US2758960A - Motor gasoline containing alkylate of isobutane and thermally cracked naphtha - Google Patents

Motor gasoline containing alkylate of isobutane and thermally cracked naphtha Download PDF

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US2758960A
US2758960A US366971A US36697153A US2758960A US 2758960 A US2758960 A US 2758960A US 366971 A US366971 A US 366971A US 36697153 A US36697153 A US 36697153A US 2758960 A US2758960 A US 2758960A
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Robert J Lee
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American Oil Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition

Description

J. T. KELLY ETAL 2,758,960 MOTOR GASOLINE CONTAINING ALKYLATE OF ISOBUTANE Aug. 14, 1956 AND THERMALLY CRACKED NAPHTHA Filed July 9, 1955 km @FQQQQRMXEQ N INVENTORS Joe 7. Kelly By 4 Robert J. Lee 7m 1444 E5 ATTO/PNFZ United States Patent O MOTOR GASOLINE CONTAINING ALKYLATE OF ISOBUTANE AND THERMALLY CRACKED NAPHTHA Joe T. Kelly, Galveston, and Robert J. Lee, La Marque, Tex., assignors, by mesne assignments, to The American Oil Company, a corporation of Texas Application July 9, 1953, Serial No. 366,9,71 1 Claim. (Cl. 196-150) This invention relates to the production of para-ditertiary-butylbenzene. More particularly the invention relates to the production of p-di-tert-butylbenzene by an alkylation process involving benzene, Cs olefins and isobutane. The invention also relates to an improved motor gasoline composition containing motor alkylate derived from the alkylation of C6 olefins and isobutane.

In recent years the motor car. manufacturers have striven for increased horsepower without increase in engine size. This result has. been obtained by increasing the compression ratio at which the engine operates. As a result of this increased compression ratio the octane number demand of present-day engines has increased markedly. Furthermore, these engines have introduced a relatively new problem to the motor gasoline producer. It has been noticed that these high horsepower, high compression ratio engines have a tendency to knock at high speed, i. e., under conditions where the engine is operating at substantially maximum horsepower output. Previously the point of maximum octane number demand was in low speed operation, i. e., when the motor car had just begun to move from standstill.

Low speed octane number demand of motor car engines can be very readily met by the addition of aromatic hydrocarbons such as benzene or toluene, or by the addition of alkylate. Unfortunately the effective octane number of aromatic hydrocarbons principally and of isobutane-butylene alkylate at high speed performance is markedly lower than the efiective octane number at low speed performance. An additional complication is introduced into the picture by the fact that motor gasoline not only must boil over the range of about 100 to about 400 F., but also must provide sufiicient volatility for easy starting of the engine and yet not so much volatility as to incur vapor locking and excessive vaporization losses from the gas tank. Therefore, the requirements of present day high compression motor car engines need a motor gasoline that is of relatively high efiective octane number throughout the boiling range. The octane number of gasolines is determined by three tests. Two of these tests are laboratory procedures using a standard one-cylinder engine. These tests are known as: F-l which is also known as the CPR-research method; F-2 which is also known as he CPR-motor method; the third test uses a motor car under specified operating conditions on the road; this method is known as the F-27 method. It has been found that the F-2 method octane number is indicative of the high speed performance of the fuel in a motor gasoline engine; and the F-1 method is indicative of the low speed performance. The difference between the F-1 number and the F-2 number is known as the sensitivity of the gasoline. Low sensitivities are desired.

An object of the invention is the production of p-di-tert-butylbenzene. A specific object of the inven- 2,758,960 Ce P tente Ana- 4,. 1. 56

tion is the recovery of p-di-tert-bntylbenzene from the alkylate produced in the alkylation of a cracked naphtha boiling in the C6 range with isqbutane. Another object is a m r gas n f impr d oct n m er in th higher boiling portion thereof. Still another object is a motor gasoline of improved octane number sensitivity. Other objects will become apparent in. the course of the detailed description of the invention.

It has been found tht p-di-tert butylbenzene is formed when a cracked naphtha boiling in the C6 range and isobutane are contacted under strong acid catalyzed alkyla; tion conditions. The hydrocarbons are separated from the alkylation catalyst and p-d-i-tert-butylbenzene is crystallized from the hydrocarbons; preferably the crystallization is carried out on a heart out obtained by distillation of the total hydrocarbons from the alkylation step.

