US2659691A - Process for refining petroleum products - Google Patents

Process for refining petroleum products Download PDF

Info

Publication number
US2659691A
US2659691A US133058A US13305849A US2659691A US 2659691 A US2659691 A US 2659691A US 133058 A US133058 A US 133058A US 13305849 A US13305849 A US 13305849A US 2659691 A US2659691 A US 2659691A
Authority
US
United States
Prior art keywords
mercaptans
oxidation
gasoline
products
petroleum products
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.)
Expired - Lifetime
Application number
US133058A
Inventor
Gislon Andre
Quiquerez Joseph
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Francaise de Raffinage SA
Original Assignee
Compagnie Francaise de Raffinage SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Compagnie Francaise de Raffinage SA filed Critical Compagnie Francaise de Raffinage SA
Priority to US133058A priority Critical patent/US2659691A/en
Application granted granted Critical
Publication of US2659691A publication Critical patent/US2659691A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/96—Water

Definitions

  • the usual process for efiecting this refining is the plumbite process which comprises treating the petroleum products in question with a solution of alkaline plumbite in the presence of sulfur, the successive reactions being: formation of lead mercaptides, oxidation of same by means of sulfur with formation of organic disulfides and lead sulfide, and finally regeneration of the plumbite solution through oxidation by air of the lead sulfide in an alkaline medium.
  • cat-ox is an abbreviation of 1 oxidation catalyst.
  • Example 1 A solution of 0.500 g. of cat-ox in 20 cubic centimeters of methanol and 180 cubic centimeters of water is prepared.
  • the quantity of active oxygen in this solution is 25 mg. and can oxidize 100 mg. of sulfur in the form of mercaptan.
  • 200 cubic centimeters of this mixture are shaken in the presence of air with 250 cubic centimeters of heptane containing 281 mg. of butyl-mercaptan. After 15 minutes allow to decant; separate the layer of heptane which does not contain any more mercaptan (Doctor test negative).
  • the operation can be repeated 30 times without the activity of the hydro-alcoholic solution of cat-ox being decreased.
  • Example 2 240 cubic centimeters of the same hydro-alcoholic solution of cat-ox were used for treating as in the previous example 250 cubic centimeters of Irak distilled gasoline containing 0.0336% of sulfur in the form of mercaptans. After 25 minutes the gasoline was sweet. The gasoline was separated and the same quantity of gasoline treated again. The operation was repeated 25 times without observing any decrease in the catalytic properties.
  • Example 3 If 250 cubic centimeters of gasoline containing 82 mg. of sulfur in the form of mercaptans are treated in air with 200 cubic centimeters of a hydro-alcoholic solution containing 0.423 g. of cat-0x, the gasoline becomes sweet after 25 minutes. The same test was repeated, adding 1 per mil of sodium isopropyl-naphthalene-sulfonate to the aqueous phase; the oxidation of the mercaptans was completed in 10 minutes.
  • the speed of reaction is proportional to the ratio between the quantity of catalytic oxidation agent and the quantity of mercaptan to be oxidized, as shown by the following example:
  • Example 4 65 cubic centimeters of gasoline containing 15 mg. of sulfur in the form of mercaptans are treated in air with 220 cubic centimeters of a hydro-acetone solution containing 1.6 per mil of cat-ox containing 5% of active oxygen and 1 per mil of sulforicinate. sweetening is obtained in 15 minutes.
  • Example 5 The reaction can be carried out in a continuous manner, and by way of example the following apparatus and process are described with reference to the accompanying drawing.
  • 1 volume of a solution comprising 25 parts by weight of methanol, parts of water, 0.5 part of bi-disalicylal ethylene diamine aquo-cobalt, 0.2 part of sodium butylnaphthalene sulfonate and a volume of gasoline to be refined, are discharged per unit of time into a static mixer A by means of a pump B.
  • a quantity of air that corresponds at least to the quantity of sulfur to be oxidized is blown in at the bottom of the mixer.
  • the emulsion of the liquid phases is conveyed to a decantation tower D, at the top of which the sweet gasoline is continuously removed at c; at the bottom of the tower the hydro-alcoholic phase containing the catalyst is exhausted by the pump B and discharged into the mixer after adding the gasoline to be treated which is admitted at d.
  • a process for refining petroleum products which comprises effecting the oxidation of the mercaptans contained in said products by the action of oxygen in the presence of organicchelate compounds that have the property of absorbing oxygen from air and of releasing it in a pure state, said chelate compounds having metallic constituents and said chelate compounds behaving in this case as oxidation catalysts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Description

