FI61514B - FOERFARANDE FOER REGENERERING AV PARTIKELFORMIG ANVAEND KATALYSATOR - Google Patents

Description

[β] Publication 51514 1 J '^ UTLAGGN I NGSSKRI FT ° 1 °' * C (45); . ! · R: ‘3 ci; 1, .3

VjöiJ / iaf ”3‘ 6 ^ tO G * 11/18 (51) Kv.ik. / Intel. B 01 J 23/90 FINLAND — FINLAND (21) Pttmttlhaknmu · - PttMCanaBkitinf 762613 (22) HakmnlipUvi —Ameknln |> dkg 10.09 · 76 ^ (23) Alkuptivi — Glttl | httsdag 10.09.76 (41) Has become public - Bllvlt off .77

Patent and Registry Administrators .... ...... .... . .....

1 (44) Date of issue and date of issue. -

Patent and Registration Office AmBlun utlagd och utl-skrlton publtcmd 3O.O4.82 (32) (33) (31) Privilege claimed — B ^ ird prlorltet 29.09.75 USA (US) 617 ^ 7 ^ (71) U0P Inc. , Ten U0P Plaza, Algonquin & Mt. Prospect Roads, Des Plaines, Illinois 600l6, USA (72) Algie James Conner, Downers Grove, Illinois, Laurence Oliver Stine,

Western Springs, Illinois, USA (US) (7 * 0 Berggren Oy Ab (5 * 0 Method for regenerating a particulate spent catalyst -Förfarande for regenerering av partikelformig, använd katalysator

Our Finnish patent application no. (a) introducing said spent catalyst and oxygen-containing regeneration gas into a first dense bed of fluidized particles and partially regenerating said catalyst therein by combusting said carbon black to form a partially used CO-containing regeneration gas; (b) directing the resulting partially regenerated catalyst and partially spent regeneration gas directly upstream of said dense bed as a dilute phase via a dilute phase transfer device and further combusting carbon black from said partially regenerated catalyst; 2,61514 (c) separating the obtained regenerated catalyst from the regeneration gas; (d) recovering the regenerated catalyst as a second dense particulate layer; and (e) removing the regenerated catalyst from the second dense sublayer for return to the conversion zone.

This application is directed to a process as described in which a liquid catalytic cracking catalyst contains catalytically effective amounts of a CO conversion accelerator.

The present invention thus relates to a process for regenerating a spent catalyst contaminated with carbon black, which catalyst is removed from a hydrocarbon conversion zone, in which the spent catalyst and oxygen-containing regeneration gas are fed to the first dense bed of fluidized particles and regenerated. providing a partially spent CO-containing regeneration gas, forming the partially regenerated catalyst and the partially used regeneration gas directly from the dense bed as a dilute phase in a dilute phase transfer device and thereby providing further combustion of carbon black from the partially regenerated catalyst; in a phase transfer device, the regenerated catalyst obtained is separated from the regeneration gas, and the process is characterized in that it is used in partial form a spent catalyst containing catalytically effective amounts of a metal oxide which promotes CO conversion.

The CO conversion promoter may contain one or more noble or non-precious metal oxides. Preferred noble metal oxides are platinum oxide and palladium oxide. Preferred non-precious metal oxides include vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and rare earth oxides.

3,61514 Catalytically effective amounts of the CO conversion agent are preferably 0.5 to 200 ppm by weight of the total FCC catalyst for the noble metals and 0.01 to 20 weight percent of the total FCC catalyst for the non-precious metals.

Another preferred feature is that substantially complete conversion from C0 to CO2 occurs in the dilute phase transfer device. The term "substantially complete" means that the CO content of the regeneration gas used has fallen below 1000 ppm by weight, preferably less than 500 ppm.

All the requirements set out in the application mentioned at the beginning are also among the recommended features of the present process.

The invention will now be described in more detail with reference to the drawings, in which Figure 1 schematically shows a particular device suitable for carrying out the present invention and Figures 2 and 3 show alternative devices also suitable for carrying out the invention, Figure 3 shows how the invention can be applied to an existing recovery vessel.

