US2225634A - Regulation of temperature of chemical reactions - Google Patents

Description

Dec. 24, 1940. E HQUDRY 2,225,634

REGULATION OF TEMPERATURE OFCHEMICAL REACTIONS Filed March 4, 1938 3 Sheets-Sheet l INVENTOR EUGENE LLHUUDRY ATTORNEY Dec, 24,1940. E. J. HOUD'RY 2,225,634

REGULATION 0E TEMPERATURE 0F lCHEMICAL REACTIONS Filed March 4, 1938 3 Sheets-Sheet 2 :Ill/xm?,

/ INVENTOR gYu GENE JH n UDRY ATTORNEY Dec. 24, 1940. E. J. HOUDRY 2,225,634

REICJUIHTIOI OF TEMPERATURE OF CHEMICAL REACTIONS Filed-March 4, 1958 3 Sheets-Sheet 3 HEAT l-MHANGL NIH "Wim E 0 Q E fri 9.5. 732 '/22 INVENTOR uENEtll-IDUDRY Patented Dec.l 24. i940 l l I JUNITED STATES PATENT .OFFICE REGULATION oF TEMPERATURE oF CHEM- A ICAI. REACTIONS Eugene, J. .Houdrm Haverford', Pa.. assigner to Houdry Process Corporation. Wilmington, Del., a corporation of Delaware Application March 4, 1938, Serial No. 19 3,8l3

' 4 Claims. (Chas-28s) This invention relates to chemical reactions the line 2-2 of Fig. 3, but'on a broken line, soI -and their control. More particularly, it relates far as-its base is concerned, in =order -to show to the regulation of temperature of such reactions -both theinlet and outlet mains in elevation; `especially wheneiected in the presence oi or by Fig.- 3 is a transversev sectlonal`view on the line the aid of solideontact materials. Y l-l of Fig. 2. showing the base of the heat ex- One object'of the -invention is to improve the change member in elevation; temperature regulation of chemical converters. Fig. i is a vertical, sectional view similar to Another object is to restrict heat exchange to the Fig l, but showing a diierent type of converter reaction chamber or to a deilnite portion thereof. and the heat exchange unit mounted in a dliier-` lo' Another object is to avoid heat exchange with reent position from Fig. 1, the section being taken -1`o actants entering a converterand/or with reaction substantially on the line 4-4 of Fig. 5; and products about to leave a converter. Another ob- Fig. 5 is a right end elevational view of the con- -ject is to devise improved forms oi converters and verter shownin Fig. 4, with the heat exchange of heat exchange apparatus therefor. Still other unit removed. and thecovering of heat insulating 15 objects will be apparent from the detailed dematerial stripped away from the converter. l `15 scription which follows. In Fig. 1, the converter comprises an annular The present invention involves the utilization casing B, closed at its lower end by a bottom plate of cooperative but independent forms of convert- 1 and at its upper end by. a'over 8. The interior ing and heatexchange apparatus. The entire of the converter has perforated 'partitions 9 and heat exchange means is arranged to be applied 9a adjacent its lower and upper ends, respee- 20 to or removedl from the converting means as a tively. dividing the interior into a large central unit andI to have extending members or elements reaction hember .N adapted t0 be filled with received by and slidable within sockets or passolid contact or catalytic material M, 8nd end sageways which extend within or through the remanifolding chambers il and I2. A conduit I3 action chamber of the converting means. The gives access to manifolding Chamber li and a 25 heat exchange unit and thevconverter are suitably Conduit I4 i0 manlfolding chamber l2. Reinsulated from' one another so that heat exchange actants may enter the converter by either conis effected solely within the reaction zone. :Ihe duif es desired. and the resulting reaction Prodtransfer there is primarily by radiation. Hence .Ilets may leave by theoiher conduit. For tem-- the extent of heat exchange is governed vby the .Peratnre regulation of the reactions takingplece .30 `temperature' difference between the walls of the in chamber I0. tne converter is provided with sockets or passageways and the heat exchange members i5 which Previde recesses within the remembers or elements inserted. therein. Accordaction Chamber Opening through a Wall 0f the 'ingly,' the maintenance of static or varying temconverter but which are sealed against al1 comperature condltionsin the reaction 'zone' 1s readily munication with the interior oi the coverter. In 35 attained by suitable adjustment of the temperathe form shown in Fig. 1, these members l5 conture and of the ilow conditions of the heat ex- Sist 0f 0ndl1its Sealed et One endfhavin'g their change medium in the heat exchange unit. 'I'he Open ends Secured i0 the bottom Well or plete 7 extending 4membersor elements on the latter are 0f the .cOnVerter in'uid-tight relation, the mempreferab1y of the nested conduit or reverse now bers l! extending through Suitable openings 40 40 type to effect substantially uniform supply or retherefor in partitionl and into the reaction moval of heat throughout the portions of the re- Chamber l0 t0 any desired extent. By Preferaction zone traversed thereby. ence, members I5 project through suitable open- In' order to illustrate the. invention, concrete ings in upper partition 9a. so that members l5 are embodiments of apparatus for practising the same maintained in fixed position within the converter 45 are shown in the accompanying drawings, in as well as in desired symmetrical pattern and in which: predetermined spaced relation with one another Fig. lis a vertical, sectional view of a converter` throughout the reaction chamber. The portions and vits heat exchange unit in operative position, of members i5 which lie within reaction chamber l5 0 the section so far as the heat exchange unit is i0 are entirely surrounded by the contact mass M. 50

