CN101798914A - Method for improving high-temperature stability of sulfonated drilling fluid - Google Patents
Method for improving high-temperature stability of sulfonated drilling fluid Download PDFInfo
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- CN101798914A CN101798914A CN 201010141330 CN201010141330A CN101798914A CN 101798914 A CN101798914 A CN 101798914A CN 201010141330 CN201010141330 CN 201010141330 CN 201010141330 A CN201010141330 A CN 201010141330A CN 101798914 A CN101798914 A CN 101798914A
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Abstract
The invention provides a method for improving the high-temperature stability of sulfonated drilling fluid, which comprises the following steps: adding a high-temperature stabilizer into the sulfonated drilling fluid containing sulfonated-pheno-formoldehyde resin, uniformly mixing, and then, immediately using. By the substitution reaction of the added stabilizer, the content of active groups causing high-temperature cross-linking in the additives of the sulfonated drilling fluid is reduced, and the content of hydrophilic carboxyl groups is increased, thereby realizing the purposes of obviously improving the high-temperature stability of the sulfonated drilling fluid and obviously reducing the water loss.
Description
Technical field
The present invention relates to a kind of method that improves high-temperature stability of sulfonated drilling fluid, belong to the oilfield chemical technology field.
Background technology
The seventies three in last century, the successful development of sulphur inorganic agent made the Drilling Fluid Technique for Deep technology obtain develop rapidly, and drilling fluid temperature resistance ability is greatly improved.The eighties, the successful development of series of polymers made the high temperature resistant drilling fluids system be transformed into the sulphonated polymer mud system by three sulphurs, and these two kinds of drilling fluid systems are applied in the deep drilling operation always widely.
Sulfonated-pheno-formoldehyde resin (SMP also claims sulfonated phenol formaldehyde resin on the oil field) is one of present domestic and international widely used oil drilling solution additive.Sulfonated-pheno-formoldehyde resin is a kind of water soluble anion polyelectrolyte, mainly be used in deep-well salt solution or the saturated brine system, have premium properties such as temperature resistance, anti-salt, but the thickening phenomenon can appear in closely saturated, saturated brine sulfonated drilling fluid system at high temperature (more than 160 ℃), creeps into thereby have a strong impact on normally.High-temperature cross-linking and influence factor thereof, so far research seldom, " high-temperature cross-linking of three sulphur inorganic agents and the influence factor " of Wang Pingquan, " drilling fluid and completion fluid " 1991 the 8th volumes the 4th phase 26-32 page or leaf, this article has been reported more hot crosslinked mechanism and influence factor, think to cause that crosslinked main cause is the high-temperature cross-linking of polymer, thereby the viscosity of system is increased, even gelling, curing occur.Sulfonated-pheno-formoldehyde resin class in the drilling fluid additive, because of containing active higher methylol in its molecular structure, the cross-linking reaction of sulfonated-pheno-formoldehyde resin is methylol on the phenol ring and the active hydrogen generation dehydration condensation on the phenol ring, generate stable phenol ring with methylene bridges, molecular weight increases, thereby the viscosity of system increases, and frozen glueization even curing take place.Mechanism of crosslinking is similar to the curing reaction mechanism of phenolic resins.The thickening of system is mainly by organic crosslinked causing, it is general invalid or cause tackify on the contrary to add thinner.
The present invention is by suppressing organic crosslinked under high temperature, the high salt condition, and the method that improves drilling fluids at high temperature stability yet there are no report so far.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method that improves high-temperature stability of sulfonated drilling fluid, be intended to effectively improve the drilling fluid high temperature resistance with the methylol group content in the control sulfonated drilling fluid by cost method low, simple to operate.
Principle of the present invention is to add high-temperature stabiliser in the existing sulfonated drilling fluid that contains sulfonated-pheno-formoldehyde resin, by replacing, control the content that can cause the active group methylol of high temperature multiviscosisty in the sulfonated drilling fluid, corresponding increase hydrophilic radical carboxylic acid group's content, strengthen the hydrophily of sulfonated-pheno-formoldehyde resin, realize improving the purpose of drilling fluid system high-temperature stability.
