CN111334278B - Sulfonated humic acid fracturing fluid and preparation method thereof - Google Patents
Sulfonated humic acid fracturing fluid and preparation method thereof Download PDFInfo
- Publication number
- CN111334278B CN111334278B CN202010301151.6A CN202010301151A CN111334278B CN 111334278 B CN111334278 B CN 111334278B CN 202010301151 A CN202010301151 A CN 202010301151A CN 111334278 B CN111334278 B CN 111334278B
- Authority
- CN
- China
- Prior art keywords
- humic acid
- guar gum
- sulfonated humic
- carboxymethyl guar
- fracturing fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000012530 fluid Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002907 Guar gum Polymers 0.000 claims abstract description 76
- 239000000665 guar gum Substances 0.000 claims abstract description 76
- 229960002154 guar gum Drugs 0.000 claims abstract description 76
- 235000010417 guar gum Nutrition 0.000 claims abstract description 76
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 73
- 238000003756 stirring Methods 0.000 claims abstract description 63
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 26
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000004021 humic acid Substances 0.000 claims abstract description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 13
- 239000004310 lactic acid Substances 0.000 claims abstract description 13
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 13
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011837 pasties Nutrition 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 230000008961 swelling Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- 238000004132 cross linking Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 206010016807 Fluid retention Diseases 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Images
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
- C09K8/68—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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- 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
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
Abstract
The invention discloses a sulfonated humic acid fracturing fluid and a preparation method thereof, wherein the method comprises the following steps: 1) completely dissolving humic acid in a sodium hydroxide solution, then adding sodium sulfite, continuously heating and stirring, and then dropwise adding a hydrochloric acid solution until brown and black pasty precipitates are generated; purifying the brown black slurry to obtain sulfonated humic acid; 2) dissolving zirconium oxychloride and ammonium chloride in water, then adding ethylene glycol and lactic acid, then dropwise adding a potassium hydroxide solution until the pH value reaches neutral, and continuously heating and stirring to obtain a colorless and transparent organic zirconium crosslinking agent; 3) preparing a carboxymethyl guar gum solution; adding sulfonated humic acid into the carboxymethyl guar gum solution, and uniformly stirring; and adding an organic zirconium crosslinking agent to obtain the sulfonated humic acid fracturing fluid. The novel fracturing fluid obtained by the invention has the advantages that the water retention is improved, the viscoelasticity is improved, and the salt resistance is also considerable due to the addition of sulfonic acid groups.
Description
Technical Field
The invention relates to the technical field of preparation of petroleum fracturing fluid, and particularly relates to sulfonated humic acid fracturing fluid and a preparation method thereof.
Background
The water-based fracturing fluid is widely applied, the guar gum fracturing fluid taking polysaccharide as a thickening agent is the most widely applied water-based fracturing fluid at present, but because guar gum raw powder is low in dissolving speed and high in water insoluble substance content, various problems of poor dissolving performance, high price, low strength, low sand carrying performance, poor salt tolerance and the like exist in oil and gas exploitation of an oil field, the guar gum raw powder is required to be modified in actual engineering application, although the gel strength of the modified carboxymethyl guar gum is improved after the modified carboxymethyl guar gum is crosslinked with an organic zirconium crosslinking agent, the sand carrying capacity is enhanced, but the modified carboxymethyl guar gum has the problem of quick dehydration after the modified carboxymethyl guar gum is crosslinked with the organic zirconium crosslinking agent.
Humic acid is a natural high-molecular aromatic polymer, has the characteristics of abundant reserves, wide sources and low price, is a natural chelating agent, has good water-retaining property, cannot be independently made into gel, and can play a greater role by being compounded with other chemical reagents.