concerned being substantially on the line I-l of Within the recesses or passageways provided by l "Fig. 3; hollow members I5 extend heat exchange e1e lFig. 2 is a vertical. sectional view of the heat ,ments a of an independent and removable heat 'exchange' unit alone, but taken substantially at exchange unitfwhich is shown by itself in Figs.

.; right 'anglesto its position in Fig. 1, namely, on 2 and 3. 'I'his unit consists oi' a base b, from 55 which elements a extendfthe base being adapted to fit in a chamber adjacent the converter. In Fig. 1, the chamber is beneath the converter and formed by an extension of the annular wall 6 of `the converter, the base being held in place by suitable detachable Supports indicated at I6 in Fig; It will be understood that the converter is either in anelevated position or has a pit therebeneath of v'sufficient size to accommodate the heat exchange unit and to permit its convenient mounting in or removal from operative relation. with the converter. form in number and in arrangement to the socket members I5 ofthe converter with which they cooperate, and, in orderto insure a'substantially l uniform rate of heat exchange with all parts of the reaction chamber adjacent thereto, elements va are preferably 'of the nested conduit type.

Hence each heat exchange element a consists' of a small inletpipe a1 which extends centrally of and substantially the full length ofouter pipe a2. Each innerl pipe alconnects with an inlet manifold c and the connection thereto may be bent or Y looped, as indicated in Fig. 1, to take care of expansions andl contractions due to changes in tem-v perature. Each outer pipe a2 is closed, save for an outlet connection to an outlet manifold d. There may be an inlet manifold c and an `outlet manifold d for each row of heat exchange elements a mounted upon base b, seven manifolds of each kind being shown in Fig. 2, the inlet manifolds connecting with Ainlet main e and the outlet manifolds with outlet main f. The;mains project through the bottoni of base b and have flanged ends for convenient connection lto conduits leading to therest of the heat 'exchange circuit.4 'The interior of base b not occupied by the manifolds, mains, etc., is filled with heat insulating material g to avoid or to restrict heat exchange between the various manifolds and mains. To

simplify the showing in Fig. 3, only inlet main e and .outlet main f are indicated in broken outline in the base b of the heat '/'f exchange unit. When the heat exchange elements a extent? through a manifolding chamberof a converter-a be and frequently is de'A `as to the parts traversing manifolding chamber Il, are expanded or enlarged. and this enlarged area is filled -with heat insulating material'l'l.

As a further protection againstundesirable heat exchange, a thick layer of heat insulating material I8 may be applied to the exterior of bottom I plate "I to be thus interposed between base b of the heat exchange unit and the converter.

