US1965828A - Nitrogen base and method of making same - Google Patents

Nitrogen base and method of making same Download PDF

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Publication number
US1965828A
US1965828A US344098A US34409829A US1965828A US 1965828 A US1965828 A US 1965828A US 344098 A US344098 A US 344098A US 34409829 A US34409829 A US 34409829A US 1965828 A US1965828 A US 1965828A
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Prior art keywords
nitrogen
bases
oil
salts
oils
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US344098A
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Denis L Fox
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Standard Oil Company of California
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Standard Oil Company of California
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/14—Preparation from compounds containing heterocyclic oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/08—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acid-forming oxides

Definitions

  • This invention relates to the recovery of nitrogen compounds from oil and particularly from hydrocarbon oils such aspetroleum.
  • object of this invention is to disclose and provide a process of removing and separating nitrogen compounds from oils.
  • Another object is to disclose and provide a process of extracting and removing nitrogen bases from petroleum oils.
  • Another object is to disclose and provide a. process of obtaining nitrogen bases in relatively the oil bodies orimpurities.
  • oils are treated .with-sulphur trioxide or with liquid sulphur di-' pure condition from petroleum-oils.
  • a still further object is to disclose and provide a method whereby nitrogen compounds and bases may be completely removed from oils in a relatively pure condition.
  • a still further object of this invention is to provide "nitrogen bases and compounds in concentrated "form. l
  • a still further object is to provide, as an article ,of manufacture, nitrogen bases of particularly desirable characteristics.
  • An-object of this invention is to provide, as an article of manufacture, mixtures; of nitrogen bases having particularly desirable properties.
  • the nitrogen bases obtained directly as relatively pure salts and not in the- :form of dilute. aqueous solutions. greatly reduces the volume of material to be handled. If an aqueous solution saturated with sulphur dioxide is employed, it is so weak that only a small proportion of the is removed from an oil.
  • distillates obtained by pounds are particularly suitable as sources of nitrogen compounds or as raw material for use in my process.
  • Any suitable apparatus may be employed in carrying out the process described herein, and I am not to be limited to any particular form of apparatus.
  • the process may be carried out either by the batch method or by a continuous counterflow method.
  • Apparatus for use in counterflow methods is well known in the art and the arrangement of various well known units so as to carry out the process does not of itself involve invention.
  • the oil to be treated in accordance .with the process of this invention may be placed in an agitator or other suitable receptacle and anhydrous acid, or acid anhydride in gaseous form, then bubbled through the oil at moderate temperatures, or temperatures somewhat lower than those ordinarily employed. Sulphur dioxide or hydrogen chloride may be employed. As stated hereinabove, the desired contact between the gaseous acid and the oil may be accomplished by counter-flow methods if desired.
  • the treatment with acid is continued until the acid gases have reacted with all, or substantially all, of the nitrogen bases present therein. Most of the nitrogen bases are precipitated by the action of the acid gas in the form of salts o nitrogen bases and may be separated from the residual oil by sedimenta tion, filtration or other methods.
  • the salts remaining in solution or suspension in the oil, being water soluble may be removed from the oil by extraction with water.
  • the salts may be used directly in theform of a water solution or they may beneutralized with alkali so as to precipitate the nitrogen bases.
  • the salts of nitrogen'bases which are precipitated from the oil by treatment with a gaseous acid, or acid anhydride may be used as such or they may be neutralized to form nitrogen bases.
  • the products obtained by this process are complex mixtures of nitrogen bases and it has been discovered that these bases and salts thereof have toxic properties which make them particularly useful in the preparation of insecticides.
  • the nitrogen compounds and bases prepared in accordance with this invention may be used in the form of the solution of the salts in water or as a solution of the free bases in oil or an emulsion of bases in oil and the salts in water or the nitrogen bases may be embodied in a dust or powder.
  • a process of recovering nitrogen bases from oils comprising treating oil containing nitrogen compounds with substantially dry gaseous sulphur dioxide, without oxidizing the oil to remove impurities therefrom, separating salts of nitrogen bases precipitated from the oil by such treatment, and extracting suspended salts of nitrogen bases from the..treated oil.
  • a petroleum distillate containing nitrogen compounds with a substantially anhydrous gaseous material selected from the group consisting of sulfur dioxide and hydrogen chloride to precipitate salts of nitrogen bases without'oxidizing the petroleum distillate to remove the impurities therefrom, and separating the precipitated salts of nitrogen bases from the distillate.

