CN117757009A - Preparation method of high-temperature-resistant high-efficiency sulfonated phenolic resin - Google Patents
Preparation method of high-temperature-resistant high-efficiency sulfonated phenolic resin Download PDFInfo
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010790 dilution Methods 0.000 claims abstract description 18
- 239000012895 dilution Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- PKGWLCZTTHWKIZ-UHFFFAOYSA-N 4-Hydroxypheoxyacetate Chemical compound OC(=O)COC1=CC=C(O)C=C1 PKGWLCZTTHWKIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 9
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 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 description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003208 petroleum Substances 0.000 abstract description 9
- 239000005011 phenolic resin Substances 0.000 abstract description 8
- 229920001568 phenolic resin Polymers 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 238000005553 drilling Methods 0.000 description 14
- 239000012530 fluid Substances 0.000 description 12
- 229960003742 phenol Drugs 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulfomethyl phenolic resin Chemical compound 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method of high-temperature-resistant high-efficiency sulfonated phenolic resin, and relates to the technical field of phenolic resin processing. The invention is characterized in that phenol, p-hydroxyphenoxyacetic acid and an alkaline sulfonic acid agent are reacted, formaldehyde is dropwise added, the temperature is raised, water is added for dilution when the viscosity of a reaction liquid is 60-80mPa.s, sodium p-hydroxyphenylsulfonate is added for reaction, an oxidant is added for reaction, the reaction is carried out, and finally a cross-linking agent is added for reaction, and the high-temperature and salt-resistant sulfonated phenolic resin is prepared by controlling the reaction conditions and parameters of each step, wherein the water loss at the high temperature and the high pressure at 150 ℃ is less than 28ml, the viscosity is low, the requirement of the medium petroleum standard Q/SYTZ0335-2018 is met, and the optimal temperature resistance can reach 220 ℃. The preparation method of the invention is simple, easy to operate and has less side reaction of the product. The sulfonated phenolic resin of the invention has the characteristic of small usage amount when used for operation.
Description
Technical Field
The invention belongs to the technical field of phenolic resin processing, and particularly relates to a preparation method of high-temperature-resistant efficient sulfonated phenolic resin.
Background
The drilling fluid filtrate reducer is an important oil field treating agent, has important roles in petroleum drilling, is an important drilling fluid treating agent for maintaining stability of drilling fluid, improving rheological property of drilling fluid, reducing filtration of harmful fluid to stratum, stabilizing well wall, ensuring well diameter rule and protecting oil-gas layer, and has important roles in safe and efficient drilling and preventing drilling accidents. Phenolic resin type fluid loss additives are one of the important branches. The phenolic resin type filtrate reducer is prepared by taking phenolic resin as a main body and sulfonating or introducing other functional groups, and can effectively reduce the high-temperature and high-pressure water loss of drilling fluid.
The conventional high-temperature-resistant and salt-resistant drilling fluid system is a trisulfonic drilling fluid system prepared from phenolic resin filtrate reducer, sulfonated lignite and sulfonated tannin extract, but has some defects in the practical application process, such as the fact that SMP-I or SMP-II is adopted as phenolic resin filtrate reducer, the addition amount is large, and the sulfonated lignite and the sulfonated tannin extract are added in a matched manner, so that the problem of foaming of the drilling fluid is easily caused; the sulfonated lignite contains chromium element, so that the environmental pollution is serious, and the use of the traditional sulfomethyl phenolic resin is limited; in addition, the temperature resistance of SMP-I and SMP-II is still limited, and the temperature can only be resistant to 180 ℃, so that the requirement of the ultra-high temperature well on the drilling fluid filtration loss can not be met.
