fHE OXIDATION 0? MBTEAN2 tj Jobn Reid Campbell, B.Se., A.R.T.O., A#I.C.. A thesis submitted in fulfilment of the requirements for the degree of Doctor of Philosophy of Glasgow tteiversity. July, 1928. ProQuest Number: 27534990 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 27534990 Published by ProQuest LLO (2019). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLO. ProQuest LLO. 789 East Eisenhower Parkway P.Q. Box 1346 Ann Arbor, Ml 48106- 1346 It is a pleasant duty for the author to record his gratitude and indebtedness to Professor Gray, Royal Technical College, for his encouraging supervision, advice and constructive criticism during the course of the work. The author also desires to thank the Governors of the Royal Technical College and the Carnegie Trust for the Universities of Scotland for grants nAiich have allowed him to carry out this work. ill. CONTENTS. PART I. THE imPUENCE OF CATALYSTS IN PROMOTING THE OXIDATION OF METHANE BŸ MEANS 0^ COPPEÈ OZID'eV Summary.............................................. Page vi Introduction........................................ 2 General Method of Procedure ........................ 9 Method of Measurement of Temperature.................. 15 Method of Conducting an Experiment.................... 17 Method of Calculation................................ 26 A. - Methane and Copper Oxide........................ 28 Experiments on Variation of Time of Contact....... 30 B. - Methane-Hydro gen and Copper Oxide............... 35 C. - (a)Ethylene and Copper Oxide.................... 39 (b )Me thane ^Ethylene and Copper Oxide............. 40 D. - Methane and Lead Ghromate (precipitated)........ 46 Methane and Lead Ghromate (fused)................ 49 Carbon Monoxide and Lead Ghromate (fused)........ 52 E. - Methane and Copper Oxide Impregnated with Cuprous Chloride........................ 56 F. - Methane and Copper Oxide Impregnated with Vanadium Pentoxide...................... 63 6. - Methane and Copper Oxide Impregnated with Cobalto-Gobaltic Oxide............ 71 H. - Methane and Copper Oxide Impregnated with Nickelous Oxide......................... 74 K. - Methane and Copper Oxide Impregnated with Manganese Dioxide....................... 78 L. - Methane and Cobalto-Cobaltic Oxide... ...... 82 General Conclusions.................................. 86 iv. PART II. THE INFLUENCE OF CATALYSTS IN THE OXIDATION OF METHANE BY HALF ITS VOLUME OF OXYGEN. Summary........... Page vi Introduction................................ 93 General Method of Procedure............... 98 Method of Conducting an Experiment.............. 104 Method of Calculation........................... 107 General Considerations.......................... 109 A. - Palladium Black on Asbestos............. 112 B. ^ Platinised Asbestos........................ 116 C. - Platinum Black on Asbestos................. 120 D. - Copper on Pumice........................... 124 E. - Silver on Pumice........................... 129 F. - Vanadium Oxides on Pumice............. 133 G. - Cuprous Chloride on Pumice................. 139 General Conclusions............................. 149 PART III. THE INFLUENCE OF THE TIME OF CONTACT ON THE OXIDATION OF METHANE BY MEANS OF GOPj^ER OXIDE. Summary............* Page vii Introduction.................... 156 A. - Circulation Method. General Method of Procedure.............. 157 Method of Conducting anExperiment ...... 161 Method of Calculation....... 163 Results and Conclusions.................. 164 B. - Single Passage Method................... ......Page 167 Method of Conducting an Experiment......... 169 Method of Calculation...................... 171 Results and Conclusions................... 172 C. - Sealed Tube Method........................... 179 I. Experiments with Manometer in Apparatus.. 179 Method of Conducting an Experiment. 181 Results and Conclusions................. 182 II. Experiments without Manometer........... 186 Method of Conducting an Experiment...... 186 Results and Conclusions................. 189 Influence of Concentration of Methane.............. 194 Influence of Increase of Surface of Copper Oxide.... 197 General Conclusions............................... 199 Appendices .... 