CN105086960B - A kind of drilling fluid and preparation method and application - Google Patents
A kind of drilling fluid and preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of drilling fluid and preparation method and application, the drilling fluid includes water, amphion modified starch, anhydrous calcium chloride, native phase, flow pattern regulator, wherein, on the basis of the weight of water, amphoteric ion polymer consumption is 0.5 5wt% of water consumption, anhydrous calcium chloride consumption is 20 70wt% of water consumption, and native phase consumption is 0 6wt% of water consumption, and flow pattern regulator consumption is 0.1 0.4wt% of water consumption.The present invention also provides a kind of water-based drilling liquid and preparation method thereof and application.Drilling fluid of the present invention makes drilling fluid have excellent rheological property, vena caval filter performance, rejection, sealing characteristics, greasy property by the synergy of calcium chloride and amphoteric ion polymer.
Description
Technical field
The present invention relates to the drilling fluid used in Process of Oil Well Drilling, the more particularly to brill containing amphoteric ion copolymer
Well liquid.
Background technology
For shale gas stratum cranny development, water sensitivity is strong, easily occur leakage, collapse, undergauge the features such as, in drilling process
The middle most important thing for solving the problems such as wellbore stability, drop resistance antifriction just as drilling fluid selection.Current country's shale gas horizontal well
Mainly oil base drilling fluid is used, but the high cost of oil base drilling fluid, high pollution are its natural flaws in drilling process.Water-base drilling fluid
If can suppressing, block, lubricate, taking and have breakthrough in terms of rock sand removal, it is very huge in the application prospect of shale gas horizontal well
Greatly.At present, the water-base drilling fluid with larger application potential has glucose glycoside drilling fluid, polyamine class drilling fluid, polymerization
Alcohol drilling fluid, drilling workers and silicate drilling fluid etc..These drilling fluid systems also need to continue on the basis of existing
In-depth research, develops supporting inorganic agent, the need for meeting shale gas development of resources, and can make drilling fluid system towards green
The direction of environmental protection is developed.
Chinese patent CN103146364A describes a kind of high inhibition water-base drilling fluid, and it includes water, polyamine inhibitor, bag
It is suppressed agent, hydrate inhibitor, tackifier, fluid loss additive and fluid lubricant.Drilling fluid is with can effectively suppressing deep water superficial part
Layer borehole well instability, its inhibition is suitable with oil base drilling fluid.Shale rolling rate of recovery is not higher than 95%.Drilling fluid can solve deep water
In drilling well in the generation problem of hydrate, the drillng operation for being applicable to the 3000m depth of waters.Chinese patent CN102250595A is public
The drilling fluid for strong retraction activated clay stratum has been opened, it is fine by bentonite, partially hydrolyzed polyacrylamide (PHPA), low adhesive aggregation anion
Tie up element, co-polymer of sulfonate tackifier, potassium chloride, polymeric alcohol, amine based polymer, fatty alcohol ether phosphate, water composition, the drilling well
Liquid rejection and greasy property are close to oil base drilling fluid.Chinese patent CN103013470A discloses a kind of for ultra-deep side
Drilling well mud stone high inhibition drilling fluid system, by bentonite slurry, alkaline conditioner, shale control agent, metal ion polymer, lignite
Resin, sulfonated phenol formaldehyde resin, cationic emulsified bitumen, lubricant, emulsifying agent, crude oil and calcium carbonate superfine powder, the drilling fluid
System is to mud shale strong inhibition capability, and shale recovery ratio is up to 90.33%, and high temperature resistance is up to 150 DEG C；The coefficient of friction resistance is distinguished before and after aging
Less than 0.1.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of drilling fluid and preparation method and application.Drilling well of the present invention
The synergy that liquid passes through calcium chloride and amphoteric ion polymer so that drilling fluid has excellent rheological property, vena caval filter
Performance, rejection, sealing characteristics, greasy property etc..
