US3019096A

US3019096A - Process for fluid catalytic reforming of hydrocarbons to gas

Info

Publication number: US3019096A
Application number: US812889A
Authority: US
Inventors: Charles G Milbourne
Original assignee: United Engineers and Constructors Inc
Current assignee: United Engineers and Constructors Inc
Priority date: 1959-05-13
Filing date: 1959-05-13
Publication date: 1962-01-30
Anticipated expiration: 1979-01-30

Description

Jan. 30, 1962 C. G. MILBOURNE PROCESS FOR FLUID CATALYTIC REFORMING OF HYDROCARBONS TO GAS Filed May 13, 1959 3 Sheets-Sheet 1 F/ G j mower /4 FEED 4 hum/0r .5. Char/e5 G M/boume By his af/omeys Jan. 30, 1962 c. G. MILBOURNE 3,019,096

PROCESS FOR FLUID CATALYTIC REFORMING 0F HYDROCARBONS TO GAS Filed May 13, 1959 3 Sheets-Sheet 2 F/G- Z 59 PRODUCT 55 ACK 7/0 60 6/ T 72 (MUS/ID? 75 y) 7i 78 63 l 'L' Burner 65 66 l kp A? FUEL j 5mm .53

/n|/ e/7/0r Char/esGM/boume By his attorneys United States Patent Office 3,019,096 Patented Jan. 30, 1962 3,019,096 PROCESS FOR FLUED CATALYTIC REFORMING F HYDROCARBONS TO GAS Charles G. Milhourne, Lausdowne, Pa., assignor to United Engineers & Constructors Inc., Philadelphia, Pa., a corporation of Delaware Filed May 13, 1959, Ser. No. 812,889 11 Claims. (Cl. 48-213) This invention relates to a new and improved process for reforming low-value hydrocarbonaceous materials to give a valuable fuel gas.

In recent years natural gas consumption by public utility companies increased at a surprising rate. The installation of pipelines for the transmission of this high heating value gas from its source to various localities at prices competitive with locally manufactured gas, and in substantial quantity, has gradually led utility companies to convert to the use of such gas. However, suppliers of natural gas are reluctant to furnish the gas at an attractive price in any manner other than at a constant flow, and occasional demands for a temporary increase in flow are met with the imposition of a premium charge.

Unfortunately the demand placed on public utilities is not constant, but varies with the seasons of the year and with the severity of the weather during any particular season, so that utility companies are faced with the problem of regularly paying premium rates for gas supplies in excess of an average flow level.

An urgent need therefore exists for an economical process for the manufacture in large quantities of a high heating value fuel gas (in the order of about 1000 B.t.u./ standard cubic foot) which would be freely interchangeable with natural gas. With such facilities on call the utility companies would be able to meet seasonal variations in demand without being forced to pay premium prices to the suppliers of natural gas.

There is also a long range interest in the development of gas making processes in that reserves of natural gas are not unlimited and in that natural gas is being used increasingly as a raw material in the manufacture of various chemicals. Thus the price of natural gas will tend to increase over the years and it would be desirable to have a process by means of which low grade hydrocarbonaceous materials could be efficiently con verted into a high B.t.u. fuel gas.

Various processes have been suggested for meeting these requirements. These processes have not been entirely satisfactory however, because the process efficiency, i.e. B.t.u. in the product gas from a unit weight of feed divided by the Btu. per unit weight of feed, has been relatively low, on the order of 50% to 65%. Moreover, prior processes using catalytic methods have been limited in the type of feed which could be used because heavy residual oils, or feedstocks having high ash or sulphur contents adversely affect the activity of the catalyst.

It is therefore a primary object of the present invention to provide a method and apparatus for the catalytic reforming of low value hydrocarbonaceous material into high value fuel gas, by means of which a greater percentage of the hydrocarbonaceous material is upgraded than has heretofore been possible.

It is another object to provide a method and apparatus for an economical peak load production of fuel gas.

It is another object to provide a method and apparatus for the catalytic reforming of low value hydrocarbonaceous materials to produce high value fuel gas whereby tar production and carbon deposition is kept at a minimum.

It is another object to provide a method and apparatus for the economical continuous production of fuel gas without the usually attendant necessity of frequent shutdowns for catalyst replacement.

It is another object to provide a method and apparatus for the catalytic reforming of low value hydrocarbonaceous materials to produce high value fuel gases whereby catalyst spalling and poisoning is substantially avoided.

In accordance with the invention, these and other objects are achieved by means of a process for making a fuel gas containing light hydrocarbons, i.e. methane, ethane, propane etc., which comprises forming a hot stream of steam, entrained finely divided solid reforming catalyst and recycled fuel gas, reforming said recycled fuel gas in said stream to form hydrogen and injecting a hydrocarbonaceous feed into said stream containing the newly formed hydrogen to reform said hydrocarbonaceous material in the presence of the newly formed hydrogen. By conducting the reforming operation in the presence of nascent hydrogen, the process elficiency (as defined above) is higher than would normally be the case.