The method of raising high-temperature stability of sulfonated drilling fluid provided by the invention, step is as follows:
The high-temperature stabiliser adding is contained in the sulfonated drilling fluid of sulfonated-pheno-formoldehyde resin, after stirring, come into operation immediately.
Described high-temperature stabiliser is one of following:
I. oxidant hydrogen peroxide, potassium bichromate, clorox, calcium hypochlorite, potassium permanganate or ammonium persulfate;
Ii. sulphite and aldehyde mixes;
Iii. the sulfonate of hydroxyl.
Described high-temperature stabiliser dosage is the 0.3-5wt% of sulfonated drilling fluid, preferred 0.3-3wt% (mass percent).Can do suitable adjustment according to bottom hole temperature (BHT), with the rising of temperature, dosage suitably increases.
The hydrogen peroxide of the preferred 30wt% of described oxidant.
Described sulphite is sodium pyrosulfite, sodium sulfite, potassium metabisulfite or potassium sulfite.
Described aldehyde is metaformaldehyde, formalin or hexa.
Described sulphite with mixing of aldehyde preferred sodium pyrosulfite and metaformaldehyde mix sodium pyrosulfite and metaformaldehyde mass ratio 4-8: 0.5-2, wherein preferred 5: 1.
The sulfonate of described hydroxyl is the sodium salt or the sylvite of methylol sulfonic acid, isethionic acid or hydroxypropyl sulfonic acid.
Sulfonated drilling fluid is the drilling fluid that contains sulfonated-pheno-formoldehyde resin commonly used.The sulfonated drilling fluid that contains sulfonated-pheno-formoldehyde resin that comprises existing bibliographical information and practical application.Following sulfonated drilling fluid prescription only for for example, is not limited to this example.
A kind of sulfonated drilling fluid prescription commonly used is:
(unit: soil paste native g/ water mL) is a radix, adds 0.1%Na to starch dense 2-3%
2CO
3(account for the soil paste mass percent, below all with), 1.0%NaOH, 2-8%SMP-2,2.0%SPNH, 3.0%PSC-2,2.0%SPC, 3.0%Tf-180 or 3.0%Tf-160,25.0%NaCl, 5.0%KCl.Add 4.2g/cm again
3High density blanc fixe to density is 2.3～2.4g/mL.
Used soil paste is generally sodium bentonite and adds water preparation in the sulfonated drilling fluid, starches dense 2-3% (unit: native g/ water mL), left standstill 24 hours.
Used SMP-2 is a sulfonated-pheno-formoldehyde resin in the sulfonated drilling fluid, and SPNH is a walchowite, and PSC-2 is a sulfomethylated humic acid chromium, SPC is a ferrochrome lignosulfonate, Tf-180 is that softening point is the asphalt powder of 180 degree, and Tf-160 is that softening point is the asphalt powder of 160 degree, but all market is buied.Sodium bentonite, sodium chloride, potassium chloride, barite etc. are the commercially available material.
The content of sulfonated-pheno-formoldehyde resin in the described sulfonated drilling fluid (SMP-2) is preferably 6%, the mass ratio of soil paste in SMP-2 and the drilling fluid.
The mechanism of sulfonated drilling fluid inorganic agent high temperature multiviscosisty is:
(1) active hydrogen on methylol on the sulfonated-pheno-formoldehyde resin and the phenol ring forms methylene by intermolecular dehydrating condensation:
(2) dehydration formation dibenzyl ether mainly occurs in below 160 ℃ between the methylol; Decompose after being higher than 160 ℃, dibenzyl ether resolves into methene key, and emits formaldehyde.
(3) condensation of phenolic hydroxyl group and methylol:
(4) condensation of methylene and methylol:
(5) raw material of production sulfonated-pheno-formoldehyde resin is generally phenol and formaldehyde or paraformaldehyde, the formaldehyde that may exist the unreacted formaldehyde of raw material, ehter bond pyrolysis to produce in the product, by formaldehyde-caused condensation, reaction mechanism is reacted with the production of phenolic resins: the active hydrogen on formaldehyde elder generation and the phenol ring generates methylol, and then cross-linking reaction takes place.
Wherein above-mentioned (1) is topmost cross-linking reaction, and its product also is the most stable.
