CN105859934A - Preparation method of solid lubricant high-polymer spheres for drilling fluids - Google Patents
Preparation method of solid lubricant high-polymer spheres for drilling fluids Download PDFInfo
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- CN105859934A CN105859934A CN201610214080.XA CN201610214080A CN105859934A CN 105859934 A CN105859934 A CN 105859934A CN 201610214080 A CN201610214080 A CN 201610214080A CN 105859934 A CN105859934 A CN 105859934A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/34—Lubricant additives
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Abstract
The invention discloses a preparation method of solid lubricant high-polymer spheres for drilling fluids. According to the lubricating mechanism of the oilfield drilling fluid lubricant, a suspension polymerization technique is utilized to synthesize the novel drilling fluid solid lubricant. The white spherical crosslinking copolymer spherical resin is prepared from styrene and divinylbenzene used as main materials doped with other auxiliary monomers. The suspension polymerization technique is utilized to effectively control the particle size distribution of the required spheres; the high-temperature-resistance monomers are subjected to mixed polymerization, so that the strength and temperature resistance of the spheres are obviously enhanced, thereby avoiding the degradation of the lubricating property in order to prevent the spheres from breaking, softening and melting under high temperature conditions in the oil well; and thus, the drilling fluid has reasonable drilling fluid type and favorable conventional properties, and also has favorable lubricating and anti-sticking properties.
Description
Technical field
The present invention relates to relate to macromolecule resin material, a kind of kollag in drilling fluid
The preparation method of macromolecule spheroid.
Background technology
At present, the prolongation along with the development time of the domestic and international oil field and the increase of yield, development difficulty the most more comes
The biggest, thus many special wells (such as deep-well, ultradeep well, directional well, horizontal well and Multilateral Wells etc.)
It is used widely.And property of drilling fluid is had higher requirement by these special wells, at Directional Drilling
In well, the probability that differential sticking occurs is bigger.To this end, require drilling fluid to remove should possess rational drilling fluid class
Outside the traditional performance of type and high-quality, it is necessary to possessing good lubrication anti-sticking performance, it directly affects and orients
Can drilling well successfully be carried out.In recent years, the water-base drilling fluid of high-quality in extended reach well, long horizontal well,
Lubricity is the key of high-quality water-base drilling fluid, especially carries lubrication antifriction, the high temperature resistant property of drilling fluid
Go out higher requirement.
Typical well liquid lubricant is generally liquid, on-the-spot transport and use inconvenience, and heat-resisting property is poor simultaneously,
So developing novel lubricant for drilling fluid there is important practical usage.Kollag macromolecule resin spheroid
Be a kind of effective anti-card material, in directional well is constructed, be widely used this lubricant, have easy to use,
Greasy property is good and the advantage such as high temperature resistance.Improve the performance of kollag macromolecule resin spheroid, to formation
The free of contamination water-base drilling fluid of high-quality is significant.
In on-the-spot application, although the spherical lubricant of solid achieves well lubrication anti-sticking effect, but there is also
Following shortcoming.
1. play the predominantly big particle diameter solid ball of lubrication anti-sticking effect, but account for the solid of more than 50% small particle
Ball does not simply fails to play lubrication anti-sticking effect, and adds the content of useless solid phase, MWD in drilling fluid
The piston of pulse generator, piston bush are easily stuck by solid phase particles, cause instrument no signal, are forced to pull out of hole
Maintenance, has not only damaged instrument, and has added the number of times that makes a trip, caused fruitless labour and economic loss.
Therefore the component of small particle should be reduced or eliminated.
2. the small particle part in baton round is more than 50%, can sieve and substantial amounts of running pulp occur by blocking vibration,
Cause the loss of drilling fluid.
3. owing to the bottom hole temperature (BHT) of most wells is higher than 200 DEG C, so more segmenting temperature, high temperature is soft
After change, the friction factor of drilling fluid has and reduces by a small margin.Therefore heat resistance, the bearing capacity to solid globules
(crushing force) proposes higher requirement.
