US2567173A - Process for production of high quality petroleum products - Google Patents

Description

Patented Sept. 11, 1951 UNITED r 2,567,175 I PROCESS FOR rnonUc'riofifdiit ififl" mi; I

QUALITY PETROLEUM PR'BDUGTS' Ewin maternaib Aefi kkailis' fi i Q N. J., assi'gii'arstb Standardgil Development Qompany, a corporation oiiljelaware T 7 Application January 12, 1949, serial Nm70;424

, 1 The invention c improved process for the mutation or high taining critical amounts of an aldehyde, pa-r= ticularly formaldehyde.

In the production pfhhighquality petroleum products as for example. in the production ,oi petroleum products boiling in the ,motor ifuel boiling range itis knownto ,usehvarious proce; dures. These procedures generaljare directed toward removing constituents from the motor fuels which cause harmful results to the engine when consumed. The procedures also are directed toward retaining? in the gasmmes thede s mmeeonstitiie'rits and also aired-ted toward securing maximum yields of the, desired prod; ucts. In the chemical treatment oipetroleu'rii fractions boiling the r'notorIuel boiling" range, the use of concentrated s'ulfuric acid is well known. This acid 'r'e'i'nov'i's sulfur compounds wen as various unsaturated di l'efi'ns and related compounds which cause deleterious results in the en ine when the' fliel is burned. Whi'lth' use of sulfuric acid pro ces a satisfactoryprodnot certain roblems eirist withrespect to use. w en a cracked sto k i treated with sub fume acid 'for the removal or mercaptans and other sulfur ,edmiaoufid's as well as olfinic con:

stituents, iicessivepoi iheri'z'ation of tom the desirable afid un ies le ii'y'drec r dn ccns'titw ents occurs, resul mg inlan incr asp? in phe 'ss of gasoline to higher boiling polymers. Further more: n a wa ver are? e i t pr -furic acid is used which is necessafy'under tier it Claims. (01.;1'9

I tain conditicnse fixd xle fti Sat the hydrocarbon ,.frac on .92 tyndesircblen qnr stituents it is necessary. tQ ubseguently ;swe eten the,=,gasoline, usually by means of the so-called doctorqtreatiw A new. ,processwhaseniiw eheened scbv igl,IQ!

the "production, oihi heq a ity. petrole m. M951:

ucts, particularlygasolinesu Inmaccordance with the, present invention ipetroleumw fractiqn parz. ticulariycracked petroleum fraction are reated. with dilute acids in, the presence of, a controlled amount of analdeh-yde as forexampleformalde;

hyde. The invention visespee a ly c nqe ened with the use o'fvvs ulfuriciacid hayingaconcentrar tion. not in,excessnofabout l9,0%pand preierably having a .concentrationinrthe range/ from, algout A particular desired wac on tra .1. v for use in, accordance with the process oj the present invention ,is a, sulfuric acid haying a on nt ations the range, .i qmi'about :67? e amount or ald h de employ dis. in tl an e ofiaboutjto 5% and is preferablyin the range from about, 11.5mm 3 0%,y The preferred aldehyde the crawlin azi eed ,,o. w ch for the pmnqse v of illustration; assumed tope a gas oil boiling in the .ran esfr'drfiap ut 400, to. 700i nfir d ceq mimic-ra kin l0- byhme neocf e ine tis m. euefiere qq t at he}??? 1 m .e Q E RE'iNSQLa ee eeedsi tu e o similar crackingied stock Ora king zone I while iiyafocazrtaii fraction motor fuel boiling range is withdrawn from zone 20 by means of line 4 and introduced into storage zone 5. Also, for the purpose of illustration it is assumed that a hydrocarbon fraction boiling in the kerosene boiling range is removed from zone 20 by means of line 6 and introduced into storage zone I. Hydrocarbon fractions boiling in the diesel fuel boiling range are removed from zone 20 by means of line 8 and introduced into storage zone 9. Higher boiling hydrocarbons are Withdrawn from zone 20 by means of line I l and further distilled or handled in any manner desired.

