method, the gel breaking viscosity of the fracturing fluid is less than or equal to 5mPa & s.
In the method, the guanidine gum fracturing fluid comprises the following components in percentage by mass:
the balance of water, and the mass percent of each component is one hundred percent.
In the method, the preparation method of the guanidine gum fracturing fluid comprises the following steps:
step 1: accurately weighing 2.5g of hydroxypropyl guar gum or carboxymethyl guar gum to prepare 1000g of 0.25% hydroxypropyl or carboxymethyl guar gum base solution at the rotating speed of 4500-5000 r/min. Swelling for 1h under the condition of 30 ℃ water bath, adding 3g of 10% borax water solution crosslinking agent, crosslinking for 10min, and measuring the viscosity of the mixture by using a rotational viscometer to be 60-65 mPa & s.
Step 2: taking 5% of fluorocarbon surfactant FLYZ and 95% of water as a cleanup additive, adding 1g of cleanup additive, 5g of clay stabilizer FLYF and 0.5g of sodium gluconate as a defoaming agent into the base solution, adding a gel breaker, and stirring for 10 min.
8. The use method of the low-temperature gel breaking activator in the claim 6 is characterized in that the gel breaker in the guanidine gum fracturing fluid is one of ammonium persulfate or 15% hydrogen peroxide; the mass percent of the ammonium persulfate is 0.07 percent, and the mass percent of the 15 percent hydrogen peroxide is 0.05 percent.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses common FeSO at the low temperature of 25-50 DEG C4Based on the activating agent, a proper amount of ferrous acetylacetonate is added, and after gel breaking, the precipitation of iron ions is inhibited, and Fe (OH) is not generated3The decomposition of the oxidant can be further promoted due to the induction and the synergistic effect among molecules while the sediments are settled; acetylacetone is generated after the decomposition of the ferrous acetylacetonate, and the acetylacetone exists mostly in an enol form at normal temperature and can also play a role of an activator; glucose is common reducing sugar, can play a role of partial activator, can generate sodium gluconate after gel breaking, can play a role of defoamer, and the factors act togetherThe rapid gel breaking can be realized. The gel breaking time is 3-4 h, the formula proportion of the gel breaking activator can be adjusted according to the gel breaking time and the temperature, and the applicability of the gel breaking activator is enhanced; the viscosity change is small within 2 hours of the initial gel breaking, and the basic requirements of construction are met; the gel breaking activator has wide application range, is suitable for an ammonium persulfate gel breaker system and a hydrogen peroxide gel breaker system, and can well break a hydroxypropyl guanidine gum and carboxymethyl guanidine gum system.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
The invention provides a low-temperature gel breaking activator which comprises the following components in percentage by mass: 0.2-0.5%; ferrous sulfate: 0.3-0.8%; glucose: 0.5-3%; the balance of water. Wherein the total effective content of the ferrous acetylacetonate is more than or equal to 98.0 percent, and the iron content is 21.5-22 percent; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg. The preparation method comprises the following steps: the components are weighed according to the mass percentage, are added into water for slightly heating and dissolving, and are stirred uniformly.
The invention also provides a use method of the low-temperature gel breaking activator, wherein the guanidine gum fracturing fluid comprises the following components in parts by mass: 0.25 percent; a crosslinking agent: 0.3 percent; 0.1% of cleanup additive; clay stabilizer: 0.5 percent; defoaming agent: 0.05 percent; a gel breaker: 0.05 to 0.07 percent. The preparation method of the fracturing fluid comprises the following steps: accurately weighing 2.5g of hydroxypropyl guar gum or carboxymethyl guar gum to prepare 990g of 0.25% hydroxypropyl guar gum or carboxymethyl guar gum base fluid at the rotating speed of 4500-5000 r/min. Swelling for 1h under the condition of 30 ℃ water bath, adding 3g of 10% borax water solution crosslinking agent, crosslinking for 10min, and measuring the viscosity of the mixture by using a rotational viscometer to be 60-70 mPa & s. 5 percent of fluorocarbon surfactant FLYZ and 95 percent of water are taken as cleanup additives, and 1g of cleanup additive is added into the base solution. Adding clay stabilizer FLYF 5g, adding sodium gluconate 0.5g as defoaming agent, adding ammonium persulfate 0.7g, hydrogen peroxide 0.07% or 0.5g 15% and gel breaker 0.05%, and stirring for 10 min.