Therefore, how to provide a sulfonated phenolic resin product which has small addition amount, strong temperature resistance and salt resistance and can be singly used and still has good drilling fluid filtrate loss reducing effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of high-temperature-resistant efficient sulfonated phenolic resin, and the sulfonated phenolic resin prepared by the method has the excellent characteristics of high temperature resistance and salt resistance, can be independently used, and has good drilling fluid filtrate loss reducing effect.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of high-temperature-resistant high-efficiency sulfonated phenolic resin comprises the following steps:
(1) Adding 60-70 parts by weight of phenol and 5-10 parts by weight of p-hydroxyphenoxyacetic acid into a reactor, adding 25-35 parts by weight of alkaline sulfonating agent into the reactor, mixing and stirring, heating to 75+/-5 ℃, and reacting for 0.5h;
(2) Dropwise adding 120-130 parts by weight of formaldehyde into the reactor while stirring, and keeping the temperature in the reactor at 75+/-5 ℃;
(3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50 parts by weight of water to dilute the reaction solution when the viscosity of the reaction solution is 60-80 mPa.s;
(4) Adding 4-12 parts by weight of sodium p-hydroxybenzenesulfonate into a reaction kettle after dilution, and reacting for 1h;
(5) After the reaction of the step (4), adding 6-9 parts by weight of oxidant into a reactor, and heating to above 95 ℃ for 2 hours;
(6) After the reaction of the step (5), adding 0.5 to 1 weight part of cross-linking agent into a reactor, and when the reaction temperature is 95 ℃ and the viscosity of a reaction system is 80 to 100mPa.s, adding 100 weight parts of water for dilution and then reacting for 1 hour;
(7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
Further, the preparation method of the high-temperature-resistant high-efficiency sulfonated phenolic resin comprises the following steps:
(1) Adding 60 parts by weight of phenol and 5 parts by weight of p-hydroxyphenoxyacetic acid into a reactor, adding 25 parts by weight of alkaline sulfonating agent into the reactor, mixing and stirring, heating to 75+/-5 ℃, and reacting for 0.5h;
(2) 130 parts by weight of formaldehyde is dropwise added into the reactor while stirring, and the temperature in the reactor is kept at 75+/-5 ℃;
(3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50 parts by weight of water to dilute the reaction solution when the viscosity of the reaction solution is 60 mPa.s;
(4) Adding 12 parts by weight of sodium parahydroxyben sulfonate into a reaction kettle after dilution, and reacting for 1h;
(5) After the reaction of the step (4), adding 9 parts by weight of oxidant into the reactor, and heating to above 95 ℃ for 2 hours;
(6) After the reaction of the step (5), adding 1.0 weight part of cross-linking agent into the reactor, and when the reaction temperature is 95 ℃ and the viscosity of the reaction system is 80-100mPa.s, adding 100 weight parts of water for dilution and then reacting for 1h;
(7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
Further, the preparation method of the high-temperature-resistant high-efficiency sulfonated phenolic resin comprises the following steps:
(1) 70 parts by weight of phenol and 10 parts by weight of p-hydroxyphenoxyacetic acid are added into a reactor, 35 parts by weight of alkaline sulfonating agent is added into the reactor, mixed and stirred, and the temperature is raised to 75+/-5 ℃ for reaction for 0.5h;
(2) Dropwise adding 120 parts by weight of formaldehyde into the reactor while stirring, and keeping the temperature in the reactor at 75+/-5 ℃;
(3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50 parts by weight of water to dilute the reaction solution when the viscosity of the reaction solution is 60-80 mPa.s;
(4) Adding 4 parts by weight of sodium parahydroxybenzenesulfonate into a reaction kettle after dilution, and reacting for 1h;
(5) After the reaction of the step (4), adding 6 parts by weight of oxidant into a reactor, and heating to above 95 ℃ for 2 hours;
(6) After the reaction of the step (5), adding 0.5 part by weight of a cross-linking agent into a reactor, and when the reaction temperature is 95 ℃ and the viscosity of a reaction system is 80-100mPa.s, adding 100 parts by weight of water for dilution and then reacting for 1h;
(7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
Further, in any one of the above preparation methods, the speed of mixing and stirring in the step (1) is 60r/min.
