US2289329A - Production of hydrocarbons - Google Patents

Description

y 1942- T. B. PRICKETT 2,289,329

PRODUCTION OF HYDRQCARBONS Filed July 16, 1938 .2 Sheets-Sheet 2 t 9/ REACTION ZONE H a. l2 SEPARATOR PURGING ZONE INVENTOR' THuMAs B.PRICKETT ATTORNEY Patented July 7, 1942 UNITED STATES PATENT OFFICE- PRODUCTION OF I- IYDROCARBONS Thomas B. Priekett, Woodbury, N. 1., assignor to Houdry Process Corporation, Wilmington, DeL, a corporation of Delaware Application July 16, 1938, Serial No. 219,537

12 Claims.

The present invention relates to the production of valuable hydrocarbons from starting material comprising or containing bitumens having origin in petroleum, coal, shale, schist and the like, or from vaporous or gaseous materials capable of reacting to yield hydrocarbon products. More particularly, it is concerned with processes for effecting synthesis, decomposition, purification and other reactions in the presence of absorbent and/or adsorbent contact material capable of promoting; entering into, or in any way assisting the desired reactions. It is particularly directed toward systems wherein reactants and solid contact material flow simultaneously through a reaction zone.

One object of the present invention is to improve systems of the above described type wherein the desired reactions are effected in vapor phase. Another object is toeffect close control over reaction conditions in such systems. Another object is to devise an improved closed circuit wherein the contact mass is flowed through the reaction zone and thereafter reactivated and returned to the reaction zone. Another object is to maintain the solid contact material in dry or substantially dry form at all times. Another object is to utilize process fluids to assist in handling oi the contact mass and/or in conditioning of the same. Other objects will be apparent from the detailed description which follows.

Concrete embodiments of the invention are disclosed in the accompanying drawings in which:

Fig. l is a diagrammatic flow chart illustrating a closed circuit of the above described type and one use of a proces fluid to assist in conditioning of the contact mass;

Fig. 2 is a modified flow chart illustrating another use of process fluids to assist in the treatment of the contact material;

Fig. 3 is another modified flow chart showing still difi'erent utilization of process fluids in handling the contact material;

Figs. 4, and 6 are somewhat diagrammatic sectional views of highly advantageous types of separating equipment for use in the circuits shown in Figs. 1, 2 and 3, Fig. 4 being a sectional elevation of one type of separator, Fig. 5 a sectional elevation of a modified form of separator and Fig. 6 a sectional plan view taken substantially on line 6-6 of Fig. 5;

And Fig. 7 is a sectional elevation of one type of impelling means for contact solid.

Referring to the drawings, and particularly to Figs. 1, 2 and 3, reactants capable of entering into the desired reaction and comprising, for example, distillate or residual higher boiling hydrocarbons capable of transformation into lower boiling products including gasoline and gas, or ordinarily gaseous hydrocarbons capable of being cracked or polymerized to yield higher boiling liquids, or hydrocarbon distillates containing corrosive or other impurities, may be forced into and through heater H to be heated to reaction temperature and then passed in vapor phase, and often in superheated condition, through lines 8 and II into reaction vessel or zone 9. Before admission to the latter the reactants are mixed with a suitably controlled quantity of desired solid contact material in heated condition supplied, for example, to line H from feed hopper or bin ID, in any known or desired manner, as for example, by means of a screw conveyor or other suitable impelling means.

The temperature of the contact mass at the instant of its presentation to the reactant vapors is preferably at or at least near the temperature of the latter, thus providing many important process advantages which reflect in improved control over the course and extent of the reactions. In some instances, as when the desired reaction is endothermic and/or when the reaction tends to proceed to completion in heater H to yield inferior products, the contact mass may be at somewhat higher temperature than the reactants. Such control of the temperatures of both reactants and contact mass minimizes or even avoids undesirable reactions leading, in many hydrocarbon processes, to formation of excess quantities of coke and light gases caused by overheating of the charge prior to its introduction into the reaction zone. It also avoids undesirable reactions and loss of activity occasioned by condensation of portions of the reactant vapors on or in the contact material.