Description

Patented July 10, 1934 PATENT OFFICE 1,9653%, NITROGEN BASE sign METHOD or MAKING Denis L. Fox, Berkeley, cam. asslgnout'o Standard Oil Company 01' California, San Francisco,
Calif., a corporation of Delaware No Drawing. Application March 2, 1929,
Serial No. 344.098
11 Claims.
- This invention relates to the recovery of nitrogen compounds from oil and particularly from hydrocarbon oils such aspetroleum.
It is well' known that most pertoleum oils,
5 shale oils andsimilar hydrocarbon oils contain nitrogen compounds in various quantities. It has been known that these nitrogen compounds 'could be extracted, in part at least, from the oils by means of dilute sulphuric acid or other mineral acids I haveals'o found that extracts obtained by treating oils with liquid sulphur dioxide contain a complex mixture of nitrogen compounds of varying strengths as bases, some of said compounds even appearing to be neutral.
From this it may be seen that the stronger the acid used in the extract of nitrogen compounds, 'the larger will be the quantity of nitrogen bases removed, but even with the strongest acids there i are nitrogen compounds weakly basic or neutral 0 which are not removed.
object of this invention is to disclose and provide a process of removing and separating nitrogen compounds from oils.
Another object. is to disclose and provide a process of extracting and removing nitrogen bases from petroleum oils.
Another object is to disclose and provide a. process of obtaining nitrogen bases in relatively the oil bodies orimpurities. When oils are treated .with-sulphur trioxide or with liquid sulphur di-' pure condition from petroleum-oils.
A still further object is to disclose and provide a method whereby nitrogen compounds and bases may be completely removed from oils in a relatively pure condition.
"Another object of this invention is to provide "nitrogen bases and compounds in concentrated "form. l A still further object is to provide, as an article ,of manufacture, nitrogen bases of particularly desirable characteristics.
An-object of this invention is to provide, as an article of manufacture, mixtures; of nitrogen bases having particularly desirable properties.
The nitrogen compounds occurring in most petroleum oils, shale oils and the like are volatile 5 at the temperatures employed in distillation, and consequently they may be found in the distillates.
I have discovered that all, or nearly all, of th'e nitrogen bases in cracked petroleum distillates arev of] relatively low molecular weight and are 5 stronger in general, as bases, than thoseoriginaily occurring in petroleum. v I
These compounds, or bases may be removed completely, or nearly so, by means of dilute acid solutions. I r When'liquid acids are used such as liquid sulpetroleum oils containing nitrogen com- 'phur dioxide and concentrated sulphuric acid, however, large amounts of oil bodies are also extracted from the oil and difficulties are encountered in separating the extractednitrogen compounds from the oil bodies; Furthermore, when aqueous acid is used, all of the acid in the water can not be made to combine with the nitrogen bases because of the hydrolysis of the resulting salts and consequent resolution of the bases in the oil. When aqueous acids are used, as much as one hundred per cent excess of acid is required in some cases to hold the bases in the water solution as salts, and this excess is all wasted since, in order to obtain the free bases, all
of the acid must be neutralized. By carrying out the extract in accordance-with the process embraced by this invention, all of the disadvantages recited hereinabove areobviated. I have discovered that the nitrogen compound present in oils can be more readily removed-by the use of gaseous acids such as hydrogen chloride or sulphur dioxide, than by the use of liquid acids such assulphuric acid or liquid sulphur dioxide. By using gaseous reagents it is possible to extract the nitrogen compounds without removing oil bodies or impurities and therefore a subsequent separation is not required for the separation of the nitrogen compounds from so intimately mixed with and included with the impurities that it is impractical to separate them from the oil bodies. As has been stated above, hydrolysis of nitrogen base salts occurs when acid solutions are used for extraction, but when an anhydrous acid in gaseous state is used, in accordance with this invention, no water is present, and consequently no hydrolysis of the salts formed occurs. A great saving in acid is made possible by this process in that no excess of acid is required beyond that needed to combine with the bases. l,
Furthermore, by employing acid in the anhydrous state, the nitrogen bases obtained directly as relatively pure salts and not in the- :form of dilute. aqueous solutions. greatly reduces the volume of material to be handled. If an aqueous solution saturated with sulphur dioxide is employed, it is so weak that only a small proportion of the is removed from an oil.
I have also found that distillates obtained by pounds are particularly suitable as sources of nitrogen compounds or as raw material for use in my process.
Any suitable apparatus may be employed in carrying out the process described herein, and I am not to be limited to any particular form of apparatus. The process may be carried out either by the batch method or by a continuous counterflow method. Apparatus for use in counterflow methods is well known in the art and the arrangement of various well known units so as to carry out the process does not of itself involve invention.
The oil to be treated in accordance .with the process of this invention may be placed in an agitator or other suitable receptacle and anhydrous acid, or acid anhydride in gaseous form, then bubbled through the oil at moderate temperatures, or temperatures somewhat lower than those ordinarily employed. Sulphur dioxide or hydrogen chloride may be employed. As stated hereinabove, the desired contact between the gaseous acid and the oil may be accomplished by counter-flow methods if desired. The treatment with acid is continued until the acid gases have reacted with all, or substantially all, of the nitrogen bases present therein. Most of the nitrogen bases are precipitated by the action of the acid gas in the form of salts o nitrogen bases and may be separated from the residual oil by sedimenta tion, filtration or other methods.
When cracked naphtha is used as the oil stock in accordance with this process, it has been found that'only about 0.007 pound of hydrogen chloride gas and/or about 0.008 pound of sulphur dioxide per gallon of naphtha is necessary to effect the extraction of substantially all the nitrogen bases present in such naphtha. These quantitles are merely illustrative and will vary with the character of the oil being treated, from about 0.002 pounds to 0.008 pounds of hydrogen chloride or sulfur dioxide per gallon.