In accordance with conventional practice, the respective streams from zones 5, I and 9 are individuallytreatedflasfollows. Forj purpose'of i1- lustration the treatment of the hydrocarbon fraction boiling in the motor fuel boiling range is described.

The hydrocarbon fraction is withdrawn from storage zone by means of line l2 and combined with concentrated sulfuric acid having the concentration in excess of about 95 weight per cent which is introduced into the system by means of line [3. Satisfactory mixing is secured by passing the streams through orifice mixing devices. and then introducing the stream into settling zone 30. Acid sludge is withdrawn from zone 30 by means of line l5 while the treated oil is withdrawn by means of line l6. -Water is introduced into the system by means of line H and the oil and water pass through orificemixing devices 18. The mixture is introduced into zone 40 and a water layer withdrawn by means of line IS. The oil layers withdrawn by means of line 2| are combined with dilute caustic which is introduced by means of line 22. Mixing is secured by orifice mixing devices or equivalents 23. The stream is introduced into zone 50 from which a spent caustic phase is withdrawn by means of line 24. The oil phaseis withdrawn by means of line 25 and introduced into distillation zone 60. Hydrocarbon constituents, as for 'example polymerized hydrocarbons boiling above the-motor fuel boiling range, are withdrawn from zone 60 bymeansof line 26, while the hydrocarbon fractions boiling in the motor fuel boiling range are withdrawn from zone 60 by means of line 21. This stream is then passed into treating zone 10 wherein the same is treated'with a doctor solution in order to convert objectionable sulfur compounds into relatively harmless disulphides. The final product is withdrawn fromzone 10 by means of line 28.- l l I In accordance with the present invention the cracked product is treated with a dilute acid, preferably a dilute sulfuric acid containing a critical amount of an aldehyde, preferably a formaldehyde. In-accordance with a preferred adaptation of the invention, the formaldehyde is introduced into the oil stream by means of line 29 and the oil and formaldehyde mixed in orifice mixer or equivalent 80. The acid is then added as described by means of line I3. It is, however, to be understood that the formaldehyde may be added to the acid and the dilute acid containing the formaldehyde then contacted with the oil. When operating in'accordan'ce with the present invention the overhead stream removed from zone 60 by means of line 21 comprises a finished product and it is thuspossible to by-pass doctor treating zone 10. The finished product is removed from the system by means of line 3|.

The present invention may be more fully understood from the following examples illustrating various embodiments of th same.

EXAMPLE 1 A thermally cracked hydrocarbon fraction boiling in the gasoline boiling range (60 F. to about 400 F.) was treated at 70 F. with 60% sulfuric acid containing 5% by weight of formaldehyde based on gasoline fed. The volume of acid used per volume of oil was 20%. The acid layer was separated from the oil layer. The oil layer was water washed, caustic washed and then steam distilled. The results of this treatment are as follows: I I

' TAB L E fi if ASTM Diolefin 1S Peroxide Total Gum, Break- Oontent [100 down N 0 Sulfur Untreated Frac- Per cent Per cent "on 2. 95 196 185 1. 1 0. 137 Treated Fraction; l. 46 5 1, i40+ 0. 2 0. 046

1 ASTM designation D 525-46. 2 Milliequivalents of peroxide 0: per liter.

It is readily apparent that the quality of the treated cracked stock is very much improved.

EXAMPLE 2 A steam cracked hydrocarbon fraction boiling in the range from about 185-400 F. was treatedsimilarly as described-in Example 1. The results ofv these tests areas follows:

TABLE II 40 Copper ASTM D1olefin Peroxide Dish Break- Content Gum down No.

