US2479366A

US2479366A - Process for the alkylation of iso paraffins with olefins

Info

Publication number: US2479366A
Application number: US679277A
Authority: US
Inventors: Minor C K Jones
Original assignee: Standard Oil Development Co
Current assignee: Standard Oil Development Co
Priority date: 1943-05-15
Filing date: 1946-06-25
Publication date: 1949-08-16
Anticipated expiration: 1966-08-16

Description

Patented Ang. 16, 1949 4soelaas ma' 'ran arm -norntinn otDehwne No DNV-fihi. 0d"

nent @am ons a la htfim thoroliglbimtntbht `1 This is pertlnii lmrl'x 'am11.3:,azlxentlze agent:t fussiez deleterious sional; effect.- u'nlesz .carefully dispers'e through the material heiligz.ixzliahe-.rzll

example, in the treatment of `oils with sulfuric vent @wiwi-@rasee d treatment oir/fame Hihi: oil's wher-e, que or t'wplstases isednventional. mulch 98m@ dir luixlui,z mir-ilumum;-Y timennunl nedsrrfx'i'acid-'m'eatlng hea-Primm @imm-cum Raimi-tovert dlsq' and lthe scemi lbs. per square meh. The Stress of these 4deides greatly reduces the-eine of the globules number. It is, ot noukie'. undestodd' that amy athen-device whichA would give m1661131 intlmnte llht uittreding metnpdk-m he :namur mj mused by effecting the; mamie alpersmn or 1 uw Dime ith-th# W1 megllniwlwon wherein n unstable emulsipn is formed wltih Y man 6 www savamment This method'is nutte be with the wen-known. methods o addinir thereagentv ta 0118 331420:!! 9: ori famine. ot-thepeagent beneath'the surface-ofthe all. It

-ther-pmentummm,-y

Intl OL.

' "ixes,dmers from that obtainedL-imtkA-mnd l:tml other industries using suci1 s. A h dispersfomplrfxiA i 'lthepreparation 0f 8 separates into. the anim thus. mi: between the rble liixuids' may' be emulsioncentaAm-mere-thxr 1% et the dispersed mth/mf' twv-liquids are free from the mechnioal dispersion of the oil with the 45 emullfying agente.. 1t 18. therefore, eminently .1,1 ll l.

$425386? e I e Thung f-Qortinued Column Number 1,0011 12 1a i4l 15 1e 11 Treated with Solutizer Soin. 3 N

wml-(b) Potassium Potassium Isobutyrate, 6- N Hydroxide 6 N, 29.6 B.

Y Potassium Hydroxide Stock and Emden (ai: (o) 300M/Sq. In. (a) (a) SDUDilfSq. In. Batch YBatfrsh Homogeniza- Batch Batch Homoganza- Trent` Y Ei-est f tiofn Treat Treat tion Operaifimr` Conditions' Per cent Treat.. m 1o e r5.4 1n 12.9 :5.o

Treating Temp., 12-.-

Gasoline Inspections Doctor Test Mercaptan suiiur, mg. 1.00 Per Cent Mercaptan Reactive sulfur mg./100 m1.. Peroxide Number Recovery Loss (a) Three minutes vi orom l. in the presence of nitrogen. (b) Equivalent to so um hy oxide soiution (11.2 B.) in "GH" concentration. (c) DrNP=does not pas.

From these data it ,can be seen that in ali eases homogenization gave better merc-.antan removal than did batch agitation. When these results are plotted on a curve so as to obtain exactly equivaient percentage treats, the improvement correspends to an increased mereapten remove-.1 up to 10%.

The greatest signieance of this incrementai improved eiiicieney of eirti'aetioifiV appears in the data in columns 14, 15, 16 and I? vo1* TableI which were obtained when using a caustic solution containing e, solutizer. Fer e\10% treat batch agitabatch agitation ieaves a fractional contant of mercaptans, whiie 25% one stage homogenizetion gives a sweet product free of mercaptains. To secure a sweet product by batch agitation in further experiments required eight eountercurrent stages.