In carrying out the invention, the reforming catalyst is normally separated from the product gas and regenerated with air or other oxygen containing gas. During regeneration the catalyst is, of course, reheated. It is then normally recycled to contact additional recycled product gas. The recycled gas, recycled hot catalyst and steam are preferably mixed and sent through a reaction duct or conduit, with the catalyst present as a disperse phase suspension. After the recycled gas has had a chance to react with the hot catalyst to form hydrogen, the hydrocarbonaceous feed is injected and reformed.

The invention has been described above in its simplest form. As such it is especially useful with relatively light hydrocarbonaceous feeds, such as gas oils, light tars and the like. In many instances however, it is desirable to process much heavier feed stocks, such as Bunker C fuel oil, heavy petroleum residues, coke oven tar and the like. These substances have high residual (Conradson) carbon and ash contents and would contaminate the reforming catalyst to an unacceptable extent. To overcome this difficulty high ash feeds are first introduced into a gasiform stream of hot, catalytically inert solids, for example, hot coke, in a disperse phase suspension in a carrying gas such. as steam. The feed is thereby volatilized, leaving its ash content deposited on the inert solids. The volatilized feed material is then mixed with hot reforming catalyst to effect reformation.

Preferably the catalyst particles and the coke particles are of substantially diflerent sizes. The volatilization stream containing finely divided coke may then be mixed directly with the catalyst containing stream, and the combined solids separated from the gases and then from each other on the basis of particle size.

While the technique just described is particularly advantageous when the reforming is carried out in the presence of nascent hydrogen, it is of more general application. Thus the present invention also includes, in a process for the catalytic reforming of a hydrocarbonaceous material which contains components tending adversely to affect the activity of reforming catalysts, the improvement which comprises introducing the hydrocarbonaceous material into a hot moving volatilization stream of gases and finely divided catalytically inert solids to volatilize said hydrocarbonaceous material with the deposition of a residue on said solids, introducing the volatili zation stream containing volatilized hydrocarbonaceous material into a gasiform reaction stream containing finely Disperse phase" suspension means a suspension whose density is not more than 10% of the loose packed bulk density of the solid.

divided solid reforming catalyst suspended therein and reforming the volatilized hydrocarbonaceous material in said reaction stream. The term gasiform as used herein means a stream of gases and entrained particles of solid or liquid or both.

The volatilization that takes place in the volatilization stream may be a simple vaporization of components having relatively low boiling points or it may include a certain amount of conversion or cracking of higher boiling components to form lower molecular weight vaporizable products.

In certain instances it may be found that in the process just described, where catalytically inert solids are combined with catalytic solids, the production rate of the ultimate reformed product is slower than is desired. To avoid this it may be desirable to have two entirely different flow paths, one for the catalyst and one for noncatalytic solids with the volatilized hydrocarbonaceous feed material being separated from the catalytically inert solids before being charged to the catalyst stream.

The invention therefore further provides a process for catalytically reforming a hydrocarbonaceous material containing components tending to adversely affect the activity of reforming catalysts comprising introducing the normally liquid hydrocarbonaceous material into a. hot gasiform volatilization stream containing finely divided catalytically inert solids entrained therein partially vaporizing said material in said vaporization stream and depositioning a non-vaporous residue containing the components adversely affecting catalyst activity on said catalytically inert solids, separating the volatilized components including volatilized hydrocarbonaceous materials from the non-vaporous components of said vaporization stream, introducing said vaporous components into a hot moving gasiform reaction stream containing finely divided reforming catalyst suspended therein and reforming the volatilized hydrocarbonaceous material in said reaction stream.

As will appear from a consideration of the foregoing general discussion the present invention can be used with a wide variety of feed stocks. When a prevolati1ization step is not employed it is preferably used with normally liquid hydrocarbonaceous materials having not more than a trace of ash. With a prevolatilization step. almost any normally solid or liquid hydrocarbonaceous material can be used including coal, oil shale, lignite, peat, residual fuel oils, such as Bunker C fuel oil, cokeoven by-product tar, low temperature coal carbonization tar, crude oil, reduced crude oil, virgin distillate gas oils, catalytic recycle gas oil, kerosenes and naphthas.

The catalyst used in the reforming sections of the proc-- ess may be selected from any of the wide variety of reforming catalysts presently available. It should however be able to sustain the temperatures involved (1200 to 2200 F.) without cracking or other adverse effect. Generally speaking a nickel catalyst deposited on alumina base having a density of about 100 pounds/ft. is preferred. A similar cobalt catalyst is readily available and may also be used.

The inert solids used in the prevolatilization section are preferably coke generated in the process. However, other inert materials may be used instead, such for example as sand or alumina.

The reaction conditions will vary to a certain extent, depending chiefly on the nature of the feed stock. In the reforming section the temperature at the point that recycled product gas is first introduced will be between about 1200 and about 2200 F. Introduction of the recycled gas at say 60125 F. will reduce this to say 11502150 F. Introduction of the hydrocarbonaceous feed, which may be preheated to as high as say 1000 F. or not at all, brings the stream to say 1100 to 1800 F., preferably 1300 to 1600 F. In this temperature range the feed is reformed.

The prevolatilization may be conducted over an even wider range of temperature, depending on the feed and on whether it is desired merely to vaporize a portion of the feed or to convert or pyrolyse it. Where vaporization only is desired, the temperature in the volatilization zone will ordinarily range from 700 to 1500 F. Where conversion is desired, the temperature may range from say 700 F. in the case of low temperature coal carbonization to on the order of 1800" ,F. for relatively light oils.

