Magnetic composites based on ultrafine polytetrafluoroethylene and cobalt containing nanoparticles

Composite materials based on ultrafine polytetrafluoroethylene and cobalt-containing nanoparticles were synthesized by the method of high-speed thermal decomposition of cobalt formate in a pseudoboiling layer of grains of ultrafine polytetrafluoroethylene. It has been found that ultrafine polytetrafluoroethylene is a composite material that consists of a core of polytetrafluoroethylene and a membrane of fluoroalkanes. In the formation of cobalt nanoparticles, interaction between them and the shell of ultrafine polytetrafluoroethylene-fluoroalkanes takes place. The result of the interaction is the formation of cobalt fluoride, which makes a significant contribution to the magnetic properties of composite materials. At room temperature, ferromagnetic behavior is characteristic for materials; the coercive force at 300 K is 700 Oe, while at 77 K it reaches 900 Oe.     

Chemical catalysed recycling of waste polymers: Catalytic conversion of polypropylene into fuels and chemicals over spent FCC catalyst in a fluidised-bed reactor

Polypropylene (PP) was pyrolysed over spent FCC commercial catalyst (FCC-s1) using a laboratory fluidised-bed reactor operating isothermally at ambient pressure. The influence of reaction conditions including catalyst, temperature, and ratio of polymer to catalyst feed and flow rates of fluidising gas was examined. The yield of gaseous and liquid hydrocarbon products at 390 °C for spent FCC commercial catalyst (87.8 wt%) gave much higher yield than silicate (only 17.1 wt%). Greater product selectivity was observed with FCC-s1 as a post-use catalyst with about 61 wt% olefins products in the C₃-C₇ range. The selectivity could be further influenced by changes in reaction conditions. Valuable hydrocarbons of olefins and iso-olefins were produced by low temperatures and short contact times used in this study. It is also demonstrated that a post-use catalyst system under appropriate conditions the resource potential of polymer waste can be economically recovered and also can address the recycling desire to see an alternative to solve a major environment problem.     

Flash pyrolysis of polystyrene wastes in a free-fall reactor under vacuum

Plastic waste minimization and recycling are important for both economical and environmental reasons. In this flash pyrolysis study, polystyrene wastes were degraded in a free-fall reactor under vacuum to regain the monomer. A set of experiments varied the temperature between 700 and 875°C and determined its effects on the phase yields, the benzene, styrene, toluene, and naphthalene distribution of the liquid output and C1–C4 content of the gaseous output. The liquid yield maximized around 750°C and the styrene yield at 825°C. In general, operating at higher temperatures lessened the solid residue and increased the gaseous yield and total conversion. Employing waste particles in four size ranges, a second set of runs indicated that the finer the waste particles fed the higher the gaseous yield and total conversion. This recycling method can be made more promising if the feed particles are allowed more time for degradation and the removal of the primary products speeded up thereby preventing their decomposition. Ways are suggested to obviate these residence time problems.     

Direct C−C Double Bond Cleavage of Alkenes Enabled by Highly Dispersed Cobalt Catalyst and Hydroxylamine

The utilization of a single-atom catalyst to break C−C bonds merges the merits of homogeneous and heterogeneous catalysis and presents an intriguing pathway for obtaining high-value-added products. Herein, a mild, selective, and sustainable oxidative cleavage of alkene to form oxime ether or nitrile was achieved by using atomically dispersed cobalt catalyst and hydroxylamine. Diversified substrate patterns, including symmetrical and unsymmetrical alkenes, di- and tri-substituted alkenes, and late-stage functionalization of complex alkenes were demonstrated. The reaction was successfully scaled up and demonstrated good performance in recycling experiments. The hot filtration test, catalyst poisoning and radical scavenger experiment, time kinetics, and studies on the reaction intermediate collectively pointed to a radical mechanism with cobalt/acid/O₂ promoted C−C bond cleavage as the key step.     

废弃SCR催化剂的循环再利用及表征分析研究

针对废弃SCR脱硝催化剂常规再利用处理后存在SO_2氧化率高的问题,提出了一种新型的废弃催化剂再利用新工艺,包括酸洗、还原酸浸和活性组分负载等步骤,以有效控制再利用催化剂的SO_2氧化率。实验考察了经不同步骤处理后所得催化剂的组分、脱硝效率和SO_2氧化率的变化情况,并对催化剂进行了深入的分析表征。结果表明,新鲜催化剂、废弃催化剂、常规再利用催化剂、新型再利用催化剂的脱硝效率和SO_2氧化率分别为99.0%和0.43%、77.0%和0.46%、94.2%和0.80%、99.3%和0.48%,采用本方法获得的再利用催化剂不仅脱硝效率完全恢复,而且SO_2氧化率得到了很好的控制。通过对催化剂的分析表征发现,采用常规再利用技术不能有效清除废弃催化剂表面的高聚态钒物种,而本方法则可以有效清理这类高聚态钒物种,并以高度分散的钒物种进行替代,从而有效控制再利用催化剂的SO_2氧化率。     