Further, in any one of the preparation methods, the alkaline sulfonating agent in the step (1) is one or more of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium persulfate.
Further, in any one of the preparation methods, the formaldehyde in the step (3) is added dropwise for 1h.
Further, in any one of the above preparation methods, the reaction temperature in the step (4) is 90 ℃.
Further, in any one of the preparation methods, the oxidizing agent in the step (5) is any one of potassium permanganate and potassium ferrate.
Further, in any one of the preparation methods, the cross-linking agent in the step (6) is any one or a combination of two of triethylene tetramine and ethylene diamine tetraacetic acid.
Another object of the present invention is to provide a high temperature resistant and efficient sulfonated phenolic resin prepared using the above method.
Compared with the prior art, the invention has the following beneficial effects:
in the preparation method of the sulfonated phenolic resin, phenol, formaldehyde and a sulfonating agent are used, and parahydroxyphenoxyacetic acid and sodium parahydroxyphenylsulfonate are also introduced, namely carboxyl and benzenesulfonic acid groups are introduced, so that the obtained product can be better adsorbed on the surface of clay to form a space grid structure, and the product has a good filtration reducing effect;
in the invention, a strong oxidant is also added at the later stage of the synthesis process, and the oxidant can continuously oxidize the non-anti Wen Jituan such as ether bond and the like generated by side reaction in the synthesis process to form the anti Wen Jituan such as carboxyl and the like, thereby enhancing the temperature resistance of the treating agent and further improving the filtration reducing effect of the treating agent;
according to the invention, a proper amount of cross-linking agent is introduced in the synthesis process, so that the cross-linking degree of the resin material is improved, the prepared sulfonated phenolic resin material can be used independently, and the sulfonated phenolic resin material has an excellent filtration reducing effect.
The preparation method of the invention is simple, easy to operate and has less side reaction of the product. The sulfonated phenolic resin of the invention has the characteristic of small usage amount when used for operation.
Detailed Description
In order to better understand the solution of the present invention, the following description will clearly and completely describe the solution of the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, not all the embodiments. This invention may be embodied in many different forms and is not limited to the embodiments described herein, but rather is provided to provide a more thorough understanding of the present disclosure. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
The advantages of the invention will be further illustrated in the following examples, which are not to be construed as limiting the invention.
Example 1
A preparation method of high-temperature-resistant high-efficiency sulfonated phenolic resin comprises the following steps:
1) 70g of phenol and 5g of p-hydroxyphenoxyacetic acid are added into a reactor, 25g of sodium monosulfate and sodium persulfate are added into the reactor, mixed and stirred, and the temperature is raised to 75+/-5 ℃ for reaction for 0.5h;
2) Dropwise adding 120g of formaldehyde (completely dropwise adding for 1 h) into the reactor while stirring, and keeping the temperature in the reactor at 75+/-5 ℃;
3) After the formaldehyde is added dropwise, heating to 90 ℃ to react until the viscosity of the reaction solution is 80mPa.s, and adding 50g of water to dilute the reaction solution;
4) Adding 4g of sodium p-hydroxybenzenesulfonate into a reaction kettle after dilution, and reacting for 1h;
5) After the reaction of the step 4), adding 9g of potassium permanganate into the reactor, heating to 95-100 ℃, and continuing the reaction for 2 hours;
6) And 5) after the reaction is finished, adding 0.5g of triethylene tetramine into the reactor, wherein the reaction temperature is 95 ℃, when the reaction is carried out until the viscosity of the system is 100mPa.s, adding 100g of water for dilution, then reacting for 1h, reducing the temperature of the reactor to 50 ℃ by using circulating water, transferring the reaction solution into a storage tank, and spray-drying in a spray drying tower to obtain powder.