Untreated; 17. 5 2 230 o. 2 Treated 3.3 2 1,340 0.2

It is evident from Examples 1 and 2 that the treatment of the cracked distillates produced a reduction of diolefin concentration, sulfur, copper dish gum and an improvement in oxidation fins, and boiled between 150?, F; and 430 F; In

operations G to K the concentration of the 'sulfuric acid'strength was varied while in operations A to F the concentration of the acid strength was also varied in the presence of 5% formaldehyde based on theweight of the hydrocarbon fraction. In all cases 20% of the acid solution was employed based upon the volume of the oil being treated. The treated fractions were finished in a manner similar to that described in Examples 1 and 2. The results of these operations are TABLE III Refining cracked distillates with. formgjdejwdei efliect of catalyst (Hedge) [In presence of ionngl de h e1 ofitglgst ASTM D'h v 2 4 0 remxide Total Di lefin Run Strength Break- Gum er ;Br.No.

Per cent down Mg/100cc. sulfur 1, content by Wt. =1

@er, cent 13a cent 95 629 12 o.9 1 f0.217 47.5 1 2.75 s 32 1 1 0.2 a 0.078 31.2 0.57 645 1 0.3 0.135 1 41.3 0.42 595 15 1 0.1 0.153- 33.7 0.52 550 10 1 0. a 0. 180 40. o o. 50 305 101 1 0. a 0.107 41.8

1 General operating conditions utilized: 5% (EH on gasoline. 6 hours at 0 Steam distillation of tre (813113I oximately 94% formaldehyde, 5% methanol and 1% water).

I g. mercaptan sulfur/100 cc. 3 Gram equivalents active oxygen/1000 liters.

4 Centigrams oi bromine/gram. Control-water washed, neutral TABLE Refining cracked d by weight on gasoline. ated gasoline. 'In'operat 2Q vol. per cent ofecid ion ions pararormaldehyde employed ized with N 22011, and steam redistilled.

, fiieetei Ma e Ji gth.

I [In-absence of formaldehydel ofiavtglgst AsTt/i 0 D 11 J V 1S .C .2 P roxide Total Diolefin Run Stren th Break: Gum, Opper e B11. No. Per tint; 1155 11" Mama. e 5 1i"? i Per. cent Per cent G e0 275 5 0.4 0.186 41.5 1.22 H. 50 205 371 6 0L 5 0. 216 44.3 1. 70. I- 40 105 485 10 0. 4 0. 233 46.4 1. 23. I- 3 .0. 60,0 12 Q. 234 44.4 2. 1; 20 85 704 16 0.6 46.9.

Genei-al operating conditions uti1izedr20 vol. per cent of acid solution on gasoline. 6; hqursat Steam distillation of treated gasoline. i lM. g. n ercaptan sulfur/100 co. 3 Grain equivalents act've oxygen/1000 hters.

{.Centigra oi bromin [gr n From the data presented in Tables. l ll and/ IV, it is apparent that the stability as measuredby the ASTM breakdown test is improved. It is also apparent that the sulfur and gum: content.

[G eneral operati ng condi of formaldehyde. A very desirable acid concentration is about 50-60%.

EXAMPLE 4 Additional operations were conducted varying the amount of H 504 employed, the formaldehyde concentration and the time of contact employing 60% sulfuric acid concentration. The results of. these operations are presented in Tables V, VI, The treated products were finished as'desoribed in Examples 1, 2, and 3.

TABLE V Efiect of Catalyst Solution Volume s: 6Q%. E 2 SO4 catalyst. 5 Wt. per cent 01120 on gasonie. 6 hour contact at, 25 0.]

Qrtam :ASTM 011131211 105 er- Peroxide Total e H8150 43x25 Gum; V No. Sulfur BLNO' A 20. s10. 32 1;- 0.2 .078 31.8 B 10. 755. 34 1 0.2 0.112 34.1 0 5V 755 11; 0. 2 0. 101 as. 2

stem-7e TABLE Vi Eject of Formaldehyde concentration {General operating conditions: 20 vol.

pe r cent 651% H2804 catalyst. 6 hour contact I Efiect of Contact Time at 25 ci IGeneral conditions: 20 vol. per cent 607 1151153); catalyst. 2.5 wt. per cent OHaO on gaso e.