An improved motor gasoline composition boiling between about and 400 F. is obtained by blending hydrocarbons boiling over the range of about 100- and 400 F. and between about 10- and. 25 volume percent, based on gasoline, of a motor alkylate which boils be tween about 185 and 410 that has been derived from the strong. acid catalyzed alkylation of butane and a k d n phtha b il ng n he Q6 a T rong d aly ed alkylat on pr c s u l e in this invention is well known to the art. The strong acids may be sulfuric acid, hydrofluoric acid, hydroflutic acid and BFs, or a RF; hydrate. The conditions necessary to obtain optimum yields of alkylate are set forth in numerous literature articles and patents. A particu-. larly good summary of strong acid catalyzed alkylation is set out in Progress and Petroleum Technology.Commercial Alkylation of Isobutane by A. V. Mrs tik et al., pp. 97-1-08 (Advances in Chemistry Series No. 5, American Chemical Society). Although certain preferred conditions are described herein, it is intended that the term alkylation conditions shall be construed broadly in light of the knowledge of the art.

The naphtha feed to the alkylation process utilized herein is a cracked naphtha boiling in the C6 range which contains appreciable amounts of benzene, i. e., between about and F.; preferably the naphtha feed comprises a mixture of C6 aliphatic hydrocarbons boiling over the entire range of about 120 to 185 P. such as is obtained by fractional distillation of a wide boiling cracked naphtha. The cracked naphtha may be ob.- tained from either a thermal cracking operation such as cracking of gas oil or reduced crude, or from a catalytic cracking operation such as Houdry fixed bed, Houdri flow and TCC moving bed, fluid catalytic cracking, etc.

Thermally cracked naphtha is the preferred feed because of the larger upgrading of the octane number.

The isoparafin used in the alkylation process is isobutane.

Surprisingly, it has been found that sulfuric acid having a strength of between about 85 and 92% produces from thermally cracked naphtha feed a motor alkylate of very low sensitivity as compared with alkylate de-. rived from the alkylation of isobutane and butylene. These particularly desirable results are obtained when operating under cold acid conditions," i. e., contactor temperatures of bet-ween about 40 and 50 F.

The improved motor gasoline composition of the invention contains between about 10 and 25 volume percent of the motor alkylate produced in the alkylation of the cracked naphtha feed and isobutane under strong acid catalyzed alkylation conditions. The motor alkylate ,"a s..... "have boils between about 185 and 410 F. Inclusion of the Cs paraflins, which are of relatively low octane nutn- 3 her, is avoided by utilizing this boiling range. The paraffins are the C6 boiling range material present in the cracked naphtha feed which do not undergo the alkylation reaction, i. e., paraifms, naphthenes and possibly some benzene.

The C7 boiling range cracked naphthas are not a suitable source of motor alkylate for improved sensitivity motor gasoline because of the relatively low efiective octane number of the product and the relatively low yields of motor alkylate obtainable; and this only at the cost of enormously higher catalyst consumption.

It has been found that the benzene present in the cracked naphtha feed is alkylated to para-di-tertiarybutylbenzene. This product is found in the alkylate residue, i. e., the hydrocarbons from the alkylation process which boil above about 410 F. The p-di-tert-butylbenzene can be recovered to an appreciable extent from the total hydrocarbons from the alkylation process. However, better yields are obtained by working with the alkylate residue and preferably with a heart out boiling about the boiling point of p-di-tert-butylbenzene. The high melting point of the p-di-tert-butylbenzene permits the material to be separated from the other hydrocarbons by crystallization at moderate temperatures. Appreciable yields of high purity material may be obtained by crystallization at temperatures of about 40 F. In general suitable operating temperatures for the crystallization procedure are between about and 40 F.

The results obtainable from the process of this invention are illustrated by the following experimental data.

The alkylation was carried out in a small continuous fiow unit having a one-gallon capacity reactor section. The particular naphtha feed and the isobutane were passed into the reactor where they were contacted with the catalyst. Intense agitation was provided in the reactor by means of an air motor driven paddle stirrer. The reactor was maintained at the desired temperature of operation by means of a refrigerant circulated in a jacket. The acid-hydrocarbon was continuously withdrawn from the reactor and passed to a settler where the hydrocarbons were separated from the spent catalyst. The product hydrocarbons were separated from the ex cess isobutane by distillation. The product hydrocarbons were then separated by distillation into a fraction boiling in about the same range as the naphtha feed, a motor alkylate fraction boiling from above the maximum boiling temperature of the naphtha feed to about 410 F., and an alkylate residue boiling above about 410 F.

