CN102876302A - Acryloyl morpholine polymer treatment agent for drilling fluid and method for preparing same - Google Patents
Acryloyl morpholine polymer treatment agent for drilling fluid and method for preparing same Download PDFInfo
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- CN102876302A CN102876302A CN2012103536539A CN201210353653A CN102876302A CN 102876302 A CN102876302 A CN 102876302A CN 2012103536539 A CN2012103536539 A CN 2012103536539A CN 201210353653 A CN201210353653 A CN 201210353653A CN 102876302 A CN102876302 A CN 102876302A
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- acryloyl morpholine
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Abstract
The invention discloses an acryloyl morpholine polymer treatment agent for a frilling fluid and a method for preparing the acryloyl morpholine polymer treatment agent. The acryloyl morpholine polymer treatment agent is prepared by polymerizing N-acryloyl morpholine (AOM), sodium 2-acrylamide-2-methyipropanesulfonate (SAMPS), a crosslinkable monomer, an initiator and water under the conditions that the pH value is 6.0-9.0, wherein the N-AOM is a hydrolysis-resisting monomer. The 1% aqueous solution has the apparent viscosity of 15-45Mpa.s, has good filtration loss reducing characteristic under the condition of high temperature (200 DEG C), high salt (saturated brine) and high calcium (40% of calcium chloride) and has a good tackifying effect in the clay-phase-free brine drilling fluid. The product has the advantages of low production cost, high production sped, high production efficiency and stable quality, also has good water solubility and is convenient to use on site.
Description
Technical field:
The present invention relates to drilling fluid acryloyl morpholine polymer treatment agent and preparation method thereof, belong to the synthetic class preparation method technical field of petroleum drilling oilfield chemistry water-soluble high-molecular material, or rather, be a kind of synthetic polymer high temperature resistance anticalcium filtrate reducer for drilling fluid and preparation method thereof.
Back of the body art background:
In Process of Oil Well Drilling, drilling strata is increasingly sophisticated, exceptional well, ultra deep well and Holes of Complicated Wells quantity increase year by year, this has higher requirement to drilling fluid, for this situation, carrying out a series of activities aspect the high temperature resistant drilling fluids treatment agent both at home and abroad, but present existing treatment agent wants to improve deep-well, the heat and salinity tolerance performance of ultra deep well drilling fluid, just must increase its consumption, but improve the viscosity that has increased again drilling fluid along with dosage, particularly at calcium, in the high situation of Mg content, property of drilling fluid control is more difficult, and existing additive for drilling fluid can not satisfy the needs of drilling well fully.Recent exploitation along with the unconventional oil gas take shale gas as representative, one-tenth for shale gas is hidden feature, the shale gas exploitation is with the shallow-layer extended reach well, clump formula horizontal well well spacing is main, because shale formation fracture development, water sensitivity is strong, leakage not only easily occurs in the long horizontal sections drilling well, collapse, undergauge etc., and because horizontal section is longer, also can bring frictional resistance, take rock and formation contaminant problem, thereby increased the probability that produces the down-hole complexity, solved wellbore stability in the shale gas horizontal well drilling for this reason, the problems such as resistance antifriction and cutting bed removing of falling become the key of drilling fluid Choice and design.In order to satisfy the needs of wellbore stability, external 60%～70% shale gas horizontal well adopts the oil base drilling fluid system, sees with regard to the domestic shale gas horizontal well of finishing in the recent period, most oil base drilling fluids that adopt.Because the oil base drilling fluid cost is high, environmental protection is had pollution, so water-base drilling fluid is final selection.Studies show that, when active shale is exposed to high salinity (35%CaCl
2) water-base drilling fluid the time, dehydration (or dehydration) phenomenon can occur in active shale.As seen, for the needs of shale gas horizontal well drilling, explore water-based CaCl
2/ polymer drilling fluid, no matter from reducing cost, or the angle of environment protection say all very necessary, present water base CaCl
2/ polymer drilling fluid difficult point is treatment agent and the drilling fluid stability problem that solves compatibility, so emphasis is that exploitation is applicable to water base CaCl
2The polymer treatment agent of/polymer drilling fluid.
