CN106047330A - Secondarily crosslinked aqueous gel crosslinking agent and preparation method and application thereof - Google Patents
Secondarily crosslinked aqueous gel crosslinking agent and preparation method and application thereof Download PDFInfo
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- CN106047330A CN106047330A CN201610424588.2A CN201610424588A CN106047330A CN 106047330 A CN106047330 A CN 106047330A CN 201610424588 A CN201610424588 A CN 201610424588A CN 106047330 A CN106047330 A CN 106047330A
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- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
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- 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
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Abstract
The invention discloses a secondarily crosslinked aqueous gel crosslinking agent and a preparation method and application thereof. The preparation method of the agent comprises the following steps: mixing and reacting metal chloride and alkali in water, and adding an organic acid into above reaction system for mixing and reacting to obtain the secondarily crosslinked aqueous gel crosslinking agent. The secondarily crosslinked aqueous gel crosslinking agent of the invention is applied to the preparation of oil displacement agents and weak gel for acid fracturing and/or profile control. The method of preparing the secondarily crosslinked aqueous gel crosslinking agent according to the invention is simple in process, high in yield, easy to perform and suitable for large-scale production. The secondarily crosslinked aqueous gel crosslinking agent may be used as both a crosslinking agent for an oil displacement agent and an acidifying liquid and fracturing liquid crosslinking agent, and has important applicable value.
Description
Technical field
The present invention relates to a kind of secondary cross-linking type aqueous gel cross-linking agent and preparation method and application.
Background technology
Crosslinking aqueous gel is by water-soluble polymer (generally partially hydrolyzed polyacrylamide (PHPA) is called for short HPAM) and crosslinking
The one that agent is formed can slowly cross-link (based on intermolecular cross-linking, intramolecular crosslinking is auxiliary), and the controlled polymer of viscosity coagulates
Colloid.Its characteristic is not only to have certain mobility but also have certain intensity.Be widely used in recent years profile control, water blockoff,
The numerous areas of the oil-gas minings such as acidifying, pressure break, is especially formed currently with this kind of system closure Thief zone water filling macropore
Delayed cross-linking aqueous gel oil reservoir transfer drive method receive much concern.At present cross-linking agent application more for phenolic crosslinkers, have
Machine aluminum crosslinker and organic chrome cross linker.Partially hydrolyzed polyacrylamide (PHPA) can only once be cross-linked by above-mentioned cross-linking agent, in order to
Improve its gel strength under reservoir conditions, the especially partially hydrolyzed polyacrylamide (PHPA) after porous media is sheared to carry out
Crosslinking, the most urgently develops a kind of cross-linking agent with secondary cross-linking feature.
Summary of the invention
It is an object of the invention to provide a kind of secondary cross-linking type aqueous gel cross-linking agent and preparation method and application.
The preparation method of the secondary cross-linking type aqueous gel cross-linking agent that the present invention provides, comprises the steps: metal chlorine
Compound and alkali hybrid reaction in water, state addition organic acid hybrid reaction in the system of reaction then up, i.e. obtains secondary and hands over
Connection type aqueous gel cross-linking agent.
In above-mentioned method, the mol ratio of described metal chloride, described alkali and described organic acid can be 1:2.4～
3.25:1.2～1.75, concretely 1:3:1.5,2.5:6.5:3,2:6.5:3,1:2.6～3:1.2～1.5 or 1:2.6～
3.25:1.2～1.5；
The quality of described metal chloride can be 1g:3～8mL with the volume ratio of described water, the matter of described metal chloride
Amount can be 1g:7～9mL with the volume ratio of described water.
In above-mentioned method, the temperature of described metal chloride and alkali reaction can be 60～70 DEG C, concretely 60 DEG C or
70℃；
Described metal chloride can be 15～20min with the time of alkali reaction, concretely 15min or 20min.
In above-mentioned method, the temperature of described addition organic acid hybrid reaction can be 60～70 DEG C, concretely 60 DEG C or
70℃；
The time of described addition organic acid hybrid reaction can be 20～30min, concretely 20min or 30min.
In above-mentioned method, described metal chloride is at least in aluminum chloride, Chlorizate chromium, zirconium chloride and titanium chloride
Kind；
Described alkali is sodium hydroxide and/or potassium hydroxide；
Described organic acid is unitary organic acid and binary organic acid.
In above-mentioned method, described unitary organic acid is at least in phenylacetic acid, benzoic acid, salicylic acid and glacial acetic acid
Kind；
Described binary organic acid is ethanedioic acid and/or phthalic acid；
Described unitary organic acid can be 1:0.8～1.2, concretely 1:1 or 1 with the mol ratio of described binary organic acid:
0.9～1.1.
Present invention also offers described secondary cross-linking type aqueous gel cross-linking agent prepared by above-mentioned method.
Secondary cross-linking type aqueous gel cross-linking agent of the present invention is applied to prepare oil displacement agent, acid fracturing and/or transfer drive
With in Weak Gels.