Except as noted otherwise, the ratio of isobutane to olefins present in the naphtha feed was maintained at between about 79:l. When using sulfuric acid catalyst the reactor temperature was maintained between about 40 and 50 F., i. e., cold acid conditions. In all runs the ratio of sulfuric acid to hydrocarbon was about 1.3. The reaction time varied between about and minutes. Sufiicient pressure was maintained on the system to keep the feed and isobutane in the liquid state.

For purposes of comparison runs were made using BFs hydrate catalyst. This catalyst consisted of about 75 weight percent BF3 and the remainder water.

The octane numbers were obtained according to the F1 and F 2 methods. A difierential technique was used and duplicate runs were made in order to improve accuracy. Blends of motor alkylate in a typical premium gasoline base stock were made and the blending octane number of the motor alkylate was calculated from the octane number of the blend and the octane number of the base stock.

Various naphtha feeds were tried. For example, the

C5 boiling range fraction of naphtha derived from the thermal cracking of gas oil and from the fluid catalytic cracking of gas oil, also the C7 boiling range cracked naphthas of the above types. For purposes of comparison an alkylation was carried out utilizing ordinary refinery mixed butylenes as the feed. Still another experiment was made using the paraffins from a thermal Cs naphtha alkylation as the isoparafiins and butene-2 as the olefin.

In general the C6 boiling range naphthas boil between about 120 and 185 F. and the C7 boiling range naphthas boil between about 185 and 216 F. A detailed inspection of typical thermal Cs naphtha and catalytic Cs naphtha is set out below:

Thermal Catalytic Ct naptha Ca naptha 1 84. 5 94. 3 F-2 72. 9 80. 4 Chromatographic analysis:

The base stock used in these experiments was a typical premium gasoline boiling between about 100 and 400 F. This gasoline was a mixture of aromatics and catalytically cracked naphthas. The octane numbers of this base stock were F-l, 91.1 and F-2, 79.6. The sensitivity of this base stock was 11.5.

The results of these tests are presented in Runs A through I set out in Table 1. Runs A, B and C show sulfuric acid catalyzed alkylation of a thermal naphtha boiling in the Cs range. Run D shows a BFs hydrate catalyzed alkylation of this thermal Cs naphtha. Runs E and F show the results of the alkylation of a thermal naphtha boiling in the 01 range using sulfuric acid and BF3 hydrate catalyst, respectively. Run G shows the results of sulfuric acid catalyzed alkylation of catalytically cracked naphtha boiling in the C6 range.

The data show that BFs hydrate does not produce as good an octane number product as does sulfuric acid. This product is of entirely acceptable quality.

Runs E and F show that no advantage in terms of F-l octane number improvement of the motor alkylate over the naphtha feed is obtained by the use of thermal cracked naphtha boiling in the C7 range.

Run G shows that in terms of blending octane number (BON) by the F-1 method a loss of quality is obtained when catalytically cracked naphtha in the Ca boiling range is used as the feed to the alkylation process.

Runs A, B and C show a significant beneficial effect of the use of C6 range thermally cracked naphtha feed. Surprisingly these runs show that when using 86% and 91.6% sulfuric acid as the catalyst, the BON-F-1 number is as good as the same number for the 98.5 acid run and the BON-F-Z numbers are about three units higher than Run C. Thus the motor alkylate from Runs A and B have a sensitivity very markedly lower than the motor alkylate from Run C or from Run G. Thus by the use of C5 range thermally cracked naphtha feed and sulfuric acid of about 85 to 92% strength, it is possible to produce a motor alkylate of improved blending octane number in both F-l and F-2 methods and of extremely low sensitivity.

reases Table 1 Run A B C D E F G H I Naphtha feed I O6 b C; d 04 iGi/olefin 7. 3 7. 5 7.1 7. 5 8. 3 8. 6 7. 3 B 4 4. 5 H 804 conc., percent 1 86 1 91. 6 98. 5 1 91. ,6 H 98-. 5 98. 5 98. 5 Temperatme, "F 43 '45 42 77 43 81 43 46 43 Yield, v. percent on olefin:

Parafiins 77. 9 59. s 88.7 107. 5 151. 3 1 40, s Motor alk'ylate 75. 9 97. 2 100. 3 99. 8 41. 4 62. 8 110 128 161. 2 Alkylate residue 23. 2 17. 17. 3 16. 8 31. 9 28. 8 30 31- 9. 8 Octane number date:

N aphtha feed: p

F-l 84; 84. 5 84. 5 84. 5 79. 8 79. 8 94; 3 F-Z 72.9 72.9 72.9 72.9 80.4 Motor F- 77; 8 79. 9 81. 7 79; 8 70. 9 68; 4 80. 2 F-2 81. 1 82.0 83. 7 78. 5 72. 6 69. 0 81. 9 BON F-l. 87. 5 85. 5 87. 5 84. 5 81. 5 78.0 90.0 BON F-2 84.- 3 84; 3 81. 5 82. 0 79. 4 77. 0 83. 5 BONA. 3.2 1.2 6.0 2.5 2.1 1.9 6.5

1 Thermal Ce. 2 Thermal C1. x Obtained from fluid catalytic cracking of gas 011. b fParaflins from run B. Naphtha feed/butene-2. v g 4 Mixed butylene's from fluid catalytieally cracking. e BF; hydrate (75% BEE) catalyst. l Partically spent alkylation acid.

Run H shows the results of alkylatmg butene-Z and Table 3 the paraflins from Run B using 98.5% sulfuric acid catalyst. This run shows the marked increase in octane Run M N 0 numbers of the alkylate as compared with the paraflin 30 charge obtalfled from Run B. Naphtha Feed. Thermal 0.... Thermal 0.. Catalytic o6.

* Qlefins, V61, percent.... 43 41 53 Inspections are presented below on the motor alkylate and the parafiins obtained in Runs B and. G, respectively:

Run 13 Run G Motor Paraflins Motor Pai-affins alkylate alkylate 79. s 62. a s0.- 2 77. 4 82.0 69. 1 81. 9 76. 2

0. 2 Nil 1. 0 Nil Table 2 V. percent Sensi- Run motor F-l F-2 tivity alkylate None 94. 0 82. 8 11. 2 93.0 83,.- 0 10. 0 92. 7 83. 3 9. 4

Para-di-tertiary-butylbenzene was recovered from the alkylate residue in the runs presented below. The pertinent information on these runs is presented in Table 3 below:

Yield Percent on Napht a) .Parafiins 47.2. Motor A-llrylate 29 58.0. Alkylate Residue--- 10.5. p'-di-tert-butylhenze1ie Appreciable;

percent on ben- 'zene).

In the above Runs M, N and 0 an initial recovery of p-di-"tertbutylbehzene was obtained by cooling the alkylate residue to about 30 F. The crystals formed during the cooling were recovered by filtration. The crystals were washed with ethyl alcohol to remove any oil film. In Run 0 no attempt was made to recover all of the p-di-te'rt-butylbenz'cne; therefore, the yield is shown merely as appreciable. In Run M the recovery of p-di-te'r't-bntylbengene was maximized by fractionating the mother li uor from the initial crystallization in an Oldershaw column. A heart out boiling between about 438 and 475 F. (226246 C.), i. e., close boiling about the boiling point of p-di-tert-butylbenzene, was taken. This hea'rt cut was cooled to about 30 F. and the crystalline material separated by a filtration. The crystals were washed with alcohol to remove any oil film. Within the limit of experimental determination the two crystalline products were identical. The sum total yield in Run M was 170.5% based onbenzene present in the naphtha feed as compared with a theoretical yield of 244%. v

The crystalline product had a melting point of 77 C. which was essentially identical to the melting point of a sample of p-di-tert-butylbenzeneknown to be 99.9+% pure. The melting point of a mixture of the unknown crystalline material and the pure material was determined; the mixed melting point was identical with the melting point of the individual components, thereby establishing identity of the two materials. The carbon-hydrogen analysi's of the unknown material was 88.23% carbon and 11.77% hydrogen; this is in close agreement with the theoretical analysis for di=tertiary-butylbenzene. The identity of the unknown material was further established by a comparison of the infrared spectra of the unknown material and the pure material. These three techniques 7 conclusively establish the identity of the crystalline product from the cooling of the alkylate residue as essentially pure para-di-tertiary-butylbenzene.

The annexed drawing which forms a part of this specification illustrates one embodiment of a process for producing p-di-tert-butylbenzene from a cracked naphtha boiling in the C6 range. Variations of this process may be readily arrived at by those skilled in this art and it is to be understood that these modifications are considered to be within the scope of the invention.

In the drawing the feed to the process is a thermally cracked naphtha boiling between 122 and 180 F. which contains about 3% of benzene and about 50% of olefins. Feed from source 11 is passed by way of line 12 into line 13.

