US1358851A - Chlorination process - Google Patents

Description

A. E. HOULEHAN. CHLORINATION PROCESS. APPLICATION FILED SEPT. 26. 1917.

1,358,851. Patented Nov. 16, 1920 Z SHEETS-SHEET I.

INVENTOR A. E. HOULEHAN.

CHLORINATION PROCESS. APPLICATION FILED SEPT- 26, m7-

1,358,85 1 Patented Nov. 16, 1920.

2 SHEETSSHET 2- IN VEN TOR Mina-l wll L -zxm ATTORNEYS T 0 all whom it may concern UNITED STATES PATENT OFFICE.

ARTHUR EARL HOULEHAN, 0E WILMINGTON, DELAWARE, ASSIGNOR TO E. I. m; PON'I. DE NEMOURS AND COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE":

CHLORINATION PROCESS.

Specification of Letters Patent.-

Patented Nov. 16, 1920.

Application filed September 26, 1917. Serial No. 193,260.

Be it known that I, ARTHUR E. HOULE- HAN, of Wilmington, in the county of New Castle and in the State of Delaware, have invented a certain new and useful Improvement in Chlorination Processes, and. do

hereby declare that the following is a full,

clear, and exact description thereof.

My invention relates particularly to fa process for the chlorination of saturated hydrocarbons. It is applicable also to the chlorination of many other compounds, and is appl cable also to operation with the other halogens.

The object of my invention is to provide .a process by means of which halogenation, and particularly chlorination, may be brought about effectively. More particularly the object is to bring about the halogenation or chlorination without depending upon the presence of light, th-us obviating the disadvantages due to the application of light, as for example, the variability and discontinuance of available sunlight and necessity of using transparent containers. A further object is to bring about such reaction by the application of heat. A further object is to operate the invention in such a manner as to prevent loss of the materials handled, and so as to bring about complete halogenation or chlorination, or

up to the degree desired. Further objects of my invention will appear from the detailed description thereof contained here-' inafter.

While my invention is capable of being carried out in 'many difierent ways, and many different ty .es of apparatus are capable of being use to carry out my process, I have shown only onetype of apparatus in the accompanying drawings, in which Figure 1 is an elevation of an apparatus made in accordance with my invention, and

Fig. 2 is a plan view of the same. p

In the drawings, I have shown a main reservoir 1 adapted to be supplied with a quantity of naphtha through a valved fill-' ing pipe 2. Said reservoir preferably also has a level indicating pipe 3. Petroleum naphtha or the like may be pumped from the reservoir 1 by means of,e. a valved pipe 4, which preferably has a valved branch. pipe 5 leading to a pump 6 which may be made of stoneware adapted to de-, liver into the top of, for example, an absorption tower -7, which may be filled with stoneware rings 8. In the construction shown the liquid passes down over the stoneware rings 8 and meets an ascending current of chlorin, or other gaseous halogen, which may be supplied into the bottom of the tower by means of a pipe 9. The solution of the chlorin in the naphtha may be pumped from, for example, the bottom of the tower by means such as a pipe 10 leading to a pump 11, which may be also made of stoneware and which may supply the liquid by means of a pipe 12 to, e. 9., heating coil 13, preferably also of stoneware. From the heating coil 13, the liquid may be delivered to a" cooling device such as coil 14, from which it is discharged by means of a pipe 15 into thereservoir 1. A water pipe 16, shown as having branches 17 and 18,

may supply water to two containers 19 and 20 in which coils 13 and 14c may be carried; and a water outlet pipe 21 as shown having branches 22 and 23, may convey away the water from the same. A steam supply pipe 24: may lead to thecontainer 19 in order to heat the water in the same. The chlorination of the naphtha may be continued in this way by the circulation of the same from the reservoir 1 through the tower 7, until the chlorination has been completed to the desired degree. Any vapors of chlorin and naphtha which reach the top of the absorption tower 7 may be conveyed by means of a pipe 25 to the bottom of a condensing tower 26 which mav contain stoneware rings 27. Any naphtha that is condensed. and any ducted by a pipe 30 to the bottom of a scrubbing tower 31. This tower 31 may be suppliedwith a current of water, or the like,

