US1183094A - Process for making chlorinated hydrocarbons. - Google Patents

Description

F. W. MANN & M. L. CHAPPELL. PROCESS FOR MAKING CHLORINATED HYDROCARBONS. APPLICATION FILED APR. 16. 1915 1,183,094, v Patented May16, 1916.

v 9 i3 L $1 Rp F \I N N Q 1 5 Y, 1 33 g Q N w UNITED STATES PATENT OFFICE.

rnnnnmcx WILLIA-MVMANNEAND mVIN LEE CHAPCPELL, or BERKELEY, cALI- ronNIA, AssIeNons-To STANDARD OIL COMPANY, or RICHMOND, CALIFORNIA,

A CORPORATION OF CALIFORNIA.

To all wkom z't may concern Be it known that WQVFREDERICK WILLIAM MANN and MARVIN LEE CHAPPELL, citizens of the United States, residing at Berkeley, in the county of Alameda and State of California, have invented certain new. and useful Improvements in Processes for Making Chlorinated Hydrocarbons, of which the following is a specification.

This invention relates to the production and separation of chlorinated hydrocarbons, and particularly to their production and separation from distillates of crude petroleun'i.

In carrying out the process, petroleum distillates are used which contain a high percentage of aromatic and unsaturated hydrocarbons, and which are acted upon by sulfuryl chlorid, forming the corresponding chlorin compounds, such, for example, as-

carbon oils by dissolving them in liquefied sulfur dioxid at I a sultable temperature,

' which for the best results is one below 32 degress Fahr.

From the above it will be seen that-for a brief statement of the nature of the process in its essentials, it may be said-to consist in treating the distillates from crude petroleum with sulfuryl chlorid dissolved in an excess of liquefied sulfur dioxid at a temperature below 32degrees Fahr. This process is lparticularly applicable for obtaining ch orinated hydrocarbons from California petroleum distillates or similar pertoleum distillates, which carry from 1 to 5% olefinic hydrocarbons, such as octylene, nonylene,

decyleneand the like, and from 10 to25% Y aromatic hydrocarbons such, as xylene,

I Speciflcation of Letters Patent. Application filed April 16, 1915. Serial No. 21,668.

'leu'm distillate to be treated. Petroleum disare separated rnocnss r03 MAKING c ILonINA'rEn HYDROCARCBONS.

Patented May 16, 1916.

mesitylene, cymene, pseudo-cumene and the like. The chemical composition of the petroleum distillate to be treated is determined and the necessary amount of chlorin calculated. This calculated amount of chlorin is added to the liquefied sulfur dioxid forming sulfuryl chlorid dissolved in an excess of liquid sulfur dioxid. The amount of liquId sulfur dioxid necessary also depends upon the chemical composition of the petrotillates containing a high percentage of aromatlc and olefinic hydrocarbons may require as much as two volumesof liquid sulfur dioxid and 5% by weight chlorin. For example, a petroleum distillate which contains 3% olefinic hydrocarbons and 20% aromatic hydrocarbons, requires of one pound of liquid chlorin dissolved in 21 pounds of liquid sulfur dioxid, for each gallon of distillate. We do not confine ourselves to these proportions since we could use 'of a pound of chlorin dissolved in 15 or 24 lbs. of liquid sulfur dioxid.

