SHALE OILS AND TARS AND THEIR PRODUCTS BY DR. W. SCHEITHAUER TRANSLATED FROM THE GERMAN BY CHAS. SALTER WITH SEVENTY ILLUSTRATIONS AND FOUR DIAGRAMS LONDON SCOTT, GREENWOOD & SON 8 BROADWAY, LUDGATE, B.C. 1913 with Greenwood [ The sole rights of translation into English remain Scott, & Son] D. VAN KOSTRAND COMPANY NEW YORK AUTHOR'S PREFACE. THE present work is intended to depict the production and utilization of the distillation tars constituting the basis of several important industries. The chief of these are : The Scottish Shale Oil Industry and the Saxon-Thuringian Mineral Oil Industry, the latter forming a branch of the lignite mining industry of Central Germany. In addition, the production and utilization of distillation-tar is practised at Messel, near Darm- and the author desires to his cordial stadt, Germany ; express thanks to Dr. Spiegel, the manager of the last-named works, for the detailed description furnished by him on the methods, etc., employed there. Bituminous tar is also subjected to dry distillation, to a smaller extent, in the south of France and in Australia, the apparatus and processes employed being adopted from the Scottish industry. A full description is given of the apparatus of the German and Scottish industries, and of the methods of applying same, the author being engaged in the Saxon-Thuringian industry and having a personal knowledge of Scottish practice, apart from the abundant literature at his disposal. Owing to increased official duties, the author regrets to have been prevented from completing the work himself; but iii 273388 IV AUTHOK S PEEFACE he has had the advantage of obtaining as a collaborator Dr. E. Grafe, whose scientific researches are well known in industrial circles, and who, in addition to writing the whole of Chapters x. and xi., prepared Chapter ix. with the exception of the historical section. For this collaboration the author again tenders his best thanks. THE AUTHOR WALDAU, NEAR OSTERFELD (HALLE), 1911. TRANSLATOR'S PREFACE. IN the German original the chief products of the distillation of both Shale. and Lignite are classed as "Tar," and though, in the case of Shale this is not strictly correct, it has been consid- ered desirable to retain this nomenclature to some extent in " the translation, it being understood that the term shale tar" " is synonymous with Crude oil ". CHAS. SALTEK. LONDON, JANUARY, 1913. CONTENTS. CHAPTER I. PAGE HISTORY OF THE SHALE AND LIGNITE-TAB INDUSTRY . 1-7 CHAPTER II. THE BITUMINOUS RAW MATERIALS. M . Occurrence . 8 Origin 4 10 Properties and Composition .12 . Working , 15 Utilization . .17 CHAPTER III. THE PRODUCTION OF DISTILLATION TAR. A. The Dry-Distillation Process 20 B. The of . Winning Lignite Tar . .21 The Retort 21 The Work of the Retort ^.27 The Condensing Plant 28 The Dry-distillation Process .29 The Distillation Plant . 33 C. The Messel Tar Industry 36 The Retorts . 36 The Work of the Retort 39 The Treatment of the Distillation Vapours 40 D. The Recovery of Shale Tar in Scotland 41 The Retorts . 41 The Work of the Retort 50 The Condensing Plant 50 ' . The Distillation Process : V . 50 The Distillation Plant . 51 VI CONTENTS CHAPTER IV. THE DISTILLATION PRODUCTS. PAGE A. The Tar 52 " Lignite Tar . 52 Shale Tar (Crude Oil) . 53 ' Value of Distillation Tars . \ . 53 E. The Tar Water (Ammonia Liquor) . 53 Lignite Tar Water . 54 Shale Tar Water . ... .56 C. Gas . .... .57 D. The Distillation Residues . ... .61 CHAPTER V. THE DISTILLATION OF THE TAB AND TAR OILS. A. The Distillation Process ... -.' 64 B. Tar in the Saxon- . 7 *-. 65 Distilling Thuringian Industry ''__ The Distilling Apparatus . 65 . 69 The Distillation Process . ;;'" -. ... The Distillation Plant . ..'... .74 w The Distillation Products . .* ., 76 The Retorts 79 Products obtained by the Distjllation of Lignite Tar (Diagrams I and II) . 78, 79 C. The Messel Distillation Process . ".*/ .- . .80 Apparatus for and Method of Distillation . .80 ' The Distillation Products . .- . 80 D. The Distillation Process in the Scottish Industry 81 Apparatus for and Method of Distillation . .81 . 83 Distillation Plant . ... .... '. The Distillation Products 83 Products obtained by the Distillation of Shale Tar (Crude Oil) (Dia- 84 gram III) . Products obtained by the Distillation of Shale Tar (Crude Oil) by Classification of the various Oils (Diagram IV) .... 84 CHAPTER VI. I. CHEMICAL TREATMENT OF THE TAR AND ITS DISTILLATES. A. The Refining Process 86 B. The Refining Process in the Saxon-Thuringian Industry .... 87 The Agitator 87 ' -. 88 The Refining Process . The Chemical Treatment of the Tar . 88 89 Refining the Tar Products . Treating the Oils before Delivery . .90 92 The Agitator House . C. Refining Process in the Messel Industry 92 S CONTENTS Vll PAGE D. Refining Process in the Scottish Industry 93 Methods 93 Chemical Treatment of the Tar Products 93 II. THE UTILIZATION OP THE REFINERY WASTE. ' Uses and Treatment . .. V . 94 . .- * . ,. 95 the Chemicals . Recovering ^ CHAPTER VII. THE MANUFACTURE OF PARAFFIN. A. The Manufacture of Paraffin in the Saxon-Thuringian Industry . 