US1009428A - Apparatus for producing chlorids of carbon. - Google Patents

Description

J. MAOKAYE.

APPARATUS FOR PRODUCING OHLORIDS OF CARBON.

APPLICATION FILED MAR. 20, 1906.

1,009,428. Patented N0v.21, 1911.

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J. MAG AYR' APPARATUS FOR PRODUCING GHLORIDS OF CARBON.

APPLICATION FILED MAR. 20, 1906.

2 I Patented Nov. 21, 1911.

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J. MAOKAYE.

APPARATUS FORPRODUOING OHLORIDS OF CARBON.

APPLICATION FILED MAR.20,1906.

Patented Nov. 21, 1911.

4 SHEETSSHEET 3.

oKAYE.

APPARATUS FOR UOING UHLORIDS OF CARBON.

- APPLIG N FILED MAR. 20. 1906. 1,009,428. Patented N0v.21, 1911.

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' leading to the mixing-chambers.

UNITED STATES PATENT, OFFICE.

JAMES MAGKAYE, OF CAMBRIDGE, MASSACHUSETTS, ASSIGNOB TO STONE AND WEBSTER, OF BOSTON, MASSACHUSETTS, A FIRM.

APPARATUS FOR PRODUCING CHLORIDS OF CARBON.

Specification of Letters Patent.

Patented Nov. 21, 1911.

Application filed March 20, 1906. Serial No. 307,070.

To all whom it may concern:

Be it known that I, JAMES MAOKAYE, of Cambridge, in the county of Middlesex and State of Massachusetts, have invented certain new and useful Improvements in Apparatus for Producing Chlorids of Carbon, of which the following is a specification.

This invention relates to a new and improved apparatus for producing chlorids of carbon.

Figure 1 is a diagrammatic plan view of an apparatus constructed in accordance with my invention. Fig. 2 is a side elevation of the reaction chamber and its stacks. Fig. 3 is a top plan view of the reaction chamber and stacks shown in Fig. 2. Fig. 4 is a vertical sectional view of the reaction chamber and the connectionof the chamber with its stacks. Fig. 5 is a cross-sectional view of the reaction chamber taken. on the line 55 of Fig. 1, looking in the direction of the arrow. 1 Fig. 6 is a cross-sectional view of the inlet portion of one of the stacks taken on the line 66=of Fig.2. Fig. 7 is a cross-sectional view of one of the stacks taken on the line 7-7 of Fig. 2, showing the;

showing the arrangement of the divided.

portion of one of the stacks with its cooling chamber or water-jacket. Fig. 9 is a detail sectional view of the three-way valve for controlling the passage of the gases to pipes Fig. 10 is a detail view showing the method of connecting the chlorin inlets of the stacks.

In using my apparatus. I bring methane CH into the presence of chlorin C1 in a closed chamber filled with porous media,

preferably granulated coke that has been GIL-{ACL CCh-l- H-ICl-l-heat where 0H,:methane, or'the main ingredient of natural gas; C1,:chlo'rin, a gas;

C(ll ztetrachlorid of carbon, a gas above 76 0., solvent, non-explosive, and non-inflammable; HCl=hydrochloric acid, a gas,

soluble in water.

The methane and chlorin, if permitted to if react without control, will not produce chlorids of carbon. This uncontrolled reaction may be expressed as follows: I

out, 1 represents a gasometer for holding.

methane or natural gas, a large percentage of which. is made up of methane, as is well known. 2 represents a gasometer for holds ing chlorin, 3 represents a meter, 4; a regulator, 5 a drier, 6 a 3-way valve, 7 a pipe leading from the'gasolneter 1 tothe meter 3, 8 a

pipe leading from the meter 3 to the regulator 4, 9 a pipe leading from the regulator 4 to thedrler 5, 10 a. pipe leading from the drier 5 to the 3-way cock 6. The meter 3,

regulator 4, and drier 5 may be of any suitable preferred design or construction. The purpose of the drier and the meter are well lmown and require no description. The