The present invention provides a kind of water-base drilling fluid, and the drilling fluid includes water, amphion modified starch, anhydrous chlorination
Calcium, native phase, flow pattern regulator, wherein, on the basis of the weight of water, amphion modified starch consumption is the 0.5- of water consumption
5wt%, preferably 1.5-3wt%；Anhydrous calcium chloride consumption is the 20-70wt%, preferably 30-60wt% of water consumption；Native phase consumption is
The 0-6wt% of water consumption, preferably 1.5-4wt%, flow pattern regulator consumption are the 0.1-0.4wt%, preferably 0.2- of water consumption
0.3wt%, the amphion modified starch is N, N- dimethyl-allyls propane sulfonic acid salt/acrylamide/starch ternary polymerization
Thing.
In water-base drilling fluid of the present invention, the soil is mutually in sodium bentonite, calcium-base bentonite, attapulgite, sepiolite
One or more.
In water-base drilling fluid of the present invention, the flow pattern regulator is one kind or several in xanthans, guar gum, welan gum
Kind.
In water-base drilling fluid of the present invention, can also include heavy weight additive, the heavy weight additive be barite, lime stone, bloodstone,
One or more in wustite, iron oxide, magnesium carbonate, can determine addition according to the requirement of drilling fluid density.
In water-base drilling fluid of the present invention, shale control agent can also be included, the shale control agent consumption is water consumption
0.1-2wt%, preferably 1-2wt%.The shale control agent can be with potassium chloride, potassium sulfate, potassium nitrate, ammonium chloride, ammonium sulfate, nitre
One or more in sour ammonium, polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol block polymer.
Amphion modified starch of the present invention is N, N- dimethyl-allyls propane sulfonic acid salt/acrylamide/starch three
Membered copolymer, it is as follows that preparation method includes step：
（1）It is 2 to weigh mass ratio respectively first:1~9:In 1 dimethylaminoethyl methacrylate and 1,3-N-morpholinopropanesulfonic acid
Ester, and PS is added into dimethylaminoethyl methacrylate, then reacted at a temperature of 10~60 DEG C
0.5~4h, eventually passes filter, extracting, dries obtained methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate；
（2）According to（7~2）：（4~1）：（2~6）Mass ratio weigh step respectively（1）In obtained methacryl
Oxygen ethyl-N, N- dimethyl propylene sulfonate, acrylamide, starch；
（3）By step（2）The starch weighed adds water in stirring 20~50min at 60~80 DEG C, obtains gelatinized starch, then
It is passed through N2Initiator is added after 15~60min of reaction；
（4）By step（2）The acrylamide and methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate weighed is used
After solvent dissolving, it is added to through step（3）In starch after processing, 4~6h is reacted at 60~80 DEG C, glue is obtained after reaction
Solid, is cleaned with acetone and obtains white precipitate；
（5）By step（4）Obtained white precipitate is dried after 16~24h at 50~80 DEG C and crushed, and obtains amphion
Modified starch.
In amphion modified starch preparation method of the present invention, step（1）Middle dimethylaminoethyl methacrylate and 1,
The mass ratio of 3-N-morpholinopropanesulfonic acid lactone is 2.5:1~8:1.
In amphion modified starch preparation method of the present invention, step（1）Middle PS is added drop-wise to methyl-prop
In olefin(e) acid dimethylaminoethyl or directly disposably it is added in dimethylaminoethyl methacrylate, preferably the side of being directly added into
Formula.Use the dimethylaminoethyl methacrylate weighed during directly disposable add and PS mass ratio for
5.2:1~7.8:1.Dimethylaminoethyl methacrylate and PS mass ratio is 2.5 when using dropwise addition mode:
1~5:1, PS can be heated and melted before dropwise addition.
In amphion modified starch preparation method of the present invention, step（1）Reaction condition be in 20~55 DEG C of temperature
1~3h of lower reaction.
In amphion modified starch preparation method of the present invention, step（1）Middle extraction solvent selects methanol or ethanol, preferably
Ethanol, extraction times are 1~3h.The drying is that 10~20h is dried under the conditions of 30~50 DEG C.
