CN104031631B - Mud acid cross-linking agent and preparation method thereof - Google Patents
Mud acid cross-linking agent and preparation method thereof Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 72
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 104
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 239000005011 phenolic resin Substances 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- JHHZLHWJQPUNKB-UHFFFAOYSA-N pyrrolidin-3-ol Chemical compound OC1CCNC1 JHHZLHWJQPUNKB-UHFFFAOYSA-N 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 26
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 23
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 43
- 238000010792 warming Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 230000003044 adaptive effect Effects 0.000 abstract 1
- 229940015043 glyoxal Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 63
- 238000004132 cross linking Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the technical field of oil and gas exploitation, and specifically relates to a mud acid cross-linking agent and a preparation method thereof. The mud acid cross-linking agent is prepared from the following materials in parts by weight: 1000 parts of 3-pyrrolidinol, 400-600 parts of glyoxal, 330 parts of water-soluble phenolic resin, 1000 parts of alcohol and 1000 parts of water, wherein the water-soluble phenolic resin comprises 94 parts of phenol, 9.2 parts of catalyst and 225 parts of formaldehyde aqueous liquor with concentration of 40%l and the catalyst is one of sodium hydroxide or potassium hydroxide. The mud acid cross-linking agent disclosed by the invention is strong in adaptive capacity and is capable of lowering acid liquor reaction speed and improving effective acting distance of the acid liquor.
Description
Technical field
The invention belongs to oil gas development technology field is and in particular to a kind of mud acid cross-linking agent and preparation method thereof.
Background technology
Step into the high maturation exploration phase with China's Land petroleum exploitation, the exploration of lithologic deposit and exploitation are increasingly
Substantially.According to statistics, 179.2 hundred million tons of the land main oil-gas bearing basin residual petroleum geological resource total amount of China, lithologic character stratum 91.3
Hundred million tons, account for the 51% of total petroleum geology stock number.But lithology geology is made up of sand grains and grain-to-grain cementation thing, and sand grains is mainly stone
English and Anhydrite, cement is mainly silicates and carbonate, carries out fracturing yield increasing with common hydrochloric acid and is often up to less than pre-
The effect of phase, for adopting the hydrochloric acid of 10%～15% concentration and the Fluohydric acid. of 3%～8% concentration this kind of oil well or water injection well more
Processed with the mixed acid of additive composition, this mixed acid is referred to as mud acid.For mud acid, there is no suitable crosslinking at present
Agent, makes the polymer solution being dissolved in mud acid be cross-linked into frozen glue.Acid fracturing is acid fracturing, is by acid under higher than rock rupture pressure
Injection stratum, forms crack in stratum, forms splitting of high flow conductivity by the uneven corrosion of acid solution fracture face goods and materials
The process of seam.The acid solution of injection can dissolve formation rock or cement, thus increasing in-place permeability, makes output, the drive of oil gas
Inject convenient for water.During acidizing treatment, in order to improve acidizing effect, can be injected using polymer viscous acid,
Become the new technologies such as glactaric acid acidifying.
Content of the invention
It is an object of the invention to overcoming defect of the prior art, and it is adaptable to provide one kind to have, and can reduce
Acid liquid reaction speed, improves mud acid cross-linking agent of EFFECTIVE RANGE of acid solution and preparation method thereof.
The object of the present invention is achieved like this: it is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
400～600 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin
Including 94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is sodium hydroxide
One of or potassium hydroxide.
A kind of preparation method of mud acid cross-linking agent, comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into
Solution, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the second sequentially adding 400～600 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6
Dialdehyde, the water of 1000 parts of ethanol and 1000 parts, so that above-mentioned solution is reacted 30 minutes at a temperature of 60 DEG C, obtain homogeneous liquid
It is mud acid cross-linking agent.