Figs. 4 and 5 show the invention applied to a converter of rectangular form, made'up of end plates 2|, side plates 22, and top and bottom plates 23 and 24, respective] The interior of the converter has upper and vlo er perforated partitions 25 and 26,- whih divide'th'e interior into a large central reaction chamber 21 adapted to be lled with solid contact or catalytic material M,

and end manifolding chambers 28 Aand 29, to which fluids' haveaccess by'conduits 30 and 3|,

Elements a conrespectively. The entire reaction chamber 21 is traversed by a plurality of members 32 in the form ofVconduits which are mounted in a fluid- .tighty manner in the opposed vend plates 2|. Hence members 32 serve to tie opposite walls of the converter together in a rigid manner and to provide passageways or recesses communicating with the exterior of the converter for the convenient insertion of heat exchange elements,

after the manner already illustrated in connection with Fig. 1. In this instance, however, the

tion with the converter by horizontal movement rather than vertical, as indicated in connection with Figs 1. l The entire converter shown in Fig. 4-is enclosed by a thick layer 33 of heat insulating material, save for openingstherethrough registering with one end of members 32 for the insertion of heat exchange lelements a of the heat exchange unit. The unit shown in Fig. l has a base b1, from which the heat exchange elements a extend, the base bf being of less depth or thickness than that shown in Figs. l and 2, and with its inlet manif`olds c closer to the outlet manifolds d due to the omission of expansion bends in the inlet pipes for the heat exchange elements.

change fluid is close to its outlet temperature, the adequacy of heatremoval or heat supply being then a function of the rapidity of circulation of the heat exchange medium. It ,will be understood that base b1 is substantially rectangular in form heat exchange unit is brought into operative rela-,

This is possible when the entering temperature of the heat ex and has the proper number of projecting heat exchange elements a and in proper relation to one another to cooperate with all the recesses or passageways provided by elements 32 in the converter. The support 45 for base'b1 may be associated with or .independent of the supporting means for the converter` with ,which the heat exchange unit cooperates.

Fig. 4 also indicates 4diagrammatically the parts of ythe exterior circuit for the heat exchange fluid.

These parts comprise a conduit 40 connected to or supplyfyffheat to the h eat ,exchange medium, anda-conduit 42 conducting the iiuid from heat exchanger 4I to the inlet main e, suitable im- I I' Ihe invention is adapted for the temperature regulation of chemical reactions of all types, endothermic or exothermic, such as those involving 1,-

outlet maglia/j, a heat exchanger 4I for removal synthesis, metathesis, decomposition, hydrogenation, etc. Any form of. solid 'contact material capable of promoting or in any way assisting -in the reaction may be utilized. In certain reactions, such as those involving the treatment or conversion of hydrocarbons derive from deposits of petroleum, coal, lignite, shl, etc., the solid contact material may be silicio in character, including silica-alumina blends, with or without small amounts of other active components, such as metals or metallic compounds, the

catalyst being in therform .of bits, fragments, or

molded lpieces to' facilitate regeneration. 'Ihe catalyst, during the on-stream reaction, accumulates a deposit of a coky, sulphurous or resinous ly different from the on-stream reaction, as exothermic instead of endothermic, or of the same nature but more intense. 1

Since the present invention seals off the heat exchange through 1 akage or otherwise, with the reactants or with the, contactfmass within the reaction chamber, any desired iluid may be used as the temperature controlling medium. -Hence the medium'may be gaseous or liquid, single phase or two phase, under low pressure or high pressure. If the fluid selected is of the single phase type, such as a gas or a liquid which does not vaporize or is not permitted to vaporize. under the conditions' of operation, the ,speed of circulation must be relied upon to remove orto supply the necessa'ry quantity of heat. vLiquids which may be used for this purpose include fused salts, certain 'metals and metal alloys, and water under pre s' sure when the temperature does not exceed its.

