CN105623638A - Resin coated hollow glass beads and preparation method therefor - Google Patents
Resin coated hollow glass beads and preparation method therefor Download PDFInfo
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- CN105623638A CN105623638A CN201410601788.1A CN201410601788A CN105623638A CN 105623638 A CN105623638 A CN 105623638A CN 201410601788 A CN201410601788 A CN 201410601788A CN 105623638 A CN105623638 A CN 105623638A
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Abstract
The invention provides resin coated hollow glass beads and a preparation method therefor. Each resin coated hollow glass bead contains a propping agent and a coating agent coating the surface of the propping agent, wherein the propping agent is hollow glass beads which have the grain size of 8-90 microns and the compressive strength not lower than 12MPa; the coating agent contains thermosensitive composite resin and a curing agent composition and can be softened and cured when the temperature reaches 100 DEG C or above, so that a plurality of resin coated hollow glass beads are cemented to form a cured integer which has the tensile strength of 10.5MPa to 14.3MPa, the compressive strength of 9MPa to 22MPa and the shearing strength of 4MPa to 6MPa; the solution ratio of the cured integer is lower than 0.2% under the condition that the cured integer is soaked by each of a 10% (mass percent concentration) HCl solution, a 10% NaOH solution and a 10% NaCl solution for 24 hours at the temperature of 100 DEG C; and the density of each resin coated hollow glass bead is 0.55g/cm<3> to 0.88g/cm<3>.
Description
Technical field
The present invention relates to a kind of resin coating hollow glass micropearl and preparation method thereof, belong to tertiary oil production in oil field gas drive matched process technology field.
Background technology
North China Oilfield buried hill oil pool is after experience ultra-high water-containing mining phase, in order to improve recovery ratio further, carries out gas drive and improves recovery efficiency technique research. From 1986, cooperate to carry out wild goose tail feather buried hill nitrogen injection with company of Total France and improve the experiment of recovery ratio well group. The research work that Yanling oil field is noted in nitrogen early stage and gas injection process by Bai Fenghan, Shen Youqing et al. in " Yanling oil field nitrogen injection improves the test of recovery ratio scene " paper that in October, 1998, " petroleum journal " was delivered has carried out detailed overview. The dynamic Feature Analysis of experiment well group is driven by gas injection, it is indicated that:
(1) inject gas flowing and be limited mainly by Crack Control, first move along large fracture under the gravity effect with driving force, thus cause the change of fracture developing zone oil gas, oil-water interfaces to be affected reaction sensitivity by gas injection.
(2) reservoir vertical fractures is grown, and based on high angle fracture. Adding up according to wild goose 33 well 169 crack, the crack more than 70 ��, the inclination angle has 134, accounts for 79%, and the performance that the high angle fracture of growth is action of gravity provides natural endowment. Due to this feature of reservoir, inject gas and substantially drive top oil to move down, it is achieved that the redistribution of crude oil.
Due to the complicated reason such as the anisotropism on stratum, the big big hole of seam of Thief zone, injected gas know from experience produce near wellbore zone gas in various degree bore into, and the flowing of big hole can be stitched so that the advantage on its mobility is preferential along big, cause injection gas to scurry into pit shaft, the effect thus impact is normally recovered the oil.
For the has channeling problem in injection gas displacement process, many employings mortar architecture in production scene blocks, and drying out owing to the hydrophilic of mortar architecture, density are big, in solidification process is easily generated the characteristic of contraction so that poor effect.
The article " carbon dioxide flooding has channeling Research on Treatment " that Liu Hui delivers in " CNPC and chemical standard and quality " is mentioned, at CO2In oil displacement process, main employing following four envelope alters technology:
1, foam blocking technology: this technical system has the characteristic of " blocking high not low blocking ", will not pollute low-permeability layer, by improving the wettability of rock surface, overcomes the capillary force of blowhole to carry out the displacement of reservoir oil. But for the oil reservoir too fast containing high permeability zone or gas injection speed, foam flooding anti-gas channeling poor effect.
2, gel envelope alters technology
This technical system is higher to the closure efficiency of fluid-channeling channel, can reach more than 90% at the SC-1 inorganic gel of tree 101 test block screening and the closure efficiency of SCA pluralgel. But gel rubber system can make high permeability zone, macropore block wholly or in part, oil phase filtrational resistance increases, and less permeable layer be will also result in and to a certain degree pollute. In addition the host concentration of gel technique is high, and injection rate is big, effect duration is not long, cost is high, therefore that the has channeling problem in preventing and treating gas injection process is also not satisfactory.
3, organic amine salt envelope alters technology
Amine envelope alter agent by with CO2, metal ion haptoreaction in formation water, generation can not consoluet crystal state polyamino formates, macropore is produced closure. But organic amine has toxicity and inflammable, has certain risk. In addition, when oil saturation is higher, its plugging strength reduces, and fleeing proof effect is not good.
4, water-air two-phase flow technology
This technology, by improving gas-to-oil mobility ratio, expands the sweep efficiency of gas, improves oil recovery factor. But this technology is subject to the impact of the many factors such as wettability, fluid properties, miscible conditions, injection technique, fluid flow geometry, and implementation process is complex simultaneously.
