CN114292636A - Titanium-zirconium cross-linking agent and preparation method thereof - Google Patents
Titanium-zirconium cross-linking agent and preparation method thereof Download PDFInfo
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- CN114292636A CN114292636A CN202111670442.3A CN202111670442A CN114292636A CN 114292636 A CN114292636 A CN 114292636A CN 202111670442 A CN202111670442 A CN 202111670442A CN 114292636 A CN114292636 A CN 114292636A
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- titanium
- zirconium
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- linking agent
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 69
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
- 239000010936 titanium Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 36
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 32
- 239000003446 ligand Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 11
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims abstract description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 9
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 9
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 9
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 8
- 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 abstract description 6
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 6
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 6
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 4
- 229920002907 Guar gum Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000665 guar gum Substances 0.000 description 4
- 229960002154 guar gum Drugs 0.000 description 4
- 235000010417 guar gum Nutrition 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- -1 diethanolamine alcohol amine Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of cross-linking agent preparation, and provides a titanium-zirconium cross-linking agent and a preparation method thereof. The titanium-zirconium cross-linking agent provided by the invention comprises the following preparation raw materials: inorganic titanium, a ligand, inorganic zirconium, protonic acid and water; the inorganic titanium comprises titanium phosphate and/or titanium sulfate; the ligand comprises one or more of diethanolamine, triethanolamine, ammonium citrate and sodium gluconate; the inorganic zirconium includes zirconium oxychloride and/or zirconium sulfate. The titanium crosslinking agent and the zirconium crosslinking agent are simultaneously introduced into the titanium-zirconium crosslinking agent, so that the titanium-zirconium crosslinking agent has the advantages of the titanium crosslinking agent and the zirconium crosslinking agent, and the pH application range of the titanium-zirconium crosslinking agent is widened; meanwhile, the titanium-zirconium cross-linking agent has excellent temperature resistance. In addition, the selection of inorganic titanium, inorganic zirconium and ligand avoids the generation of alcohol micromolecule compound in the preparation process, so that the titanium-zirconium cross-linking agent has good stability and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of cross-linking agent preparation, in particular to a titanium-zirconium cross-linking agent and a preparation method thereof.
Background
The acidic cross-linking agent is an important cross-linking agent in the field of oil field fracturing. The commonly used acidic cross-linking agent is an organic zirconium cross-linking agent, but the organic zirconium cross-linking agent is sensitive to the pH value under an acidic condition, and has better cross-linking performance only when the pH value of a use environment is about 3; when the pH value of the use environment is higher than 5.5, the crosslinking and hanging performance is obviously deteriorated.
Disclosure of Invention
In view of the above, the present invention is directed to a titanium zirconium crosslinking agent and a preparation method thereof. The titanium-zirconium cross-linking agent has good cross-linking and hanging properties at a pH value of 3-7.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a titanium zirconium cross-linking agent, which comprises the following preparation raw materials:
inorganic titanium, a ligand, inorganic zirconium, protonic acid and water;
the inorganic titanium comprises titanium phosphate and/or titanium sulfate;
the ligand comprises one or more of diethanolamine, triethanolamine, ammonium citrate and sodium gluconate;
the inorganic zirconium includes zirconium oxychloride and/or zirconium sulfate.
Preferably, the preparation method comprises the following preparation raw materials in parts by weight:
2-5 parts of inorganic titanium, 5-20 parts of ligand, 0.5-5 parts of inorganic zirconium, 2-10 parts of protonic acid and 40-85 parts of water.
Preferably, the protonic acid comprises an inorganic protonic acid and/or an organic protonic acid; the inorganic protonic acid comprises hydrochloric acid; the organic protonic acid comprises acetic acid and/or citric acid.
Preferably, the mass concentration of the inorganic protonic acid is 10% to 20%.
The invention also provides a preparation method of the titanium zirconium cross-linking agent in the technical scheme, which comprises the following steps:
mixing inorganic titanium, a ligand and water to obtain a suspension;
and mixing the suspension with inorganic zirconium, carrying out a first coordination reaction, and then adding protonic acid to carry out a second coordination reaction to obtain the titanium-zirconium crosslinking agent.
Preferably, the temperature of the first coordination reaction is 20-60 ℃ and the time is 1-10 h.
Preferably, the temperature of the second coordination reaction is 20-60 ℃ and the time is 1-10 h.