Disclosure of Invention
The invention provides a sulfonated humic acid fracturing fluid and a preparation method thereof, aiming at improving the application range of humic acid and providing a fracturing fluid with more excellent performance. According to the invention, sulfonated humic acid and carboxymethyl guar gum are crosslinked through the organic zirconium crosslinking agent, and compared with fracturing fluid obtained by crosslinking single carboxymethyl guar gum and organic zirconium crosslinking agent, the novel fracturing fluid obtained by the invention has the advantages that the water retention property is improved, the viscoelasticity is improved, and the salt resistance is also considerable due to the addition of sulfonic acid groups.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of sulfonated humic acid fracturing fluid comprises the following steps:
1) heating sodium hydroxide solution to 50-55 ℃, completely dissolving humic acid in the sodium hydroxide solution, then adding sodium sulfite, continuously heating and stirring, and then dropwise adding hydrochloric acid solution until brown and black pasty precipitates are generated; purifying the brown black slurry to obtain sulfonated humic acid;
2) heating deionized water to 50-55 ℃, dissolving zirconium oxychloride and ammonium chloride in the deionized water, then adding ethylene glycol and lactic acid, then dropwise adding a potassium hydroxide solution until the pH value reaches neutrality, and continuously heating and stirring to obtain a colorless and transparent organic zirconium crosslinking agent;
3) preparing a carboxymethyl guar gum solution, and standing and swelling; adding sulfonated humic acid into the carboxymethyl guar gum solution, and uniformly stirring; adjusting the acid of the mixed carboxymethyl guar gum solution by using dilute hydrochloric acid; and adding an organic zirconium crosslinking agent to obtain the sulfonated humic acid fracturing fluid.
As a further improvement of the invention, in step 3), the concentration of the carboxymethyl guar gum is 0.5 wt%.
As a further improvement of the invention, in the step 3), the addition amount of the sulfonated humic acid is 0.1-1 percent of the mass of the carboxymethyl guar gum solution, and the stirring time is 1-5 min.
As a further development of the invention, in step 3), the acid is adjusted until the pH is 2.
As a further improvement of the invention, in step 3), the crosslinker is added in a ratio of 100: 1.
As a further improvement of the invention, in the step 3), the stirring time is 1-2 min.
As a further improvement of the invention, the mass ratio of the carboxymethyl guar gum solution to the organic zirconium cross-linking agent is 100: 1.
The sulfonated humic acid fracturing fluid is characterized in that sulfonated humic acid and carboxymethyl guar gum are crosslinked by an organic zirconium crosslinking agent; the concentration of the carboxymethyl guar gum is 0.5wt%, the addition amount of the sulfonated humic acid is 0.1-1% of the mass of the carboxymethyl guar gum solution, and the mass ratio of the carboxymethyl guar gum solution to the organic zirconium cross-linking agent is 100: 1.
Compared with the prior art, the invention has the following advantages:
compared with the conventional carboxymethyl guar gum fracturing fluid, the sulfonated humic acid and carboxymethyl guar gum are crosslinked by the organic zirconium crosslinking agent, and compared with the fracturing fluid obtained by crosslinking the independent carboxymethyl guar gum and the organic zirconium crosslinking agent, the novel fracturing fluid obtained by the invention has the advantages that the water retention is improved, the viscoelasticity is improved, and the salt resistance is also considerable due to the addition of the sulfonic group.
Drawings
FIG. 1 is a schematic diagram of a cross-linking structure of a sulfonated humic acid fracturing fluid;
FIG. 2 is an infrared spectrum of sulfonated humic acid of example 2;
FIG. 3 is a graph of the rheological test data of the sulfonated humic acid fracturing fluids of examples 1 to 6 at different levels of sulfonated humic acid addition.
Detailed Description
The invention relates to a preparation method of a sulfonated humic acid fracturing fluid, which is characterized in that sulfonated humic acid and carboxymethyl guar gum are crosslinked by an organic zirconium crosslinking agent; the concentration of the carboxymethyl guar gum is 0.5wt%, the addition amount of the sulfonated humic acid is 0.1-1% of the mass of the carboxymethyl guar gum solution, and the mass ratio of the carboxymethyl guar gum solution to the organic zirconium cross-linking agent is 100: 1.
The principle of the invention is as follows:
the gel strength of the carboxymethyl guar gum is improved after the carboxymethyl guar gum is crosslinked with the organic zirconium crosslinking agent, the sand carrying capacity is enhanced, but the modified carboxymethyl guar gum has the problem of fast dehydration after the carboxymethyl guar gum is crosslinked with the organic zirconium crosslinking agent. The invention adopts sulfonated humic acid and carboxymethyl guar gum to carry out cross linking through an organic zirconium cross-linking agent, the humic acid occupies partial cross-linking active sites under the cross linking condition, so that the cross linking strength of the carboxymethyl guar gum is weakened, the dehydration property of the prepared fracturing fluid is weakened due to the water retention of the sulfonated humic acid and the water absorption of a sulfonic acid group, and the solid property of the gel of the fracturing fluid is improved due to the rigid structure of the sulfonated humic acid, which means that the sand carrying capacity of the fracturing fluid is enhanced.
