CN102899006A - Phosphonic acid group-containing polymer drilling fluid viscosity reducer and preparation method thereof - Google Patents
Phosphonic acid group-containing polymer drilling fluid viscosity reducer and preparation method thereof Download PDFInfo
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- CN102899006A CN102899006A CN2012103536967A CN201210353696A CN102899006A CN 102899006 A CN102899006 A CN 102899006A CN 2012103536967 A CN2012103536967 A CN 2012103536967A CN 201210353696 A CN201210353696 A CN 201210353696A CN 102899006 A CN102899006 A CN 102899006A
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Abstract
Belonging to the technical field of oilfield chemical drilling fluid treating agents, the invention relates to a phosphonic acid group-containing polymer drilling fluid viscosity reducer and a preparation method thereof. The polymer viscosity reducer is obtained by subjecting a 2-acrylamido-2-methylpropanephosphonic acid monomer A, and a sulfonic acid group-containing monomer B, and a carboxylic acid group-containing monomer C, an initiator and a molecular weight regulator to a polymerization reaction. The beneficial effects of the phosphonic acid group-containing polymer drilling fluid viscosity reducer provided in the invention are that: molecules of the phosphonic acid group-containing polymer drilling fluid viscosity reducer contain phosphonic acid groups, sulfonic acid groups as well as carboxylic acid groups, the product has good heat resistance, and strong contamination resistance and high solid phase tolerance, and especially, complexation of the phosphonic acid groups and calcium ions greatly improves the anti-calcium pollution ability of the product.
Description
Technical field
The present invention relates to a kind of drilling fluid thinner and preparation method thereof, be specifically related to a kind of phosphonic acid group containing polymer drilling fluid thinner and preparation method thereof, belong to oilfield chemistry additive for drilling fluid technical field.
Background technology
In deep-well, ultra deep well drilling process, because drilling fluid is under the condition of high temperature for a long time, cause the high temperature such as drilling fluid medium clay soil, drilling cuttings to disperse, can impel drilling fluid the high temperature multiviscosisty to occur, cause Drilling Fluid Viscosity to raise the rheological variation.Along with the development of oil-gas exploration and development to the deep, drilling strata becomes increasingly complex, and is harsher to the requirement of drilling fluid.For this reason, countries in the world are around the needs of ultra deep well drilling well, carrying out a series of research work aspect the high temperature resistant drilling fluids viscosity-depression agent, analyze these and study synthetic polymers such as mainly concentrating on vinylformic acid, vinyl sulfonic acid and organophosphate etc., these viscosity-depression agents have very strong temperature resistance ability, owing to containing carboxyl and containing sulfonic acid synthetic polymer viscosity reducing effect meeting variation under salt-water drilling fluid and high solid loading, organic phosphate exists the problems such as maintenance intervals is short, narrow application range, can not satisfy the demand.Therefore, how to satisfy the needs of deep-well and ultra deep well drilling well, be control drilling fluids at high temperature stability inferior matter of utmost importance.Chinese patent on December 29th, 2010 (publication number: CN 101928366A) disclose a kind of preparation method of drilling fluid thinner, may further comprise the steps: be that 0.5～10: 1 mixture is dissolved in clear water with reaction monomers vinylformic acid (AA) and 2-acrylamide-2-methylpro panesulfonic acid (AMPS) molar ratio; The ammonium persulphate that accounts for monomer consumption 0.5%～5% is dissolved in clear water; Two kinds of molecular weight regulators that account for respectively monomer consumption 0.3%～5% are dissolved in clear water and add reactor be warming up to 55 ℃～65 ℃, then add together reaction monomers solution and ammonium persulfate solution in the reactor, then system is warming up to 85 ℃～95 ℃ reaction 1h, obtain the viscosity-depression agent product of monomer content 10%～50%, after reaction finishes with in the sodium hydroxide and system to pH value be 7, obtain after dried, crushed resisting the drilling fluid thinner of high temperature more than 220 ℃.
Summary of the invention
The objective of the invention is to be suitable for well high solid phase, high density drilling fluid in order to overcome existing drilling well with the temperature resistance viscosity-depression agent, heat and salinity tolerance is indifferent, action time is short, safeguards the problems such as the work for the treatment of amount is large, and a kind of phosphonic acid group containing polymer drilling fluid thinner is provided; Be simultaneously to provide the preparation method of above-mentioned phosphonic acid group containing polymer drilling fluid thinner.