A kind of mud acid cross-linking agent, this mud acid cross-linking agent is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
350 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin includes
94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is sodium hydroxide；Its system
Preparation Method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into
Solution, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the Biformyl sequentially adding 350 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6,
The water of 1000 parts of ethanol and 1000 parts, makes above-mentioned solution react 30 minutes at a temperature of 60 DEG C, obtains homogeneous liquid and be
Mud acid cross-linking agent.
A kind of mud acid cross-linking agent, this mud acid cross-linking agent is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
550 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin includes
94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is sodium hydroxide；Its system
Preparation Method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into
Solution, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the Biformyl sequentially adding 550 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6,
The water of 1000 parts of ethanol and 1000 parts, makes above-mentioned solution react 30 minutes at a temperature of 60 DEG C, obtains homogeneous liquid and be
Mud acid cross-linking agent.
For acrylamide copolymer, according to the functional group on its macromolecular chain and cross-linking agent and these institutes of functional group
Crosslink type can be divided into three kinds: ionic crosslinking, coordination bond cross-linking and covalently cross-linked, ion by the chemical reaction occurring
The crosslinked connection mainly passing through bivalence or high valence ion and carboxylate radical formation ionic bond of key；Coordination bond cross-linking is by suitable
Central ion and carboxyl, amide groups form coordinate bond and crosslinked, and for example chromium, aluminum, zirconium plasma can be used as central ion；Covalently
Key crosslinking refers to that cross-linking agent is reacted with the functional group on polymeric chain, forms new covalent bond and obtains with sky
Between network structure crosslinked gel.By consulting literatures, the fluorine atom in Fluohydric acid. is very capable with metallic ion coordination,
Idea is crosslinked here it is clear that unpractical by ionic bond or coordinate bond.Mud acid of the present invention is crosslinked
Agent, is to react, using covalently cross-linked mechanism and acrylamide polymer, the principle obtaining crosslinked gel.The present invention can be in mud acid
Property environment under use, can form fracturing fluid under the conditions of mud acid with thickening agent, can not only reduce acid liquid reaction speed, raising acid solution
EFFECTIVE RANGE, and this cross-linking agent is adaptable, either carbonate rock is still respectively provided with good to silicate rock
Good corrosion performance；The present invention has adaptable, can reduce acid liquid reaction speed, improve the EFFECTIVE RANGE of acid solution
Advantage.
Specific embodiment
The present invention is mud acid cross-linking agent and preparation method thereof, in conjunction with specific embodiment, the present invention is carried out furtherly
Bright.Specific embodiment is as follows:
Embodiment 1
A kind of mud acid cross-linking agent, this mud acid cross-linking agent is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
400 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin includes
94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is sodium hydroxide；Its system
Preparation Method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into
Solution, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the Biformyl sequentially adding 400 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6,
The water of 1000 parts of ethanol and 1000 parts, makes above-mentioned solution react 30 minutes at a temperature of 60 DEG C, obtains homogeneous liquid and be
Mud acid cross-linking agent.
Embodiment 2
A kind of mud acid cross-linking agent, this mud acid cross-linking agent is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
500 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin includes
94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is potassium hydroxide；Its system
Preparation Method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into
Solution, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the Biformyl sequentially adding 500 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6,
The water of 1000 parts of ethanol and 1000 parts, makes above-mentioned solution react 30 minutes at a temperature of 60 DEG C, obtains homogeneous liquid and be
Mud acid cross-linking agent.
Embodiment 3
A kind of mud acid cross-linking agent, this mud acid cross-linking agent is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
600 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin includes
94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is potassium hydroxide；Its system
Preparation Method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, water-soluble by falling the formaldehyde that 180 parts of concentration is 40% in the phenol solution of the addition catalyst described in step 2
Liquid, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the Biformyl sequentially adding 600 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6,
The water of 1000 parts of ethanol and 1000 parts, makes above-mentioned solution react 30 minutes at a temperature of 60 DEG C, obtains homogeneous liquid and be
Mud acid cross-linking agent.