Summary of the invention:
The object of the present invention is to provide a kind of drilling fluid with the agent of acryloyl morpholine polymer treatment, can satisfy the needs that bottom temperature is higher than the safety drilling construction under 200 ℃ and/or high salt (sodium-chlor) the high calcium environment, can control water base CaCl
2Rheological and filter loss under/the polymer drilling fluid high-temperature and high-pressure conditions.
Second purpose of the present invention provides the preparation method that a kind of drilling fluid is used the agent of acryloyl morpholine polymer treatment.
The present invention is realized by the following technical programs: drilling fluid acryloyl morpholine polymer treatment agent, by following consumption, be to be polymerized under 6.0～9.0 the condition by hydrolysis monomer N-acryloyl morpholine (AOM) and 2-acrylamide-2-methyl propane sulfonic sodium (SAMPS), cross-linkable monomer, initiator and water in the pH value:
2-acrylamide-2-methyl propane sulfonic sodium (SAMPS) aqueous solution 180 grams of massfraction 50%, the N-acryloyl morpholine
(AOM) 6～79 grams, cross-linkable monomer 0.2～0.6 gram, initiator 0.15～0.9 gram, 5～70 milliliters in water.
Described cross-linkable monomer is a kind of in N hydroxymethyl acrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate or the Propylene glycol monoacrylate.
Described initiator is oxidation-reduction trigger system, and oxygenant is a kind of in Potassium Persulphate, the ammonium persulphate, and reductive agent is a kind of in sodium bisulfite, Sodium Pyrosulfite, S-WAT, the Sulfothiorine.
Drilling fluid acryloyl morpholine polymer treatment agent, its structural formula is when adopting N hydroxymethyl acrylamide to make linking agent:
In the formula: (m+x): (n+z)=1:(0.1～1.4).
When a kind of in adopting Hydroxyethyl acrylate, hydroxyethyl methylacrylate or Propylene glycol monoacrylate made linking agent, its structural formula was:
In the formula: R1=H, CH
3, R2=CH
2CH
2, CH
2CH
2CH
2, (m+x): (n+z)=1:(0.1～1.4).
The drilling fluid preparation method of acryloyl morpholine polymer treatment agent may further comprise the steps:
(1) water, 2-acrylamide-2-methyl propane sulfonic sodium water solution are added reactor, after stirring, with the sodium hydroxide of massfraction 10%～20% the pH value of system is adjusted to 6.0～9.0, then adds N-acryloyl morpholine (AOM) and cross-linkable monomer, stir and make its dissolving;
(2) reaction mixture with step (1) goes in the polymer reactor, under agitation adds oxidation-reduction initiator, and the starting temperature of polyreaction is 30～60 ℃, and keeping polymerization reaction time is 15～60 minutes, obtains at last thick product;
(3) the thick product that step (2) is obtained in 90～100 ℃ of lower constant temperature 2～6 hours, obtains gel elasticity under sealed state;
(4) the gel elastomerics that step (3) is obtained namely gets drilling fluid acryloyl morpholine polymer treatment agent through shearing, dry, pulverizing.
Described initiator is oxidation-reduction trigger system, and oxygenant is a kind of in Potassium Persulphate, the ammonium persulphate, and reductive agent is a kind of in sodium bisulfite, Sodium Pyrosulfite, S-WAT, the Sulfothiorine.
Described cross-linkable monomer is N hydroxymethyl acrylamide, Hydroxyethyl acrylate, a kind of in hydroxyethyl methylacrylate and the Propylene glycol monoacrylate.
The invention has the beneficial effects as follows: the hydrolysis monomer by adopting large side group with contain sulfonic acid monomer, copolymerization in the presence of cross-linkable monomer, make product have suitable degree of crosslinking, the acryloyl morpholine polymer treatment agent that obtains, both had stronger heat and salinity tolerance ability, can treatment agent fall as the polymkeric substance in the calcium chloride drilling liquor again, the product good water solubility, adopt aqueous solution rapid polymerization, the further constant temperature cross-linking method preparation of product, reaction process is controlled easily, simple to operate, constant product quality, production and drying course power consumption are low, environmentally safe has under high temperature (200 ℃) high salt (saturated brine) and high calcium (40% calcium chloride) condition and falls preferably filtration characteristics, has good Efficient Adhesive Promotion in without clay phase salt-water drilling fluid.