98 - : . .. 98 Process . ... ::. The . Crystallization .."'. .:;.., . The Pressing Process V' . '.''. 100 ' : ' ' ' ' ' : The Press Plant . '. '. \ . 105 ? . ' : '- The Steam Jet Treatment . ;- -.- ; -. .. ; .' '. 106 ' Decolorizing the Paraffin . 107 B. Manufacture of Paraffin in the Messel Industry 108 . 108 Crystallization , ...._% The Pressing Process . -. 108 C. Paraffin Manufacture in the Scottish Industry 109 Crystallization * . 109 The Sweating Process . 109 Decolorizing the Paraffin 112 CHAPTER VIII. PRODUCTS FURNISHED BY SHALE OIL AND LIGNITE TAR. A. Products Obtained in the Saxon-Thuringian Industry .... 113 % Quantitative Yield .' . 113 The Oils - - . v .. 113 . The By-Products 119 The Paraffin . 120 B. The Products of the Messel Industry 122 Yield Obtained from the Tar .122 The Oils . 122 The Paraffin 122 ' C. The Products of the Scottish Industry . .122 Yield from the Crude Oil 122 The Oils . 122 The . By-Products . .... .123 The Paraffin . 123 viii CONTENTS CHAPTER IX. CANDLEMAKING. PAGE Historical 125 The Raw Materials 127 (a) The Candle Material 127 (b) The Wick.- 130 Matters (c) The Colouring 131 The Manufacture . .132 (a) The Moulding Process 132 (6) Finishing . .136 the Candles (c) Packing 137 (d) Working up Candle Waste .137 CHAPTER X. CHEMICAL COMPOSITION OP THE TABS AND THEIR DISTILLATES. A. Lignite Tar 138 of Tar . 144-145 Constituents Lignite (Table) , ( B. Shale Tar (Crude Oil) , . .146 CHAPTER XI. THE LABORATORY WORK. - . Testing the Raw Materials . i . , 147 . Testing the Tars and other Distillation Products . , . 151 Testing the Tar Oils . 154 Testing the Reagents used for Refining the Oils and Paraffin . 157 the Paraffin 158 Testing " Tests Applied in Candle Works . , . 159 Testing the By-Products of Tar Distillation . ,. 163 CHAPTER XII. STATISTICS. ' A. The Saxon-Thuringian Industry . ,. 16& B. Statistics of the Scottish Shale Industry . ,^ 174 INDEX 177-185 CHAPTEE I. HISTORY OF THE SHALE AND LIGNITE-TAR INDUSTRY.. WOOD was the first material to be subjected to dry distillation, andL furnished the earliest known distillation tar, the composition of which " " was described by Boyle in his Chemista scepticus (1661). As long ago as the seventeenth century tar was recovered from the dry distilla- tion of pine on a manufacturing scale in heavily timbered countries* like Norway and Sweden. At the same period coal was also put through a process of dry" distillation. A patent (19 August, 1681) was taken out in England by Becher for the of and tar coal this recovery pitch from ; and inventor was the first to produce coke l in addition to coal-tar. Coal is also known to have been subjected to dry,distillation in Germany about the middle of the but this of coal did eighteenth century ; application not attain any general importance until illuminating gas began to be made from that material early in the last century, and the employment of coal as a raw material for dye-stuffs became known towards the 'fifties two great achievements of man's talent for investigation. Neither of these kinds of tar, however, comes within the scope of the present work, both of them being by-products, whereas the other distillation products constitute valuable main products. At the pres- ent time tar is obtained as the main product of dry distillation by dis- tilling bituminous lignite and bituminous shale. The distillation tar obtained from peat is also only, a by-product. Lignite tar was known, as the result of distillation experiments on 2 a small scale, about the end of the eighteenth century, Kriinitz having mentioned in 1788 that rock oil could be obtained from Langen- bogen "earth coal" (meaning lignite) by distillation. For several de- cades, however, no useful application was discovered for this tar, though it was occasionally used medicinally. The discovery of paraffin in 1830 was of the greatest importance for the utilization of distillation tars and the name of ; consequently the discoverer of this substance, Carl von Eeichenbach, is closely con- nected with the history and development of the shale and lignite- 1 " " " This is the correct spelling. Coak is first mentioned in Plot's History of Staffordshire". According to Erdmann, coke is derived from coquere (to- cook). 'J " " E. Erdmann, Chemie der Braunkohle (" Chemistry of Lignite"), p. 9.. 1 2 :" *'*/. ; SHALE OILS AND TAES ;\ ; /; tar industry. Carl, Baron von Eeichenbach, was born at Stuttgart on 12 February, 1788, studied at Tubingen, and became manager of Count Salm's mines and factories at Blansko in Moravia. He died at Leipzig on 19 January, 1869. Although other workers, like I. N. Fuchs and A. Buchner, had previously prepared paraffin, Von Eeichenbach was the first to investi- gate this substance and to describe its chemical and physical pro- " l from his statement that a wick with it burns } and impregnated perties " like a fine wax candle, and without smell it is evident that he even recognized the great economic importance of paraffin as a candle ma- " " terial.