US2891904A - Process of catalytic cracking with a siliceous catalyst containing lithium hydroxide - Google Patents
Process of catalytic cracking with a siliceous catalyst containing lithium hydroxide Download PDFInfo
- Publication number
- US2891904A US2891904A US541820A US54182055A US2891904A US 2891904 A US2891904 A US 2891904A US 541820 A US541820 A US 541820A US 54182055 A US54182055 A US 54182055A US 2891904 A US2891904 A US 2891904A
- Authority
- US
- United States
- Prior art keywords
- cracking
- gasoline
- catalyst
- lithium hydroxide
- siliceous
- 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
Links
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims description 48
- 239000003054 catalyst Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 39
- 238000004523 catalytic cracking Methods 0.000 title description 3
- 238000005336 cracking Methods 0.000 claims description 45
- 238000009835 boiling Methods 0.000 claims description 22
- 238000005120 petroleum cracking Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000571 coke Substances 0.000 description 21
- 229930195733 hydrocarbon Natural products 0.000 description 21
- 150000002430 hydrocarbons Chemical class 0.000 description 21
- 229940006116 lithium hydroxide Drugs 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
Definitions
- This invention relates to a process for cracking hydrocarbons. More particularly the invention relates to a process for the catalytic cracking of hydrocarbons to obtain a high yield of gasoline and only a minor quantity of coke.
- An object of the present .invention is .toprovide a process for converting hydrocarbons of relatively high boiling petroleum fractions to hydrocarbons boiling in the gasoline range without concomitant production of appreciable amounts of coke. Another object is to provide a process for cracking hydrocarbons wherein long operation with a good yield of gasoline is obtained without catalyst deactivation. A further object is to provide a process for converting relatively high boiling petroleum fractions to gasoline in goodyield without substantial catalyst deactivation, wherein the higher boiling fractions have an increased content of normal paraflins which are readily converted to desirable products in subsequent operations.
- a relatively high boiling petroleum fraction having a substantial content of straight chain hydrocarbons, or substantially straight chain hydrocarbons is contacted under cracking conditions with a siliceous cracking catalyst, such as a silica-alumina cracking catalyst, which contains a small quantity of lithium hydroxide.
- a siliceous cracking catalyst such as a silica-alumina cracking catalyst, which contains a small quantity of lithium hydroxide.
- the hydrocarbon effluent from the process is distilled to separate a gasoline fraction and at leastone fraction boiling above the gasoline range.
- the higher boiling fraction or fractions contain a proportion of straight chain hydrocarbons, by which term is included substantially straight chain hydrocarbons, i.e. hydrocarbons which have only a slightly branched chain, substantially greater than the proportion thereof in the initial feed stock.
- Such fractions are especially suitable ctor use in thermal cracking, in processes which combine dehydrogenation and cyclization to produce aromatic hydrocarbons, or in isomerization processes to produce materials which are valuable without further 2 processing
- the relatively high boiling petroleum fractions which can be used in the process of the invention are the petroleum cracking stocks boiling above the gasoline range, say above about 400 F. Such fractions normally contain straight chain p'arafiins, and the process of the inventiori is especially valuable with such fractions containing substantial quantities thereof, say from about 10-60% by volume straight chain parafiins'.
- the remaining hydrocarbons of the fraction generally consist of isoparaffins, naphthenes and aromatics, including alkyl-substituted naphthenes and aromatics.
- Straight run petroleum fract'ion's generally are suitable, but other fractions, such as cracked fractions including olefins, can be used if desired.
- the catalyst used in the process ofthe invention is a siliceous'cracking catalyst which contains a small amount of lithium hydroxide.
- siliceous cracking catalyst and terms of similar import as used herein, is meant a synthetic or natural siliceous composition known to be efifective for the cracking of hydrocarbons.
- Synthetic silica-alumina cracking catalysts form the preferred catalyst o'fthe process of the invention, and the process is hereinafter largely described in terms thereof.