In amphion modified starch preparation method of the present invention, step（2）Described in starch be green starch, para arrowroot
Powder, sweet potato starch, starch from sweet potato, farina, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch, one kind in cornstarch or several
Plant, preferably cornstarch or farina.
In amphion modified starch preparation method of the present invention, step（3）The middle initiator used is potassium peroxydisulfate, over cure
It is any in sour sodium, ammonium persulfate；The initiator amount accounts for the 0.5~1.5% of monomer and starch gross mass.
In amphion modified starch preparation method of the present invention, step（4）Described in solvent be deionized water or salt solution,
It is that the NaCl concentration added in 15%~30%, the salt solution is 0~1.0mol/ to add monomer and starch total mass concentration after solvent
L。
Water-base drilling fluid of the present invention is prepared via a method which, is first according to ratio and is weighed water, amphion respectively
Modified starch, anhydrous calcium chloride, native phase, flow pattern regulator, then add native phase into water, abundant aquation or it is scattered after, add
Flow pattern regulator, high-speed stirred makes it add anhydrous calcium chloride after fully dissolving, and adds temperature after anhydrous calcium chloride and rises, waits to drop
Amphion modified starch is added after to room temperature, 24~48h of maintenance is stood after high-speed stirred is scattered, drilling fluid is obtained.
, can be with now with the current in drilling process the present invention relates to a kind of application of water-base drilling fluid in drilling process.
Compared with prior art, drilling fluid of the present invention has the following advantages that：
（1）CaCl in water-base drilling fluid of the present invention2Played the role of a nucleus with amphion modified starch, its synergy is played
Multifunctional effect, including rheological property, vena caval filter, rejection, greasy property etc..Wherein amphion modified starch is viscous
Degree is with CaCl2The increase of content and gradually increase, embody obvious thickening and carry and cuts effect；Due to high content CaCl2Presence, screen
The internal salt structure in amphion modified starch structure is covered so that contained sulfonic group and ammonium fully expose, has further made
For native phase, the filtrate reducing ability of system is enhanced；High content CaCl2Itself it is respectively provided with amphion modified starch stronger
Rejection, their collaboration make it that the inhibition of system is stronger；The greasy property of system has met or exceeded oil base brill
The level of well liquid；The overall excellent properties of the above are that current water-base drilling fluid is short of.
（2）PS is added to excessive metering system by amphion modified starch synthetic method of the present invention
In sour dimethylaminoethyl, excessive dimethylaminoethyl methacrylate acts not only as raw material and participates in reaction, and
Solvent can be played a part of, it is to avoid the use of poisonous acetone is solvent in conventional method, is a kind of green synthetic method.
（3）Amphion modified starch synthetic method of the present invention is by controlling PS and methacrylic acid two
The quality of methylamino when feeding mode, solves PS and dimethylaminoethyl conventionally
When directly being reacted（Generally equimolar is than reaction）, it is impossible to the problem of obtaining monomer DMAPS.
（4）Amphion modified starch prepared by the inventive method belongs to interior salt form amphoteric ion polymer, with tradition two
Property polymer except that its in fresh water intermolecular electrostatic attraction act on, show as strand and curl.And it is high in high salt
In calcium solution, due to the presence of small molecule salt, intermolecular association is shielded, is converted into intermolecular electrostatic attraction quiet
Electric repulsion so that strand is more unfolded.Obvious " anti-polyelectrolyte " effect that it is shown resists the salt resistance of polymer
Calcium performance gradually strengthens with the increase of salt amount.Can anti-NaCl saturations, anti-CaCl2Up to more than 20%.This is current modified starch
The anti-calcium and anti-salt performance that amphoteric ion polymer does not possess.
Embodiment
The effect and effect of the inventive method are illustrated with reference to embodiment, but following examples are not constituted to this
The limitation of scheme of the invention.