ASTM Contact On Dish Copper Peroxide Total Run Time 32% Gum No. No. sum]:

Hours A 6 580 287 1 0. 1 0. 144 36. 4 B 3 680 16 1 0. 1 0. 119 38. 0 O 1 550 4 1 0. 2 0. 122 I 35. 9

From Table V it is apparent that an increase in the volume of acid catalyst solution produces a reduction in the sulfur content with very little effect on the breakdown, the gum, the copper number and the peroxide number. A preferred treat of 60% concentrated acid (H2804) is about 10 to by volume of acid per volume of oil.

It is also apparent that an increase in the formaldehyde concentration produces an improvement in the breakdown characteristic, 2. reduction in the copper number, a reduction in the sulfur content Without appreciably efiecting the peroxide number or gumcontent.

Also when the contact time is increased, the gum and sulfur contents are increased without changing the stability, copper number or peroxide number. It is therefore apparent that short contact times are desirable.

It is to be noted that the copper dish gum values as shown in Examples 3 and 4 are relatively high due probably to the fact that the condensation products of formaldehyde with the undesirable gasoline constituents distill overhead with steam but do not evaporate in the copper dish gum determination. Superior results can be obtained particularly as regards gum content of the finished gasoline by distilling the treated product dry instead of in the presence of steam as is shown by the examples.

EXAMPLE 5 Additional operations were conducted wherein the treated cracked gasolines were removed from the acid layer, neutralized with caustic soda, water washed and rerun in the absence of steam to an end point of 400 F. The effects of varying; formaldehyde concentration, acid solution volume and temperature'were also determined. The results are listed in Tables VIII, IX, X, and in.

TABLE VIII Control runs [One hour contact time at 25 0.]

ASTM Cu Copper Peroxide Total Per Cent Run Treat 3 83 No. No. Sulfur Polymer! A 10 vol. per cent water"-.. I25 535 17 0. 4 0. 206 46.3 as B 0.8 vol. per cent 96.6% 85 46 2 0. 1 0. 097 36. 3 8.0 H2804.

TABLE IX Effect of formaldehyde concentration:

, 1 t v [General conditions: 10 vol. per cent 60% H2804 catalyst solution. 1 hour contact at 25 0.]

l ASTM Cu Per Cent CHzO on 00 per Peroxide Total Per Cent Gasoline 32 bFo. N o Sulfur Polymer 2,507,173 I 9 y y 1o.

nae-x I Eflect of acid solution volume [One hour contact at 25 0.]

ASTM Cu Copper Peroxlde Total Per Cent Run Treat #323 No. N o. Sulfur N Polymer l L v l. per cent 60% nisol 210 22 1 0 0. 5 0.187 39. 4 5. 7

a One. M 10 V10]. per cent 60% H2504 V 215 16 10 0. 3 0- 171 41. 1 5. 7

a one. N- 5 V01. per cent 60% H2804 375 62 1 0. 2 0. 140 38. 5 5. 1 +2% H2 0 locxglb 60% 1a,s0i2+2'7;, 345 s 2 0.1 0.125 40. s r 0 4.4 7

i i j.