We are aware that the art of making chlorinated hydrocarbons by the action of sulfuryl chlorid on coal-ear distillates is well known. The novelty of our invention, however, consists in the application of sul furyl chlorid in the presence of an excess of sulfur dioxid, and applying the same to petroleum distillates containing a high percentage of olefinic and aromatic hydrocarbons, which results in the formation and separation of chlorinated hydrocarbons. By the action of the sulfur'yl chlorid we'*90 form chlorinated olefinic and aromatic hydrocarbons, such as dichlor-octane 0 11 01 dichlor nonane C H Cl dichlor decane O H Ch, chlor-xylene C H CI, chlormesitylene C H Cl, chlor-cymene O H Cl, chlor-pseudo-cumene C H CI and the like. The function of the large excess of liquid sulfur dioxid is to dissolve and separate the chlorinated hydrocarbons by the action stated' The process more particularly stated is as follows:,The oil to be treated is charged into a tank. Liquefied sulfur dioxid containing chlorin is added from the top, preferably by being sprayed. For example, onehalf to two volumes of the liquefied sulfur dioxid containing the predetermined percentage of chlorin are used for each volume or the oil tobe treated. This treating mixture is made by adding the predetermined amount of chlorill, say 1% to by weight, to the liquid sulfur dioxid, under pressure, say 0175 to 100 pounds. The suliuryl chlorid thus formed is dissolved in an excess of liquid sulfur dioxid. After introducing this heat interchanger used in the manufacture of ticularly 1 adapted.

second treating -miXture, the contents of the tank are agitated, this being best done by means of a vacuum pump, communicating with the top of the tank, the vacuum causing some of the liquefied sulfur dioxid to'vaporize, thus producing sulficient agitatiomandat the same time lowering the temperature to the desired point. The sulfur dioxid, which-is thus 'va-' porized, is condensed and recovered. the oil under treatment has had sufiicie'nt agitation and the reaction. is finished, the" vacuum pump is stopped and the chlorinated hydrocarbons dissolved in the liquefied sulfur dioxid settle to the bottom. In this way formed. The bottom layer oil is drawn off through a where it partially cools down theincoming charge of oil which at two layers are of the treated this time is being delivered to a second treat-- ing tank, a companion ofthe first tank. From the heat interchanger the bottom layer enters a still in which the remaining sulfur dioxid is distilled ofi, condensed and conducted to a storage tank for use again. The

separated chlorinated aromatic and chlorun into a st ll, in which the sulfur dioxld is distilled oil, condensed and conductedto the storage tankfor use again. In some cases, the top layer oil thus-obtained is not for-[the market, and it is necessary to treat it with a small amount or sufficiently pure sulfuric acid.

The process will be more understocd by reference to the accompanying drawing in which the. figure illustrates one form of an apparatus adapted for carrying it out.

1 and 2 are treating tanks.

3 is the oil supply pipe controlled by a valve4.- .j r

5 is a feed pump-with which the supply pipe 3 communicates,and-6is the charging pipe, which: leads'into thejitreating tank 1 by a branch 7 controlled Zia valves, leads iiltothe charging ta 9 controlled-thy. avalve 10.

11 is a storage .tank fcr the mixture bf.

' sulfuryl chlorid and liquefied sulfur dioxid.

' From this stora 4 leads a delivery pipe 12, controlled byavalve 13,said pipe ter- When ,1 and 2 issues a pipe 'pipe leading to a pipe 37 with a valve 38 leads to a still 39 the into the treating I --11 is charged 2,,hy a branch pipes 21 ,cea

minating in a branch 14 controlled by a valve 15, and entering the tank 1, its extremity being fitted with a spraying device 16. From the pipe 12, a similar branch 17' controlled by a valve 18, enters the tank 2 and is fitted with a spraying device 19.

20 is a compressor which on its suction side has a pipe 21, with a controlling valve 22. With this suction pipe a pipe 23, which, by a branch 24, having a valve 25, communicates with the top of the tank 1, and by a branch 26, having a valve 27, communicates with the top of the tank 2.

' From the pressure side of the compressor 20 leads a pipe 28, which is coiled through a condenser box 29, and then enters the storage tank 11. From the bottom of the tanks 30, from which a pipe 31, with a valve 32, leads to a heat inter changer shell 33 in which the charging pipe 6 is coiled. From thisheat interchanger shell issues a pipe 34 with a valve 35, said pump 36,. from which a in which is a. steam coil 40. From the still 39 leads a pipe 41, having a valve 42, to a second still 43,'fitted with a steam coil 44.

