一种可回用瓜尔胶压裂液体系的研究

针对渭北油田水资源短缺、压裂用水困难,结合渭北长3油藏储层的特征,研发了一种可回用压裂液体系,合成了可回用压裂液稠化剂磺酸基羟丙基瓜尔胶。采用有机硼交联,通过对返排液进行处理后再配液,实现了瓜尔胶压裂液的三级回用。三次配液综合性能良好,耐温耐剪切性优、破胶彻底、残渣少、对储层伤害小,可以满足同类储层压裂施工的需要。     

低残渣压裂液体系的形成及性能评价

针对现场所用的传统压裂液体系存在的残渣量高、易堵塞储层的有效孔隙和裂缝、降低油气产量等问题,本文通过在大分子半乳聚糖上接入新的化学基团,制备得到改性的羟丙基瓜胶。研究了反应时间、反应温度和酸碱度对所形成体系的影响,评价了该体系的稳定性、携砂性能和破胶性能,认为所形成的低残渣压裂液体系具有良好的热稳定性、强的携砂能力和破胶性能。     

高温低浓度压裂液研究与应用

针对改性瓜胶高温压裂液增稠剂使用质量分数高、破胶性能低、成本高的问题,制备了可与羟丙基瓜胶交联且使形成的压裂液体系具备良好性能的硼交联剂,得到了适用于深层致密油气藏的高温羟丙基瓜胶压裂液体系。对影响交联剂的主要因素进行了分析和优选,基于优选结果制备了络合硼交联剂,并对其交联形成的羟丙基瓜胶压裂液体系进行了综合性能评价。结果表明:硼酸质量分数20%,交联促进剂质量分数7%,多元醇混合物质量分数25%～30%,可制备出优良的硼交联剂,其性能优于国内通常使用的有机硼交联剂。羟丙基胍胶使用质量分数为0.5%时,形成的高温低质量分数压裂液黏度提高74.5%,残渣质量分数降低48.7%,满足180℃储层改造的需要。     

羧甲基羟丙基胍胶压裂液性能评价与研究

目前我国各大油田使用的压裂液主要是水基压裂液,胍胶原粉广泛用作水溶液增稠剂,胍胶经过改性后,增加了分子的分支程度,使其水溶速度加快,粘度提高,热稳定性增强,防腐储存性因改性而改善。将羟丙基胍胶(HPG)稠化剂部分基团改为羧甲基,使形成的胍胶压裂液具有了一些新的性能,在相同温度下,稠化剂使用浓度大幅下降,水不溶物含量降低,聚合物网状结构更好,弹性好,携砂能力强,并且在施工摩阻较小,对深井、大排量施工井更有利。该论文评价了羧甲基羟丙基胍胶(CMHPG)压裂液基础性能和在一定温度下的耐温性、破胶性能,评价出羧甲基羟丙基胍胶压裂液具有易配制、高弹性、高悬砂性及低稠化剂、低基液黏度、低残渣的特性。     

聚合物清洁压裂液在河南油田的应用

聚合物清洁压裂液增稠剂水不溶物极低，在防止储层二次伤害，提高返排方面明显优于羟丙基胍胶、瓜尔胶压裂液。聚合物清洁压裂液有别于VES清洁压裂液，它克服了VES清洁压裂液胶束稳定性差，在水和油存在下失效，对配制环境要求高，配制繁琐的弱点，具有较好的悬砂性、耐温耐剪切性，易破胶返排。经现场试验表明，该压裂液具有较好的推广应用前景。     

致密砂岩油藏低浓度胍胶压裂储层伤害实验

为分析低浓度胍胶压裂对致密砂岩储层带来的伤害,以A、B、C等低含水区块为研究实例,构建压裂液耐温抗剪切性能、黏弹性和携砂性能、破胶性能和岩心配伍性实验。研究得出:所研配方在充分剪切2 h后黏度仍然大于50 mPa·s,评定为合规。而在配方质量分数对比上,60～120℃的不同井温前提下都表现出羧甲基羟丙基胍胶(CMHPG)压裂液与羟丙基胍胶(HPG)压裂液用量的巨大差异,其中明显是CMHPG更省和成本更优;所研压裂液180℃高温下的残渣质量浓度为270 mg·L~(-1),显著优于HPG体系破胶情况;正向注入3 PV过硫酸铵破胶液后渗透率急剧下降至1.389×10~(-2)μm~2,返向注入3 PV 3%NH_4Cl解除伤害后渗透率恢复至2.586×10~(-2)μm~2,为初始值的89%,判定该压裂液对储层伤害低。     

