CN101745435A - Regeneration method and device of catalyst of fluid catalytic cracking - Google Patents
Regeneration method and device of catalyst of fluid catalytic cracking Download PDFInfo
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- CN101745435A CN101745435A CN200810183154A CN200810183154A CN101745435A CN 101745435 A CN101745435 A CN 101745435A CN 200810183154 A CN200810183154 A CN 200810183154A CN 200810183154 A CN200810183154 A CN 200810183154A CN 101745435 A CN101745435 A CN 101745435A
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Abstract
On the basis of the regeneration method of the current catalyst of fluid catalytic cracking, the invention provides a regeneration method and a device of two sections which are regenerated into serial two sections of reverse flow scorching, which can improve scorching efficiency, and is characterized by reliable running, flexible adjustment, reduced usage of oxygen-containing gas, saved energy, compact structure, reduced occupied space and saved investment. The regeneration method and the device in the invention have wide application, can be used in various fluid catalytic cracking processes such as resid fluid catalytic cracking, wax oil fluid catalytic cracking, gasoline catalytic conversion and modification and the like, and can also be used in other gas-solid reaction process including residue oil pretreatment, preparing ethylene by alcohol, fluid coking, flexicoking and the like.
Description
Technical field
The invention belongs to the catalytic cracking field, particularly heavy oil and/or residual oil fluid catalytic cracking carbon-contained catalyst coke burning regeneration technology.More particularly, the reclaimable catalyst that the present invention relates in heavy oil and/or residual oil course of reaction seriously descends because of coking causes catalyst activity, must deliver in the regenerator, at high temperature imports oxygen-containing gas, most incipient scorch are gone, to recover activity of such catalysts.
Background technology
Fluidized catalytic cracker is one of most important petrochemical industry machining process, and purpose is to produce high-quality gasoline and as the liquefied petroleum gas of petrochemical materials from mink cell focus.
Recently, because oil price rise, crude oil itself becomes to heavily waiting factor, and oil refining manufacturer is the higher economic benefit of pursuit, thereby turns to processing more or mix refining normal pressure and/or decompression residuum.So that under the condition that consumes as much crude oil, produce more light liquids oil product.But in heavy oil and/or residual oil, carbon residue and poisonous metal content are higher, in course of reaction, catalyst will deposit a large amount of coke, cause catalyst activity seriously to descend, for this reason must be with the coke burning-off that deposits, to recover its activity in the regenerative process of catalyst.Because the internal surface area of catalyst is very big, the charcoal amount of regenerated catalyst remnants is very big to recovering the influence of activity of such catalysts and selectivity, particularly just more remarkable to molecular sieve type catalyst.For this reason, the regeneration effect of catalyst is had higher requirement.
For the coke on the reclaimable catalyst is burnt the desired degree of technology that reduces to, in order in high temperature coke burning regeneration process, to avoid or reduce the hydrothermal deactivation of catalyst, with abundant recovery activity of such catalysts, it is rational that each patent merchant both domestic and external develops diversified economy, can satisfy the renovation process of above-mentioned requirements.
Adopt the method for segmentation regeneration, can reduce in the regenerative process catalyst inventory effectively and improve the catalyst regeneration effect.USP3,494,858 and USP3,563,911st, the typical example of this respect.Wherein, the former belongs to two-phase up-flow regeneration technology.And the latter is by two fluid beds with the reclaimable catalyst order.At first dense-phase fluidized bed, carry out partial regeneration with first section regeneration oxygen-containing gas, in second dense-phase fluidized bed, contact, to finish whole regenerative processes with second section regeneration oxygen-containing gas.
Above-mentioned patented technology, the reclaimable catalyst order is finished whole regenerative processes by two fluid beds.No matter two-section flowing bed is arranged in parallel (USP3,563,911) or coaxial-type layout (USP3,494,911), because a public dilute phase sedimentation separation section belongs to single device two-stage regeneration type on the structure.In the above-mentioned various two-stage regeneration technologies, what two-stage regeneration adopted is low linear speed back-mixing fluid bed.Under hot conditions, the burning process of catalyst regeneration mainly is subjected to the control of oxygen mass transfer speed, and it is low that gas-affixed touches efficient, makes the overall efficiency of two-stage regeneration technology can not obtain due performance.
