CN103965390B - Polystyrene propping agent and preparation and application thereof - Google Patents

Polystyrene propping agent and preparation and application thereof Download PDF

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CN103965390B
CN103965390B CN 201410181659 CN201410181659A CN103965390B CN 103965390 B CN103965390 B CN 103965390B CN 201410181659 CN201410181659 CN 201410181659 CN 201410181659 A CN201410181659 A CN 201410181659A CN 103965390 B CN103965390 B CN 103965390B
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proppant
peroxide
parts
initiator
monomer
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CN103965390A (en )
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王文军
宋海韬
张百平
柳青
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辽宁德成科技集团有限公司
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Abstract

本发明涉及有机聚合物材料领域,特别是一种聚苯乙烯支撑剂及其制备和应用。 The present invention relates to the field of organic polymeric material, especially polystyrene, a proppant its preparation and use. 本发明的目的在于提供一种通过改变支撑剂的组成来达到提高油气井的产量及延长油气井压裂有效期的聚苯乙烯有机聚合物支撑剂,根据质量份数包括:100份单体、0.11-8份引发剂、2-10份无机分散剂、2-7份有机分散剂、0.2-1份补强剂、200-500份去离子水、0.8-3份表面活性剂;所述单体为苯乙烯或苯乙烯-二乙烯苯混合物。 Object of the present invention is to provide an agent by altering the composition to the support, to increase production of oil and gas wells and extend polystyrene organic polymer proppant validity wells, according to the quality of parts comprising: 100 parts of monomer, 0.11 -8 parts of initiator, 2-10 parts of an inorganic dispersant, 2-7 parts of organic dispersant, 0.2 parts of a reinforcing agent, 200-500 parts of deionized water, 0.8-3 parts surfactant; said monomer styrene or styrene - divinylbenzene mixture. 具有比重低、无静电、不易破碎、成本低、无污染等优点。 Having a low specific gravity, no static, not broken, low cost and no pollution.

Description

一种聚苯乙烯支撑剂及其制备和应用 One kind of polystyrene proppant and preparation and application

技术领域 FIELD

[0001] 本发明涉及有机聚合物材料领域,特别是一种聚苯乙烯支撑剂及其制备方法和应用。 [0001] The present invention relates to the field of organic polymeric material, in particular a polystyrene support and preparation method and application.

背景技术 Background technique

[0002]目前在油气钻井领域,压裂技术被广泛地采用。 [0002] Currently in the field of oil and gas drilling, fracturing technology has been widely adopted. 压裂技术不仅广泛应用于低渗透油气藏,而且中、高渗透油气藏的增产改造中也取得了很明显的效果。 Fracturing technology is not only widely used in low-permeability reservoirs, but also in high permeability reservoir stimulations also achieved very significant results. 就是在钻井后通过向井内注射高压流体,在井底憋起高压,当此压力大于井壁附近的地应力和地层岩石抗张强度时,在井底附近地层产生裂缝,继续注入带有支撑剂的液体,裂缝向前延伸并填以支撑剂,关井后裂缝闭合在支撑剂上,从而在井底附近地层形成具有一定几何尺寸和导流能力的填有支撑剂的裂缝,使油气井达到增产、增注及延长油气井二次或多次压裂周期的目的。 After drilling is by injecting high pressure fluid into the well, since the bottom hold pressure, when the pressure is greater than the ground near the wall stress and tensile strength of the formation rock, cracks in the formation near the bottom, with the continued injection of proppant liquid, and filled with a forwardly extending fracture proppant in the fracture closure shut on the proppant, thereby forming a filling with a geometry and conductivity of the formation near the fracture proppant with a bottom, so that oil and gas wells reach yield, by injection wells and prolong fracturing cycle two or more times. 传统的支撑剂为玻璃球、金属球、石英砂、陶粒等无机物或其包覆物,这些支撑剂普遍存在如下缺点:1、比重大,都在2.0以上,导致在压裂过程中传输支撑剂时流体粘度大、泵压高、能耗大;2、圆度及球度低,表面不光滑,对设备的磨损严重;3、容易破碎,导致裂缝过早闭合,影响产量;4、表面有覆膜,容易产生粘连,造成管道堵塞。 Conventional proppants glass balls, metal balls, quartz sand, ceramic, or inorganic substances such as coverings, proppants common disadvantage: 1, specific gravity, are not less than 2.0, resulting in a fracturing process in the transmission proppant fluid viscosity, high pressure pumps, energy consumption; 2, low sphericity and roundness, surface is not smooth, severe wear on the equipment; 3, easily broken, leading to premature fracture closure, yield; 4, surface coating film prone to blocking, resulting in pipe clogging.

发明内容 SUMMARY

[0003] 本发明的目的在于提供一种通过改变支撑剂的组成来达到提高油气井的产量及延长油气井压裂有效期的聚苯乙烯有机聚合物支撑剂。 [0003] The object of the present invention is to provide an agent by altering the composition to the support, to increase production of oil and gas wells and extend polystyrene organic polymer proppant validity wells.

