CN103275690B - Crosslinking agent for polymer hydrofracturing fluid as well as preparation and application of crosslinking agent - Google Patents
Crosslinking agent for polymer hydrofracturing fluid as well as preparation and application of crosslinking agent Download PDFInfo
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Abstract
The invention relates to a crosslinking agent for polymer hydrofracturing fluid as well as preparation and application of the crosslinking agent. The crosslinking agent comprises the following percentage by weight: 15-30 percent of organic acid, 4-8 percent of inorganic base, 10-18 percent of organic amine, 4-10 percent of trivalent metal ion salt, 7-15 percent of tetravalent zircon salt, 1-5 percent of aldehyde and the balance of water. The crosslinking agent is controllable in crosslinking time within 10-180 seconds and high in crosslinking agent and has the gel cross-linking temperature tolerance reaching 150DEG C; the crosslinking agent does not contain phenol, and the damages to the environment are reduced; the crosslinking agent can be synthesized in need of the condition of 35-65DEG C, and the finished product of the crosslinking agent can be obtained in a one-time manner without secondary blending; and the crosslinking agent contains triethanolamine, so that the gel crosslinking stability of the crosslinking agent is greatly improved.
Description
Technical field
The invention relates to a kind of polymer fracturing fluid linking agent and Synthesis and applications thereof.
Background technology
Fracturing technique is one of major measure of Middle-later Development Stage of Oilfield volume increase, and the quality of fracturing fluid system performance directly affects fracturing reform effect.At present, China uses more fracturing fluid system is still guanidine gum fracturing fluid.Because hydroxypropyl guar (one-level) prices of raw and semifnished materials to be risen to 158000 yuan/ton of 2012 by 18300 yuan/ton in 2010, significantly increase pressure break cost, constrain the popularization of fracturing technique.New polymers fracturing liquid, owing to having the advantages such as low cost, low frictional resistance, low residue, the easily row of returning, little, the period of storage of formation injury are long, can substitute conventional guanidine gum fracturing fluid.
At present in the profile control and water plugging of oil field, widespread use polyacrylamide and supporting linking agent thereof, this type of linking agent is mainly organic chromium class, Tiorco 677 class.
For example, describe low-molecular(weight)polymer fracturing liquid cross-linking agent, it is characterized in that in patent CN102634329A: linking agent is made up of A agent and B agent, A agent and B agent weight ratio are 4:1, mix, obtain linking agent.The each weight percentages of components of A agent: aluminum chloride, 10%; Zirconium oxychloride, 10%; Sodium hydroxide, 8%; Glycerine, 10%; Lactic acid, 10%; Methyl alcohol, 20%; Water, 32%; The preparation of A agent: first add water, aluminum chloride and zirconium oxychloride at reactor, stir 10 minutes, then add glycerine, lactic acid, stirring reaction 10min, then add sodium hydroxide, stirring reaction 5min, obtain A agent; The each weight percentages of components of B agent is: oxalic dialdehyde, 60%; Phenol, 40%; The preparation of B agent: first phenol is heated 60-65 DEG C and make it melt; Secondly, add oxalic dialdehyde in a kettle., then the phenol of thawing is poured in reactor, under temperature 70-75 DEG C of condition, stir 30-40 minute, obtain B agent.
When being applied to such linking agent containing carboxylic acid group polymer's fracturing liquid, the frozen glue of formation hangs out of order, hangs frozen glue with glass stick, effectively can not provoke, be unfavorable for pressing crack construction.
In order to solve the problem, the invention provides a kind of and the matching used additive of polymer fracturing fluid thickening material, be particularly useful for containing carboxylic acid group polymer's fracturing liquid.
Summary of the invention
One object of the present invention is to provide a kind of polymer fracturing fluid linking agent.
Another object of the present invention is to the preparation method that described polymer fracturing fluid linking agent is provided.