- other siliceous cracking catalysts give good results, such as silica-magnesia, silica-zirconia, silica-alumina-zirconia, and acid activated clays, such as acid activated montmorillonite.
- the siliceous cracking catalyst used in the process of the invention may be prepared by means heretofore known.
- the silica-alumina portion of the catalytic composition can be prepared by impregnating silica with aluminum salts, by directly combining precipitated hydrated alumina andsilica, or by joint precipitation of alumina and silica from aqueous solutions of their salts.
- the lithium hydroxide is advantageously deposited on the cracking catalyst by means of an aqueous solution.
- an aqueous solution of lithium hydroxide containing a quantity of lithium hydroxide sufficient to impart the desired quantity thereof to the final catalyst is contacted with the silicaalumina composition.
- Excess solution is drained, if nesessary, and the resulting composition dried and calcined.
- the quantity of litlnum hydroxide must be within the range of from 0.2 to 2 milli-equivalents (meq) per gram of catalyst. If smaller amounts are used, substantial coke formation is observed, whereas if larger quantities above the stated maximum range are used, the cracking activity of the composition is decreased so that an operable yield of gasoline is not obtained.
- a significant advantage of the process is the high yield of gasoline obtained compared to the yield of coke formed, i.e. the selectivity of the process for producing gasoline is excellent, whereas the selectivity for producing coke is poor.
- the ratio of gasoline produced to coke formed is a convenient measure of selectivity, and is determined by dividing the volume percent gasoline formed by the weight percent coke formed.
- processes heretofore described give a gasoline to coke ratio of from about 8 to 20.
- cracking conditions are used.
- cracking conditions is meant the conditions known to the art to be useful for the catalytic cracking of hydrocarbons.
- temperatures of from about 750 F. to 1100 square inch gauge (p.s.i.g.), and space rates of from 0.5-5 volumes of hydrocarbons per volume of catalyst per hour (v./v./hr.), give good results.
- the process of the invention can be operated using fixed bed or continuous bed techniques, or fluidized operation may be used.
- a petroleum fraction consisting of about volume percent straight chain paraffins and about 30 volume percent naphthenes, the remainder being isoparaflins and aromatics, and which boils in the range of from about 407 F. to about 750 F., as contacted with a synthetic silica-alumina cracking catalyst containing about 0.6 meq.
- Process for the preparation of gasoline from a petroleum cracking stock which comprises: contacting, under cracking conditions, said relatively high boiling cracking stock with a siliceous cracking catalyst which contains from about 0.2 to 2 milli-equivalents of lithium hydroxide per gram of catalyst.
- Process for the preparation of gasoline from a relatively high boiling petroleum cracking stock containing at least 10% by volume straight chain hydrocarbons which comprises: contacting, under cracking conditions, said relatively high boiling cracking stock with a siliceous cracking catalyst which contains from about 0.2 to 2 milli equivalents of lithium hydroxide per gram of catalyst, and separating from the hydrocarbon effluent a gasoline fraction and a higher boiling. fraction having an increased proportion of straight chain parafiins.
- Process for the preparation of gasoline from a relatively high boiling petroleum cracking stock containing from about 10% to by volume straight chain paraffins which comprises: contacting said relatively high boiling petroleum cracking stock with a catalyst consisting essentially of a siliceous cracking catalyst which contains from about 0.2 to 2 milli-equivalents of lithium hydroxide per gram of catalyst under cracking conditions to produce gasoline and coke in a ratio of gasoline to coke of at least 25.
- Process for the preparation of gasoline from. a relatively high boiling petroleum cracking stock containing from about 10% to 60% by volume straight chain paraffins which comprises, contacting said relatively high boiling petroleum cracking stock with a catalyst consisting essentially of a siliceous cracking catalyst which contains from about 0.2 to 2 milli-equivalents of lithium hydrox ide per gram of catalyst under cracking conditions to pro Jerusalem gasoline and coke in a ratio of gasoline to coke of at least 25, separating gasoline from the reaction product and separating a relatively high boiling fraction having an increased content of straight chain hydrocarbons.