Embodiment 1
Methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is prepared first（DMAPS）
Weigh 630gDM to be put into reactor, be then placed in thermostat water bath, heat and start stirring.Weigh again
122gPS, is added directly into DM, and reaction temperature is 35 DEG C, and DMAPS crude product is obtained after stirring reaction 1.5h.By DMAPS
Crude product is transferred in large stretch of filter paper and wrapped, and is positioned in Soxhlet extraction device, the use of ethanol is solvent extraction 1h, and extracting is finished
Filter paper bag is placed in drying box afterwards, is dried at 40 DEG C, finally gives pure DMAPS monomers, yield is 92.8%,（Yield
For the ratio for actually obtaining the quality of product Yu stoichiometrically reacting obtained theoretical product quality）.
Comparative example 1（Directly react）
According to stoichiometric proportion DM：PS is 1:1 reaction.Weigh 157gDM to pour into reactor, be then placed in water bath with thermostatic control
In pot, heat and start stirring.122gPS is weighed again, is added directly into DM, and reaction temperature is 20 DEG C, after stirring reaction 0.5h
Mass polymerization product is obtained, without DMAPS monomers, yield is 0.During according to stoichiometric reaction, produce substantial amounts of in reaction
Heat can not disperse in time, and temperature moment steeply rises, and cause raw material DM and product DMAPS all to polymerize.
Comparative example 2（Conventional method, using acetone as solvent reaction）
Weigh 170gDM to pour into reactor, be then placed in thermostat water bath, heat and start stirring.Weigh again
122gPS is dissolved in 1170g acetone, and mixed solution is added directly into DM, and reaction temperature is 60 DEG C, obtains after stirring reaction 4h
DMAPS crude product.DMAPS crude products are transferred in large stretch of filter paper and wrapped, are positioned in Soxhlet extraction device, ethanol is used
For solvent extraction 2h, filter paper bag is placed in drying box by extracting after finishing, and is dried at 35 DEG C, is finally given pure DMAPS
Monomer, yield is 82.4%.
Embodiment 2
Weigh 100g starch and add deionized water in 60 DEG C of gelatinization 30min, be passed through N2 5g potassium peroxydisulfates are added after 30min,
Weigh after 100g AM, 170g DMAPS add deionized water dissolving and be transferred in gelatinized starch reactor respectively, monomer gross mass
Concentration is 25%, obtains colloidal solid after reaction 5h, is cleaned with acetone and obtain white depositions.White depositions are done at 70 DEG C
Final products are crushed to obtain after dry 12h.
Embodiment 3
Weigh 100g starch and add deionized water in 60 DEG C of 30 min of gelatinization, be passed through N2 3g potassium peroxydisulfates are added after 30min,
Weigh after 80g AM, 150g DMAPS add deionized water dissolving and be transferred in gelatinized starch reactor respectively, monomer gross mass
Concentration is 20%, obtains colloidal solid after reaction 6h, is cleaned with acetone and obtain white depositions.White depositions are done at 70 DEG C
Final products are crushed to obtain after dry 12h.
Embodiment 4
350ml running water is weighed first, adds and 1.2g xanthans is added after 6g attapulgites, high-speed stirred 10min, is continued
High-speed stirred 10min, stands maintenance 2h；Add the anhydrous CaCl of 140g2, stand after high-speed stirred 10min and be cooled to room temperature；Add
Polymer prepared by 7g embodiments 2, high-speed stirred 10min stands maintenance 24h, obtains drilling fluid system.
Embodiment 5
350ml running water is weighed first, adds and 1.3g welan gums are added after 9.5g calcium-base bentonites, high-speed stirred 10min,
Continue high-speed stirred 10min, stand maintenance 2h；Add the anhydrous CaCl of 210g2, stand after high-speed stirred 10min and be cooled to room temperature；
Polymer prepared by 10g embodiments 3 is added, high-speed stirred 10min stands maintenance 36h, obtains drilling fluid system.
Embodiment 6
Same as Example 4, difference is that drilling fluid is free of calcium chloride.
Embodiment 7
Same as Example 4, difference is the 2wt% that calcium chloride consumption is water consumption in drilling fluid.
Embodiment 8
Same as Example 4, difference is the 5wt% that calcium chloride consumption is water consumption in drilling fluid.
Embodiment 9
Same as Example 4, difference is the 10wt% that calcium chloride consumption is water consumption in drilling fluid.