1 Material boiling above 400 F. exgressed as per cent of volume of original feed. 3 Molar equivalent to 2% formalde yde.

TABLE XI Effect of temperature .-[-Genera1 conditions: 5 vol. per cent 60% HiSO cattsol. 1a wt. per cent 01120 (on gasoline). 1 hour contact an atc tint: Stir. rate 375 62 1 0.2 0.140 38.5 5.1 53 39c 34 2 0.1 0.126 37.0 as

1 Material boiling above 400 F. expressed as per cent of volume of original feed.

From Table VIII it is apparent that strong conproducts may be somewhat greater. Formalin centrated sulfuric acid per seis not particularly (37% formaldehyde solution in water) can be desirable in that the. extent of polymer formation used in place of paraformaldehyde by adding conis relatively high. Table IX indicates that a p centrated sulfuric acid thereto and adjusting the fcrred concentration o formaldehyde s in the acid solution concentration to the desired level range from about 1% to 3%. with water,

The data also show in Table X that by increas- 5 ing the acid solution volume a reduction in gum 40 EXAMPLE 6 content, a reduction in peroxide number and a V reduction insulfur with no appreciable effect on Additional p a s we e conducted wherein breakdown or copper number is secured. In a the time of contacting was Varied and the product continuous process the-use of 5 volume by acid redistilled. The resultsofthese operations are is adequate. It is apparent (Table XI) that by 4 given in Table XII.

TABLE XII Refining cracked distillates with formaldehyde Efiect of contact time and rerunning [General conditions: 10 vol. per cent H2804 catalyst. 2 wt. per cent 01120 (on gasoline) ASTM CuDish 00 per Peroxide Total Per cent Gum N o. No. 7

Run Contact Time at 25 0. Break- I awn1 Sulfur Polymer 160 987 0ily 1 0 5 O. 179 37. 9

Control 25 535 oily-- 17 0 4 0. 6 46. 3 3. 8

1 Material boiling above 400 Rexpressed as per cent of volume of original feed.

increasing the treating temperature, the sulfur, Although rerunning is necessary to reduce the content is slightly reduced as well as the gum sulfur, the gum and the peroxide contents and to content. However, the stability, the copper numimprove the Stability, the mercap n content can bar and the peroxide number are not substanbe greatly reduce even Withoutrerunnin F rtially changed. It is also apparent that as the .thermore, the acid lay an be r y 1 d ut t contact time is reduced, the sulfur and peroxide: 7o acid concentration should be held constant in contents increase. r order to secure uniform removal of the sulfur.

Gasolines treated with acetaldehyde (in molar equivalent quantities) possess properties substanv tially equal to those treated with formaldehyde The value of. aformaldehyde dilute acid treat although theloss of gasoline to higher boiling 7 overv a conventional concentrated acid treat :is

ii further-illustrated by the following operational data: (Table XIII).

12 At, the end of 40 hours operation, the engine was dismantled and inspected. The deposits on TABLE XIII Comparison of formaldehyde and acid treating Motor 0. N. A ASTM T Run Treat Egreak- 333 83 55; 5323 Br. N 0. cc

Clear Pb o. N.

Per cent Per cent A- 18. 0 1. 55 0. 127 40 0. 4 69. 6 77. 7. 9

o--- {contr61'--.. 125 303 2.25 0. 230 51.1 2.2 70.3 16.3 5.5

lhourat 25 C----.;;--.;

From the above it is apparent that although the diene content is somewhat higher, the formaldehydetreated distillate possesses somewhat better stability (as measured by ASTM breakdown test) than the concentrated acid treat. Thiswould indicate that the formaldehyde-dilute acid process is more selective. In addition, the same gasoline lead susceptibility is obtained as can be obtained with the strong sulfuric acid process, but the sulfur content of the formaldehyde treated distillate is not as low as that of the acid treated distillate. EXAMPLE 8 Engine test data have indicated that the thermal and catalytic naphtha fractions of the finished gasoline apparently contain the major valves, pistons, rings and combustion chamber were noted and the sludge in the lubricating oil measured. Allthese factors were taken into sults secured when running a high quality and satisfactory gasoline considered as a reference fuel and rated as 100%. From the data it is evident that the use of formaldehyde markedly improves the engine cleanliness characteristics of the motor fuel. It is also evident that the dilute acid treat plus formaldehyde is superior to the concentrated acid treat, as a means of improving the engine cleanliness characteristics of thermally and catalytically cracked fuels.

