Fuels from tyres by pyrolysis in molten salts

The current annual arisings of used car/van tyres in the U.K. has been found to be around 25m (188,000 tonnes). After the established reuse industries have taken their requirements this leaves 13.5m (102,000 tonnes) waste tyres; a quantity that can no longer be satisfactorily tipped. Laboratory scale experiments have shown that tyre can be pyrolised, using a molten carbonate system as the reaction medium, at rates corresponding to 14.9-42.7 g tyre/min. per litre of melt over the range 475 and 650°C. The product yields by weight of tyre input between the same temperatures are: hydrocarbon oil 23-36 wt. %, hydrocarbon gas 7- 18 wt. %, carbonaceous char 35-40 wt. %, steel 16.7 wt. % and inorganics 5.4 wt. %. The oil and gas evolve from the reactor and can easily be collected by conventional means. The steel and inorganics remain in the reactor although on the commercial scale it is proposed that they would be removed by physical and chemical methods respectively. The char was found to pose considerable handling problems and so a method was devised by which it could be gasified in the reactor. This was best achieved by passing air at a less than stoichiometric rate which gave a gaseous product rich in carbon monoxide. In addition this action provides heat for the system as a whole. The rates at 675-9000C were in the range corresponding to 5.6- 14.89 char/min. per litre of melt. A process flow chart has been proposed for a continuous operation based on these systems. Data from theoretical and experimental studies has enabled economic evaluations of several commercial scales to be carried out. These have shown that 4,000 and 10,000 t/yr operations show a DCF rate of return around 30% while a 50,000 t/yr operation shows 60% which would be attractive to an experienced scrap operator.

Oxidation of organic compounds in molten salts

The objective of this research was to investigate the oxidation of organic compounds in molten alkali metal hydroxides containing manganates. It has been shown that controlled oxidation can be readily achieved with high specificity to give products in high yield with very short reaction times. The concurrent changes in the melt were monitored using a vibrating platinum indicator electrode with a quazi-reference electrode which was successfully developed for use in molten (Na-K)OH eutectic at 523K. Henry's Law constants for water in the molten eutectic system (Na-K)OH have been measured and used to calculate the water concentration in the melt. The electrochemistry of manganates in molten (Na-K)OH eutectic at 523K has been studied using the vibrating platinum electrode, and the existence of the species Mn(II), Mn(II!), Mn(IV), Mn(V) and Mn(VI) in such melts has been investigated at various water concentrations. The half-wave potentials of the voltammetric waves were measured versus the cathodic limit of the melt. The stability of Mn(V) or Mn(VI) in the melt was achieved by varying the water concentration. A range of organic chemicals has been passed through molten (Na-K)OH at 523K and the reactions of these chemicals with the melt have been studied. The same organics were then passed through molten (Na-K)OH containing stabilized Mn(V) or Mn{VI) without violent reaction. Methanol, allyl alcohol, propane 1, 2 diol, I-heptene and acetone were oxidized by Mn(V) and Mn(VI). Ethanol was only oxidized by Mn(VI), isopropanol and benzyl alcohol were only oxidized by Mn(V). Npropanol, butanol, 2 methyl propan-2-ol, n-hexane, n-heptane toluene and cyclohexane were unchanged by both Mn(V) and Mn(VI). Detailed experiments have been performed on the reactions of ethanol, iso-propanol and methanol in molten (Na-K)OH containing stabilized Mrt(V) or Mn(VI), and reaction mechanisms have been postulated. Ethanol and iso-propanol were oxidized to acetaldehyde and acetone respectively with a potential for useful chemical process. The oxidation of methanol could be developed as a basis for an industrial methanol disposal process.

The pyrolysis of plastics in molten salts

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Ionic liquid-accelerated N-arylation of benzoazoles with diaryliodonium salts, an efficient method for the synthesis of N-aryl azoles

N-Arylation of benzoazoles with diaryliodonium salts can be performed in good yields in the room-temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4), which provides an efficient method for the synthesis of N-arylbenzoazoles. The ionic liquid can be recycled and reused.

Organic reactions in ionic liquids: synthesis of alkyl aryl trithiocarbonates by the S-arylation of potassium carbonotrithioates with diaryliodonium salts

Various alkyl aryl trithiocarbonates were readily prepared in good yields by the S-arylation of potassium carbonotrithioates with diaryliodonium salts in the room-temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4). The ionic liquid can be recycled and reused.

Hypervalent iodine in synthesis 92. A facile synthesis of 3-substituted-5,6-dihydroimidazo[2,1-b]thiazoles by cyclocondensation of alkynyl(phenyl)iodonium salts and imidazolidine-2-thione

A simple method for the synthesis of 3-substituted 5,6-dihydroimidazo[2,1-b]thiazoles is achieved by cyclocondensation of alkynyl(phenyl)iodonium salts with imidazolidine-2-thione.