The control sulfonated drilling fluid high-temperature cross-linking that the present invention taked, the mechanism of multiviscosisty are as follows:
Content by appropriate oxidation reduction methylol suppresses the generation of cross-linking reaction.
The present invention has following excellent results:
1. the additive amount of the used control high temperature multiviscosisty of the present invention is few, and cost is low;
2. the inventive method is simple to operate, easy to use, easily control;
3. the inventive method can significantly improve the high temperature stability performance of drilling fluid, and can reduce the sticking of drilling fluid and cut and filter loss; Other compositions all do not change, and saturated brine, nearly saturated brine sulfonated drilling fluid can be improved more than 30 ℃ on the original basis, have enlarged the range of application of sulfonated drilling fluid effectively, can make it be applied to 150-230 ℃ high-temperature stratum.
4. method therefor of the present invention has versatility, can be used for the improvement of all sulfonation class drilling fluid system performances, improves its heat and salinity tolerance performance, improves high temperature stability performance.
The specific embodiment
The present invention will be further described below in conjunction with embodiment.Percentage such as nothing among each embodiment particularly point out, and all are weight percentage, and used medicine is the situ of drilling well common drug.
SMP-2 is a sulfonated-pheno-formoldehyde resin, and crust state ternary petroleum assistant company produces.
SPNH is a walchowite, and Yunnan Jin Sida auxiliary chemicals company produces.
PSC-2 is a sulfomethylated humic acid chromium, and emerging petroleum assistant development company of Beijing section produces.
SPC is a ferrochrome lignosulfonate, and Yanqing, Beijing company of humic acid factory produces.
Tf-180 is that softening point is the asphalt powder of 180 degree, and brand-new material company in Lanzhou produces.
Tf-160 is that softening point is the asphalt powder of 160 degree, and brand-new material company in Lanzhou produces.
The high density blanc fixe, density 4.2g/cm
3, tower north petroleum assistant company produces.
Embodiment 1:
The sulfonated drilling fluid prescription: (unit: soil paste native g/ water mL) is a radix, adds 0.1%Na to starch dense 2-3%
2CO
3, 1.0%NaOH (mass percent, down together), 6.0%SMP-2,2.0%SPNH, 3.0%PSC-2,2.0%SPC, 3.0%Tf-160,2.0%SY-A07,25.0%NaCl, 5.0%KCl, excess water.Add 4.2g/cm then
3High density blanc fixe to density is 2.3g/mL.
The drilling fluid adding concentration of measuring the above-mentioned prescription of 300mL is 30% hydrogen peroxide 6mL, stir, be transferred in the aging reactor, behind 180 ℃ of rolling 16h, compare after the same terms is handled down with the reference that does not increase temperature stabilizing agent, apparent viscosity reduces by 10%, and shear force reduces by 40%, and the HTHP fluid loss reduces to original 50%.
Embodiment 2:
As described in embodiment 1, the stabilizing agent that different are to use is a sodium dichromate, compares with the drilling fluid that does not add stabilizing agent under the same terms, and apparent viscosity reduces by 10%, and shear force reduces by 30%, and the HTHP fluid loss reduces to original 66%.
Embodiment 3:
As described in embodiment 1, different is to replace hydrogen peroxide with clorox, compares with the drilling fluid that does not add stabilizing agent under the same terms, and apparent viscosity reduces by 15%, and shear force reduces by 40%, and the HTHP fluid loss reduces to original 80%.
Embodiment 4:
As described in embodiment 1, different is to replace hydrogen peroxide with ammonium persulfate.Compare with the drilling fluid that does not add stabilizing agent under the same terms, apparent viscosity reduces by 10%, and shear force reduces by 20%, and the HTHP fluid loss reduces to original 80%.
Embodiment 5:
As described in embodiment 1, different is to replace hydrogen peroxide with potassium permanganate.Compare with the drilling fluid that does not add stabilizing agent under the same terms, apparent viscosity reduces by 10%, and shear force reduces by 25%, and the HTHP fluid loss reduces to original 80%.
Embodiment 6:
As described in embodiment 1, different is to replace hydrogen peroxide with potassium bichromate.Compare with the drilling fluid that does not add stabilizing agent under the same terms, apparent viscosity reduces by 10%, and shear force reduces by 28%, and the HTHP fluid loss reduces to original 75%.