critical temperature. Two phase fluids, such as water, mercury, diphe yl, etc., are -useful`when very large amounts of removed. Elements a of the heat exchange unit 4may be provided with suitable guide or spacing means (notJ shown) to facilitate their insertion into the recesses or passageways formed by mem- 'bers l5 or 3 2 and to maintain them suitably centered therein. y

material whici has been used for the conversion or treatment of hydrocarbons. Since this reaction l is not productive, it is usually desirable to oomlli) plete the reaction asv soon. as possible, in order that the contact materialmay be put back on stream and again used for a productive operation, as in the conversion or cracking of higher boiling hydrocarbons to produce lower boiling hydrocarbons including gasoline. The on-stream temperature may be in the range of 775 to 925 F., while the regeneration' by oxidation oi' contaminants will produce a large amount of heat at a. rapid'rate, and, when the deposit is consider'- 'ab1e, may carry the catalyst to such a temperature that its adsorptive capacity may be impaired or, destroyed. Hence it isdesirable to restrain `the catalyst from exceeding a temperatureof4 1200 r". during the regenerating period and to bring thecatalyst back quickly to the eri-stream temperature after regeneration is completed. For the control of such a regeneration, water offers a convenient and cheap solution, especially when utilized in accordance with the present invention. The water can be sent into the inlet manifolds e of a heat exchange unit of the types shown at a low temperature as soon as the regeneration or burning starts o'r is well under way. It will remove heat rapidly and in large quantities from the reaction chamber both as sensible heat and as heat vof vaporization, the vaporized water or steam being withdrawn through the outlet manifolds f. Insulation within the base b or b1 of the heat exchange unitand between the latter and the converter serves to confine the heat exchange to the reaction chamber of the converter, and, since the heat exchange elements a are of the nested conduit type, and, since the heat exchange between the unit and the socket members I 5 or 32 is'- primarily by radiation, heat is withdrawn uniuid from 'any possibility of admixture.'

eat are to be supplied or formly from all parts of the contact mass, land excessive cooling of localizedportions of the same is avoided. By continuing to supply water lup to the end of the regeneration 'and even somewhat tliereafter, the reaction chamber can be quickly cooled down to on-stream temperature. The circulation of water can then be stopped, and the heat exchange unit can be -completely emptied of all heat exchange uid, since the mains e and f represent the low points in the heat exchange unit and any liquid' remaining will Y drain thereto by gravity.

When more time is available for the regeneration, as several hours instead .of an hour or less,

and especially when the on-stream reaction is.`

conducted at a lower temperature, such as in the refining andstabilizing of light hydrocarbons, in-

cluding motor fuels ofthe gasoline type, which may be effected in the range of 400 to 700"v F.

and usually between 500 and 600 F., the Iegenerating'reactionmay be conducted somewhatV ing or regeneration is initiated, after preheating the catalyst if necessary, and the salt is circulated at sucha rate that it rises in temperature following the increase in temperature of the catalyst- As the burning becomesduring regeneration. less intense and 'ilnally ceases, heat-is removed from thecirculated salt, and the reaction chamber and the catalyst then follow the salt down in temperature. By suitable adjustment of the rate of circulating the salt, heat can be recovered atl a constant rate by such means as heat' exchanger ll during the entire regenerating opera tion. Thus, if water is used as the cooling medium in heat exchanger 4I, steam'cari be produced at a constant rate v during -the entire regenerating period. Of course, in a commercial installation two or more converters will be utilized,so that at least one is always on stream while at least one other is always in regeneration, thus effecting continuity of both reactions and permitting an economical operation of the heat exchange circuit.

From the above it will beapparent that the 4present invention has important advantages and wide flexibility in the'control of chemical reactions. For example, the heat exchange medium may be utilized only during a portion of the cycle of operation, as when there is large evolution of change is accurately controlled by adjusting the temperature of the'heat exchange medium and/or its rate of flow. Hence the movement of heat to or from the reaction chamber may be 4made as gradual or as abrupt as desired, while effectingthe same with al high degree of uniformity throughout the reaction chamber and with an avoidance of chilling or 'over heating of localized 4portions of the contact mass. Moreover. since the heat exchange unit is separate .and distinct from the converter and is'readily withdrawn from l"Joperative relation therewith, all danger of leakage of the heat exchange medium intothe re- 'action chamber of the converter is avoided. This gives complete freedom of choice of heat exchange media, and facilitates inspection and repair of both the converter and the heat exchangeunit.