The precoated sand granule that Zhang Jianjun et al. is mentioned in Chinese patent literature CN203319922U, CN203238214U can form high compressive strength sand block barrier by cementation solidifying in the earth formation, good effect is achieved at oil field artificial borehole wall sand prevention and FRACTURING SAND CONTROL TECHNOLOGY field, but owing to this precoated sand density is big, in the stifled control problem that can not be applied in injection gas displacement process stratum has channeling passage.
Summary of the invention
Goal of the invention
It is an object of the present invention to provide resin coating hollow glass micropearl, safety is high, application process is simple and easy to operate, it is adaptable to solves slit formation buried hill oil pool development late stage and improves the stifled control problem of stratum has channeling passage in recovery ratio injection gas displacement process.
The preparation method that it is a further object to provide above-mentioned resin coating hollow glass micropearl.
Summary of the invention
Described resin coating hollow glass micropearl, including proppant and the covering being coated on proppant surface, wherein,
Described proppant is the hollow glass micropearl that particle diameter 8��90 ��m, comprcssive strength are not less than 12MPa,
Described covering includes thermal sensitivity composite resin and curing agent composition, described covering can soften when temperature reaches more than 100 DEG C, solidify, making multiple resin coating hollow glass micropearl cementing is 10.5��14.3MPa for tensile strength, comprcssive strength is 9��22MPa, the solidification that shear strength is 4��6MPa is overall, it is described that to solidify overall be the HCl of 10% with mass percent concentration respectively under 100 DEG C of conditions, the NaOH of 10%, the NaCl solution of 10% is soaked 24 hours corrosion rates and is respectively less than 0.2%, described curing agent composition occurs the firming agent of curing reaction and curing accelerator to form by can make described thermal sensitivity composite resin when temperature reaches 100 DEG C,
The density of described resin coating hollow glass micropearl is 0.55��0.8g/cm3��
Preferably, the comprcssive strength of described resin coating hollow glass micropearl is 18��25MPa.
The comprcssive strength of described hollow glass micropearl or resin coating hollow glass micropearl be its percentage of damage less than or equal to 10% time the maximum compressive strength that bears, method of testing is prior art.
The composition of described curing agent composition and consumption can be determined according to the performance that the forming of described thermal sensitivity composite resin, structure and described solidification are overall by those skilled in the art.
Preferably, the preparation method of described thermal sensitivity composite resin is as follows:
(1) 1.8��2.3 mass parts phenol, 2.2��2.6 mass parts formaldehyde, 0.6��1.0 mass parts nonyl phenol and 1��1.5 mass parts water mix homogeneously are made, pH value be 8��9, temperature be under 85��90 DEG C of conditions, carry out polycondensation reaction 45��60min, the mass percent concentration of described formaldehyde is 36%��37%;
(2) adding 1.4��1.8 mass parts epoxy furfural acetone resins, mix homogeneously at 85��90 DEG C, the solids content of described furfural epoxy resin is more than 99%, and viscosity is 18��22mPa s;
(3) at 70 DEG C, vacuum dehydration fractionates out to anhydrous.
Heretofore described solids content is mass percentage content, it is referred to GB12005.2-89 " polyacrylamide determination of solid content method ", measure resin quality of dry front and back in vacuum drying oven, dried quality obtain divided by the Mass Calculation before drying; Described viscosity can be recorded at normal temperatures by rotating cylinder viscometer. As this area general knowledge, above-mentioned drying condition should ensure that degradation reaction will not occur resin. Generally, baking temperature is not higher than 120 DEG C.
The polycondensation under alkaline environment of phenol, nonyl phenol, formaldehyde obtains aralkyl modified phenolic resin, to increase the toughness of thermal sensitivity composite resin under ensureing higher-strength premise, and improves the fragility of covering; Described epoxy furfural acetone resin is a kind of epoxide modified furane resins, temperature tolerance is higher than epoxy resin, improve the fragility of epoxy and furane resins, for commercial goods, add epoxy furfural acetone resin and can improve heat-resisting, the acid-proof alkaline of thermal sensitivity composite resin, and improve the fragility under covering hot conditions. Wherein, when polycondensation obtains phenolic resin, generally select the ammonia that performance relaxes to regulate pH value and the synthesis of alkaline environment catalytic resin is provided.
When adopting above-mentioned thermal sensitivity composite resin, it is preferable that described firming agent is hexamethylenamine, and described curing accelerator is calcium hydroxide.
Described hollow glass micropearl is commercial goods, for different formation conditions and construction requirement, it is possible to select the hollow glass micropearl of different-grain diameter as proppant. The hollow glass micropearl of different-grain diameter, its mechanical property and solidify with thermal sensitivity composite resin, cementing after obtain to solidify overall size all different. Such as the hollow glass micropearl that Sinosteel Maanshan Institute of Mining Research Co., Ltd. produces, model be T32, T40, T46, T60 density respectively 0.32,0.40,0.46,0.60g/cm3, particle diameter respectively 10��90,8��85,8��80,8��60 ��m, comprcssive strength respectively 12��15MPa, 28��33MPa, 38��42MPa, > 60MPa. Preferably, it is 0.32��0.60g/cm as the density of the hollow glass micropearl of proppant3��
Density in the present invention refers to the quality of glass microballoon and the ratio of its volume, and described volume includes the closed hollow part of glass microballoon, does not include the gap between glass microballoon. Glass microballoon includes the aforesaid hollow glass micropearl as proppant and resin coating hollow glass micropearl herein. Described density can use Density Measuring Instrument to be measured.