[0004] 为实现上述目的,本发明的技术方案如下: [0004] To achieve the above object, the technical solution of the present invention is as follows:

[0005] 一种聚苯乙烯支撑剂,其特征在于,根据质量份数包括:100份单体、0.11-8份引发剂、2-10份无机分散剂、2-7份有机分散剂、0.2-1份补强剂、200-500份去离子水;所述单体为苯乙稀-二乙稀苯混合液。 [0005] A proppant polystyrene, characterized in that, according to the quality of parts comprising: 100 parts of monomer, 0.11-8 parts of initiator, 2-10 parts of an inorganic dispersant, 2-7 parts of organic dispersant, 0.2 1 part reinforcing agent, 200-500 parts of deionized water; the monomer is the styrene - ethylene two benzene mixture. 所述单体为苯乙稀、或苯乙稀-二乙稀苯混合物,优选地,交联剂二乙烯苯为苯乙烯质量的0-60%。 The monomer is the styrene, or Styrene - Ethylene two benzene mixture, preferably, the crosslinking agent is divinylbenzene of 0-60% by mass of styrene.

[0006] 所述支撑剂还可以包括0.01-5份增韧剂。 The [0006] proppant may further include 0.01 to 5 parts toughener.

[0007] 所述引发剂为有机过氧化物类引发剂,无机过氧化物类引发剂,自偶氮类引发剂,氧化-还原类引发剂的一种或几种。 [0007] The initiator is an organic peroxide-based initiator, an inorganic peroxide initiators, azo initiators from the oxide, - one or several redox-based initiator.

[0008] 优选地,所述有机过氧化物类引发剂包括氢过氧化异丙苯、氢过氧化特丁基、过氧化二苯甲酰、过氧化十二酰、过氧化二特丁基、过氧化二异丙苯、过氧化二碳酸二异丙酯中。 [0008] Preferably, the organic peroxide-based initiators include cumene hydroperoxide, t-butyl hydroperoxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, peroxide, dicumyl peroxide, di-isopropyl.

[0009] 所述无机过氧化物类引发剂包括过硫酸钾、过硫酸钠、过硫酸铵; [0009] The inorganic peroxide type initiators include potassium persulfate, sodium persulfate, ammonium persulfate;

[0010] 所述自偶氮类引发剂包括偶氮二异丁腈、偶氮二异庚腈; [0010] Since the azo initiators include azobisisobutyronitrile, azobis iso-heptyl-carbonitrile;

[0011] 所述氧化-还原类引发剂包括氧化还原体系的有过氧化苯甲酰/蔗糖、叔丁基过氧化氢/雕白块、叔丁基过氧化氢/焦亚硫酸钠、过氧化苯甲酰/N,N- 二甲基苯胺。 [0011] The oxidation - reduction type initiators include benzoyl peroxide, oxidation-reduction system / sucrose, t-butyl hydroperoxide / carved white block, t-butyl hydroperoxide / sodium metabisulfite, benzoyl peroxide, acid / N, N- dimethylaniline. 过硫酸铵/亚硫酸氢钠、过硫酸钾/亚硫酸氢钠、过氧化氢/酒石酸、过氧化氢/雕白块、过硫酸铵/硫酸亚铁、过氧化氢/硫酸亚铁、过氧化苯甲酰//N,N- 二乙基苯胺、过氧化苯甲酰/焦磷酸亚铁、过硫酸钾/硝酸银、过硫酸盐/硫醇、异丙苯过氧化氢/氯化亚铁、过硫酸钾/氯化亚铁、过氧化氢/氯化亚铁、异丙苯过氧化氢/四乙烯亚胺等。 Ammonium persulfate / sodium bisulfite, potassium persulfate / sodium bisulfite, hydrogen peroxide / tartaric acid, hydrogen peroxide / carved white block, ammonium persulfate / ferrous sulfate, hydrogen peroxide / ferrous sulfate, peroxide benzoyl // N, N- diethylaniline, benzoyl peroxide / ferrous pyrophosphate, potassium persulfate / silver nitrate, persulfate / thiol, cumene hydroperoxide / ferrous chloride , potassium persulfate / ferrous chloride, hydrogen peroxide / ferrous chloride, cumene hydroperoxide / tetraethylenepentamine imide and the like.

[0012] 更优选地,所述引发剂为过氧化苯甲酰和/或过氧化(2-乙基)己酸叔丁基。 [0012] More preferably, the initiator is benzoyl peroxide and / or peroxide (2-ethyl) hexanoate, tert-butyl group.

[0013] 优选地,所述无机分散剂为无水硫酸钠,活性磷酸钙,滑石粉的一种或几种;更优选为活性磷酸钙; [0013] Preferably, the inorganic dispersing agent is over anhydrous sodium sulfate, active calcium phosphate, one or more of talc; more preferably calcium activity;

[0014] 优选地,所述有机分散剂为聚乙烯醇,明胶,羟甲基纤维素,聚乙烯基吡咯烷酮的一种或几种;更优选为明胶; [0014] Preferably, the organic dispersing agent is polyvinyl alcohol, gelatin, hydroxymethyl cellulose, polyvinyl pyrrolidone is one or more; more preferably gelatin;

[0015] 优选地,所述补强剂采用炭黑,或是具有网状结构的无机物,如二氧化硅,碳化硼, [0015] Preferably, the inorganic reinforcing agent using carbon black, or having a mesh structure, such as silica, boron carbide,

白炭黑等; White carbon;

[0016] 优选地,所述表面活性剂为十二烷基苯磺酸钠,十二烷基磺酸钠,十二烷基硫酸钠,山梨醇糖酐油酸酯,山梨醇酐单硬脂酸酯,烷基酚聚氧乙烯醚或非离子表面活性剂壬基酚聚氧乙烯醚中的一种或几种。 [0016] Preferably, the surfactant is sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium lauryl sulfate, dextran sorbitan monooleate, sorbitan monostearyl esters, polyoxyethylene alkyl phenol or nonionic surfactant nonylphenol one or more vinyl ether.