Nov. 17, 1953 A. GISLON ETAL 2,659,691
PROCESS FOR REFINING PETROLEUM PRODUCTS Filed Dec. 15, 1949 SWEETENED GASOLINE GAS OUTLET DEOANTER GAS SEPARATOR AIR INLET REGIROULATED TREATING SOLUTION CHARGE [2 VOLUME GASOLINE d VOLUME TREATING SOLUTION couTAmme= METHANOL 25 PARTS WATER I80 PARTS cAT-ox 0.5 PARTS WETTING AGENT 0.2 PARTS INyENTO 5 Andre Q05 on da s'gph Quz/guerez A OR s Patented Nov. 17, 1953 PROCESS FOR REFINING' PETROLEUM PRODUCTS Andr Gislon, Paris, and Joseph Quiquerez, Saint- Cloud, France, assignors'to; Societe Anonyme dite Compagnie Francaise de Raflinage, Paris, France, a corporation of France Application December 15, 1949, Serial No. 133,058
19 Claims.
It is known that the mercaptans in petroleum products, and in particular in light products such as gasolines, naphthas, solvents, kerosenes, are eliminated by means of a refiningoperation which is generally known by the name of sweetening and which consists in converting the mercaptans into disulfides by oxidation. The usual process for efiecting this refining is the plumbite process which comprises treating the petroleum products in question with a solution of alkaline plumbite in the presence of sulfur, the successive reactions being: formation of lead mercaptides, oxidation of same by means of sulfur with formation of organic disulfides and lead sulfide, and finally regeneration of the plumbite solution through oxidation by air of the lead sulfide in an alkaline medium.
The recognized drawbacks of this process are also known: since lead mercaptide is soluble in hydrocarbons, the lead sulfide is formed in the colloidal state in said hydrocarbons; since the decantation is slow, in order to accelerate it, it is necessary to add an excess of sulfur and this excess may be detrimental as regards corrosion, the octane number and susceptibility to lead. Furthermore, the exact quantity of sulfur to be used is often difiicult to ascertain and the regeneration of the plumbite is a slow and comparatively costly operation. e
Other processes, in which the oxidation is effected by means of metallic salts such as copper salts, also have serious drawbacks owing to the solubility of the metalic salt in the hydrocarbons treated.
Endeavours have been made in various manners to effect the oxidation of the mercaptans by means of air, but heretofore no simple process has been discovered.
We have noted that certain organic substances and more especially organometallic compounds with chelated bonds, have the property of absorbing oxygen from air and of releasing it under certain conditions; such products include hemoglobin amongst the natural products, and also, amongst the synthetic products, the iron-indigo complex disalicylal ethylene diamlno cobalt I C=1TT N=c CH2H2 or bi-disalicylal ethylene diamine-aquo dicobalt In a general manner, these compounds, some of which have now become industrial, absorb the oxygen from air at ordinary temperature and/or under pressure and release it in the pure state, either by increase of temperature, or in vacuo.
We have however observed this unexpected fact, viz. that in the presence of reducing agents. and in particular of mercaptans, the absorption and the exchangeof oxygen are effected at the same temperature. The organic compounds in question behave in this case like real oxidation catalysts and the invention essentially lies in the novel application of said compounds to the elimination of the mercaptans contained in petroleum products.
In order to simplify the terminology, the compounds in question are hereinafter designated by the word cat-ox which is an abbreviation of 1 oxidation catalyst.
Thus, if 1 litre of gasoline containing 0.02% of sulfur in the form of mercaptans isshaken in air inthe presence of 1 gram of cat-oxibidisalicylal ethylene diamineaquo dicobalt, for example) it is found that, after 15, 30, 45 minutes, the proportion of mercaptans is successively 0.008; 0.005, 0.003 per cent. The gasoline can then be separated, the same quantity of gasoline containing mercaptans added, and the operation repeated. It is again found that there is a gradual oxidation of the mercaptans, and this takes place several times consecutively. This exepriment clearly shows the catalytic effect of the'cat-ox since it is well known that if gasoline containing mercaptans is merely shaken in air, such a result is not obtained.
However, in this method of operation, the reaction speed is very slow and would not allow of the process being worked industrially.
We have furthermore observed that this reaction speed is considerably increased if certain organic compounds which are solvents for catox are added to the hydrocarbon; amongst such compounds mention may be made, without this list being limitative, of methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and the like, ketones, dioxane, pyridine, and the like.