The preparation method of the invention specifically comprises the following operations:
a three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 to 55 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring were continued for 4-6h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid.
Deionized water was charged into a three-necked flask, heated to 50-55 deg.C, and 15g of zirconium oxychloride and 0.01g of ammonium chloride were dissolved therein, followed by addition of 20g of ethylene glycol and 16g of lactic acid. Then, a potassium hydroxide solution is added dropwise until the pH value reaches neutral, heating and stirring are continued for 4-5h, and then the colorless and transparent organic zirconium crosslinking agent is obtained.
Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is (0.1-1)% of the mass of the carboxymethyl guar gum solution, the stirring time is 1-5min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1-2min to obtain the sulfonated humic acid fracturing fluid.
The invention is further illustrated by the following specific examples and figures:
example 1
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 4h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 50 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0% of the mass of the carboxymethyl guar gum solution, the stirring time is 3min, adjusting the acid of the mixed solution by using dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring for 1min by using a glass rod to obtain the sulfonated humic acid fracturing fluid.
Fig. 1 is a schematic diagram of the cross-linking structure of the sulfonated humic acid fracturing fluid, and it can be seen that the humic acid occupies part of the cross-linking active sites, so that the cross-linking strength of the carboxymethyl guar gum is weakened, and the dehydration rate of the fracturing fluid is reduced, which is consistent with the results of our example.
Example 2
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 4h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 50 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.1% of the mass of the carboxymethyl guar gum solution, the stirring time is 3min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1min to obtain the sulfonated humic acid fracturing fluid.
FIG. 2 is an IR spectrum of sulfonated humic acid of example 2, and it can be seen that the peak of vibration of the sulfonic acid group appears at 1191cm-1And 1139cm-1This indicates that the humic acid has been successfully sulfonated.
Example 3
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 4h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 50 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.2% of the mass of the carboxymethyl guar gum solution, the stirring time is 3min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1min to obtain the sulfonated humic acid fracturing fluid.
FIG. 3 is a graph of the rheological test data of the sulfonated humic acid fracturing fluids of examples 1 to 6 at different levels of sulfonated humic acid addition. The storage modulus (G ') and loss modulus (G') of the gel samples vary with the angular frequency. It can be seen from the figure that the storage modulus G' is greater than the loss modulus G ", indicating that the samples are all standard elastomeric behavior. As can be seen from the figure, the storage modulus of the hydrogel system containing the humic acid sulfonate is larger than that of the hydrogel system without the humic acid sulfonate, which shows that the addition of the humic acid sulfonate has an enhanced effect on the original spatial network structure. However, as the amount of sulfonated humic acid increased, the storage modulus G' of the hydrogel sample exhibited a characteristic of increasing and then decreasing, indicating that the amount of sulfonated humic acid had an optimum value, with the optimum amount at 0.3G. From the figures, we can clearly see that the dehydration rate of the sulfonated humic acid crosslinked gel can be significantly reduced after 10 hours of crosslinking.
Example 4
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 4h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 50 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.3% of the mass of the carboxymethyl guar gum solution, the stirring time is 3min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1min to obtain the sulfonated humic acid fracturing fluid.
Example 5
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 4h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 50 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.4% of the mass of the carboxymethyl guar gum solution, the stirring time is 3min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1min to obtain the sulfonated humic acid fracturing fluid. Fig. 2 is a schematic diagram of a mechanism for preparing a stable conductive sponge electrode by a reduction method, and it can be seen from the diagram that graphene oxide uniformly dispersed on a fiber thin layer is reduced to graphene by hydrazine hydrate, the position of a graphene conductive agent in the electrode is not changed too much, the graphene conductive agent is still uniformly dispersed on the fiber thin layer, and a complete conductive layer is formed. Fig. 3 is an impedance test chart of the stable conductive sponge electrode in example 2, which is impedance data of the tenth circle tested after the manufactured electrode and the lithium sheet are assembled into a battery, and it can be clearly seen that the measured impedance value is very small and is also expected.