[0017] 优选地,所述增初剂为烧氧基稀土中的一种或—种以上;烧氧基为二异丙氧基、二异丁氧基、三异戊氧基或三异辛氧基;所述稀土为钬、镨、铕、钆、铽、镝或铒。 [0017] Preferably, the solubilizing agent is the beginning of a sintered rare earth group or - more species; diisopropoxy group is burning, di-iso-butoxy, pentoxy or triisocyanate triisooctyl group; said rare holmium, praseodymium, europium, gadolinium, terbium, dysprosium or erbium.

[0018] 所得支撑剂成品优选球型固体,进一步优选直径为0.1-4.0mm的球型固体;支撑剂可以是白色,黑色或其它颜色;此颜色是根据加入不同的补强剂变化的。 [0018] The resulting finished product preferably spherical proppant solids, more preferably 0.1-4.0mm diameter of the spherical solid; proppant may be white, black or other color; this color is added in accordance with changes in various reinforcing agents.

[0019] 所述支撑剂的制备方法,包括如下步骤: [0019] The method for preparing proppants, comprising the steps of:

[0020] I)补强剂的预处理: [0020] I) pretreated reinforcing agent:

[0021] 表面活性剂:去离子水=1:5-1:30-50的质量比混匀,80_90°C搅拌8_12h,真空抽滤并水洗数次,滤至泥饼状袋装密封保存备用; [0021] Surfactant: Deionized water = 1: 5-1: 30-50 mass ratio of mixing, 80_90 ° C with stirring 8_12h, vacuum filtration and washed with water several times, mud filter cake to spare sealed bag ;

[0022] 2)交联聚苯乙烯微球的制备:在反应釜中加入表面活性剂,去离子水,无机分散剂,搅匀;将步骤I)所得补强剂和去离子水超声分散后加入反应釜中搅均;再将引发剂和单体混匀后加入反应釜中搅均,使补强剂由水相进入单体;缓慢升温至70-80°C,补加无机分散剂;90-100°C保温5-8h ;将物料放出后洗涤、固液分离、干燥,筛分,即得到聚苯乙烯支撑剂。 After step I) a reinforcing agent, and the resulting deionized water, ultrasonic dispersion; added to the reaction kettle surfactant, deionized water, inorganic dispersant, mix: Preparation of [0022] 2) crosslinked polystyrene microspheres stirred autoclave were added; then, after mixing initiator and monomer mix was added to the kettle, so that the reinforcing agent into the monomer from the aqueous phase; was slowly warmed to 70-80 ° C, supplemented with the inorganic dispersant; 5-8h incubation 90-100 ° C; after release the material is washed, solid-liquid separation, drying and sieving to obtain a polystyrene supported agent.

[0023] 所述支撑剂作为支撑剂应用于油气钻井压裂过程中,可承受大于170Mpa的闭合压力或作为离子交换树脂、或催化剂载体应用于其他方面。 [0023] The proppant applied as a proppant in fracturing oil and gas drilling, can withstand pressures greater than 170Mpa or closed as an ion resin exchange or catalyst support applied to other aspects.

[0024] 本发明的优点在于: [0024] The advantage of the present invention:

[0025] 1.比重低,在0.9-1.2之间,是有机物合成的,因为支撑剂是通过液体携带,经过高压泵传送到井底的。 [0025] 1. Low specific gravity between 0.9-1.2, is organic synthesis, because the proppant is carried by a liquid, is transferred to the bottom through the high-pressure pump. 如果比重大,对携带支撑剂液体的要求就高,否则支撑剂就容易沉淀,成本就高,同时泵在传输的过程中势必需要较高的的压力,能量消耗巨大; If the specific gravity of the liquid is required to carry the proppant is high, it is easy to precipitate or proppant, the cost will be high, while the pump is in the process of transmission will inevitably require higher pressures, huge energy consumption;

[0026] 2.圆度及球度高,表面光滑,本发明的支撑剂是完全光滑的球体,没有棱角,减少对设备的磨损; [0026] 2. high sphericity and roundness, surface smoothness, proppants of the present invention is a perfectly smooth sphere, no edges, to reduce wear on the device;

[0027] 3.不溶于酸、碱、油、水,无静电所以没有相互粘连的情况,不会出现早期粘连堵塞管道; [0027] 3. insoluble in acid, alkali, oil, water, non-static so without mutual adhesion, blocking does not occur early clogging pipes;