From the still 43 issues a valve controlled discharge pipe 45.

From the bottom leading to a pump 48 from which a pipe 49 extends to and communicates with a heatinterchanger shell50' in which the delivery p1pe 12 is coiled. From this shell 50 leads a pipe 51 having a valve 52, said pipe entering a still 53, in which is a steam coil 54. This still is connected by a pipe 55, having a valve 56, with a still 57 in which is a steam coil 58. The still 57 has a valve con trolled discharge pipe 59.

The suction ipe 21 of the compressor 20 connects with tie still 43 by a branch pipe 60 having a valve 61, and it connects with the still 57 by a branch pipe 62 having 'a valve 63.

' From the pressure pipe 28 of comki pressor 20 leads a pipe 64, which connects with the still-39 by a branch pipe 65 having a valve 66, and it connects with the still 53 by a branch pipe 67 having a. valve 68.

Thecourses of the several fluids through the apparatus are indicated by the arrows. The method carried out in this apparatus is, in detail, as tollowsz supplied through pipe 3, is, by means of the pump 5, p1pef6 and branch pipe 7, charged with liquefied sulfur dioxid containing 1% to. 5%, by weight, of chlorin.

This mixture is introduced into the tank 1 through the pipe 12, branch pipe 14 and spraying device 16. Then the compressor 20 i is started, which taking suction through 21 is connected of the tanks 1 and 2 'issues a pipe 46 having a valve 47, said pipe Petroleum distillate,

tank 1. The storage tank and 23 and branch pipe 24, reduces 1 the pressure in the tank 1,"and cauxs a porpassed through the pipe 28 coiled in the condenser 29, through which a constant flow of cold water is mamtained. In-this coil under suflicient pressure it becomes llq uefied and flows into the storage tank 11. he heat of compression is neutralized by the cold water in the condenser. When the treated oil in the tank 1 has had sufiicient agitation and has reached the desired temperature, the

compressor 20 is stop ed and the valve 25 at the branch 24 into t e tank is closed. The mixture in said tank separates into two layers. The bottom layer, consisting of chlorinated aromatic oils, and chlorinated unsaturated hydrocarbons held in solution b the liquid sulfur dioxid, is drawn 0 through the pipes 30 and 31, into. the heat exchanger shell 33, and at the same time the other treating tank-2 is charged by the pump 5 with fresh distillate for the next treatment. Thus in the charging pipe 6 and the shell 33 there is an exchange of heat be-' tween the incomin distillate and the outgoing chlorinated ydrocarbons and liquid sulfur dioxid. After this exchange of heat,

- partial vacuum produced throu the chlorinated liquid sulfur dioxid mixture is delivered. by the pi e 34.to the pump 36, by which it is fo'rced through the pipe 37 into the still 39. Inthis still, by means of the steam coil 40, the temperature is raised sufiiciently to va orize nearly all the liquid sulfur dioxid. he vaporized sulfur dioxid passes from the still 39, through the pipes 65 and 64 into the compressor pipe 28, in the condensing coil of which it is under suflicient pressure to beliquefied, and as a liquid it then runs into the storage tank 11.

In order to separate morecompletely the chlorinated bottom layer oil from the sulfur dioxid, it is drawn from the still 39, through the'pipe 41 into the still'43, which is heated bythe steam coil 44 and is ke t under a pressor suction pipe 21 and the ranch pipe 60. The top layer oil in the tank 1, is next taken off through the pipe 46, and by meansof the pump 48 is assed through the ipe 49 into the heat exc anger shell 50, in w ich i it part1 cools down the liquid sulfur dioxid s'ulfury chlorid mixture, which is, at the 1 same time, passing through the coil pipe 12 on its 'way to the second treating tank2 tobe delivered therein through the spraying device 19; From the exchanger shell 50,the topla er oil overflowsthrough the pipe 51 into the still 53, wherein, under the heat from the steam coil 54, most of the remain order to free more complete y oil from sulfur dioxid, it is drawn from thepipe 55 into the still 57,