Summary of the invention
It is an object of the invention to provide the system of a kind of kollag macromolecule spheroid in drilling fluid
Preparation Method, mainly solves the technical problem existing for above-mentioned prior art, and the present invention utilizes suspension to be polymerized work
Skill has synthesized a kind of novel drilling fluid kollag；By special polymerization technique and dispersion, energy
The required spheroid particle size distribution of effective control, the monomer mixed polymerization high by adding temperature tolerance, make spheroid strong
Degree and temperature tolerance are significantly improved, adapt to hot conditions lower sphere in oil well do not soften, melted and
Greasy property is made to reduce.
To achieve these goals, the technical solution adopted in the present invention is:
A kind of preparation method of the kollag macromolecule spheroid in drilling fluid, it is characterised in that: join
System based on styrene, add account for the divinylbenzene of its weight ratio 6%～10% and weight ratio be 0.4%～
The benzoyl peroxide of 0.8%, is sufficiently stirred for making benzoyl peroxide be completely dissolved；Prepare in a kettle.
In the deionized water solution suitable with monomer molar ratio 1:1～1.25 concentration, add in advance and account for aqueous phase weight
Ratio 0.6～the dispersant of 6.8%；Then under conditions of continuous stirring, the monomer solution that will have configured is logical
Cross and be added drop-wise in still, drip complete later continuation and stir 100-140min；Then heat up under stirring
To 60 DEG C, react 1.5～2 hours, after heat to be polymerized, be progressively warmed up to 95 DEG C, be incubated 2.5～4
Hour, cool to room temperature；The Archon obtained is dehydrated after cyclic washing again, dries and sieves, it is thus achieved that grain
Footpath > the white spherical copolymer sphere resin of 0.315mm.
The preparation method of the described kollag macromolecule spheroid in drilling fluid, it is characterised in that:
Described dispersant is animal gelatin, polyvinyl alcohol or hydroxyethyl cellulose.
The preparation method of the described kollag macromolecule spheroid in drilling fluid, it is characterised in that:
By prepared particle diameter < the once polymerization bead of 0.315mm, sub-sieve remove <bead of below 0.06mm,
Dry at a temperature of not higher than 105 DEG C；Preparation styrene is main body, adds and accounts for its weight ratio 2%～6%
Divinylbenzene and benzoyl peroxide that weight ratio is 0.4%～0.8%；Or add and account for its weight ratio
0.5%～2% there is the monomer that temperature tolerance is high；It is sufficiently stirred for making BPO be completely dissolved；In a kettle.
Preparation and 10%～the saturated common salt aqueous solution of monomer molar ratio 1:1～1.25；It is dried Archon to add,
And under conditions of continuous stirring by the monomer solution configured by being added drop-wise in still, monomer absorption ratio is
95%～100%, by polyreaction, obtain particle diameter respectively > the white spherical copolymer spheroid of 0.315mm
Shape resin.
A kind of preparation method of the kollag macromolecule spheroid in drilling fluid, it is characterised in that: join
System, based on styrene, adds the divinylbenzene accounting for its weight ratio 6%～8%, adds and account for its weight ratio
0.5%～2% there is the high monomer of temperature tolerance and benzoyl peroxide that weight ratio is 0.4%～0.8%；
Wherein: the described high monomer of temperature tolerance that has is phenyltriethoxysilane or dimethyl diethoxy silicon
Alkane or methltriethoxysilone or 1.3 piperazine-2-ketone；It is sufficiently stirred for making benzoyl peroxide the most molten
Solve；In the deionized water solution that preparation is suitable with monomer molar ratio 1:1～1.25 concentration in a kettle.,
Add in advance and account for aqueous phase weight ratio 0.6～the dispersant of 6.8%；Then, under conditions of continuous stirring, will join
The monomer solution put, by being added drop-wise in still, drips complete later continuation and stirs 100-140min；So
After under stirring, be warmed up to 60 DEG C, react 1.5～2 hours, after heat to be polymerized, be progressively warmed up to
95 DEG C, it is incubated 2.5～4 hours, cools to room temperature；The Archon obtained is dehydrated after cyclic washing again,
Dry and screening, it is thus achieved that particle diameter the white spherical copolymer sphere resin of 0.315mm.
The preparation method of the described kollag macromolecule spheroid in drilling fluid, it is characterised in that:
Described dispersant is animal gelatin, polyvinyl alcohol or hydroxyethyl cellulose.