purpose of the regulator is to maintain a predetermined rate of flow of the contents of the gasometer 1 through the system. 12 represents a regulator, 13 a drier, 14 a pipe leading from the chlorin gasometer 2 to the regulator 12,15 a. 'pipe leading from the regulator 12 to the drier 13'. 16 a pipe leading from the drier 13 to a 3-way cock 17. The regulator 12 is to maintin a predetermined rate of flow from the contents of the chlorin gasometer through the system. The drier 13 is like drier 5. 20 represents a suitable base or support for holding the chamber 21. 22, 23 represent stacks each connected to one side of the reaction chamber 21 the said stacks and chamber constituting, in eflect one chamber. From the the stack 23 and a pipe 31 leads to the end of the stack 22, while from the 3-way cock 17 a pipe 32 leads to theend of the stack 23 and the pipe 33 leads to the end of the and'any reaction inthe mixing zone. Each of the stacks 22, 23, connects at its lower end, as shown in the drawings, with the bottom of chamber 21. From the top of chamber 21 a pipe 50 leads and connects with a condenser 51. 52 represents a pipe connectlng the condenser 51 with the condenser 53. A pipe 54 connects condenser 53 with condenser 55, while a pipe 56 connects the condenser 55 with the pump 57, the pump acting as an exhaust to maintain the flow of gases through the system. The condensers 55 may be of any suit-able design or construction to hold and condense the products of the reaction. The reaction chamber should be maintained in any preferred way at a temperature between 250 and 600 C.

The regulators 4 and 12, as shown, are connected together by shafts 12", 4 and gears 4 12 so that the said regulators travel together in predetermined order with relation to each other. Assuming the regulators sand 12 to have the same capaclty under the same speed and pressure; as the amount of chlorin in the mixture is greater than the amount of methane, the wheel 12 is made smaller than the wheel 4", it being understood that gearing of any desired speed ratio may be employed. When using this arrangement above described, the ordinary wet gas-meter may be used for the regulators 4 and 12.

From the foregoing it will be seen that the system starts with two branches, gasometer 1 for the methane, gasometer 2 for the chlorin, the methane and chlorin branches uniting in the outer end of the stacks 22 and 23, the chlorin and methane being brought into the presenceof each other at this point. From the end of the stacks 22 or 23 the apparatus proceeds as one system up to and including the exhaust pump 57, from which the uncondensed gases may be carried to any desired point. It will be seen that the exhaust pump 57 is eflective throughout the whole system, not only up to the chamber 21 but also through the methane and chlorin branch. At the exhaust end of the system the pressure is less than at the feed end, so to speak, which difference in pressure can be varied as. desired by varying the speed or work of the exhaust 57. An inspectlon of the drawings shows that I have one control of each branch, chlorin and methane, to wit, the regulators, a control for the regulation of the heat in the reaction chamber, and a control for the rate of work, to wit, the exhaust.

My process is carried out as follows ,The gasometers 1 and 2 being supplied respectively with natural gas and chlorin, the

cocks 6 and 17 are operated to connect their respective ports with the end of the stack 22 or the end of the stack 23, the purpose being to conduct both the natural gas and the chlorin in combining proportions into the end of the same stack. .If carbon tetrachlorid is to be made, the proportion should be, roughly, four parts of chlorin to one part of methane; proper allowance being made for any impurities in the gases. If chloroform is to be made, the proportions should be, substantially, three parts of chlorin to one part of methane with a similar allowance for impurities. The dichlor methane, 011 01 or monochlor methane, CH Cl, are produced by this process, ordinarily, only as by-products when the carbon tetrachlorid or chloroform are being made. If, for any reason, it is desired to make them by this apparatus, the theoretical combining proportions should be used,-that is, two parts of chlorin to one of methane for the dichlor methane and one part of chlorin to one or more of methane for the monochlor methane. The exhaust 57 is then started. This compels the flow of the natural gas and chlorin in predetermined quantities through their respective'regulators 4: and 12, into the upper end of the stack 22 or stack 23 or both stacks, according to whether one or both are being used where the methane and chlorin enter the material with which the stacks of the chamber are filled, forming a mixture and thereafter passing as a mixture to that point in the stack or the chamber where the temperature is suflicient to permit the desired reaction to be accomplished. 'It is Within the contemplation of my invention to employ any such valve means for regulating the flow of the gases to the stacks as will enable the gases to pass into either stack exclusively, or into both simultaneously, as may be desired. In practice the temperature for the reaction is about 400 (1, but may vary from 250 to 600 C., depending upon the speed of the apparatus, the relative purity of the ingredients, etc. Any desired means may be employed to establish in the reaction chamber the desired temperature. As the mixture enters the chamber 21,