Embodiment:
The present invention will be further described below in conjunction with specific embodiment.
Embodiment 1
In the reaction flask of belt stirrer, add 5 ml waters, then add 180g massfraction 50%2-acrylamide-2-methyl propane sulfonic sodium water solution, rear adding 6g N-acryloyl morpholine, 0.2g N hydroxymethyl acrylamide stir, stirring makes its dissolving, with the aqueous sodium hydroxide solution of massfraction 10%～20%, the pH value of system is adjusted to 6; The reaction mixture of above-mentioned monomer is gone in the polypropylene plastic container, under agitation add according to this ammonium persulphate 0.15g, sodium bisulfite 0.15g, the rear standing and reacting that stirs 15 minutes, obtain at last thick product, with the thick product sealing that obtains, in 100 ℃ of lower constant temperature 2 hours, obtain gel elasticity.The gel elasticity that obtains is namely got the ultrahigh-temperature polymer filtrate reducer through shearing, dry, pulverizing.
Embodiment 2
In the reaction flask of belt stirrer, add 10 ml waters, then add 180g massfraction 50%2-acrylamide-2-methyl propane sulfonic sodium water solution, rear adding 25.5gN-acryloyl morpholine, 0.3g N hydroxymethyl acrylamide stir, stirring makes its dissolving, with massfraction 10%～20% aqueous sodium hydroxide solution, the pH value of system is adjusted to 7; The reaction mixture of above-mentioned monomer is gone in the polypropylene plastic container, under agitation add according to this Potassium Persulphate 0.3g, Sodium Pyrosulfite 0.3g, the rear standing and reacting that stirs 25 minutes, obtain at last thick product, with the thick product sealing that obtains, in 95 ℃ of lower constant temperature 3 hours, obtain gel elasticity.The gel elasticity that obtains is namely got the ultrahigh-temperature polymer filtrate reducer through shearing, dry, pulverizing.
Embodiment 3
In the reaction flask of belt stirrer, add 30 ml waters, then add 180g massfraction 50%2-acrylamide-2-methyl propane sulfonic sodium water solution, rear adding 42gN-acryloyl morpholine, 0.4g N hydroxymethyl acrylamide stir, stirring makes its dissolving, with massfraction 10%～20% aqueous sodium hydroxide solution, the pH value of system is adjusted to 7.5; The reaction mixture of above-mentioned monomer is gone in the polypropylene plastic container, under agitation add according to this Potassium Persulphate 0.4g, S-WAT 0.4g, the rear standing and reacting that stirs 25 minutes, obtain at last thick product, with the thick product sealing that obtains, in 95 ℃ of lower constant temperature 3.5 hours, obtain gel elasticity.The gel elasticity that obtains is namely got the ultrahigh-temperature polymer filtrate reducer through shearing, dry, pulverizing.
Embodiment 4
In the reaction flask of belt stirrer, add 70 ml waters, then add 180g massfraction 50%2-acrylamide-2-methyl propane sulfonic sodium water solution, rear adding 79gN-acryloyl morpholine, 0.6N-n-methylolacrylamide stir, stirring makes its dissolving, with massfraction 10%～20% aqueous sodium hydroxide solution, the pH value of system is adjusted to 8; The reaction mixture of above-mentioned monomer is gone in the polypropylene plastic container, under agitation add according to this ammonium persulphate 0.6g, Sulfothiorine 0.3g, the rear standing and reacting that stirs 15 minutes, obtain at last thick product, with the thick product sealing that obtains, in 100 ℃ of lower constant temperature 5 hours, obtain gel elasticity.The gel elasticity that obtains is namely got the ultrahigh-temperature polymer filtrate reducer through shearing, dry, pulverizing.