Example 6
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 4h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 50 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.5% of the mass of the carboxymethyl guar gum solution, the stirring time is 3min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1min to obtain the sulfonated humic acid fracturing fluid.
Fig. 2 is a schematic diagram of a mechanism for preparing a stable conductive sponge electrode by a reduction method, and it can be seen from the diagram that graphene oxide uniformly dispersed on a fiber thin layer is reduced to graphene by hydrazine hydrate, the position of a graphene conductive agent in the electrode is not changed too much, the graphene conductive agent is still uniformly dispersed on the fiber thin layer, and a complete conductive layer is formed. Fig. 3 is an impedance test chart of the stable conductive sponge electrode in example 2, which is impedance data of the tenth circle tested after the manufactured electrode and the lithium sheet are assembled into a battery, and it can be clearly seen that the measured impedance value is very small and is also expected.
Example 7
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 55 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 6h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 55 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 6 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.4% of the mass of the carboxymethyl guar gum solution, the stirring time is 1min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1min to obtain the sulfonated humic acid fracturing fluid.
Example 8
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 55 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 4h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 55 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then a colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, standing and swelling the carboxymethyl guar gum solution, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.1 percent of the mass of the carboxymethyl guar gum solution, the stirring time is 5min, adjusting the mixed solution to be acidic by using dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring the mixed solution by using a glass rod for 2min to obtain the sulfonated humic acid fracturing fluid.
Example 9
A three-necked flask was charged with 3g of sodium hydroxide and 150g of deionized water. The mixture was heated to 50 ℃ to completely dissolve humic acid therein, and then 1.6g of sodium sulfite was added. Heating and stirring was continued for 6h, then a dilute hydrochloric acid solution was added dropwise until a brown and black pasty precipitate was produced. And finally, purifying the brown black slurry to obtain the sulfonated humic acid. Deionized water was charged into a three-necked flask, heated to 55 ℃ to dissolve 15g of zirconium oxychloride and 0.01g of ammonium chloride therein, and then 20g of ethylene glycol and 16g of lactic acid were added. Then, a potassium hydroxide solution was added dropwise until the pH value reached neutrality, heating and stirring were continued for 4 hours, and then the obtained colorless transparent organic zirconium crosslinking agent was obtained. Preparing a carboxymethyl guar gum solution, wherein the preparation concentration is 0.5wt%, standing and swelling, adding sulfonated humic acid into the carboxymethyl guar gum solution, stirring, wherein the addition amount of the sulfonated humic acid is 0.4% of the mass of the carboxymethyl guar gum solution, the stirring time is 2min, adjusting the mixed solution with dilute hydrochloric acid until the pH value is 2, then adding an organic zirconium cross-linking agent, wherein the addition ratio of the cross-linking agent is 100: 1, and stirring with a glass rod for 1.5min to obtain the sulfonated humic acid fracturing fluid.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (7)
1. The preparation method of the sulfonated humic acid fracturing fluid is characterized by comprising the following steps:
1) heating sodium hydroxide solution to 50-55 ℃, completely dissolving humic acid in the sodium hydroxide solution, then adding sodium sulfite, continuously heating and stirring, and then dropwise adding hydrochloric acid solution until brown and black pasty precipitates are generated; purifying the brown black slurry to obtain sulfonated humic acid;
2) heating deionized water to 50-55 ℃, dissolving zirconium oxychloride and ammonium chloride in the deionized water, then adding ethylene glycol and lactic acid, then dropwise adding a potassium hydroxide solution until the pH value reaches neutrality, and continuously heating and stirring to obtain a colorless and transparent organic zirconium crosslinking agent;
3) preparing a carboxymethyl guar gum solution, and standing and swelling; adding sulfonated humic acid into the carboxymethyl guar gum solution, and uniformly stirring; adjusting the acid of the mixed carboxymethyl guar gum solution by using dilute hydrochloric acid; and adding an organic zirconium crosslinking agent to obtain the sulfonated humic acid fracturing fluid.