Example 2
A preparation method of high-temperature-resistant high-efficiency sulfonated phenolic resin comprises the following steps:
1) Adding 60g of phenol and 5g of p-hydroxyphenoxyacetic acid into a reactor, adding 25g of sodium sulfite and sodium bisulfite into the reactor, mixing and stirring, heating to 75+/-5 ℃, and reacting for 0.5h;
2) 130g of formaldehyde is dropwise added into the reactor (complete dropwise addition is carried out for 1 h) while stirring, and the temperature in the reactor is kept at 75+/-5 ℃;
3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50g of water to dilute the reaction solution when the viscosity of the reaction solution reaches 60 mPa.s;
4) Adding 12g of sodium p-hydroxybenzenesulfonate into a reaction kettle after dilution, and reacting for 1h;
5) After the reaction of the step 4), adding 9g of potassium ferrate into the reactor, heating to 95-100 ℃, and continuing the reaction for 2 hours;
6) After the reaction of the step 5), adding 1.0g of ethylenediamine tetraacetic acid into a reactor, and when the reaction is carried out at 95 ℃ until the system viscosity reaches 80mPa.s, adding 100g of water for dilution and then reacting for 1h;
7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
Example 3
A preparation method of high-temperature-resistant high-efficiency sulfonated phenolic resin comprises the following steps:
1) 70g of phenol and 10g of p-hydroxyphenoxyacetic acid are added into a reactor, 35g of sodium monosulfate is added into the reactor, mixed and stirred, and the temperature is raised to 75+/-5 ℃ for reaction for 0.5h;
2) Dropwise adding 120g of formaldehyde (completely dropwise adding for 1 h) into the reactor while stirring, and keeping the temperature in the reactor at 75+/-5 ℃;
3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50g of water to dilute the reaction solution when the viscosity of the reaction solution reaches 60 mPa.s;
4) Adding 4g of sodium p-hydroxybenzenesulfonate into a reaction kettle after dilution, and reacting for 1h;
5) After the reaction of the step 4), adding 6g of potassium ferrate into the reactor, heating to 95-100 ℃, and continuing the reaction for 2 hours;
6) After the reaction of the step 5), adding 0.5g of triethylene tetramine into a reactor, and when the temperature of 95 ℃ is reacted to the system viscosity of 90mPa.s, adding 100g of water for dilution and then reacting for 1h;
7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
Table 1 component content of preparing high temperature resistant high efficiency sulfonated phenolic resin
| Content of each component (g) | Example 1 | Example 2 | Example 3 |
| Phenol (P) | 70 | 60 | 70 |
| Para-hydroxy phenoxyacetic acid | 5 | 5 | 10 |
| Sodium p-hydroxy benzene sulfonate | 4 | 12 | 4 |
| Formaldehyde | 120 | 130 | 120 |
| Basic catalyst | 25 | 25 | 35 |
| Oxidizing agent | 9 | 9 | 6 |
| Crosslinking agent | 0.5 | 1 | 0.5 |
The performance of the high temperature resistant high efficiency sulfonated phenolic resin prepared in examples 1-3 of the present invention, and model SMP-I (product of Jing Zhou science industries, inc. meeting medium petroleum standards) and SMP-II (product of Jing Zhou science industries, inc. meeting medium petroleum standards) were evaluated by indoor comparison using petroleum standard Q/SYTZ0335-2018, specifically: preparing experimental slurry according to the medium petroleum standard Q/SYTZ0335-2018, aging at 180 ℃ for 16 hours, and detecting and calculating the apparent viscosity of the sample slurry; the experimental slurry is prepared according to the medium petroleum standard Q/SYTZ0335-2018, and the prepared experimental slurry is filled into an aging tank and is respectively put into a roller furnace to be aged for 16 hours at the constant temperature of 180 ℃, 200 ℃ and 220 ℃. Taking out, cooling to room temperature, pouring out the test slurry, stirring at high speed for 5min, and respectively detecting high-temperature high-pressure filtration loss at 150 ℃, 180 ℃, 200 ℃ and 3.45MPa according to 3.3 in GB/T16783-1997. The specific results are shown in Table 2.