The use method of the low-temperature gel breaking activator comprises the following steps: preheating the prepared guanidine gum fracturing fluid at 30 ℃ or 40 ℃ for 15-20min, adding 0.1-0.4% of low-temperature gel breaking activator, stirring for 5-10min, starting timing, measuring the viscosity of the fracturing fluid once every half hour, and determining that gel breaking is finished when the viscosity of the fracturing fluid is less than or equal to 5mPa & s. The gel breaking of an ammonium persulfate and hydrogen peroxide system can be completed within 3-4 h by adjusting the proportion and the addition concentration of each component of the gel breaking activator, and the fracturing construction requirement is met.
Example 1
The low-temperature gel breaking activator described in embodiment 1 comprises, by mass, ferrous acetylacetonate: 0.5 percent; ferrous sulfate: 0.8 percent; glucose: 0.5 percent; the balance of water. Wherein the total effective content of the ferrous acetylacetonate is more than or equal to 98.0 percent, and the iron content is 21.5-22 percent; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg. The preparation method comprises the following steps: the components are weighed according to the mass percentage, added into water, dissolved by slight heating and stirred evenly.
The invention also provides a use method of the low-temperature gel breaking activator, wherein the hydroxypropyl guanidine gum fracturing fluid comprises the following components in parts by mass: 0.25 percent; a crosslinking agent: 0.3 percent; 0.1% of cleanup additive; clay stabilizer: 0.5 percent; defoaming agent: 0.05 percent; a gel breaker: 0.07 percent. The preparation method of the fracturing fluid comprises the following steps: accurately weighing 2.5g of hydroxypropyl guar gum, and preparing 990g of 0.25% hydroxypropyl guar gum base liquid at the rotating speed of 4500-5000 r/min. Swelling for 1h under the condition of 30 ℃ water bath, adding 3g of 10% borax water solution crosslinking agent, crosslinking for 10min, and measuring the viscosity of the mixture by using a rotational viscometer to be 60-65 mPa & s. 5 percent of fluorocarbon surfactant FLYZ and 95 percent of water are taken as cleanup additives, and 1g of cleanup additive is added into the base solution. Adding clay stabilizer FLYF 5g, adding sodium gluconate 0.5g as defoaming agent, adding ammonium persulfate 0.7g, adding 0.07% as gel breaker, and stirring for 10 min.
The use method of the low-temperature gel breaking activator comprises the following steps: preheating the prepared hydroxypropyl guanidine gum fracturing fluid at 30 ℃ for 20min, adding 0.4% of low-temperature gel breaking activator, stirring for 5min, measuring the viscosity of the fracturing fluid once every half hour, and judging that the gel breaking is finished when the viscosity of the fracturing fluid is less than or equal to 5mPa & s.
Table 1 fracturing fluid viscosity as a function of time in example 1
| Time/h | 0 | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 |
| viscosity/mPas | 61 | 55 | 52 | 49 | 45 | 20 | 17 | 8.48 | 4.92 |
At 30 ℃, the hydroxypropyl guanidine gum fracturing fluid takes 0.07 percent of ammonium persulfate as a gel breaker, and takes the weight ratio of ferrous acetylacetonate: 0.5 percent; ferrous sulfate: 0.8 percent; glucose: 0.5 percent; the balance of water forms the low-temperature gel breaking activator. As shown in table 1, 0.4% of low-temperature gel breaking activator is added into the fracturing fluid, the viscosity of the fracturing fluid is reduced slightly in the first 2h, the basic fracturing construction condition is met, the viscosity is reduced greatly after 2h, the effective content of the original low-temperature gel breaking activator is only 1.8%, the adding concentration is 0.4%, the effective content of the low-temperature gel breaking activator added into the fracturing fluid is extremely low, the low-temperature gel breaking activator has the characteristic of small adding amount, and the performance of the gel breaker can be effectively excited, so that the ammonium persulfate residue of the fracturing fluid after gel breaking is low, and the damage to a rock stratum is reduced; the viscosity of the fracturing fluid is reduced to 4.92mPa & s after the fracturing fluid is broken for 4 hours, and the flowback requirement of the fracturing fluid is met.
Example 2
The low-temperature gel breaking activator described in embodiment 2 comprises, by mass, ferrous acetylacetonate: 0.5 percent; ferrous sulfate: 0.8 percent; glucose: 0.5 percent; the balance of water. Wherein the total effective content of the ferrous acetylacetonate is more than or equal to 98.0 percent, and the iron content is 21.5-22 percent; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg. The preparation method comprises the following steps: the components are weighed according to the mass percentage, are added into water for slightly heating and dissolving, and are stirred uniformly.