Pressure is not a critical factor. The pressure in the reforming zone and volatilization zone will normally range from say 1 to p.s.i.a. Pressures above or below this range are operable, but will not normally be used.

Reaction time is an important factor in certain phases of the process. Thus, for example, it is desirable that the time between introduction of the recycled gas into the reforming zone and introduction of the hydrocarbonaceous feed be not more than say 2 seconds and preferably between about 0.01 and about 1.0 second. By keeping the time in this stage short, the presence of free hydrogen radicals is favored. As pointed out above the presence of H- radicals results in more combined hydrogen in the product gas, or looked at another way, converts more of the carbon in the feed into gaseous fuel.

To assist in securing the short contact time, it is preferred to have the velocity of the combined stream in the initial portion of the reforming zone quite high, say 30 to 300 ft./sec. At these velocities the solid catalyst is as a practical matter, necessarily present as a dilute or disperse phase suspension.

The reaction time in the remainder of the reforming zone, i.e. after introduction of the hydrocarbonaceous feed is not especially critical and will normally range .from say 0.2 to 20 seconds.

In the volatilization zone the contact time is again not especially important and need only be sufiicient to volatilize a maximum proportion of the hydrocarbonaceous feed. Usually this will range from say 0.05 to 10 seconds.

The propontion of the various components introduced into the reaction zone will vary considerably, depending on factors such as the composition of the hydrocarbonaceous feed, the product desired and the temperatures employed. Based on one part by weight of feed, or of volatilized feed where a prevolatilization step is used, between about 0.3 and about 3.0 parts by weight of steam, between about 0.1 and about 1.0 part by weight of recycled gas and between about 5 and about parts by weight of catalyst are introduced into the reaction zone.

So far as the volatilization zone is concerned, the proportions of the several materials introduced thereto are not especially significant. Since the solids present in the zone are normally the source of heat for the volatilization it is of course usually necessary that the amount of such solids be sufficient to supply enough heat to carry out the desired volatilization. Similarly carrying gas will be present in a sufiicient amount to give a disperse phase sus pension. As a general indication, it may be said that in the volatilization zone, per unit weight of feed introduced there will be present between about 5 and about 150 units of hot recirculated solids and between about .01and about 3.0 units of carrying gas.

The particle size of the catalyst and catalytically inert particles will depend on details of the specific process to be used. Where no pre-volatilization is carried out, the particle size of the catalyst will normally range from 0.0008 to 0.08 inch. If a prevolatilization step is used and the inert solids are mixed with the catalyst the inert solids are preferably smaller or larger than the catalyst to facilitate the mechanical separation of the two solids. It will be understood that other bases for separating catalyst from inert solids than particle size may be used. For example, an extremely dense catalyst may be employed and separation by elutriation may be carried out.

In such case the catalyst and inert solid may have the same particle size range.

Where completely different flow paths are established for the catalyst and inert solids, there need be no particular relation between the particle sizes of the two types of solids. Generally both will be between about 0.0008 and about 0.08 inch.

The invention will be further described with reference to the accompanying drawings in which:

FIG. 1 is a schematic flow diagram of a system embodying the invention in which there is no prevolatilization zone.

FIG. 2 is a schematic flow diagram of another system embodying the invention in which a prevolatilization step is carried out using catalytically inert solids and the catalytically inert solids are subsequently mixed with solid reforming catalyst.

FIG. 3 is a schematic flow diagram of a further system embodying the invention in which a prevolatilization step is carried out using catalytically inert solids and in which there is no mixing of catalytically inert solids and solid reforming catalyst.

Referring first to FIG. 1, a simple reforming system according to the invention comprises a reaction tube having an upstream section 11 and a downstream section 12. The upstream section 11 is separated from the downstream section 12 by a feed line 13. The reaction tube empties into a separation device 14 which may be a cyclone separator or may be any other conventional type of solids-gas separating apparatus. A line 15 is provided for conveying gases separated in the separation device 14 to a Venturi scrubber 16. A line 17 furnishes water or liquid hydrocarbons to the scrubber 16 and water and/ or liquid hydrocarbons are removed from the scrubber through a line 1%. A line 19 is provided for conveying gases from the scrubber 16 to further recovery apparatus, not shown. A line 20 connecting to the line 19 is provided for conveying a portion of the gases flowing through line 19 back to upstream section 11 of the reaction tube 10. A line 21 also connected to the upstream portion 11 of the reaction tube 10 is provided for furnishing steam to the reaction tube.

The solids separated from gases in the separation device 14' are drawn from the device 14 by means of a line 22. The line 22 discharges into a regeneration tube 23. A burner 24 is provided at one end of the regeneration tube 23 and

lines

25 and 26 are provided for furnishing fuel and air to the burner 24. The regeneration tube 23 discharges into a separation device 27 which is preferably also a cyclone separator. A line 28 is provided for removing the gases separated from solids in the separator 27. A line 29 is provided for conveying solids from the separator 27 back to the upstream section of the reaction tube 10.