The preparation method of the described kollag macromolecule spheroid in drilling fluid, it is characterised in that:
By prepared particle diameter < the once polymerization bead of 0.315mm, sub-sieve remove <bead of below 0.06mm,
Dry at a temperature of not higher than 105 DEG C；Preparation styrene is main body, adds and accounts for its weight ratio 2%～6%
Divinylbenzene and benzoyl peroxide that weight ratio is 0.4%～0.8%；Or add and account for its weight ratio
0.5%～2% there is the monomer that temperature tolerance is high；It is sufficiently stirred for making BPO be completely dissolved；In a kettle.
Preparation and 10%～the saturated common salt aqueous solution of monomer molar ratio 1:1～1.25；It is dried Archon to add,
And under conditions of continuous stirring by the monomer solution configured by being added drop-wise in still, monomer absorption ratio is
95%～100%, by polyreaction, obtain particle diameter respectively > the white spherical copolymer spheroid of 0.315mm
Shape resin.
Present invention have the advantage that
1, process for suspension polymerization is used to synthesize white spherical copolymer sphere resin, to improve oilwell drilling
The lubrication of liquid, antifriction performance, can effectively control required spheroid particle size distribution simultaneously.
2, in building-up process, introduce the high monomer of temperature tolerance participate in polyreaction, the gained spherical copolymerization of white
Thing sphere resin, to improve at oil well the lubrication antifriction of drilling fluid, spheroid degree, heat resistance, with
Time can effectively control required spheroid particle size distribution.
3, process for suspension polymerization use after polymerization technique synthesize white spherical copolymer sphere resin,
Fine-grained resin can be effectively reduced produce, make spheroid particle size distribution within rational claimed range.
Detailed description of the invention
Illustrate the present invention by example below, but be not limitation of the invention.
Embodiment 1
By 94 kilograms of styrene (St) monomers add 6 kilograms of divinylbenzenes (DVB), add monomer
Weight ratio is 0.4% initiator benzoyl peroxide (BPO), mix homogeneously；Put into molten in a kettle.
The poly-vinyl alcohol solution solved accounts for aqueous phase weight ratio 1%, stirs；Then by monomer under stirring
Put into reactor, aqueous phase and monomer molar ratio 1:0.8；60 DEG C it are warmed up to, 60 DEG C of insulations under stirring
About 1.5 hours；After being warmed up to 3 hours heat to be polymerized of 80 DEG C of reactions, progressively it is warmed up to 90 DEG C of reactions 1 little
Time, 98 DEG C of aging reactions 3 hours, boiling water washs, drains, and dries, sieve at 105 DEG C > 0.315mm
The spherical copolymer sphere resin of white.
Embodiment 2
90 kilograms of styrene (St) monomers will add 10 kilograms of divinylbenzenes (DVB), add list
Body weight ratio is 0.4% initiator benzoyl peroxide (BPO), mix homogeneously；Put in a kettle.
The poly-vinyl alcohol solution dissolved accounts for aqueous phase weight ratio 1%, stirs；Then will be single under stirring
Body puts into reactor, aqueous phase and monomer molar ratio 1:0.8；60 DEG C it are warmed up to, 60 DEG C of guarantors under stirring
Temperature about 1.5 hours；After being warmed up to 3 hours heat to be polymerized of 80 DEG C of reactions, progressively it is warmed up to 90 DEG C of reactions 1
Hour, 98 DEG C of aging reactions 3 hours, boiling water washs, drains, and dries, sieve at 105 DEG C
> the 0.315mm spherical copolymer sphere resin of white.
Embodiment 3
90 kilograms of styrene (St) monomers will add 6 kilograms of divinylbenzenes (DVB), 4 kilogram of one benzene
Ethyl triethoxy silicane alkane, adding monomer weight ratio is 0.4% initiator benzoyl peroxide (BPO),
Mix homogeneously；Putting into the poly-vinyl alcohol solution dissolved in a kettle. and account for aqueous phase weight ratio 1%, stirring is all
Even；Then under stirring, monomer is put into reactor, aqueous phase and monomer molar ratio 1:0.8；At stirring shape
Being warmed up to 60 DEG C under state, 60 DEG C are incubated about 1.5 hours；After being warmed up to 3 hours heat to be polymerized of 80 DEG C of reactions,
Progressively being warmed up to 90 DEG C react 1 hour, 98 DEG C of aging reactions 3 hours, boiling water washs, drains, 105
Dry at DEG C, sieve the 0.315mm spherical copolymer sphere resin of white.