The invention provides a titanium zirconium cross-linking agent, which comprises the following preparation raw materials: inorganic titanium, a ligand, inorganic zirconium, protonic acid and water; the inorganic titanium comprises titanium phosphate and/or titanium sulfate; the ligand comprises one or more of diethanolamine, triethanolamine, ammonium citrate and sodium gluconate; the inorganic zirconium includes zirconium oxychloride and/or zirconium sulfate. The titanium crosslinking agent and the zirconium crosslinking agent are simultaneously introduced into the titanium-zirconium crosslinking agent, so that the titanium-zirconium crosslinking agent has the advantages of the titanium crosslinking agent and the zirconium crosslinking agent, and the pH application range of the titanium-zirconium crosslinking agent is widened; meanwhile, the titanium-zirconium cross-linking agent has excellent temperature resistance. In addition, the selection of inorganic titanium, inorganic zirconium and ligand avoids the generation of alcohol micromolecule compound in the preparation process, so that the titanium-zirconium cross-linking agent has good stability and is environment-friendly.
The invention also provides a preparation method of the titanium zirconium cross-linking agent in the technical scheme, which comprises the following steps: mixing inorganic titanium, a ligand and water to obtain a suspension; and mixing the suspension with inorganic zirconium, carrying out a first coordination reaction, and then adding protonic acid to carry out a second coordination reaction to obtain the titanium-zirconium crosslinking agent. The preparation method provided by the invention is simple to operate and easy to industrialize.
Drawings
FIG. 1 is a graph of the pendant morphology of a cross-linked modified guar gum (pH 6.0) with a titanium zirconium cross-linking agent obtained in example 2;
FIG. 2 is a graph showing the hanging morphology of the organozirconium crosslinker crosslinked modified guar gum (pH 6.0) obtained in comparative example 1;
FIG. 3 rheological profile of Ti-Zr crosslinker crosslinked modified guar (pH 6.0) obtained in example 2 at 90 ℃;
fig. 4 is a rheological profile at 90 ℃ of the organotitanium crosslinker crosslinked modified guar (pH 6.0) obtained in comparative example 2.
Detailed Description
The invention provides a titanium zirconium cross-linking agent, which comprises the following preparation raw materials:
inorganic titanium, a ligand, inorganic zirconium, protonic acid and water;
the inorganic titanium comprises titanium phosphate and/or titanium sulfate;
inorganic titanium, a ligand, inorganic zirconium, protonic acid and water;
the inorganic titanium comprises titanium phosphate and/or titanium sulfate;
the ligand comprises one or more of diethanolamine, triethanolamine, ammonium citrate and sodium gluconate;
the inorganic zirconium includes zirconium oxychloride and/or zirconium sulfate.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The titanium-zirconium cross-linking agent provided by the invention comprises inorganic titanium as a preparation raw material; the inorganic titanium includes titanium phosphate and/or titanium sulfate, and is further preferably titanium phosphate or titanium sulfate. In the invention, the weight part of the inorganic titanium is 2-5 parts.
The titanium cross-linking agent provided by the invention comprises a raw material ligand; the ligand comprises one or more of diethanolamine, triethanolamine, ammonium citrate and sodium gluconate, further preferably comprises one or more of diethanolamine, triethanolamine and ammonium citrate, more preferably diethanolamine, or a mixture of ammonium citrate and triethanolamine. In the present invention, the mass ratio of ammonium citrate to triethanolamine in the mixture of ammonium citrate and triethanolamine is preferably 2: (10-15). The ligand is preferably used in the form of an aqueous solution of the ligand. The weight part of the ligand is preferably 5 to 20 parts, and more preferably 10 to 15 parts based on the weight part of the inorganic titanium.
The titanium cross-linking agent provided by the invention comprises inorganic zirconium as a raw material; the inorganic zirconium preferably includes zirconium oxychloride and/or zirconium sulfate, and more preferably zirconium oxychloride or zirconium sulfate. The weight part of the inorganic zirconium is preferably 0.2 to 5 parts, and more preferably 1 to 5 parts, based on the weight part of the inorganic titanium.
The titanium cross-linking agent provided by the invention comprises the following raw materials of protonic acid; the protic acid preferably comprises an inorganic protic acid and/or an organic protic acid. In the invention, the inorganic protonic acid preferably comprises hydrochloric acid, and the mass concentration of the inorganic protonic acid is preferably 10-20%. In the present invention, the organic protonic acid preferably includes acetic acid and/or citric acid, and more preferably citric acid. In the present invention, the organic protonic acid is preferably used in the form of an organic protonic acid solution, and the concentration of the organic protonic acid solution is preferably 10% to 98%. The weight part of the protonic acid is preferably 2 to 10 parts, and more preferably 2 to 5 parts, based on the weight part of the inorganic titanium.