2. The method for preparing the sulfonated humic acid fracturing fluid according to claim 1, wherein in the step 3), the concentration of the carboxymethyl guar gum agent is 0.5 wt%.
3. The method for preparing the sulfonated humic acid fracturing fluid according to claim 1, wherein in the step 3), the addition amount of the sulfonated humic acid is 0.1-1% of the mass of the carboxymethyl guar gum solution, and the stirring time is 1-5 min.
4. The method for preparing the sulfonated humic acid fracturing fluid according to claim 1, wherein in the step 3), the acid is adjusted until the pH = 2.
5. The method for preparing the sulfonated humic acid fracturing fluid according to claim 1, wherein in the step 3), the stirring time is 1-2 min.
6. The method for preparing the sulfonated humic acid fracturing fluid according to claim 1, wherein in the step 3), the mass ratio of the carboxymethyl guar gum solution to the organic zirconium cross-linking agent is 100: 1.
7. The sulfonated humic acid fracturing fluid is characterized in that sulfonated humic acid and carboxymethyl guar gum are crosslinked by an organic zirconium crosslinking agent; the concentration of the carboxymethyl guar gum is 0.5wt%, the addition amount of the sulfonated humic acid is 0.1-1% of the mass of the carboxymethyl guar gum solution, and the mass ratio of the carboxymethyl guar gum solution to the organic zirconium cross-linking agent is 100: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010301151.6A CN111334278B (en) | 2020-04-16 | 2020-04-16 | Sulfonated humic acid fracturing fluid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010301151.6A CN111334278B (en) | 2020-04-16 | 2020-04-16 | Sulfonated humic acid fracturing fluid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111334278A CN111334278A (en) | 2020-06-26 |
| CN111334278B true CN111334278B (en) | 2022-05-13 |
Family
ID=71179106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010301151.6A Active CN111334278B (en) | 2020-04-16 | 2020-04-16 | Sulfonated humic acid fracturing fluid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111334278B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898592A (en) * | 2021-01-22 | 2021-06-04 | 濮阳市诚信钻采助剂有限公司 | Lignite resin sulfonation modification method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1363872A (en) * | 1970-08-03 | 1974-08-21 | Dresser Ind | Drilling fluids |
| US4572789A (en) * | 1980-11-27 | 1986-02-25 | Japan Metals And Chemicals Co., Ltd. | Drilling fluid additives |
| US4737295A (en) * | 1986-07-21 | 1988-04-12 | Venture Chemicals, Inc. | Organophilic polyphenolic acid adducts |
| CN103113862A (en) * | 2013-03-07 | 2013-05-22 | 邓小刚 | Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL171280C (en) * | 1971-09-28 | 1983-03-01 | Dresser Ind | METHOD FOR PREPARING A DRILLING FLUID ADDITIVE |
| CN85106524B (en) * | 1985-08-31 | 1987-09-16 | 中国科学院化学研究所 | Humic acid-bearing drilling slurry conditioner and its preparetion method |
| CN101220260A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Method of producing novel sulfonation humic acid drilling mud modifying agent |
| CN102329606B (en) * | 2011-08-03 | 2013-11-27 | 西安长庆化工集团有限公司 | Cross-linking agent for carboxymethyl guar gum acidic fracturing fluid and preparation method thereof |
| CN104357030B (en) * | 2014-06-04 | 2019-02-22 | 中国石油化工集团公司 | A kind of drilling fluid branched polymer inorganic agent and preparation method thereof |
| CN104946215A (en) * | 2015-06-11 | 2015-09-30 | 西安石油大学 | Method for preparing drilling fluid using guar gum fracturing fluid waste water |
| CN108018035B (en) * | 2016-10-31 | 2020-09-29 | 中国石油化工股份有限公司 | Shearing-resistant low-concentration guar zirconium gel fracturing fluid |
| CN112694885B (en) * | 2020-12-08 | 2023-03-31 | 中国石油天然气股份有限公司大港油田分公司 | High-activity drag reducer, self-imbibition energy-increasing extraction type slickwater fracturing fluid system suitable for shale oil reservoir, and preparation method and application thereof |
| CN113150789A (en) * | 2020-12-30 | 2021-07-23 | 陕西品物皆春生态科技有限公司 | Guar gum-humic acid type oil and gas field fracturing fluid flowback fluid water retention and sand fixation agent and preparation method and application thereof |
