CN105885819A - Ultralow-density spherical silicon resin oil proppant and preparation method thereof - Google Patents
Ultralow-density spherical silicon resin oil proppant and preparation method thereof Download PDFInfo
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- CN105885819A CN105885819A CN201410422348.XA CN201410422348A CN105885819A CN 105885819 A CN105885819 A CN 105885819A CN 201410422348 A CN201410422348 A CN 201410422348A CN 105885819 A CN105885819 A CN 105885819A
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Abstract
The invention provides an ultralow-density spherical silicon resin oil proppant and its preparation method. according to preparation of the proppant, several organosilicone monomers and several organic solvents are violently stirred under the action of an emulsifier to be dispersed to obtain an aqueous emulsion; an aqueous hydrochloric acid solution is added dropwise as a catalyst; and temperature rises according to different temperature step processes so as to successively carry out a series of reactions, such as catalytic hydrolysis, polycondensation, transesterification, polymer structure ageing reforming, high-temperature curing and the like, so as to finally obtain the micro-spherical silicon resin oil proppant. Volume density of the product is 1.10-1.15 and its apparent density is 1.20-1.25. The surface of the product is smooth, particle size is controllable, and sphericity reaches 0.95 and above. The product has high strength, and breakage rate of the product under closing pressure of 80 Mpa isles than 5%. The product has good chemical stability, is resistant to high temperature of 400 DEG C and above, will not be softened, decomposed or broken, and will not undergo a chemical reaction with a fracturing fluid or oil gas. The product has excellent lipophilicity and hydrophobicity. By the use of the product, oil gas output can be effectively raised and lifetime of oil gas well can be prolonged.
Description
Technical field
The present invention relates to chemical field, particularly to the fracturing propping agents used in oil gas field field, there is excellent oil gas and water separation function, improve oil
The rate of oil and gas recovery of well and the useful life of prolongation oil well.
Background technology
In oilfield explorating developing process, especially in the exploration and development of hypotonic oil gas field and the transformation of old Oil/gas Well, add petroleum fracturing propping agent and have become as
Volume increase and the Main Means improving the rate of oil and gas recovery.Described petroleum propping agent injects oil-gas Layer by highly pressurised liquid, makes oil gas crack under highly pressurised liquid effect
Denomination of invention
A kind of extremely-low density spherical shaped silicone petroleum propping agent and preparation method thereof
Technical field
The present invention relates to chemical field, particularly to the fracturing propping agents used in oil gas field field, there is excellent oil gas and water separation function, improve oil
The rate of oil and gas recovery of well and the useful life of prolongation oil well.
Background technology
In oilfield explorating developing process, especially in the exploration and development of hypotonic oil gas field and the transformation of old Oil/gas Well, add petroleum fracturing propping agent
Become volume increase and the Main Means improving the rate of oil and gas recovery.Described petroleum propping agent injects oil-gas Layer by highly pressurised liquid, makes oil gas crack make at highly pressurised liquid
It is split up with lower, stays in pressurization stopping rear support agent and crack keeps cracks open will not subside, become the transmission channel that oil gas is drawn, effectively carry
The oil gas field yield of high oil well.Proppant used by fracturing technology mainly has natural siliceous sand, sintering ceramsite, organic resin overlay film proppant the most both at home and abroad
Deng.
1. natural siliceous sand
Material source is wide, low cost, is widely used in early days.But quartz sand ball-type degree is poor, density is big (near apparent density 3.0), and flow conductivity is poor,
It is mainly used in the fracturing work of shallow-layer low clossing pressure well, is not suitable for the deep-well that clossing pressure is high；
2. use the ceramsite propping agent of aluminum vanadine high temperature sintering
Its advantage is that the performances such as sphericity is good, corrosion-resistant, high temperature resistant, high pressure resistant are good, is that current oil gas field is used most proppants (US 4977116).
Made in China ceramsite propping agent occupies the share that ceramsite propping agent market, the world is the biggest.Shortcoming is by bauxite high temperature sintering more than 1300 DEG C, work
Skill is complicated, and energy consumption is big；Product hydrophobicity is poor, the best to the separating degree of oil gas and water；Density is big, and apparent density is typically more than 3, and flow conductivity is poor,
Easily occur when the transmission of pump and transmission liquid layering and blocking oil circuit.It is mainly used in middle-deep well fracturing technology.
3. the proppant that organic resin film covers
On quartz sand, haydite, the surface of shuck skeleton body, coat one layer of thermoplasticity or thermosetting resin, proppant oil, water separation energy can be effectively improved
Power.The compositions etc. of these film covered resins such as phenolic resin, epoxy resin, furane resins, acrylic resin, alkyd resin and these resins, is mesh
Front research and the principal direction of application, can be used as the fracturing propping agents of partial high pressure well.But their density is the biggest, typically 2.5～more than 3, water conservancy diversion energy
Power is the most poor；Particularly their heat-resisting quantity is the best, typically there will be softening, bonding below 250 DEG C, even thermally decomposes, still can not meet perhaps
The requirement of many deep Oil/gas Wells.