In operation a hydrocarbonaceous feed, normally a liquid hydrocarbonaceous material having not more than a trace of ash is delivered to the reaction tube 10 through the line 13. In the reaction tube 10 the feed meets a stream of steam and finely divided solid reforming catalysts entrained therein. This stream is at a temperature of about 1150 F. and 2150 F. and is moving at between 30 and 300 ft./ second. The catalyst is present as a dilute or disperse phase suspension. The stream also contains newly formed hydrogen produced as the result of reforming recycled product gas as will be described in more detail below.

Under the conditions set forth the hydrocarbonaceous feed is reformed to produce a fuel gas containing light hydrocarbons normally having a heating value of about 1000 B.t.u. per cubic foot. The stream flowing through the reaction tube 10 is delivered into the separation device 14. Here the solids, i.e. catalyst and non-vaporous residue of reformation which is deposited on the catalyst, are separated and removed through line 22. The gaseous product which comprises light hydrocarbons, some hydrogen and steam are removed overhead through the line 15. It is then delivered to the Venturi scrubber 16 where it meets a stream of water or liquid hydrocarbons at substantially ambient temperatures. In the scrubber 16, very finely divided solids which may escape from separator 14 are removed from the gases and the temperature of the gases which is usually about 1100 F. to 1800 F. is reduced as they enter the scrubber to a suitable temperature, such that further reaction is prevented. In the scrubber 16 the steam introduced through the line 15 is condensed and is removed through the line 18 along with the quenching water and/or liquid hydrocarbons. The major portion of the product gas is removed from the scrubber through line 19 and sent to fuel lines or burners or else treated for further recovery in a manner not shown. A fraction of the product gas is drawn off the line 1% through the line 20 and is returned to the upstream section 11 of the reaction tube 10. Steam is also furnished to the upstream section 11 through the line 21.

Returning to the solids removed from the reaction stream in the separation device 14, these solids are delivered to the regeneration tube 23 via line 22. A mixture of fuel and air is delivered to the burner 24 through

lines

25 and 26. The air furnished is in excess of that required to burn the fuel introduced through line 25. In the burner 24 the fuel undergoes combustion and a mixture of flue gas and excess air is delivered into the regeneration tube 23 where it meets the solids drawn from line 22. The carbonaceous residue deposited on the solids in the reaction tube 10 is burned by means of the excess air and the catalyst is thereby regenerated and reheated to 1200 to 2200 F. The mixture of the regenerated catalyst and flue gas is delivered through the tube 23 into the separation device 27. Flue gas is drawn off through the line 28 whence it may be sent to the stack, or to heat recovery equipment as desired. This is not shown.

The regenerated catalyst separated in the device 27 is drawn off through line 29 and charged to the upstream section 11 of tube 10. Thus it will be seen that in the upstream section 11, there is formed a mixture of steam, recycled product gas and hot catalyst. The catalyst at this point is between about 1150 F. and 2150 F. Under these conditions the recycled product gas undergoes reformation producing hydrogen, the catalyst functioning as a catalyst and also as a heat carrier to furnish the necessary heat for the endothermic reforming of the recycled product gas and subsequently for the reforming of the hydrocarbonaceous feed. The velocity of the mix ture in the section 11 of tube 10 is high, i.e. between about 30 and 300 ft./sec. The length of the upstream section 11 of tube 10 is such that the time involved be tween the introduction of hot catalyst from line 29 and the introduction of the hydrocarbonaceous feed through the line 13 is on the order of 0.01 to 2 seconds. This insures that the mixture into which the feed is delivered will contain a relatively high proportion of free hydrogen radicals. The effect of these radicals on the feed being introduced is to increase the proportion of light hydrocarbons in the product gas or to increase the proportion of carbon atoms present in the feed which are converted to light hydrocarbons.

As pointed out earlier in this application the introduction of a hydrocarbonaceous feed containing high proportions of ash, sulfur or Conradson carbon tend to deactivate the reforming catalyst in short order and thus adversely affect the economic operation of the process. The system shown in FIG. 2 is designed to avoid this possibility.

Referring to FIG. 2, a system according to a second embodiment of the invention comprises a reaction tube 50 comprising a volatilization section 51 and a reforming section 52. A feed line 79 empties into the volatization section 51. A preliminary reforming tube 53 empties into the reaction tube Stl, and the point at which the preliminary reforming tube 53 joins the reaction tube i) marks the division between the volatilization section 51 and the reforming section 52 of the tube 56.

The tube 52 discharges into a classifier 54. The classifier may be any of the types well known to the art which is capable of separating solids of two difierent particle sizes from gases and from each other. One convenient arrangement comprises a cyclone separator 5dr: discharging separated solids into a mechanical gas separator 54b. A line 55 is provided for delivering gases separated in the classifier 54 to a Venturi scrubber S6. A line 57 supplies Water or liquid hydrocarbon to the scrubber 56 and a line 58 is provided for removing liquids from the scrubber. A line 59 is provided for removing non-condensed gases from the scrubber 56. A line 66 is provided at the bottom of the classifier 5 5 for removing small size solids therefrom. The line 60 empties into a regeneration tube 61. A burner 62 connects to the tube 61 via a line 63. The tube 61 discharges into a cyclone separator 64.