Embodiment 7:
As described in embodiment 1, different is to replace hydrogen peroxide with calcium oxychloride (its active ingredient is calcium hypochlorite).Compare with the drilling fluid that does not add stabilizing agent under the same terms, apparent viscosity reduces by 5%, and shear force reduces by 10%, and the HTHP dehydration is constant substantially.
Embodiment 8:
As described in embodiment 1, the drilling fluid of getting 300mL adds the sodium pyrosulfite of 1g and the metaformaldehyde of 0.2g, behind 160 ℃ of rolling 16h, compare after the same terms is handled down with the reference that does not increase temperature stabilizing agent, apparent viscosity reduces by 17%, shear force reduces by 45%, and the HTHP fluid loss is constant substantially.
Embodiment 9:
As described in embodiment 8, different is to replace sodium pyrosulfite with sodium sulfite, behind 160 ℃ of rolling 16h, compares with the drilling fluid after the same terms that does not add is handled, and apparent viscosity reduces by 15%, and shear force reduces by 38%, and the HTHP fluid loss changes little.
Embodiment 10:
As described in embodiment 8, different is replaces metaformaldehyde (make wherein effectively the amount of formaldehyde is identical) with formalin (concentration 37%).Behind 160 ℃ of rolling 16h, compare with the drilling fluid after the same terms that does not add is handled, apparent viscosity reduces by 18%, and shear force reduces by 45%, and the HTHP fluid loss changes little.
Embodiment 11:
As described in embodiment 8, different is to replace metaformaldehyde with hexa.Behind 160 ℃ of rolling 16h, compare with the drilling fluid after the same terms that does not add is handled, apparent viscosity reduces by 10%, and shear force reduces by 30%, and the HTHP fluid loss changes little.
Embodiment 12:
As described in embodiment 8, different is to use sodium sulfite separately, the amount of its adding is increased to 5 times of institute's dosage among the embodiment 8.Behind 160 ℃ of rolling 16h, compare with the drilling fluid after the same terms that does not add is handled, apparent viscosity reduces by 10%, and shear force reduces by 30%, and the HTHP fluid loss changes little.
Embodiment 13:
As described in embodiment 8, different is only to add sodium pyrosulfite.Behind 160 ℃ of rolling 16h, compare with the drilling fluid after the same terms that does not add is handled, apparent viscosity reduces by 10%, and shear force reduces by 20%, and the HTHP fluid loss changes little.
Embodiment 14:
As described in embodiment 8, different is to use the sodium hydroxymethane sulfonate of 1.2g to replace sodium pyrosulfite and metaformaldehyde, behind 160 ℃ of rolling 16h, compare with the drilling fluid after the same terms that does not add is handled, apparent viscosity reduces by 15%, and shear force reduces by 40%, and the HTHP fluid loss slightly reduces.
Embodiment 15:
As described in embodiment 8, different is to use the sodium isethionate of 1.3g to replace sodium pyrosulfite and metaformaldehyde, behind 160 ℃ of rolling 16h, compare with the drilling fluid after the same terms that does not add is handled, apparent viscosity reduces by 15%, and shear force reduces by 30%, and the HTHP dehydration also slightly reduces.
Embodiment 16:
As described in embodiment 8, different is to use the hydroxypropyl azochlorosulfonate acid sodium of 1.3g to replace sodium pyrosulfite and metaformaldehyde, behind 160 ℃ of rolling 16h, compare with the drilling fluid after the same terms that does not add is handled, apparent viscosity reduces by 12%, and shear force reduces by 30%, and the HTHP dehydration also slightly reduces.
Embodiment 17:
As described in embodiment 8, different is to add 1.5g sodium pyrosulfite and 0.2g metaformaldehyde, behind 160 ℃ of rolling 16h, compare after the same terms is handled down with the reference that does not increase temperature stabilizing agent, apparent viscosity reduces by 18%, and shear force reduces by 50%, and the HTHP fluid loss is constant substantially.