Similar results are shown on the comparison between bat-ch operation and homogeniation when extracting mereaptans from a naphtha containing e large amount of sulfur, presented in Table II, the oil and the reagent being Pumped through a homogenization valve as in the previous tion did not give a. product passing the doctor 40 experiment. 'Y

TABLE II Extraction of mercaptans from untreated high sulfur naphtha with sodium hydroxide solutions by batch agitation and by homogenizatiofn Column Number 1 2 3 4 5 6 7 8 9 Treated with Sodium Hydrox- Treated with Sodium Hydroxide, 11.2 B. ide, 30 B. Untreated Stock and Procedure High Sulfur Naphtha (u) (a) 3000 #/Sq. In. (a) (a) 3000 #/Sq. In. Batch Batch Homogeniza- Batch Batch Homogeniza- Treat Treat tion Treat Treat tion Operation Conditions Per Cent Treat Not treated- 10 20 11 23. 3 10 20 11 19 Treating Temp., F.- 75 75 75 75 75 75 75 75 Gasoline Inspections Doctor Test Mercaptan sulfur, mg. 00 m1.-. 35

Per Cent Mercaptan Reactive sulfur, mg [100 Gravity, API. Distilla ion, Naph.

I. B. P., F

Per Cent Loss...

n) Three minutes agitation in the presence of nitrogen.

b) DNP-doesnot poss.

test, while essentially similar percentage treat These data. show an improvement in mercapby homogenization did give a sweet product, tan removal by homogenization in comparison i. e., passing the doctor test. For a 20% treat 75 with batch agitation ranging up to 4.6% greater l TABLE III E'ect of time of agitation on percent mercaptan removal from .untreated high sulfur naphtha using 10% by vol. of 11.2 B. NaOH {Pei-cent merca tan removal vs. time of agltaion feed stock mg. mercaptan sulfur/100 ml.

Hoiinogen za tion Time ofAgitation (Min,) 3 5 10 20 30 00 1 Per Cent Metcaptans Removed 33 35 37 38 38.6 40 40 These data show that 60 minutes agitation gives only a 7% greater mercaptan removal than 3 minutes o1' agitation. Although the 60-minute agitation did not give results exactly equivalent :to a theoretical stage, it is evident that homogenization eiiected instantaneously the same percentage (40%) mercaptan removal as 60 minutes of batch agitation.

It is thus evident that this invention affords an economical process for the contacting of two immiscible liquids assuring greater efliciency with very short times of contact.

The nature and objects of the present invention having thus been set forth and speciiic examples of the same given, what is -claimed as new and useful and desired to be secured by Letters Patent is:

1. An improved process for the alkylation of isoparamns with olens in the presence of sulfuric acid comprising mixing the isoparafiins and olens with sulfuric acid, subjecting the mixture for exactly equivunder alkylation conditions to a mechanical shearing pressure between 2,000 and 5,000 lbs. per square inch, obtained by forcing the mixture through a. homogenizing value.

2. An improved process for the alkylation of isoparaflns with oleflns in the presence of sulfuric acid comprising mixing the isoparafilns and olens with sulfuro acid, passing the mixture under alkylation conditions through a homogenizing value whereby the mixture is subjected to a shearing pressure of 2,000 to 5,000 pounds per square inch, continuously removing the mixture from the valve, continuously recycling a portion of the mixture so removed through the valve, continuously passing the remainder of the mixture so removed to a settling vessel and immedately separating the reaction product from the a d.

l 3. An improved process for the alkylation of isoparafiins with oleiins in the presence or sulfurie acid comprising pumping said isoparamggs, oleiins. and sulfuric acid through a comm n orice at a pressure oi. 2000 to 5000 pounds per square inch. x

MINOR C. K. JONES.

REFERENCES CITED The following references are of record in the file of this patent;

UNITED Y' STATES PATENTS Number Name Date 1,621,475 Cross Mar. 15, 1927 2,016,336 Merchant Oct. 8, 1935 2,085,525 DeSimo et al. June 29, 1937 V2,238,802- Altshuler et al. Apr. 15, 1941 2,311,144 Wickham etal Feb. 16, 1943 2,322,482 Stahly et al; June 22, 1943 2,383,189 Hancock Aug. 21, 1945 2,385,123 Atkins Sept. 18, 1945 2,413,105 Hatch et al. Dec. 24, 1946