Castor Oil-Based Environmentally Friendly Waterborne Polyurethane Filming Agent CWPU
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摘要: 随着油气勘探的进行，低渗透油气层易受损害，且难恢复的问题愈加严重，成膜剂的研发有助于解决这一难题。然而，目前成膜剂合成的原料为石油类产品，对环境保护不利。蓖麻油作为一种价廉易得的生物质资源，是自然界中存在的不需要改性就具有羟基的植物油，还含有多种活性化学键，可用于制备各种高效的处理剂。在蓖麻油分子上，引入异佛尔酮和扩链剂，制备了一种环保水性聚氨酯成膜剂CWPU-1。该改性产物粒径主要分布在40～200 nm之间，能够覆盖在微纳米孔隙及裂隙上。通过AFM观察，其微观表面是连续、平滑的，表明聚氨酯成膜剂可通过吸附、疏水缔合和电中和作用形成一层薄膜。这种薄膜使泥饼更加紧致，降低钻井液的滤失量，在常温与150℃老化16 h后的滤失量降低率分别可达64.7%和61.1%。通过黏土小球对抑制性进行评价，结果表明，在添加CWPU-1的钻井液中浸泡6 h后，黏土小球的质量降低率可达46%，可降低小球的吸水膨胀。经使用某地区地层水进行测试，CWPU-1不易发生结垢损害。因此，CWPU-1具有良好的防止钻井液侵入和对储层的保护效果。Abstract: In the exploration of oil and gas resources, low-permeability oil and gas reservoirs are easily damaged and are difficult to recover. This problem has become more and more serious. The development of filming agents can help solve this problem, however, the raw materials currently used for the synthesis of filming agents are generally petroleum products, which is harmful to environmental protection. As an inexpensive and easily available biomass resource, castor oil is a vegetable oil that exists in nature, with hydroxyl groups in its molecular structure that do not need modification. It also contains a variety of active chemical bonds and can be used to prepare various high-efficiency additives. Isophorone and a chain extender were introduced onto the castor oil molecules to prepare an environmentally friendly waterborne polyurethane filming agent CWPU-1. The particle sizes of this modified product are distributed mainly between 40 nm and 200 nm, and the particles can cover the micro-nano pores and fractures. Observation with AFM shows that the microscopic surfaces of the CWPU-1 particles are continuous and smooth, indicating that CWPU-1 can form a film through adsorption, hydrophobic association and electro-neutralization. This film makes the mud cake more compact and reduces the filtration rate of the drilling fluid. The reduction rates of the filtration at room temperature and after aging at 150℃ for 16 hours can reach 64.7% and 61.1% respectively. The inhibitive property was evaluated with small clay balls. The results show that after being soaked in the drilling fluid treated with CWPU-1 for 6 hours, the mass reduction rate of the clay balls can reach 46%, meaning that the water absorption swelling of the clay balls is inhibited. After being tested with the formation water in a certain area, CWPU-1 does not produce scale. It is thus concluded that CWPU-1 has a good effect on preventing the invasion of drilling fluids and protecting reservoirs from being damaged.
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Key words:
- Castor oil /
- Polyurethane /
- Filming agentt
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表 1 成膜剂优选参数及加量
原料 TEA/ mol Na2S2O8/ mol R值（—NCO∶—OH） CWPU-1 0.016 0 1.8∶1 CWPU-2 0.080 0 1.8∶1 CWPU-3 0.016 0 1.6∶1 CWPU-4 0.016 0 2.0∶1 CWPU-5 0.016 0.0408 1.8∶1 
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表 2 不同成膜剂（加量2%）对蒙脱土浆流变性能的影响
成膜剂 T老化/
℃AV/
mPa·sPV/
mPa·sYP/
PaYP/PV/
Pa/mPa·s空白 未老化 11.5 4 7.5 1.875 150 7.5 6 1.5 0.25 180 10.0 10 1.0 0.10 CWPU-1 未老化 21.5 18 3.5 0.19 150 9.0 8 1.0 0.12 180 12.5 9 3.5 0.38 CWPU-2 未老化 12.0 9 3.0 0.33 150 12.5 9 3.5 0.39 CWPU-3 未老化 14.5 9 5.5 0.61 150 13.5 8 5.5 0.69 180 7.5 1 6.5 6.50 CWPU-4 未老化 18.0 13 5.0 0.38 90 11.0 8 3.0 0.38 CWPU-5 未老化 5.0 5 1.0 0.20 90 11.5 9 2.5 0.28 150 12.0 8 4.0 0.50
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表 3 某油藏地层水性质参数
主要离子/（mg·L−1） 总矿化度/
mg·L−1水型 Na++K+ Ca2+ Mg2+ Ba2+ Cl− SO42− CO32− HCO3− 3430.22 1919.59 31.75 0 8292.66 43.63 0 775.52 14 463.37 CaCl2
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