USP3,844,973 catalyst regeneration process is finished in first dense bed and dilute phase carrier pipe.Reclaimable catalyst is at first regenerated in first dense bed, and catalyst enters the dilute phase carrier pipe and continues to burn residual charcoal behind partial regeneration, and oxygen concentration remains on higher level in the regenerated flue gas.Regenerated catalyst enters second dense-phase fluidized bed at last.Second dense-phase fluidized bed does not have the function of burning, and this regeneration techniques belongs to the single hop regenerative process basically.But, be the quick conveying type fluid bed of high temperature, elevated oxygen level and high linear speed because this patent adopts at first dense-phase fluidized bed, accelerated the reproduction speed of catalyst greatly.This patent in improvement technology thereafter, as USP4,371,453 and USP4,387,043, second dense bed becomes from stripping section and is settling section, because the restriction of structural design,, a no small catalyst inventory is arranged and do not obtain reasonable use although second dense bed does not have the function of burning.
Chinese patent 97121795.5 adopts two sections fast fluidized bed regenerative operations, and two sections regeneration are on top, and one section regeneration is in the bottom.To contain the coke catalyst at first at the catalyst first fluidized bed, burn reaction; The catalyst of partial regeneration and oxygen gas pass distributor together and on flowing to then, enter catalyst second fluid bed, proceed to burn reaction.For improving the temperature of the first fluidized bed, a part of high-temperature regenerated catalyst returns the first fluidized bed, and flue gas enters smoke energy recovering system.Because first section regeneration oxygen gas is as second section regeneration gas, i.e. reclaim equiment and technological process have been simplified in regeneration gas series connection, and first section regenerated flue gas heat is fully used.But,, can't realize normal control, so commercial plant adopts seldom because catalyst inventory resists the fluctuation anti-jamming capacity poor very little in the regenerative system.
Two regenerators of Chinese patent 97121795.5 arranged superposed, one section regeneration is on top, and two sections regeneration are in the bottom; Be connected as a single entity with the low pressure drop distribution grid between two regenerators, second regenerator flue gas enters first regenerator by the low pressure drop distribution grid, to guarantee the first regenerator dense bed fluidisation.Because eclipsed form is arranged two-stage regeneration, and one section regeneration is on top, and two sections regeneration adopt the low pressure drop distribution grid to connect in the bottom between two sections, help making full use of the flue gas that two sections regeneration contain a certain amount of excess oxygen, thereby can save the oxygen-containing gas consumption.But because one section regeneration is on top, two sections regeneration are in the bottom, and reacting-settler and regenerator all need higher absolute altitude, so the commercial plant investment is very big.
Summary of the invention
The objective of the invention is on the basis of the renovation process that has FCC catalysts now, propose a kind of two sections and be regenerated as two sections renovation process and devices thereof that series connection is regenerated that adverse current is burnt, improve and burn efficient, and it is reliable to have running, regulates flexibly, reduces the oxygen-containing gas consumption, energy savings, compact conformation reduces and takes up an area of the characteristics of reducing investment outlay.
The renovation process of fluidized catalytic cracking catalyst of the present invention and device thereof comprise: the beaded catalyst that 1) contains coke at first in the catalyst first fluidized bed (one section regeneration), under the oxidizing condition of coke, burns reaction; 2) catalyst and the flue gas from the first fluidized bed (one section regeneration) partial regeneration enters catalyst dispenser through burning carrier pipe together and on flowing to; 3) evenly enter the top of catalyst second fluid bed (two sections regeneration) from the partial regeneration catalyst of described catalyst dispenser, catalyst from top to bottom, oxygen-containing gas is counter current contacting from bottom to top, proceed to burn reaction, 4) second fluid bed (two sections regeneration) regenerated flue gas separates the catalyst carry after the regenerated flue gas pipeline, entering smoke energy recovering system, 5) a part of high-temperature regenerated catalyst returns or do not return the described first fluidized bed (one section regeneration) by described second fluid bed (two sections regeneration) through the high temperature catalyst circulation pipe.
The described catalyst that contains coke is to be catalyst or the contact agent or the burnt grain of any carbon content; The catalyst that enters the described first fluidized bed is from 1,2 or the reclaimable catalyst of a plurality of settler stripping sections or their mixture, and the reclaimable catalyst of 2 or a plurality of settler stripping sections enters or enters separately respectively after mixing; Or the regenerated catalyst of any carbon content behind the coke burning regeneration or incomplete regen-eration catalyst comprise regenerated catalyst, half regenerated catalyst etc. or their mixture.