It is to be understood that converters need not be mounted in a vertical position, such as shown in the drawings. Some, if not all, of the advantages of the present invention are available 1-0 when converters are mounted in other positions.

i... auch minor changes, modications and variations are intended to be within the'scope of the appended claims.

I claim as my invention:

1. A casing having side and end walls and partitions extending thereacross providing area'cton chamber containing Icontact material and adjacent manifolds for supplying iiuid to and removing fluid from the contact-material, apertures in an outer wall of the casing, conduits secured in said apertures and extending through the contact material providing passageways therein, in combination withl a heat exchange unit, said unit comprising a container having an apertured end Wall, means for detachably securing the container to the casing with the container end wall apertures in alignment` with the casing conduits, tubes for heat exchange fluid disposed within the casing conduits and extend- 3o ing substantially the length ofsaid conduits. said tubes having inlet andoutlet end portions ex-I tending through the apertures in the container end wall and into said container, means for securing said tube end portions in the container and positioning the tubes IWithin said casing conduits, manifolds within said container, atleast 4one'manifold in communication with tube inlet en d partions and at least one other manifold in communication with the tube outlet end portions, means for supplying fluid to one manifold for passage through the tubes and means for removing fluid from another manifold after passage through the tubes,^said means being so constructed and arranged with respect to the casing that the heat exchange unit is readily detachable from the casing. 2. A casing having side and end walls and partltionsdextending thereacross providing a reaction chamber containing contact material and adjacent manifolds for supplying iiuid to and removing uid from the contact material, apertures in an outer wall of the casing, conduits secured in said apertures and extending through the contact material providing passageways therein, in combination with a heat exchange unit, said unit comprising a container having an apertured end wall, means for d tachably securing the container to the casing with the .,70outer tubes', manifolds within said container, at

`4least one'manifold in communication with the Y endportions of the inner tubes and at least one other manifold, in communication with the end portions of the outer tubes, means for supplying fluid to one manifold for vpassage through the tubes and means for removing fluid from another manifold afte'r passage through the tubes, said means being so constructed and arranged with 5 respect to the casing that the heat exchange unit is readily detachable from the casing.

3. A casing having sideand end walls -and partitions extending thereacross providing a reaction chamber containing contact material and 10 adjacent manifolds -for supplying fluid to and removing fluid from the contact material, apertures in an outer wall of the casing, conduits secured in said apertures and extending through the' contact material providing passageways 15 therein, in combination with a heat exchange unit, said vunit comprising a container having an apertured `end wall, means for detachably securing thecontainer to' the casing with the container end wall apertures in: alignment with 20 the casing conduits, sets of inner and outer nested tubes for passage of heat'- exchange iiuid disposed within the casing conduits, and extending substantially the length of said conduits,v eachl of said tubes having an end portion pass- 25 ing through the container end wall and into the container, rsaid outer tubes being secured to the container end wall and having closed ends disposed Within the casing conduits and apertured end walls Withinithe container, said inner tubes 30 being secured in the apertured end walls ,of the outer tubes, said inner tubeshaving an 'open endl positioned adjacent the closed ends of the outer tubes, manifolds Within said container, at least one^manifold in communication with the 35 end portions of the inner tubes and at least one other manifold in communication with the endv portions of the outer'tubes, fluid connections secured to said manifolds and openingl outwardly of the container for supplying fluid to and re- 40 moving fluid from the manifolds.

apertured end wall, means for detachably securing the container to the casing with the container end Wall apertures inlalignment with the casing' conduits, tubes for heat exchange fluid disposed 55` within the casing conduits and extending substantially the length of said conduits, said tubes having inlet and outlet end portions extending through the apertures in the container end wall and into said container, means for securing said tube end portions in' the container and positioning the-tubes within said casing conduits, manifolds within said container, at least one manifold in communication with tube inlet end portions and at least one other manifold .in communication with the tube outlet end portions, insulating material within said container and surrounding said tube ends and manifolds, uid connections secured to said manifolds and opening outwardly of the container for supplying fluid to and re moving uid from the manifolds., A

f f EUGENE .1.HouDRY.

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