[0028] 4.目前常规聚苯乙烯系微球均采用苯乙烯与二乙烯基苯交联反应,以过氧化苯甲酰为引发剂,聚乙烯醇为分散剂进行悬浮聚合,其产物抗高温和抗压性均较低,本品热稳定性优异,可达到245摄氏度以上,不易破碎,一般压裂支撑剂最高的闭合压力为lOOMPa,本发明提供的支撑剂抗闭合压力可以达到170MPa以上,远远高于SY/T5108—2006的规定要求; [0028] 4. Current conventional polystyrene microspheres are used in the crosslinking reaction of benzene with a styrene divinyl, benzoyl peroxide as the initiator, the suspension polymerization of polyvinyl alcohol as dispersant, the product of high temperature and pressure resistance are low, the product is excellent in thermal stability, can reach more than 245 degrees Celsius is broken, the proppant typically highest pressure Loompa closed, the proppant of the present invention provides an anti-closing pressure can reach 170MPa or more, much higher than the predetermined SY / T5108-2006 requirements;

[0029] 5.反应温度较低,在常压下工作,工艺简单,且成本较低,适合大规模工业生产; [0029] The lower reaction temperature, operating at atmospheric pressure, the process is simple, and low cost, suitable for large scale industrial production;

[0030] 6.无毒,对环境没有危害; [0030] 6. The non-toxic, no harm to the environment;

[0031] 7.本品应用范围广,除用于支撑剂外,也可用于但不限于如离子交换树脂、催化剂载体等。 [0031] 7. A wide product range of the present application, except for the proppant, but may also be used such as, but not limited to ion exchange resin, catalyst carrier exchange.

具体实施方式 Detailed ways

[0032] 实施例1: [0032] Example 1:

[0033] 炭黑改性:将炭黑4g,十二烧基苯磺酸钠8g,去离子水200g混勾,80°C搅拌8h,真空抽滤并水洗数次,滤至泥饼状袋装密封保存备用。 [0033] Modified Carbon black: carbon black 4g, twelve burning benzene sulfonate 8g, hook mixing 200g deionized water, 80 ° C was stirred for 8h, vacuum filtration and washed with water several times, to the mud filter cake bags sealing means for use.

[0034] 黑色交联聚苯乙烯微球的制备:在反应釜中加入表面活性剂十二烷基苯磺酸钠2.8g,去离子水400mL,无机分散剂活性磷酸妈7g,机械搅拌20min,速度160rpm。 [0034] prepare a black crosslinked polystyrene microspheres: in the kettle was added the surfactant sodium dodecylbenzene sulfonate 2.8g, deionized water, 400mL, inorganic dispersant activity of phosphate mother 7g, mechanical stirring 20min, speed 160rpm. 将改性炭黑Ig和去离子水40mL,超声分散60min,加入反应藎中,搅拌60min。 The modified carbon black, and deionized water Ig 40mL, ultrasonic dispersion 60min, Jin added to the reaction and stirred 60min. 将引发剂过氧化苯甲酰2g,苯乙烯90g,二乙烯苯10g,混匀后加入反应釜中,保持速度160rpm搅拌lOmin,使改性炭黑由水相进入单体。 The initiator benzoyl peroxide 2g, styrene 90g, divinylbenzene 10g, added to the kettle after mixing, holding stirring speed 160rpm lOmin, the modified carbon black from the aqueous phase into the monomer. 在1.5h内缓慢升温至75°C,随着温度上升,单体被引发聚合,单体粘度逐渐上升,补加明胶溶液50mL,搅拌增速至250rpm。 Over 1.5h was slowly warmed to 75 ° C, as the temperature rises, polymerization of the monomer is initiated, gradual increase in viscosity of the monomer, complement plus gelatin solution 50mL, growth was stirred to 250rpm. 95°C保温6h。 95 ° C incubation 6h. 将物料放出后洗涤、固液分离、干燥,筛分,即得到交联聚苯乙烯有机聚合物支撑剂。 After the release material was washed, solid-liquid separation, drying and sieving to obtain a crosslinked organic polymer polystyrene proppant.

[0035] 经检测,产品各项指标如下:比重:0.9—1.2g/cm3,抗压强度彡60N,闭合压力^ 170MPa (抗压强度是个体属性,闭合压力是整体体现出来的能力),热稳定性多245°C,粒径:0.4—1.2mm,酸溶解度〈4.0%,破碎率〈3.0%,球度和圆度多0.95。 [0035] After testing, the product of the indicators are as follows: specific gravity: 0.9-1.2g / cm3, compressive strength San 60N, closure pressure ^ 170MPa (compressive strength is an individual property, the closure pressure is reflected overall capacity), heat stability of multi-245 ° C, particle diameter: 0.4-1.2mm, acid solubility <4.0%, the crushing rate of <3.0%, sphericity and roundness multi 0.95.

[0036] 实施例2: [0036] Example 2:

[0037] 炭黑改性:将炭黑4g,十二烧基苯磺酸钠6g,去离子水220g混勾,80°C搅拌8h,真空抽滤并水洗数次,滤至泥饼状袋装密封保存备用。 [0037] Modified Carbon black: carbon black 4g, twelve burning benzene sulfonate 6g, hook mixing 220g deionized water, 80 ° C was stirred for 8h, vacuum filtration and washed with water several times, to the mud filter cake bags sealing means for use.