Embodiment 10
Same as Example 4, difference is the 25wt% that calcium chloride consumption is water consumption in drilling fluid.
Testing performance of drilling fluid：
Testing performance of drilling fluid includes rheological property, vena caval filter, rejection, the test of greasy property.Test result
It is shown in Table 1~table 4.Wherein, rheological property is measured using the fast rotation viscometer of ZNN-D6 types six, passes through obtained φ 600, φ
300th, φ 6, the data of φ 3 calculate and obtain each rheological parameter；Filter loss is committed a breach of etiquette using the multi-joint middle press filtration of SD-6A types filters with HTHP
Commit a breach of etiquette and be measured, testing time 30min；Rejection is that shale rolls recovery test, and method is：By the shale of certain mass
Add in drilling fluid, aging 16h is rolled at 120 DEG C, take out and reclaimed with 0.42mm standard screens, calculate primary recovery.Reclaim
Shale afterwards is positioned in clear water the rolling aging 2h at 120 DEG C, takes out and is reclaimed with 0.42mm standard screens, calculates secondary recovery
Rate；Greasy property is measured using extreme boundary lubrication instrument EP-B and sticking coefficient analyzer NF-2.
The rheological property of table 1
The vena caval filter of table 2
The rejection of table 3
The greasy property of table 4
Claims (20)
1. a kind of water-base drilling fluid, it is characterised in that the drilling fluid include water, amphion modified starch, anhydrous calcium chloride,
Native phase, flow pattern regulator, wherein, on the basis of the weight of water, amphion modified starch consumption is the 0.5-5wt% of water consumption,
Anhydrous calcium chloride consumption is the 20-70wt% of water consumption, and native phase consumption is the 0-6wt% of water consumption, and flow pattern regulator consumption is water
The 0.1-0.4wt% of consumption, the amphion modified starch is methylacryoyloxyethyl-N, N- dimethyl propylene sulfonic acid
Salt/acrylamide/starch terpolymer.
2. according to the water-base drilling fluid described in claim 1, it is characterised in that：On the basis of the weight of water, amphion is modified
Starch consumption is the 1.5-3wt% of water consumption；Anhydrous calcium chloride consumption is the 30-60wt% of water consumption；Native phase consumption is water consumption
1.5-4wt%, flow pattern regulator consumption be water consumption 0.2-0.3wt%.
3. according to the water-base drilling fluid described in claim 1, it is characterised in that：The soil is mutually sodium bentonite, calcium base swelling
One or more in soil, attapulgite, sepiolite.
4. according to the water-base drilling fluid described in claim 1, it is characterised in that：The flow pattern regulator be xanthans, guar gum,
One or more in welan gum.
5. according to the water-base drilling fluid described in claim 1, it is characterised in that：The amphion modified starch by walking as follows
It is rapid to prepare：（1）It is 2 to weigh mass ratio respectively first:1~9:In 1 dimethylaminoethyl methacrylate and 1,3-N-morpholinopropanesulfonic acid
Ester, and PS is added into dimethylaminoethyl methacrylate, then reacted at a temperature of 10~60 DEG C
0.5~4h, eventually passes filter, extracting, dries obtained methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate；（2）Press
According to（7~2）：（4~1）：（2~6）Mass ratio weigh step respectively（1）In obtained methylacryoyloxyethyl-N, N-
Dimethyl propylene sulfonate, acrylamide, starch；（3）By step（2）The starch weighed add water at 60~80 DEG C stirring 20~
50min, obtains gelatinized starch, then passes to N2Initiator is added after 15~60min of reaction；（4）By step（2）The propylene weighed
After acid amides and methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate solvent dissolve, it is added to through step（3）Processing
In starch afterwards, 4~6h is reacted at 60~80 DEG C, colloidal solid is obtained after reaction, is cleaned with acetone and obtain white precipitate；
（5）By step（4）Obtained white precipitate is dried after 16~24h at 50~80 DEG C and crushed, and obtains amphion modified starch.
