US519036A - Hans a - Google Patents

Description

one part of nitric acid to three parts of sul-.

fu-ric acid in the mixture,

UNITED STATES.

PATENT QFFEQEO HANS A. FRASCII, OF CLEVELAND, OHIO, 'ASSIGNOR TO THE GRASSELLI I CHEMICAL COMPANY, OF SAME PLACE.

BROWN PETROLEUM DYE.

SPECIFICATION forming part of Letters Patent No. 519,036, dated May 1, 1894.

Original-application 5185 April 1 1393, iial No 71,018. Divided and this application filed October 24, 1893. Serial No.

489,042. (Specimens) 'zen of the United States, residing at Clevel'and,in the county of Cuyahoga andState of Ohio, have invented certain new and useful Improvements inProcesses of Producing D ye- Stufis by Nitration; and I do hereby declarethat the following is a full,clear, and exact description of the invention, which will enable others skilled in the art to which it appertains to make and use the same.

In the manufacture of anilin, artificial alizarin, and kindred d yestulfs and bases for dyestuifs and colors, coal tar obtained from illuminating gas works has hitherto been employed. The ordinary process of conversion is by fractional distillation of the coal tar. The aromatic series of hydrocarbons contained in such coal tar furnishes the source whence these dyestuffs or colors have been derived. A kindred or similar series of hydrocarbons exists also in petroleum or natural mineral oil or the distillates or derivatives, residual or otherwise, thereof; and it is upon these hydrocarbons of the petroleum series as distinguished from the hydrocarbons of the coal tar series that I act for obtaining my new dyestuifs.

My invention relates, first, to a method of obtaining dyestuffs from hydrocarbons contained in such natural oils by nitration, and,

second, to the product so obtained.

In practicing my invention, I subject crude petroleum or its distillates or products, residual or otherwise, to the action of a mixture of sulfuric and nitric acids until all the aromatic hydrocarbons, oletines, naphthenes, and unsaturated hydrocarbons in the oil are taken as oxidized and cor-- up in the acid mixture k I prefer to use responding nitro products.

and so, also, the propor- Lions may be varied;

to oil may be varied, ac-

tion of acid mixture cording to the quality of the oil being treated,

and according to the quantity of sulfuric and other acids that may be in the petroleum or its products being treated. Crude oil requires about twenty-five per cent., while distillates require from two to ten per cent, and sludge 1 parent application, Serial No. 471,018, filed roe but these pro'por'-' from nothing to five per cent, according to the quantity of acid remaining in the substance.

In all cases, the treatment proceeds alike, substantially as follows: The mixture of acid and oil is agitated, mechanically or by a forced current of air, at ordinary temperatures, say,

15 to 20 Celsius, until a samplefrom which the acid has been permitted to settle'will discolor little, if any, upon the addition thereto of fresh concentrated acid. The mixture of acid and oil is then permitted to rest until the acid is separated from the oil, when the acid containing the aromatic hydrocarbons and tarry substances is drawn from the oil. The acid mixture taken from the oil is then heated to from to 80 Celsius, until the hydrocarbons contained therein are converted into nitro or oxidized products. Nitration may be effected without heat by keeping the mixture agitated a long time, say, from four to eight weeks, and even longer, thus permitting the acid to act upon the hydrocarbons. The requisite degree or extent of nitration is determined when the bulk of a test sample will dissolve in a hot solution of alkali. The free acid is then removed and this may be readily accomplished by repeatedly washing the mixture with cold water or by precipitating the nitro compound from the acid by a suitable reagent, such as hydrochloric acid. After the free acid is removed, the residuum is heated with water until the water is' saturated with the more soluble nitro products. The solution is left-to settle, whereby the soluble products and the insoluble matter and oily matter separate from one another in accordance with their insolubility and specific gravity. The

soluble products are then drawn ofi and consist in a mixture of different higher or lower' ceases, whereby a soluble and an insoluble calcium salt are obtained. Any other substance which will form a soluble and insoluble salt with the nitro product may be substituted for the calcium.

The soluble salt forms the subject of the April 19, 1893, while the insoluble salt is the subject of this present case, filed as a division of said Serial No. 171,018.

The insoluble salt is separated from the solution by filtration or other means and may be converted into a soluble salt by the addition thereto of carbonate of sodium, potassium, ammonium, or any other substance that will unite therewith and form a soluble com-' pound or dyestuff and displace the calcium. This conversion of the insoluble salt into a soluble salt may be eifected by dissolving the insoluble salt in a solution of the carbonate of sodium or other reagents, or by fusing the salt and its reagent. The dyestuif itself is precipitated from the solution thereby obtained by the addition of hydrochloric acid, sodium chlorid, or any other salt in whose solution the dyestufi is insoluble.

The dyestuif obtained is ofa distinct brown colorand in the form of a powder. It has a resinous appearance or texture when first pulverized. This dyestuif is soluble, slightly in cold water, but readily. soluble in hot water. It is also soluble in ac etone and glycerin. It for-msan insoluble calcium salt. It emits the characteristic odor of burning coal oil when highly heated, and dyes cotton, without mordant, a brownish color.

If,-instead of using a mixture of sulfuric acidandnitric acid, sulfuric acid be substi tilted-in the processabove described, a sulfo product will be obtained, The sulfo product made, but can be "referred tq -fnay be treated to obtain a nitro product by 'dissolving the duct in water and heating it with nitric acid until efiervescenceceases, after which the product is precipitated from the solution as finished sulfo pro- 7 before. The same or a similar body may be obtained by the addition to a watery solution of the sulfo product of sodium nitrite and hydrochloric acid, and it can be obtained also by the addition of nitrous acid to the sulfo product.

What I claim is- 1. The art of manufacturing dyestufis from petroleum, natural mineraloils, or the distillates or residuums thereof, which consists in nitrating the substance, washing with water, dissolving the nitro products in hot water and decanting or otherwise removing the solution from the remainder and treating it with a base, such as wise separating the insoluble salt thereby formed and rendering it soluble by the addition thereto of an alkali, such as sodium carbonate, dissolving it in water and precipitating the dyest'uif from the solution by the addition of a reagent in whose solution the dye stuff is insoluble, such as sodium chlorid substantially as described.

2. As an article of manufacture, a dyestufi which isa brown powder derived from petroleum, emitting the characteristic odor of coal oil when highly'heated, soluble in water, acetone and glycerin, and capable of dyeing cotton, without'mordant, and whose calcium salt is insoluble in water, substantially as described.

Witness my hand to the foregoing specification this 9th day of August, 1893.

HANS A. FRASCH.

Witnesses: I

H. 'l. FISHER, GEORGIA SOHAEFFER.

lime, filtering or other-