In the present invention, concrete selects metal chloride (ReCl with reactant3), as a example by sodium hydroxide and ethanedioic acid, on
State the chemical equation of method, as shown in following formula (1)-(2):
(1)ReCl3+3NaOH→Re(OH)3+3NaCl
(2)3Re(OH)3+3COOH-COOH+3RCOOH→Re2(COO-OOC)3+(RCOO)3Re+9H2O
In above-mentioned formula (2), RCOOH is phenylacetic acid, benzoic acid, salicylic acid or glacial acetic acid.
The invention have the advantages that
(1) having relatively low concentration, for 500-1000mg/L, usefulness is good；(2) to partially hydrolyzed polyacrylamide (PHPA),
The propionic acid amide. polymerization species oil displacement agents such as hydrophobic associated polymer, amphipathic polymer and comb-shaped polymer are respectively provided with good crosslinking and make
With, when concentration is 1000mg/L, it is possible to forming cross-linked structure, once after crosslinking, solution viscosity is risen to by 155.6mPa.s
5358.7mPa.s, after secondary cross-linking, solution viscosity rises to 35797.8mPa.s.(3) one times gelation time is 2-4 hour, two
Secondary gelation time is 24-28 hour.The present invention prepares the method for secondary cross-linking type aqueous gel cross-linking agent, simple process, productivity
High, it is easy to operation, it is suitable for large-scale production.Secondary cross-linking type aqueous gel cross-linking agent of the present invention can be used as the friendship of oil displacement agent
Connection agent, it is also possible to as acidifying solution and fracturing liquid cross-linking agent, there is relatively low concentration.
Accompanying drawing explanation
Fig. 1 is the secondary cross-linking type aqueous gel cross-linking agent gelation time curve of the embodiment of the present invention 1 preparation.
Fig. 2 is the secondary cross-linking type aqueous gel cross-linking agent gelation time curve of the embodiment of the present invention 2 preparation.
Fig. 3 is the secondary cross-linking type aqueous gel cross-linking agent gelation time curve of the embodiment of the present invention 3 preparation.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
In following embodiment, metal chloride used is respectively aluminum chloride, Chlorizate chromium, zirconium chloride, molecular weight is respectively 133,
266、233；Unitary organic acid be glacial acetic acid, binary organic acid be ethanedioic acid, molecular weight is respectively 60,90；Partial hydrolysis used
The viscosity-average molecular weight of polyacrylamide is 16,000,000, and degree of hydrolysis is 29.8%.
Embodiment 1, prepare secondary cross-linking type aqueous gel cross-linking agent
Aluminum chloride 26.6g (0.2mol) and sodium hydroxide 24g (0.6mol) is dissolved in 200mL water, is heated to 60 DEG C,
Under agitation after reaction 15min, adding 9.0g (0.15mol) glacial acetic acid, 13.5g (0.15mol) ethanedioic acid is in stirring
Under the conditions of 60 DEG C carry out react 20min, react complete and obtain secondary cross-linking type aqueous gel cross-linking agent of the present invention.
The specific experiment process using secondary cross-linking type aqueous gel cross-linking agent of the present invention is:
(1) 0.4% polymer solution is prepared.199.2g simulated injection water is added, under stirring in 250mL beaker
Adding 0.8g polymer, stirring is to the most molten.
(2) claim the 0.4% polymer solution 49.85g dissolved, add the cross-linking agent of 0.15g synthesis, stir with Glass rod
Uniformly solution.
(3) by joined solution sampling and measuring sample viscosity at set intervals, record sample viscosity over time, is tied
Fruit is as shown in Figure 1.
As shown in Figure 1, the consumption of this secondary cross-linking type aqueous gel cross-linking agent when 500mg/L, gelation time for the first time
It is 3 hours, gelling strength 5358.7mPa.s, for the second time gelation time 24 hours, gelling strength 35797.8mPa.s.
Embodiment 2, prepare secondary cross-linking type aqueous gel cross-linking agent
Chlorizate chromium 66.5g (0.25mol) and sodium hydroxide 26g (0.65mol) is dissolved in 200mL water, is heated to 60
DEG C, under agitation after reaction 15min, adding 9.0g (0.15mol) glacial acetic acid, 13.5g (0.15mol) ethanedioic acid is stirring
Carry out reacting 20min at 60 DEG C under the conditions of mixing, react complete and obtain the secondary cross-linking type aqueous gel cross-linking agent that the present invention provides.
The specific experiment process using secondary cross-linking type aqueous gel cross-linking agent of the present invention is:
(1) 0.4% polymer solution is prepared.199.2g simulated injection water is added, under stirring in 250mL beaker
Adding 0.8g polymer, stirring is to the most molten.
(2) claim the 0.4% polymer solution 49.85g dissolved, add the cross-linking agent of 0.15g synthesis, stir with Glass rod
Uniformly solution.
(3) by joined solution sampling and measuring sample viscosity at set intervals, record sample viscosity over time, is tied
Fruit is as shown in Figure 2.
As shown in Figure 2, the consumption of this secondary cross-linking type aqueous gel cross-linking agent when 1000mg/L, gelation time for the first time
It is 2 hours, gelling strength 5864.5mPa.s, for the second time gelation time 26 hours, gelling strength 32456.4mPa.s.