Embodiment 4
85 kilograms of styrene (St) monomers will add 10 kilograms of divinylbenzenes (DVB), 4 kilograms of diformazans
Ethyl triethoxy silicane alkane.Adding monomer weight ratio is 0.4% initiator；Benzoyl peroxide (BPO),
Mix homogeneously；Putting into the poly-vinyl alcohol solution dissolved in a kettle. and account for aqueous phase weight ratio 1%, stirring is all
Even, then under stirring, monomer is put into reactor, aqueous phase and monomer molar ratio 1:0.8；At stirring shape
Being warmed up to 60 DEG C under state, 60 DEG C are incubated about 1.5 hours, after being warmed up to 3 hours heat to be polymerized of 80 DEG C of reactions,
Progressively being warmed up to 90 DEG C react 1 hour, 98 DEG C of aging reactions 3 hours, boiling water washs, drains 105
Dry at DEG C, sieve the 0.315mm spherical copolymer sphere resin of white.
Embodiment 5
It is 1,2,3,4 embodiment techniques are produced particle diameter < the once polymerization bead of 0.315mm,
Sub-sieve removes <bead of below 0.06mm, drying at a temperature of not higher than 105 DEG C respectively.By 50 kilograms
Styrene (St) monomer adds 3 kilograms of divinylbenzenes (DVB).Adding monomer weight ratio is 0.4%
Initiator；Benzoyl peroxide (BPO), or add account for its weight ratio 0.5%～2% there is heatproof
The monomer that property is high, such as: phenyltriethoxysilane or dimethyldiethoxysilane or monomethyl three ethoxy
Base silane or 1.3 piperazine-2-ketone, mix homogeneously；Preparation is dense with monomer molar ratio 1:1～1.25 in a kettle.
Spend suitable saline solution (10%～saturated) solution.Will < 0.315mm (sub-sieve removing <below 0.06mm
Bead) following bead 50 kilograms puts in reactor, and under conditions of continuous stirring, will join
The monomer solution put is by being added drop-wise in still, and monomer absorption ratio is 95%～100%, respectively according to 1,2,
3, the process conditions polyreaction of 4 embodiment technique items, it is thus achieved that particle diameter > white of 0.315mm is spherical common
Polymers sphere resin.
Embodiment combination property table
It is only presently preferred embodiments of the present invention in sum, is not used for limiting the enforcement model of the present invention
Enclose.The most all equivalence changes made according to the content of scope of the present invention patent and modification, all should be the present invention
Technology category.
Claims (6)
1. the preparation method of the kollag macromolecule spheroid in drilling fluid, it is characterised in that:
Preparation, based on styrene, adds and accounts for the divinylbenzene of its weight ratio 6%～10% and weight ratio is 0.4
The benzoyl peroxide of %～0.8%, is sufficiently stirred for making benzoyl peroxide be completely dissolved；In a kettle.
Prepare in the deionized water solution suitable with monomer molar ratio 1:1～1.25 concentration, add in advance and account for aqueous phase
Weight ratio 0.6～the dispersant of 6.8%；Then under conditions of continuous stirring, the monomer solution that will have configured,
By being added drop-wise in still, drip complete later continuation and stir 100-140min；Then rise under stirring
Temperature, to 60 DEG C, is reacted 1.5～2 hours, after heat to be polymerized, is progressively warmed up to 95 DEG C, is incubated 2.5～4
Hour, cool to room temperature；The Archon obtained is dehydrated after cyclic washing again, dries and sieves, it is thus achieved that
Particle diameter > the white spherical copolymer sphere resin of 0.315mm.
The preparation of the kollag macromolecule spheroid in drilling fluid the most according to claim 1
Method, it is characterised in that: described dispersant is animal gelatin, polyvinyl alcohol or hydroxyethyl cellulose.