[0038] 黑色交联聚苯乙烯微球的制备:在反应釜中加入表面活性剂十二烷基苯磺酸钠2.5g,去离子水350mL,无机分散剂活性磷酸妈6g,机械搅拌20min,速度170rpm。 [0038] prepare a black crosslinked polystyrene microspheres: in the kettle was added the surfactant sodium dodecylbenzene sulfonate 2.5g, 350 mL of deionized water, inorganic dispersant activity of phosphate mother 6g, mechanical stirring 20min, speed 170rpm. 将改性炭黑0.8g和去离子水40mL,超声分散50min,加入反应藎中,搅拌60min。 The modified carbon black 0.8g of deionized water and 40mL, ultrasonic dispersion 50min, Jin added to the reaction and stirred 60min. 将引发剂过氧化(2-乙基)己酸叔丁基1.6g,苯乙稀92g,二乙稀苯8g,增韧剂三异丙氧基镨3g,混勾后加入反应Il中,保持速度170rpm搅拌lOmin,使改性炭黑由水相进入单体。 The peroxide initiator (2-ethyl) hexanoate, t-butyl 1.6g, 92 g Styrene, ethylene two benzene 8g, praseodymium toughener triisopropoxide 3g, Il added to the reaction mixture after the hook, retaining stirring speed 170rpm lOmin, the modified carbon black from the aqueous phase into the monomer. 在1.5h内缓慢升温至72°C,随着温度上升,单体被引发聚合,单体粘度逐渐上升,补加明胶溶液55mL,95°C保温6h。 Over 1.5h was slowly warmed to 72 ° C, as the temperature rises, polymerization of the monomer is initiated, gradual increase in viscosity of the monomer, complement plus gelatin solution 55mL, 95 ° C incubation 6h. 将物料放出后洗涤、固液分离、干燥,筛分,即得到交联聚苯乙烯有机聚合物支撑剂。 After the release material was washed, solid-liquid separation, drying and sieving to obtain a crosslinked organic polymer polystyrene proppant.

[0039] 经检测,产品各项指标如下:比重:0.9—1.2g/cm3,抗压强度彡60N,闭合压力彡170MPa,热稳定性彡245°C,粒径:0.3—1.2mm,酸溶解度〈4.0%,破碎率〈3.0%,球度和圆度彡0.95。 [0039] After testing, the product of the indicators are as follows: specific gravity: 0.9-1.2g / cm3, compressive strength San 60N, San closure pressure 170MPa, San thermal stability 245 ° C, particle diameter: 0.3-1.2mm, acid solubility <4.0%, the crushing rate of <3.0%, sphericity and roundness San 0.95.

[0040] 实施例3: [0040] Example 3:

[0041] 炭黑改性:将炭黑4g,十二烧基苯磺酸钠6g,去离子水180g混勾,90°C搅拌9h,真空抽滤并水洗数次,滤至泥饼状袋装密封保存备用。 [0041] Modified Carbon black: carbon black 4g, twelve burning benzene sulfonate 6g, hook mixing 180g deionized water, 90 ° C with stirring 9H, vacuum filtration and washed with water several times, to the mud filter cake bags sealing means for use.

[0042] 黑色交联聚苯乙烯微球的制备:在反应釜中加入表面活性剂十二烷基苯磺酸钠 [0042] prepare a black crosslinked polystyrene microspheres: adding a surfactant of sodium dodecylbenzenesulfonate in an autoclave

1.3g,去离子水300mL,无机分散剂活性磷酸妈4g,机械搅拌20min,速度200rpm。 1.3g, 300 mL of deionized water, inorganic dispersant activity of phosphate mother 4g, mechanical stirring 20min, the speed of 200rpm. 将改性炭黑0.2g和去离子水20mL,超声分散60min,加入反应藎中,搅拌40min。 The modified carbon black 0.2g of deionized water and 20mL, ultrasonic dispersion 60min, Jin added to the reaction and stirred 40min. 将引发剂过氧化苯甲酰和过氧化(2-乙基)己酸叔丁基混合物1.2g,苯乙烯96g,二乙烯苯4g,增韧剂三异丁氧基钬3g,混勾后加入反应Il中,保持速度200rpm搅拌20min,使改性炭黑由水相进入单体。 The initiator benzoyl peroxide and peroxy (2-ethylhexyl) mixture of tert-butyl 1.2g, styrene 96g, divinylbenzene 4g, isobutoxy toughener three holmium 3g, was added after the mixing hook Il reactions, the retention rate 200rpm stirring 20min, the modified carbon black from the aqueous phase into the monomer. 在1.5h内缓慢升温至73°C,随着温度上升,单体被引发聚合,单体粘度逐渐上升,补加明胶溶液50mL。 Over 1.5h was slowly warmed to 73 ° C, as the temperature rises, polymerization of the monomer is initiated, gradual increase in viscosity of the monomer, complement plus gelatin solution 50mL. 90°C保温8h。 90 ° C incubation 8h. 将物料放出后洗涤、固液分离、干燥,筛分,即得到交联聚苯乙烯有机聚合物支撑剂,。 After the release material was washed, solid-liquid separation, drying and sieving to obtain a crosslinked organic polymer polystyrene proppants.

[0043] 经检测,产品各项指标如下:比重:0.9—1.2g/cm3,抗压强度彡60N,闭合压力彡170MPa,热稳定性彡245°C,粒径:0.1—1.2mm,酸溶解度〈4.0%,破碎率〈3.0%,球度和圆度彡0.95。 [0043] After testing, the product of the indicators are as follows: specific gravity: 0.9-1.2g / cm3, compressive strength San 60N, San closure pressure 170MPa, San thermal stability 245 ° C, particle size: 0.1-1.2 mm, acid solubility <4.0%, the crushing rate of <3.0%, sphericity and roundness San 0.95.