- siliceous cracking catalyst is a silica-alumina cracking catalyst.
- siliceous cracking catalyst is a silica-magnesia cracking catalyst.
- siliceous cracking catalyst is a silica-zirconia cracking catalyst.
- siliceous cracking catalyst is a silica-alumina-zirconia cracking catalyst.
- siliceous cracking catalyst is an acid activated natural clay cracking catalyst.
Description
United States Patent Sun Oil Company, Philadelphia, Pa.,- a corporation of New Jersey No Drawing. Application October 20, 1955 Serial No. 541,820
This invention relates to a process for cracking hydrocarbons. More particularly the invention relates to a process for the catalytic cracking of hydrocarbons to obtain a high yield of gasoline and only a minor quantity of coke.
Processes for cracking hydrocarbons using a variety of catalysts and reaction conditions have heretofore been described. Such processes generally seek to obtain a high yield of gasoline while producing only minor quantities of coke since, as is well known, coke formation'causes rapid catalyst deactivation. However, heretofore described processes generally operate so that when a satisfactory gasoline yield is obtained, a high yieldof coke is also obtained. This necessitates frequent catalyst'regenerati'on or replacement. v I
An object of the present .inventionis .toprovide a process for converting hydrocarbons of relatively high boiling petroleum fractions to hydrocarbons boiling in the gasoline range without concomitant production of appreciable amounts of coke. Another object is to provide a process for cracking hydrocarbons wherein long operation with a good yield of gasoline is obtained without catalyst deactivation. A further object is to provide a process for converting relatively high boiling petroleum fractions to gasoline in goodyield without substantial catalyst deactivation, wherein the higher boiling fractions have an increased content of normal paraflins which are readily converted to desirable products in subsequent operations. Other objects and their achievement in accordance with the invention will be apparent hereinafter.
It has now been found that by contacting a relatively high boiling petroleum fraction with a siliceous cracking catalyst which contains a small quantity of lithium hydroxide, as hereinafter described, the hydrocarbons of the high boiling petroleum fraction are converted in good yield to hydrocarbons boiling within the gasoline range with concomitant formation of only a relatively small quantity of coke.
In accordance with the process of the invention, a relatively high boiling petroleum fraction having a substantial content of straight chain hydrocarbons, or substantially straight chain hydrocarbons, is contacted under cracking conditions with a siliceous cracking catalyst, such as a silica-alumina cracking catalyst, which contains a small quantity of lithium hydroxide. The hydrocarbon effluent from the process is distilled to separate a gasoline fraction and at leastone fraction boiling above the gasoline range. The higher boiling fraction or fractions contain a proportion of straight chain hydrocarbons, by which term is included substantially straight chain hydrocarbons, i.e. hydrocarbons which have only a slightly branched chain, substantially greater than the proportion thereof in the initial feed stock. Such fractions are especially suitable ctor use in thermal cracking, in processes which combine dehydrogenation and cyclization to produce aromatic hydrocarbons, or in isomerization processes to produce materials which are valuable without further 2 processing or which can advantageously be recycled in the present process.
The relatively high boiling petroleum fractions Which can be used in the process of the invention are the petroleum cracking stocks boiling above the gasoline range, say above about 400 F. Such fractions normally contain straight chain p'arafiins, and the process of the inventiori is especially valuable with such fractions containing substantial quantities thereof, say from about 10-60% by volume straight chain parafiins'. The remaining hydrocarbons of the fractiongenerally consist of isoparaffins, naphthenes and aromatics, including alkyl-substituted naphthenes and aromatics. Straight run petroleum fract'ion's generally are suitable, but other fractions, such as cracked fractions including olefins, can be used if desired.
The catalyst used in the process ofthe invention is a siliceous'cracking catalyst which contains a small amount of lithium hydroxide. By siliceous cracking catalyst, and terms of similar import as used herein, is meant a synthetic or natural siliceous composition known to be efifective for the cracking of hydrocarbons. Synthetic silica-alumina cracking catalysts form the preferred catalyst o'fthe process of the invention, and the process is hereinafter largely described in terms thereof. However, other siliceous cracking catalysts give good results, such as silica-magnesia, silica-zirconia, silica-alumina-zirconia, and acid activated clays, such as acid activated montmorillonite.