The present invention is realized by following technical proposals:
A kind of phosphonic acid group containing polymer drilling fluid thinner carries out polyreaction with 2-acrylamido-2-methylpropanephosphonic acid (AMPP) monomer A with the monomer C, initiator, the molecular weight regulator that contain the monomers B of sulfonic acid group and carboxy-containing acid group and can obtain polymer viscosity reducer.
The ratio of above-mentioned 2-acrylamido-2-methylpropanephosphonic acid monomer A, the monomers B that contains sulfonic acid group and carboxy-containing acid group's monomer C three's amount of substance is 10%～85%: 10%～75%: 5%～55%.
The above-mentioned monomers B that contains sulfonic acid group can be any one in 2-acrylamide-2-methylpro panesulfonic acid (AMPS), sodium vinyl sulfonate (VSA), Sodium styrene sulfonate (SSA), the sodium allyl sulfonate (ASA).
Above-mentioned carboxy-containing acid group's monomer C can be any one in vinylformic acid (AA), methacrylic acid (MAA), maleic anhydride (MA) or the methylene-succinic acid (IA).
Above-mentioned molecular weight regulator can be a kind of or both combination among both of Thiovanic acid (TGA), Virahol (IPA).
Above-mentioned initiator can be any one in ammonium persulphate, the Potassium Persulphate.
A kind of preparation method of phosphonic acid group containing polymer drilling fluid thinner may further comprise the steps:
(1) with 2-acrylamido-2-methylpropanephosphonic acid (AMPP) monomer A with contain the monomers B of sulfonic acid group and carboxy-containing acid group's monomer C, be 10%～85%: 10%～75% according to molar ratio: 5%～55% ratio is mixed, the gained monomer mixture is water-soluble, be made into massfraction and be 10%～40% the monomer mixture aqueous solution;
(2) will account for the monomer mixture total mass is that 1%～8% initiator is made into 10% initiator solution;
(3) will account for the monomer mixture total mass is that 0.1%～4% molecular weight regulator is dissolved in water and adds reactor and is warming up to 50 ℃～80 ℃;
(4) add monomer mixture solution and initiator solution in the reactor in batches, adding speed is no more than 80 ℃ with temperature of reaction kettle and is as the criterion, after monomer mixture solution and initiator solution add, system is warming up to 85 ℃～100 ℃ reaction 1～10h, with being 8 with system to pH value in the sodium hydroxide, the product that obtains namely got drilling fluid thinner after dried, crushed after reaction finished.
The above-mentioned monomers B that contains sulfonic acid group can be any one in 2-acrylamide-2-methylpro panesulfonic acid (AMPS), sodium vinyl sulfonate (VSA), Sodium styrene sulfonate (SSA), the sodium allyl sulfonate (ASA).
Above-mentioned carboxy-containing acid group's monomer C can be any one in vinylformic acid (AA), methacrylic acid (MAA), maleic anhydride (MA) or the methylene-succinic acid (IA).
Above-mentioned molecular weight regulator can be a kind of or both combination among both of Thiovanic acid (TGA), Virahol (IPA).
Above-mentioned initiator can be any one in ammonium persulphate, the Potassium Persulphate.
The invention has the beneficial effects as follows: not only contain phosphonate group, sulfonic group but also contain the carboxylic acid group in the phosphonic acid group containing polymer drilling fluid thinner molecule, product has good temperature resistance ability, have again stronger antipollution and high solid phase tolerance, the complexing action of phosphonate group and calcium ion has particularly improved the calcium fouling resistance ability of product greatly.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.
Embodiment 1
With 2-acrylamido-2-methylpropanephosphonic acid (AMPP) and 2-acrylamide-2-methylpro panesulfonic acid (AMPS) and vinylformic acid (AA), be water-soluble after 85%: 10%: 5% ratio is mixed according to molar ratio, be made into massfraction and be 35% the monomer mixture aqueous solution; The ammonium persulphate that accounts for monomer mixture total mass 3% is made into 10% the aqueous solution; The Thiovanic acid (TGA) that accounts for monomer mixture total mass 1.5% is dissolved in water and adds reactor be warming up to 65 ℃; Add monomer mixture solution and ammonium persulfate aqueous solution in the reactor in batches, adding speed is no more than 80 ℃ with temperature of reaction kettle and is as the criterion, after monomer mixture solution and ammonium persulfate aqueous solution add, system is warming up to 85 ℃ of reaction 5h, after reaction finishes with being 8 with system to pH value in the sodium hydroxide, obtain thick product, obtain after dried, crushed viscosity depressant for drilling fluid.