The titanium crosslinking agent provided by the invention comprises preparation raw material water, wherein the water preferably comprises deionized water. The weight part of the water is preferably 40-85 parts based on the weight part of the inorganic titanium.
The invention also provides a preparation method of the titanium zirconium cross-linking agent in the technical scheme, which comprises the following steps:
mixing inorganic titanium, a ligand and water to obtain a suspension;
and mixing the suspension with inorganic zirconium, carrying out a first coordination reaction, and then adding protonic acid to carry out a second coordination reaction to obtain the titanium-zirconium crosslinking agent.
The invention mixes inorganic titanium, ligand and water to obtain suspension.
In the invention, the mixing temperature of the inorganic titanium, the ligand and water is preferably 20-40 ℃, and more preferably 30-35 ℃; the mixing time of the inorganic titanium, the ligand and the water is preferably 1-3 h. In the present invention, the mixing of the inorganic titanium, the ligand and water is preferably performed under stirring. In the present invention, the inorganic titanium, the ligand and water are preferably mixed in a manner of: inorganic titanium and water are mixed, and then ligand is added.
After the suspension is obtained, the suspension and inorganic zirconium are mixed to perform a first coordination reaction, and then protonic acid is added to perform a second coordination reaction, so that the titanium-zirconium crosslinking agent is obtained.
In the invention, the temperature of the first coordination reaction is preferably 20-60 ℃, more preferably 30-50 ℃, and more preferably 30-40 ℃; the time of the first coordination reaction is preferably 1 to 10 hours, and more preferably 2 to 5 hours.
In the invention, the temperature of the second coordination reaction is preferably 20-60 ℃, more preferably 30-50 ℃, and more preferably 35-40 ℃; the time of the second coordination reaction is preferably 1 to 10 hours, and more preferably 2 to 5 hours.
After the ligand reaction, the titanium zirconium cross-linking agent is obtained preferably without post-treatment.
The titanium-zirconium cross-linking agent provided by the invention is strongly acidic, and the pH value of the titanium-zirconium cross-linking agent is preferably adjusted by adding organic amine so as to adapt to different use conditions. In the present invention, the organic amine preferably includes hexamethylenediamine and/or ethanolamine; the addition amount of the organic amine is not particularly limited, as long as the final use pH value of the titanium zirconium crosslinking agent can be met.
The titanium zirconium cross-linking agent and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Adding 5g of titanium phosphate and 60mL of water into a 250mL three-neck flask, fully stirring, adding 10mL of diethanolamine (10.9g) into the three-neck flask, stirring, simultaneously heating the water bath temperature to 30 ℃, and keeping the temperature for 1 h; adding 3g of zirconium oxychloride, reacting at 30 ℃ for 2h, then adding 3g of citric acid, and reacting at 40 ℃ for 2h to obtain the titanium-zirconium crosslinking agent.
Example 2
Adding 5g of titanium sulfate and 60mL of water into a 250mL three-neck flask, fully stirring, adding 5mL of 40 wt% ammonium citrate solution and 10mL of triethanolamine (11.36g) into the three-neck flask, stirring, simultaneously raising the temperature of a water bath to 35 ℃, and keeping the temperature for 1 h; adding 2g of zirconium sulfate, reacting at 40 ℃ for 3h, adding 3mL of pure acetic acid, and reacting at 35 ℃ for 2h to obtain the titanium-zirconium crosslinking agent.
Comparative example 1
Adding 5g of zirconium oxychloride into a 250mL flask, adding 10mL of diethanolamine alcohol amine into the flask, stirring, heating the flask to 30 ℃, fully reacting for 1h, adding 3mL of pure acetic acid into the flask, and reacting for 4h at 35 ℃ to obtain the organic zirconium crosslinking agent.
Comparative example 2
Adding 5g of titanium phosphate into a 250mL flask, adding 10mL of diethanolamine alcohol amine into the flask, stirring, heating the flask to 40 ℃, fully reacting for 1h, adding 2mL of pure acetic acid into the flask, and reacting for 2h at 35 ℃ to obtain the organic titanium crosslinking agent.
And respectively adding 0.5mL of the titanium-zirconium cross-linking agent obtained in the example 2, the organic zirconium cross-linking agent obtained in the comparative example 1 and the organic titanium cross-linking agent obtained in the comparative example 2 into 100mL of guar gum water solution with the mass concentration of 0.45%, adjusting the pH value of a cross-linking system to 6.0 by adopting hexamethylene diamine, and then stirring for 1.5min to obtain the cross-linked modified guar gum.