Preferably, described covering is 20��80 ��m at the cladding thickness of proppant surface. The method of testing of described cladding thickness can be: adopt particle size analyzer test overlay film before and after size and particle size distribution, then pass through analysis overlay film before and after particle diameter to calculate cladding thickness; Scanning electron microscope (SEM) can also be adopted to scan, and information that sample surfaces obtains obtains characteristic image after treatment, recognizes particle diameter from characteristic image is qualitative, and the method for scanning electron microscope is observation measurements method.
The preparation method of described resin coating hollow glass micropearl comprises the following steps:
(1) clean, dry hollow glass micropearl;
(2) with coupling agent, hollow glass micropearl is carried out surface modification;
(3) overlay film: make the hollow glass micropearl after surface modification 40��55 mass parts, thermal sensitivity composite resin 15��22 mass parts and curing agent composition 1.9��3 mass parts, coupling agent 0.05��0.1 mass parts, lubricant 0.1��0.3 mass parts, solvent 26��30 mass parts at 200��210 DEG C, cooling after mixing under 210��320r/min rotating speed stirring condition, making thermal sensitivity composite resin and curing agent composition be coated on hollow glass micropearl surface, described curing agent composition is made up of firming agent 1.3��2.0 mass parts and curing accelerator 0.6��1 mass parts.
Wherein,
(1) clean, dry hollow glass micropearl adopts conventional method, as: clean hollow glass micropearl using the ethanol water that ethanol and distilled water mass ratio are 2.5:1��3:1 as cleaning solvent, hollow glass micropearl and solvent 1:2��1:2.3 mix and blend 10min in mass ratio, dry 60min under 120 DEG C of conditions;
(2) with coupling agent, hollow glass micropearl is carried out surface modification and may be used without this area conventional method, as: using ethanol and distilled water mass ratio be 8:1��10:1 ethanol water as modified solvent, in the modified solvent of 0.3��0.6 mass parts, add the coupling agent of quality is hollow glass micropearl 1 �롫2 ��, obtain coupling agent-ethanol water, under 500��1000r/min rotating speed stirs, above-mentioned coupling agent-ethanol water is injected to the hollow glass micropearl spraying that the cleaning-drying of 1��1.2 mass parts is good in 30��50min, continuing stirring makes coupling agent-ethanol water be uniformly distributed on hollow glass micropearl surface, hollow glass micropearl after processing is dried at 70��80 DEG C, obtain the hollow glass micropearl after surface modification,
(3) overlay film step should control strict incorporation time, in order to avoid thermal sensitivity composite resin generation curing reaction, mixing should be abundant simultaneously, makes covering fully be coated on proppant surface. solvent therein can be selected by the requirement of those skilled in the art's physicochemical characteristic according to reaction system and overlay film step. preferred solvent is acetone and ethanol mass ratio is the mixture of 1.8:1��2.5:1. preferred overlay film step is: at 200��210 DEG C, under 210��320r/min rotating speed stirring condition, add in 40��55 modified mass parts hollow glass micropearls and be pre-mixed uniform thermal sensitivity composite resin 7.5��11 mass parts, coupling agent 0.025��0.05 mass parts, firming agent 0.65��1.0 mass parts, curing accelerator 0.3��0.5 mass parts, lubricant 0.05��0.15 mass parts, solvent 13��15 mass parts, continue stirring 2��5min, add and be pre-mixed uniform remaining thermal sensitivity composite resin 7.5��11 mass parts, coupling agent 0.025��0.05 mass parts, firming agent 0.65��1.0 mass parts, curing accelerator 0.3��0.5 mass parts, lubricant 0.05��0.15 mass parts, solvent 13��15 mass parts, cooling after stirring 3��6min, thermal sensitivity composite resin and curing agent composition is made to be coated on hollow glass micropearl surface. adopt this repeatedly continuous overlay film step that covering can be made more sufficiently and uniformly to be coated on proppant surface. as state of the art, described solvent does not need other heating, drying, and after cladding, solvent is evaporated by the waste heat of overlay film hollow glass micropearl.
The coupling agent that the present invention adopts can be selected by those skilled in the art's material according to hollow glass micropearl and forming of thermal sensitivity composite resin; And lubricant adopts this area conventional substances. Preferably, described coupling agent is the mixture that mass ratio is 1:2.3��1:2.8 of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters (hereinafter referred to as DN-201) and ��-glycidyl ether oxygen propyl trimethoxy silicane (hereinafter referred to as A-187); Described lubricant is calcium stearate.
The method applying resin coating hollow glass micropearl of the present invention is the same with the gel that existing envelope is altered in technology, injects stratum, according to concrete geological conditions, can select suitable injection means, be such as layered injection, generally inject.