which by the means hereinafter described has been heated to the required temperature from 450 to 550 0., reaction begins and is completed, the products of reaction passing out through the pipe 50. After the reaction has started in the chamber 21, the zone of reaction works backward into the inclined parts 22 and .23 of the stacks 22, 23, and. into the lower part of the stacks 22 and 23 that are surrounded by water circulation 77, such backward travel of the zone of reaction being due to the heat given off by the reaction. While the reaction is started in the first instance in the chamber 21, yet, after the reaction has commenced, the lower parts of the stacks 22 and 23, their inclined portions 22 and 23, together with the chamber 21, constitute the reaction chamber, since,

- after the reaction is once started, the reaction zone works back-into the water-jacketed portions of. the reaction-chamber, the temperature being prevented from falling too low by the independent source of heat in the chamber 21, while the temperature is prevented from rising too high by means of the water circulation, hereinafter described.' Although, after the process is once well started, the principal reaction goes on in the water-cooled portions of the reaction chamber, it is advisable in practice to maintain a temperature in the chamber 21, suflicient to cause reaction which is between 450 and 550 (1., since this will prevent portions of the mixture which might come through the main reaction zone uncombined, from going through the apparatus in that condition; and will also permit the prompt starting of the process, if, for any reason, it should have to be temporarily discontinued. This backward movement of the zone of reaction enables me in some cases to rely upon the reaction itself for the necessary heat after the reaction is once set up. In order to prevent the zone of reaction from extending too far into the stack and encroaching upon the mixi-ng zone, I employ any preferred means for so controlling the temperature as to prevent the reaction zone from extending back into the mixing zone, which rearward action if not controlled would manifestly interfere with the mixing and the efiiciency of the apparatus and the method.

The tetrachlorid of carbon and hydrochloric acid together with the other products of reaction among which may be one or all of the following;

CHO13,GH,C1,, 011,01, 0 01,, and 0 01.

pass, as stated, through the pipe 50 into the condenser 51, where the gases are reduced to such a temperature below 76 C., that the tetrachlorid of carbon will liquefy, so that it can be drawn off from the condenser and the hydrochloric acid will be dissolved by the water in the condenser. For commercial purposes the temperature of the gases should be reduced to the vicinity of 35 C., in order to dissolve the hydrochloric acid to a sutficient state of concentration so that it can be drawn OH in commercial form.

The gases that remain uncondensed in the condenser 51 will in like manner be taken care of by condensers 53 and 55, as many condensers being used as is necessary, the residual gases, if any, other than the tetrachlorid of carbon or hydrochloric acid being taken care of by the exhaust.

Reference to Figs. 2 to 8,wwherein I have illustrated my improved form of reaction chamber 21 with its stacks 22, 23, 60 represents a pan,- or other suitable receptacle,

adapted to hold water and maintained on any suitable frame or support, not shown. 61, 62 represent two slats arranged crosswise .of the -pan 60 and having a sufiicient length to permit their ends to extend beyond the sides of the pan, as shown, in

order to rest upon and be supported by a nected at its end by bolts 64 with the underside of the slat 61 (see Figs. 3 and 4). 65 represents a complemental slat in like man ner connected to the underside of slat 62 by bolts 66. 67, 68 represent I two slats, one near each end of the pan having their ends extending beyond the edge of the pan and adapted to rest upon the support which carries the slats 61, 62, or' any other support independent of the support of the pan. 69 represents a slat connected at its ends by bolts 70, to the underside of the slat 67 (see Fig. 2). 71 represents a slat connected at its ends by bolts 72 to the underside of the slats 68. The slats 61, 62 serve to support the reaction chamber and at the same time the slats 63, 65, the latter together with the slats 69 and 71' serving to support inclined longitudinal slats 73. Three of the slats 7 3 are arranged at one end of the water jacket, three at the other, each set of three slats forming in effect a grid, one set of the slats or grid supporting the inclined part 22 of the stack-22, while the other set of slats on the right hand .end of the pan supportthe inclined part 23*. of the stack 23.