After flowing the entire or substantially the entire length of reaction zone 9 the mixture of vapors and contact material discharges through line l2.into separator I 3 in which the dry solid settles and is withdrawn by line H. The latter preferably leads to a zone for reactivatin'g or revivifying the contact mass. Meanwhile, vaporous reaction products are conducted by line l5 to a suitable finishing or other treatment, the nature of which depends upon the character of the reaction products, and may comprise rectification, for example, in a fractionator such as 43 (Fig. 1) discharging distillate and residual fractions by lines 44 and 45. Such distillate fraction may. if desired, be condensed in cooler 46 and conducted by line 41 to any further desired or required treatment. Any mall quantity of finely divided contact material which may leave separator I3 by line I5 may be recovered from the residual fraction in line 45 as by filtration or the like.

The reaction chamber or space in the vessel comprising reaction zone 9 is so designed and disposed that settling and accumulation of solid therein is avoided, due consideration being taken of the velocity of flow therethrough and of the density, size and other characteristics of the contact mass. Although satisfactory results may be obtained by high velocity flow, through a horizontal chamber, of vapors carrying finely divided or powdered contact mass in suspension, the reaction chamber is preferably disposed in inclined or vertical position thereby to permit free or substantially free fall of contact mass from the inlet to outlet of the same, whether the mass be in powdered, granulated, fragmentary or molded form.

According to a preferred aspect of the invention, centrifugal action is utilized to effect separation of vaporous reaction products and dry contaminated contact solid in separator I3. One simple way of inducing such centrifugal action is to admit the mixture of solid and vapor to the separation chamber tangentially and at high velocity to provide rapid rotary or whirling motion therein, as indicated for example in Figs. 4, 5 and 6. In Fig. 4, the stream of solid and fluid enters enlarged chamber C of separator I3a through substantially tangentially disposed inlet line In, preferably having its discharge opening above the lower end of vapor line I5a, separated solid material settling to the bottom of chamber C and being withdrawn by line Ila.v When the contact mass leaving reaction zone 9 is in very fine state of division, part of it sometimes remains in suspension even under the low velocity vertical flow conditions obtaining in the lower portions of the chamber and tends to be carried into conduit Ia. In such cases, it is desirable to mechanically induce centrifugal action in substitution for or to supplement the effect of the tangential flow in chamber C. One method of utilizing supplementary separation is illustrated in Figs. 5 and 6.

In these figures, separator I3b contains a lower chamber CI provided with inner annular shell I 30 and fed by tangentially disposed line I2b. This lower chamber discharges vapor, with possibly some finely divided solid held in suspension therein, through line I51) and into a second and upper separating chamber or zone C2 containing fan blades B or the like rotated at high speed, as by motor M. The finely divided solid separated by mechanically induced centrifugal action in chamber C2 falls down annular chamber C3 to combine with the somewhat larger material separated in chamber CI prior to withdrawal by line I 4b. Simultaneously vapors flow to the desired treating or processing equipment by line I50.

The dry, hot contact material in line I4, prior to reintroduction into reaction zone 9, has adherent fluid and/or solid reaction products removed from it. Since the used contact mass usually contains valuable adsorbed fiuid reaction products, it is preferable to remove such products by a purging operation utilizing vacuum and/or a purging medium, for example, a suitable inert fluid such as flue gases or steam. This purging operation may be conducted in a single container, such as I6, through which the contact mass is allowed to flow slowly. It is preferable, however,