Figure 1 shows a regeneration device 100. The first dense mattress] is connected via a transfer zone 28 to one end of the vertical dilute phase riser 2. The catalyst gas separation device 3 is connected to the outlet 7 of the transfer riser 2. The regeneration gas from the separation device 3 enters the separation space 5, then to the separation device 4 and then exits at 26 to the pressure chamber 27. The gas exits the chamber 27 and the regenerator 100 through the outlets 8 and 8. The separated catalyst from the separators 3 and 4 is led to a second sealed mattress 6.

The spent catalyst enters the first sealed mattress 1 via a pipe 9. The surface of the mattress 1 shown in 10 is in the transfer zone 28 between the mattress 1 and the riser 2. Fresh regeneration gas enters the mattress 1 through a pipe 11 through a distributor 12 which disperses the gas into the mattress 1. As air is preferred, the invention 4,61514 is described below in connection with the use of air, but this statement does not exclude the use of other gas mixtures. with very oxygen-enriched or oxygen-poor air. The dispensing device 12 may be a metal plate with holes or slits, or preferably a pipe mesh. Both types of dispensers are well known. In the dense mattress 1 there is a controlled oxidation of the carbonaceous karsts. The gas and catalyst are transported from the mattress 1 through the transfer zone 28 to the transport riser 2, where the oxidation of carbon monoxide can take place.

The suction pipe 2 is vertical and its inlet opening is at the bottom and the outlet opening 7 near the upper end. The outlet 7 may be one or more openings located at or near the upper end of the riser 2 to allow the catalyst and gas to enter the separation device 3. The separation device 3 connected to the outlet 7 is usually a cyclone separator which substantially separates the gas from the accompanying catalyst. The separator 3 may have 1 to 4 cyclones. Substantially catalyst-free gas passes through the outlet 13 as the catalyst flows through the immersion tube 14 directed towards the second sealed mattress 6. The separation device 3 can be dispensed with to allow the gas leaving the outlet 7 and the catalyst to enter the space 5. The gas can be separated to some extent from the catalyst, but not as much as with the cyclone 3, as shown.

The separation device 4, which is usually a cyclone, has an inlet 16 which receives the regeneration gas and the accompanying catalyst from space 5. The gas and the accompanying catalyst are then substantially separated from each other. The gas leaves the regenerator through the outlet 26, the pressure chamber 27 and the outlets 8 and 8 '. The gas-separated catalyst is led downwards through an immersion pipe 17 to a second sealed mattress 6. One separation device 4 is shown, but more than one can be used.

The immersion tubes 14 and 17 of cyclones 3 and 4 preferably have catalyst outlets above the dense mattress of the catalyst. The submersible outlets may include a butterfly valve at the catalyst outlets to prevent gas and catalyst from flowing up the submersible. The cyclones are designed to operate with open submersible tubes, because if the submersible tubes were "closed" with a dense catalyst bed it would vary the cyclocomposition with variations in the tight mattress height of 5,61514. Thus, the cyclone separation remains constant with the immersion tubes 14 and 17 even if the height of the tight mattress varies. The sinkers 14 and 17 may protrude into the sealed mattress, but this is not preferred.

A combustible fluid, such as fuel gas or liquid hydrocarbon, can be added to the riser 2 through a pipe 20 and a distributor 21. The combustion of such a fluid assists in initiating the process and initiating the afterburning of carbon monoxide in riser 2. Combustion of this combustible material preferably raises the temperature of the catalyst passing through the riser, allowing the temperature of the regenerated catalyst to be controlled.

The second air flow can be led to the riser 2 through the pipe 18 and the distributor 19 to supply oxygen and to maintain the combustion of the added combustible fluid or carbon monoxide.

The height of the catalyst 15 of the second dense mattress 6 is sufficient to overcome the pressure drop in the outlet pipe 22, the control valve 23 and other subsequent devices of any regenerated catalyst.