TABLE 2
As can be seen from Table 2, when the addition amount of SMP-I and SMP-II is 2.5%, the water loss at high temperature and high pressure at 150 ℃ is far more than 28mL required by the medium petroleum standard Q/SYTZ0335-2018, and the water loss at high temperature and high pressure is larger as the temperature is increased; the high-temperature and high-pressure water loss of the high-temperature and high-pressure sulfonated phenolic resin synthesized by the method is less than 28ml at the temperature of 150 ℃, the viscosity is low, the requirements of the medium petroleum standard Q/SYTZ0335-2018 are met, in addition, the high-temperature and high-pressure filtration loss of the embodiments 1-3 is increased along with the increase of the temperature, but the high-temperature and high-pressure water loss of the embodiments is increased by 7ml compared with the high-temperature and high-pressure water loss corresponding to the temperature of 150 ℃, which indicates that the high-temperature resistance of the high-temperature and high-pressure sulfonated phenolic resin obtained by the preparation method is weakened along with the increase of the temperature, but the tolerance is stable. The example 3 in the 3 formulations has the best effect and the strongest heat resistance, the high-temperature high-pressure water loss at 220 ℃ aged 200 ℃ is only 23mL, and the good high-temperature salt resistance is shown, and the heat resistance reaches 220 ℃.
What is not described in detail in this specification is prior art known to those skilled in the art. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that the present invention may be modified or equivalents substituted for some of the features thereof. All equivalent substitutions made by the content of the specification of the invention are directly or indirectly applied to other related technical fields, and are also within the scope of the invention.
Claims (10)
1. The preparation method of the high-temperature-resistant high-efficiency sulfonated phenolic resin is characterized by comprising the following steps of:
(1) Adding 60-70 parts by weight of phenol and 5-10 parts by weight of p-hydroxyphenoxyacetic acid into a reactor, adding 25-35 parts by weight of alkaline sulfonating agent into the reactor, mixing and stirring, heating to 75+/-5 ℃, and reacting for 0.5h;
(2) Dropwise adding 120-130 parts by weight of formaldehyde into the reactor while stirring, and keeping the temperature in the reactor at 75+/-5 ℃;
(3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50 parts by weight of water to dilute the reaction solution when the viscosity of the reaction solution is 60-80 mPa.s;
(4) Adding 4-12 parts by weight of sodium p-hydroxybenzenesulfonate into a reaction kettle after dilution, and reacting for 1h;
(5) After the reaction of the step (4), adding 6-9 parts by weight of oxidant into the reactor, heating to above 95 ℃ and continuing the reaction for 2 hours;
(6) After the reaction of the step (5), adding 0.5 to 1 weight part of cross-linking agent into a reactor, and when the reaction is carried out at 95 ℃ until the viscosity of the system is 80 to 100mPa.s, adding 100 weight parts of water for dilution and then reacting for 1 hour;
(7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
2. The method for preparing the high-temperature-resistant and high-efficiency sulfonated phenolic resin according to claim 1, which is characterized by comprising the following steps:
(1) Adding 60 parts by weight of phenol and 5 parts by weight of p-hydroxyphenoxyacetic acid into a reactor, adding 25 parts by weight of alkaline sulfonating agent into the reactor, mixing and stirring, heating to 75+/-5 ℃, and reacting for 0.5h;
(2) 130 parts by weight of formaldehyde is dropwise added into the reactor while stirring, and the temperature in the reactor is kept at 75+/-5 ℃;
(3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50 parts by weight of water to dilute the reaction solution when the viscosity of the reaction solution is 60-80 mPa.s;
(4) Adding 12 parts by weight of sodium parahydroxyben sulfonate into a reaction kettle after dilution, and reacting for 1h;
(5) After the reaction of the step (4), adding 9 parts by weight of oxidant into the reactor, heating to above 95 ℃, and continuing the reaction for 2 hours;