Laser ablation of polytetrafluoroethylene

Anomalous behavior of polytetrafluoroethylene (PTFE) under the action of CO₂ laser radiation in vacuum is discussed. A feature of the ablation process is formation of polymer fibers which quantity depends on the target preliminary treatment and the ablation conditions. Experimental results are set out and possible mechanisms of the polymer fibering are discussed. A conclusion is made concerning two dynamic polymer components differ by the resistance to the laser beam action, appearing in the ablation crater. A method is proposed for producing unique fiber-porous polytetrafluoroethylene materials and other useful products as well as for the polytetrafluoroethylene wastes recycling. The results of industrial application of these new fiberporous materials are discussed.     

Reaction of acetyloxiranes with acetonitrile

2-Acetyloxiranes react with acetonitrile in the presence of equimolar amounts of Lewis acids. It was established that the use of boron trifluoride etherate or sulfuric acid as the catalyst leads to 2,7- and 3,6-diepoxy-1,5-dioxocanes, the use of aluminum trichloride, as well as stannic chloride, leads to the corresponding chlorohydrins, while the use of gaseous boron trifluoride leads to 2-oxazolines in satisfactory yields. It is shown that the reaction is regio- and stereospecific and that the resulting substituted 2-methyl-5-acetyl-2-oxazolines have a cis configuration.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 8, pp. 1022–1024, August, 1982.     

Recycling technology of poly(ethylene terephthalate) materials

Poly(ethylene terephthalate) (PET) has become one of major post consumer plastics wastes, in addition to polyethylene (PE), polypropylene (PP), polystyrene (PS) and poly(vinyl chloride) (PVC). The challenge to large-volume plastics companies is to learn how to collect, separate, reprocess and market their low-cost products and make a profit, too. The effort of PET recycling, however, is the most successful story in the plastic recycling technology, including both reclaim and upgrade of PET waste. Beverage bottles made of PET are recycled more than 20% of the total production. The technology of today can reclaim the post-consumer PET bottles to produce high-quality granulated PET with better than 99% purity. A practical reclaim process for recycling PET bottles (including bottle, HDPE base cup, aluminum cap, liner, label and adhesive) is available by the Center for Plastics Recycling Research in USA. PET recycling process, like for other plastics, can be divided into three categories: incineration, physical recycling, and chemical recycling. To make the plastic recycling business pay requires more than simple recovery and marketing. Greatest profit potential is in upgraded and value-added reclaim products. Upgrading involves compounding with additives to make material more processable, adding reinforcement, or producing extrusions or finished parts from reclaim resins. For instance, a modified injection-moldable resin made from PET bottle scrap is claimed to provide high impact and processability at less cost than competitive materials. It is foreseen that chemical recycling of waste PET bottle becomes feasible if the price of raw material goes up. Three economical processes are involved in this technology: pyrolysis, hydrocracking, and hydrolysis. The hydrolysis process is presently employed to recover the raw material for unsaturated polyester resin manufacture or polyols for the production of polyurethane resin. It is reported in this presentation that polymer concrete could be a huge potential market for chemical reclaim of PET materials, especially for green or mixed-color PET, which are priced lower than colorless PET reclaim materials.     

Environmental application of gamma technology: Update on the Canadian sludge irradiator

Waste treatment and disposal technologies have recently been subjected to increasing public and regulatory scrutiny. Concern for the environment and a heightened awareness of potential health hazards that could result from insufficient or inappropriate waste handling methods have combined to push waste generators in their search for new treatment alternatives. Gamma technology can offer a new option for the treatment of potentially infectious wastes, including municipal sewage sludge.

Sewage sludge contains beneficial plant nutrients and a high organic component that make it ideal as a soil conditioning agent or fertilizer bulking material. It also carries potentially infectious microorganisms which limit opportunities for beneficial recycling of sludges. Gamma irradiation-disinfection of these sludges offers a reliable, fast and efficient method for safe sludge recycling.