The siliceous cracking catalyst used in the process of the inventionnmay be prepared by means heretofore known. For example, the silica-alumina portion of the catalytic composition can be prepared by impregnating silica with aluminum salts, by directly combining precipitated hydrated alumina andsilica, or by joint precipitation of alumina and silica from aqueous solutions of their salts. It is preferred'to prepare the cracking component before deposition" thereon of lithium hydroxide, i,e., the cracking catalyst should be dried and. calcined prior to the deposition of lithium hydroxide. The lithium hydroxide is advantageously deposited on the cracking catalyst by means of an aqueous solution. For example, an aqueous solution of lithium hydroxide containing a quantity of lithium hydroxide sufficient to impart the desired quantity thereof to the final catalyst is contacted with the silicaalumina composition. Excess solution is drained, if nesessary, and the resulting composition dried and calcined. The quantity of litlnum hydroxide must be within the range of from 0.2 to 2 milli-equivalents (meq) per gram of catalyst. If smaller amounts are used, substantial coke formation is observed, whereas if larger quantities above the stated maximum range are used, the cracking activity of the composition is decreased so that an operable yield of gasoline is not obtained.
A significant advantage of the process is the high yield of gasoline obtained compared to the yield of coke formed, i.e. the selectivity of the process for producing gasoline is excellent, whereas the selectivity for producing coke is poor. The ratio of gasoline produced to coke formed is a convenient measure of selectivity, and is determined by dividing the volume percent gasoline formed by the weight percent coke formed. In general, processes heretofore described give a gasoline to coke ratio of from about 8 to 20. In the process of the present invention a gasoline to coke ratio of at least 25, say from 25 to 37, is achieved.
In carrying out the process of the invention, cracking conditions are used. By cracking conditions is meant the conditions known to the art to be useful for the catalytic cracking of hydrocarbons. To illustrate operable conditions, temperatures of from about 750 F. to 1100 square inch gauge (p.s.i.g.), and space rates of from 0.5-5 volumes of hydrocarbons per volume of catalyst per hour (v./v./hr.), give good results. The process of the invention can be operated using fixed bed or continuous bed techniques, or fluidized operation may be used.
The following example illustrates the process of the invention:
A petroleum fraction consisting of about volume percent straight chain paraffins and about 30 volume percent naphthenes, the remainder being isoparaflins and aromatics, and which boils in the range of from about 407 F. to about 750 F., as contacted with a synthetic silica-alumina cracking catalyst containing about 0.6 meq.
of lithium hydroxide per gram of catalyst, cracking conditions of about 900 F., atmospheric pressure, and a eifluent from the catalyst contacting is distilled to obtain a yield of gasoline of about 40% by volume. The amount of coke formed is minor, being about 1.2% by weight. The gasoline to coke ratio (yield of gasoline in volume percent divided by yield of coke in weight percent) is therefore 33.3. The fraction remaining after the removal of gasoline has an increased proportion, about 35% by volume, of normal paraffins.
Repeating the process using the same silica-alumina composition without lithium hydroxide, and using substantially the same cracking conditions, a yield of about 42 percent by volume gasoline with a gasoline to coke ratio of about 12 is obtained.
The invention claimed is:
1. Process for the preparation of gasoline from a petroleum cracking stock which comprises: contacting, under cracking conditions, said relatively high boiling cracking stock with a siliceous cracking catalyst which contains from about 0.2 to 2 milli-equivalents of lithium hydroxide per gram of catalyst.
2. Process for the preparation of gasoline from a relatively high boiling petroleum cracking stock containing at least 10% by volume straight chain hydrocarbons which comprises: contacting, under cracking conditions, said relatively high boiling cracking stock with a siliceous cracking catalyst which contains from about 0.2 to 2 milli equivalents of lithium hydroxide per gram of catalyst, and separating from the hydrocarbon effluent a gasoline fraction and a higher boiling. fraction having an increased proportion of straight chain parafiins.