The crosslinked modified guar obtained in example 2 and in comparative example 1 were subjected to a hooking test, the results of which are shown in figures 1 and 2. As can be seen from fig. 1 and 2: the titanium zirconium cross-linking agent obtained in example 2 has superior overhang properties at a pH of 6.0 compared to the organic zirconium cross-linking agent.
The crosslinked modified guar obtained in example 2 and in comparative example 2 were placed on a rheometer to test the rheology profile, the results of which can be seen in figures 3 and 4: the titanium zirconium cross-linking agent obtained in example 2 has excellent temperature resistance at a pH of 6.0.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The titanium-zirconium cross-linking agent is characterized by comprising the following preparation raw materials:
inorganic titanium, a ligand, inorganic zirconium, protonic acid and water;
the inorganic titanium comprises titanium phosphate and/or titanium sulfate;
the ligand comprises one or more of diethanolamine, triethanolamine, ammonium citrate and sodium gluconate;
the inorganic zirconium includes zirconium oxychloride and/or zirconium sulfate.
2. The titanium zirconium cross-linking agent of claim 1, comprising the following raw materials in parts by weight:
2-5 parts of inorganic titanium, 5-20 parts of ligand, 0.5-5 parts of inorganic zirconium, 2-10 parts of protonic acid and 40-85 parts of water.
3. The titanium zirconium cross-linking agent of claim 1 or 2, characterized in that the protic acid comprises an inorganic protic acid and/or an organic protic acid; the inorganic protonic acid comprises hydrochloric acid; the organic protonic acid comprises acetic acid and/or citric acid.
4. The titanium zirconium crosslinking agent of claim 3, wherein the inorganic protonic acid has a mass concentration of 10% to 20%.
5. The method of producing a titanium zirconium crosslinking agent according to any one of claims 1 to 4, comprising the steps of:
mixing inorganic titanium, a ligand and water to obtain a suspension;
and mixing the suspension with inorganic zirconium, carrying out a first coordination reaction, and then adding protonic acid to carry out a second coordination reaction to obtain the titanium-zirconium crosslinking agent.
6. The preparation method according to claim 5, wherein the temperature of the first coordination reaction is 20-60 ℃ and the time is 1-10 h.
7. The preparation method according to claim 5, wherein the temperature of the second coordination reaction is 20-60 ℃ and the time is 1-10 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421372A (en) * | 2006-02-14 | 2009-04-29 | 纳幕尔杜邦公司 | Cross-linking composition and method of use |
| CN101668764A (en) * | 2007-03-30 | 2010-03-10 | 纳幕尔杜邦公司 | Zirconium-based cross-linker compositions and their use in high ph oil field applications |
| CN101688112A (en) * | 2007-05-11 | 2010-03-31 | 普拉德研究及开发股份有限公司 | Well treatment with complexed metal crosslinkers |
| CN102367380A (en) * | 2011-09-22 | 2012-03-07 | 东北石油大学 | Fracturing fluid which resists temperature of 200 DEG C |
| CN112126420A (en) * | 2020-09-04 | 2020-12-25 | 四川省威沃敦化工有限公司 | Crosslinking agent for fracturing and preparation method thereof |
| CN113121581A (en) * | 2019-12-31 | 2021-07-16 | 中石化石油工程技术服务有限公司 | Preparation method of metal chelate and high-temperature polymer fracturing fluid |
-
2021
- 2021-12-31 CN CN202111670442.3A patent/CN114292636A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421372A (en) * | 2006-02-14 | 2009-04-29 | 纳幕尔杜邦公司 | Cross-linking composition and method of use |
| CN101668764A (en) * | 2007-03-30 | 2010-03-10 | 纳幕尔杜邦公司 | Zirconium-based cross-linker compositions and their use in high ph oil field applications |
| CN101688112A (en) * | 2007-05-11 | 2010-03-31 | 普拉德研究及开发股份有限公司 | Well treatment with complexed metal crosslinkers |
| CN102367380A (en) * | 2011-09-22 | 2012-03-07 | 东北石油大学 | Fracturing fluid which resists temperature of 200 DEG C |
| CN113121581A (en) * | 2019-12-31 | 2021-07-16 | 中石化石油工程技术服务有限公司 | Preparation method of metal chelate and high-temperature polymer fracturing fluid |
| CN112126420A (en) * | 2020-09-04 | 2020-12-25 | 四川省威沃敦化工有限公司 | Crosslinking agent for fracturing and preparation method thereof |
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