6. according to the water-base drilling fluid described in claim 5, it is characterised in that：Step（1）Middle dimethylaminoethyl second
The mass ratio of ester and PS is 2.5:1~8:1.
7. according to the water-base drilling fluid described in claim 5, it is characterised in that：Step（1）Middle PS is added drop-wise to
In dimethylaminoethyl methacrylate or directly disposably it is added in dimethylaminoethyl methacrylate.
8. according to the water-base drilling fluid described in claim 7, it is characterised in that：The methyl weighed during using directly disposable addition
Dimethylaminoethyl acrylate and PS mass ratio are 5.2:1~7.8:1.
9. according to the water-base drilling fluid described in claim 7, it is characterised in that：Using dimethylaminoethyl acrylate methyl ammonia during the mode of dropwise addition
Base ethyl ester and PS mass ratio are 2.5:1~5:1.
10. according to the water-base drilling fluid described in claim 5, it is characterised in that：Step（1）Described in extraction solvent select methanol
Or ethanol, extraction times are 1~3h.
11. according to the water-base drilling fluid described in claim 5, it is characterised in that：Step（2）Described in starch be green starch,
One in tapioca, sweet potato starch, starch from sweet potato, farina, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch
Plant or several, preferably cornstarch or farina.
12. according to the water-base drilling fluid described in claim 5, it is characterised in that：Step（3）Described in initiator be persulfuric acid
Any in potassium, sodium peroxydisulfate, ammonium persulfate, the initiator amount accounts for the 0.5~1.5% of monomer and starch gross mass.
13. according to the water-base drilling fluid described in claim 5, it is characterised in that：Step（4）Monomer and starch after middle addition solvent
Total concentration is 15%~30%.
14. as according to the water-base drilling fluid described in claim 5, it is characterised in that：Step（4）Described in solvent be deionized water
Or salt solution, the NaCl concentration added in the salt solution is 0~1.0mol/L.
15. according to the water-base drilling fluid described in claim 1, it is characterised in that：The drilling fluid includes shale control agent, described
Shale control agent consumption is the 0.1-2wt% of water consumption.
16. according to the water-base drilling fluid described in claim 15, it is characterised in that：The shale control agent consumption is water consumption
1-2wt%。
17. according to the water-base drilling fluid described in claim 15, it is characterised in that：The shale control agent is potassium chloride, sulfuric acid
In potassium, potassium nitrate, ammonium chloride, ammonium sulfate, ammonium nitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol block polymer
It is one or more of.
18. according to the water-base drilling fluid described in claim 1, it is characterised in that：The drilling fluid includes heavy weight additive, the exacerbation
Agent is barite, lime stone, bloodstone, wustite, iron oxide, and the one or more in magnesium carbonate can be according to drilling fluid density
Requirement determine addition.
19. application of the water-base drilling fluid described in any claim in drilling process in claim 1 to 18.
20. the preparation method of water-base drilling fluid described in any claim in claim 1 to 18, including following content, first
Water, amphion modified starch, anhydrous calcium chloride, native phase, flow pattern regulator are proportionally weighed respectively, are then added into water
Native phase, abundant aquation or it is scattered after, add flow pattern regulator, high-speed stirred makes it add anhydrous calcium chloride after fully dissolving, plus
Enter temperature after anhydrous calcium chloride to rise, amphion modified starch is added after room temperature is down to, stands and supports after high-speed stirred is scattered
24~48h is protected, drilling fluid is obtained.
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| CN111088001A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Oil-gas reservoir protection material and preparation method and application thereof |
| CN111088000A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Oil-gas layer protection material and its preparation method and application |
| CN111087983A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Oil-gas reservoir protection material and preparation method and application thereof |
| CN111088003A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Oil-gas layer protection material and preparation method and application thereof |
| CN111087982A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Oil-gas reservoir protection material and preparation method and application thereof |
| CN113073952B (en) * | 2021-03-31 | 2023-04-21 | 中国石油化工股份有限公司 | On-site treatment process of starch-based drilling fluid |
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| CN105086960A (en) | 2015-11-25 |
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