US2275441A - Conversion of hydrocarbons - Google Patents
Conversion of hydrocarbons Download PDFInfo
- Publication number
- US2275441A US2275441A US282067A US28206739A US2275441A US 2275441 A US2275441 A US 2275441A US 282067 A US282067 A US 282067A US 28206739 A US28206739 A US 28206739A US 2275441 A US2275441 A US 2275441A
- Authority
- US
- United States
- Prior art keywords
- silica
- hydrocarbons
- gasoline
- alumina
- zirconia
- 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
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Classifications
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
Definitions
- This invention relates to the conversion of mixtures of hydrocarbons comprising olefin-containtion so that a gasoline saturated in respect to the bromine number and consisting essentially only of parafiln and aromatic hydrocarbons is produced.
- Cracked gasolines produced either by strictly thermal or thermal-catalytic processes contain varying percentages of olefinic hydrocarbons depending upon the type of stock cracked and the severity of the cracking conditions employed, high with suitably chosen catalysts under the conditions specified that a number of simultaneous and concurrent reactions occur among the hydrocarbons so that not only are the olefins present in the cracked gasoline hydrogenated to produce the corresponding paraflins, but that the olefins in the gasoline produced by the cracking of the gas oil are also hydrogenated.
- the present invention comprises the treatment of mixtures of cracked gasolin-es and distillate fractions of the nature of kerosene or gas oil by contacting saidmixtures with granular catalytic material formed .by calcining an alkali metal-free composite of Cyclohexane Hexene Benzene Horace more complex reactions involving the splitting of carbon-to-carbon bonds, isomerization, recombination of radicals, etc.
- cyclohexane typifies naphthene hydrocarbons present in kerosenes or gas oils While the hexene typifies an olefinic constituent of a low boiling distillate of the nature of gasoline.
- the process requires a relatively active catalytic material to be presently described, the use of temperatures materially below the ordinary cracking range of either strictly thermal or thermal-catalytic processes and moderately long times of contact with the catalyst.
- the reactions are further favored by increased pressure which assists the secondary hydrogenation reactions;
- the catalysts which are preferred for use in the present processare of a very specific character and require the use of an exact method of preparation.
- precipitated alumina hydrogel and/or zirconia hydrogel are composited with silica hydrogel, and then the composite is washed, dried, formed into particles, and calcined to produce a catalytic mass.
- the different catalysts which may be so produced do not necessarily give equivalent results.
- silicaalumina, silica-zirconia, and silica-alumina-zirconia masses are used in a broad sense. Inasmuch as the chemical knowledge of the solid state has not been developed perfectly, it is not possible to give the structure of all solid substances. All that can be said definitely concerning these masses is that they contain silicon, oxygen, alu- 'minum, and/or zirconium. Generally speaking,
- silica which has been prepared by precipitation from solution as a hydrogel within or upon which the alumina and/or zirconia are deposited also by precipitation as hydrogels.
- the most convenient and ordinary method of preparation of a satisfactory silica gel is to acidify an aqueous solution of sodium silicate by the addition of the required amount of hydrochloric acid. The excess of acid and the concentration of the solution-in which the precipitation is brought about will determine the eventual primary activity of the silica and its suitability for compositing with the alumina and/or zirconia hydrogels to produce a catalyst of high activity.
- the most active silica is produced by adding only enough acid to cause gel formation to occur 'in the sodium silicate, but the material formed at such a point is rather gelatinous and is filtered with difliculty. Further the silica hydrogel is coagulated incompletely at this point.
- the more desirable physical characteristics in regard to catalyst activity are conserved while the filtrability is generally improved and the silica hydrogel is precipitated more completely.
- Fairly good hydrated silica for present catalytic purposes may be made by employing as highas a excess of hydrochloric acid, but'beyond this point the more desirable properties are lost.
- After precipitating the silica gel it is preferably washed until substantially free from salts by using several alternative reagents, which will be described later.
- the silica hydrogel may be boiled either with separately precipitated aluminum hydroxide and/or zirconium hydroxide gel, which is added in the wet condition to the silica/suspension, or th silica hydrogel may be suspended in and boiled within an aluminum chloride or the silica gel may be treated similarly by an aqueous solution containing both aluminum and zirconium salts.
- the final precipitate comprising essentially the hydrated silica and hydrafted alumina and/or zirconia is finally washed to substantially complete removal of water soluble materials and dried at about 300 F. to produce a rather crumbly and granular material which may be ground and pelleted or sized to produce particles of catalyst.
- this material is calcined at a temperature in the approximate range of 1000-1500 F. and is used at a temperature of the order of 500-900 F. its water content sulfide to aqueous solutions of aluminum and/or zirconium salts, followed by suitable washing to remove impurities.
- the alumina and/or zirconia hydrogels may be precipitated from such solution inwhich previously prepared and washed hydrated silica is suspended, followed by a washing of the-total composite precipitate.
- purified silica may be suspended in a solution of an aluminate, such as sodium aluminate and alumina precipitated by the addition of the aluminum salts or by the requisite quantities of acid.
- aluminum and/or zirconium salts may be added to a solution of an alkali metal silicate to jointly precipitate silica hydrogel with the hydrogels of alumina and/or zirconia and further amounts of silica hydrogel may then be precipitated by the addition of acid.
- a characteristic equation illustrating the preparation of a silica-alumina catalyst is given below, although in it no account is taken of water of hydration:
- the weight ratio of silica to alumina and/or zirconia may vary within a considerable range, for example from 30 to 0.1, although as a rule catalyst composites having optimum activity basedon yields'and quality of gasoline produced will correspond to silica-oxide weight ratios of theorder of about 30 to 10 in which the term oxide is used in reference to alumina and/or zirconia. These proportions will vary considerably with the particular fractions subjected to treatment and the degree of conversion found to be optimum in any particular case.