A certain proportion of the salts of nitrogen bases remains in solution or suspension in the oil and suchsalt may be recovered separately, by extraction with an aqueous solvent. For example, the salts remaining in solution or suspension in the oil, being water soluble may be removed from the oil by extraction with water. The salts may be used directly in theform of a water solution or they may beneutralized with alkali so as to precipitate the nitrogen bases.
The salts of nitrogen'bases which are precipitated from the oil by treatment with a gaseous acid, or acid anhydride, may be used as such or they may be neutralized to form nitrogen bases. The products obtained by this process are complex mixtures of nitrogen bases and it has been discovered that these bases and salts thereof have toxic properties which make them particularly useful in the preparation of insecticides. The nitrogen compounds and bases prepared in accordance with this invention may be used in the form of the solution of the salts in water or as a solution of the free bases in oil or an emulsion of bases in oil and the salts in water or the nitrogen bases may be embodied in a dust or powder.
Obviously these toxic salts and bases when used for insecticidal purposes may be used alone ortogether with other ingredients and insecticides.
While the process has been described as being applied to petroleum oils, it is to be understood that the process is also applicable to other nitrogen-bearing hydrocarbon oils and is not limited to the particular details described herein, but embodies all the changes and modifications which come within the scope of the appended claims.
I claim:
, 1. A process of recovering nitrogen bases from oils comprising treating oil containing nitrogen compounds with substantially dry gaseous sulphur dioxide, without oxidizing the oil to remove impurities therefrom, separating salts of nitrogen bases precipitated from the oil by such treatment, and extracting suspended salts of nitrogen bases from the..treated oil.
2.-A process of recovering nitrogen bases from oils comprising treating a distillate obtained by cracking oil containing nitrogen compounds with gaseous sulphur dioxide to form salts of nitrogen compounds without oxidizing the oil to remove impurities therefrom, separating salts of nitrogen bases precipitated by such treatment from the oil, and extracting suspended-salts of nitrogen bases from the treated oil.
, 3. A mixture of salts of nitrogen bases substantially. free from hydrocarbon oils precipitated from petroleum oils by treating a petroleum oil containing nitrogen compounds with a material selected from the group consisting of substantially anhydrous gaseous sulfur dioxide and hydrogen chloride.
4. In a method of recovering nitrogen bases from petroleum oils, the steps of treating a petroleum oil with a substantially dry gaseous material selected from the group consisting of sulfur dioxide and hydrogen chloride, without oxidizing the oil to removeimpurities therefrom, to
form salts of nitrogen compounds present in said oil, and then separating such salts from' the oil. 5. In a method of recovering nitrogen bases from petroleum distillates, the steps of treating.
a petroleum distillate containing nitrogen compounds with a substantially anhydrous gaseous material selected from the group consisting of sulfur dioxide and hydrogen chloride to precipitate salts of nitrogen bases without'oxidizing the petroleum distillate to remove the impurities therefrom, and separating the precipitated salts of nitrogen bases from the distillate.
6. In a method of recovering nitrogen bases from petroleum distillates, the steps of treating a petroleum distillate containing nitrogen compounds with a substantially anhydrous gaseous material selected from the group consisting of sulfur dioxide and hydrogen chloride to precipitate salts of nitrogen bases without oxidizing the petroleum distillate to remove impurities therefrom, separating the precipitated salts of nitrogen bases from the distillate, and extracting suspended salts of nitrogen bases from the treated distillate. I
7. In a method of recovering nitrogen bases frompetroleum distillates, the-steps of treating a petroleum distillate containing nitrogen compounds with a substantially anhydrous sulfur dioxide in gaseous state to precipitate salts of nitrogen bases without oxidizing the petroleum distillate to remove impurities therefrom,- and separating the precipitated salts of nitrogen bases from the distillate.
8. In a method of recovering nitrogen bases from petroleum distillates, the steps of treating a petroleum distillate containing nitrogen compounds with a substantially anhydrous hydrogen chloride in gaseous state to precipitate salts of nitrogen bases without oxidizing the petroleum distillate to remove impurities therefrom, and separating precipitated salts of nitrogen from the distillate.
9. In a method or recovering nitrogen ba's'es Raw.
compounds precipitated from petroleum oil by treating an oil containing nitrogen compounds with substantially anhydrous sulfur dioxide in I gaseous state.
11. A.mixture of salts of nitrogen bases substantially free from hydrocarbon oils precipitat ed from petroleum oil by treating a petroleum oil containing nitrogen compounds with substan-' tially anhydrous hydrogen chloride in gaseous state.
DENIS L. FOX.
III
US344098A 1929-03-02 1929-03-02 Nitrogen base and method of making same Expired - Lifetime US1965828A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2420529A (en) * 1947-05-13 Resolution of hetebocyclic nitro
US2426442A (en) * 1947-08-26 Separation of z
US2456377A (en) * 1948-12-14 Process of separating z
US2502839A (en) * 1946-01-18 1950-04-04 American Cyanamid Co Process for preparing sulfur trioxide compounds of 4-alkyl morpholines
US2510875A (en) * 1946-02-16 1950-06-06 Allied Chem & Dye Corp Recovery of quinaldine
US2510877A (en) * 1950-06-06 Resolution of nitrogen base
US2519412A (en) * 1950-08-22 Swietoslawski
US2704758A (en) * 1949-11-22 1955-03-22 Houdry Process Corp Pyrolytic hydrogemnolysis of nitrogen bases
US2754248A (en) * 1950-10-04 1956-07-10 Houdry Process Corp Refining hydrocarbon oils with sulfur dioxide
US2755282A (en) * 1956-07-17 hachmuth
US2772269A (en) * 1953-08-31 1956-11-27 Phillips Petroleum Co Separation of mixed heterocyclic nitrogen compounds
US2800427A (en) * 1954-07-29 1957-07-23 Standard Oil Co Catalytic cracking of pretreated hydrocarbon oils
US2853489A (en) * 1953-12-28 1958-09-23 Phillips Petroleum Co Pyridine extraction process