to utilize a plurality of purging containers I6 arranged and adapted alternately to receive contact material from line I4 as through valved branches I1 and to discharge the purged contact mass, as for example, into line I8 by valved branches 20. When a plurality of purging chambers are used, each may be sealed from the rest of the system, thus providing for use of any desired purging method without interrupting or in any way interfering with the operating conditions in the rest of the plant. If further regeneration of the contact mass is necessary, as for example to remove coky, pitchy, sulphurous or other burnable deposits, the purged material, substantially free of volatile products, may be conducted by line I8 into regenerating zone I9, which may comprise or contain any known or desired type of equipment for removing combustible deposits from contact masses. This equipment may be a rotary kiln or a single or multiple hearth burner, as for example, a multiple hearth burner provided with cooled rabble arms, as commonly used for burning clays and other contact masses. When the contact mass is in the form of comparatively large pieces of uniform or substantially uniform size and shape it may advantageously be regenerated in a reaction zone provided with one or more series of perforated inlet and/or outlet members for regenerating medium and/or products embedded in the mass as disclosed for example in United States Patents 1,987,904 and 2,042,468, issued to Eugene J Houdry, January 15, 1935, and June 2, 1936, respectively. The burned or regen erated contact material issuing from regenerating zone I9, as by line 2I, is then returned, while still hot and at controlled temperature to feed bin or hopper In. Any known or desired conveying means, including bucket elevators or pneumatic conveyors may be utilized for this purpose.

In certain of its aspects, the invention involves utilizing process fluids to assist in conditioning the used and contaminated contact material for further treatment or use, or in presenting the contact mass in active form to the reaction zone. One economically advantageous use of a process fluid is indicated in Fig. 1, in which all or any desired portion of the regeneration fumes issuing from regenerating zone I9 by line 22 may be utilized to regulate the temperature of fresh or regenerated contact material entering or about to 1 enter reaction zone 9. To this end, regeneration fumes at suitable temperature, regulated in any known or desired manner, as for example by admission thereto of a heating or cooling fluid, such as steam or air, as by line 25, may be passed in heat exchange relation with the contact mass in feed hopper I0, as through a jacket such as 23 or through a coil or other suitable heat exchange device contained within or otherwise associated with hopper ID. The regeneration fumes may then be discharged by line 24.

One of the process fluids, and particularly regeneration fumes, may'find valuable use in removing reaction products from used contact material preparatory to further reactivation or regeneration. As shown in Fig. 2, any desired portion of the regeneration fumes in line 22 may be conducted by line 26 to all or any desired one or group of the purging containers I6 as through valved branches 21. The hot fumes coming into contact with the contaminated solid in the purging zone, in addition to effecting removal of fluid adsorbed therein, assist in adjusting the temperature of the contact mass to the level suitable for regeneration. The hot fumes loaded with purged hydrocarbon fluid issuing from the purging zone by valved branches 28 leading to line 48 maybe cooled in a suitable cooler 29 to effect condensation of valuable hydrocarbons. The latter may then be separated in any known manner as in a conventional vaporliquid separator, such as indicated at 30. If desired or necessary, the composition of the regeneration fumes may be modifled prior to their use as purging fluid to insure against combustion in the purging zone. To this end, the fumes may be diluted with a suitable inert fluid, such as steam, supplied by line 4i. Or, bumable components such as carbon monoxide and hydrocarbon vapors may be removed along with oxygen by a suitable catalytic combustion process, for ex ample, one employing a copper catalyst. One

suitable process is disclosed in the copending application of Eugene J. Houdry, Serial No. 78,542, filed May 8, 1936, replaced by substitute application Serial No. 266,010, filed April 4, 1939, which issued as Patent No. 2,248,994 on July 15, 1941.