[0044] 实施例4: [0044] Example 4:

[0045] 白炭黑改性:将白炭黑4g,十二烷基磺酸钠6g,去离子水180g混匀,90°C搅拌9h,真空抽滤并水洗数次,滤至泥饼状袋装密封保存备用。 [0045] The modified silica: A silica 4g, sodium dodecyl sulfate 6g, mixing 180g deionized water, 90 ° C with stirring 9H, vacuum filtration and washed with water several times, to mud filter cake sealed bags were stored.

[0046] 白色交联聚苯乙烯微球的制备:在反应釜中加入表面活性剂十二烷基磺酸钠 [0046] Preparation of white crosslinked polystyrene microspheres: addition of a surfactant sodium dodecyl sulfate in an autoclave

1.3g,去离子水300mL,无机分散剂滑石粉4g,机械搅拌20min,速度200rpm。 1.3g, deionized water, 300mL, inorganic dispersants talc 4g, mechanical stirring 20min, the speed of 200rpm. 将改性白炭黑0.2g和去离子水20mL,超声分散60min,加入反应釜中,搅拌40min。 The modified silica and 0.2g deionized water 20mL, ultrasonic dispersion 60min, added to the reaction kettle, stirred 40min. 将引发剂过硫酸钾0.2g,苯乙烯96g,二乙烯苯4g,增韧剂三异丁氧基铕2g,混匀后加入反应釜中,保持速度200rpm搅拌20min,使改性白炭黑由水相进入单体。 The initiator of potassium persulfate 0.2g, styrene 96g, divinylbenzene 4g, isobutoxy europium toughener three 2g, added after mixing kettle, 200rpm stirring speed to maintain 20min, the modified silica of monomer into the aqueous phase. 在1.5h内缓慢升温至73°C,随着温度上升,单体被引发聚合,单体粘度逐渐上升,补加聚乙烯醇溶液50mL。 Over 1.5h was slowly warmed to 73 ° C, as the temperature rises, polymerization of the monomer is initiated, gradual increase in viscosity of the monomer, additional polyvinyl alcohol solution 50mL. 100°C保温5h。 100 ° C incubation 5h. 将物料放出后洗涤、固液分离、干燥,筛分,即得到交联聚苯乙烯有机聚合物支撑剂。 After the release material was washed, solid-liquid separation, drying and sieving to obtain a crosslinked organic polymer polystyrene proppant.

[0047] 经检测,产品各项指标如下:比重:0.9—1.2g/cm3,抗压强度彡60N,闭合压力彡170MPa,热稳定性彡245°C,粒径:0.1—1.2mm,酸溶解度〈4.0%,破碎率〈3.0%,球度和圆度彡0.95。 [0047] After testing, the product of the indicators are as follows: specific gravity: 0.9-1.2g / cm3, compressive strength San 60N, San closure pressure 170MPa, San thermal stability 245 ° C, particle size: 0.1-1.2 mm, acid solubility <4.0%, the crushing rate of <3.0%, sphericity and roundness San 0.95.

[0048] 实施例5: [0048] Example 5:

[0049] 碳化硼和炭黑改性:将碳化硼2g和炭黑2g,十二烷基硫酸钠Sg,去离子水200g混匀,80°C搅拌8h,真空抽滤并水洗数次,滤至泥饼状袋装密封保存备用。 [0049] The modified boron carbide and carbon black: carbon black and boron carbide 2g 2g, sodium lauryl sulfate Sg, mixing 200g deionized water, 80 ° C was stirred for 8h, vacuum filtration and washed with water several times, filtered mud cake sealed bags to spare.

[0050] 黑色交联聚苯乙烯微球的制备:在反应釜中加入表面活性剂十二烷基硫酸钠 [0050] prepare a black crosslinked polystyrene microspheres: surfactant is added sodium lauryl sulfate in an autoclave

2.8g,去离子水400mL,无机分散剂活性磷酸妈和无水硫酸钠各3.5g,机械搅拌20min,速度160rpm。 2.8g, deionized water, 400mL, inorganic dispersant activity and dried over anhydrous sodium phosphate mother each 3.5g, mechanical stirring 20min, the speed of 160rpm. 将改性碳化硼和炭黑各0.5g和去离子水40mL,超声分散60min,加入反应藎中,搅拌60min。 The modified carbon black and boron carbide each of deionized water and 0.5g 40mL, ultrasonic dispersion 60min, Jin added to the reaction and stirred 60min. 将引发剂8g,苯乙稀90g,二乙稀苯10g,增韧剂三异丁氧基钬5g,混勾后加入反应Il中,保持速度160rpm搅拌lOmin,使改性碳化硼和炭黑由水相进入单体。 The initiator 8g, Styrene 90g, two ethylene benzene 10g, isobutoxy toughener three holmium 5g, after the reaction mixture was added Il hook, the retaining lOmin stirring speed 160rpm, the modified carbon black and boron carbide by a monomer into the aqueous phase. 在1.5h内缓慢升温至75°C,随着温度上升,单体被引发聚合,单体粘度逐渐上升,补加明胶溶液50mL,搅拌增速至250rpm。 Over 1.5h was slowly warmed to 75 ° C, as the temperature rises, polymerization of the monomer is initiated, gradual increase in viscosity of the monomer, complement plus gelatin solution 50mL, growth was stirred to 250rpm. 95°C保温6h。 95 ° C incubation 6h. 将物料放出后洗涤、固液分离、干燥,筛分,即得到交联聚苯乙烯有机聚合物支撑剂,。 After the release material was washed, solid-liquid separation, drying and sieving to obtain a crosslinked organic polymer polystyrene proppants.