(6) After the reaction of the step (5), adding 1.0 weight part of cross-linking agent into a reactor, and reacting for 1h after adding 100 weight parts of water for dilution when the system viscosity is 80-100mPa.s at 95 ℃;
(7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
3. The method for preparing the high-temperature-resistant and high-efficiency sulfonated phenolic resin according to claim 1, which is characterized by comprising the following steps:
(1) 70 parts by weight of phenol and 10 parts by weight of p-hydroxyphenoxyacetic acid are added into a reactor, 35 parts by weight of alkaline sulfonating agent is added into the reactor, mixed and stirred, and the temperature is raised to 75+/-5 ℃ for reaction for 0.5h;
(2) Dropwise adding 120 parts by weight of formaldehyde into the reactor while stirring, and keeping the temperature in the reactor at 75+/-5 ℃;
(3) After the formaldehyde is added dropwise, heating to 90 ℃ for reaction, and adding 50 parts by weight of water to dilute the reaction solution when the viscosity of the reaction solution is 60-80 mPa.s;
(4) Adding 4 parts by weight of sodium parahydroxybenzenesulfonate into a reaction kettle after dilution, and reacting for 1h;
(5) After the reaction of the step (4), adding 6 parts by weight of oxidant into a reactor, heating to above 95 ℃, and continuing the reaction for 2 hours;
(6) After the reaction of the step (5), adding 0.5 part by weight of a cross-linking agent into a reactor, and reacting at 95 ℃ until the viscosity of the system is 80-100mPa.s, adding 100 parts by weight of water, diluting and then reacting for 1h;
(7) After the reaction is finished, the temperature of the reactor is reduced to 50 ℃ by using circulating water, and then the reaction liquid is transferred into a storage tank and is spray-dried into powder in a spray drying tower.
4. A process for preparing a sulfonated phenol formaldehyde resin resistant to high temperature and high efficiency as claimed in any one of claims 1 to 3, characterized in that the speed of mixing and stirring in step (1) is 60r/min.
5. The method for preparing the high-temperature-resistant high-efficiency sulfonated phenolic resin according to any one of claims 1 to 3, wherein the alkaline sulfonating agent in the step (1) is one or more of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium persulfate.
6. A method for preparing a sulfonated phenol formaldehyde resin resistant to high temperature and high efficiency according to any one of claims 1 to 3, wherein the dropping time of formaldehyde in step (3) is 1h.
7. A process for the preparation of a sulphonated phenol formaldehyde resin resistant to high temperature and high efficiency according to any one of claims 1 to 3, characterised in that the reaction temperature in step (4) is 90 ℃.
8. The method for preparing the high-temperature resistant and high-efficiency sulfonated phenolic resin according to any one of claims 1 to 3, wherein the oxidant in the step (5) is any one of potassium permanganate and potassium ferrate.
9. The method for preparing the high-temperature resistant and high-efficiency sulfonated phenolic resin according to any one of claims 1 to 3, wherein the crosslinking agent in the step (6) is any one or a combination of two of triethylene tetramine and ethylene diamine tetraacetic acid.
10. A high temperature resistant high efficiency sulphonated phenolic resin prepared by the method of any one of claims 1 to 9.
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| DE2653835C3 (en) * | 1976-11-26 | 1981-10-01 | Vsesojuznyj naučno-issledovatel'skij institut sintetičeskich smol, Vladimir | Liquid phenolic resin for curing thermoreactive resins |
| CN101798914B (en) * | 2010-04-08 | 2013-01-02 | 中国石油大学(华东) | Method for improving high-temperature stability of sulfonated drilling fluid |
| CN110560161A (en) * | 2019-08-21 | 2019-12-13 | 浙江大学 | Preparation method of sulfonated phenolic resin type solid acid catalyst and application of sulfonated phenolic resin type solid acid catalyst in glycerol esterification reaction |
| CN114085343A (en) * | 2020-08-24 | 2022-02-25 | 中石化石油工程技术服务有限公司 | Modified sulfonated phenolic resin filtrate reducer for drilling fluid and preparation method thereof |
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