Embodiment 18:
As described in embodiment 8, different is to add 2.0g sodium pyrosulfite and 0.2g metaformaldehyde, behind 160 ℃ of rolling 16h, compare after the same terms is handled down with the reference that does not increase temperature stabilizing agent, apparent viscosity reduces by 16%, and shear force reduces by 46%, and the HTHP fluid loss is constant substantially.
Embodiment 19:
As described in embodiment 8, different is to add 1.0g sodium pyrosulfite and 0.3g metaformaldehyde, behind 160 ℃ of rolling 16h, compare after the same terms is handled down with the reference that does not increase temperature stabilizing agent, apparent viscosity reduces by 18%, and shear force reduces by 40%, and the HTHP fluid loss is constant substantially.
Embodiment 20:
As described in embodiment 8, after different are 160 ℃ of rolling 72h, to compare with the drilling fluid after the same terms that does not add stabilizing agent is handled, apparent viscosity reduces by 50%, and shear force reduces about 70%, and the HTHP dehydration reduces by 33%.
Embodiment 21:
As described in embodiment 9, after different are 160 ℃ of rolling 72h, to compare with the drilling fluid after the same terms that does not add stabilizing agent is handled, apparent viscosity reduces by 47%, and shear force reduces by 68%, and the HTHP dehydration reduces by 30%.
Embodiment 22:
As described in embodiment 10, after different are 160 ℃ of rolling 72h, behind 160 ℃ of rolling 72h, to compare with the drilling fluid after the same terms that does not add stabilizing agent is handled, apparent viscosity reduces by 52%, and shear force reduces by 70%, and the HTHP dehydration reduces by 35%.
Embodiment 23:
As described in embodiment 8, after different are 180 ℃ of rolling 16h, to compare with the drilling fluid after the same terms that does not add stabilizing agent is handled, apparent viscosity reduces by 48%, and shear force reduces by 80%, and the HTHP dehydration reduces by 20%.
Embodiment 24:
As described in embodiment 9, after different are 180 ℃ of rolling 16h, to compare with the drilling fluid after the same terms that does not add stabilizing agent is handled, apparent viscosity reduces by 45%, and shear force reduces by 74%, and the HTHP dehydration reduces by 20%.
Embodiment 25:
As described in embodiment 9, after different are 180 ℃ of rolling 16h, to compare with the drilling fluid after the same terms that does not add stabilizing agent is handled, apparent viscosity reduces by 50%, and shear force reduces by 81%, and the HTHP dehydration reduces by 21%.
Embodiment 26:
As described in embodiment 8, after different are 180 ℃ of rolling 72h, compare with the drilling fluid after the same terms that does not add is handled, good (the apparent viscosity: 85.0mPas) of the drilling fluid rheology performance of oiling high-temperature stabiliser, the serious multiviscosisty of reference that is not added with high-temperature stabiliser can't be measured its rheological parameter, and the HTHP dehydration reduces by 60%.
Embodiment 27:
As described in embodiment 9, different is in 180 ℃ of rolling 72h, compare with the drilling fluid that does not add inorganic agent under the same terms, good (the apparent viscosity: 90.0mPas) of the drilling fluid rheology performance of oiling high-temperature stabiliser, the serious multiviscosisty of reference that is not added with high-temperature stabiliser can't be measured its rheological parameter, and the HTHP dehydration reduces by 60%.
Embodiment 28:
As described in embodiment 10, after different are 180 ℃ of rolling 72h, compare with the drilling fluid after the same terms that does not add is handled, good (the apparent viscosity: 83.0mPas) of the drilling fluid rheology performance of oiling high-temperature stabiliser, the serious multiviscosisty of reference that is not added with high-temperature stabiliser can't be measured its rheological parameter, and the HTHP dehydration reduces by 62%.
Claims (9)
1. method that improves high-temperature stability of sulfonated drilling fluid, step is as follows:
The high-temperature stabiliser adding is contained in the sulfonated drilling fluid of sulfonated-pheno-formoldehyde resin, after stirring, come into operation immediately;
Described high-temperature stabiliser is one of following:
I. oxidant hydrogen peroxide, potassium bichromate, clorox, calcium hypochlorite, potassium permanganate or ammonium persulfate,
Ii. mixing of sulphite and aldehyde,
Iii. the sulfonate of hydroxyl;
Described high-temperature stabiliser dosage is the 0.5-5wt% of sulfonated drilling fluid quality.
2. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 1 is characterized in that described high-temperature stabiliser dosage is the 1-3wt% of sulfonated drilling fluid.
3. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 1 is characterized in that described oxidant is the hydrogen peroxide of 30wt%.
4. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 1 is characterized in that described sulphite is sodium pyrosulfite, sodium sulfite, potassium metabisulfite or potassium sulfite.
5. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 1 is characterized in that described aldehyde is metaformaldehyde, formalin or hexa.
6. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 1 is characterized in that described sulphite and mixing of aldehyde are that sodium pyrosulfite and metaformaldehyde mix.
7. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 6 is characterized in that sodium pyrosulfite and metaformaldehyde mass ratio are 4-8: 0.5-2.
8. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 6 is characterized in that described sodium pyrosulfite and metaformaldehyde mass ratio are 6: 1.
9. the method for raising high-temperature stability of sulfonated drilling fluid as claimed in claim 1, the sulfonate that it is characterized in that described hydroxyl are the sodium salt or the sylvite of methylol sulfonic acid, isethionic acid or hydroxypropyl sulfonic acid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086163A (en) * | 2010-11-24 | 2011-06-08 | 山东大学 | Preparation method and application of high temperature and high salinity stabilizer for drilling fluid |
| CN104140794A (en) * | 2013-10-28 | 2014-11-12 | 中国石油化工股份有限公司 | High temperature resistant oil-in-water drilling fluid |
| CN104293324A (en) * | 2014-05-30 | 2015-01-21 | 中国石油化工集团公司 | Ultrahigh-temperature drilling fluid filtrate reducer and its preparation method |
| CN104559967A (en) * | 2013-10-27 | 2015-04-29 | 中国石油化工集团公司 | Superhigh-density high-temperature-resistant saturated salt-water drilling fluid and preparation method thereof |
| CN104650830A (en) * | 2013-11-25 | 2015-05-27 | 中国石油化工集团公司 | High-temperature resistant high-density organic salt drilling fluid |
| CN114736342A (en) * | 2022-05-27 | 2022-07-12 | 荆州市学成实业有限公司 | Preparation method of high-temperature-resistant efficient sulfonated phenolic resin |
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| CN1212258A (en) * | 1997-09-25 | 1999-03-31 | 中国科学院化学研究所 | Method for preparation of water soluble sulfomethyl phenolic resin |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086163A (en) * | 2010-11-24 | 2011-06-08 | 山东大学 | Preparation method and application of high temperature and high salinity stabilizer for drilling fluid |
| CN102086163B (en) * | 2010-11-24 | 2013-04-03 | 山东大学 | Preparation method and application of high temperature and high salinity stabilizer for drilling fluid |
| CN104559967A (en) * | 2013-10-27 | 2015-04-29 | 中国石油化工集团公司 | Superhigh-density high-temperature-resistant saturated salt-water drilling fluid and preparation method thereof |
| CN104140794A (en) * | 2013-10-28 | 2014-11-12 | 中国石油化工股份有限公司 | High temperature resistant oil-in-water drilling fluid |
| CN104140794B (en) * | 2013-10-28 | 2017-11-17 | 中国石油化工股份有限公司 | A kind of high temperature-resisting oil-in-water drilling fluid |
| CN104650830A (en) * | 2013-11-25 | 2015-05-27 | 中国石油化工集团公司 | High-temperature resistant high-density organic salt drilling fluid |
| CN104293324A (en) * | 2014-05-30 | 2015-01-21 | 中国石油化工集团公司 | Ultrahigh-temperature drilling fluid filtrate reducer and its preparation method |
| CN104293324B (en) * | 2014-05-30 | 2019-01-01 | 中国石油化工集团公司 | A kind of ultra-high temperature drilling liquid fluid loss additive and preparation method thereof |
| CN114736342A (en) * | 2022-05-27 | 2022-07-12 | 荆州市学成实业有限公司 | Preparation method of high-temperature-resistant efficient sulfonated phenolic resin |
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|---|---|
| CN101798914B (en) | 2013-01-02 |
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