Lines

65 and 66 are provided for furnishing air and fuel to the burner as. A line 67 is provided for conveying solids from the bottom of separation device 54 to the preliminary reforming tube 53. A line 68 is provided for recycling product gas from the line 59 to the tube 53. A steam line 69 furnishes steam to the preliminary reforming tube 53.

A line 7t} is provided for removing relatively large size solids from the classifier 54. A portion of these solids is delivered through a branch 71 to a crusher 72. The remaining solids removed from the classifier flow from line 70 to a second branch 71a. A line 73 is provided for removing solids from the crusher 72. A line '74 having a valve 75 is provided for moving a portion of the solids in the branch 71a to the line 73. A line 76 is provided for conveying the combined solids from

lines

73 and 74 to the volatilization section 51 of the reaction tube 50. A line 77 having a valve 78 is provided for removing a part of the solids in branch 71a as product.

In operation a hydrocarbonaceous feed is introduced through the line 79 into the volatilization section 51. This feed may be a comparatively light hydrocarbon as in the embodiment of FIG. 1 or it may be a heavy hydrocarbon such as Bunker C fuel oil, or even a solid material such a coal, oil shale or lignite. As it is introduced into the section 51 the feed meets a swiftly moving gasiform stream of hot finely divided catalytically inert solids. These solids are preferably coke or char formed in the process but may be other materials such for example as sand or alumina. They are at a temperature which is suflicient to volatilize the feed, which, as indicated above, may range from say 1000 F. to 1500 F. The solids in the stream are preferably present as a disperse phase and the stream moves at a velocity on the order of 30 to 300 ft./sec.

Upon introduction into the section 51 the feed is volatilized. This may occur either as a simple vaporization process or a certain degree of pyrolysis may be effected. In any case, the combined stream including inert solids, carrying gas and volatilized feed are delivered into the reforming section 52 of the reaction tube 50. Here it meets a stream comprising hot reforming catalyst, steam and newly formed hydrogen introduced into the reaction tube 50 from the preliminary reforming tube 53. Just prior to its introduction into the duct Stl the stream in tube 53 is at say 1150 F. to 2150 F. After mixing in reforming section 52 the combined stream has a temperature of say 1100 F. to 1800" F.

In the reforming section 52 the hydrocarbonaceous feed introduced through line 79 is reformed to give a gas consisting principally of light hydrocarbons. The mixture of product gas, catalyst, steam and catalytically inert solids is introduced from the reaction tube 50 into the cyclone 54a of classifier 54. The vaporons components of the stream are removed via line 55 and are introduced into the scrubber 56 where they are cleaned and quenched by means of water or liquid hydrocarbons. Steam is thereby condensed leaving hydrocarbonaceous. gases to be removed through line 59.

The solids separated from the product gas in cyclone 54a are divided into two portions in the mechanical air separator 54b. The smaller'sized solids, which are preferably the catalytic material, are removed from the classifier 54 through the line 60 and are delivered into the regenerating tube 61. A mixture of air and fuel is formed in the burner 62 and is burned to give a mixture of hot flue gases and air. This mixture is delivered through line d3 into the tube 61. It picks up the contaminated catalyst from the line 60 and carries it along the tube 61. In the tube 61 the catalyst is regenerated and reheated, the excess air introduced through line 65 serving to burn off any residue deposited on the catalyst. The regenerated catalystis delivered to separator 64 where it is separated from flue gases. It is then returned via line 67 to the preliminary reforming tube 53.

A portion of the product gas removed through line 59 is taken through line 68 to the preliminary reforming tube 53. Steam is delivered to this tube through line 67. When the hot catalyst (1200 F. to 2200 F.) is delivered into the mixture of recycled product gas and steam, the product gas is reformed to produce hydrogen. The length of the tube 53 and the velocity of the gas are again calculated so that the gases introduced into the reaction tube 59 contain a relatively large proportion of free hydrogen radicals. As indicated above this enhances the heating value of the product gas.

Returning to the classifier 54, larger size solids are removed therefrom through the line 70, A portion of these solids is sent via branch 71 to the crusher 72. Here they are reduced in size. This is desirable because there is always a certain amount of build up in the particle size during the volatilization process. Upon being removed from the crusher the solids are mixed with non-crushed solids from branch 71a, transferred via line 74 and valve 75. The mixture is sent via line 76 to the volatilization section 51 of reaction tube 50 and is entrained as a dilute or disperse suspension in a carrying gas such as steam, introduced into the tube 54) via a line 80. The solids at a temperature of about 1100 F. to 1800 F. are carried through the section 51 at a velocity of 30 to 300 ft./sec. and are contacted with fresh feed as described above. If desired a portion of the solids removed from the classifier 54 through line 70 can be removed as product through line 77 and valve 78.

In certain instances the introduction of large quantities of catalytic inert solids into the reaction tube of the system shown in FIG. 2 may seriously cut down the output rate of product gas. To avoid this difficulty it may be desirable to completely divorce the volatilization zone from the reaction zone.

The embodiment of FIG. 3 provides this separation. Referring to FIG. 3 the system shown therein comprises a volatilization section indicated generally as and a reaction section indicated at 101. The volatilization section comprises a volatilization tube 102 which empties into a separator 105. A line 104 is provided for removing the volatilized products from separator 103. Line 104 connects with the reaction section in a manner to be described.