Embodiment 3, prepare secondary cross-linking type aqueous gel cross-linking agent
Zirconium chloride 46.6g (0.2mol) and sodium hydroxide 26g (0.65mol) is dissolved in 200mL water, is heated to 70
DEG C, under agitation after reaction 20min, adding 9.0g (0.15mol) glacial acetic acid, 13.5g (0.15mol) ethanedioic acid is stirring
Carry out reacting 30min at 70 DEG C under the conditions of mixing, react complete and obtain the secondary cross-linking type aqueous gel cross-linking agent that the present invention provides.
The specific experiment process using secondary cross-linking type aqueous gel cross-linking agent of the present invention is:
(1) 0.4% polymer solution is prepared.199.2g simulated injection water is added, under stirring in 250mL beaker
Adding 0.8g polymer, stirring is to the most molten.
(2) claim the 0.4% polymer solution 49.85g dissolved, add the cross-linking agent of 0.15g synthesis, stir with Glass rod
Uniformly solution.
(3) by joined solution sampling and measuring sample viscosity at set intervals, record sample viscosity over time, is tied
Fruit is as shown in Figure 3.
From the figure 3, it may be seen that the consumption of this secondary cross-linking type aqueous gel cross-linking agent is when 1000mg/L, gelation time for the first time
It is 2 hours, gelling strength 5568.3mPa.s, for the second time gelation time 24 hours, gelling strength 32925.8mPa.s.
Claims (8)
1. a preparation method for secondary cross-linking type aqueous gel cross-linking agent, comprises the steps: to exist metal chloride and alkali
Hybrid reaction in water, states addition organic acid hybrid reaction in the system of reaction then up, i.e. obtains secondary cross-linking type water base solidifying
Rubber cross linker.
Method the most according to claim 1, it is characterised in that: described metal chloride, described alkali and described organic acid
Mol ratio is 1:2.4～3.25:1.2～1.75；
The quality of described metal chloride is 1g:3～8mL with the volume ratio of described water, the quality of described metal chloride and institute
The volume ratio stating water is 1g:7～9mL.
Method the most according to claim 1 and 2, it is characterised in that: described metal chloride is 60 with the temperature of alkali reaction
～70 DEG C；
Described metal chloride is 15～20min with the time of alkali reaction.
4. according to the method according to any one of claim 1-3, it is characterised in that: the temperature of described addition organic acid hybrid reaction
Degree is 60～70 DEG C；
The time of described addition organic acid hybrid reaction is 20～30min.
5. according to the method according to any one of claim 1-4, it is characterised in that: described metal chloride is aluminum chloride, chlorine
Change at least one in chromium, zirconium chloride and titanium chloride；
Described alkali is sodium hydroxide and/or potassium hydroxide；
Described organic acid is unitary organic acid and binary organic acid.
Method the most according to claim 5, it is characterised in that: described unitary organic acid is phenylacetic acid, benzoic acid, salicylic acid
With at least one in glacial acetic acid；
Described binary organic acid is ethanedioic acid and/or phthalic acid；
Described unitary organic acid is 1:0.8～1.2 with the mol ratio of described binary organic acid.
7. the described secondary cross-linking type aqueous gel cross-linking agent that prepared by the method according to any one of claim 1-6.
8. secondary cross-linking type aqueous gel cross-linking agent described in claim 7 is preparing oil displacement agent, acid fracturing and/or transfer drive with weak
Application in gel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502326A (en) * | 2017-09-04 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of secondary cross-linking carries liquid |
| CN113337259A (en) * | 2021-03-16 | 2021-09-03 | 任丘市油联化工有限公司 | Ultralow-temperature oligomeric polyphenol cross-linked polymer profile control agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935272A (en) * | 2010-08-18 | 2011-01-05 | 中国海洋石油总公司 | Rare earth type water-base gel crosslinking agent and preparation method thereof |
| CN104449615A (en) * | 2014-11-21 | 2015-03-25 | 天津大港油田滨港集团博弘石油化工有限公司 | Organic acid chromium crosslinking agent for oil production and preparation method thereof |
-
2016
- 2016-06-15 CN CN201610424588.2A patent/CN106047330A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935272A (en) * | 2010-08-18 | 2011-01-05 | 中国海洋石油总公司 | Rare earth type water-base gel crosslinking agent and preparation method thereof |
| CN104449615A (en) * | 2014-11-21 | 2015-03-25 | 天津大港油田滨港集团博弘石油化工有限公司 | Organic acid chromium crosslinking agent for oil production and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 杨红斌，等: "低温高矿化度油藏弱凝胶调驱体系的研制及性能评价", 《油田化学》 * |
| 陈东明: "双基团二次交联调剖体系试验研究", 《石油钻探技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502326A (en) * | 2017-09-04 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of secondary cross-linking carries liquid |
| CN113337259A (en) * | 2021-03-16 | 2021-09-03 | 任丘市油联化工有限公司 | Ultralow-temperature oligomeric polyphenol cross-linked polymer profile control agent and preparation method thereof |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China Offshore Oil Group Co., Ltd. Applicant after: CNOOC research institute limited liability company Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Research Institute |
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Application publication date: 20161026 |