' By the described construction it will be seen that the water circulation can be maintained about the inclined parts '22, .23 of the stacks and the lower part of the reaction chamber.21 by means of a pipe 210 for introducing a supply of water to the bottom of the water jacket of the stack, and 2.

pipe 211 for removing heated water from the top of the said water .jacket of the stack. Any other preferred means for maintaining the water circulation may be employed. Gravity, or other form of power, may be relied upon for maintaining the circulation. In like manner a pipe 212 may be employed for introducing. water into the bottom of the pan 60, and a pipe 213 may be employed for withdrawing the heated water from the pan 60, the circulation being maintained either by gravity, or any other form of power desired. The lower part of the stack 23 immediately above the inclined part 23 is divided, as shown in Figs. 2, 7, and 8, for a short distance to subdivide the cross-sectional area of the stack and increase the cooling surface by means of the chamber 76. 77 represents a water-jacket of any suitable material, arranged about the subdivided part of the stack 23. This chamber has a closed bottom through which the stack passes, but may be open at the top, and water circulation may be maintained in this chamber about the two branches 120, 121, of the stack and through the chamber 76 between said branches by any desired means. The stack 22 may if desired be formed with a like subdivision provided with a like water-jacket, itbeing understood that the circulation in the water-jacket 77 is or may be lndependent of the circulation in the pan 60. While I have shown in the drawings a stack divided into two branches, such subdivisions maybe made into any desired number of branches,

the idea being to subd1v1de the stack into a sufficient number of branches to enable the cooling media to maintain the desired temperature by disslpating the heat of the reaction. The upper end of the stack 23 is closed and provided with three inlet ports 80, 81, 82, the middle port being for methane or natural gas and the ports 80, 81 for chlorin. The ports 80, 81 being connected by a T, or other connection, 400, to which the pipe 32 is connected. Two diaphragms 83, 84:, are arranged one on either side of the port 82 and extend down a substantial distance into the stack, permltting the natural gas to enter the stack, but keeping it separate from the chlorin which enters through the ports 81, 80 on either side respectively of the diaphragms 84, 83. -The stack 22 in like manner is provided with ports 86, .87, for the chlorin and the port 88 for the natural gas. The ports 86, 87 are connected by a T, or other connecs tion, like 400 (see Fig. 10) to the pipe 33.

This connection for the ports 86, 87, 15 not shown, but is like the connection shown in Fig. 10 for the ports 80, and 81. The stack 22 is further providedwith diaphragms 89 and 90, corresponding to the diaphragms 83, 84. Each of the stacks and their branches 22*, 23 are filled with comminuted material 100 of any suitable kind to permit the mixing of the chlorin and natural gas without explosion. I have found in practice comminuted coke very satisfactory for this purpose, care, however, being exercised not to have the coke comminuted so fine as to create powder to cause back pressure. The coke comminuted material 100 in each stack extends substantially up to the point indicated by line 66-, that is, above the lower ends of the diaphragms '83 to 84 and 90 to 89 so that the chlorin and natural gas are in contact with coke or other material before they come in contact with each other.