Thus, if the foregoing test is repeated by treating 1 litre of gasoline containing 0.02% of sulfur in the form of mercaptans with air in the presence of 1 gram of cat-ox, after adding 1 cubic centimeter of methanol, it is found that in five minutes the oxidation of the mercaptans is complete.
The same effect is obtained in the presence of water, that is to say if an emulsion of hydrocarbon containing mercaptans to be oxidized and a solution or a dispersion of cat-ox in a mixture of alcohol and water, acetone and water, pyridine and water, or the like, is treated with air.
From an'industrial standpoint this modification of the invention has numerous advantages:
(a) The solvent is not lost in the hydrocarbon phase;
(1)) No catalyst is lost by being carried away in the hydrocarbon;
(c) The quick decantation of the aqueous ,phase carries away the cat-ox in the hydroorganic medium and makes it possible to avoid any filtration of the hydrocarbon;
(d) It is possible to operate without a solid dispersion by using the solution of the catalyst in the hydro-organic medium chosen. 7
Various non-limitative examples of applications of the invention according to this modification are given hereinafter:
Example 1 A solution of 0.500 g. of cat-ox in 20 cubic centimeters of methanol and 180 cubic centimeters of water is prepared. The quantity of active oxygen in this solution is 25 mg. and can oxidize 100 mg. of sulfur in the form of mercaptan. 200 cubic centimeters of this mixture are shaken in the presence of air with 250 cubic centimeters of heptane containing 281 mg. of butyl-mercaptan. After 15 minutes allow to decant; separate the layer of heptane which does not contain any more mercaptan (Doctor test negative). Add the same quantity of heptane and mercaptan to the hydro-alcoholic phase; the mixture is sweet again after 15 minutes. The operation can be repeated 30 times without the activity of the hydro-alcoholic solution of cat-ox being decreased.
Example 2 240 cubic centimeters of the same hydro-alcoholic solution of cat-ox were used for treating as in the previous example 250 cubic centimeters of Irak distilled gasoline containing 0.0336% of sulfur in the form of mercaptans. After 25 minutes the gasoline was sweet. The gasoline was separated and the same quantity of gasoline treated again. The operation Was repeated 25 times without observing any decrease in the catalytic properties.
We have furthermore found that the speed of reaction is increased if the contact between the phases is improved by adding a surface-active or wetting agent as is apparent in the next example.
Example 3 If 250 cubic centimeters of gasoline containing 82 mg. of sulfur in the form of mercaptans are treated in air with 200 cubic centimeters of a hydro-alcoholic solution containing 0.423 g. of cat-0x, the gasoline becomes sweet after 25 minutes. The same test was repeated, adding 1 per mil of sodium isopropyl-naphthalene-sulfonate to the aqueous phase; the oxidation of the mercaptans was completed in 10 minutes.
The addition of any other surface-active or wetting agent, and in particular a sodium sulforicinate, produced similar results.
Furthermore, it was observed that the addition of such a surface-active or wetting agent favors the breaking up of the gasoline-aqueous solution emulsion and accelerates the separation of the phases.
The speed of reaction is proportional to the ratio between the quantity of catalytic oxidation agent and the quantity of mercaptan to be oxidized, as shown by the following example:
Example 4 65 cubic centimeters of gasoline containing 15 mg. of sulfur in the form of mercaptans are treated in air with 220 cubic centimeters of a hydro-acetone solution containing 1.6 per mil of cat-ox containing 5% of active oxygen and 1 per mil of sulforicinate. sweetening is obtained in 15 minutes.
If only 30 cubic centimeters of gasoline are treated with the same volume of the same solution, sweetening is obtained in 3 minutes.
Example 5 The reaction can be carried out in a continuous manner, and by way of example the following apparatus and process are described with reference to the accompanying drawing.