Another object of the present invention is the application providing described polymer fracturing fluid linking agent.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of polymer fracturing fluid linking agent, described linking agent is prepared from primarily of following weight percent composition: organic acid: 15 ~ 30%, mineral alkali: 4 ~ 8%, organic amine: 10 ~ 18%, trivalent metal ion salts: 4 ~ 10%, tetravalence zirconates: 7 ~ 15%, aldehyde: 1 ~ 5%, surplus is water.
According to linking agent of the present invention, described organic acid can be any organic acid of state of the art, those skilled in the art know that know this area the kinds of organic acids that is suitable for, those skilled in the art, after reading the present invention, can select the organic acid being suitable for this area in the prior art.
But the preferred organic acid of the present invention is the one in tartrate, citric acid, lactic acid, Main Function is complexation of metal ions.
According to linking agent of the present invention, described mineral alkali can be any mineral alkali of state of the art, those skilled in the art know that know this area the mineral alkali kind that is suitable for.But the preferred mineral alkali of the present invention is one or more the mixing in sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, Main Function be in and organic acid.
The preferred organic amine of the present invention is trolamine, and Main Function is for improving frozen glue cross-link intensity.
The preferred trivalent metal ion salts of the present invention is one or more the mixing in chromium trichloride, aluminum chloride, Tai-Ace S 150, and Main Function is for providing cross-linking set.
The preferred tetravalence zirconates of the present invention is zirconium tetrachloride, zirconium oxychloride or the mixing of the two, and Main Function is for providing cross-linking set.
The preferred aldehyde of the present invention be formaldehyde, oxalic dialdehyde, one or more mixing in glutaraldehyde, Main Function is the heat-resisting property improving frozen glue.
On the other hand, present invention also offers the preparation method of described polymer fracturing fluid linking agent, described method comprises the steps:
Be basic raw material by organic acid, water, alkali, organic amine, trivalent metal ion salts, tetravalence zirconates and aldehyde chemical, under 35-65 DEG C of condition, feed intake synthesis in order.
According to method of the present invention, said components adds according to said sequence and mixes by the present invention, and in order to improve the linking agent performance of the present invention's synthesis further, the present invention further preferably, first add organic acid, water, add mineral alkali after stirring, maintenance system temperature of reaction is 35-65 DEG C, stirs after dissolving completely and adds trivalent metal ion salts, tetravalence zirconates, stir 3 hours, add organic amine and aldehyde again, stir 3 hours, get product after cooling.
Wherein preferably add organic acid, water further, stir and add mineral alkali after 1 hour.
Again on the one hand, present invention also offers described polymer fracturing fluid and preparing the application in oil field fracturing fluid.
Wherein preferred described fracturing liquid is carbonyl bearing polymer fracturing liquid.
When using linking agent preparing fracturing fluid of the present invention, can first prepare mass concentration be 0.5-0.6% containing carboxylic acid group polymer's solution, with mineral acid, for example salt acid for adjusting pH value is 5.5-6, add the linking agent of the present invention containing carboxylic acid group polymer's liquor capacity 0.3% ~ 0.5% that volume is preparation again, stir 35 ~ 50 seconds and get final product.
Wherein said carbonyl bearing polymer fracturing liquid is known in the art, and those skilled in the art can select applicable described carbonyl bearing polymer fracturing liquid according to prior art, such as anionic polyacrylamide fracturing liquid.
In sum, the invention provides a kind of polymer fracturing fluid linking agent and Synthesis and applications thereof.Linking agent tool of the present invention has the following advantages:
1, crosslinking time 10-180s is controlled, and cross-link intensity is high, and crosslinked gel temperature tolerance reaches 150 DEG C.
2, not containing phenol, the harm to environment is reduced.
3, this linking agent need synthesize under the condition of 35-65 DEG C, and for disposable go out finished product, without the need to secondary mixture.
4, contain trolamine in this linking agent, substantially increase the frozen glue cross-linked stable performance of linking agent.