According to arts demand, the described carrier pipe that burns can be 1,2 or a plurality of, it is outside or/and second fluid bed (two sections regeneration) is inner partly or entirely to be arranged on the first fluidized bed (one section regeneration), can overlapping (coaxial) formula arrange, also can block form arrange.
According to arts demand, described catalyst circulation pipe can be 1,2 or a plurality of, can partly or entirely be arranged on the described first fluidized bed (one section regeneration) or/and the inside of second fluid bed (two sections regeneration) or/and the outside, can overlapping (coaxial) formula arrange, also can block form arrange.
According to arts demand, described one section carrier pipe of regenerating and burn can adopt same diameter, also can adopt different-diameter.
The described first fluidized bed (one section regeneration) can not established yet, and forms two sections regeneration by burning the carrier pipe and second fluid bed (two sections regeneration), can overlapping (coaxial) formula arrange, can block form arrange yet.
According to arts demand, two sections regeneration can be adopted holomorphosis, also can adopt incomplete regen-eration.
Described catalyst dispenser can adopt industrial various catalyst dispensers commonly used.
According to arts demand, for less device, described catalyst dispenser can not established yet.
The dense bed and the dilute phase of second fluid bed of regenerating unit of the present invention (two sections regeneration) regeneration are same diameter, or/and be different-diameter.The dense bed of second fluid bed is cone or Rotary-table; Or/and be the cylinder identical with the dilute phase diameter; Or/and be two cylinders with the dilute phase different-diameter, described two cylinders are with cone or Rotary-table transition.
The described first fluidized bed (one section regeneration) and second fluid bed (two sections regeneration) can overlapping (coaxial) formula be arranged, also can block form arrange.The described first fluidized bed (one section regeneration) can be various forms of fluid beds, as burns jar, coke-burning riser etc.Those of ordinary skills are perfectly clear to its concrete structure, connection pattern, operation and control procedure, do not constitute the restriction to any specific embodiment of the present invention's design.
The catalyst that enters the first fluidized bed of the present invention can be from 1,2 or the reclaimable catalyst of a plurality of settler stripping sections or their mixture, enter after the reclaimable catalyst of 2 or a plurality of settler stripping sections can mix, also can enter separately respectively; The regenerated catalyst or the incomplete regen-eration catalyst that also can be any carbon content behind the coke burning regeneration comprise regenerated catalyst, half regenerated catalyst etc. or their mixture.
Described regenerated catalyst is meant the regenerated catalyst of holomorphosis or two sections regenerated catalysts behind the two-stage regeneration; Half regenerated catalyst is meant the regenerated catalyst of incomplete regen-eration or one section regenerated catalyst of two-stage regeneration.
Method of the present invention and device thereof also can be used for other gas-solid fluidization reaction burning process and comprise residual oil preliminary treatment, methyl alcohol system ethene, fluid coking, flexicoking etc.Catalyst that the described beaded catalyst that contains coke can be any carbon content or contact agent or burnt grain.
When heat is superfluous in regenerator,, can also be provided with interior or/and external warmer, so that control the requirement of catalyst regeneration process and course of reaction effectively to temperature for keeping reaction-regeneration system thermal balance.
The operating condition of renovation process of the present invention and device thereof is as follows: the gas superficial velocity of the described first fluidized bed: 0.3～10m/s, reaction bed temperature: 630～800 ℃; Described gas superficial velocity of burning carrier pipe: 0.3～30m/s, reaction bed temperature: 630～800 ℃; Described second fluidized bed gas superficial linear vilocity: 0.1～3.0m/s, reaction bed temperature: 630～800 ℃.
The operating condition of renovation process of the present invention and device thereof is preferably: the gas superficial velocity 0.5～5m/s of the described first fluidized bed, reaction bed temperature 650-750 ℃; The described gas superficial velocity 2～15m/s that burns carrier pipe, reaction bed temperature 680-750 ℃; The described second fluidized bed gas superficial linear vilocity, 0.5～2.0m/s, reaction bed temperature: 650～750 ℃.