[0051] 经检测,产品各项指标如下:比重:0.9—1.2g/cm3,抗压强度彡60N,闭合压力彡170MPa,热稳定性彡245°C,粒径:0.4—1.2mm,酸溶解度〈4.0%,破碎率〈3.0%,球度和圆度彡0.95。 [0051] After testing, the product of the indicators are as follows: specific gravity: 0.9-1.2g / cm3, compressive strength San 60N, San closure pressure 170MPa, San thermal stability 245 ° C, particle diameter: 0.4 to about 1.2mm, acid solubility <4.0%, the crushing rate of <3.0%, sphericity and roundness San 0.95.

[0052] 本发明的检测方法以及数据参照中华人民共和国石油天然气行业标准《压裂支撑剂性能指标及测试推荐方法》SY/T5108—2006。 [0052] and a data detecting method of the present invention with reference to the oil and gas industry standards PRC "proppant performance and Recommended Test Method" SY / T5108-2006.

Claims (10)

  1. 1. 一种聚苯乙烯支撑剂,其特征在于,根据质量份数,原料包括:100份单体、O. 11-8份引发剂、2-10份无机分散剂、2-7份有机分散剂、O. 2-1份补强剂、200-500份去离子水、O. 8-3份表面活性剂;所述单体为苯乙烯和二乙烯苯的混合物;所述单体中二乙烯苯的质量小于或等于苯乙烯质量的60%,但不等于零;支撑剂组成成份中还包括有O. 01-5份增韧剂。 A proppant polystyrene, wherein the number of copies according to the quality of raw materials comprising: 100 parts of monomer, O 11-8 parts of initiator, dispersing agent, 2-10 parts of an inorganic, organic dispersion parts 2-7. . agent, O 2-1 parts of a reinforcing agent, 200-500 parts of deionized water, O 8-3 parts surfactant; and mixtures of said monomer is styrene and divinylbenzene; the two monomers DVB mass less than or equal to 60% by mass of styrene, but not equal to zero; constituent proppant further comprises a toughener parts O. 01-5.
  2. 2.根据权利要求I所述的支撑剂,其特征在于,所述增韧剂为烷氧基稀土中的一种或二种以上;烷氧基为三异丙氧基、三异丁氧基、三异戊氧基或三异辛氧基;所述稀土为钬、镨、铕、钆、铽、镝或铒。 The proppant of claim I, wherein said toughener is a rare earth alkoxy of one or two or more; alkoxy three isopropoxy, isobutoxy three , triisobutyl or tri-isooctyl pentoxy group; said rare holmium, praseodymium, europium, gadolinium, terbium, dysprosium or erbium.
  3. 3.根据权利要求I或2所述的支撑剂,其特征在于,所述引发剂为有机过氧化物类引发剂,无机过氧化物类引发剂,自偶氮类引发剂,氧化-还原类引发剂中的一种或二种以上。 3. The proppant of claim I or claim 2, wherein the initiator is an organic peroxide-based initiator, an inorganic peroxide initiators, azo initiators from the oxidation - reduction type initiator, one or more agents in combination.
  4. 4.根据权利要求3所述的支撑剂,其特征在于,所述有机过氧化物类引发剂包括氢过氧化异丙苯、氢过氧化特丁基、过氧化二苯甲酰、过氧化十二酰、过氧化二特丁基、过氧化二异丙苯、过氧化二碳酸二异丙酯中的一种或二种以上; 所述无机过氧化物类引发剂包括过硫酸钾、过硫酸钠、过硫酸铵中的一种或二种以上; 所述自偶氮类引发剂包括偶氮二异丁腈、偶氮二异庚腈中的一种或二种以上; 所述氧化-还原类引发剂包括氧化还原体系的有过氧化苯甲酰/蔗糖、叔丁基过氧化氢/雕白块、叔丁基过氧化氢/焦亚硫酸钠、过氧化苯甲酰/N,N- 二甲基苯胺。 4. The proppant according to claim 3, wherein said organic peroxide initiators include cumene hydroperoxide, hydrogen peroxide, t-butyl peroxide, dibenzoyl peroxide, ten dicarboxylic acid, t-butyl peroxide, dicumyl peroxide, di over an oxidation isopropyl or two or more species; the inorganic peroxide type initiators include potassium persulfate, persulfuric acid sodium, ammonium persulfate, one or two or more kinds; from the azo-based initiators include azobisisobutyronitrile, azobis isobutyl nitrile heptyl one or two or more; the oxidation - reduction based initiator include a redox system benzoyl peroxide / sucrose, t-butyl hydroperoxide / carved white block, t-butyl hydroperoxide / sodium metabisulfite, benzoyl peroxide / N, N- dimethyl aniline. 过硫酸铵/亚硫酸氢钠、过硫酸钾/亚硫酸氢钠、过氧化氢/酒石酸、过氧化氢/雕白块、过硫酸铵/硫酸亚铁、过氧化氢/硫酸亚铁、过氧化苯甲酰//N,N- 二乙基苯胺、过氧化苯甲酰/焦磷酸亚铁、过硫酸钾/硝酸银、过硫酸盐/硫醇、异丙苯过氧化氢/氯化亚铁、过硫酸钾/氯化亚铁、过氧化氢/氯化亚铁、异丙苯过氧化氢/四乙烯亚胺中的一种或二种以上。 Ammonium persulfate / sodium bisulfite, potassium persulfate / sodium bisulfite, hydrogen peroxide / tartaric acid, hydrogen peroxide / carved white block, ammonium persulfate / ferrous sulfate, hydrogen peroxide / ferrous sulfate, peroxide benzoyl // N, N- diethylaniline, benzoyl peroxide / ferrous pyrophosphate, potassium persulfate / silver nitrate, persulfate / thiol, cumene hydroperoxide / ferrous chloride , potassium persulfate / ferrous chloride, hydrogen peroxide / ferrous chloride a cumene hydroperoxide / tetrachloroethane ethylenimine or more kinds.