Simplicity and economy of operation are realized when process fluids, including reactants and regeneration fumes, are utilized to. pneumatically convey the contact solid from the regenerating zone to the reaction zone. When comparatively large quantities of contact material are desired or required for the reaction, as is the case in some processes for transforming higher boiling starting material into lower boiling or distillate products, regeneration fumes may advantageous- 1y be utilized for this purpose. As illustrated in Fig. 3, regenerated contact material discharged by line 2| from regenerating zone l9 may be collected in feed hopper 3|. Thence it may flow by gravity through line 32 to be picked up in any suitable type of impelling means, indicated at D, by regeneration fumes forced through line 22 by compressor or blower 33, the fumes and suspended solid then passing through' line 34 to feed bin or hopper l0. One simple form of impelling means for combining the selected process fluid with the contact mass is somewhat diagrammatically illustrated in Fig. '7, in which the desired quantity of conveying fluid in line 22 is injected at high velocity through nozzle 22ainto chamber K. The jetted fluid then picks up the contact solid M admitted to chamber K by. conduit 32 and impels the same into and through conduit 34.

When desired or required, the temperature of either or both the contact mass and regeneration fumes may be regulated-by means of suitable heat exchangers, located in either or both lines32 and 22 respectively, as for example, cooler 36 in line 22 provided'with a by-pass therearound (Fig. 3). When the quantity of regeneration fumes is insufficient to convey the total desired amount of contact material it may be augmented by controlled quantities of a suitable fluid, preferably of inert nature, supplied by valved line 31 from any desired source; When regeneration fumes or other diluent fluid is utilized as conveying medium, feed hopper i preferably assumes a form (Fig. 3) capable of separating vapors from solid and provided with a gas outlet 38. Hopper l0 may then be, for example, a centrifugal separator of the type utilized for separa or l3. Insome processes it is desirable hopper and separator l0 as through valved bypass 39. If regeneration fumes intended for use as a conveying fluid contain undesirable components, such as free oxygen, carbon monoxide or "tmaterial are needed for the desired reaction, as

for example, for refining comparatively sweet quired heat exchanger. such as heater or cooler 49, for the regenerated contact material may be located in line ll before its junction with line 8. The heated reactant vapors in line 8 may then pick up the contact solid in any desired type of pneumatic impeller D and convey the solid through line H to reaction zone 9, proper compensation due to time in the former being made for the contact time in the latter.

With some hydrocarbon reactions, as may be illustrated by certain polymerization processes, the contact material acquires only small amounts of contaminating deposit and may be advantageously and economically reused after being purged of adsorbed fluid reaction products and.

the purging containers It may be supplemented or replaced by vacuum, utilized, for example,

i the desired reactions.

to include another process fluid, for example, a I

diluting or carrying agent, in the charge to the reaction zone. In such cases, anydesired por tion of the mixture of solid and flue gas, steam or other conveying fluid may short-circuit feed after the manner disclosed and claimed in United States Patent 2,095,265, issued October 12, 1937, to J. H. Pew, or in United States Patent 2,095,264, issued October 12, 1937, to A. E. Pew, Jr. Such vacuum may be derived from any suitable source, as from a steam evacuating jet such as 42 (Fig. 1) located in line 48.

The invention, in its broad aspects, is not limited to the use of any particular contact mass but embraces utilization of any known or desired contact solid capable of promoting or assisting The mass may, for example, be of silicious and/or aluminous nature and of natural or artificial origin, or it may comprise any' metal or oxide, alone, admixed with, incorporated within or otherwise associated with a support of silicious or other nature. In-one of the more common applications of the invention a silicious adsorbent contact mass, for example, a synthetic blend of silica and alumina or an active or activated hydrosilicate of alumina may be utilized to promote transformation of higher boiling distillate or residual hydrocarbons into the higher boiling vapors, heated to about 850 F'., for example, may be mixed with the adsorptive mass in the form of powdered or fragmentary particles of a size not in excess of about 8 mesh and supplied at a temperature within the range of 800 to 900 F. After flowing through the reaction zone and being separated from the vaporous reaction products by centrifugal action in a separator of the type disclosed, for example, in Fig. 4,- the dry, hot contact mass is preferably purged of adsorbed and absorbed vapors and regenerated by combustion at controlled temperature not in excess of 1150 to 1200 F. and preferably of the order of 1000 F. before being re-introduced at adjusted temperature into the stream of reactant vapors.