- Blends were made of a gasoline produced by thermally cracking an East Texas gas oil and further quantities of the gas oil itself. These blends were passed through a silica-aluminazirconia composite catalyst under conditions indicated in the appended table.
- the catalyst was prepared by the general procedure outlined in the preceding specification and consisted of approximately 100 molar proportions of silica, 2 molar proportions of alumina, and 4 molar proportions of zirconia.
- A refers to the-cracked gasoline
- B to the gas oil.
- the 400 F. endpoint material in the products from run No. 1 and particularly the 300 F. endpoint material from the products of run No. 2 at the lower temperature had a considerably increased susceptibility to the action of tetraethyl lead.
- the octane number was three points lower than the corresponding material in the charge, but was nine points higher when the same amount of tetraethyl lead was added.
- the low bromine numbers indicate substantially complete saturation and absorption of material amounts of olefins or diolefins, either of a straight chain or cyclic character.
- a process for producing motor fuel of high anti-knock value and relatively low olefin content which comprises combining olefinic gasoline with a hydrocarbon oil heavier than gasoline and containing a substantial proportion of saturated hydrocarbons, and subjecting the resultant mixture to the action of a catalyst comprising a calcined mixture of precipitated silica hydrogel and precipitated alumina hydrogel at a temperature in the approximate range of 500- 800 F. for a contact time sufficient to convert a substantial portion of said heavier oil into gasoline and to efiect substantial saturation of gasoline boiling olefins.
- a process for producing motor fuel of high anti-knock Value and relatively low olefin content which comprises combining olefinic gasoline with a hydrocarbon oil heavier than gasoline and containing a substantial proportion of saturated hydrocarbons, and subjecting the resultant mixture to the action of a catalyst comprising a calcined mixture of precipitated silica hydrogel and precipitated zirconia hydrogel at a temperature in the approximate range of SOD-800 F. for a contact time sufficient to convert a substantial portion of said heavier oil into gasoline and to efiect substantial saturation of gasoline boiling 4.
- the process as defined in claim 1 further.
- hydrocarbon oil is a straight run naphthenic petroleum fraction.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Description
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US282067A US2275441A (en) | 1939-06-30 | 1939-06-30 | Conversion of hydrocarbons |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US282067A US2275441A (en) | 1939-06-30 | 1939-06-30 | Conversion of hydrocarbons |
Publications (1)
Publication Number | Publication Date |
---|---|
US2275441A true US2275441A (en) | 1942-03-10 |
Family
ID=23079963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US282067A Expired - Lifetime US2275441A (en) | 1939-06-30 | 1939-06-30 | Conversion of hydrocarbons |
Country Status (1)
Country | Link |
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US (1) | US2275441A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2424637A (en) * | 1943-06-03 | 1947-07-29 | Tide Water Associated Oil Comp | Process and catalyst for aromatizing aliphatic hydrocarbons |
US2487564A (en) * | 1942-06-18 | 1949-11-08 | Kellogg M W Co | Silica gel-alumina supported catalyst |
US2487563A (en) * | 1942-06-18 | 1949-11-08 | Kellogg M W Co | Catalyst for hydrocarbon conversion process |
US2580641A (en) * | 1938-12-20 | 1952-01-01 | Houdry Process Corp | Method of preparing a silica-zir-conium oxide catalyst for the conversion of hydrocarbons |
US10087372B2 (en) * | 2009-04-09 | 2018-10-02 | Titanium Corporation Inc. | Methods for separating a feed material derived from a process for recovering bitumen from oil sands |
-
1939
- 1939-06-30 US US282067A patent/US2275441A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2580641A (en) * | 1938-12-20 | 1952-01-01 | Houdry Process Corp | Method of preparing a silica-zir-conium oxide catalyst for the conversion of hydrocarbons |
US2487564A (en) * | 1942-06-18 | 1949-11-08 | Kellogg M W Co | Silica gel-alumina supported catalyst |
US2487563A (en) * | 1942-06-18 | 1949-11-08 | Kellogg M W Co | Catalyst for hydrocarbon conversion process |
US2424637A (en) * | 1943-06-03 | 1947-07-29 | Tide Water Associated Oil Comp | Process and catalyst for aromatizing aliphatic hydrocarbons |
US10087372B2 (en) * | 2009-04-09 | 2018-10-02 | Titanium Corporation Inc. | Methods for separating a feed material derived from a process for recovering bitumen from oil sands |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CITICORP NORTH AMERICA, INC., AS "AGENT", NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNORS:HLI OPERATING COMPANY, INC.;HAYES LEMMERZ INTERNATIONAL, INC.;HAYES LEMMERZ INTERNATIONAL-OHIO, INC.;AND OTHERS;REEL/FRAME:014178/0834 Effective date: 20030603 |
|
AS | Assignment |
Owner name: CITICORP NORTH AMERICA, INC.,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNORS:HAYES-LEMMERZ INTERNATIONAL, INC.;HLI OPERATING COMPANY, INC.;HAYES-LEMMERZ INTERNATIONAL-EQUIPMENT AND ENGINEERING, INC.;AND OTHERS;REEL/FRAME:015991/0242 Effective date: 20050411 Owner name: CITICORP NORTH AMERICA, INC., NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNORS:HAYES-LEMMERZ INTERNATIONAL, INC.;HLI OPERATING COMPANY, INC.;HAYES-LEMMERZ INTERNATIONAL-EQUIPMENT AND ENGINEERING, INC.;AND OTHERS;REEL/FRAME:015991/0242 Effective date: 20050411 |