| CN112778045A (en) * | 2021-01-06 | 2021-05-11 | 陕西科技大学 | Humic acid liquid fertilizer and method for preparing same by utilizing fracturing flowback fluid of oil and gas field |
-
2020
- 2020-04-16 CN CN202010301151.6A patent/CN111334278B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1363872A (en) * | 1970-08-03 | 1974-08-21 | Dresser Ind | Drilling fluids |
| US4572789A (en) * | 1980-11-27 | 1986-02-25 | Japan Metals And Chemicals Co., Ltd. | Drilling fluid additives |
| US4737295A (en) * | 1986-07-21 | 1988-04-12 | Venture Chemicals, Inc. | Organophilic polyphenolic acid adducts |
| CN103113862A (en) * | 2013-03-07 | 2013-05-22 | 邓小刚 | Amphoteric ionic ultra-high-temperature polysulfonate drilling fluid |
Non-Patent Citations (1)
| Title |
|---|
| 钻井液用天然材料接枝共聚物研究进展;杨小华等;《应用化工》;20100128(第01期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111334278A (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107216467B (en) | Preparation method of high-strength anion-cation intelligent functional gel | |
| CN110628053B (en) | Polyvinyl alcohol-tannic acid-boric acid ternary crosslinked hydrogel, and preparation method and application thereof | |
| CN110760152B (en) | Anti-freezing hydrogel and preparation method and application thereof | |
| CN110885476B (en) | Secondary doped graphene oxide/alkali-soluble chitosan-polyaniline-polyacrylamide composite conductive hydrogel prepared by one-pot method | |
| CN108641099B (en) | Cellulose-based temperature-sensitive conductive hydrogel and preparation method and application thereof | |
| CN111334278B (en) | Sulfonated humic acid fracturing fluid and preparation method thereof | |
| CN110563968B (en) | Preparation method of high-strength high-tensile ionic conductive hydrogel | |
| CN111944510A (en) | Thickening agent for clean fracturing fluid and preparation method thereof | |
| CN111995770A (en) | Preparation method of physical combined network hydrogel | |
| CN110085846A (en) | A kind of graphene-silicon dioxide composite aerogel carries sulfur materials and its preparation method and application | |
| CN113717405A (en) | Flexible conductive hydrogel and preparation method and application thereof | |
| CN112979892B (en) | Ion conductive gel and preparation method thereof | |
| CN113372574A (en) | Polyvinyl alcohol hydrogel and preparation method thereof | |
| CN111063891B (en) | Preparation method of aqueous conductive adhesive | |
| CN111704728B (en) | Transparent ion-conductive cellulose hydrogel and preparation method and application thereof | |
| CN110724503A (en) | High-temperature salt-resistant filtrate reducer modified gum resin for drilling fluid | |
| CN112615066A (en) | Mixed gel polymer electrolyte, preparation method thereof and all-solid-state zinc ion battery | |
| CN111312528A (en) | Chitin regenerated hydrogel and preparation method and application thereof | |
| CN112310490A (en) | Preparation method of gel electrolyte for double-cross-linked-water-system metal ion energy storage device | |
| CN114874463A (en) | Anti-freezing conductive hydrogel with excellent mechanical properties and preparation method and application thereof | |
| CN112251204B (en) | Nano-cellulose cross-linking agent for high-temperature-resistant fracturing fluid and preparation method and application thereof | |
| CN114350095A (en) | High-concentration salt double-network hydrogel electrolyte and preparation method and application thereof | |
| US20230034496A1 (en) | Chitin regenerative hydrogel and preparation method and application thereof | |
| CN115394568B (en) | Cellulose-based hydrogel flexible electrolyte containing spiropyran | |
| CN110571480A (en) | Preparation method of high-strength high-tensile alkaline solid polymer electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240109 Address after: 710000 No. B49, Xinda Zhongchuang space, 26th Street, block C, No. 2 Trading Plaza, South China City, international port district, Xi'an, Shaanxi Province Patentee after: Xi'an Huaqi Zhongxin Technology Development Co.,Ltd. Address before: 710021 Shaanxi province Xi'an Weiyang University Park Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
|
| TR01 | Transfer of patent right |