1 volume of a solution comprising 25 parts by weight of methanol, parts of water, 0.5 part of bi-disalicylal ethylene diamine aquo-cobalt, 0.2 part of sodium butylnaphthalene sulfonate and a volume of gasoline to be refined, are discharged per unit of time into a static mixer A by means of a pump B. A quantity of air that corresponds at least to the quantity of sulfur to be oxidized is blown in at the bottom of the mixer. After passing through a gas remover C in which the excess of air is separated at b, the emulsion of the liquid phases is conveyed to a decantation tower D, at the top of which the sweet gasoline is continuously removed at c; at the bottom of the tower the hydro-alcoholic phase containing the catalyst is exhausted by the pump B and discharged into the mixer after adding the gasoline to be treated which is admitted at d.
By way of a modification, it is possible to use an excess of cat-ox dispersed in the hydro-alcoholic phase, so that the same is constantly saturated; it is also possible to cause the gasolinemethanol-water emulsion to flow towards a solid mass of cat-ox while air is being blown; all these techniques also produce the sweetening of the gasoline treated.
What we claim is:
1. A process for refining petroleum products, which comprises effecting the oxidation of the mercaptans contained in said products by the action of oxygen in the presence of organicchelate compounds that have the property of absorbing oxygen from air and of releasing it in a pure state, said chelate compounds having metallic constituents and said chelate compounds behaving in this case as oxidation catalysts.
2. Process according to claim 1, wherein the absorption and exchange of oxygen are efiected without change of temperature or pressure.
3. Process according to claim 1, wherein the oxidation is efiected in the presence of a third substance chosen among the solvents for the chelate compound which is used.
4. Process according to claim 1, wherein the oxidation is effected in the presence of an alcohol.
5. Process according to claim 1, wherein the oxidation is effected in the presence of a ketone.
6. Process according to claim 1, wherein the oxidation is effected in the presence of a solution of the compound used in a mixture of water and an organic solvent for said compound.
'7. Process according to claim 1, wherein theoxidation is effected in the presence of a dispersion of the compound used in a mixture of water and an organic solvent for the said compound.
8. Process according to claim 1, wherein the oxidation is efiected in the presence of a solution of the compound used in a mixture of water and an organic solvent for said compound and in the presence of a surface active compound.
9. Process according to claim 1, wherein the oxidation is effected in the presence of a dispersion of the compound used in a mixture of Water and an organic solvent for said compound, and in the presence of a surface active compound.
10. Process according to claim 1, which is carried out in a continuous manner.
11. Process according to claim 1, which is carried out in a discontinuous manner.
12. Process according to claim 1, which is carried out at ordinary pressure.
13. Process according to claim 1, which is carried out at a pressure that difiers from ordinary pressure.
14. The process of refining liquid petroleum products which comprises oxidizing mercaptans contained in said products by the action of oxygen in the presence of a catalyst which is comprised of cobalt and organic components which react to form a compound having a chelate bond.
15. The process of refining liquid petroleum products which comprises oxidizing mercaptans contained in said products by the action of oxygen in the presence of a catalyst which is comprised of disalicylal imino cobalt.
16. The process of refining liquid petroleum products which comprises oxidizing mercaptans contained in said products by the action of oxygen in the presence of a catalyst which is comprised of iron and organic components which react to form a compound having a chelate bond.
17. The process of refining liquid petroleum products which comprises oxidizing mercaptans contained in said products by the action of oxygen in the presence of a catalyst which is comprised of disalicylal ethylene diamino cobalt.
18. The process of refining liquid petroleum products which comprises oxidizing mercaptans contained in said products by the action of oxygen in the presence of a catalyst which is comprised of lei-disalicylal ethylene diamine-aquo dicobalt.
19. The process of refining liquid petroleum products which comprises oxidizing mercaptans contained in said products by the action of oxygen in the presence of a catalyst which is comprised of the iron-indigo complex NH NH/ 2,. NH& )NH 0 oo oo ANDRE GISLON. JOSEPH QUIQUEREZ.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,081,801 Wohl Dec. 16, 1913 2,302,352 Schultze Nov. 1'7, 1942 2,450,276 Folger Sept. 28, 1948 2,494,687 Bond Jan. 17, 1950 OTHER REFERENCES Calvin et al. J. A. C. 53., vol. 68, pages 2254 to

