Synthesis Technics And Property Research Of WZ Polyacrylates Series High Oil-Absorbency Resins And Optimization Design Of Countermeasures To Cleanup Marine Oil-Spillage Pollution

Marine oil pollution, especially an increasing amount of oil spillage from vesselsresulted from the ever-growing use and transport of cured oil and oil products hasbecome the major issue in the protection of the aquatic environment over the pastdecades. Based on the above situations, how to minimize the oil spillage is the keyand foremost point to solve the ocean pollution problem. This dissertation presentsan operational synthesis of major methods used for oil spillage response, includingmechanical, chemical, natural degradation, bioremediation and in situ burning aswell as advanced clean methods, and the corresponding oil response equipment forsea context, such as booms, skimmers, etc. The important features of oil spillresponse are also focused on, capable of supporting the development of a completeoil spill response operation.At present in China sorbent market, most commonly used commercial sorbents arethe polyacrylate sorbents that most imported from Japan. There are still noindustrialization products come out until now, as the related research withpolyacrylic category materials in china is relatively underdeveloped.Based on mentioned above, the emphasis of this dissertation is to investigate thesynthesis technics of polyacrylic high oil absorbency resin, as well as to provide anoptimization oil spillage response system. The conclusions are as follows:Ⅰ. A series of polyacrylic high oil absorbency resins, named by WZ series highoil absorbency resins were prepared by suspension copolymerization arid thesophisticated synthesis technics of polyacrylic high oil absorbency resin wasobtained. The suspension copolymerization using Polyvinyl Alcohol (PVA) andGemini surfactant DTDPA composite system as dispersant first time, Ethyleneglycol Dimethacrylate (EGDMA) as crosslinking monomer, and series acrylates LaurylAcrylate (LA), hexadecanol Acrylate (HA) and 1-Octadecanol Acrylate (SA) asmonomer respectively initiated by Benzoyl Peroxide (BPO), as well as the fillersused to promote the absorption performance. The optimized recipe was as follows:the ratio of DTDPA and PVA is 2:3, monomer: EGDMA: BPO=100:1:2. The fillerscan play an important role in improving performance of resin by changing the spacenetwork structure of resin to make it easy to swell, by which the steric hindrance ofcross-link can be reduced and the resin structure will become loose. The oilabsorption capacity could reach 25.2g of oil/g of sorbent when the crude oil wasused in the test.Ⅱ. FT-IR spectroscopy identified the chemical structure of both Geminisurfactant DTDPA and WZ series high oil absorbency resins. The results revealedthat DTDPA and WZ resins were the goal product.Ⅲ. The symmetric Gemini quaternary ammonium salt cationic surfactantdichloride- N, N, N', N' -tetra methyl-N, N'-dicetyl-2-propanol-1,3-ammonium(DTDPA) was synthesized based on the laboratory study. Heat analysis wasconducted by DTA and TG and the melting point of DTDPA is 73.0℃. The surfaceactivity of DTDPA solution demonstrated more excellent than traditional classicamphiphilic moieties surfactants. The interfacial tension (IFT) between crude oilfrom Zhongyuan Oil Filed of China and DTDPA solution was measured and thestudy results demonstrated that DTDPA was effective in lowering crude oil-watersystem interfacial tension.Ⅳ. The optimized temperature of polymerization is 80℃. The initiatordecomposed slowly when the polymerization temperature was low. Meantime, thesteric hindrance of side groups of the long carbon chain of acrylates was alsoobvious. Therefore, the polymerization reacted incompletely due to the two reasonsmentioned above, and led monomers could not polymerize into the resin particles.However, the initiator would decomposed rapidly when the polymerizationtemperature was higher than 80℃. The molecular weight of resin would drop downand correspondingly, the resin oil absorbency would decrease, contrast to the rise ofthe polymerization rates. At the same time, the higher temperature than normalwould further increase the dispersancy instability of polymerization systemcharacterized by flocked resin particles and reduced adsorptive interface of resin,both of which would lead to oil-absorption Capacities decreased.Ⅴ. The optimized polymerization time is 6h. The oil absorption capacity of reinincreased with reaction time increasing, which would remain almost the same value when the time exceeded 6h. The polymerization unit is the suspended dropletsfeatured with small volumes. The water used as the diluents can remove the reactionheat more easily.Ⅵ. The optimum concentration of DTDPA involved in the polymerization is0.05wt percentage. The oil absorption capacity increased as the increasingconcentration of DTDPA. However, when the concentration of DTDPA exceeded0.05 wt percentage, the oil absorption capacity would decrease. On the other hand,the oil absorption balanced time decrease as the increasing of DTDPA'sconcentration.Ⅶ. The fillers play a crucial role in the oil-absorption capacity improvement ofWZ series resins. The oil-absorption capacity increased a lot as the increasing of thefillers. In addition, the test results revealed that the optimum concentration of fillersis 1.0 wt percentage, in the case of olefin.Ⅷ. The proper concentration of chemical crosslinker (EGDMA) is 0.40 wtpercentage. The study results indicated that as the concentration of EGDMAexceeded the normal, the crosslinking degree and density became higher and the gelfraction rate increased contrast to the decreased of the oil-absorption capacity. Thereason is that it is the resin's three-dimensional network that the resin sorbent couldabsorb the oil efficiently. Based on that, it is improper to use higher or lowerEGDMA.Ⅸ. Five types of common spillage oil were tested to measure the oil-absorptioncapacity as well as the capacity from the water surface. The oil types are petrol,diesel oil, mineral oil, synthetic oil and heavy fuel oil. The test results revealed thatWZ series high oil-absorbency rein exhibited an excellent performance for the allfive types of oil. When the synthetic oil was used to be test oil, the oil-absorptioncapacity value was 25.6. As the mineral oil was tested to measure the capacity fromthe water surface, the value was 27.9. The overall test results indicated that WZ resinhad big potential to be applied into the related oil-spillage treatment fields.