The invention also provides a use method of the low-temperature gel breaking activator, wherein the carboxymethyl guanidine gum fracturing fluid comprises the following components in parts by mass: 0.25 percent; a crosslinking agent: 0.3 percent; 0.1% of cleanup additive; clay stabilizer: 0.5 percent; defoaming agent: 0.05 percent; a gel breaker: 0.05 percent. The preparation method is the same as that of the example 1, and the gel breaker and 15% hydrogen peroxide with the concentration of 0.05% are added.
Preheating the prepared carboxymethyl guanidine gum fracturing fluid at 30 ℃ for 15min, adding 0.4% of low-temperature gel breaking activator, stirring for 10min, starting timing, measuring the viscosity of the fracturing fluid every half hour, and judging that gel breaking is finished when the viscosity of the fracturing fluid is less than or equal to 5mPa & s.
Table 2 fracturing fluid viscosity as a function of time in example 2
| Time/h | 0 | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 |
| viscosity/mPas | 66 | 58 | 56 | 42 | 39 | 23 | 12 | 6.53 | 4.36 |
At 30 ℃, under the condition that 15% of hydrogen peroxide of 0.05% is used as a gel breaker, 0.4% of a low-temperature gel breaking activator is added into the fracturing fluid as shown in table 2, the formula of the low-temperature gel breaking activator is the same as that of example 1, the system takes the hydrogen peroxide as the gel breaker, the hydroxypropyl guar gum is used as a thickening agent, the hydrogen peroxide has smaller influence on the environment relative to ammonium persulfate, the viscosity of the fracturing fluid is slowly reduced in the first 2 hours, the viscosity is 39mPa & s at the moment, the basic fracturing construction conditions are met, the low-temperature gel breaking activator has the characteristic of small additive amount, and has good adaptability to both the ammonium persulfate and the hydrogen peroxide gel breaking system, the viscosity of the fracturing fluid is reduced to 4.36mPa & s after 4 hours of gel breaking, and the requirement of flowback of the fracturing fluid is met.
Example 3
The low-temperature gel breaking activator described in embodiment 3 comprises, by mass fraction, ferrous acetylacetonate: 0.2 percent; ferrous sulfate: 0.3 percent; glucose: 3 percent; the balance of water. Wherein the total effective content of the ferrous acetylacetonate is more than or equal to 98.0 percent, and the iron content is 21.5-22 percent; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg. The preparation method comprises the following steps: the components are weighed according to the mass percentage, added into water, dissolved by slight heating and stirred evenly.
The invention also provides a use method of the low-temperature gel breaking activator, wherein the mass fraction of each component of the guanidine gum fracturing fluid is as follows: 0.25 percent; a crosslinking agent: 0.3 percent; 0.1% of cleanup additive; clay stabilizer: 0.5 percent; defoaming agent: 0.05 percent; a gel breaker: 0.07 percent. The formulation was the same as in example 1, with the breaker being 0.05% 15% hydrogen peroxide. The gel breaker was 0.7g of ammonium persulfate, added at a concentration of 0.07%.
Preheating the prepared hydroxypropyl guanidine gum fracturing fluid at 40 ℃ for 18min, adding 0.1% of low-temperature gel breaking activator, stirring for 8min, starting timing, measuring the viscosity of the fracturing fluid once every half hour, and judging that gel breaking is finished when the viscosity of the fracturing fluid is less than or equal to 5mPa & s.
Table 3 fracturing fluid viscosity as a function of time in example 3
| Time/h | 0 | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 |
| viscosity/mPas | 63 | 59 | 56 | 49 | 41 | 32 | 12 | 4.87 | 3.95 |
Hydroxypropyl guar fracturing fluid at 40 ℃ under the condition of 0.07% ammonium persulfate as a gel breaker, the weight ratio of ferrous acetylacetonate: 0.2 percent; ferrous sulfate: 0.3 percent; glucose: 3 percent; the balance of water, which constitutes the low-temperature gel breaking activator. As shown in table 3, 0.1% of low-temperature gel breaking activator is added into the fracturing fluid, the viscosity of the fracturing fluid is reduced slightly in the first 2.5 hours, the basic fracturing construction condition is met, and the addition concentration is low and is only 0.1%; the viscosity of the fracturing fluid is reduced to 4.87 mPa.s after 3.5h of gel breaking, and the flowback requirement of the fracturing fluid is met.