Accompanying drawing explanation
Fig. 1 is fracturing liquid 90 DEG C of flow curves that Application Example 1 of the present invention is mixed with.
Fig. 2 is fracturing liquid 110 DEG C of flow curves that Application Example 2 of the present invention is mixed with.
Fig. 1, Fig. 2 testing conditions is: RV20 rheometer, 110 DEG C, 170s
-1shear 120min, pH value of solution=6.5.
Embodiment
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
Embodiment 1
Be add 150kg tartrate, 590kg water in the reactor of 2 sides at volume, stir three minutes, slowly add 40kg sodium bicarbonate, maintaining temperature of reaction is 35 DEG C, be stirred to after dissolving completely and add 40kg aluminum chloride, 70kg zirconium oxychloride, stir 3 hours, add 100kg trolamine, 10kg oxalic dialdehyde, constant temperature 45 DEG C stir within 3 hours, namely obtain product.
Embodiment 2
Be add 220kg citric acid, 335kg water in the reactor of 2 sides at volume, stir three minutes, slowly add 60kg sodium hydroxide, maintaining temperature of reaction is 45 DEG C, be stirred to after dissolving completely and add 80kg aluminum chloride, 120kg zirconium oxychloride, stir 3 hours, add 150kg trolamine, 35kg oxalic dialdehyde, constant temperature 55 DEG C stir within 3 hours, namely obtain product.
Embodiment 3
Be add 300kg lactic acid, 140kg water in the reactor of 2 sides at volume, stir three minutes, slowly add 80kg potassium hydroxide, maintaining temperature of reaction is 55 DEG C, be stirred to after dissolving completely and add 100kg aluminum chloride, 150kg zirconium oxychloride, stir 3 hours, add 180kg trolamine, 50kg oxalic dialdehyde, constant temperature 65 DEG C stir within 3 hours, namely obtain product.
Embodiment 4
Be add 250kg tartrate, 290kg water in the reactor of 2 sides at volume, stir three minutes, slowly add 60kg sodium carbonate, maintaining temperature of reaction is 45 DEG C, be stirred to after dissolving completely and add 80kg aluminum chloride, 120kg zirconium oxychloride, stir 3 hours, add 160kg trolamine, 40kg oxalic dialdehyde, constant temperature 55 DEG C stir within 3 hours, namely obtain product.
Application Example 1
Preparation mass concentration be 0.6% containing carboxylic acid group polymer's solution, adding hydrochloric acid regulation system pH value is 5.5, adds embodiment 3 linking agent that volume is the polymer solution volume 0.3% of preparation, is formed and can hang frozen glue after stirring 35s.
This hangs the flow curve of frozen glue as shown in Figure 1.
Application Example 2
Preparation mass concentration be 0.6% containing carboxylic acid group polymer's solution, adding hydrochloric acid regulation system pH value is 5.5, adds embodiment 1 linking agent that volume is the polymer solution volume 0.5% of preparation, is formed and can hang frozen glue after stirring 50s.
This hangs the flow curve of frozen glue as shown in Figure 2.
Test example 1
On August 2nd, 2012, limit, Liaohe Oil Field 35-20 well pressing crack construction, adopt and carry out pressure break containing carboxylic acid group polymer's fracturing liquid, pump into 325 side's liquid altogether, wherein adopt 1.2 side's embodiment 2 linking agents, 43 side's haydites, discharge capacity 3.0-5.0 side/min, construction completes smoothly, closing well 1 hour after pressure, the row of returning 183 side liquid, returning discharge opeing viscosity is 2mPas.
Test example 2
On September 19th, 2012, Liaohe Oil Field victory 26-12 well pressing crack construction, adopt and carry out pressure break containing carboxylic acid group polymer's fracturing liquid, pump into 400 side's liquid altogether, wherein adopt 1.6 side's embodiment 3 linking agents, 47 side's haydites, discharge capacity 3.4-4.6 side/min, construction completes smoothly, closing well 1 hour after pressure, the row of returning 216 side liquid, returning discharge opeing viscosity is 2mPas.