Isobutane from source 14 is passed into line 13 where it meets the feed. In this embodiment nine parts of isobutane are present in the reaction zone per part of olefin present in the feed.

The feed contains H28 and mercaptans. These sulfur compounds preferably are removed prior to contacting the feed with sulfuric acid. In this embodiment the contents of line 13 are introduced at a lower portion of vessel 16. Vessel 16 is a vertical cylindrical vessel adapted to provide intimate intermingling of two immiscible liquids. Aqueous caustic from source 17 is passed by way of line 18 into an upper part of vessel 16. Herein the aqueous caustic solution is a 20% solution of NaOH in water. Herein volume percent of aqueous caustic solution is used. The aqueous caustic, feed and isobutane are intermingled in vessel 16. An aqueous phase consisting of water, caustic mercaptides and sodium sulfide is withdrawn from the bottom of vessel 16 by way of line 19.

Essentially HzS-free-naphtha-isobutane is withdrawn from the upper part of vessel 16 by way of line 21 and is introduced into vessel 22. Vessel 22 is similar in construction to vessel 16. Water from source 23 is passed byway of line 24 into an upper part of vessel 22. The

water removes from the naphtha-isobutane the occluded aqueous caustic solution. Herein about volume percent of water is used. An aqueous phase is withdrawn from the bottom of vessel 22 by way of line 26.

The washed naphtha-isobutane is withdrawn from vessel 22 and is passed by way of line 28 into heat exchanger 29. In heat exchanger 29 the temperature of the naphthaisobutane is lowered to about that of the reactor, i. e., about 40 F. The cold stream is passed by way of line 31 into reactor 32.

Reactor 32 is shown schematically herein. The reactor may be any form of vessel such as is conventionally used in this art. In reactor 32 the naphtha and isobutane are contacted with sulfuric acid having a concentration of 90%. About 1.5 parts of acid are present per part of naphtha-isobutane. The emulsion of isobutane product hydrocarbons and acid is withdrawn from reactor 32 by way of line 34 and is introduced into acid separator 36.

Acid separator 36 is shown herein as an inclined cylindrical vessel. However, any conventional form of liquid- ]iquid separator may be used. The acid phase is withdrawn from separator 36 by way of line 38 and is recycled to the reactor by way of line 39. The phase may be withdrawn from the system by way of valved line 41. Fresh makeup acid from source 43 is passed by way of valved line 44 into line 39.

Although in this illustration 90% fresh sulfuric acid is used, it is to be understood that motor alkylate of satisfactory octane number quality may be obtained by using spent alkylation acid as long as the spent acid has an effective acid content of at least about 85%.

isobutane and product hydrocarbons are withdrawn from acid separator 36 by way of line 46 and are introduced into vessel 47. Vessel 47 is similar in construction to vessel 16. Aqueous caustic solution from source 48 is introduced by way of line 49 into an upper part of vessel 47. An aqueous phase is withdrawn from the bottom of vessel 47 by way of line 51. Substantially neutral isobutane and product hydrocarbons are withdrawn from vessel 47 by way of line 53 and are introduced into fractionator 54 which is provided with reboiler 56.

In fractionator 54 the unreacted isobutane is withdrawn overhead and is recycled to the reactor by way of lines 58 and 13.' The debutanized hydrocarbons are withdrawn from fractionator 54 by way of line 61 and are passed into fractionator 62 which is provided with reboiler 63.

Under the conditions of alkylation described hereinabove, apparently only the C6 olefins and benzene react. The unreacted materials from the Ca feedparaflinsare taken overhead from fractionator 62 and are passed to storage not shown by way of line 64. The hydrocarbons boiling above about 185 F. are withdrawn from the bottom of fractionator 62 by way of line 66.

The total alkylate in line 66 is introduced into fractionator 68 which is provided with internal heat exchanger 69. In fractionator 68 a motor alkylate fraction boiling between about 185 and 410 F. is taken overhead and is passed to storage by way of line 71. This motor alkylate is blended with premium quality gasoline base stock to produce a motor gasoline of improved octane sensitivity. In this instance 20 volume percent of motor alkylate is present in the motor gasoline.