Example 4
The low-temperature gel breaking activator described in embodiment 4 comprises, by mass fraction, ferrous acetylacetonate: 0.2 percent; ferrous sulfate: 0.3 percent; glucose: 3 percent; the balance of water. Wherein the total effective content of the ferrous acetylacetonate is more than or equal to 98.0 percent, and the iron content is 21.5-22 percent; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg. The preparation method comprises the following steps: the components are weighed according to the mass percentage, added into water, dissolved by slight heating and stirred evenly.
The invention also provides a use method of the low-temperature gel breaking activator, wherein the weight percentage of each component of the guanidine gum fracturing fluid is as follows: 0.25 percent; a crosslinking agent: 0.3 percent; 0.1% of cleanup additive; clay stabilizer: 0.5 percent; defoaming agent: 0.05 percent; a gel breaker: 0.07 percent. The formulation was the same as in example 1, with the breaker being 0.05% 15% hydrogen peroxide.
Preheating the prepared carboxymethyl guanidine gum fracturing fluid at 40 ℃ for 20min, adding 0.15% of low-temperature gel breaking activator, stirring for 5min, starting timing, measuring the viscosity of the fracturing fluid every half hour, and judging that gel breaking is finished when the viscosity of the fracturing fluid is less than or equal to 5mPa & s.
Table 4 fracturing fluid viscosity as a function of time in example 4
| Time/h | 0 | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 |
| viscosity/mPas | 67 | 59 | 55 | 46 | 32 | 24 | 4.68 | 4.12 | 3.78 |
At 40 ℃, under the condition that carboxymethyl guanidine gum fracturing fluid takes 0.05% of 15% hydrogen peroxide as a gel breaker, the weight ratio of ferrous acetylacetonate: 0.2 percent; ferrous sulfate: 0.3 percent; glucose: 3 percent; the balance of water forms the low-temperature gel breaking activator. As shown in Table 4, 0.15% of low-temperature gel breaking activator is added into the fracturing fluid, the viscosity of the fracturing fluid is reduced slightly in the first 2h, the basic fracturing construction condition is met, the viscosity of the fracturing fluid is reduced to 4.68mPa & s in the gel breaking 3h, and the flowback requirement of the fracturing fluid is met.
Example 5
The low-temperature gel breaking activator described in embodiment 5 includes, by mass fraction, ferrous acetylacetonate: 0.3 percent; ferrous sulfate: 0.5 percent; glucose: 2 percent; the balance of water. Wherein the total effective content of the ferrous acetylacetonate is more than or equal to 98.0 percent, and the iron content is 21.5-22 percent; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg. The preparation method comprises the following steps: the components are weighed according to the mass percentage, added into water, dissolved by slight heating and stirred evenly.
The invention also provides a use method of the low-temperature gel breaking activator, wherein the weight percentage of each component of the guanidine gum fracturing fluid is as follows: 0.25 percent; a crosslinking agent: 0.3 percent; 0.1% of cleanup additive; clay stabilizer: 0.5 percent; defoaming agent: 0.05 percent; a gel breaker: 0.07 percent. The formulation was the same as in example 1, with the breaker being 0.7g ammonium persulfate hydrogen and 0.07% added.
Preheating the prepared carboxymethyl guanidine gum fracturing fluid at 40 ℃ for 15min, adding 0.1% of low-temperature gel breaking activator, stirring for 10min, starting timing, measuring the viscosity of the fracturing fluid every half hour, and judging that gel breaking is finished when the viscosity of the fracturing fluid is less than or equal to 5mPa & s.
Table 5 fracturing fluid viscosity as a function of time in example 5
| Time/h | 0 | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 |
| viscosity/mPas | 61 | 55 | 52 | 49 | 43 | 20 | 17 | 8.29 | 4.61 |
At 40 ℃, the carboxymethyl guanidine gum fracturing fluid takes 0.07 percent of ammonium persulfate as a gel breaker, and takes the weight ratio of ferrous acetylacetonate: 0.3 percent; ferrous sulfate: 0.5 percent; glucose: 2 percent; the balance of water; forming the low-temperature gel breaking activator. As shown in Table 5, 0.1% of low-temperature gel breaking activator is added into the fracturing fluid, the viscosity of the fracturing fluid is reduced within the first 2h, the basic fracturing construction conditions are met, the viscosity of the fracturing fluid is reduced to 4.61mPa & s within 4h of gel breaking, and the flowback requirement of the fracturing fluid is met.