4. extremely-low density microspheroidal silicones petroleum propping agent
The present invention is directed to the technological deficiencies such as the oil gas proppant density height of current organic polymer cladding, resistance to elevated temperatures difference, it is provided that a kind of spherical silicon of extremely-low density
Resin petroleum propping agent, body density is low, can reach 1.0～1.2；The particle diameter of proppant is controlled at 0.5～1.0 millimeter；Smooth surface, sphericity reaches 95%
Above；There is superior resistance to water and the separating power of oil gas water；The intensity of proppant is high, and resistant to breakage ability is high, broken under clossing pressure 80Mpa
Rate is less than 5%；Chemical stability is good, high temperature resistant with fracturing fluid and oil gas, any chemical reaction can not occur to more than 400 DEG C；Long-term water conservancy diversion is effective.
Being described below in detail of the synthesis of described microspheroidal organic siliconresin.
1) preparation method of extremely-low density spherical shaped silicone petroleum propping agent, is by different types of alkoxy silane, in the presence of aromatic hydrocarbons and alcoholic solvent, aqueous solution,
Adding surfactant, drip hydrochloric aqueous solution under strong stirring, system is by dispersion and emulsion submillimeter level emulsion droplet, then is pressed not by this emulsion system
Equality of temperature rank program from 30～95 DEG C of slow intensifications, make siloxanyl monomers in succession hydrolyze, polycondensation, ester exchange, resin structure ripening reformation, high temperature
The differential responses such as lower crosslinking curing, finally give microspheroidal silicones petroleum propping agent.The chemical constitution signal formula of described organic siliconresin petroleum propping agent
It is shown below:
Wherein R1For methyl, ethyl, phenyl, pi-allyl, epoxy alkyl, amine propoxyl group；
R2For methyl, phenyl, methoxyl group, the one in ethyoxyl；
R3For methyl, ethyl, isopropyl, butyl, isobutyl group, the tert-butyl group；
N is the integer of 10-30, and degree of polymerization molecular weight is within the scope of 1500～2500.
2) manufacturing condition of proppant of the present invention: by 10 parts of methyl trimethoxy oxosilanes of volume ratio, 0.1～0.5 part of dimethyldimethoxysil,ne and 0.1～
1.0 parts of phenyltrimethoxysila,e, the solvent alcohol of 1～5 part of carbon number 3～5,1～5 part of toluene；Selection 1～the carbon 8～20 alkylol polyoxy of 5%
Vinyl Ether (EO8～15) nonionic surfactant (or Tween 80), 1～5% dodecylbenzene sodium sulfonate (or sodium lauryl sulphate) cloudy
Ionic surface active agent；Under strong stirring drip 10 parts of dilute HCL catalyst (pH2～3), make the dispersion of emulsion drop at submillimeter level,
Emulsion system is slowly heated and maintains 2～3 hours at 30～50 DEG C；Then it is warmed up to 65～75 DEG C of backflows keep 1～2 hour；It is warmed up to again
80～90 DEG C and the holding 1～2 hour that refluxes；With 1～3% pH to 5～6 of HMDS (or Feldalat NM) neutralized system；Add
1～3%560 firming agent, i.e. disengage microspheric solid silicon resin, through filtering, washing, after drying, obtain microsphere sample；Finally microsphere sample
In 180～220 degree of crosslinking curings, cooling, sieve, i.e. obtain microspheroidal silicones petroleum propping agent.
3) in silane, structure and the performance of silicones are had a great impact by carbon number and the structure of alkoxyl, need for this to be changed in silicones by ester exchange reaction
Methoxyl group is the alkoxyl of longer carbon number, as selected propanol, isopropanol, isobutanol, n-butyl alcohol etc., sends out with methoxyl group in silane at 85～95 DEG C
Raw ester exchange, generates corresponding propoxyl group, isopropoxy, isobutoxy, n-butoxy etc., and control exchange degree is 5～10%, to increase microspheroidal
The ductile strength of silicones proppant.
4) chemical constitution of synthesis silicones need to make silicon compound molecular side chain alkyl or aryl flex outward so that the appearance mask of proppant through arrangement of reforming
Having hydrophobic oleophilic oil gas characteristic, being conducive to improving has preferable separating effect to oil gas and water, keeps long-term flow conductivity；And the active group of silicones is stretched
To inner side, at high temperature crosslinking curing becomes microspheric silicones proppant.