The volatilization section further comprises a heating tube 195 which empties into a separator 106. A line 107 is provided for carrying solids removed in the separator F3 to the heating tube 165. A line 108 is provided for furnishing a carrying gas to the heating tube 105. A line 169 extends from the bottom of the separator 106 to the volatilization tube 102. A line 110 is provided for furnishing a carrying gas to the volatilization tube and a line 111 is used to deliver feed to the volatilization tube 102.

The reaction section 101 comprises a reforming tube 112 having an upstream section 113 and a downstream section 114. The line 104 which, as noted above, is provided for removing vapors from the separator 103 of the volatilization section 100 empties into the reforming tube 112 of the reaction section 101. The point at which the line 104 joins the tube 112 divides the upstream section of that tube from the downstream section.

The tube 112 empties into a separator 115. A line 116 is provided for removing gases from the separator 115 and delivering them to a Venturi scrubber 117. A line 113 is provided for delivering a quenching liquid such as water or liquid hydrocarbons to the scrubber 117. A line 119 removes liquid from the scrubber. Scrubbed and quenched gases are removed from thescrubber through line 120. A line 121 is provided for returning a portion of the gases removed through line 120, to the upstream section 113.

A line 123 extends from the bottom of separator 115 and empties into a regeneration tube 124. The regenerattion tube 124 empties into a separator 125. Line 126 is provided for removing gases from the separator 125. A line 127 extends from the bottom of separator 125 to the upstream section 113 of reforming tube 112 and permits solids separated in separator 125 to be returned to the upstream section 113. A burner 128 is provided and is connected via line 125 to the regeneration tube 124. Lines 130 and 131 furnish air and fuel to the burner 128.

In operation, a hydrocarbonaceous feed is delivered to the volatilization tube 102 via line 111. As in the embodiment of FIG. 2 this feed may be almost any solid or liquid hydrocarbonaceous material. In the volatilization tube 102 the feed meets a swiftly moving stream of carrying gas and dispersed solids. The solids are catalytically inert and may be coke, sand, alumina or any similar material. The temperature of the stream into which the feed is introduced is sufficient to cause volatilization of the feed either by vaporization, by pyrolysis or by a combination of the two. The combined stream containing volatilized product, carrying gas and non-volatile material is delivered into the separator 103. The volatile material is removed via line 104 and delivered to the reaction section 101 for further processing as will be described below.

The non-volatile material containing solids and volatilization residue deposited thereon is carried via line 107 to the heating tube 105. Here this material meets a stream of carrying gas introduced through line 108 containing free oxygen and is partially burned. As a result the unburned remainder is raised in temperature. The mixture of products of combustion and unburned residue is delivered into the separator 106.

The gases are removed via line 132 and the solids, which are now at a temperature between about 800 and 1600 F., are returned via line 109 to the volatilization line 102. They are entrained in a carrying gas, e.g. steam, introduced through line 110, meet fresh feed from line 111 and volatilize it as described above.

An auxiliary fuel may be introduced along with air in the line 108. An auxiliary fuel will normally be used where the amount of residue produced in the volatilization tube 102 is not suficient to meet the heating requirements of the volatilization step or where it is desired to recover a part of the residue as product. For example, when the feed is a residuel fuel oil such as Bunker C fuel oil and the solids circulated in the volatilization section are coke, additional coke will usually be formed in the volatilization zone, both as an outer layer on the coke already in the process and as fresh particles. It may be desirable to recover coke as product and for this purpose a line 133 is provided leading from separator 106.

Turning now to the volatilized material removed from separator 103 through line 104 this is introduced into the reforming tube 112. As it is introduced it meets a swiftly flowing stream of steam, newly formed hydrogen, recycled product gas and dispersed therein a solid finely divided reforming catalyst. The volatilized material from line 104 is thereby reformed to produce a gas comprising light hydrocarbons and having a relatively high heating value. The combined product stream is delivered to separator 115. Gaseous components are removed via line 116 and sent to the scrubber 117 where they are cleaned and quenched to between about 60 and about 125 F. Product gas is removed through line 120.

The solids separated in separator are carried through line 123 to the regeneration tube 124. Excess air and fuel are furnished to the burner 128 through lines 130 and 131 respectively. The fuel is burned and the resulting mixture of air and flue gases are delivered via line 129 to the regeneration tube 124. Here they pick up foul catalyst introduced into the line 124 through line 123, and by means of the excess air and hot flue gas, the catalyst is regenerated and reheated. The reheated catalyst is separated from flue gases in the separator and is returned to the upstream section 113 of the reforming tube 112 via line 127. Steam is furnished to the section 113 via line 122, where it mixes with recycled product gas introduced through line 121 and with hot regenerated catalyst introduced through line 127. The mixture is at a temperature of 1150 F. to 2150 F. The recycled product gas is thereby reformed, producing hydrogen and the length of the upstream section 113 is again calculated so that when the feed is introduced through line 104, the hydrogen produced by reforming the recycled product gas is present to a relatively large extent in the form of free radicals. As indicated above this greatly increases the yield of high heating value product gas.

