CN100445345C - Amphoteric ion polymeric alcohol for drilling fluid and its preparation method - Google Patents

Amphoteric ion polymeric alcohol for drilling fluid and its preparation method Download PDF

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CN100445345C
CN100445345C CNB2006101020169A CN200610102016A CN100445345C CN 100445345 C CN100445345 C CN 100445345C CN B2006101020169 A CNB2006101020169 A CN B2006101020169A CN 200610102016 A CN200610102016 A CN 200610102016A CN 100445345 C CN100445345 C CN 100445345C
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drilling fluid
polymeric alcohol
amphoteric ion
alkenyl
ion polymeric
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乔孟占
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TANGSHAN JIYOU RUIFENG CHEMICAL CO Ltd
Petrochina Co Ltd
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Jidong Petroleum Exploration and Development Co
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Abstract

The invention relates to a kind of amphion poly-alcohol used in well boring liquid as well as its preparing method which belongs to the domain of accessory ingredient for well boring liquid. The ingredient of the invention includes olefinic acid, alkenyl amide, alkenyl sulfonic acid, alkenyl quaternary ammonium salt, ekibon, epoxypropane, alkenyl metamer. The ratio of alkenyl metamer, ekibon and epoxypropane is 10-30%:15-30%: 20-80%. The preparing procedure includes the following steps: putting the material into the polymerizing reactor and adding the initiator and polymerization catalyst to let them react at 100-150DEG C, 0.1 -2Mpa for 1-5h; neutralizing the polymerized product with carstic potash solution to get the product. The invention has many characteristics such as high temperature proof, salt proof, strong rejection capability, oil gas protection and environment-friendly. It can be used to prevent the collapse, protect the oil gas or be used as the slime stabilizing agent in the proving and exploring of oil and natural gas.