Nordion International's Market Development Division was created in 1987 as part of a broad corporate reorganization. It was given an exclusive mandate to develop new applications of gamma irradiation technology and markets for these new applications. Nordion has since explored and developed opportunities in food irradiation, pharmaceutical/cosmetic products irradiation, biomedical waste sterilization, airline waste disinfection, and sludge disinfection for recycling. This paper focuses on the last of these -a proposed sludge recycling facility that incorporates a cobalt 60 sludge irradiator.     

Catalytic reactions in ionic liquids

The chemical industry is under considerable pressure to replace many of the volatile organic compounds (VOCs) that are currently used as solvents in organic synthesis. The toxic and/or hazardous properties of many solvents, notably chlorinated hydrocarbons, combined with serious environmental issues, such as atmospheric emissions and contamination of aqueous effluents is making their use prohibitive. This is an important driving force in the quest for novel reaction media. Curzons and coworkers, for example, recently noted that rigorous management of solvent use is likely to result in the greatest improvement towards greener processes for the manufacture of pharmaceutical intermediates. The current emphasis on novel reaction media is also motivated by the need for efficient methods for recycling homogeneous catalysts. The key to waste minimisation in chemicals manufacture is the widespread substitution of classical 'stoichiometric' syntheses by atom efficient, catalytic alternatives. In the context of homogeneous catalysis, efficient recycling of the catalyst is a conditio sine qua non for economically and environmentally attractive processes. Motivated by one or both of the above issues much attention has been devoted to homogeneous catalysis in aqueous biphasic and fluorous biphasic systems as well as in supercritical carbon dioxide. Similarly, the use of ionic liquids as novel reaction media may offer a convenient solution to both the solvent emission and the catalyst recycling problem.     

Recycling of End-of-Life Poly(bisphenol A carbonate) via Alkali Metal Halide-Catalyzed Phenolysis

The chemical recycling of end-of-life plastic waste streams can contribute to a resource-conserving and sustainable society. This matter of recycling is composed of a sequence of depolymerization and subsequent polymerization reactions. In this regard, we have studied the chemical recycling of end-of-life poly(bisphenol A carbonate) applying phenol as depolymerization reagent. In the presence of catalytic amounts of alkali metal halides as products bisphenol A and diphenyl carbonate were obtained in excellent turnover frequencies of up to 1392 h⁻¹ and short reaction times. These depolymerization products offer the straightforward possibility to close the cycle by producing new poly(bisphenol A carbonate) and as second product phenol, which can be reused for further depolymerizations.     

电感耦合等离子体发射光谱(ICP-OES)法分析废钴钼催化剂中关键助剂元素钛含量

通过改变传统的灼烧再酸化处理催化剂的实验方法,采用硝酸-氢氟酸-高氯酸法将石化工业中常用的难溶废钴钼催化剂快速溶解并利用ICP-OES分析法准确测定样品中关键助剂元素钛,为钴钼催化剂后续工艺研究提供了一定的分析依据以及对钛金属元素的回收循环利用具有重要意义。实验优化了ICP-OES仪器最佳工作参数,确定了酸试剂体系及钛元素的分析谱线,对比了不同前处理方法的精密度。结果表明：相比于灼烧再酸化,直接采用硝酸-氢氟酸-高氯酸法溶解样品更为理想,这是由于在灼烧的过程中相当部分金属元素钴与Al2O3反应生成钴青（CoO·n Al2O3）使得回收率降低。在仪器最佳测定条件下校准曲线回归方程的线性相关系数为1,钛的相对标准偏差为0.54%,加标回收率在99%-101%之间。对同一样品与采用分光光度法分析和EDTA滴定法分析做对照实验,结果吻合,但本实验方法简便易操作且适合大批量的检测分析工作。     

Thermal degradation of polyethylene and polystyrene from the packaging industry over different catalysts into fuel-like feed stocks

Thermal degradation of waste polymers was carried out as a suitable technique for converting plastic polymers into liquid hydrocarbons, which could be used as feed stock materials. The catalytic degradation of waste plastics (polyethylene and polystyrene) was investigated in a batch reactor over different catalysts (FCC, ZSM-5 and clinoptillolite). The effects of catalysts and their average grain size on the properties of main degradation products (gases, gasoline, diesel oil) are discussed. The temperature range of 410-450 °C was used in the process. Both equilibrium FCC catalyst and natural clinoptilolite zeolite catalyst had good catalytic activity to produce light hydrocarbon liquids, and ZSM-5 catalyst produced the highest amount of gaseous products. Gases and liquids formed in cracking reactions were analyzed by gas chromatography. The liquid products consisted of a wide spectrum of hydrocarbons distributed within the C₅-C₂₈ carbon number range depending on the cracking parameters. The composition of hydrocarbons had linear non-branched structure in case of polyethylene, while from polystyrene more aromatics (ethyl-benzene, styrene, toluene, and benzene) were produced. The yields of volatile products increased with increasing degradation temperature. The olefin content of liquids was measured with an infrared technique and an olefin concentration of 50-60% was observed. The concentration of unsaturated compounds increased with decreasing temperature, and in the presence of catalysts. The activation energies were calculated on the basis of the composition of volatile products. The apparent activation energies were decreased by catalysts and catalyst caused both carbon-chain and double bond isomerisation.     