Embodiment 5～8 steps are identical with embodiment 1, concrete reactive material and reaction conditions such as table 1:
Table 1 embodiment 5～8 prescription and conditions
Comparative Examples 1
In the reaction flask of belt stirrer, add 80 ml waters, then add sodium hydroxide 11.6g, after its dissolving, under agitation 2-acrylamide-2-methyl propane sulfonic 60g is added, be stirred to whole dissolvings; Then add the 26g acrylamide, stir and to make its dissolving, with massfraction 20%～45% aqueous sodium hydroxide solution, the pH value of system is adjusted to 9; The reaction mixture of above-mentioned monomer is gone in the polypropylene plastic container, under agitation add according to this Potassium Persulphate 0.25g, sodium bisulfite 0.25g, the rear standing and reacting that stirs 15 minutes obtains the visco-elasticity product at last.The gel elasticity that obtains is namely got the ultrahigh-temperature polymer filtrate reducer through shearing, dry, pulverizing.Its 1% aqueous solution apparent viscosity 36.0mPas.
Comparative Examples 2
In the reaction flask of belt stirrer, add 80 ml waters, then add sodium hydroxide 15.5g, after its dissolving, under agitation 2-acrylamide-2-methyl propane sulfonic 80g is added, be stirred to whole dissolvings; Then add the 6gN-acryloyl morpholine, stir and to make its dissolving, with massfraction 20%～45% aqueous sodium hydroxide solution, the pH value of system is adjusted to 6; The reaction mixture of above-mentioned monomer is gone in the polypropylene plastic container, under agitation add according to this Potassium Persulphate 0.25g, sodium bisulfite 0.25g, the rear standing and reacting that stirs 15 minutes, obtain at last thick product, with the thick product sealing that obtains, in 100 ℃ of lower constant temperature 2 hours, then dry, pulverize and namely get polymer filtrate reducer.Its 1% aqueous solution apparent viscosity 4.5mPas.
The said products is carried out the evaluation of drilling fluid application performance, the results are shown in Table 2.
220 ℃/16h of table 2 drilling fluid aged properties measurement result
Experiment forms with the base slurry:
(1) compound salt-water basic slurry: in 1000ml distilled water, add the NaCl of 45g, the anhydrous CaCl of 5g
2, 13gMgCl
26H
2O, 150g calcium bentonite and 9g anhydrous Na
2CO
3, high-speed stirring 20min, maintenance 24h under room temperature namely gets compound salt-water basic slurry.
(2) high calcium brine mud: 5% sodium bentonite slurry+40%CaCl
2+ 2.5% soda ash+5.0% sulfonated lignite+1.0%SSMA viscosity-depression agent, with barite increase the weight of to density be 1.5g/cm
3, high-speed stirring 20min, maintenance 24h under room temperature namely gets the high calcium brine mud.
(3) the water base slurry of saturated salt: 6% sodium bentonite slurry+36%NaCl+2.5% soda ash+2% sulfonated lignite, increase the weight of to density 1.5g/cm with barite
3, high-speed stirring 20min, maintenance 24h under room temperature namely gets the water base slurry of saturated salt.
Can find out from evaluation result, acryloyl morpholine polymer drilling fluid finishing agent of the present invention is in compound salt-water basic slurry, high calcium brine mud and the water base slurry of saturated salt, all show after aging through 220 ℃/16h and fall significantly leak-off and Efficient Adhesive Promotion, its result is far superior to the effect of Comparative Examples multipolymer, show good heat and salinity tolerance ability, gone for ultra deep well, high pressure and high salty formation drilling well.
Claims (7)
1. drilling fluid acryloyl morpholine polymer treatment agent, it is characterized in that: by following consumption, be to be polymerized under 6.0～9.0 the condition by hydrolysis monomer N-acryloyl morpholine and 2-acrylamide-2-methyl propane sulfonic sodium, cross-linkable monomer, initiator and water in the pH value:
2-acrylamide-2-methyl propane sulfonic sodium water solution 180 grams of massfraction 50%, N-acryloyl morpholine 6～79 grams, cross-linkable monomer 0.2～0.6 gram, initiator 0.15～0.9 gram, 5～70 milliliters in water.
2. drilling fluid according to claim 1 acryloyl morpholine polymer treatment agent, it is characterized in that: described cross-linkable monomer is N hydroxymethyl acrylamide, the polymer architecture formula after it is crosslinked is:
In the formula: (m+x): (n+z)=1:(0.1～1.4).
3. drilling fluid according to claim 1 is characterized in that with the agent of acryloyl morpholine polymer treatment: described cross-linkable monomer is a kind of in Hydroxyethyl acrylate, hydroxyethyl methylacrylate or the Propylene glycol monoacrylate, and the polymer architecture formula after it is crosslinked is:
In the formula: R1=H, CH
3, R2=CH
2CH
2, CH
2CH
2CH
2, (m+x): (n+z)=1:(0.1～1.4).