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2755282A (en) * 1956-07-17 hachmuth
US2426442A (en) * 1947-08-26 Separation of z
US2456377A (en) * 1948-12-14 Process of separating z
US2510877A (en) * 1950-06-06 Resolution of nitrogen base
US2519412A (en) * 1950-08-22 Swietoslawski
US2420529A (en) * 1947-05-13 Resolution of hetebocyclic nitro
US2502839A (en) * 1946-01-18 1950-04-04 American Cyanamid Co Process for preparing sulfur trioxide compounds of 4-alkyl morpholines
US2510875A (en) * 1946-02-16 1950-06-06 Allied Chem & Dye Corp Recovery of quinaldine
US2704758A (en) * 1949-11-22 1955-03-22 Houdry Process Corp Pyrolytic hydrogemnolysis of nitrogen bases
US2754248A (en) * 1950-10-04 1956-07-10 Houdry Process Corp Refining hydrocarbon oils with sulfur dioxide
US2772269A (en) * 1953-08-31 1956-11-27 Phillips Petroleum Co Separation of mixed heterocyclic nitrogen compounds
US2853489A (en) * 1953-12-28 1958-09-23 Phillips Petroleum Co Pyridine extraction process
US2800427A (en) * 1954-07-29 1957-07-23 Standard Oil Co Catalytic cracking of pretreated hydrocarbon oils

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