Hypervalent Iodine in Synthesis. 94. A Facile Synthesis of 2-Substituted-imidazo[1,2-a]pyridines by Cyclocondensation of Alkynyl(phenyl) iodonium Salts and 2-Aminopyridine

A facile method for the synthesis of 2-substituted-imidazo[1,2-a]pyridines is achieved by cyclocondensation of alkynyl(phenyl)iodonium salts with 2-aminopyridine.

Ionic liquid-accelerated arylation of sodium arenesulfinates with diaryliodonium salts used for the synthesis of diaryl sulfones

Arylation of sodium arenesulfinates with diaryliodonium salts can be performed with good yields in the room-temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMim]BF4), which provides an efficient method for the synthesis of diaryl sulfones; the ionic liquid can be recycled and reused.

Organic reactions in ionic liquids: ionic liquid-accelerated nucleophilic substitution reaction of alpha-tosyloxyketones with potassium salts of aromatic acids

The room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) is used as a ‘green' recyclable alternative to classical molecular solvents for the nucleophilic substitution reaction of a-tosyloxy ketones with potassium salts of aromatic acids. Significant rate enhancement and improved yields have been observed.

Hypervalent iodine in synthesis 93. A facile synthesis of 2-substituted imidazo[1,2-a]pyrimidines by cyclocondensation of alkynyl(phenyl)iodonium salts and 2-aminopyrimidine

Simple stirring of a mixture of the alkynyl(phenyl)iodonium salts 1 with 2-aminopyrimidine 2 in chloroform under reflux for two hours in the presence of K2CO3 gave, after workup, the 2-substituted imidazo[1,2-]pyrimidines 3 in moderate to good yields. A possible mechanism for the formation of 3 involves the intramolecular cyclization of the intermediate alkylidenecarbene 6.

Interaction of metal salts with polyethers

The dielectric properties of pure low to medium molecular weight poly(ethylene glycol) and poly(propylene glycol) and a variety of their salt complexes have been studied through the measurement of the dielectric permittivity and dielectric loss over a range of frequency and temperature. The major proportion of this study has been concerned with the examination of the nature of the interaction between mercuric chloride and poly(propylene glycol) (PPG). Other salt-poly-ether combinations have also been considered such as cobalt chloride-PPG cadmium chloride-PPG zinc chloride-PPG and ferric chloride-PEG (polyethylene glycol). Some of this work was also supported by chemical shift and spin-lattice Nuclear Magnetic Resonance (N.M.R.) spectroscopy. The dielectric permittivity data were analysed using the Onsager relation to calculate the mean dipole moment per dipolar unit. This approach was employed in the discussion of various models proposed for the structure of salt-polyether complexes. The effect of mercuric chloride on the statistical conformations of poly(propylene-glycol) was studied in a quantitative manner using the relationships of marchal-Benoit. The dielectric relaxation activation energy and mean energy difference between gauche and trans conformations of poly(propylene glycol) in the presence of mercuric chloride, both showed a distinct minimum when the concentration of mercuric chloride was close to 5 mole %. Opposite behaviour was observed for the Cole-Cole parameter. It was concluded that the majority of the dielectric data could be rationalised in terms of a 5-membered cyclic complex formed between mercuric chloride and PPG in which the complexed segment of the polyether-(OMeCH2CH2O)- adopted either gauche or cis conformations.

Heat transfer from molten materials to liquids

An apparatus was designed and constructed which enabled material to be melted and heated to a maximum temperature of 1000C and then flooded with a pre-heated liquid. A series of experiments to investigate the thermal interaction between molten metals (aluminium, lead and tin) and sub-cooled water were conducted. The cooling rates of the molten materials under conditions of flooding were measured with a high speed-thermocouple and recorded with a transient recorder. A simplified model for calculating heat fluxes and metal surface temperatures was developed and used. Experimental results yielded boiling heat transfer in the transition film and stable film regions of the classic boiling curve. Maximum and minimum heat fluxes were observed at nucleate boiling crisis and the Leidenfrost point respectively. Results indicate that heat transfer from molten metals to sub-cooled water is a function of temperature and coolant depth and not a direct function of the physical properties of the metals. Heat transfer in the unstable transition film boiling region suggests that boiling dynamics in this region where a stationary molten metal is under pool boiling conditions at atmospheric pressure would not initiate a fuel-coolant interaction. Low heat fluxes around the Leidenfrost point would provide efficient fuel-coolant decoupling by a stable vapour blanket to enable coarse mixing of the fuel and coolant to occur without appreciable loss of thermal energy from the fuel. The research was conducted by Gareph Boxley and was submitted for the degree of PhD at the University of Aston in Birmingham in 1980.

Geochemistry of some sulphides and sulpho-salts from Parys Mountain, Anglesey

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