Example 6
With FeSO of the prior art4As a low-temperature gel breaking activator, 1 percent of FeSO is added4Adding water to dissolve the mixture to obtain the gel breaking activator in the prior art.
The guanidine gum fracturing fluid comprises the following components in percentage by mass: 0.25 percent; a crosslinking agent: 0.3 percent; 0.1% of cleanup additive; clay stabilizer: 0.5 percent; defoaming agent: 0.05 percent; a gel breaker: 0.07 percent. The formulation was the same as in example 1, with the breaker being 0.7g ammonium persulfate hydrogen and 0.07% added.
The prepared carboxymethyl guanidine is addedPreheating the gel fracturing fluid at 40 deg.C for 20min, adding 1% FeSO4Stirring the low-temperature gel breaking activator for 5min, starting timing, measuring the viscosity of the fracturing fluid once every half hour, and judging that gel breaking is finished when the viscosity of the fracturing fluid is less than or equal to 5mPa & s.
Table 6 example 6 prior art fracturing fluid viscosity as a function of time
| Time/h | 0 | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 |
| viscosity/mPas | 61 | 8.36 | 4.65 | 4.58 | 4.35 | 4.12 | 4.02 | 3.95 | 3.62 |
The viscosity of the fracturing fluid is greatly reduced within 0.5h, complete gel breaking can be realized within 1h, the gel breaking time is too short, basic fracturing construction conditions are difficult to meet, the addition concentration of the gel breaking activator is too large, the construction cost is not favorably reduced, and the adverse effect on the environment is increased.
In conclusion, compared with the prior art, the low-temperature gel breaking activator and the use method thereof are improved to a certain extent in all aspects, and can be applied to the field of oilfield fracturing construction.
Claims (8)
1. The low-temperature gel breaking activator is characterized by comprising the following components in percentage by mass:
0.2-0.5% of ferrous acetylacetonate;
0.3-0.8% of ferrous sulfate;
0.5-3% of glucose;
the balance of water; the mass percentage of each component is one hundred percent.
2. The low-temperature gel breaking activator according to claim 1, characterized in that the total effective content of ferrous acetylacetonate is not less than 98.0%, and the iron content is 21.5-22%; the ferrous sulfate is ferrous sulfate heptahydrate; the specific optical rotation of glucose is +52.5 DEG to +53.0 deg.
3. The use method of the low-temperature gel breaking activator in the claims 1-2 is characterized in that the prepared guanidine gum fracturing fluid is preheated at a specified temperature for 15-20min to 30-40 ℃, 0.1-0.4% of the low-temperature gel breaking activator is added, and the mixture is stirred for 5-10 min.
4. The use method of the low-temperature gel breaking activator according to claim 3, wherein the gel breaking temperature is 30 ℃ or 40 ℃.
5. The use method of the low-temperature gel breaking activator according to claim 3, wherein the gel breaking viscosity of the fracturing fluid is less than or equal to 5 mPa-s.
6. The use method of the low-temperature gel breaking activator according to claim 3, wherein the guanidine gum fracturing fluid comprises the following components in percentage by mass:
the balance of water, and the mass percent of each component is one hundred percent.
7. The use method of the low-temperature gel breaking activator according to claim 6, characterized in that the guanidine gum fracturing fluid is prepared by the following steps:
step 1: accurately weighing 2.5g of hydroxypropyl guar gum or carboxymethyl guar gum to prepare 1000g of 0.25% hydroxypropyl or carboxymethyl guar gum base solution at the rotating speed of 4500-5000 r/min. Swelling for 1h under the condition of 30 ℃ water bath, adding 3g of 10% borax water solution crosslinking agent, crosslinking for 10min, and measuring the viscosity of the mixture by using a rotational viscometer to be 60-65 mPa & s.
Step 2: taking 5% of fluorocarbon surfactant FLYZ and 95% of water as a cleanup additive, adding 1g of cleanup additive, 5g of clay stabilizer FLYF and 0.5g of sodium gluconate as a defoaming agent into the base solution, adding a gel breaker, and stirring for 10 min.
8. The use method of the low-temperature gel breaking activator in the claim 6 is characterized in that the gel breaker in the guanidine gum fracturing fluid is one of ammonium persulfate or 15% hydrogen peroxide; the mass percent of the ammonium persulfate is 0.07 percent, and the mass percent of the 15 percent hydrogen peroxide is 0.05 percent.
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