Claims (1)

1. A PROCESS FOR REFINING PETROLEUM PRODUCTS, WHICH COMPRISES EFFECTING THE OXIDATION OF THE MERCAPTANS CONTAINED IN SAID PRODUCTS BY THE ACTION OF OXYGEN IN THE PRESENCE OF ORGANICCHELATE COMPOUNDS THAT HAVE THE PROPERTY OF ABSORBING OXYGEN FROM AIR AND OF RELEASING IT IN A PURE STATE, SAID CHELATE COMPOUNDS HAVING
US133058A 1949-08-26 1949-12-15 Process for refining petroleum products Expired - Lifetime US2659691A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US133058A US2659691A (en) 1949-08-26 1949-12-15 Process for refining petroleum products

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR832312X 1949-08-26
US133058A US2659691A (en) 1949-08-26 1949-12-15 Process for refining petroleum products

Publications (1)

Publication Number Publication Date
US2659691A true US2659691A (en) 1953-11-17

Family

ID=26223751

Family Applications (1)

Application Number Title Priority Date Filing Date
US133058A Expired - Lifetime US2659691A (en) 1949-08-26 1949-12-15 Process for refining petroleum products

Country Status (1)

Country Link
US (1) US2659691A (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2723222A (en) * 1954-12-06 1955-11-08 Phillips Petroleum Co Use of chelating agents to improve color and color stability of petroleum distillate
US2723221A (en) * 1954-12-06 1955-11-08 Phillips Petroleum Co Use of chelating agents to improve acid treatment of hydrocarbon streams
US2744854A (en) * 1952-06-30 1956-05-08 Universal Oil Prod Co Oxidation of mercaptans
US2823173A (en) * 1952-06-19 1958-02-11 Raffinage Cie Francaise Methods of refining petroleum products
US2848374A (en) * 1955-06-06 1958-08-19 Standard Oil Co Oxygen sweetening process
US2853432A (en) * 1954-12-28 1958-09-23 Universal Oil Prod Co Regeneration of used alkaline reagents by oxidizing the same in the presence of a phthalocyanine catalyst
US2859176A (en) * 1955-06-27 1958-11-04 Standard Oil Co Sweetening of sour hydrocarbons
US2882224A (en) * 1958-02-13 1959-04-14 Universal Oil Prod Co Process for sweetening sour hydrocarbon distillates with metal phthalocyanine catalyst in the presence of alkali and air
US2889287A (en) * 1954-10-04 1959-06-02 California Research Corp Catalyst and method of catalyst preparation
US2918426A (en) * 1957-05-10 1959-12-22 Raffinage Cie Francaise Sweetening of hydrocarbons containing mercaptans and/or mercaptides with a chelate and oxygen
US2921020A (en) * 1957-12-18 1960-01-12 Universal Oil Prod Co Treatment of sour hydrocarbon distillate
US2921021A (en) * 1957-12-18 1960-01-12 Universal Oil Prod Co Treatment of sour hydrocarbon distillate
US2967824A (en) * 1956-06-18 1961-01-10 Raffinage Cie Francaise Process of deodorizing hydrocarbons of petroleum
US3053756A (en) * 1958-07-03 1962-09-11 Basf Ag Refining of industrial hydrocarbon mixtures
US3068065A (en) * 1956-08-24 1962-12-11 Humphreys & Glasgow Ltd Method of removing hydrogen sulphide from gases
DE1175813B (en) * 1959-02-13 1964-08-13 Raffinage Cie Francaise Continuous process for refining petroleum distillates
US3247138A (en) * 1962-06-06 1966-04-19 Thiokol Chemical Corp One-package liquid polysulfide sealant
US4794097A (en) * 1986-07-11 1988-12-27 Compagnie De Raffinage Et De Distribution Total France Catalytic composite product for the oxidation of mercaptans and its use for the sweetening of petroleum fractions
US5174973A (en) * 1989-12-05 1992-12-29 University Of Toronto Innovations Foundation Method and apparatus for effecting gas-liquid contact
US5352421A (en) * 1989-12-05 1994-10-04 University Of Toronto Innovations Foundation Method and apparatus for effecting gas-liquid contact
US5366698A (en) * 1989-12-05 1994-11-22 The University Of Toronto, Innovations Foundation Apparatus for effecting gas liquid contact
US5403567A (en) * 1989-12-05 1995-04-04 Smith; James W. Dual impeller method and apparatus for effecting chemical conversion
US5500130A (en) * 1994-11-29 1996-03-19 The University Of Toronto Innovations Foundation And Apollo Environmental Systems Corp. Method for effecting gas-liquid contact
US5500135A (en) * 1989-12-06 1996-03-19 The University Of Toronto Innovations Foundation Method for effecting gas-liquid contact
US20050163571A1 (en) * 2003-01-16 2005-07-28 Kittle Paul A. Gas recovery from landfills using aqueous foam