Crankcase Vent, C. F. H

varnish and sludge forming and stability reduce P se t invention is conc rned w th he ing constituents. In order to demonstrate the production of high quality petroleum oil prodsuperiority of the formaldehyde dilute acid treatucts. The invention is particularly directed to ment over the concentrated sulfuric acid treatan improved processfor improving the engine ment as a means of improving the engine cleanlicleanliness characteristics and oxidation stability ness characteristics of gasolines, further operaof motor fuels especially thermally and catalytitions were conducted on a blend containing 90% cally cracked gasolines. The invention is also untreated thermal naphtha and 10% heavy catadirectedtoward the production of gasolines havlytic naphtha. The treating results obtained on ing lower sulfur, gum, diene, and peroxide conthis blend are listed in Table XIV. I tents thereof. The process employed broadly TABLE XIV Treating Losses 1 Engine Motor Test, Run Treat Total Octane per cent Sludge Polymer N0 rang/nee 1-.-. Blend rerun to 400 F. vapor tempnm'fnm 71.3 144 2..-. Blend treated with 66 30. E2804 (5 lbs.lbbl.),

water washed, neutralized and rerun to 400 F 2. 2 3. 2 5. 4 70.0 118 3.-.- Blend treated with 1.5 Wt. per cent formaldehyde in the presence of 10 Vol. per cent, H1504,

k2 hr. contact time finished as in run 2 3. 0 0. 4 3. 4 71. 3 113 4.-.- Sameasrun3butemploying3wt.percentformaldehyde 2. e 2. 2 4. s 70. a 100 '1 As per cent by volume based on feed.

It will be noted that the loss of gasoline .to utilized a dilute treating acid, preferably a sulhigher boiling polymer is lower on formaldehyde furic acid having a concentration not in excess dilute acid treating than on concentrated sulof about 80% and preferably having a concentrafuric acid treating in the absence of formaldeti in the ran e from ab ut 55% t i cony mples of the treated gasolines were then junction with an aldehyde, preferably formalderun in a single cylinder Lauson engine operated hyde. und r th f l w n nditi s: I The stock treated may have a boiling ran e Engine Speed, M 1800 from about 50 F. to 700 F. although it is pre- Cmnkcase Temp" 145 ferred that the final boiling point he not inex- Jacket Temp 95 7o cess of 450 F. It is also preferred that the I t k i T 1 0 bromine number of the feed be at least 15 C. g. 011 Charge, Quarts. 0 5 Br./gm. The process can also be applied to the Test Duration, Hours 40 treatment of other hydrocarbon distillates such Power Output, H. P 2.2 as heavy naphthas, kerosenes, heating oils, diesel .0- fuels and the like. It is to be understood that 13 the entire fraction may be treated or that specific boiling range fractions may be segregated and separately treated. Various cycle stocks secured from refining operations can likewise be treated in the manner described.

With respect to the method of treatment, it is preferred that the formaldehyde be added to the oil and mixed therewith followed by the addition of acid. It is, however, to be understood that the formaldehyde can be added to the acid and this mixture used to contact the oil. The acid layer segregated from the oil containing the formaldehyde may be recycled in order to contact fresh untreated oil. If sulfuric acid be used, it is preferred that the concentration be in the range from about 30% to 80%, preferably in the range from 55% to 65%. The amount of acid solution used is preferably from about 0.5 to volume per cent based upon the gasoline. The aldehyde concentration used is in the range from 0.5 to 5% preferably from 1 to 3% by weight based upon the gasoline. The concentration of the aldehyde employed will to some extent depend upon the unsaturation of the stock being treated. The time of contact may be as high as 60 minutes, although it is preferred that it not exceed to 30 minutes. The temperature of contacting also is preferably in the range from about to 60 C. Other acids of sulfur and phosphorus may be used, as for example H2804, H3PO4 and the various sulfonic acids.