The tight mattress can be above, below or next to the tight mattress 1. Likewise, the entire regenerator may be above, below or on the side of the reactor using the regenerated catalyst.

The dense mattress 6 may be a stripper as in Figures 1, 2 and 3 or may simply assemble a sufficiently regenerated catalyst in a dense mattress for "pressure" and barrier purposes without stripping.

The catalyst in the mattress 6 moves downwards through a pipe 22 and through a valve 23 which controls the exit of the catalyst from the mattress 6. The valve 23 is usually a spool valve controlled by a reactor temperature controller or a height controller.

The stripping medium can be added to the second sealed mattress 6 through the tube 24 and the distributor 25 to strip the regenerated gas adsorbed and in the intermediate spaces from the regenerated catalyst. Superheated steam is a preferred stripping medium.

.4.- ..

6 61514

Most of the catalyst in the regenerator 2 is preferably in the dense mattress 1, with a smaller part in the dense mattress 6. When steam stripping is used in the mattress 6, the catalyst delay time in this mattress should be less than 1 minute, preferably less than 30 seconds.

Figure 2 shows an alternative device 200 for practicing the present invention.

The spent catalyst enters the first sealed mattress 201 through the inlet pipe 209. The catalyst surface at 210 is in the transfer zone 228. Air is supplied through the tube 211 and distributor 212 to the dense mattress 201. Controlled oxidation of the carbonaceous karsts occurs in the dense mattress 201, allowing the amount of regenerated catalyst karst to be adjusted. The gas and catalyst exit the mattress 201 through the transfer zone 228 to the transport riser 202, where carbon monoxide oxidation can occur.

The transport riser 202 is vertical, with its inlet at the bottom and near the top of its outlets 207 and 207 '. Outlets 207 and 207 'are at or near the upper end of riser 202 and allow catalyst and gas to escape from riser 202. Separation devices 203 and 203', which are usually cyclones, are connected to outlets 207 and 207 *. These cyclones essentially separate the gas from the catalyst. Gas exits the cyclones through outlets 213 and 213 '. The substance in the separation space 205 is essentially a gas with some entrained catalyst. The catalyst exits the cyclones through immersion tubes 214 and 214 'down to a second sealed mattress 206 having a surface at 215. The immersion tubes 214 and 214' may extend below surface 215, although not shown in Figure 2.

Cyclones 203 and 203 'are not required, so that the separation of the catalyst gas after it leaves the riser 202 decreases slightly in efficiency. This would increase the catalyst remaining in space 205 and thus increase the load on the separation device 204.

The separator 204 is usually a cyclone. It has an inlet 216 which receives the gas and the accompanying catalyst from the separation space 205. The gas and the catalyst are substantially separated from each other. The gas exits the cyclone 204 and the regenerator 200 through the outlet 208. The catalyst exits the cyclone 204 through the immersion tube 207 down to the second sealed mattress 206.

The combustible fluid may be added externally through the riser 202 through the manifold 220 and manifold 221 or to raise the temperature in zone 2 sufficiently to initiate afterburning or possibly to raise the temperature of the catalyst passing through the riser. Air can be supplied through line 218 and manifold 219 to provide the oxygen required for combustion in riser 202. Alternatively, gas may be fed through line 218 to cool the catalyst to a predetermined temperature if desired.

The surface 215 in the mattress 206 is high enough to maintain the pressure of the regenerated catalyst high enough to overcome the pressure drops in the outlet pipe 222, the control valve 223, and subsequent devices. Surface 215 can be adjusted to provide the desired catalyst lag time in the mattress.

The catalyst in the mattress 206 moves downward and out of the regenerator 200 through the tube 222. The catalyst discharge rate control valve 223 is a spool valve controlled by a reactor temperature controller or level controller.

A stripping medium, preferably superheated steam, may be fed to the mattress 206 through tubes 224 and 224 'and through manifolds 225 and 225' to strip out the adsorbed and intermediate regeneration gas.

As shown in Figure 1, most of the catalyst in the regenerator 200 is in the first dense mattress. Likewise, if the steam stripping takes place in the second dense mattress, the catalyst has a delay time of less than 1 minute, preferably less than 30 seconds.