3. Process for the preparation of gasoline from a relatively high boiling petroleum cracking stock containing from about 10% to by volume straight chain paraffins which comprises: contacting said relatively high boiling petroleum cracking stock with a catalyst consisting essentially of a siliceous cracking catalyst which contains from about 0.2 to 2 milli-equivalents of lithium hydroxide per gram of catalyst under cracking conditions to produce gasoline and coke in a ratio of gasoline to coke of at least 25.
4. Process for the preparation of gasoline from. a relatively high boiling petroleum cracking stock containing from about 10% to 60% by volume straight chain paraffins which comprises, contacting said relatively high boiling petroleum cracking stock with a catalyst consisting essentially of a siliceous cracking catalyst which contains from about 0.2 to 2 milli-equivalents of lithium hydrox ide per gram of catalyst under cracking conditions to pro duce gasoline and coke in a ratio of gasoline to coke of at least 25, separating gasoline from the reaction product and separating a relatively high boiling fraction having an increased content of straight chain hydrocarbons.
5. Process according to claim 4 wherein said siliceous cracking catalyst is a silica-alumina cracking catalyst.
6. Process according to claim 4 wherein said siliceous cracking catalyst is a silica-magnesia cracking catalyst.
7. Process according to claim 4 wherein said siliceous cracking catalyst is a silica-zirconia cracking catalyst.
8. Process according to claim 4 wherein said siliceous cracking catalyst is a silica-alumina-zirconia cracking catalyst.
9. Process according to claim 4 wherein said siliceous cracking catalyst is an acid activated natural clay cracking catalyst.
References Cited in the file of this patent UNITED STATES PATENTS 2,474,440 Smith et a1. June 28, 1949
Claims (1)
1. PROCESS FOR THE PREPARATION OF GASOLINE FROM A PETROLEUM CRACKING STOCK WHICH COMPRISES: CONTACTING, UNDER CRACKING CONDITIONS, SAID RELATIVELY HIGH BOILING CRACKING STOCK WITH A SILICEOUS CRACKING CATALYST WHICH CONTAINS FROM ABOUT 0.2 TO 2 MILL-EQUIVALENTS OF LITHIUM HYDROXIDE PER GRAM OF CATALYST.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US541820A US2891904A (en) | 1955-10-20 | 1955-10-20 | Process of catalytic cracking with a siliceous catalyst containing lithium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US541820A US2891904A (en) | 1955-10-20 | 1955-10-20 | Process of catalytic cracking with a siliceous catalyst containing lithium hydroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2891904A true US2891904A (en) | 1959-06-23 |
Family
ID=24161207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US541820A Expired - Lifetime US2891904A (en) | 1955-10-20 | 1955-10-20 | Process of catalytic cracking with a siliceous catalyst containing lithium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2891904A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3072187A (en) * | 1960-05-12 | 1963-01-08 | Phillips Petroleum Co | Production and upgrading of hydrocarbons in situ |
| US3412039A (en) * | 1964-03-13 | 1968-11-19 | Gen Mills Inc | Clay catalyst for polymerization of unsaturated fatty acids |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474440A (en) * | 1947-03-03 | 1949-06-28 | Shell Dev | Process for the production of a lithium-aluminum compound as a base for a conversioncatalyst |
-
1955
- 1955-10-20 US US541820A patent/US2891904A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474440A (en) * | 1947-03-03 | 1949-06-28 | Shell Dev | Process for the production of a lithium-aluminum compound as a base for a conversioncatalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3072187A (en) * | 1960-05-12 | 1963-01-08 | Phillips Petroleum Co | Production and upgrading of hydrocarbons in situ |
| US3412039A (en) * | 1964-03-13 | 1968-11-19 | Gen Mills Inc | Clay catalyst for polymerization of unsaturated fatty acids |
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