202 Bibliography...................................... viii. VI* SUMMARY. PART I. In this section a comprehensive study of the combustion of methane by means of copper oxide has been carried out. The influence of temperature on the amount of methane burned by a constant weight of côpper oxide has been investigated, together with a few preliminary experiments on the effect of varying the time of contact of the gas and the oxidising agent (pp.28-34). Details of the effect of the addition of hydrogen or ethylene to the methane on the temperature of combustion of the latter hydrocarbon are given, together with figures illustrating the oxidation of the olefine by means of copper oxide (pp.35-45). The activity of lead chromate, both precipitated and fused, in causing the oxidation of methane has been investigated, together with the effect of temperature on the oxidation of carbon monoxide by the fused salt (pp.46-55). Details are then given of the effect of the addition of the following catalysts to the copper oxide in causing a decrease in the temperature of combustion of methane:- 1. Cuprous Chloride...... pp.56-62. 2. Vanadium Pentoxide....pp.63-70. 3. Cobalt Oxide..........pp.71-73. 4. Nickel Oxide......... pp.74-77. 5. Manganese Dioxide.....pp»78-81. while in the case of vanadium pentoxide the effect of varying the amount of catalyst present has been studied. Finally, the oxidation of methane by means of pumice impregnated with cobalt oxide has been investigated (pp.82-85). In each case complete tables of results, from the point where no combustion takes place to the temperature at which all the hydrocarbon is completely oxidised, are given and the results shown graphically. PART II. In this section a study of the influence of catalysts in promoting the oxidation of methane, in a mixyure containing two volumes of methane and one volume of oxygen, has been undertaken. The influence of temperature on the quantities of methane oxidised to the various products of oxidation has been studied and the reaction between the two gases followed out until 25^ of the methane supplied has been oxidised to carbon dioxide, this being the maximum value possible under the circumstances. Details are given of the efficiencies of the following vil. catalysts in promoting the oxidation of methane by means of gaseous oxygen: - 1. Palladium Black on Asbestos.... pp. 112-115 2. Platinised Asbestos............ pp.116-119 3. Platinum Black on Asbestos..... pp. 120-123 4. Copper on Pumice............... pp. 124-128 5. Silver on Pumice................pp.129-132 6. Vanadium Oxides on Pumice...... pp.133-138 7. Cuprous Chloride on Pumice..... pp. 139-148. In all cases except the last, complete tables of results from the point at which oxidation commences or, in cases where this is below atmospheric temperature, from atmospheric temperature, are given and the results shown graphically. PART III. The influence of the time of contact in determining the amount of methane oxidised by means of copper oxide has been investigated in this section. Various types of apparatus have been considered and two main methods of procedure finally adopted. The results obtained by these methods have been fully analysed and two subsidiary investigations, suggested from the conclusions drawn from these results, have been carried out. These were investigations into the effects caused by varying the concentration of methane in the gaseous mixture and by varying the amount of surface of copper oxide exposed to the gas. PARTI. THE INFLUMCE OF CATALYSTS IN PROMOTING THE OXIDATION OF METHANE BY MEANS OF COPPER OXIDE. a' : .1 ^ % a,.; : i V , ' . ' !- .. E. Introduction. In many problems in fuel technology and organic chemistry where analyses by means of combustion are necessary the issue is partially dependent on the complete oxidation of methane, either by means of an oxidising agent which furnishes the oxygen necessary for oxidation or by means of an external supply of oxygen in the presence of an oxidation catalyst, the medium being heated to a suitable temperature. Many organic substances on decomposing give off large quantities of methane and it is well known that coals and oils evolve methane on heating. Thus Haas (1)* has drawn attention to the fact that certain basic compounds, derived from reduced benzene nuclei and having two methyl groups attached to the same carbon atom, of the type % ( OH)-------- CH yield an appreciable quantity of methane when heated with copper oxide in the Dumas absolute method of estimation of nitrogen and this methane, not being completely oxidised, is measured as nitrogen in the azotometer and leads to results which are Z% - 5fo too high. Lambris (2) has described a very elaborate method for estimating nitrogen in such substances, involving the passage of the gas obtained, mixed with excess * The numbers refer to the bibliography at end of book. 3. oxygen, over a red-hot platinum spiral and then