Embodiment 2～9 is according to the method for embodiment 1, and prescription and condition see Table 1:
Table 1 reactive material consumption and reaction conditions
Comparative Examples
With 2-acrylamide-2-methylpro panesulfonic acid (AMPS) monomer and vinylformic acid (AA) monomer, according to the amount of substance proportioning be 85%: 15% ratio, monomer is water-soluble, be made into massfraction 15%～40% monomer mixture aqueous solution; The initiator potassium persulfate that accounts for monomer mass 3% is made into 10% the aqueous solution; The molecular weight regulator Thiovanic acid (TGA) that accounts for monomer mass 1.5% is dissolved in water and adds reactor be warming up to 65 ℃; Add monomer mixture solution and initiator solution in the reactor in batches, adding speed is no more than 80 ℃ with temperature of reaction kettle and is as the criterion, until monomer mixture solution and initiator is water-soluble add after, system is warming up to 90 ℃ of reaction 8h, after reaction finishes with being 8 with system to pH value in the sodium hydroxide, obtain thick product, obtain after dried, crushed P(AMPS-AA) viscosity depressant for drilling fluid.
The said products is carried out the viscosity reducing effect evaluation, estimates with base slurry and method as follows:
(1) base slurry preparation
1. bentonite base is starched: add 100g calcium bentonite and 5g anhydrous Na in 1000ml water
2CO
3, high-speed stirring 20min, maintenance 24h under room temperature namely gets the bentonite base slurry.
2. the high-density base is starched: add 30g calcium bentonite and 5g anhydrous Na in 1000ml water
2CO
3, high-speed stirring 20min, then maintenance 24h under room temperature adds 3g P(AMPS-DMAM in base slurry) and tackifier, 15g SMC, then high-speed stirring 20min increases the weight of to density 1.8g/cm with barite
3, obtain high-density base slurry.
3. compound salt-water basic slurry: in the bentonite base slurry of 1000ml volume fraction 10%, add 40g NaCl, 5g CaCl
2, the 3g anhydrous Na
2CO
3, high-speed stirring 20min increases the weight of to density 1.4g/cm with barite
3, obtain compound salt-water basic slurry.
(2) drilling fluid filtration and viscosity break ratio test
Institute's synthetic copolymer sample adds in the base slurry, high-speed stirring 5min, behind 200 ℃ of lower aging 16h that roll under room temperature high-speed stirring 5min, with the rheological parameter of ZNN-D6 type six fast rotary viscosity design determining drilling fluids, measure the filter loss of drilling fluid with ZNS type drilling fluid filter press.Take the viscosity break ratio D of base slurry as the benchmark product, the larger viscosity reduction ability of viscosity break ratio is stronger:
In the formula: (ф 100)
0---the rotational viscosimeter 100 of base slurry turns/ reading under the min;
ф 100---add that the rotational viscosimeter 100 of mud turns behind the sample/ reading under the min.
Evaluation result sees Table 2.
Filter loss and viscosity break ratio measurement result after table 2 drilling fluid is aging through 220 ℃/16h
Can find out from measurement result, phosphonic acid group containing polymer viscosity depressant for drilling fluid of the present invention is in wilkinite drilling fluid, high density drilling fluid and composite salt aqueous drilling fluid, all show significant viscosity reduction effect after aging through 220 ℃/16h, its result is better than 2-acrylamide-2-methylpro panesulfonic acid and the vinylformic acid copolymer viscosity depressant for drilling fluid of Comparative Examples, show good heat and salinity tolerance ability, be applicable to ultra deep well and high pressure formation drilling well.
Claims (10)
1. phosphonic acid group containing polymer drilling fluid thinner is characterized in that: carry out polyreaction with 2-acrylamido-2-methylpropanephosphonic acid monomer A and the monomers B that contains sulfonic acid group and carboxy-containing acid group's monomer C, initiator, molecular weight regulator and make.
2. a kind of phosphonic acid group containing polymer drilling fluid thinner according to claim 1, it is characterized in that: the ratio of described monomer A, monomers B and monomer C three's amount of substance is 10%～85%: 10%～75%: 5%～55%.