The invention will be further described with reference to the following specific examples which are given for purposes of illustration only and are not to be taken as in any way restricting the invention beyond the scope of the appended claims.

Example 1 Using the system of FIG. 1, 10,000 lbs/hr. of a gas oil feed having the characteristics set forth below are introduced through line 13 at 210 F.:

Wt. Percent Total H 15 Total C 84.5

Ash trace Conradson carbon 0.015

Specific gravity, 0.8431.

1,850 lbs/hr. of steam and 286,000 lbs/hr. of catalyst at 1700 F. are introduced into tube 10 through

lines

21 and 29. The catalyst has the following specification:

Percent Nickei 5 Ceramic support 95 smaoas 1 1 isrecovered, exclusive of material recycled. This gas analyses as follows:

Percent by volume Using the system of FIG. 2, 10,000 lbs/hr. of a Bunker C fuel oil are charged to reaction tube 50 through line 79. This oil has the following characteristics:

Specific gravity, 0.970

Analysis: Percent by weight C 87.1 H 10.9 S 2.0 Ash 0.047

Conradson carbon (percent by Weight), 10.5.

In the tube 50 the feed is met by a stream of steam containing 2 lbs/cu. ft. of 50x14 mesh coke at 1400" F. The feed is thereby volatilized.

297,000 lbs./ hr. of a reforming catalyst 200 X 100 mesh consisting of 5% nickel on 95% ceramic base, 840 lbs/hr. of 15 p.s.i.g. steam, and 4,850 lbs/hr. of recycle gas are mixed in the preliminary reforming tube 53. The temperature of the mixed stream is 1630 F. and the pressure is 17.5 p.s.i.a. After a total contact time of 2 seconds the mixture in preliminary reforming tube 53 is delivered to reaction tube 50. The combined stream is at a temperature of 1500 F. Pressure is 17.0 p.s.i.a. Reaction time (before quenching) is 3 seconds.

257,000 lbs/hr. of coke are removed through line 70. 256,000 lbs./hr. are returned to tube 50. 1,000 lbs/hr. are Withdrawn through valve 78.

7,200 lbs/hr. of product gas are removed from the system. This gas analyses as follows:

Example 3 10,000 lbs./hr. of a Bunker C fuel oil are charged to the system of FIG. 3 through line 111. This oil has the following characteristics:

Specific gravity, 0.946.

Percent Analysis: by weight S 1.4 Ash 0.0-1

Conradson Carbon (percent by weight), 7.09.

In the line 102, the feed meets a stream of steam containing 2.0 lbs/cu. ft. of 50x14 mesh coke at 1400 F. The feed is thereby volatilized. 149,000 lbs./ hr. of coke at 1250 F. are delivered to line 105 via line 107, where they.meet.l1,100 lbs/hr. of air. The coke is partially burned together with 175 lbs/hr. of Bunker C fuel oil introduced through line 132. 9,250 lbs/hr. of volatilized feed is delivered to duct 114 via line 104. Here it meets a stream of reforming catalyst, steam and newly-formed hydrogen at .1625 F. The volatilized feed is thereby reformed to give 7500 lbs/hr. of product gas which is withdrawnfrorn line 120 and which analyses as follows:

Percent by volume H 26.6 CH, 21.8 C l-I 23.8 C H 2.0 C H 34 C 51 01 (34 8 0 5 C s 03 CO 13 1 C6 84 4,650 lbs/hr. of product gas is recycled through line 121. 79,000 lbs./ hr. of regenerated catalyst are recycled through line 127. The total contact time in the upstream portion 113 of the tube 112 between the introduction of regenerated catalyst from 127 and the intro duction of volatilized feed from 104 is about 0.2 second.

The pressure in both the volatilization section and the reforming section 101 is substantially atmospheric.

I claim:

1. In a process for the catalytic reforming of solid and liquid hydrocarbonaceous material to make a product gas comprising light hydrocarbons, the improvement which comprises forming a hot gasiform stream of steam, entrained finely divided solid reforming catalyst and recycled product gas, reforming said product gas in saidstream to form hydrogen, injecting a hydrocarbonaceous material selected from the group consisting of solid and liquid hydrocarbonaceous materials into said stream containing newly formed hydrogen to reform said hydrocarbonaceous material and to give a product containing normally gaseous components, and recovering said product from said last named stream.

2. A 'method for the catalytic reforming of solid and liquid hydrocarbonaceous materials which comprises injecting a hydrocarbonaceous material selected from the group consisting of solid and liquid hydrocarbonaceous materials into a hot moving gasiform stream containing steam, entrained finely divided solid reforming catalyst and newly formed hydrogen to give a combined gasiform stream and reforming said hydrocarbonaceous material in said combined stream to form vaporous components including normally gaseous components and non-vaporous components, separating the vaporous components from the non-vaporous components of said combined stream, recovering a portion of the vaporous components of said combined stream as product gas and recycling another portion of said vaporous components to said hot moving stream.

3. The method claimed in claim 2 and comprising regenerating the catalyst separated from the combined stream and using the regenerated catalyst in forming the hot moving stream.