Embodiment 4
A kind of mud acid cross-linking agent, this mud acid cross-linking agent is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
350 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin includes
94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is sodium hydroxide；Its system
Preparation Method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into
Solution, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the Biformyl sequentially adding 350 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6,
The water of 1000 parts of ethanol and 1000 parts, makes above-mentioned solution react 30 minutes at a temperature of 60 DEG C, obtains homogeneous liquid and be
Mud acid cross-linking agent.
Embodiment 5
A kind of mud acid cross-linking agent, this mud acid cross-linking agent is to be prepared by the raw materials in: 1000 parts of 3- pyrrolidinol,
550 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenol resin includes
94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, described catalyst is sodium hydroxide；Its system
Preparation Method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stir
Mix reaction 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into
Solution, is warming up to 60 DEG C, continues stirring reaction 50min；
4th, 2.8 parts of catalyst will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again, so
After be warming up to 70 DEG C, isothermal reaction 20min；
5th, the formaldehyde that 45 parts of concentration is 40% will be continuously added in the phenol solution after the isothermal reaction described in step 4
Aqueous solution, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, heat
To 40 DEG C, stir 15 minutes；
7th, the Biformyl sequentially adding 550 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6,
The water of 1000 parts of ethanol and 1000 parts, makes above-mentioned solution react 30 minutes at a temperature of 60 DEG C, obtains homogeneous liquid and be
Mud acid cross-linking agent.
Above example only in order to explain technical solution of the present invention, is not intended to limit；Although right with reference to the foregoing embodiments
The present invention has been described in detail, it will be understood by those within the art that, it still can be to aforementioned each example institute
The technical scheme recorded is modified, or carries out equivalent to wherein some technical characteristics；And these modifications or replacement, and
Do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution.
Benchmark test: take the mud acid cross-linking agent using the inventive method preparation, carry out crosslinking experiments.
Crosslinking experiments method is as follows: measures 242ml water, pours 128g technical hydrochloric acid, 30g40% Fluohydric acid. into, in stirring
Under the conditions of be uniformly dispersed.It is slowly added to 4g acid fracturing thickening agent under stirring condition, be continuously stirring to fully swelling, obtain 400ml
Cross-linked acid base fluid.Measure the cross-linked acid base fluid 100ml of preparation, add the mud acid cross-linking agent using the inventive method preparation, with the second
Table record is from addition cross-linking agent until hanging the required time.
Acid fracturing thickening agent is the copolymer of acrylamide (am) and 2- acrylamido -2- methyl-propanesulfonic acid (amps),
Between 6,000,000-1,000 ten thousand, the mol ratio of am and amps is 7: 3 to molecular weight.
Crosslinking experiments result is as follows: table 1 cross-linking agents performance
| Cross-linking agent | Temperature (DEG C) | Dosage (%) | Crosslinking time (s) | Cross-linked state |
| Cross-linking agent a | 60 | 3.0 | 140 | Can hang |
| Cross-linking agent b | 60 | 3.0 | 155 | Can hang |
| Cross-linking agent c | 60 | 3.0 | 142 | Can hang |
| Cross-linking agent d | 60 | 3.0 | 150 | Can hang |
Note: concentration of hydrochloric acid 12%, hydrofluoric acid concentration 3%, polymer concentration 1%.
As seen from the results in Table 1, under the conditions of 60 DEG C, with the mud acid cross-linking agent prepared by the inventive method at 2 minutes about all
The cross-linked polymer gel that can hang can be obtained, site operation requirement can be met.
Temperature resistant capability determination experiment method: with rv20 type rotary viscosity agent, after loading crosslinked gel sample, to sample plus
Heat, controls programming rate to be (3.0 ± 0.2) DEG C/min, rotor is with shear rate 170s simultaneously-1Rotate, sample is in heating condition
It is subject to down continuous shear stress to degrade, the temperature resistant capability that corresponding temperature during 50mpa.s characterizes sample is reduced to apparent viscosity.