Description

Amphoteric ion polymeric alcohol for drilling fluid and preparation method thereof
Technical field
The present invention relates to a kind of drilling fluid used additives and preparation method thereof, particularly relate to a kind of amphoteric ion polymeric alcohol for drilling fluid that hydrocarbon zone protects environment again and preparation method thereof of promptly protecting.
Background technology
Use oil base drilling fluid to creep into water-sensitive strata for a long time, to solve shale stability, pressure differential sticking and drill bit bag mud problem always.Oil base drilling fluid has pollution to environment, and is influential to logging operation, the cost height, and use is restricted.Polyglycol drilling fluid is one of the state-of-the-art technology of international drilling fluid of nineteen nineties, is a kind of favorable substitutes of oil base drilling fluid.The polymeric alcohol that U.S.Pat.No.5602082 (Hale AH.) and U.S.Pat.No.5945386 (Alonso-DeboltM A.) have proposed oxyethane and propylene oxide polymerization generation is used for water-base drilling fluid; play and suppress the shale hydration expansion, prevent the effect of slump in and protection hydrocarbon zone.Because polymeric alcohol poisonless biological degradable, be widely used in the oil-gas exploration of environment sensitive and region, ocean, the acting body of polymeric alcohol reduces the chemically reactive of drilling fluid filtrate now and is adsorbed on surface of clay at the undissolved polymeric alcohol particulate of the above temperature of cloud point, stop up and the passivation space, stop clay to contact with water.
Summary of the invention
Goal of the invention of the present invention is: in order to improve the adsorptive power of polymeric alcohol to clay, improve the polymeric alcohol cloud point, improve the polymeric alcohol high temperature resistant property, be used for (3500~5500m) the hydrocarbon zone probing of land and bathypelagic, solve the drilling fluid tackify problem that positive polarity causes because of high temperature action, a kind of amphoteric ion polymeric alcohol for drilling fluid and preparation method who is generated by olefin(e) acid, alkenyl amide, olefin sulfonic acid, thiazolinyl quaternary ammonium salt and oxyethane, propylene oxide polyreaction is provided, reaches the purpose of improving the polymeric alcohol performance.
Realize the foregoing invention purpose by the following technical solutions: a kind of amphoteric ion polymeric alcohol for drilling fluid, it is characterized in that, the mass percent that described amphoteric ion polymeric alcohol is pressed following component by alkenyl monomer (olefin(e) acid, alkenyl amide, olefin sulfonic acid, thiazolinyl quaternary ammonium salt) and oxyethane and propylene oxide constitutes: alkenyl monomer: oxyethane: propylene oxide=10~30%: 15~30%: 20~80%, and each components contents sum is 100%; This alkenyl monomer constitutes by the mass percent of following component: olefin(e) acid: alkenyl amide: olefin sulfonic acid: thiazolinyl quaternary ammonium salt=5~20%: 20~50%: 5~20%: 5~20%, and each components contents sum is 100%.
A kind of method for preparing amphoteric ion polymeric alcohol for drilling fluid, it is characterized in that, may further comprise the steps: join alkenyl monomer, oxyethane, propylene oxide in the polymerization reactor respectively, add the reaction of initiator and polymerizing catalyst, reaction conditions: temperature of reaction is 100~150 ℃, reaction pressure is 0.1~2Mpa, and the reaction times is 1~5h; The polyreaction resultant obtains PH=7~8 with the potassium hydroxide aqueous solution neutralization, and mass percent concentration is 40~45% amphoteric ion polymeric alcohol for drilling fluid.
Owing to adopted technique scheme, the present invention produces absorption on the end face of clay Belt positive charge and electronegative plane, clay is produced the effect of very strong inhibition aquation.In addition, because its cloud point effect, amphoteric ion polymeric alcohol was rendered as bundle glue form when promptly cloud point was above, and energy shutoff stratum micro-cracks has good anti-collapse effect.The present invention can be used for being used for the clay stabilizer of well control fluid, workover fluid and well finishing liquid in the probing of oil field, land and marine oil field.
Embodiment
The invention will be further described below in conjunction with embodiment.
Amphoteric ion polymeric alcohol for drilling fluid is the amphoteric ion polymeric alcohol that is generated by olefin(e) acid, alkenyl amide, olefin sulfonic acid, thiazolinyl quaternary ammonium salt and oxyethane, propylene oxide polyreaction.Olefin(e) acid is vinylformic acid, methacrylic acid, and the best is a vinylformic acid.Alkenyl amide is acrylamide, Methacrylamide, bestly is acrylamide.Olefin sulfonic acid is propene sulfonic acid, vinylformic acid-2-sulfonic group ethyl ester, 2-acrylamido-2-methyl propane sulfonic acid, and the best is 2-acrylamido-2-methyl propane sulfonic acid.The thiazolinyl quaternary ammonium salt is allyl group trimethyl ammonium chloride, allyl group trimethylammonium bicarbonate of ammonia, diallyldimethylammonium chloride, and the best is the allyl group trimethyl ammonium chloride.
Amphoteric ion polymeric alcohol for drilling fluid provided by the invention is by vinylformic acid, acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, allyl group trimethyl ammonium chloride and oxyethane, propylene oxide, at the initiator propylene glycol, under the effect of polymerizing catalyst benzoyl peroxide, the polymkeric substance that reaction generates reacts with potassium hydroxide aqueous solution again, generate the drilling fluid amphoteric ion polymeric alcohol, its structure is as follows:
Figure C20061010201600061
Figure C20061010201600062
In the formula: x, y, z, m, n and q are respectively the mole numbers of oxyethane, propylene oxide, vinylformic acid, acrylamide, 2-acrylamido-2-methyl propane sulfonic acid and propenyl trimethyl ammonium chloride, and mole number is by various monomer add-on decisions.Monomer constitutes by following ratio of component (mass percent): alkenyl monomer: oxyethane: propylene oxide=10~30%: 15~30%: 20~80%, and the best is an alkenyl monomer: oxyethane: propylene oxide=20~25%: 15~20%: 55~65%.Alkenyl monomer constitutes by following ratio of components (mass percent): olefin(e) acid: alkenyl amide: olefin sulfonic acid: thiazolinyl quaternary ammonium salt=5~20%: 20~50%: 5~20%: 5~20%, and the best is an olefin(e) acid: alkenyl amide: olefin sulfonic acid: thiazolinyl quaternary ammonium salt=10~20%: 30~40%: 15~20%: 15~20%.