from a reservoir 32 by meansof a pipe 33, a stoneware pump 34, and a stoneware cooling coil 35 leading to the top of the tower 31. The liquid-passing down through the tower 31 absorbs hydrochloric acid vapors from the ascending gases, and also causes some of the naphtha to be condensed by reason of the cooling effect of the liquid. Liquid from the tower 31 may be returned to the tank 32by means of, e. g., a pipe 36. In the operation of the embodiment described the solution of hydrochloric acid thus obtained is circulated in this manner through the tank 32 and the tower 31 until it reaches the proper strength, and is then withdrawn and replaced by a fresh body of water. Fresh water may be introduced by means of a valved pipe 37 leading to, e. 9., a funnel 38, which may be connected to a trapped pipe 39, which may lead to the pipe which enters the top of the tower 31 from the coil 35. Liquid may be drawn off from the system through a valved pipe 40, which also preferably connects with the pipe located at the discharge end of the coil 35. The tank 32 is furthermore preferably provided with a level indicating pipe 41, and an overflow pipe 42 which may lead to the sewer. There may be also provided a pipe 43 to vent the top of the tank 32 to the tower 31. Any naphtha which accumulates at the top of the tank 32 may be withdrawn by, e. 9., a valved pipe 44 which may lead to the pipe 5 and thence to the stoneware pump 6, so that it may be supplied to the tower 7. If desired, however, the naphtha may be withdrawn from the tank 32 by means of a branch pipe 44 which may be connected to the pipe 44, and means such as a stoneware pump 44", which preferably has an outlet pipe such as 44 provided with two branches, such as 44 and 44 which may be arranged to convey the naphtha to, e. 9., the reservoir 1, or away from the apparatus, as desired. Any vapors which reach the top of the tower 31 may be conveyed by a pipe, such as pipe 45, to the bottom of, e. 9., a chamber 46, which may have a plurality of trays 47 carrying slaked lime, so as to take up any chlor1n remaining in the as. The vapors which reach the top of the c amber 46 may be conveyed by a pipe 48 through the bottom of, e. 9., a scrubbing tower 49, which may be supphed with a downward current of, for enample, kerosene by any means such as a pipe 50 which may lead from, c. 9., a stoneware pump 51, which may be supplied with kerosene, or the like, by a pipe, such pipe 52 from a tank 53, or the like. Said tank 53 1s preferably vented to the tower 49 by a pipe 54. The kerosene, or the like, thus clrculated absorbs the last traces of naphtha, and any gases which are not thus retained may be allowed to pass out to the atmosphere by, e. 9.,- valved pipe 55..

.reservoir 1. The heat applied in the coil 13 causes the chlorin to act upon the hydrocarbon, thus producing a 'chlor-hydrocarbon. The chlorination is continued in this manner until it has reached the desired degree of completion. During the chlorination, any vapors escaping from the top of the absorption tower 7 are conveyed to the condensing tower 26 in which naphtha is condensed from the gases, as is also any chlor-hydrocarbons formed therein, so that the same may pass downwardly and back to the main naphtha reservoir 1. Any gases which are not so condensed are then conveyed to the scrubbing tower 31 where they are subjected to a current of water, so that the hydrochloric acid gas is recovered and additional naphtha vapors are condensed. The naphtha vapors which accumulate in the form of a liquid are drawn off from time to time and transferred to the absorption tower 7, and when the hydrochloric acid solution has reached the required strength, it is replaced by a fresh body of water. The gases which escape from the top of the scrubbing tower are conveyed to the chamber 46 containing slaked lime, so that the chlorin in the gases may be recovered. The gases which are not thus absorbed are finally conveyed to the scrubbing tower 49,

where the remainder of the naphtha is re-' covered by solution in the current of kerosene, or the like, which is circulated through this tower.

In this way the naphtha becomes chlorinated to the desired degree, and any gases escaping during the process are recovered so as; to avoid loss of the same. I

"While I have described my invention above in detail, I wish it to be understood,

that many changes may be made therein without departing from the spirit thereof.

F urthermore', wherever I have used the term chlorin, or referred to chlorina-' tion, I wish it to be understood that I thereby mean to include the other halogens, and halogenation in general.

I claim: p

1. The process which comprises absorbing chlorin in a hydrocarbon liquid in the absence of light, and then heating the liquid to bring about its chlorination.

2. The process which comprises absorbing ing chlorin in naphtha in the absence of light, and then heating the naphtha to bring 10 about its chlorination.

In testimony that I claim the foregoing I have hereunto'set my hand.

ARTHUR EARL 'HOULEHAN.

Witnesses:

CHAS. E. WEBB, Jr., EDWARD BERNHARDT.

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