the coming dioxid seemed-sates itsa vapor passin through'pipes 67 and 64 enter pipe 28 and is condensed in the coil of said ipe in the water box 29, and thence as a quid runs into the stem thistop layer still 53 through the which is heated by the steam coil 58 and is" kept under partial vacuum through the pipes 62 and 21. From the still 57"the oil runs to a storage tank through the pipe 59, while the contents their destination throughth pipe 49.

If necessary the oil from still 5,? is treated finally with a small amount of -sulfuric acid, washed and neutralized acording; to the well known methods. y

The separated A chlorinated hydrocarbon oils are used in the dye industry; for-fire extinguishers, and in the manufacture of various chemicals. The oil from which the chlorinated hydrocarbons have been 're-. moved, that is, the non-chlorinated saturated hydrocarbons, can be used-for lamp oils, or for otherpurposes for which they ma be adapted.

- i e claim:-

L-That step. in the process consists in treating petroleum distillates with sulfuryl "chlorid in the presence of liquefied sulfur dioxid.

2. .That step in the recess of making chlorinated hydrocarbons which consists in treating petroleum .distillates .with sulfuryl chlorid -1n thedioxid at temperatures below 32 degrees Fahr. The process of making chlorinated hydrocarbons, which consists 1n first treating petroleum ,distillate's with sulfuryl chlo ri in the presence of liquefied sulfur dioxid to chlorinate the unsaturated and aromatic hydrocarbons present. and to dissolve said chlorinated products; and then separating the-resultant liquids. a

4; They process of making chlorinated hydrocarbons, which consists in first treatin petroleum distillates withsulfuryl chlori m the presence of liquefied sulfur dioxid, at temperatures below 32 degrees Fahr., to chlorinate the unsaturated and. aromatic hydrocarbon present and to dissolve said chlorinated products; andfthen separating the resultant liquids. I

5. The process of making ri 1n thepre'sence of liquefied sulfur dioxid to chlorinate the unsaturated and aromatic hydrocarbons present and to dissolve said chlorinated products; vaporizing suflicient' of the sulfur dioxid, during'said treatment, to produce a temperature of below 32' de-- tank 11., 11170 of the still.43 pass to presence of liquid sulfur r chlorinated hydrocarbons, which consists 1n first treatin petroleumdistillates with sulfuryl chlo- I" grees Fahr. and finally separating the re-= sultant liquids.

' 6. The process of making chlorinated hydrocarbons, which consists in first treat ing petroleum distillates with sulfuryl ch10 rid in the presence of liquefied sulfur dioxid to chlorinate the unsaturated and aromatic hydrocarbons present and to dissolve said chlorinated products; vaporizing suiiicient of the sulfur dioxid, during said treatment, to produce a'temperature of below 32 degrees Fahrz; separating'the resultant liquids; and finally separating the remaining sulfur dioxid from each of said resultant liquids.

7. The process of making chlorinated hydrocarbons which consists in first sepa rately treating petroleum distillates in successive charges, with sulfuryl chlorid in the presenoe of sulfur dioxid,'at temperatures asse ses below 32'degrees Fahu, to ehloriiiaee the unsaturated and aromatic hydroearbonspresent and to dissolve said chlorinated products; then separating the resultant liquids, and, in said separation, exchanging the heat of the liquids of one charge, with the incoming. petroleum distillates, and the chlorinated sulfur dioxid treating mixture of the succeeding charge; and finally separating; the sulfur dioxid from each of said resultant liquids.

in testimony whereof we have signed our names to this specification in the presence of two subsoribi witnesses. FREDERI K WILLIAM MANN}. MARVIN LEE CHAPPELL. Witnesses:

WM; F. 300113, D, B. Rronmus.

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