It is apparent from the above that the invention provides for control of reaction conditions in a manner to minimize side or other undesired reactions caused by overheating or condensation of reactants prior to or during the desired contact operation. Important advantages are realized by maintaining the contact mass in hot, dry condition during all phases of its handling or treatment. These advantages may be augmented by economical use of process fluid to assist in treatment or handling of the contact solid in one or more steps of the operation.

I claim as my invention:

1. In effecting hydrocarbon reactions involving simultaneous flow of reactants and contact solids, the process comprising flowing com-- mingled reactant vapors and solid contact material through a reaction zone, separating used contact material from reaction product vapors, subjecting contact material so separated to regeneration by controlled combustion to remove burnable deposit therefrom, returning regenerated contact material at controlled and approximately reaction temperature to said reaction zone, and contacting flue gases resulting from said combustion with said mass before contacting the latter with said reactants at controlled temperature to adjust the temperature of said mass to reaction level.

2. In effecting hydrocarbon reactions in the presence of solid contact masses, the process of simultaneously flowing hydrocarbon reactant vapors and preheated solid contact material through a reaction zone, feeding used contact solid separated from reaction products to a re generation zone, therein removing burnable de- P posit from said solid by combustion, conveying regenerated solid issuing from said regeneration zone while still in heated condition to said reaction zone, and adjusting the temperature of the regenerated mass to approximately reaction level before admitting the same to said reaction zone by passing flue gases withdrawn from said regeneration zone while still hot from said combustion and at controlled temperature in heat exchange relation therewith.

3. In effecting vapor phase hydrocarbon reactions in the presence of solid contact masses, the process comprising simultaneously flowing reactant vapors and solid adsorptive contact mass through a reaction chamber, separating said contact mass in substantially dry form from hydrocarbon products, conducting said mass to a purging chamber separate and distinct from said reaction chamber and therein purging said mass of reaction fluid, feeding the purged mass to a regeneration chamber and therein subjecting it to combustion conditions to remove burnable deposit therefrom, and utilizing a regulated quantity of fumes produced by said combustion to effect said purging.

4. In effecting hydrocarbon reactions involving simultaneous flow of reactants and adsorptive contact solids, the process comprising commingling adsorptive solid heated to at least approximately reaction temperature with reactant vapors, concurrently flowing a continuous stream of the commingled reactant vapors and adsorptive contact mass through substantially the entire extent of a reaction zone, separating contaminated solid from the resulting products, feeding said solid to a regeneration zone, therein removing contaminating reaction products from said solid by combustion, conveying the regenerated contact mass to said reaction zone, utilizing spent regenerating medium to assist in the movement of the regenerated contact material, and controlling the temperature of the regeneration fumes so utilized to adjust the temperature of the mass during its conveyance to approximately reaction level.

5. In effecting hydrocarbon reactions involving simultaneous flow of reactants and adsorptive contact solids, the process comprising commingling adsorptive solid heated to at least approximately reaction temperature with reactant vapors, concurrently flowing a continuous stream of the commingled reactant vapors and adsorptive contact mass through substantially the entire extent of a reaction zone, separating contaminated solid in dry form from the resulting reaction product vapors, feeding said solid to a regeneration zone, therein removing contaminating reaction products from said solid by combustion, conveying the regenerated contact mass while still in heated condition to said reaction zone, and utilizing hot spent regenerating medium to assist in the movement of the regenerated contact material and to maintain the latter at controlled temperature desired for its introduction into the reaction zone.

6. Ineffecting hydrocarbon reactions involving simultaneousflow of reactants and an adsorptive contact solid through a reaction zone, the process comprising combining solid contact mass in heated condition with reactant vapors, flowing a continuous stream of the commingled vapors and solid through the reaction zone, separating contaminated solid from the resulting products, feeding the separated solid to a regenerating zone, therein removing burnable deposits from said solid by combustion, returning regenerated solid issuing from said combustion zone while still in heated condition into contact with said reactants, subjecting spent regenerating medium issuing from said regenerating zone to promoted combustion to remove active components therefrom, and contacting fumes so treated and at controlled temperature with said regenerated solid to condition the latter for contact with said reactants.