The reaction chamber 21 is composed of a piece of soapstone 91, through which is cut a rectangular hole (see Figs. 4 and 5) and is filled with powdered coke 100; While any desired material may be used for the body of the chamber, I have found soapstone very eflicient to withstand the various phenomena attendant upon the reaction that takes place, as well as the action of the mixture and the products of the reaction. The sides of the soapstone block 91 are preferably covered with lead 92, which, at the bottom is bent under the lower end of the block, as shown in Fig. then extended downward a short distance and then bent at an angle and extended to form inclined connections 22*- and 23*, with the stacks 22 and 23, respectively, thus making the chamber 21, the connections 22, 23, and the stacks 22, 23, continuous. The stacks 22, 23, and their connections 22, 23 are duplicates. Either or both stacks may be used, or thrown into or out of action.

97 (Fig. 4) represents a block of lead arranged in a pocket formed by the lead covering 92 and serves as a terminal. This block, as shown, is rectangular in shape and extends the whole length of the chamber, which at this point is of lead. 102, 103 represent a row of carbon rods, one on either side of the chamber in the soapstone. The lower ends of these rods are arranged in complemental recesses in the lead terminal 97. The upper ends of the row of rods 103 are arranged in the carbon terminal 104 at the top of the chamber, while the upper ends of the rods 102 are arranged in the carbon terminal 105. 106 represents a car? bon strip arranged between the two termi nals 105, 104, and provided with a marginal lip, as shown, engaging the tops of the termmals in order to prevent its slipping downward. 110- represents a dome formed of lead arranged 'over the carbon strip 106} as shown, and over the chamber in the soapstone. The ends of the sheet of lead forming this dome are carried down and in-.'

serted in a suitable recess in the soapstone, as shown in Fig. 4.- This construction leaves a strip, as 301, at the top end of the block 91, uncovered by the lead lining. In order to seal the chamber against a leak of gases at this point, I interpose between the lining at this point, and the block 91, a layer of material, such as 302, composed of cement, or any preferred material capable of reslsting the passage of gases, but nothaving any substantial conductivity for an electric current. In practice, one'wire 117, from the source of electrical heating, is connected to the lining 110 on one of the inclined parts, as stacks 23, the other wire 116 being connected to the portion of the lead lining forming the extension 110. By this means the current is compelled to pass through the carbon rods, it being understood that the lead lining isof sufiiciently large area to prevent any harmful action dueto the use of the lining as a part of the electric current carrying circuit. Of course, any other suitable form of connecting the wires up to the heating unit may be employed.

The upper edge of the sheet of lead 92 that covers the soapstone is not turned down, in order to prevent any contact between this and the lead forming the dome. 112, 113 represent two bars one on either side and at the lower part of the dome. These bars are adapted to be clamped together by means of bolts 115 at each end, in order to bind the parts firmly in position, the carbon strip 106 serving as ,an abutment againstwhich the terminals 104 can be pressed. 116 represents a wire running from the top of the dome 110 to any suitable source of power. 117 represents a wire running from one of the inclined members of the stacks, here shown as 23*, to the source of power, the current passmg from the source of power to the stack, thence to the lead terminal 97,

through the rods 102, 103,- to the terminals 104, 105, to the dome 110, thence back. Any

apparatus are designed and intended for I the production of all chlorids of carbon,

includin chloroform, in the same manner. Obvious y, however, the proportions of chlorin and methan'e'should, as above stated,

he changed so as to supply the gases in the proportions proper for the particular chlorid of carbon desired; but the operator must, regardless. of the product desired,

. proceed asabove described, that is, he must heat the reaction chamber until he perceives by-the product obtained, and by the working back of the heat toward the mixing zone, that the reaction has begun, and then he must be ready to reduce or shut off the interior heat, decrease his gas supply, or cause it to run through the other mixing arm of the reaction chamber, supply more or cooler water for cooling, or stop the reaction temporarily altogether, if he perceives by the presence of soot in the product, or by the progress of the heat too far backward toward the mixing zone, that the reaction is becoming too violent; and, conversely, he must be ready to change his gas supply, cut off his cold water, or increase his interior, heat, if the reaction stops or becomes inefiicient and gases begin to go through unchanged. The proper use of these'various steps will readily be understood and applied by one familiar with the art, as soon as the idea above set forth of keeping the reaction zone from working back to the mixing-zone, as above explained, is understood.

