US2022619A

US2022619A - Method of chlorination

Info

Publication number: US2022619A
Application number: US652491A
Authority: US
Inventors: Galisworthy Benjamin
Original assignee: Texaco Inc
Current assignee: Texaco Inc
Priority date: 1933-01-19
Filing date: 1933-01-19
Publication date: 1935-11-26
Anticipated expiration: 1952-11-26

Description

Nov. 26, 1935;

B. GALLSWORTHY 2,022,619 METHOD OF GHLORINATION Filed Jan. 19, 1955 BE/lUflM/V GWALSWOPTHY? 11v VENTOR 5 A TTOR/VEY catalysts and promoters.

Patented Nov. 26, 1935 METHOD OF CHLORINATIQN Gallsworthm'Glenham, N. Y., casino: to The-Texas Company, New York, N. Y a. corporation of Delaware Application January 19,1933, Serial No. 652,491

Claims. (cl. 260-102) This invention relates to the chlorination of petroleum hydrocarbons and more particularly to the chlorination of petroleum hydrocarbon oils.

More specifically, my invention relates to the chlorination of petroleum hydrocarbon oils by contacting them with an aqueous solution of hypochlorous and hydrochloric acids whereby the petroleum hydrocarbon oils are chlorinated to the desired chlorine content.

A large number of chlorination methods have been proposed in the past. Some of these have featured the chlorination of petroleum hydrocarbons by reacting them with gaseous chlorine in the presence of ultra-violet light or chemical Other methods have disclosed the interaction of hydrocarbon oils and chlorine in the presence of contact catalysts and under varying conditions of temperature and pressure. These methods, when applied to the chlorination of petroleum hydrocarbon oils, have.

been found to result in the discoloration of the oils, the formation of sludges, as well as in the production of large quantities of undesirable chlorinated lay-products. The reactions are either extremely slow or else when accelerated by increasing the temperatures, pressures or chlorine concentration tend to proceed violently and may, in many cases, result in the utter decomposition of the petroleum hydrocarbon oil.

In accordance with my process, petroleum hy-v and then agitating a petroleum hydrocarbon with this chlorine water whereby a smooth and complete chlorination of the petroleum hydrocarbon is effected. i

The use of ultra-violet light, reaction catalysts, contact agents or reaction promotors is unnecessary. The reaction proceeds quite rapidly and there is no apparent production of exothermic energy. Petroleum hydrocarbon oils chlorinated in accordance with my invention are not discolored and do not contain any sludge, nor does the chlorinated oil suffer from the formation of undesirable, unsaturated hydrocarbons due to the cracking of the unstable petroleum hydrocarbons. My invention is readily applicable to all types of PATENT OFFICE petroleum hydrocarbons and elaborate apparatus is unnecessary for carrying out the process.

The herein disclosed invention may be applied in a variety of ways. For example, a petroleum hydrocarbon oil may simply be agitated with 5 chlorine water for a sumcient period of time to permit the reaction to take place, or else the, oil may be mixed with chlorine water in a tower filled with contact materials such as Raschig rings, coke or refractory materials. The process also lends itself quite successfully to application in a countercurrent process wherein the petroleum hydrocarbon oil is flowed countercurrently to a stream of chlorine water. Here the oil and chlorine water are successively agitated together and separated, the 'unchlorinated hydrocarbon oil being contacted with chlorine water containing the lowest percentage of hypochlorous acid and the most highly chlorinated hydrocarbon oil coming into contact with the highest concentration of hypochlorous acid.

The accompanying drawing discloses an apparatus suitable for carrying out my invention and the following description taken in connection therewith will serve for a better understanding of 'my invention.

The numeral II indicates a tank for untreated oil. This tank is provided with a drawoff line H fitted with a valve I! which connects the tank with the intake side of the pump l3. This pump discharges through the line H controlled by the valve I5 into the mixing chamber l6. This mixing device may be of any suitable construction. It is fitted around its circumference with heating coils through which a suitable heating medium may be circulated. These coils are indicated by the numeral 11. It is also equipped with a mechanical agitating device 88 which is used for bringing the untreated oil into intimate contact with chlorine water. The bottom of the mixing 4 chamber I6 is provided with a draw-off line it controlled by the valve 26 which line discharges into the settling chamber 2! wherein the partly chlorinated oil separates from the spent chlorine water. The latter is drawn off from the bottom of the settling chamber through the drawofi line 22 controlled by the valve 23.

The top of the settling chamber 2! is equipped with a drawoif line 24 controlled by the valve 25 through which the partly chlorinated oil drawn 59 off from the top of the settling chamber is delivered into the mixing chamber 26. The mixing chamber 26 may advantageously be of the same construction as the previously described; mixing chamber it.

Q mixing chamber 26 is connected by means of the line 21 controlled by the valve 28 with a source 29 of chlorine water. This source consists of a chamber wherein water and chlorine gas are reacted to form an aqueous solution of hydro-- chloric and hypochlorous acids which is spoken of herein as chlorine 'water. The chamber is preferably fitted-with a filling 30- of refractory material which assists in the proper interaction of the water and gaseous chlorine. This material is preferably supported on the perforated tray 31 at a small distance above the bottom of the chamber. Gaseous chlorine is delivered into the bottom of the tower throughthe line-32 controlled by the valve 33 while water is injected through the line 34 controlled by the valve 35 at a point above the tray' 3l.

The mixing chamber 26 is fitted at its bottom with a drawofi line 3'! controlled by the valve 38 which connects it with the settling chamber 39 wherein the chlorinated oil-is separated from the partly spent chlorine water. The chlorinated oil is drawn off ,from-the top of the settling chamber through the'llne 40 controlled by the valve 4| and delivered to the storage tank 42. The bottom of the settling chamber 39 is fitted with a drawoff line 44 controlled by the valve 45 which leads to the mixing chamber l8.