In the present invention any suitable aldehyde may be employed as for example, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde and acrolein. The preferred treating agent comprises formaldehyde which may be used as such, but is preferably utilized in a commercial operation as an aqueous solution. A particularly de sirable aqueous solution comprises formalin (37 formaldehyde in water). However, it is to be understood that with respect to the present invention, if an aqueous carrier be employed the concentration of the added acid must be adjusted accordingly, since the acid concentrations specified are defined with respect to the total water present in the treating zone irrespective as to whether the water is introduced with the acid, or aldehyde or from other sources.

Other substances such as paraformaldehyde, trioxane, hexamethylene tetramine, methylal or equivalent substances which yield formaldehyde may be utilized.

Having described the invention it is claimed:

1. Improved process for removing constituents from hydrocarbons boiling in the motor fuel boiling range which tend to cause engine uncleanliness when burned in internal combustion engines which comprises contacting a liquid petroleum hydrocarbon boiling in the motor fuel boiling range with a dilute aqueous mineral acid of about -80% concentration and containing from about .5 to 5% of an aldehyde by weight based upon the hydrocarbon feed.

2. Process as defined by claim 1 wherein said petroleum hydrocarbon comprises a cracked petroleum hydrocarbon.

3. Process as defined by claim 1 wherein said dilute acid comprises sulfuric acid and said aldehyde comprises formaldehyde.

4. Process as defined by claim 1 wherein said acid comprises sulfuric acid having a concentration in the range from about to 5. Process as defined by claim 1 wherein said petroleum hydrocarbon boils in the range from about F. to 400 F.

6. Improved process for the production of a high quality gasoline, which comprises contacting a liquid cracked petroleum fraction boiling in the motor fuel boiling range with a dilute mineral acid of about 30-80% concentration and containing from about .5 to 5.0% of formaldehyde by weight based upon the hydrocarbon feed, separating the acid layer, contacting the treated hydrocarbon fraction with a caustic solution and then redistilling the same.

7. Improved process for the production of high quality motor fuels from cracked distillates which comprises adding to said cracked distillates from about .5 to 5.0% of formaldehyde, mixing the formaldehyde and the distillate, thereafter adding to the distillate and the aldehyde a relatively dilute sulfuric acid of about 30-80% concentration, separating the acid sludge therefrom, treating the distillate with water and thenwith a dilute caustic, separating the treated distillate and rerunning the same to segregate a hydrocarbon fraction boiling in the motor fuel boiling range.

8. Process as defined by claim '7 wherein the acid separated from the distillate is recycled.

9. Process for removing constituents from hy- ERVING ARUNDALE. LOUIS A. MIKESKA.

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

UNITED STATES PATENTS Number Name Date 1,964,953 Lazar July 3, 1934 1,998,292 Smith Apr. 16, 1935 2,011,199 Pele Aug. 13, 1935 2,080,732 Morrell May 18, 1937 2,216,027 Smtih Sept. 24, 1940 OTHER REFERENCES J. I. P. T., 10, 99-100 (1924).

Claims (1)

1. IMPROVED PROCESS FOR REMOVING CONSTITUENTS FROM HYDROCARBONS BOILING IN THE MOTOR FUEL BOILING RANGE WHICH TEND TO CAUSE ENGINE UNCLEANLINESS WHEN BURNED IN INTERNAL COMBUSTION ENGINES WHICH COMPRISES CONTACTING A LIQUID PETROLEUM HYDROCARBON BOILING IN THE MOTOR FUEL BOILING RANGE WITH A DILUTE AQUEOUS MINERAL ACID OF ABOUT 30-80% CONCENTRATION AND CONTAINING FROM ABOUT .5 TO 5% OF AN ALDEHYDE BY WEIGHT BASED UPON THE HYDROCARBON FEED.

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