4. drilling fluid according to claim 1 acryloyl morpholine polymer treatment agent, it is characterized in that: described initiator is oxidation-reduction trigger system, oxygenant is a kind of in Potassium Persulphate, the ammonium persulphate, and reductive agent is a kind of in sodium bisulfite, Sodium Pyrosulfite, S-WAT, the Sulfothiorine.
5. a drilling fluid is characterized in that: may further comprise the steps with the preparation method of acryloyl morpholine polymer treatment agent:
(1) water, 2-acrylamide-2-methyl propane sulfonic sodium water solution are added reactor, after stirring, with the sodium hydroxide of massfraction 10%～20% the pH value of system is adjusted to 6.0～9.0, then adds N-acryloyl morpholine and cross-linkable monomer, stir and make its dissolving;
(2) reaction mixture with step (1) goes in the polymer reactor, under agitation adds oxidation-reduction initiator, and the starting temperature of polyreaction is 30～60 ℃, and keeping polymerization reaction time is 15～60 minutes, obtains at last thick product;
(3) the thick product that step (2) is obtained in 90～100 ℃ of lower constant temperature 2～6 hours, obtains gel elasticity under sealed state;
(4) the gel elastomerics that step (3) is obtained namely gets drilling fluid acryloyl morpholine polymer treatment agent through shearing, dry, pulverizing.
6. drilling fluid according to claim 5 is with the preparation method of acryloyl morpholine polymer treatment agent, it is characterized in that: described cross-linkable monomer is N hydroxymethyl acrylamide, Hydroxyethyl acrylate, a kind of in hydroxyethyl methylacrylate and the Propylene glycol monoacrylate.
According to claim 5 or 6 described drilling fluids with the preparation method of acryloyl morpholine polymer treatment agent, it is characterized in that: described initiator is oxidation-reduction trigger system, oxygenant is a kind of in Potassium Persulphate, the ammonium persulphate, and reductive agent is a kind of in sodium bisulfite, Sodium Pyrosulfite, S-WAT, the Sulfothiorine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103536539A CN102876302A (en) | 2012-09-20 | 2012-09-20 | Acryloyl morpholine polymer treatment agent for drilling fluid and method for preparing same |
| CN201310282326.3A CN103665261A (en) | 2012-09-20 | 2013-07-05 | Acryloylmorpholine polymer and application thereof as well as drilling fluid filtrate loss reducer |
| US14/031,115 US9085722B2 (en) | 2012-09-20 | 2013-09-19 | Acryloylmorpholine polymer and use thereof and filtrate reducer for drilling fluid |
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| CN2012103536539A CN102876302A (en) | 2012-09-20 | 2012-09-20 | Acryloyl morpholine polymer treatment agent for drilling fluid and method for preparing same |
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| CN104371062B (en) * | 2013-08-16 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of acrylamide quadripolymer and its preparation method and application |
| CN105837758A (en) * | 2015-01-13 | 2016-08-10 | 中国石油天然气股份有限公司 | Water-absorbent material and preparation method and application thereof |
| CN105837758B (en) * | 2015-01-13 | 2018-06-01 | 中国石油天然气股份有限公司 | Absorbent material and its preparation method and application |
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| CN106520107A (en) * | 2016-11-07 | 2017-03-22 | 重庆科技学院 | Acryloyl morpholine polymer oil-displacing agent and preparation method thereof |
| CN109651563A (en) * | 2018-12-24 | 2019-04-19 | 成都欧美克石油科技股份有限公司 | A kind of multipolymer fluid loss agent and preparation method thereof |
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| CN114989348A (en) * | 2022-07-21 | 2022-09-02 | 中国石油大学(华东) | High-temperature-resistant salt-resistant organic silicon filtrate reducer and preparation method and application thereof |
| CN114989348B (en) * | 2022-07-21 | 2024-01-19 | 中国石油大学(华东) | High-temperature-resistant salt-resistant organosilicon fluid loss additive and preparation method and application thereof |
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Application publication date: 20130116 |