In a typical operation of my invention in connection with the apparatus shown in Figure 1, a petroleum hydrocarbon oil which is to be chlorinated, is drawn from the storage tank It) and passed to the charge pump l3 by which it is delivered under suitable pressure through the line H into the mixing chamber l8. Herein the untreated oil is thoroughly agitated at an elevated temperature with partly spent chlorine water from a succeeding step in the process. The hypochlorous acid readily reacts with the hydrocarbon oil to form substituted chlor compounds. The mixture of partly chlorinated oil and spent chlorine water is drawn off from the bottom or the mixer l6 and delivered into the settling chamber 2| wherein a substantial separation of the oil and water is brought about. The spent chlorine water is drawn oil through the bottom drawofl. line 22 controlled by the valve 23 and delivered to a suitable storage tank or, ii desirable, to a hydrochloric acid concentration system.'- The partly chlorinated 011 which forms the supernatant layer in the settling chamber 2| is drawn vofl! through the line 24 and delivered into the mixing chamber 26 wherein it is agitated with a proportioned amount of fresh chlorine water.

The chlorine water used-in the operation of this process is prepared in the chamber. 29. Herein correctly proportioned quantities of waterand gaseous chlorine are intermixed and interacted to form an aqueous solution of hydrochloric and hypochlorous acids. This solution is delivered into the mixing chamber 28 through the line 21.

The partly chlorinated oil and fresh chlorine water react quite readily and the mixture'which is drawn or! from the mixing chamber 28 through the drawoif line 21 consists essentially of chlorinated oil and partly spent chlorine water. These two materials are substantially separated in the settling chamber 2!, the partly spent chlorine water being delivered to the mixing chamber l8 through the line 44 while the chlorinated oil is drawn off from the top of the chamberthrough the line and deliveredlto-the storage tank 42. i l

The chlorination process be applied any petroleum hydrocarbon oil irre p tive of its viscosity, the only requirement being that it be fluid enough at elevated temperatures to permit of its being readily reacted with the chlorine water. As an example of how the process may be applied to various petroleum hydrocarbons. I an .oil having the following tests may be submitted to treatment:

Gravity, A. P. I l;;r; r. Visc. Univ. at 100 F 183 Pour, "F 25- X By interacting this oil with a chlorine water at a' temperature T01 approximately 150 F. and under-a; pressure of 25 lbs. per sq. in., a chlorinated oil having the following tests may be produced: ll 1 Gravity, A. P. I 20.2 Visc. Univ. at 100 F 305 Visc. Univ. at 210 F 52 Pour, r 15 m Chlorine, per cent... 5.81

.Speciiic'gravity'at 60 1'' 1.014 Flash -i 535 Fire- 5'10 Visc. Univ. at 100 F 828 Solid point F Chlorine content per cent; 23.20

The temperatures used in the operation of process lie preferably in the range of from to 200 F. although higher or lower temperatures may be found especially applicable in chlorinat- 0 ing certain hydrocarbons. Similarly. the pressures used while interacting petroleum hydrocarbon oils and chlorine water are preferably below 500 lbs. per sq. in.

In actual practice it is found that certain hydrocarbons are less reactive than others and that their hydrogen atoms are .not as readily replaced by chlorine. Such oils require longer time of contact with the chlorine water as well as'hisher temperatures and pressures. The longer time o! contact in an apparatus such as that shown in Figure 1 is readily obtainable by reducing the rate of flow of the oil while substantially increasing the quantity of chlorine water used. '.In this 1 manner smaller volumes of petroleum h'ydroc'arbon oil are contacted with proportionately larger quantities of chlorine water andthe flow "rites being low, these two materials will be contacted for proportionately longer periods of time.

Obviously many modifications and variations of n the invention, as hereinbeiore set forth. may be 1 made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the sppendedclaims.' u

I claim: 1. The method of chlorinating hydrocarbons which comprises agitating petroleum hydrocorbons selected from the group consisting of lubricating oils and paraihn war with an'aqueous so- 7 lution of hydrochloric and hypochlorous with at a temperature in therange of to 200' l". and under a pressure of between 20 and 500 pounds .per square inch.

2. The method oilchlorinatinl II r which comprises agitating petroleum hydrocarbons selected from the group consisting of lubricating oils and paratlln was with chlorine water at a temperature of about 150 1''. and under a pressure of about .25 pounds per square inch.

3. The method of chlorinating hydrocarbons which comprises agitating petroleum hydrocarbons selected from the group consisting oi lubricating oils and paraflln wax with chlorine water at a temperature of between 150 and 200' I. and under a pressure oi between 25 and 500 pounds per square inch to form a mixture, and then subjecting the mixture to settling to eilect the separation of the chlorinated hydrocarbons from the spent chlorine water.

4. The method of chlorinating hydrocarbons which comprises alternately mixing petroleum hydrocarbons selected from the group consisting of lubricating oils and paraflln wax and separating them from a countercurrently flowing stream of chlorine water while maintained at a temperature in the range oi'150' to 200' it. and under superatmospheric pressure, the unchlorinated by;

drocarbons coming into contact with partly spent chlorine water and the partly chlorinated hydrocarbons coming in contact with iresh chlorine g 5. The method oi chlorinating hydrocarbons which comprises flowing petroleum hydrocarbons selected from the group consisting of lubricating oils and paraflln wax while maintained at a temperature in the range of 150 to 200 1. and under i apressure of between 25 and 500 pounds per square inch countercurrently to a stream 0! chlorine water, the relatively unreacted hydrocarbons coming into contact with partly spent chlol5