Chloropolyfluorodiethyl ethers

Fluorination of 2-chlorodiethyl ether by cobalt trifluoride at 110–150 °C afforded isomers of 2-chloro-pentafluoro-, -hexafluoro-, and -heptafluorodiethyl ethers. Chlorine was lost in similar fluorinations of 2-chloro-2,2-difluoroethyl ethyl ether, the only products isolated being a heptaand a hexa-fluoro diethyl ether. Structures were established spectroscopically.     

Fluorination of Organic Compounds with Cobalt Trifluoride and Elemental Fluorine in the Presence of Cobalt Trifluoride

Fluorination of organic compounds with cobalt trifluoride and elemental fluorine in the presence of cobalt trifluoride was studied. Fluorination with elemental fluorine proceeds under external-kinetic control at a constant rate. Examples of fluorination with elemental fluorine of certain fluorinated olefins and polyfluorinated paraffins in the presence of CoF₃ are presented.     

A review on synthesis of value added products from polyethylene terephthalate (PET) waste

Many research papers have been contributed by several authors for making PET waste recycling economically and ecologically more viable. Recycling of PET waste was started in last two decades. Most of the authors are devoting their time in getting economically viable solution for development of methods based on either mechanical or chemical recycling. Some success has been obtained in development of chemical recycling methods which provides value added products from PET waste. However, different products developed by chemical recycling have not provided economically enough and reliable methods of recycling of PET waste.     

Composite electrochemical coatings with a carbon-containing dispersed phase or polytetrafluoroethylene

Composite electrochemical coatings based on nickel, zinc, and chromium were studied. The dispersed phase of these coatings is constituted by graphite, diamond, and polytetrafluoroethylene produced from wastes formed in manufacture of fluoroplastic and ultradispersed diamond produced from industrial waste. The conditions in which high-quality coatings with best characteristics, such as microhardness and corrosion resistance, were determined. The wear resistance was additionally found for the chromium-diamond coating.     

Composition of aromatic products in the catalytic degradation of the mixture of waste polystyrene and high-density polyethylene using spent FCC catalyst

In this chemical recycling process, spent FCC catalyst used had an advantage with an economical and environment aspect, such as a low catalyst price in liquid-phase reaction and a reuse of waste catalyst. The characteristics of oil product and its aromatic product distribution, as a function of reaction time in the reactor and also proportion of HDPE and PS in the mixture, were compared. Main products obtained were light hydrocarbons within the gasoline range that were mainly produced during initial reaction time. The formation of aromatic products such as styrene and ethylbenzene as major components depended appreciably on the reaction time, as well as the composition of HDPE and PS in the mixture used for degradation. For the distribution of C₉-C₁₂ alkylaromatic components as by-products, methylstyrene (C₁-styrene) and isopropylbenzene (C₃-benzene) components were the main products formed by β-scission and hydrogen transfer of PS, while the rest of alkylaromatic products showed very low fraction being 1% or less.     

The influence of recycling on the properties of wood fibre — Plastic composites

The manufacture of composites offers the greatest flexibility to convert and utilize waste plastics, paper and wood into high-value products. This paper reports on two studies regarding the recycling of these materials. In one study, recycling was simulated by regrinding and injection-moulding composites of polypropylene (PP), polyethylene (PE) and old newsprint (ONP) eight times. The results indicated that reprocessing had only minor deleterious effect on the mechanical properties (tensile and flexural). The viscosity of neat PP decreased with repeated recycling indicating some thermo-oxidative degradation. The overall rheological character of PP composites did not change much. PE composites, on the other hand, showed increasing melt flow with reprocessing. The second study examined the effects of various coupling agents on the properties of multicomponent PP composites. Maleated polypropylene (MAPP) was the most effective coupling agent.     

α,ω-Glycols from copolymers of isobutylene and 2,5-dimethyl-2,4-hexadiene

Isobutylene has been copolymerized with 2,5-dimethyl-2,4-hexadiene using a boron trifluoride catalyst in petroleum ether solution. Ozonization of the products followed by reduction with lithium aluminum hydride has furnished polyisobutylene glycols in good yield.