Resin coating hollow glass micropearl of the present invention is under stratum high-temperature condition (more than 100 DEG C), surface coating resin again softens and solidifies cementing, making gained solidify entirety and reach certain mechanical strength, the time that completing this process needs is 5��8 hours. It should be noted that, when with film covering method hollow glass micropearl Surface coating thermal sensitivity composite resin (hereinafter referred to as cladding process) time, operating time is very short, only need 5��11min, therefore add curing agent composition when hollow glass micropearl Surface coating thermal sensitivity composite resin, the application performance of described resin coating hollow glass micropearl can't be affected. Thermal sensitivity composite resin and curing agent composition is included due to described covering, curing agent composition described in cladding process can make thermal sensitivity composite resin be wrapped in hollow glass micropearl surface curing molding at short notice, simultaneously, being used for resin coating hollow glass micropearl blocking up when controlling the stratum has channeling passage occurred in injection gas displacement process also without it is possible to additionally incorporate curing agent composition, applying very convenient.
Proppant described in the overlay film hollow glass micropearl structure that the present invention relates to and covering use safety, all will not at high temperature discharge dangerous substance, under overlay film hollow glass micropearl room temperature, there is excellent mechanical performance simultaneously, when stratum high-temperature, (more than 100 DEG C) surface coating resin softens and solidifies cementing, solidify cementing after sample tensile strength be 10.5��14.3MPa, comprcssive strength is 9��22MPa, shear strength is 4��6MPa, it is the HCl of 10% with mass percent concentration respectively under 100 DEG C of conditions after solidification, the NaOH of 10%, the NaCl solution of 10% is soaked 24 hours corrosion rates and is respectively less than 0.2%. this resin coating hollow glass micropearl density is 0.55��0.8g/cm3Less than water, can effectively be arranged in gas-liquid interface and solidify cementing under the high temperature conditions after injecting stratum, enormously simplify the construction procedure of preventing and treating gas coning, has channeling, reduce construction cost, the formation gas effectively prevented and treated in injection gas displacement process can bore the problem into, has channeling, improve the effect of injection gas displacement. The group such as alkane of resin during described preferred thermal sensitivity composite resin is adopted to be respectively provided with hydrophobic performance so that overlay film hollow glass micropearl surface is hydrophobicity, not easily reunites in water, thus having good dispersibility and injection.
Detailed description of the invention
For different formation conditions and construction requirement, the present invention can select the hollow glass micropearl of different-grain diameter as proppant, and is coated with the thermal sensitivity composite resin of different ratio. Provide four kinds preferred embodiment below in conjunction with specific embodiment, can adjust targetedly on this basis.
The method of testing that following example relate to is as follows:
Cladding thickness: adopt particle size analyzer test overlay film before and after size and particle size distribution, then pass through analysis overlay film before and after particle diameter to calculate cladding thickness. Described particle size analyzer is the LA-950S type laser particle analyzer of HORIBA company;
The comprcssive strength of resin coating hollow glass micropearl: adopt the YAW-300B type petroleum fracturing propping agent compression Strength testing machine of Jinan spark testing machine company limited, with reference to SY/T5108-2006 " fracturing propping agents performance indications and test recommendation method ", record the comprcssive strength of resin coating hollow glass micropearl percentage of damage��10%;
Comprcssive strength after overlay film microballon consolidation, shear strength, tensile strength: adopt Jinan Si Date measuring technology company limited WDS-50 type universl tester with reference to GB/T1010.1-2006 " the mensuration part 1 of plastic tensile performance: general provisions ", GB/T8813-2008 " mensuration of rigid foam compression performance ", HG/T3839-2006 " plastics shear strength test method perforation method " tested for tensile strength, comprcssive strength, shear strength.
Corrosion rate: under 100 DEG C of conditions, respectively be equipped with mass percent concentration 10% HCl, NaOH, NaCl solution hermetic container in Soak Test sample 24 hours, weigh the quality before and after soaking and draw.
Manufacturer and the model of chemical substance involved by following example are as follows:
Phenol: Yun great Chemical Co., Ltd. of Jinan City, technical grade, content >=99.9%;
Formaldehyde: Jinan Ying Wangtong Chemical Co., Ltd., technical grade, content >=37%;
Nonyl phenol: Jinan Chuan Shi Chemical Co., Ltd., technical grade, content >=99%;
Ammonia: Cangzhou Wen Cheng chemical products company limited, NH3Content >=25%;
Hexamethylenamine: Shandong Runyin Biology Chemical Industry Co., Ltd, primes, content >=99%;
Calcium hydroxide: Tianjin is with Xin Huali factory, technical grade, content >=95%;
Acetone: the southeast, Kunshan chemical materials company limited, top grade product, content >=99.5%;
Ethanol: refreshed Chemical Co., Ltd., technical grade content >=99.9% are contained in Tianjin;
Calcium stearate: Shijiazhuang City De Su auxiliary agent company limited, HG/T2424-2012 " People's Republic of China's chemical industry standard " primes, active substance content >=99.9%;
Epoxy furfural acetone resin: the easy board novel environment friendly epoxy furfural acetone resin of generation of Shijiazhuang Worldwide Furfural & Furfuryl Alcohol Co., Ltd., solids content 99%, viscosity 20mPa s.