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1081801A (en) * 1910-04-26 1913-12-16 Wohle Mineral Oil Products 1910 Ltd Process of treating petroleum or other hydrocarbon oils.
US2302352A (en) * 1940-08-04 1942-11-17 Standard Oil Dev Co Refining mineral oils
US2450276A (en) * 1944-07-07 1948-09-28 Little Inc A Process for production of oxygen
US2494687A (en) * 1947-11-15 1950-01-17 Pure Oil Co Oxidation of mercaptans in the presence of c-nitroso aromatic compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1081801A (en) * 1910-04-26 1913-12-16 Wohle Mineral Oil Products 1910 Ltd Process of treating petroleum or other hydrocarbon oils.
US2302352A (en) * 1940-08-04 1942-11-17 Standard Oil Dev Co Refining mineral oils
US2450276A (en) * 1944-07-07 1948-09-28 Little Inc A Process for production of oxygen
US2494687A (en) * 1947-11-15 1950-01-17 Pure Oil Co Oxidation of mercaptans in the presence of c-nitroso aromatic compounds

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2823173A (en) * 1952-06-19 1958-02-11 Raffinage Cie Francaise Methods of refining petroleum products
US2744854A (en) * 1952-06-30 1956-05-08 Universal Oil Prod Co Oxidation of mercaptans
US2889287A (en) * 1954-10-04 1959-06-02 California Research Corp Catalyst and method of catalyst preparation
US2723221A (en) * 1954-12-06 1955-11-08 Phillips Petroleum Co Use of chelating agents to improve acid treatment of hydrocarbon streams
US2723222A (en) * 1954-12-06 1955-11-08 Phillips Petroleum Co Use of chelating agents to improve color and color stability of petroleum distillate
US2853432A (en) * 1954-12-28 1958-09-23 Universal Oil Prod Co Regeneration of used alkaline reagents by oxidizing the same in the presence of a phthalocyanine catalyst
US2848374A (en) * 1955-06-06 1958-08-19 Standard Oil Co Oxygen sweetening process
US2859176A (en) * 1955-06-27 1958-11-04 Standard Oil Co Sweetening of sour hydrocarbons
US2967824A (en) * 1956-06-18 1961-01-10 Raffinage Cie Francaise Process of deodorizing hydrocarbons of petroleum
US3068065A (en) * 1956-08-24 1962-12-11 Humphreys & Glasgow Ltd Method of removing hydrogen sulphide from gases
US2918426A (en) * 1957-05-10 1959-12-22 Raffinage Cie Francaise Sweetening of hydrocarbons containing mercaptans and/or mercaptides with a chelate and oxygen
US2921020A (en) * 1957-12-18 1960-01-12 Universal Oil Prod Co Treatment of sour hydrocarbon distillate
US2921021A (en) * 1957-12-18 1960-01-12 Universal Oil Prod Co Treatment of sour hydrocarbon distillate
US2882224A (en) * 1958-02-13 1959-04-14 Universal Oil Prod Co Process for sweetening sour hydrocarbon distillates with metal phthalocyanine catalyst in the presence of alkali and air
US3053756A (en) * 1958-07-03 1962-09-11 Basf Ag Refining of industrial hydrocarbon mixtures
DE1175813B (en) * 1959-02-13 1964-08-13 Raffinage Cie Francaise Continuous process for refining petroleum distillates
US3247138A (en) * 1962-06-06 1966-04-19 Thiokol Chemical Corp One-package liquid polysulfide sealant
US4794097A (en) * 1986-07-11 1988-12-27 Compagnie De Raffinage Et De Distribution Total France Catalytic composite product for the oxidation of mercaptans and its use for the sweetening of petroleum fractions
US5174973A (en) * 1989-12-05 1992-12-29 University Of Toronto Innovations Foundation Method and apparatus for effecting gas-liquid contact
US5352421A (en) * 1989-12-05 1994-10-04 University Of Toronto Innovations Foundation Method and apparatus for effecting gas-liquid contact
US5366698A (en) * 1989-12-05 1994-11-22 The University Of Toronto, Innovations Foundation Apparatus for effecting gas liquid contact
US5403567A (en) * 1989-12-05 1995-04-04 Smith; James W. Dual impeller method and apparatus for effecting chemical conversion
US5407646A (en) * 1989-12-05 1995-04-18 The University Of Toronto Innovations Foundation Dual impeller method and apparatus for effecting chemical conversion
US5527475A (en) * 1989-12-06 1996-06-18 The University Of Toronto Innovations Foundation Method for determining the parameters of a gas-liquid contact apparatus
US5500135A (en) * 1989-12-06 1996-03-19 The University Of Toronto Innovations Foundation Method for effecting gas-liquid contact
US5520818A (en) * 1989-12-06 1996-05-28 The University Of Toronto Innovations Foundation Method for effecting gas-liquid contact
US5552061A (en) * 1989-12-06 1996-09-03 Univ Toronto Method for effecting gas-liquid contact
US5585005A (en) * 1989-12-06 1996-12-17 University Of Toronto Innovations Foundation Method for effecting gas-liquid contact
US5730784A (en) * 1989-12-06 1998-03-24 The University Of Toronto Innovations Foundation Process for the removal of hydrogen sulfide from a gas stream
US5500130A (en) * 1994-11-29 1996-03-19 The University Of Toronto Innovations Foundation And Apollo Environmental Systems Corp. Method for effecting gas-liquid contact
US20050163571A1 (en) * 2003-01-16 2005-07-28 Kittle Paul A. Gas recovery from landfills using aqueous foam
US6994491B2 (en) 2003-01-16 2006-02-07 Kittle Paul A Gas recovery from landfills using aqueous foam