  5. 5.根据权利要求3所述的支撑剂,其特征在于,所述引发剂为过氧化苯甲酰和/或过氧化(2-乙基)己酸叔丁基。 5. A proppant according to claim 3, wherein the initiator is benzoyl peroxide and / or peroxide (2-ethyl) hexanoate, tert-butyl group.
  6. 6.根据权利要求I或2所述的支撑剂,其特征在于,所述无机分散剂为无水硫酸钠,活性磷酸钙,滑石粉中的一种或二种以上;所述有机分散剂为黄原胶,聚乙烯醇,明胶,羟甲基纤维素,羟乙基纤维素,聚乙烯基吡咯烷酮中的一种或二种以上。 6. The proppant of claim I or claim 2, wherein the inorganic dispersing agent is over anhydrous sodium sulfate, active calcium phosphate, talc, one kind or two or more kinds; the organic dispersant xanthan gum, polyvinyl alcohol, gelatin, hydroxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone one kind or two or more.
  7. 7.根据权利要求I或2所述的支撑剂,其特征在于,所述补强剂为炭黑、白炭黑、二氧化硅、或碳化硼中的一种或二种以上;所述表面活性剂为十二烷基苯磺酸钠,十二烷基磺酸钠,十二烷基硫酸钠,山梨醇糖酐油酸酯,山梨醇酐单硬脂酸酯,烷基酚聚氧乙烯醚或非离子表面活性剂壬基酚聚氧乙烯醚中的一种或二种以上。 7. The proppant of claim I or claim 2, wherein the reinforcing agent is carbon black, white carbon black, silica, boron carbide, or of one or two or more; the surface active agents are sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium lauryl sulfate, dextran sorbitan monooleate, sorbitan monostearate, polyoxyethylene alkyl phenol surfactant nonylphenol polyoxyethylene ether or a nonionic an ethylene ether or two or more kinds.
  8. 8.根据权利要求I或2所述的支撑剂,其特征在于,所述支撑剂制得成品优选球型固体。 8. The proppant of claim I or claim 2, wherein the proppant prepared products preferably spherical solids.
  9. 9. 一种权利要求1-8任一所述支撑剂的制备方法,其特征在于,包括如下步骤: 1)补强剂的预处理: 补强剂:表面活性剂:去离子水=1:5-1:30-50的质量比混匀,80-90°C搅拌8-12h,真空抽滤并水洗数次,滤至泥饼状袋装密封保存备用; 2)交联聚苯乙烯微球的制备:在反应釜中加入表面活性剂,去离子水,无机分散剂,搅匀;将步骤I)所得补强剂和去离子水超声分散后加入反应釜中搅均;再将引发剂、增韧剂和单体混匀后加入反应釜中搅均,使补强剂由水相进入单体;缓慢升温至70-80°C,补加无机分散剂;90-100°C保温5-8h ;将物料放出后洗涤、固液分离、干燥,筛分,即得到聚苯乙烯支撑剂。 9. A method for preparing the proppant any one of claims 1-8, characterized in that it comprises the following steps: 1) pre-treating the reinforcing agent: reinforcing agent: surfactant: Deionized water = 1: 5-1: mixing mass ratio of 30-50, 80-90 ° C was stirred for 8-12h, vacuum filtration and washed with water several times, mud filter cake to spare sealed bag; 2) crosslinked preparation ball: added to the reaction kettle surfactant, deionized water, inorganic dispersant, mix; step I) the resulting reinforcing agent, and deionized water was added after ultrasonic dispersion was stirred kettle; then the initiator , toughening agents, and after mixing the monomer mix was added to the kettle, so that the reinforcing agent into the monomer from the aqueous phase; was slowly warmed to 70-80 ° C, supplemented with the inorganic dispersant; 90-100 ° C incubation 5 8h west; material discharged after washing, solid-liquid separation, drying and sieving to obtain a polystyrene supported agent.
  10. 10. 一种权利要求1-8任一所述支撑剂作为支撑剂在油气钻井压裂过程中的应用,或作为离子交换树脂、或催化剂载体方面的应用。 The proppant of any one of claims 1-8 10. The use as a proppant in fracturing during oil and gas drilling or resin application, or aspect of the catalyst support as the ion exchange.
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