The preparation method of the thermal sensitivity composite resin used in embodiment 1,2 is:
Phenol 1.8 mass parts, formaldehyde 2.2 mass parts, nonyl phenol 0.6 mass parts, ammonia 0.1 mass parts, water 1 mass parts are sequentially added in reactor, after uniform stirring 5min clock, it is 8 that pH value is surveyed in sampling, and cooling water control temperature used by reacting by heating still, temperature is made to rise to 87 DEG C, response time 50min, adds 1.4 mass parts epoxy furfural acetone resins, reacting by heating still to 87 DEG C, uniform stirring 10min, reaction terminates. Starting vacuum pump makes reactor reach 6kPa in 14min, and temperature passes into steam from chuck after dropping to 70 DEG C and keeps constant temperature, processed 15min, is cooled to room temperature standby.
Embodiment 1:
The each component preparing this resin coating hollow glass micropearl is:
Proppant: hollow glass micropearl, employing is the hollow glass micropearl of Sinosteel Maanshan Institute of Mining Research Co., Ltd., and model is T32, density 0.32g/cm3, particle diameter is 10��90 ��m, and comprcssive strength is 12��15MPa;
Thermal sensitivity composite resin;
Coupling agent: coupling agent DN-201 and the A-187 that Nanjing Pin Ning coupling agent company limited produces;
Firming agent: hexamethylenamine;
Curing accelerator: calcium hydroxide;
Lubricant: calcium stearate.
The preparation method of described resin coating hollow glass micropearl is:
1) clean: clean hollow glass micropearl, hollow glass micropearl and solvent 2:1 mix and blend 10min in mass ratio using ethanol water (ethanol and distilled water mass ratio are for 3:1) as cleaning solvent. 60min is dried under 120 DEG C of conditions.
2) proppant surface modifiies: using ethanol and distilled water mass ratio be 9:1 ethanol water as modified solvent, in the modified solvent of 20kg, add 0.04kg coupling agent, obtain coupling agent-ethanol water. Hollow glass micropearl dried for 40kg is put in high-speed mixer and stir, speed of agitator 550r/min, whipping process injects coupling agent-ethanol water by sprayer unit in 35min, continue stirring 10min, the hollow glass micropearl dry 3h under 80 DEG C of conditions after processing is obtained modified hollow glass micropearl.
3) overlay film:
A, each component proportioning be:
Modified hollow glass micropearl 40kg; Thermal sensitivity composite resin 20kg; Coupling agent (DN-201 and A-187 mass ratio 1:2.5) 0.1kg; Hexamethylenamine 2.0kg; Calcium hydroxide 1kg; Calcium stearate 0.3kg; Acetone 20kg; Ethanol 10kg.
B, adopt repeatedly continuous film mulching method: put in puddle mixer by modified for above-mentioned 40kg hollow glass micropearl, it is heated to 200 DEG C, under the stirring of 210r/min rotating speed, by thermal sensitivity composite resin 10kg, coupling agent 0.05kg, hexamethylenamine 1kg, calcium hydroxide 0.5kg, calcium stearate 0.15kg, acetone 10kg, puddle mixer is added after ethanol 5kg mixing, stirring 2min, again by thermal sensitivity composite resin 10kg, coupling agent 0.05kg, hexamethylenamine 1kg, calcium hydroxide 0.5kg, calcium stearate 0.15kg, acetone 10kg, ethanol 5kg mixes addition, continue stirring 5min, cooling, sieve, obtain resin coating hollow glass micropearl. this resin coating hollow glass micropearl room temperature lower density is 0.55g/cm3, cladding thickness is 20��40 ��m, and comprcssive strength is 22MPa.
Sample (namely solidifying entirety) tensile strength after this resin coating hollow glass micropearl 100 DEG C solidification cementing (6 hours hardening times) is 14MPa, comprcssive strength is 20MPa, shear strength is 5.8MPa, soak 24 hours by the HCl that mass percent concentration is 10%, the NaOH of 10%, the NaCl solution of 10% respectively under 100 DEG C of conditions after solidification, corrosion rate respectively 0.11%, 0.16%, 0.01%.
Embodiment 2:
The each component preparing this resin coating hollow glass micropearl is:
Proppant: hollow glass micropearl, employing is the hollow glass micropearl of Sinosteel Maanshan Institute of Mining Research Co., Ltd., and model is T40, density 0.40g/cm3, particle diameter is 8��85 ��m, and comprcssive strength is 28��33MPa;
Thermal sensitivity composite resin;
Coupling agent: DN-201 and the A-187 that Nanjing Pin Ning coupling agent company limited produces;
Firming agent: hexamethylenamine;
Curing accelerator: calcium hydroxide;
Lubricant: calcium stearate.
The preparation method of resin coating hollow glass micropearl is:
1) clean: clean hollow glass micropearl, hollow glass micropearl and solvent 2:1 mix and blend 10min in mass ratio using ethanol water (ethanol and distilled water mass ratio are for 2.8:1) as cleaning solvent. 60min is dried under 120 DEG C of conditions.
2) proppant surface modifiies: using ethanol and distilled water mass ratio be 9:1 ethanol water as modified solvent, in the modified solvent of 16kg, add 0.04kg coupling agent (in coupling agent DN-201 and A-187 mass ratio 1:2.5), obtain coupling agent-ethanol water. Hollow glass micropearl dried for 40kg is put in high-speed mixer and stir, speed of agitator is 750r/min, whipping process injects coupling agent-ethanol water by sprayer unit in 40min, continue stirring 10min, the hollow glass micropearl dry 3h under 80 DEG C of conditions after processing is obtained modified hollow glass micropearl.