3. a kind of phosphonic acid group containing polymer drilling fluid thinner according to claim 1 and 2 is characterized in that: the described monomers B that contains sulfonic acid group is a kind of in 2-acrylamide-2-methylpro panesulfonic acid, sodium vinyl sulfonate, Sodium styrene sulfonate, the sodium allyl sulfonate.
4. a kind of phosphonic acid group containing polymer drilling fluid thinner according to claim 1 and 2 is characterized in that: described carboxy-containing acid group's monomer C is a kind of in vinylformic acid, methacrylic acid, maleic anhydride, the methylene-succinic acid.
5. a kind of phosphonic acid group containing polymer drilling fluid thinner according to claim 1 and 2 is characterized in that: described initiator is a kind of in ammonium persulphate, the Potassium Persulphate, and the amount of adding is 1%～8% of monomer A, monomers B and monomer C three total mass.
6. a kind of phosphonic acid group containing polymer drilling fluid thinner according to claim 1 and 2, it is characterized in that: described molecular weight regulator is one or both in Thiovanic acid, the Virahol, and the amount of adding is 0.1%～4% of monomer A, monomers B and monomer C three total mass.
7. the preparation method of a phosphonic acid group containing polymer drilling fluid thinner is characterized in that: may further comprise the steps:
(1) with 2-acrylamido-2-methylpropanephosphonic acid monomer A with contain the monomers B of sulfonic acid group and carboxy-containing acid group's monomer C, be 10%～85%: 10%～75% according to molar ratio: 5%～55% ratio is mixed, the gained monomer mixture is water-soluble, be made into massfraction and be 10%～40% the monomer mixture aqueous solution;
(2) will account for the monomer mixture total mass is that 1%～8% initiator is made into 10% initiator solution;
(3) will account for the monomer mixture total mass is that 0.1%～4% molecular weight regulator is dissolved in water and adds reactor and is warming up to 50 ℃～80 ℃;
(4) add monomer mixture solution and initiator solution in the reactor in batches, adding speed is no more than 80 ℃ with temperature of reaction kettle and is as the criterion, after monomer mixture solution and initiator solution add, system is warming up to 85 ℃～100 ℃ reaction 1～10h, after reaction finishes with in the sodium hydroxide and system to pH value be 8, the product drying that obtains, pulverizing namely get drilling fluid thinner.
8. the preparation method of a kind of phosphonic acid group containing polymer drilling fluid thinner according to claim 7 is characterized in that: the described monomers B that contains sulfonic acid group is a kind of in 2-acrylamide-2-methylpro panesulfonic acid, sodium vinyl sulfonate, Sodium styrene sulfonate, the sodium allyl sulfonate.
9. it is characterized in that according to claim 7 or the preparation method of 8 described a kind of phosphonic acid group containing polymer drilling fluid thinners: described carboxy-containing acid group's monomer C is a kind of in vinylformic acid, methacrylic acid, maleic anhydride, the methylene-succinic acid.
10. it is characterized in that according to claim 7 or the preparation method of 8 described a kind of phosphonic acid group containing polymer drilling fluid thinners: described molecular weight regulator be in Thiovanic acid, the Virahol one or both.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103536967A CN102899006A (en) | 2012-09-20 | 2012-09-20 | Phosphonic acid group-containing polymer drilling fluid viscosity reducer and preparation method thereof |
| CN201310282648.8A CN103665263B (en) | 2012-09-20 | 2013-07-05 | A kind of phosphonic acid group containing polymer and application thereof and phosphonic acid group containing polymer drilling fluid thinner |
| US14/031,191 US9206342B2 (en) | 2012-09-20 | 2013-09-19 | Phosphonate-containing polymer and use thereof and phosphonate-containing polymer viscosity reducer for drilling fluid |
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| CN2012103536967A CN102899006A (en) | 2012-09-20 | 2012-09-20 | Phosphonic acid group-containing polymer drilling fluid viscosity reducer and preparation method thereof |