纳米二氧化硅改性有机硼交联剂的制备与性能评价

为重复利用有机硼交联剂制备的压裂液,将N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷表面改性的纳米二氧化硅与乙二醇丁醇硼酸酯发生硼酰化反应,制得纳米二氧化硅有机硼交联剂(NSOBCL),对制备条件进行了优化,通过红外光谱仪表征了NSOBCL的结构,研究了NSOBCL和破胶液配制压裂液的耐温抗剪切性。结果表明,制备有机硼交联剂中间体时,N,N-二胺乙基丙酸甲酯单体与表面氨基改性二氧化硅的最佳质量比为54∶1;制备NSOBCL时,硼酸脂与交联剂中间体的最佳质量比为1∶2。红外表征结果表明合成产物与预期结构相符。0.25%羟丙基胍胶与0.3%NSOBCL等配制的压裂液耐温抗剪切性能较好,在80℃、170 s^(-1)下剪切60 min的黏度约为178 mPa·s;破胶剂过硫酸铵可使压裂液在80℃、120 min内完全破胶,破胶液黏度为2.68 mPa·s。NSOBCL可用于压裂液破胶液的再次交联。在破胶液中补加0.25%羟丙基胍胶和0.4%NSOBCL,于80℃、170 s(-1)下剪切60 min的黏度约为178 mPa·s;破胶剂过硫酸铵可使压裂液在80℃、120 min内完全破胶,破胶液黏度为2.68 mPa·s。NSOBCL可用于压裂液破胶液的再次交联。在破胶液中补加0.25%羟丙基胍胶和0.4%NSOBCL,于80℃、170 s^(-1)下剪切60 min后的黏度为175 mPa·s;而现场使用的JL-13交联剂无法满足重复使用的要求。     

压裂液长期滞留对低渗透储层的伤害试验研究

针对当前低渗透油藏中大量使用的压裂液给储层带来的伤害,导致开采量降低的问题,以羟丙基瓜尔胶压裂液作为研究对象,以适应充填装置作为储层模拟,以渗透损失率作为评价指标,探讨不同因素对羟丙基瓜尔胶滞留的影响。结果表明,不同羟丙基瓜尔胶压裂液浓度、pH值和温度对渗透损失率和压裂液滞留量都有着影响。其中浓度越大,对渗透损失率的影响越大,但随着浓度的持续增加,其影响也逐步变小;pH值越大,对渗透损失率的影响越小;温度与渗透损失率和滞留量呈现为正相关关系。由此通过上述的研究,为石油开采中压裂液的配比提供了参考,对减少压裂液对储层的损害具有可借鉴性。     

羧甲基压裂液在苏里格气田的初步应用与认识

2011年羟丙基瓜胶价格开始上涨,由昆山公司生产的羧甲基羟丙基瓜胶压裂液体系在苏里格气田某区块现场试验两口井。苏里气田属于低渗透气藏,储层埋藏深度在3150-3510m,温度在100-115℃之间。现场应用表明羧甲基羟丙基瓜胶压裂液的携砂性能与羟丙基瓜胶压裂的携砂性能相当,但是返排效果明显优于羟丙基瓜胶压裂液体系,并且该体系具有耐高温,低浓度、低残渣、低伤害、低摩阻、价格低等特点,是今后压裂液发展的方向。     

改性瓜胶压裂液的制备及性能研究

分别以十二烷基和磺酸盐甜菜碱为修饰基团,以瓜胶原粉为主剂,制备了2种改性瓜胶增稠剂:疏水改性羟丙基瓜胶和磺酸盐甜菜碱型瓜胶。模拟现场配方,对其配制的压裂液的抗剪切性能和耐温性能进行评价。通过对比发现磺酸盐甜菜碱型胍胶比油田提供CJ2-6胍胶耐温抗剪切能力有所下降,疏水改性羟丙基胍胶比油田提供CJ2-6胍胶耐温抗剪切能力有明显改善。其中,疏水改性羟丙基瓜胶80℃下剪切60 min后,表观粘度为93.4 m Pa·s,比油田提供CJ2-6瓜胶耐温抗剪切能力有明显改善。可以考虑疏水改性羟丙基瓜胶在压裂液体系的进一步应用。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。