3) overlay film:
A, each component proportioning be:
Modified hollow glass micropearl 40kg; Thermal sensitivity composite resin 17kg; Coupling agent (DN-201 and A-187 mass ratio 1:2.5) 0.07kg; Hexamethylenamine 1.5kg; Calcium hydroxide 0.7kg; Calcium stearate 0.1kg; Acetone 20kg; Ethanol 10kg.
B, adopt repeatedly continuous film mulching method: put in puddle mixer by modified for above-mentioned 40kg hollow glass micropearl, it is heated to 200 DEG C, under 230r/min rotating speed stirs, by thermal sensitivity composite resin 8.5kg, coupling agent 0.035kg, hexamethylenamine 0.75kg, calcium hydroxide 0.35kg, calcium stearate 0.05kg, acetone 10kg, puddle mixer is added after ethanol 5kg mixing, stirring 2min, again by thermal sensitivity composite resin 8.5kg, coupling agent 0.035g, hexamethylenamine 0.75kg, calcium hydroxide 0.35kg, calcium stearate 0.05kg, acetone 10kg, ethanol 5kg mixes addition, continue stirring 5min, cooling, sieve, obtain resin coating hollow glass micropearl. this resin coating hollow glass micropearl room temperature lower density is 0.62g/cm3, cladding thickness is 30 ��m��50 ��m, and comprcssive strength is 23MPa.
Sample (namely solidifying entirety) comprcssive strength after this resin coating hollow glass micropearl 100 DEG C solidification cementing (6 hours hardening times) is 13.6MPa, comprcssive strength is 13.6MPa, shear strength is 5.2MPa, soak 24 hours by the HCl that mass percent concentration is 10%, the NaOH of 10%, the NaCl solution of 10% respectively under 100 DEG C of conditions after solidification, corrosion rate respectively 0.11%, 0.16%, 0.01%.
The preparation method of the thermal sensitivity composite resin used in embodiment 3,4 is:
Phenol 2.0 mass parts, formaldehyde 2.5 mass parts, nonyl phenol 0.8 mass parts, ammonia 0.1 mass parts, water 1.3 mass parts are sequentially added in reactor, after uniform stirring 5min clock, it is 8 that pH value is surveyed in sampling, and cooling water control temperature used by reacting by heating still, temperature is made to rise to 87 DEG C, response time 50min, adds 1.6 mass parts epoxy furfural acetone resins, reacting by heating still to 88 DEG C, uniform stirring 10min, reaction terminates. Starting vacuum pump makes reactor reach 6kPa in 14min, and temperature passes into steam from chuck after dropping to 70 DEG C and keeps constant temperature, processed 15min, is cooled to room temperature standby.
Embodiment 3:
The each component preparing resin coating hollow glass micropearl is:
Proppant: hollow glass micropearl, employing is the hollow glass micropearl of Sinosteel Maanshan Institute of Mining Research Co., Ltd., and model is T46, density 0.46g/cm3, particle diameter is 8��80 ��m, and comprcssive strength is 38��42MPa;
Thermal sensitivity composite resin;
Coupling agent: coupling agent DN-201 and the A-187 that Nanjing Pin Ning coupling agent company limited produces;
Firming agent: hexamethylenamine;
Curing accelerator: calcium hydroxide;
Lubricant: calcium stearate.
The preparation method of resin coating hollow glass micropearl is:
1) clean: clean hollow glass micropearl, hollow glass micropearl and solvent 2:1 mix and blend 10min in mass ratio using ethanol water (ethanol and distilled water mass ratio are for 3:1) as cleaning solvent. 60min is dried under 120 DEG C of conditions.
2) proppant surface modifiies: using ethanol and distilled water mass ratio be 9:1 ethanol water as modified solvent, in the modified solvent of 15kg, add 0.05kg coupling agent (in coupling agent DN-201 and A-187 mass ratio 1:2.6), obtain coupling agent-ethanol water. Being put into by hollow glass micropearl dried for 40kg in high-speed mixer and stir, speed of agitator is 850r/min, injects coupling agent-ethanol water by sprayer unit in whipping process in 50min. Continue stirring 10min, the hollow glass micropearl dry 3h under 80 DEG C of conditions after processing is obtained modified hollow glass micropearl.
3) overlay film:
A, each component proportioning be:
Modified hollow glass micropearl 40kg; Thermal sensitivity composite resin 15kg; Coupling agent (DN-201 and A-187 mass ratio 1:2.5) 0.05kg; Hexamethylenamine 1.3kg; Calcium hydroxide 0.6kg; Calcium stearate 0.1kg; Acetone 20kg; Ethanol 8kg.