Figure 3 shows a possible modification of existing regenerators to provide an apparatus suitable for carrying out the present invention. The existing regenerator 300 is primarily modified to provide a first sealed mattress 301, 8 6151 4 dilute phase transport riser 302, and a second sealed mattress 306.

The spent catalyst enters the mattress 301 through the inlet pipe 309, where the surface is at 310 in the transfer zone 328 between the mattress 301 and the riser 302. Air is supplied through line 311 and manifold 312. Oxidation of the carbon scale takes place in a dense mattress 301. Gas and fluidized catalyst are removed from the mattress 301 through a transfer zone 328 to a riser 302 where oxidation of carbon monoxide can occur.

The combustible fluid can be fed to the riser 302 through the manifold 321 of the pipe 320 to heat the catalyst in the riser. Additional air can be supplied to the riser 302 through the pipe 318 and the manifold 319.

The catalyst and gas exit the riser 302 through the outlet 307 to the separation space 305, The outlet 307 is not a cyclone. The outlet 307 preferably sprays the catalyst and gas downward to reduce the amount of catalyst remaining in the space 305.

The separation device 304, which is usually a cyclone, has an inlet 316 and receives gas and entrained catalyst from space 305. Gas exits the cyclone 304 and regenerator 300 through the outlet 308. The catalyst exits the cyclone 304 through the immersion tube 317 down to the second sealed bed 306. The surface 315 defines the boundary between the second sealed bed 306 and the separation space 305.

The catalyst in the mattress 306 moves downward and exits the regenerator 300 through a tube 322. The catalyst outlet is controlled by a valve 323 controlled by a reactor temperature or height controller.

A stripping medium, preferably superheated steam, may be added to the mattress 306 through a tube 324 and a distributor 325 to strip the regeneration gas from the regenerated catalyst.

The use of a conversion promoter allows the same CO conversion efficiency to occur at or above 55 ° C, which is lower than required when no CO 6 conversion agent is used, or a faster CO conversion efficiency at a specific temperature than which would occur at the same temperature without the use of a CO conversion promoter. The latter advantage is particularly important for commercial use. The use of an agent without a CO conversion promoter requires the uneven distribution of unused regeneration gas in the dense catalyst bed often at higher regeneration zone temperatures or higher regeneration gas rates than is desired to maintain a sufficiently rapid CO conversion so that substantially complete CO conversion occurs. Raising the regeneration zone temperature may require burning the burner oil in the regeneration zone or recirculating larger amounts of waste oil back to the hydrocarbon reaction zone so that the spent catalyst contains more coke that can be combusted in the regeneration zone to raise the temperature. Higher unused regeneration gas velocities, in addition to the need to use fan capacity for them, often overload the separation equipment and produce higher amounts of flue gas-containing waste materials (catalysts) than are allowed by anti-pollution regulations. The use of a CO conversion aid allows the recovery efficiency of the burner oil or increased waste oil to be eliminated, as well as a reduction in the amount of excess unused regeneration gas, thus giving the purifier device more flexibility for the FCC process.

The oxidation rate of coke is not in itself affected by the use of a liquid catalytic cracking catalyst containing a CO conversion promoter, but the rate of CO conversion increases. By using a CO conversion promoter, the constant kinetic rate associated with CO conversion to CO2 can normally be increased by a factor of 2 to 5 and even greater. In this way, a higher rate of CO conversion can be achieved by using a CO conversion promoting agent at a certain regeneration zone temperature as compared with the case where this agent is not used. On the other hand, the same C0 conversion rate can be achieved at a lower regeneration zone temperature than that required in the case where a CO conversion promoting agent is not used.

Suitable catalysts for use in the process of the present invention are generally those that can be liquefied in their physical form in an FCC process that affect hydrocarbon cracking and contain catalytically effective amounts of a CO conversion aid.