Method of the present invention and device thereof can be applicable to the fluidized catalytic cracker of various reaction regeneration patterns (as coaxial-type, block form etc.); Also can be used for other gas-solid fluidization reaction burning process, comprise residual oil preliminary treatment, methyl alcohol system ethene, fluid coking, flexicoking etc.Catalyst that the described beaded catalyst that contains coke can be any carbon content or contact agent or burnt grain.
Method of the present invention and device thereof can use separately; Also two regenerating units of the present invention can be used in combination, can overlapping (coaxial) formula arrange, also can block form arrange.
Method of the present invention and device thereof can also be used in combination with other forms of catalyst recovery process and equipment thereof, as second regenerator etc., can overlapping (coaxial) formula arrange, also can block form arrange.When regenerating unit of the present invention is used in combination or is used in combination with other forms of catalyst regeneration equipment, can adopt the flue gas shunting flow process, smoke catalytic agent piece-rate system is set respectively, be provided with respectively or shared smoke energy recovering system.Method of the present invention and device thereof can also be provided with the interior of various versions or/and external warmer or regenerative agent cooler (as up flow type, downflow system, Pneumatic-control type, back-mixing formula etc.).Those of ordinary skills are perfectly clear to its concrete structure, connection pattern, operation and control procedure, do not constitute the restriction to any specific embodiment of the present invention's design.
Technical characterictic of the present invention is:
1, the present invention is two sections series connection regenerative operations that two sections adverse currents are burnt.Therefore, regeneration techniques of the present invention has adverse current simultaneously and burns characteristics with the fast fluidized bed regeneration techniques.Two sections regeneration adverse currents are burnt the hydrothermal deactivation that can alleviate catalyst under the high temperature.
2, one section regenerated flue gas and two sections shared same cyclone separation systems of regenerated flue gas and smoke energy recovering system have been simplified reclaim equiment and technological process, and one section regenerated flue gas heat is fully used.Only need a flue and attached guiding valve or butterfly valve this moment, simple in structure, and control is convenient.
3, because the excess oxygen content of one section regeneration of strict control, regenerated flue gas does not have the after-burning phenomenon at regenerator dilute phase and flue to be taken place, and can guarantee that third level cyclone separator and cigarette captain cycle keep the safety in production and obtain the regenerative power of maximum.
4, compare with eclipsed form layout two-stage regeneration (one section regeneration is on top, and two sections regeneration are in the bottom), the absolute altitude of reacting-settler and regenerator can reduce about 20 meters.
5, because to contain coke catalyst agent conveying circuit resistance little, thereby can reduce and contain oxygen regeneration gas consumption and pressure, it is about about 20% to save power consumption, thereby reduces producing cost.
6, adopt the flue gas shunting flow process, smoke catalytic agent piece-rate system is set respectively, be provided with respectively or shared smoke energy recovering system.
7, compare with existing two-stage regeneration technology,, simplified the structure and the regeneration technology flow process of regenerator, reduced equipment, can reduce investment outlay about 15-30% approximately owing to reduce the absolute altitude of reacting-settler and regenerator.
Description of drawings
Accompanying drawing 1-4: be the renovation process of fluidized catalytic cracking catalyst of the present invention and the canonical schema of device thereof.
Describe content of the present invention in detail below in conjunction with accompanying drawing, accompanying drawing is drawn for the present invention is described, does not constitute the restriction to any specific embodiment of the present invention's design.
Accompanying drawing 1: be the canonical schema (block form reaction-regeneration system) of one section fast bed regeneration of the present invention (burning jar).
As shown in Figure 1 renovation process of the present invention and device thereof, the two-stage regeneration system that adopts overlapping (coaxial) formula to arrange, the two-stage regeneration system also can block form arrange that comprise two fluid bed regenerator, two-stage regeneration has only a flue 4 and attached guiding valve or butterfly valve.Burn carrier pipe 7 and can also partly or entirely be arranged on the outside or inner of two fluid bed regenerator.