The preparation method of amphoteric ion polymeric alcohol for drilling fluid provided by the invention is: at first alkenyl monomer, oxyethane and propylene oxide are added in the polymerization reactor, add initiator and polymerizing catalyst again.Initiator is glycerol, propylene glycol, and the best is a propylene glycol.The initiator dosage is 0.1~10% (mass percent) of reaction-ure mixture, and the best is 2~8%.Polymerizing catalyst is a peroxidation base formyl, lauroyl peroxide, ammonium persulphate, and the best is a benzoyl peroxide, and the polymerizing catalyst add-on is 0.1~10% (mass percent) of reaction-ure mixture, and the best is 0.5~3%.Polymeric reaction temperature is 100~150 ℃, and reaction pressure is 0.1~2Mpa, and the reaction times is 1~5h, and the best is 120~135 ℃ of temperature of reaction, and reaction pressure is 0.3~0.5Mpa, and the reaction times is 2~3h.After polyreaction finishes, be cooled to 30~90 ℃, best 70~80 ℃, polymkeric substance and 10~30% (mass percent) potassium hydroxide aqueous solution that generates carries out neutralization reaction, obtain pH=7~8, polymer concentration is 40~45% (mass percent) aqueous solution, is amphoteric ion polymeric alcohol for drilling fluid.
Further specify the present invention's (the present invention is not confined in these example scopes) with specific embodiment below.
Embodiment 1. adds vinylformic acid 50g in polymerization reactor, acrylamide 165g, 2-acrylamido-2-methyl propane sulfonic acid 95g, allyl group trimethyl ammonium chloride 45g, oxyethane 750g and propylene oxide 1650g, initiator propylene glycol 65g, polymerizing catalyst benzoyl peroxide 25g, be heated to 105 ℃ under constantly stirring, polyreaction begins and carries out fierceness, feeds the chilled water modulation temperature of reaction.
Keeping temperature of reaction is 120-135 ℃, and reaction pressure is 0.3-0.5Mpa, after the 2-3h reaction, feeds water quench to 70-80 ℃.Polymkeric substance is slowly added in another reaction vessel, it is 20% (mass percent) potassium hydroxide solution that the concentration for preparing is in advance arranged in this reaction vessel, neutralization reaction is heat release, reactor passes through the cooling water control temperature at 80-90 ℃, when solution PH=7-8, obtain the amphoteric ion polymeric alcohol for drilling fluid that 6850g concentration is 41% (mass percent).
Embodiment 2, in polymerization reactor, add methacrylic acid 65g, acrylamide 145g, 2-acrylamido-2-methyl propane sulfonic acid 100g, allyl group trimethyl ammonium chloride 37g, oxyethane 900g and propylene oxide 1600g, initiator glycerol 73g, polymerizing catalyst benzoyl peroxide 22g, be heated to 105 ℃ under constantly stirring, polyreaction begins, by the chilled water modulation temperature of reaction, controlled temperature is in 110-140 ℃ of scope, reaction pressure 0.2-0.6MPa, through after the 2-3h reaction, by water quench to 70-80 ℃.Slowly add polymkeric substance and carry out neutralization reaction in the reaction vessel that concentration is 20% (mass percent) potassium hydroxide solution is housed, temperature of reaction is controlled at 80-90 ℃.When the PH=7-8 of solution, neutralization reaction finishes, and obtains the amphoteric ion polymeric alcohol for drilling fluid that 7400g concentration is 43% (mass percent).
Embodiment 3, drilling fluid rheology test
Test is 4% Anqiu sodium bentonite with fresh water base slurry, and brine mud is to add 10% Anqiu sodium bentonite in the 4%NaCl aqueous solution, and test method is pressed SY/T5621-93 drilling fluid test procedure, and test-results sees Table 1.
Table 1 amphoteric ion polymeric alcohol influences drilling fluid rheology
Figure C20061010201600081
Embodiment 4, mud shale recovery test
The base slurry is 4% Anqiu sodium bentonite fresh water slurry, and mud shale is certain well 3204m place core, and broken back is crossed the 8-10 mesh sieve and is test core rock.Add 1% sample and 50g core in base slurry, in 150 ℃ of rolling 16h, 40 mesh sieves are crossed in the cooling back, wash clean core after, 105 ± 3 ℃ of oven dry, be primary recovery.Once in 150 ℃ of rolling 4h, receive with 40 mesh sieves is the secondary recovery rate to the core of Hui Shouing in clear water.Test-results sees Table 2.
Table 2 recovery test
Sample Primary recovery, % The secondary recovery rate, %
The base slurry 8.5 21.8
Example 1 sample 63.3 78.1
Example 2 samples 65.9 77.4
Polymeric alcohol 27.2 44.9
The positive electricity polymeric alcohol 30.7 46.6
Embodiment 5, the distributed test of inhibition wilkinite
The base slurry is 4% Anqiu sodium bentonite fresh water slurry, and the sample add-on is 2%, and test method is that 4.4.5 suppresses wilkinite dispersive mensuration among the SY/T5696-95.Test-results sees Table 3.
Table 3 suppresses the wilkinite distributed test
Sample The base slurry Example 1 sample Example 2 samples Polymeric alcohol The positive electricity polymeric alcohol
The apparent viscosity rate of rise, % 286 55 49 103 223
Embodiment 6, cloudy test
In the 100ml beaker, add 50ml distilled water, add the 1.00g sample, after stirring, pour in the 50ml colorimetric cylinder.In colorimetric cylinder, put into a thermometer.Colorimetric cylinder is put into 80-90 ℃ of water-bath to be heated.When the unexpected feculence of solution, read thermometer reading, be the cloud point of this sample, cloudy test the results are shown in Table 4.
Table 4 cloudy test
Sample Example 1 sample Example 2 samples Polymeric alcohol The positive electricity polymeric alcohol
Cloud point, ℃ 52 51 38 33
Amphoteric ion polymeric alcohol for drilling fluid of the present invention contains a large amount of active groups:
Negatively charged ion-COO -,-SO 3 -, And nonionic-OH ,-CONH-, on the end face of clay Belt positive charge and electronegative plane, produce absorption, clay is produced the effect of very strong inhibition aquation.In addition, because its cloud point effect, amphoteric ion polymeric alcohol was rendered as bundle glue form when promptly cloud point was above, and energy shutoff stratum micro-cracks has good anti-collapse effect.