Having thus explained the nature of my invention and described a way of constructing and using the same, though without attempting to set forth all of the forms in which it may be made or all of the modes of its use, what I claim and desireto secure by Letters Patent is V D 1. An apparatus for producing chlorids of carbon, comprising a mixing-chamber, filled with a porous medium, means for supplying methane and chlorin to said chamber in predetermined proportions, a reaction chamber filled with a porous medium connected with the mixing chamber, means for heating said chamber to the temperature required to produce the desired reaction, means for cooling the chamber at a different point to prevent the reaction from working backward into the mixing chamber, and means for separating the products of the reaction.

2. An apparatus for producing chlorids of carbon, comprising a reaction chamber filled with a porous medium, a source of heat arranged in said chamber, means for supplying a mixture of methane and chlorin them to be mixed in one portion or zone thereof, a reaction portion or zone within.

the chamber, and means for bringing said mixture in the zone of reaction to the temperature required for reaction, .means for controlling the zone of reaction with relation to the zone of mixing, and means for separating the products of reaction.

4. An apparatus for producing chlorids of carbon comprising a chamber filled with a porous medium, a device within the chamber for supplying a variable amount of heat at one part of the chamber, means for supplying natural gas and chlorin to said chamber in predetermined proportions; devices for cooling the chamber between said heatable portion and the entrance point of the gases and means for collecting the products of the reaction.

5. An apparatus for producing chlorids of carbon comprising a. reaction chamber, a porous corrosion resisting filling arranged in said chamber, said chamber being formed with branches, porous filling arranged in said branches, a heating device for said chamber, cooling devices for each branch ofsaid chamber, means for supplying methane and chlorin in predetermined proportions to each said branch and cutting ofi such supply from any branch, and means for collecting and saving the products of the reaction.

6 A reaction chamber having a corrosion resisting porous filling and soapstone walls, and an outlet, and supplied with an internal heating device, sald chamber having branches with lead walls supplied with an exterior cooling device and gas inlets, and means for cutting off the supply of as from one or all of the branches, as desired.

7. An apparatus for producing chlorids of carbon comprising a mixing chamber, means for preventing reaction during the mixing of the gases, a reaction chamber connected therewith, means for subjecting the mixture in the reaction chamber to a reacting temperature, means, including a water circulation for maintaining the re-. acting material at a proper temperature for the proper reaction, and means for separating the products of reaction.

8. A reaction chamber having walls composed of non-conducting material, a sheathing connected to said walls, composed of material adapted to resist corrosive action of the contents of the chamber and maintain said chamber gas tight, said sheathing being extended beyond said walls to form a stack or inlet member, and means for subjecting said stack to water circulation.

. 9. A reaction chamber having Walls composed of non-conducting material, a sheathing arranged upon said Walls, composed of material adapted to resist corrosive action of the contents of said chamber, and maintain said chamber gas tight, said sheathing being extended beyond said walls to form a stack or inlet member, and means for cooling the walls of said stack or inlet member.

10. A reaction chamber having walls composed of non-conducting material, a sheathing arranged upon the said walls, composed of material adapted to resist corrosive action of the contents of the said chamber and maintain said chamber gas tight, said sheathing being extended beyond said walls to form a stack or inlet member, said stack between its ends being subdivided to form Y a plurality of passages, the Walls of one passage being separated from the Walls of the other to permit circulation of a cooling medium between said walls.

11. An apparatus for producing chlorids of carbon, comprising a reaction chamber with branches, the walls being of material which Will resist cold chlorin, said chamber and its branches being filled with a porous corrosion resisting material, a lining adapted to resist hot chlorin in the main body of the chamber within the walls, and heating means within said lined part of the chamber, a liquid cooling circulation about the branches of the chamber, inlets for chlorin and methane at one end of the branches of the chamber, and means for supplying the gases in the proper proportions to said branches and mixing them therein in the presence of the porous medium before they, are permitted to react, and an outlet for the products of the reaction, and means for collecting and retaining the same.

In testimony whereof I have aflixed my signature, in presence of two witnesses.

- JAMES MACKAYE.

Witnesses:

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