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| CN103305194A (en) * | 2013-06-26 | 2013-09-18 | 西南石油大学 | Synthesis method of polymer type drilling fluid viscosity reducer |
| CN103665263A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Phosphonic acid base containing polymer and application thereof as well as phosphonic acid base containing polymer drilling fluid viscosity reducer |
| CN104176837A (en) * | 2014-09-09 | 2014-12-03 | 武汉理工大学 | Scale inhibitor |
| CN104312548A (en) * | 2014-08-22 | 2015-01-28 | 中国石油化工集团公司 | Phosphorus-containing high-temperature-resistant drilling-fluid viscosity reducer and preparation method thereof |
| CN106832115A (en) * | 2016-12-30 | 2017-06-13 | 汪逸凡 | A kind of drilling fluid preparation method of high temperature resistant thinner |
| CN107201218A (en) * | 2017-06-16 | 2017-09-26 | 中国石油集团渤海钻探工程有限公司 | A kind of water base bentonite viscosity depressant for drilling fluid and preparation method thereof |
| CN108264620A (en) * | 2016-12-30 | 2018-07-10 | 江苏苏博特新材料股份有限公司 | A kind of phosphonic acid base block polymer, preparation method and application |
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| CN109851710A (en) * | 2017-11-30 | 2019-06-07 | 中石化石油工程技术服务有限公司 | A kind of organic phospho acid polymer fluid loss agent resistant to high temperatures and its preparation method and application |
| CN114685712A (en) * | 2020-12-25 | 2022-07-01 | 中石化石油工程技术服务有限公司 | Phosphonic acid group-containing polymer viscosity reducer and preparation method thereof |
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| CN103665263A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Phosphonic acid base containing polymer and application thereof as well as phosphonic acid base containing polymer drilling fluid viscosity reducer |
| CN103665263B (en) * | 2012-09-20 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of phosphonic acid group containing polymer and application thereof and phosphonic acid group containing polymer drilling fluid thinner |
| CN103305194A (en) * | 2013-06-26 | 2013-09-18 | 西南石油大学 | Synthesis method of polymer type drilling fluid viscosity reducer |
| CN104312548A (en) * | 2014-08-22 | 2015-01-28 | 中国石油化工集团公司 | Phosphorus-containing high-temperature-resistant drilling-fluid viscosity reducer and preparation method thereof |
| CN104312548B (en) * | 2014-08-22 | 2019-02-01 | 中国石油化工集团公司 | A kind of phosphorous high temperature resistant drilling fluids thinner and preparation method thereof |
| CN104176837A (en) * | 2014-09-09 | 2014-12-03 | 武汉理工大学 | Scale inhibitor |
| CN104176837B (en) * | 2014-09-09 | 2015-09-16 | 武汉理工大学 | Scale inhibitors |
| CN108264620A (en) * | 2016-12-30 | 2018-07-10 | 江苏苏博特新材料股份有限公司 | A kind of phosphonic acid base block polymer, preparation method and application |
| CN106832115A (en) * | 2016-12-30 | 2017-06-13 | 汪逸凡 | A kind of drilling fluid preparation method of high temperature resistant thinner |
| CN108264620B (en) * | 2016-12-30 | 2020-06-26 | 江苏苏博特新材料股份有限公司 | Phosphonic acid group block polymer, preparation method and application thereof |
| CN107201218A (en) * | 2017-06-16 | 2017-09-26 | 中国石油集团渤海钻探工程有限公司 | A kind of water base bentonite viscosity depressant for drilling fluid and preparation method thereof |
| CN107201218B (en) * | 2017-06-16 | 2019-12-03 | 中国石油集团渤海钻探工程有限公司 | A kind of water base bentonite viscosity depressant for drilling fluid and preparation method thereof |
| CN109852352A (en) * | 2017-11-30 | 2019-06-07 | 中石化石油工程技术服务有限公司 | A kind of organic phospho acid polymer fluid loss agent and its preparation method and application |
| CN109851710A (en) * | 2017-11-30 | 2019-06-07 | 中石化石油工程技术服务有限公司 | A kind of organic phospho acid polymer fluid loss agent resistant to high temperatures and its preparation method and application |
| CN109652053A (en) * | 2019-01-22 | 2019-04-19 | 西南石油大学 | A kind of full suspension fracturing fluid with low damage and its preparation method resistant to high temperatures |
| CN109652053B (en) * | 2019-01-22 | 2021-09-21 | 西南石油大学 | High-temperature-resistant full-suspension low-damage fracturing fluid and preparation method thereof |
| CN114685712A (en) * | 2020-12-25 | 2022-07-01 | 中石化石油工程技术服务有限公司 | Phosphonic acid group-containing polymer viscosity reducer and preparation method thereof |
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