US519036A - Hans a - Google Patents
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- Publication number
- US519036A US519036A US519036DA US519036A US 519036 A US519036 A US 519036A US 519036D A US519036D A US 519036DA US 519036 A US519036 A US 519036A
- Authority
- US
- United States
- Prior art keywords
- acid
- soluble
- oil
- salt
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002253 acid Substances 0.000 description 34
- 239000000203 mixture Substances 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000011780 sodium chloride Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 239000003208 petroleum Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229940108066 Coal Tar Drugs 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000011280 coal tar Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 238000006396 nitration reaction Methods 0.000 description 8
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 8
- 159000000007 calcium salts Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000010742 number 1 fuel oil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001376 precipitating Effects 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 235000015450 Tilia cordata Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000802 nitrating Effects 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000001187 sodium carbonate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/05—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of rings other than six-membered aromatic rings
Definitions
- 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,
- 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.
- 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.
- a suitable reagent such as hydrochloric acid.
- 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.
- 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.
- a sulfo product will be obtained,
- 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.
- an alkali such as sodium carbonate
- a dyestufi which is a 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.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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-
Publications (1)
Publication Number | Publication Date |
---|---|
US519036A true US519036A (en) | 1894-05-01 |
Family
ID=2587835
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US519036D Expired - Lifetime US519036A (en) | Hans a |
Country Status (1)
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US (1) | US519036A (en) |
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- US US519036D patent/US519036A/en not_active Expired - Lifetime
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