Hydrocarbons boiling above about 410-alkylate res idue-are withdrawn as the bottoms fraction from fractionator 68 by way of line 73. The alkylate residue is passed into fractionator 76 which is provided with internal heater 77. In fractionator 76 a heart out of hydrocarbons boiling closely about the boiling point of p-ditert-butylbenzene is produced and is withdrawn therefrom by way of line 78. This heart out boils between about 438 and 475 F. Lower boiling hydrocarbons are taken overhead and are passed to storage not shown by way of line 81. A higher boiling fraction is produced as a bottoms product and is passed to storage not shown by way of line 82.

The heart out is introduced by way of line 78 into chiller 84. Chiller 84 is schematically represented herein and may be any conventional form of cooler which permits the formation of crystals therein. In this embodiment the temperature of the heart out is reduced to about 15 F. in chiller 84. The chilled oil-crystal mixture is introduced by way of line 86 into crystallizer 87.

Crystallizer 87 may be any form of conventional appa ratus permitting separation of crystals from a mother liquor. Herein a crystallizer is schematically illustrated which permits Withdrawal of substantially oil-free crystals. Mother liquor is withdrawn from crystallizer 87 by way of line 88. The mother liquor may be given further treatment if the absolute maximum yield of the p-di-tertbutylbenzene is desired. Product p-di-tert-butylbenzene is withdrawn from crystallizer 87 by way of line 89.

If essentially pure crystalline material is desired the product from line 39 may be given further treatment to remove occluded oil.

Thus having described the invention, what is claimed is:

A motor gasoline of improved octane in the higher boiling range which contains between about 10 and 25 volume percent of a motor alkylate boiling between about 185 and 410 F. that has been obtained by the cold acid alkylation of isobutane and a thermally cracked naphtha boiling over the range of about and F. using sulfuricacid of a strength between about 85 and 92% as the alkylation catalyst.

References Cited in the file of this patent UNITED STATES PATENTS 2,421,331 Johnson May 27, 1947 2,433,020 Becker Dec. 23, 1947 2,579,421 Egan Dec. 18, 1951 2,653,980 Condon Sept. 29, 1953 2,659,761 Frevel et al Nov. 17, 1953 2,665,316 Bennett Jan. 5, 1954

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2923751A (en) * 1956-04-30 1960-02-02 American Oil Co Production of high octane alkylate using a permeable membrane separation system
US3257312A (en) * 1962-03-27 1966-06-21 Standard Oil Co Petroleum refining process
US4048250A (en) * 1975-04-08 1977-09-13 Mobil Oil Corporation Conversion of natural gas to gasoline and LPG
US4334115A (en) * 1981-06-18 1982-06-08 Phillips Petroleum Company Process for making tert-butyltoluenes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2421331A (en) * 1944-02-29 1947-05-27 Standard Oil Co Production of alkylaromatics
US2433020A (en) * 1944-08-14 1947-12-23 Standard Oil Co Catalytic alkylation of aromatic hydrocarbons by paraffins
US2579421A (en) * 1949-04-30 1951-12-18 California Research Corp Fractional solidification process
US2653980A (en) * 1946-08-30 1953-09-29 Phillips Petroleum Co Alkylation of aromatic hydrocarbons with isoparaffins
US2659761A (en) * 1948-08-23 1953-11-17 Dow Chemical Co Fractional crystallization method
US2665316A (en) * 1950-10-21 1954-01-05 Standard Oil Dev Co Recovery of durene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2421331A (en) * 1944-02-29 1947-05-27 Standard Oil Co Production of alkylaromatics
US2433020A (en) * 1944-08-14 1947-12-23 Standard Oil Co Catalytic alkylation of aromatic hydrocarbons by paraffins
US2653980A (en) * 1946-08-30 1953-09-29 Phillips Petroleum Co Alkylation of aromatic hydrocarbons with isoparaffins
US2659761A (en) * 1948-08-23 1953-11-17 Dow Chemical Co Fractional crystallization method
US2579421A (en) * 1949-04-30 1951-12-18 California Research Corp Fractional solidification process
US2665316A (en) * 1950-10-21 1954-01-05 Standard Oil Dev Co Recovery of durene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2923751A (en) * 1956-04-30 1960-02-02 American Oil Co Production of high octane alkylate using a permeable membrane separation system
US3257312A (en) * 1962-03-27 1966-06-21 Standard Oil Co Petroleum refining process
US4048250A (en) * 1975-04-08 1977-09-13 Mobil Oil Corporation Conversion of natural gas to gasoline and LPG
US4334115A (en) * 1981-06-18 1982-06-08 Phillips Petroleum Company Process for making tert-butyltoluenes

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