5) size tunable of the silicones proppant that the present invention manufactures, smooth surface, sphericity reaches more than 0.95, and body density can reach 1.10～1.15, depending on
Density 1.20～1.25；Intensity is high, and resistant to breakage ability is high, and under clossing pressure 80Mpa, percentage of damage is less than 5%；High temperature resistant can to more than 400 DEG C,
Chemical stability is good, with fracturing fluid and oil gas, any chemical reaction, free from environmental pollution and underground water source does not occurs.
It is embodied as example as follows.
Embodiment 1
By 10 parts of methyl trimethoxy oxosilanes of volume ratio, 0.1～0.5 part of dimethyldimethoxysil,ne and 0.1～1.0 part of phenyltrimethoxysila,e, 1～5
Part butanol, 1～5 part of toluene；3～the polyoxyethylene lauryl ether (EO8～10) of 5%, 3～5% dodecylbenzene sodium sulfonate, drip under strong stirring
Add 5～10 parts of HCL aqueous solutions (pH2.5), make system be emulsified into emulsion droplet near submillimeter level, emulsion system is slowly heated also at 30～50 DEG C
Keeping 2～3 hours, be then warmed up to 70～75 DEG C, cooling for reflux keeps 1～2 hour, then is warmed up to 80～90 DEG C and keeps 1～2 hour, adds
Enter 1～3% HMDS adjust system to pH5～6, add 1～3%560 firming agent, from solution, be settled out microspheric silicones, process
Filter, washing, dried, obtain microsphere sample, then in 180～220 DEG C of crosslinking curings, cooling, sieve, i.e. obtain the microspheroidal silicon tree of 20～40 mesh
Fat petroleum propping agent.The silicones proppant surface of synthesis is smooth, and sphericity reaches more than 0.95, and body density can reach 1.10～1.15, apparent density 1.20～
1.25；Resistant to breakage ability percentage of damage under clossing pressure 80Mpa is less than 5%；High temperature resistant more than 400 DEG C.
Embodiment 2
By 10 parts of methyl trimethoxy oxosilanes of volume ratio, 0.1～0.5 part of dimethyldimethoxysil,ne, 1～3 part of butanol；10 parts adjust pH2 with HCL
Pure water；Add 3～the Tween 80 of 5%, 3～5% sodium lauryl sulphate, under strong stirring, make system be emulsified into emulsion droplet near submillimeter level,
Emulsion system being slowly heated and kept at 30～50 DEG C 2～3 hours, is then warmed up to 70～75 DEG C, cooling for reflux keeps 1～2 hour, and decompression is steamed
Fraction solvent, adds 3～5 parts of n-butyl alcohol, then is warmed up to 80～90 DEG C of backflows and keeps reaction in 1～2 hour to terminate, with 2% HMDS neutralization
System to pH5～6, Precipitation microspheric silicones from solution, through filtering, washing, dried, obtain microsphere sample, then 180～220
DEG C crosslinking curing, cooling, sieve, i.e. obtain the microspheroidal silicones petroleum propping agent of 20～40 mesh；Silicones microsphere features smooth surface, sphericity reaches
More than 0.95, body density can reach 1.15～1.20, apparent density 1.20～1.25；Resistant to breakage ability percentage of damage under clossing pressure 80Mpa is less than 5%；
High temperature resistant 400 DEG C
Embodiment main performance index Comparative result is as follows.
Extremely-low density high intensity silicones petroleum propping agent main performance index
Claims (4)
1. extremely-low density spherical shaped silicone petroleum propping agent and preparation method thereof, is characterized in that in MTMS, the alcohol of addition and toluene solvant,
Nonionic and anion surfactant, and the HCL aqueous solution of 2-5% makees catalysts, under strong stirring, system is emulsified is dispersed into microlayer model
Emulsion, then by this emulsion system slowly from 30～50 DEG C, 65～75 DEG C, the not equality of temperature rank temperature programming of 80～95 DEG C, makes siloxanyl monomers phase secondary
The differential responses such as unboiled water solution, polycondensation, ester exchange, polymer architecture ripening reformation, ultimately generate microspheric silicones precipitation, through filtering, washing, are dried
After, obtain microsphere sample, add curing catalysts and in 200～250 DEG C of crosslinking curings, cooling, sieve, i.e. obtain microspheroidal silicones petroleum propping agent；
The structural representation formula of described organic siliconresin petroleum propping agent is shown below:
Wherein R1For methyl, ethyl, phenyl, pi-allyl, epoxy alkyl, amine propoxyl group；
R2For methyl, phenyl, methoxyl group, the one in ethyoxyl；
R3For methyl, ethyl, isopropyl, butyl, isobutyl group, the tert-butyl group；
N is the integer of 15～30.