By above-mentioned mud acid cross-linking agent a, b, c, d 60 DEG C formation frozen glue be heated to 100 DEG C, viscosity all 80mpa.s with
On, show that the mud acid cross-linking agent heat resistance of the present invention is not less than 100 DEG C.
Claims (2)
1. a kind of preparation method of the cross-linking agent making the polymer solution being dissolved in mud acid be cross-linked into frozen glue it is characterised in that: this makes
To be cross-linked into the cross-linking agent of frozen glue be to be prepared by the raw materials in: 3- pyrrolidinol 1000 to be dissolved in the polymer solution of mud acid
Part, 400～600 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, 1000 parts of water；Described water soluble phenolic
Resin includes 94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%, and described catalyst is hydrogen-oxygen
Change one of sodium or potassium hydroxide；
Its preparation method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stirring is anti-
Answer 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into,
It is warming up to 60 DEG C, continue stirring reaction 50min；
4th, 2.8 parts of catalyst, Ran Housheng will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again
Temperature to 70 DEG C, isothermal reaction 20min；
5th, water-soluble by continuously adding the formaldehyde that 45 parts of concentration is 40% in the phenol solution after the isothermal reaction described in step 4
Liquid, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, it is heated to 40
DEG C, stir 15 minutes；
7th, the second two sequentially adding 400～600 parts in the water soluble phenol resin of 3- pyrrolidinol will be dissolved with step 6
Aldehyde, the water of 1000 parts of ethanol and 1000 parts, so that above-mentioned solution is reacted 30 minutes at a temperature of 60 DEG C, obtaining homogeneous liquid is
For mud acid cross-linking agent.
2. the preparation side of a kind of cross-linking agent making the polymer solution being dissolved in mud acid be cross-linked into frozen glue according to claim 1
Method it is characterised in that: the described cross-linking agent that the polymer solution being dissolved in mud acid is cross-linked into frozen glue that makes is by following weight portion
Raw material is made: 1000 parts of 3- pyrrolidinol, 550 parts of Biformyl, 330 parts of water soluble phenol resin, 1000 parts of ethanol, water 1000
Part；Described water soluble phenol resin includes 94 parts of phenol, 9.2 parts of catalyst and 225 parts of the formalin that concentration is 40%,
Described catalyst is sodium hydroxide；Its preparation method comprises the steps:
First, 94 parts of phenol is positioned in reactor and is heated to 50 DEG C so as to be melt into liquid phenol；
2nd, 6.4 parts of catalyst will be added in the liquid phenol described in step one, and maintain 50 DEG C of reaction temperature, stirring is anti-
Answer 20 minutes；
3rd, will pour, in the phenol solution of the addition catalyst described in step 2, the formalin that 180 parts of concentration is 40% into,
It is warming up to 60 DEG C, continue stirring reaction 50min；
4th, 2.8 parts of catalyst, Ran Housheng will be added in the phenol solution of the formaldehyde of the addition 40% described in step 3 again
Temperature to 70 DEG C, isothermal reaction 20min；
5th, water-soluble by continuously adding the formaldehyde that 45 parts of concentration is 40% in the phenol solution after the isothermal reaction described in step 4
Liquid, is warming up to 90 DEG C, and constant temperature stirs 30min, that is, obtain the Water-soluble phenolic resin solution of clear brown；
6th, by after the 3- pyrrolidinol of 1000 parts of addition in the Water-soluble phenolic resin solution described in step 5, it is heated to 40
DEG C, stir 15 minutes；
7th, will be dissolved with the Biformyl sequentially adding 550 parts in the water soluble phenol resin of 3- pyrrolidinol in step 6,1000
Part ethanol and 1000 parts of water, so that above-mentioned solution is reacted 30 minutes at a temperature of 60 DEG C, obtain homogeneous liquid and be mud acid
Cross-linking agent.
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