B, adopt repeatedly continuous film mulching method: put in puddle mixer by modified for above-mentioned 40kg hollow glass micropearl, it is heated to 200 DEG C, under 260r/min rotating speed stirs, by thermal sensitivity composite resin 7.5kg, coupling agent 0.025kg, hexamethylenamine 0.65kg, calcium hydroxide 0.3kg, calcium stearate 0.05kg, acetone 10kg, puddle mixer is added after ethanol 4kg mixing, stirring 2min, again by thermal sensitivity composite resin 7.5kg, coupling agent 0.025kg, hexamethylenamine 0.65kg, calcium hydroxide 0.3kg, calcium stearate 0.05kg, acetone 10kg, ethanol 4kg mixes addition, continue stirring 5min, cooling, sieve, obtain resin coating hollow glass micropearl. this resin coating hollow glass micropearl room temperature lower density is 0.74g/cm3, cladding thickness is 40��60 ��m, and comprcssive strength is 25MPa.
Sample (namely solidifying entirety) tensile strength after this resin coating hollow glass micropearl 100 DEG C solidification cementing (7 hours hardening times) is 12.2MPa, comprcssive strength is 15MPa, shear strength is 4.8MPa, after solidification under 100 DEG C of conditions respectively with HCl that mass percent concentration is 10%, 10% NaOH, 10%, NaCl solution is soaked 24 hours, corrosion rate respectively 0.11%, 0.13%, 0.01%.
Embodiment 4:
The each component preparing resin coating hollow glass micropearl is:
Proppant: hollow glass micropearl, employing is the hollow glass micropearl of Sinosteel Maanshan Institute of Mining Research Co., Ltd., and model is T60, density 0.60g/cm3, particle diameter is 8��60 ��m, comprcssive strength > 60MPa;
Thermal sensitivity composite resin;
Coupling agent: DN-201 and the A-187 that Nanjing Pin Ning coupling agent company limited produces;
Firming agent: hexamethylenamine;
Curing accelerator: calcium hydroxide;
Lubricant: calcium stearate.
The preparation method of resin coating hollow glass micropearl is:
1) clean: clean hollow glass micropearl, hollow glass micropearl and solvent 2:1 mix and blend 10min in mass ratio using ethanol water (ethanol and distilled water mass ratio are for 3:1) as cleaning solvent. 60min is dried under 120 DEG C of conditions.
2) proppant surface modifiies: using ethanol and distilled water mass ratio be 9:1 ethanol water as modified solvent, in the modified solvent of 12kg, add 0.07kg coupling agent (in coupling agent DN-201 and A-187 mass ratio 1:2.7), obtain coupling agent-ethanol water. Being put into by hollow glass micropearl dried for 40kg in high-speed mixer and stir, speed of agitator is 950r/min, injects coupling agent-ethanol water by sprayer unit in whipping process in 50min. Continue stirring 10min, the hollow glass micropearl dry 3h under 80 DEG C of conditions after processing is obtained modified hollow glass micropearl.
3) overlay film:
A, each component proportioning be:
Modified hollow glass micropearl 40kg; Thermal sensitivity composite resin 15kg; Coupling agent (DN-201 and A-187 mass ratio 1:2.5) 0.05kg; Hexamethylenamine 1.3kg; Calcium hydroxide 0.6kg; Calcium stearate 0.1kg; Acetone 18kg; Ethanol 8kg.
B, adopt repeatedly continuous film mulching method: put in puddle mixer by modified for above-mentioned 40kg hollow glass micropearl, it is heated to 200 DEG C, under the stirring of 320r/min rotating speed, by thermal sensitivity composite resin 7.5kg, coupling agent 0.025kg, hexamethylenamine 0.65kg, calcium hydroxide 0.3kg, calcium stearate 0.05kg, acetone 9kg, puddle mixer is added after ethanol 4kg mixing, stirring 2min, again by thermal sensitivity composite resin 7.5kg, coupling agent 0.025kg, hexamethylenamine 0.65kg, calcium hydroxide 0.3kg, calcium stearate 0.05kg, acetone 9kg, ethanol 4kg mixes addition, continue stirring 5min, cooling, sieve, obtain resin coating hollow glass micropearl. this resin coating hollow glass micropearl room temperature lower density is 0.78g/cm3, cladding thickness is 40 ��m��80 ��m, and comprcssive strength is 23MPa.
Sample (namely solidifying entirety) tensile strength after this resin coating hollow glass micropearl 100 DEG C solidification cementing (7 hours hardening times) is 11.5MPa, comprcssive strength is 12MPa, shear strength is 4.1MPa, soak 24 hours by the HCl that mass percent concentration is 10%, the NaOH of 10%, the NaCl solution of 10% respectively under 100 DEG C of conditions after solidification, corrosion rate respectively 0.11%, 0.13%, 0.01%.