2. according to the production method of the extremely-low density spherical shaped silicone petroleum propping agent described in claim 1, it is characterised in that reaction system is 10 parts of methyl of volume ratio
Trimethoxy silane, 0.1～1.0 part of dimethyldimethoxysil,ne and 01～1.0 part of phenyltrimethoxysila,e, 1～3 part of toluene, 1～3 part of long carbon
Under chain alcohol, 3～5 portions of nonionic surfactants and 3～5 parts of anion surfactant effects, strong stirring emulsifying, it is dispersed into submillimeter level
Emulsion droplet, drips 3～5 parts of HCL aqueous solutions (pH2～3), then with not equality of temperature rank ramped heating schedule: maintain 2～3 hours from 30～50 DEG C,
Then being warmed up to 65～75 DEG C of backflows keep 1～2 hour, then be warmed up to 80～90 DEG C, backflow keeps 1～2 hour；First 1～3% Feldalat NM or
Hexamethyl silicon diazane, system pH that neutralizes is to 5～6, and decompression distillation separates solvent, and final precipitation disengages microspheric silicon resin particle, through filtering,
Washing, dried, obtain microsphere sample, add 1～3%560 firming agent methanol solutions, be heated to 180～220 DEG C of crosslinkings, solidification, cool down, sieve,
I.e. obtain microspheroidal silicones petroleum propping agent.
3. in the production method of the silicones petroleum propping agent described in claim 1, it is characterised in that lauryl alcohol polyoxyethylenated alcohol (EO8～15) 1～5%
Nonionic surfactant (or Tween 80), 1～5% dodecylbenzene sodium sulfonate (or sodium lauryl sulphate) anion surfactant,
Under strong stirring, make system dispersion and emulsion, when control emulsion drop dispersion is near submillimeter level, heats up and chemical reaction occurs.
4. in the production method of the extremely-low density spherical shaped silicone petroleum propping agent described in claim 1, it is characterised in that select propanol, isopropanol, isobutanol,
N-butyl alcohol, the tert-butyl alcohol etc., with the methoxyl group generation part ester exchange in silane at 85～95 DEG C, generate containing mol ratio 1.0～10% corresponding third oxygen
Base, isopropoxy, isobutoxy, n-butoxy, the silicones of tert-butoxy, to increase the toughness of resin.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019016304A1 (en) | 2017-07-20 | 2019-01-24 | Danmarks Tekniske Universitet | Quick-setting elastomer plugging composition |
| CN109386271A (en) * | 2017-08-03 | 2019-02-26 | 中国石油化工股份有限公司 | A kind of horizontal well wears lamination cracking method |
| CN109804039A (en) * | 2016-09-30 | 2019-05-24 | 瓦克化学股份公司 | The support device of coating for pressure break extraction system |
| CN112876684A (en) * | 2021-03-18 | 2021-06-01 | 新辉（中国）新材料有限公司 | Micron-level high-crosslinking-degree organic silicon polymer microspheres with controllable particle sizes and preparation method thereof |
| CN115850678A (en) * | 2023-03-02 | 2023-03-28 | 山东科兴化工有限责任公司 | Micromolecule polysilicon pore throat dredging agent for fracturing and preparation method thereof |
| CN117363337A (en) * | 2023-12-07 | 2024-01-09 | 铜川秦瀚陶粒有限责任公司 | Preparation process of petroleum fracturing propping agent based on solid waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109804039A (en) * | 2016-09-30 | 2019-05-24 | 瓦克化学股份公司 | The support device of coating for pressure break extraction system |
| WO2019016304A1 (en) | 2017-07-20 | 2019-01-24 | Danmarks Tekniske Universitet | Quick-setting elastomer plugging composition |
| CN109386271A (en) * | 2017-08-03 | 2019-02-26 | 中国石油化工股份有限公司 | A kind of horizontal well wears lamination cracking method |
| CN112876684A (en) * | 2021-03-18 | 2021-06-01 | 新辉（中国）新材料有限公司 | Micron-level high-crosslinking-degree organic silicon polymer microspheres with controllable particle sizes and preparation method thereof |
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| CN115850678A (en) * | 2023-03-02 | 2023-03-28 | 山东科兴化工有限责任公司 | Micromolecule polysilicon pore throat dredging agent for fracturing and preparation method thereof |
| CN115850678B (en) * | 2023-03-02 | 2023-06-23 | 山东科兴化工有限责任公司 | Small molecular polysilicone pore throat dredging agent for fracturing and preparation method thereof |
| CN117363337A (en) * | 2023-12-07 | 2024-01-09 | 铜川秦瀚陶粒有限责任公司 | Preparation process of petroleum fracturing propping agent based on solid waste |
| CN117363337B (en) * | 2023-12-07 | 2024-03-08 | 铜川秦瀚陶粒有限责任公司 | Preparation process of petroleum fracturing propping agent based on solid waste |
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Application publication date: 20160824 |