Kollag macromolecule spheroid in drilling fluid the most according to claim 1 and 2
Preparation method, it is characterised in that: by prepared particle diameter, < the once polymerization bead of 0.315mm, sub-sieve removes
Go <bead of below 0.06mm, drying at a temperature of not higher than 105 DEG C；Preparation styrene is main body,
Add and account for the divinylbenzene of its weight ratio 2%～6% and benzoyl peroxide first that weight ratio is 0.4%～0.8%
Acyl；Or add account for its weight ratio 0.5%～2% there is the monomer that temperature tolerance is high；It is sufficiently stirred for making BPO
It is completely dissolved；Preparation is water-soluble with the 10% of monomer molar ratio 1:1～1.25～saturated Sal in a kettle.
Liquid；It is dried Archon to add, and passes through to drip by the monomer solution configured under conditions of continuous stirring
Being added in still, monomer absorption ratio is 95%～100%, by polyreaction, obtains particle diameter respectively > 0.315mm
White spherical copolymer sphere resin.
4. the preparation method of the kollag macromolecule spheroid in drilling fluid, it is characterised in that:
Preparation, based on styrene, adds and accounts for the divinylbenzene of its weight ratio 6%～8%, adds that to account for it heavy
Amount has the high monomer of temperature tolerance and benzoyl peroxide first that weight ratio is 0.4%～0.8% than 0.5%～2%
Acyl；Wherein: the described high monomer of temperature tolerance that has is phenyltriethoxysilane or dimethyl diethyl
TMOS or methltriethoxysilone or 1.3 piperazine-2-ketone；It is sufficiently stirred for making benzoyl peroxide
It is completely dissolved；Prepare the deionized water solution suitable with monomer molar ratio 1:1～1.25 concentration in a kettle.
In, add in advance and account for aqueous phase weight ratio 0.6～the dispersant of 6.8%；Then under conditions of continuous stirring,
The monomer solution that will have configured, by being added drop-wise in still, drips complete later continuation and stirs 100-140min；
Then under stirring, it is warmed up to 60 DEG C, reacts 1.5～2 hours, after heat to be polymerized, progressively heat up
To 95 DEG C, it is incubated 2.5～4 hours, cools to room temperature；The Archon obtained is dehydrated after cyclic washing again,
Dry and screening, it is thus achieved that particle diameter the white spherical copolymer sphere resin of 0.315mm.
The preparation of the kollag macromolecule spheroid in drilling fluid the most according to claim 4
Method, it is characterised in that: described dispersant is animal gelatin, polyvinyl alcohol or hydroxyethyl cellulose.
6. according to the kollag macromolecule spheroid in drilling fluid described in claim 4 or 5
Preparation method, it is characterised in that: by prepared particle diameter, < the once polymerization bead of 0.315mm, sub-sieve removes
Go <bead of below 0.06mm, drying at a temperature of not higher than 105 DEG C；Preparation styrene is main body,
Add and account for the divinylbenzene of its weight ratio 2%～6% and benzoyl peroxide first that weight ratio is 0.4%～0.8%
Acyl；Or add account for its weight ratio 0.5%～2% there is the monomer that temperature tolerance is high；It is sufficiently stirred for making BPO
It is completely dissolved；Preparation is water-soluble with the 10% of monomer molar ratio 1:1～1.25～saturated Sal in a kettle.
Liquid；It is dried Archon to add, and passes through to drip by the monomer solution configured under conditions of continuous stirring
Being added in still, monomer absorption ratio is 95%～100%, by polyreaction, obtains particle diameter respectively > 0.315mm
White spherical copolymer sphere resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108559028A (en) * | 2018-05-14 | 2018-09-21 | 苏州知益微球科技有限公司 | A kind of preparation method of the carboxyl magnetic microsphere of size tunable |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108559028A (en) * | 2018-05-14 | 2018-09-21 | 苏州知益微球科技有限公司 | A kind of preparation method of the carboxyl magnetic microsphere of size tunable |
| CN108559028B (en) * | 2018-05-14 | 2020-08-11 | 苏州知益微球科技有限公司 | Preparation method of carboxyl magnetic microspheres with controllable particle size |
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