The CO conversion agent can be incorporated as a cracking catalyst component into any commonly known silicon and / or alumina-containing amorphous FCC catalyst or "molecular sieve" containing FCC catalysts in the preparation of the catalysts by salting or heating by well known methods such as precipitation or coagulation. by means of an aqueous solution which is heated to dryness and then the salt is removed. Suitable "molecular sieves" include both natural and artificial aluminosilicate-containing substances known in the art, such as faujasite, mordenite, chabasite, zeolite X and zeolite Y.

Example This example demonstrates the benefits of a particular FCC process using a catalyst containing a CO conversion enhancer containing about 10 ppm by weight of platinum oxide. The results obtained before and after the use of this catalyst, which show the advantages, are shown in Table 1 for Experiments 1 and 2.

table 1

Regenerated with and without CO conversion promoter

Test 1 Test 2

Without CO conversion with a CO conversion enhancer

Regeneration zone temperatures, ° C

cyclones 761 705 regenerated catalyst 759 705 first dense layer 737 682

Iina heating device outlet 379 171

Pre-heating feed outlet 308 271 Return of waste oil to the hydrocarbon conversion zone, nvVh 17.2 10.5

Flue gas analysis,% by volume CO2 14.6 15.0 O, 2.8 2.6 CO 2 500 parts by volume <500 parts by volume (parts per million) (parts per million) 11 61514

Prior to the use of the catalyst containing the CO conversion agent, it was necessary to burn continuously without a heater, use a preheater feeder and increase the amount of waste oil returned to the hydrocarbon conversion zone to raise the regeneration zone temperature to less than 500 million flue gas. As shown in Experiment 1, the air heater temperature was 308 ° C and the waste oil recovery rate was 17.2 m / h. Under these operating conditions, the regeneration zone temperatures of 737-761 ° C were obtained, with a C0 content in the flue gas of less than 500 ppm.

The results obtained in Experiment 2 show that the use of a catalyst containing a platinum oxide CO conversion promoter achieved the desired CO content, i.e., less than 500 ppm by volume at a regeneration zone temperature of 55 ° C, which was lower than in Experiment 1. This lower regeneration zone temperature requirement reducing the temperature of the heater from 379 ° C to 171 ° C and reducing the temperature of the preheating feeder from 308 ° C to 271 ° C and reducing the return temperature of the waste oil from 3 3 17.2 m / h to 10.5 m / h. These reductions allowed for savings in operating costs and a small increase in unused gas supply power.

In addition to lower temperatures, the use of a catalyst containing a CO conversion enhancer in other FCC processes allows for a reduction in the rate of unused regeneration gas (air) for the specific feed power required to achieve the desired CO content in the flue gas. In an FCC process unit that is used almost in accordance with the operating principles of cyclone separators, such as in the case of reduction, waste from the unit can in turn be reduced. If the efficiency of the cyclone separation is not a problem, the feed power of the unused regeneration gas may be increased in other units, but not higher than before, resulting in a lower feed power without the use of a catalyst containing a CO conversion additive.

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Claims (7)

A process for regenerating a coke-contaminated particulate used catalyst removed from a piston wheat conversion zone, in which process the spent catalyst and oxygen-containing regeneration gas are fed to a first dense layer of fluidized particles and regenerating a catalyst therein partially burning the coke and producing a partially used, CO-containing regenerating gas, puts the formed, partially regenerated catalyst and the formed, partially used regenerating gas directly from the dense layer into a diluted phase into a transport lift device for the diluted phase and further combustion from the partially regenerated catalyst and further oxidation of at least a portion of CO to CO effective amounts of a CO conversion accelerating metal oxide. Process according to Claim 1, characterized in that the CO conversion of the accelerating metal oxide contains an oxide of one or more base metals. Process according to claim 2, characterized in that the oxide of the base metal is a vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide or an oxide of rare earth alkali metals. Process according to claim 2 or 3, characterized in that the catalytically effective amounts are 0.01-20% by weight of the catalyst. Method according to claim 1, characterized in that the CO conversion of the accelerating metal oxide consists of one or more noble metal oxides.