The oxygen regeneration gas that contains that catalyst regeneration process needs is entered by main air duct 8, through distributor pipe of cardinal wind (or distribution grid) 9, enter the first fluidized bed 6 inlet, mixed with the high-temperature regenerated catalyst that contains the coke catalyst and enter through catalyst circulation pipeline 5 that enters through catalyst transport pipeline 1.In the first fluidized bed, contain the coke reclaimable catalyst after oxidation, can remove the part of coke amount, in the oxygen gas that produces in the regenerative process, contain CO
2, H
2O, O
2And trace amounts of CO, emit a large amount of heats simultaneously, this is one of main thermal source of keeping temperature in the first fluidized bed.
Contain the oxygen regeneration gas and carry the flow direction of catalyst for entering catalyst dispenser 10 through burning carrier pipe 7 from bottom to top; Described partial regeneration catalyst is evenly entered the top of catalyst second fluid bed 12 (two sections regeneration) dense bed 2, catalyst from top to bottom, oxygen-containing gas is counter current contacting from bottom to top, proceeds to burn reaction.The oxygen regeneration gas that contains of the second regenerating catalyst in fluidized bed process need is entered by main air duct 3, through distributor pipe of cardinal wind (or distribution grid) 16, enters the bottom of the second fluid bed dense bed 2 of regenerator.
Above second fluid bed, can be provided with conventional dilute phase settling section and cyclone separator (not shown), recovery is carried out the part catalyst of second fluid bed, 12 dense beds 2 by flue gas, through the cyclone dip-leg (not shown), returns the second fluid bed dense bed 2.
Regenerated catalyst is installed in second fluid bed is extracted out the facility (not shown), guiding also carries regenerated catalyst to arrive reactor through regenerated catalyst 15.Draw a part of high-temperature regenerated catalyst at second fluid bed and return the described first fluidized bed, to improve the initial regeneration temperature of the first fluidized bed, to improve the fluid bed antijamming capability by catalyst circulation pipeline 5.Regenerated flue gas enters smoke energy recovering system through regenerated flue gas pipeline 4.
According to arts demand, enter the catalyst temperature of the first fluidized bed 6 when higher, catalyst circulation pipeline 5 can not established yet.
Required oxygen-containing gas in the catalyst regeneration process is normally through the cheap air of overcompression.
In catalyst, can also add and promote the CO oxidation conversion to become CO
2Combustion adjuvant.It not only can improve the heat energy utilization rate of regenerative process, also can alleviate in the regenerated flue gas CO effectively to the pollution of atmosphere.
When burning liberated heat in the regenerative process greater than reaction during needed heat, can also be provided with interior or/and external warmer, so that control the requirement of catalyst regeneration process and course of reaction effectively to temperature.
The operating condition of above-mentioned regenerating unit is: the gas superficial velocity of the first fluidized bed: 0.3～10m/s, reaction bed temperature: 630～800 ℃; Burn the gas superficial velocity of carrier pipe: 0.3～30m/s, reaction bed temperature: 630～800 ℃; Second fluidized bed gas superficial linear vilocity: 0.1～3.0m/s, reaction bed temperature: 630～800 ℃.
Be preferably: the gas superficial velocity 0.5～5m/s of the first fluidized bed, reaction bed temperature 650-750 ℃; Burn the gas superficial velocity 2～15m/s of carrier pipe, reaction bed temperature 680-750 ℃; The second fluidized bed gas superficial linear vilocity, 0.5～2.0m/s, reaction bed temperature: 650～750 ℃.
The catalyst that enters the above-mentioned regenerating unit first fluidized bed can be from 1,2 or the reclaimable catalyst of a plurality of settler stripping sections or their mixture, enter after the reclaimable catalyst of 2 or a plurality of settler stripping sections can mix, also can enter separately respectively; The regenerated catalyst or the incomplete regen-eration catalyst that also can be any carbon content behind the coke burning regeneration comprise regenerated catalyst, half regenerated catalyst etc. or their mixture.
Accompanying drawing 2: be the canonical schema (block form reaction-regeneration system) of one section fast bed regeneration of the present invention (burning carrier pipe).
As shown in Figure 2 renovation process of the present invention and device thereof adopt overlapping (coaxial) formula two-stage regeneration system, comprise and burn carrier pipe 7 and fluid bed regenerator 12 that two-stage regeneration has only a flue 4 and attached guiding valve or butterfly valve.Burn carrier pipe 7 and can also partly or entirely be arranged on the outside or inner of two fluid bed regenerator.