Claims (7)
1. a polymer fracturing fluid linking agent, it is characterized in that, described linking agent is prepared from primarily of following weight percent composition: organic acid: 15 ~ 30%, mineral alkali: 4 ~ 8%, organic amine: 10 ~ 18%, trivalent metal ion salts: 4 ~ 10%, tetravalence zirconates: 7 ~ 15%, aldehyde: 1 ~ 5%, surplus is water; Described organic acid is the one in tartrate, citric acid, lactic acid; Described organic amine is trolamine; Described trivalent metal ion salts is one or more the mixing in chromium trichloride, aluminum chloride, Tai-Ace S 150; Described aldehyde be formaldehyde, oxalic dialdehyde, one or more mixing in glutaraldehyde.
2. linking agent according to claim 1, is characterized in that, described mineral alkali is one or more the mixing in sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide.
3. linking agent according to claim 1, is characterized in that, described tetravalence zirconates is zirconium tetrachloride, zirconium oxychloride or the mixing of the two.
4. the preparation method of linking agent described in claims 1 to 3 any one, it is characterized in that, described method comprises the steps: organic acid, water, mineral alkali, trivalent metal ion salts, tetravalence zirconates, organic amine and aldehyde under 35-65 DEG C of condition, and feed intake synthesis in order.
5. method according to claim 4, it is characterized in that, first add organic acid, water, add mineral alkali after stirring, maintenance system temperature of reaction is 35-65 DEG C, stirs after dissolving completely and adds trivalent metal ion salts, tetravalence zirconates, stir 3 hours, add organic amine and aldehyde again, stir 3 hours, get product after cooling.
6. the application in oil field fracturing fluid prepared by linking agent described in claims 1 to 3 any one.
7. application according to claim 6, is characterized in that, described fracturing liquid is carbonyl bearing polymer fracturing liquid.
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| CN104513654B (en) * | 2013-10-08 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of modifier and oil displacement agent composition and oil displacement agent and preparation method thereof |
| CN104559995A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Delayed crosslinking fracturing fluid composition |
| CN103912258B (en) * | 2014-04-02 | 2016-05-04 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | A kind of mechanism that controls crosslinking agent |
| CN105441059B (en) * | 2014-08-29 | 2019-01-18 | 中国石油天然气股份有限公司 | Crosslinker composition, acidic preflush and its application |
| CN104388074B (en) * | 2014-10-29 | 2019-03-01 | 河南师范大学 | A kind of carboxymethyl guanidine rubber cross linker and its preparation method and application |
| CN106281271A (en) * | 2016-07-26 | 2017-01-04 | 中国石油天然气股份有限公司 | Polynary complexed organo-metallic cross-linking agent and preparation method thereof |
| CN108456513B (en) * | 2017-02-20 | 2021-09-10 | 中国石油化工股份有限公司 | Organic aluminum crosslinking agent for fracturing fluid, preparation method and application |
| CN111171797A (en) * | 2018-11-13 | 2020-05-19 | 中国石油化工股份有限公司 | Cross-linking agent and preparation method thereof |
| CN111943990B (en) * | 2020-09-15 | 2022-08-30 | 昆山京昆油田化学科技有限公司 | Organic aluminum zirconium boron crosslinking agent, preparation method thereof and acidic guar gum fracturing fluid |
| CN116751576A (en) * | 2023-06-19 | 2023-09-15 | 东营众悦石油科技有限公司 | Delayed crosslinking agent for water-based fracturing fluid and preparation method and application thereof |
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| US6767868B2 (en) * | 2001-02-22 | 2004-07-27 | Bj Services Company | Breaker system for fracturing fluids used in fracturing oil bearing formations |
| CN102634329B (en) * | 2012-03-09 | 2013-12-04 | 中国石油天然气股份有限公司 | Low-molecular-weight polymer fracturing liquid |
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