7. In effecting hydrocarbon reactions involving simultaneous flow of reactants and an adsorptive contact solid through a reaction zone, the process comprising combining solid contact mass in heated condition with reactant vapors, flowing a continuous stream of the commingled vapors and solid through the reaction zone, separating contaminated solid in dry form from the resulting reaction product vapors, feeding the separated solid to a regenerating zone, therein removing burnable deposits from said solid by combustion, returning regenerated solid issuing from said regeneration zone while still in heated condition into contact with said reactants, subjecting spent regenerating medium issuing from said regenerating zone to catalytic combustion to remove active components therefrom, and utilizing the fumes resulting from said catalytic combustion to assist in conveying the regenerated contact material back to said reaction zone.

8. In effecting vapor phase hydrocarbon reactions in the presence of solid contact masses,

1 the process comprising flowing commingled reactant vapors and solid adsorbent contact material through substantially the entire extent of a reaction zone, separating said contact mass in dry form from the resulting reaction products by centrifugal action, burning combustible deposits from said separated solid, pneumatically conveying burned solid while still hot from said burning back into contact with reactant vapors, and passing hot flue gases at controlled temperature issuing from said burning operation in heat exchange relation with said mass prior to contacting the same with reactants to regulate the temperature of the mass prior to said contacting step.

9. In apparatus for producing hydrocarbons, in combination, a vessel providing a reaction chamber, means for supplying a stream of heated reactant vapors commingled with heated contact mass to said chamber, a separator adapted to separate solid from vapors, said separator being provided with an inlet connection, an overhead outlet for vapors, and a bottom draw-oil for solid, means for purging spent contact mass of adsorbed fluid, said purging means being provided with an inlet and an outlet for purging chamber, means for supplying a stream of reactant vapors commingled with contact mass to a said chamber, a separator for separating reaction products from contaminated contact material connected to said vessel, regenerating means arranged and adapted to receive contaminated mass from said separator and to burn contaminating deposit from said mass, pneumatic conveying means arranged. and adapted to conduct regenerated contact mass from said regenerating means toward said vessel, a conduit connection for conducting regeneration fumes from said means to serve as pneumatic conveying medium in the latter, and means for effecting promoted combustion of said regenerated fumes disposed in circuit between said regenerating means and. said conveying means, thereby to remove burnable components from said fumes and provide conveying medium free of such contaminants.

11. In apparatus for producing hydrocarbons, in combination, a vessel providing a reaction chamber, means for supplying a stream of heated reactant vapors commingled with contact solid to said chamber, a centrifugal separator for separating reaction product vapors from contaminated contact material, said separator comprising inner and outer casings providing an inner chamber communicating with an outer chamber and an upper chamber, means disposed in said upper chamber for mechanically inducing centrifugal action therein, an inlet connection to said inner chamber for admitting reaction product vapors and contact solid thereto, an outlet connection in said outercasing disposed above said last named means for discharging vapors from the separator, a bottom draw-oil in said outer casing for discharging contact solid therefrom, a conduit connecting said reaction chamber and said inlet connection, means for re-.

generating spent contact solid by controlled combustion provided with inlet and outlet connections for regenerating medium and regeneration fumes respectively, a conduit interconnecting said bottom draw-off and said regenerating means for conducting contact mass to the latter, means for pneumatically impelling contact solid, means for conducting regenerated contact material from said regenerating means to said impelling means, a, conduit for conducting regeneration fumes from said last named outlet connection to said impelling means to serve as impelling medium therein, and a conduit interconnecting said impelling means and said first named means for conducting regenerated contact solid to the latter.

12. A separator for separating hydrocarbon vapors from dry solid contact material comprising an. outer casing provided with an overhead vapor line and a bottom draw-off for solid, an

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