The oxygen regeneration gas that contains that catalyst regeneration process needs is entered by main air duct 8, through the distributor pipe of cardinal wind (not shown), enter and burn carrier pipe 7 inlet, mixed with the high-temperature regenerated catalyst that contains the coke catalyst and enter through catalyst circulation pipeline 5 that enters through catalyst transport pipeline 1.In burning carrier pipe 7, contain the coke reclaimable catalyst after oxidation, can remove the part of coke amount, in the oxygen gas that produces in the regenerative process, contain CO
2, H
2O, O
2And trace amounts of CO, emit a large amount of heats simultaneously.
Contain the oxygen regeneration gas and carry the flow direction of catalyst for entering catalyst dispenser 10 through burning carrier pipe 7 from bottom to top; Described partial regeneration catalyst is evenly entered the top of catalyst second fluid bed 12 (two sections regeneration) dense bed 2, catalyst from top to bottom, oxygen-containing gas is counter current contacting from bottom to top, proceeds to burn reaction.The oxygen regeneration gas that contains of the second regenerating catalyst in fluidized bed process need is entered by main air duct 3, through distributor pipe of cardinal wind (or distribution grid) 16, enters the bottom of the second fluid bed dense bed 2 of regenerator.
Above second fluid bed, can be provided with conventional dilute phase settling section and cyclone separator (not shown), recovery is carried out the part catalyst of second fluid bed, 12 dense beds 2 by flue gas, through the cyclone dip-leg (not shown), returns the second fluid bed dense bed 2.
The installation regenerated catalyst is extracted the bucket (not shown) out in second fluid bed, and guiding also carries regenerated catalyst to arrive reactor through regenerated catalyst 15.Draw a part of high-temperature regenerated catalyst at second fluid bed and return the described first fluidized bed, to improve the initial regeneration temperature of the first fluidized bed, to improve the fluid bed antijamming capability by catalyst circulation pipeline 5.Regenerated flue gas enters smoke energy recovering system through regenerated flue gas pipeline 4.
According to arts demand, enter the catalyst temperature of the first fluidized bed 6 when higher, catalyst circulation pipeline 5 can not established yet.
Required oxygen-containing gas in the catalyst regeneration process is normally through the cheap air of overcompression.
In catalyst, can also add and promote the CO oxidation conversion to become CO
2Combustion adjuvant.It not only can improve the heat energy utilization rate of regenerative process, also can alleviate in the regenerated flue gas CO effectively to the pollution of atmosphere.
When burning liberated heat in the regenerative process greater than reaction during needed heat, can also be provided with interior or/and external warmer, so that control the requirement of catalyst regeneration process and course of reaction effectively to temperature.
The operating condition of above-mentioned regenerating unit is: the gas superficial velocity of burning carrier pipe: 0.3～30m/s, reaction bed temperature: 630～800 ℃; Second fluidized bed gas superficial linear vilocity: 0.1～3.0m/s, reaction bed temperature: 630～800 ℃.
Be preferably: burn the gas superficial velocity 2～15m/s of carrier pipe, reaction bed temperature 680-750 ℃; The second fluidized bed gas superficial linear vilocity, 0.5～2.0m/s, reaction bed temperature: 650～750 ℃.
The catalyst that enters the above-mentioned regenerating unit first fluidized bed can be from 1,2 or the reclaimable catalyst of a plurality of settler stripping sections or their mixture, enter after the reclaimable catalyst of 2 or a plurality of settler stripping sections can mix, also can enter separately respectively; The regenerated catalyst or the incomplete regen-eration catalyst that also can be any carbon content behind the coke burning regeneration comprise regenerated catalyst, half regenerated catalyst etc. or their mixture.
Accompanying drawing 3: be the canonical schema (coaxial-type reaction-regeneration system) of one section fast bed regeneration of the present invention (burning jar).
As shown in Figure 3 renovation process of the present invention and device thereof, adopt eclipsed form two-stage regeneration system, two fluid bed regenerator that comprise arranged superposed, the flow sequence of renovation process is that the first fluidized bed 6 is in the bottom, second fluid bed 12 is on top, and two-stage regeneration has only a flue 4 and attached guiding valve or butterfly valve.Two fluid bed regenerator and settler 18 coaxial arrangement, settler 18 has reaction oil gas pipeline 20 and stripping section 19.The first fluidized bed 6 also can be set up in parallel the side at coaxial-type reaction (second) regenerator, burns carrier pipe 7 and can also partly or entirely be arranged on the outside or inner of two fluid bed regenerator.