Similar Documents

Publication Publication Date Title
US2659691A (en) Process for refining petroleum products
US2853432A (en) Regeneration of used alkaline reagents by oxidizing the same in the presence of a phthalocyanine catalyst
US3980582A (en) Method and catalyst for removing mercaptans and mercaptide compounds from aqueous alkaline solutions
US2966453A (en) Oxidation of mercapto compounds
US4120865A (en) Metal complex and method for preparing
US3108081A (en) Catalyst and manufacture thereof
US2794767A (en) Refining process including regeneration of used alkaline reagents
US3686094A (en) Process for oxidizing mercaptans to disulfides in the presence of solid catalytic masses
US2897140A (en) Process for the oxidation of mercaptans in the presence of alkali and sulfur dye
US3708421A (en) Process to remove mercaptan sulfur from sour oils
Guo et al. Optimization study on deep extractive oxidative desulfurization with tetrabutylammonium bromide/polyethylene glycol DES
US2937986A (en) Spent caustic treating process
US3260665A (en) Oxidation of difficultly oxidizable mercaptans
US2319738A (en) Refining mineral oils
US3352777A (en) Oxidation of mercaptans
US2102796A (en) Oil refining process
US4243551A (en) Catalyst for oxidizing mercaptans and mercaptide compounds and method for preparing
Tarkhanova et al. Heterogeneous catalysts based on immobilized copper complexes in the oxidation of mercaptans
US2893951A (en) Sweetening petroleum hydrocarbons and method for regenerating the treating solution
US3154483A (en) Oxidation of mercaptans
US3097158A (en) Treating hydrocarbon distillates
US4069138A (en) Method and catalyst for removing mercaptans and mercaptide compounds from aqueous alkaline solutions and hydrocarbon distillates
US2646389A (en) Sweetening hydrocarbon distillates
US3252891A (en) Oxidation of mercaptans
US3252890A (en) Oxidation of mercaptans using phthalocyanine and mercury catalyst