Claims (12)
1. a resin coating hollow glass micropearl, including proppant and the covering being coated on proppant surface, it is characterised in that
Described proppant is the hollow glass micropearl that particle diameter 8��90 ��m, comprcssive strength are not less than 12MPa,
Described covering includes thermal sensitivity composite resin and curing agent composition, described covering can soften when temperature reaches more than 100 DEG C, solidify, making multiple resin coating hollow glass micropearl cementing is 10.5��14.3MPa for tensile strength, comprcssive strength is 9��22MPa, the solidification that shear strength is 4��6MPa is overall, it is described that to solidify overall be the HCl of 10% with mass percent concentration respectively under 100 DEG C of conditions, the NaOH of 10%, the NaCl solution of 10% is soaked 24 hours corrosion rates and is respectively less than 0.2%, described curing agent composition occurs the firming agent of curing reaction and curing accelerator to form by can make described thermal sensitivity composite resin when temperature reaches 100 DEG C,
The density of described resin coating hollow glass micropearl is 0.55��0.8g/cm3��
2. resin coating hollow glass micropearl as claimed in claim 1, it is characterised in that the preparation method of described thermal sensitivity composite resin is as follows:
(1) 1.8��2.3 mass parts phenol, 2.2��2.6 mass parts formaldehyde, 0.6��1.0 mass parts nonyl phenol and 1��1.5 mass parts water mix homogeneously are made, pH value be 8��9, temperature be under 85��90 DEG C of conditions, carry out polycondensation reaction 45��60min, the mass percent concentration of described formaldehyde is 36%��37%;
(2) adding 1.4��1.8 mass parts epoxy furfural acetone resins, mix homogeneously at 85��90 DEG C, the solids content of described furfural epoxy resin is more than 99%, and viscosity is 18��22mPa s;
(3) at 70 DEG C, vacuum dehydration fractionates out to anhydrous.
3. resin coating hollow glass micropearl as claimed in claim 2, it is characterised in that described firming agent is hexamethylenamine, and described curing accelerator is calcium hydroxide.
4. the resin coating hollow glass micropearl as according to any one of claims 1 to 3, it is characterised in that the density of described hollow glass micropearl is 0.32��0.60g/cm3��
5. the resin coating hollow glass micropearl as according to any one of claims 1 to 3, it is characterised in that described covering is 20��80 ��m at the cladding thickness of proppant surface.
6. the resin coating hollow glass micropearl as according to any one of claims 1 to 3, it is characterised in that the comprcssive strength of described resin coating hollow glass micropearl is 18��25MPa.
7. the preparation method of the resin coating hollow glass micropearl according to any one of claim 1��6, it is characterised in that comprise the following steps:
(1) clean, dry hollow glass micropearl;
(2) with coupling agent, hollow glass micropearl is carried out surface modification;
(3) overlay film: make the hollow glass micropearl after surface modification 40��55 mass parts, thermal sensitivity composite resin 15��22 mass parts and curing agent composition 1.9��3 mass parts, coupling agent 0.05��0.1 mass parts, lubricant 0.1��0.3 mass parts, solvent 26��30 mass parts at 200��210 DEG C, cooling after mixing under 210��320r/min rotating speed stirring condition, making thermal sensitivity composite resin and curing agent composition be coated on hollow glass micropearl surface, described curing agent composition is made up of firming agent 1.3��2.0 mass parts and curing accelerator 0.6��1 mass parts.
8. the preparation method of resin coating hollow glass micropearl as claimed in claim 7, it is characterized in that, the method of overlay film is: at 200��210 DEG C, under 210��320r/min rotating speed stirring condition, add in 40��55 modified mass parts hollow glass micropearls and be pre-mixed uniform thermal sensitivity composite resin 7.5��11 mass parts, coupling agent 0.025��0.05 mass parts, firming agent 0.65��1.0 mass parts, curing accelerator 0.3��0.5 mass parts, lubricant 0.05��0.15 mass parts, solvent 13��15 mass parts, continue stirring 2��5min, add and be pre-mixed uniform remaining thermal sensitivity composite resin 7.5��11 mass parts, coupling agent 0.025��0.05 mass parts, firming agent 0.65��1.0 mass parts, curing accelerator 0.3��0.5 mass parts, lubricant 0.05��0.15 mass parts, solvent 13��15 mass parts, cooling after stirring 3��6min, thermal sensitivity composite resin and curing agent composition is made to be coated on hollow glass micropearl surface.
9. the preparation method of resin coating hollow glass micropearl as claimed in claim 7 or 8, it is characterized in that, described coupling agent is the mixture that mass ratio is 1:2.3��1:2.8 of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters and ��-glycidyl ether oxygen propyl trimethoxy silicane.
10. the preparation method of resin coating hollow glass micropearl as claimed in claim 7 or 8, it is characterised in that described lubricant is calcium stearate.
11. the as claimed in claim 7 or 8 preparation method of resin coating hollow glass micropearl, it is characterised in that during overlay film, described solvent is acetone and ethanol mass ratio is the mixture of 1.8:1��2.5:1.
12. the preparation method of resin coating hollow glass micropearl as claimed in claim 7 or 8, it is characterized in that, the method that hollow glass micropearl carries out surface modification with coupling agent is: using ethanol and distilled water mass ratio be 8:1��10:1 ethanol water as modified solvent, in the modified solvent of 0.3��0.6 mass parts, add the coupling agent of quality is hollow glass micropearl 1 �롫2 ��, obtain coupling agent-ethanol water, under 500��1000r/min rotating speed stirs, above-mentioned coupling agent-ethanol water is injected to the hollow glass micropearl spraying that the cleaning-drying of 1��1.2 mass parts is good in 30��50min, continuing stirring makes coupling agent-ethanol water be uniformly distributed on hollow glass micropearl surface, hollow glass micropearl after processing is dried at 70��80 DEG C, obtain the hollow glass micropearl after surface modification.
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| CN116200184A (en) * | 2022-12-06 | 2023-06-02 | 中塑新材料技术(吉林)有限公司 | Petroleum fracturing propping agent and preparation method thereof |
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