4. In a process for the catalytic reforming of solid and liquid hydrocarbonaceous materials, to form a product gas comprising normally gaseous hydrocarbons, the improvement which comprises forming a gasiform reaction stream comprising steam, recycled product gas and entrained finely divided reforming catalyst, and reforming said product gas in said stream to produce hydrogen, introducing a hydrocarbonaceous feed selected from the group consisting of solid and liquid hydrocarbonaceous materials into a gasiforrn volatilization stream of entrained hot finely divided catalytically inert solids and thereby volatilizing said hydrocarbonaceous feed with the deposition of a residue on said inert solids, introducing the volatilized feed into said reaction stream, reforming said volatilized feed in the presence of the newly produced hydrogen to give a product containing normally gaseous components and recovering said product.

5. In a process for the catalytic reforming of solid and liquid hydrocarbonaceous materials which contain components tending adversely to afiect the activity of reforming catalysts to produce a gas containing light hydrocarbons, the improvement which comprises introducing a hydrocarbonaceous material selected from the group consisting of solid and liquid hydrocarbonaceous materials into a hot moving gasiform volatilization stream of entrained finely divided catalytically inert solids to volatilize said hydrocarbonaceous material, introducing the volatilization stream containing volatilized hydrocarbonaceous material into a gasiform reaction stream containing entrained finely divided reforming catalyst, steam, and newly formed hydrogen, reforming the volatilized hydrocarbonaceous material in said reaction stream to give a product comprising normally gaseous components and recovering said product from said reaction stream.

16. The process claimed in claim and comprising forming a gasiform mixture of the product gas with steam and hot finely divided catalyst, reforming said product gas in said mixture to produce hydrogen and using the mixture including the newly produced hydrogen as the gasiform reaction stream into which the volatilized hydrocarbonaceous material is introduced.

7. The process claimed in claim 5 wherein the particle size of said inert solids is substantially ditferent from the particle size of said catalyst and comprising the steps of separating solids from the combined vaporization and reaction streams and separating the catalyst from the inert solids.

8. The process claimed in claim 7 and comprising reheating the separated catalyst and returning it to the reaction stream.

9. The process claimed in claim 8 and comprising regenerating the catalyst during the reheating step.

10. A process for catalytically reforming solid and liquid hydrocarbonaceous materials to produce a gas containing light hydrocarbons which contains components tending adversely to affect the activity of reforming catalysts comprising introducing a hydrocarbonaceous material selected from the group consisting of solid and liquid hydrocarbonaceous materials into a hot gasiform volatilization stream containing entrained finely divided catalytically inert solids, at least partially volatilizing said material in said volatilization stream and depositing components adversely affecting catalyst activity on said catalytically inert solids, separating the vaporous components including volatilized hydrocarbonaceous material from non-vaporous components of said volatilization stream, introducing the volatilized hydrocarbonaceous material into a hot gasiform reaction stream containing entrained finely divided reforming catalyst, steam, and newly formed hydrogen, reforming the volatilized hydrocarbonaceous material in said reaction stream in the presence of said newly formed hydrogen and recovering product gas from said reaction stream.

11. The process claimed in claim 10 and comprising forming a gasiform mixture of the product gas with steam and hot finely divided catalyst, reforming said product gas in said mixture to produce hydrogen and using the mixture including the newly produced hydrogen as the gasiform reaction stream into which the volatilized hydrocarbonaceous material is introduced.

References Cited in the file of this patent UNITED STATES PATENTS 1,681,238 James Aug. 21, 1928 1,951,725 Christ Mar. 20, 1934 2,840,462 Gorin June 24, 1958 2,860,959 Pettyjohn Nov. 18, 1958 2,882,138 Pettyjohn et al Apr. 14, 1959 2,884,303 Metrailer Apr. 28, 1959 2,907,647 Linden Oct. 16, 1959 FOREIGN PATENTS 522,640 Great Britain June 24, 1948

Claims

4. IN A PROCESS FOR THE CATALYTIC REFORMING OF SOLID AND LIQUID HYDROCARBONACEOUS MATERIALS, TO FORM A PRODUCT GAS COMPRISING NORMALLY GASEOUS HYDROCARBONS, THE IMPROVEMENT WHICH COMPRISES FORMING A GASIFORM REACTION STEAM COMPRISING STEAM, RECYCLED PRODUCT GAS AND ENTRAINED FINELY DIVIDED REFORMING CATALYST, AND REFORMING SAID PRODUCT GAS IN SAID STREAM TO PRODUCE HYDROGEN, INTRODUCING A HYDROCARBONACEOUS FEED SELECTED FROM THE GROUP CONSISTING OF SOLID AND LIQUID HYDROCARBONACEOUS MATERIALS INTO A GASIFORM VOLATILIZATION STREAM OF ENTRAINED HOT FINELY DIVIDED CATALYTICALLY INERT SOLIDS AND THEREBY VOLATILIZING SAID HYDROCARBONACEOUS FEED WITH THE DEPOSITION OF A RESIDUE ON SAID INERT SOLIDS, INTRODUCING THE VOLATILIZED FEED INTO SAID REACTION STREAM, REFORMING SAID VOLATILIZED FEED IN THE PRESENCE OF THE NEWLY PRODUCED HYDROGEN TO GIVE A PRODUCT CONTAINING NORMALLY GASEOUS COMPONENTS AND RECOVERING SAID PRODUCT.