Claims (8)

1, a kind of amphoteric ion polymeric alcohol for drilling fluid, it is characterized in that, described amphoteric ion polymeric alcohol is made of alkenyl monomer and oxyethane and the propylene oxide mass percent by following component: alkenyl monomer: oxyethane: propylene oxide=10~30%: 15~30%: 20~80%, and described each components contents sum is 100%; This alkenyl monomer constitutes by the mass percent of following component: olefin(e) acid: alkenyl amide: olefin sulfonic acid: thiazolinyl quaternary ammonium salt=5~20%: 20~50%: 5~20%: 5~20%, and described each components contents sum is 100%.
2, amphoteric ion polymeric alcohol for drilling fluid according to claim 1 is characterized in that, the olefin(e) acid of described alkenyl monomer is acrylic or methacrylic acid.
3, amphoteric ion polymeric alcohol for drilling fluid according to claim 1 is characterized in that, the alkenyl amide of described alkenyl monomer is acrylamide or Methacrylamide.
4, amphoteric ion polymeric alcohol for drilling fluid according to claim 1, the olefin sulfonic acid that it is characterized in that described alkenyl monomer are vinyl sulfonic acid, propene sulfonic acid, vinylformic acid-2-sulfonic group ethyl ester or 2-acrylamido-2-methyl propane sulfonic acid.
5, amphoteric ion polymeric alcohol for drilling fluid according to claim 1, the thiazolinyl quaternary ammonium salt that it is characterized in that described alkenyl monomer are allyl group trimethyl ammonium chloride, allyl group trimethylammonium bicarbonate of ammonia or diallyldimethylammonium chloride.
6, a kind of preparation method of amphoteric ion polymeric alcohol for drilling fluid as claimed in claim 1, it is characterized in that, may further comprise the steps: join alkenyl monomer, oxyethane, propylene oxide in the polymerization reactor respectively, add the reaction of initiator and polymerizing catalyst, reaction conditions: temperature of reaction is 100~150 ℃, reaction pressure is 0.1~2Mpa, and the reaction times is 1~5h; The polyreaction resultant obtains PH=7~8 with the potassium hydroxide aqueous solution neutralization, and mass percent concentration is 40~45% amphoteric ion polymeric alcohol for drilling fluid.
7, the preparation method of amphoteric ion polymeric alcohol for drilling fluid according to claim 6 is characterized in that, described initiator is glycerol, propylene glycol.
8, the preparation method of amphoteric ion polymeric alcohol for drilling fluid according to claim 6 is characterized in that, described polymerizing catalyst is benzoyl peroxide, lauroyl peroxide or ammonium persulphate.
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CN102618237B (en) * 2012-03-02 2013-11-20 西南石油大学 Polymer clay stabilizer containing Beta-cyclodextrin structure and synthesis method thereof
CN103539902B (en) * 2012-07-11 2017-05-03 中国石油化工股份有限公司 Preparation method of high temperature resistant contraction-expansion system for promoting stratum clay modification
CN103768991B (en) * 2012-10-25 2015-09-09 中国石油化工股份有限公司 Cloudy non-sulfosalt surfactant and preparation method thereof
CN104418984B (en) * 2013-09-04 2017-02-22 中国石油化工股份有限公司 High-temperature resistant clay stabilizer and preparation method thereof
CN104962256A (en) * 2015-06-17 2015-10-07 成都高普石油工程技术有限公司 Preparation process of positive-charged polyglycol anti-sloughing drilling fluid
CN108117639B (en) * 2016-11-30 2021-04-30 中国石油天然气股份有限公司 Unsaturated fatty alcohol polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN1142837A (en) * 1993-12-22 1997-02-12 施托克豪森公司 Graft copolymers of unsaturated monomers and polyhydroxy compounds, process for producing them and their use
CN1210752A (en) * 1997-07-18 1999-03-17 可泰克斯股份有限公司 Use of copolymer with surface-active structure as dispersing and/or crushing agent
CN1263140A (en) * 2000-03-02 2000-08-16 王斌 High-temp. high-pressure hypersalinity drilling fluid rheological property stabilizing agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1142837A (en) * 1993-12-22 1997-02-12 施托克豪森公司 Graft copolymers of unsaturated monomers and polyhydroxy compounds, process for producing them and their use
CN1210752A (en) * 1997-07-18 1999-03-17 可泰克斯股份有限公司 Use of copolymer with surface-active structure as dispersing and/or crushing agent
CN1263140A (en) * 2000-03-02 2000-08-16 王斌 High-temp. high-pressure hypersalinity drilling fluid rheological property stabilizing agent

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