The oxygen regeneration gas that contains that catalyst regeneration process needs is entered by main air duct 8, through distributor pipe of cardinal wind (or distribution grid) 9, enter the first fluidized bed 6 inlet, mixed with the high-temperature regenerated catalyst that contains the coke catalyst and enter through catalyst circulation pipeline 5 that enters through catalyst transport pipeline (regeneration standpipe) 1.In the first fluidized bed, contain the coke reclaimable catalyst after oxidation, can remove the part of coke amount, in the oxygen gas that produces in the regenerative process, contain CO
2, H
2O, O
2And trace amounts of CO, emit a large amount of heats simultaneously, this is one of main thermal source of keeping temperature in the first fluidized bed.
Contain the oxygen regeneration gas and carry the flow direction of catalyst for entering catalyst dispenser 10 through burning carrier pipe 7 from bottom to top; Described partial regeneration catalyst is evenly entered the top of catalyst second fluid bed 12 (two sections regeneration) dense bed 2, catalyst from top to bottom, oxygen-containing gas is counter current contacting from bottom to top, proceeds to burn reaction.The oxygen regeneration gas that contains of the second regenerating catalyst in fluidized bed process need is entered by main air duct 3, through distributor pipe of cardinal wind (or distribution grid) 16, enters the bottom of the second fluid bed dense bed 2 of regenerator.
Above second fluid bed, can be provided with conventional dilute phase settling section and cyclone separator (not shown), recovery is carried out the part catalyst of second fluid bed, 12 dense beds 2 by flue gas, through the cyclone dip-leg (not shown), returns the second fluid bed dense bed 2.
Regenerated catalyst is installed in second fluid bed is extracted out the facility (not shown), guiding also carries regenerated catalyst to arrive reactor through regenerated catalyst 15.Draw a part of high-temperature regenerated catalyst at second fluid bed and return the described first fluidized bed, to improve the initial regeneration temperature of the first fluidized bed, to improve the fluid bed antijamming capability by catalyst circulation pipeline 5.Regenerated flue gas enters smoke energy recovering system through regenerated flue gas pipeline 4.
According to arts demand, enter the catalyst temperature of the first fluidized bed 6 when higher, catalyst circulation pipeline 5 can not established yet.
Required oxygen-containing gas in the catalyst regeneration process is normally through the cheap air of overcompression.
In catalyst, can also add and promote the CO oxidation conversion to become CO
2Combustion adjuvant.It not only can improve the heat energy utilization rate of regenerative process, also can alleviate in the regenerated flue gas CO effectively to the pollution of atmosphere.
When burning liberated heat in the regenerative process greater than reaction during needed heat, can also be provided with interior or/and external warmer, so that control the requirement of catalyst regeneration process and course of reaction effectively to temperature.
The operating condition of above-mentioned regenerating unit is: the gas superficial velocity of the first fluidized bed: 0.3～10m/s, reaction bed temperature: 630～800 ℃; Burn the gas superficial velocity of carrier pipe: 0.3～30m/s, reaction bed temperature: 630～800 ℃; Second fluidized bed gas superficial linear vilocity: 0.1～3.0m/s, reaction bed temperature: 630～800 ℃.
Be preferably: the gas superficial velocity 0.5～5m/s of the first fluidized bed, reaction bed temperature 650-750 ℃; Burn the gas superficial velocity 2～15m/s of carrier pipe, reaction bed temperature 680-750 ℃; The second fluidized bed gas superficial linear vilocity, 0.5～2.0m/s, reaction bed temperature: 650～750 ℃.
The catalyst that enters the above-mentioned regenerating unit first fluidized bed can be from from 1,2 or the reclaimable catalyst of a plurality of settler stripping sections or their mixture, enter after the reclaimable catalyst of 2 or a plurality of settler stripping sections can mix, also can enter separately respectively; The regenerated catalyst or the incomplete regen-eration catalyst that also can be any carbon content behind the coke burning regeneration comprise regenerated catalyst, half regenerated catalyst etc. or their mixture.
Accompanying drawing 4,5: be the canonical schema (flue gas shunting) of two sections adverse current combination regenerations of the present invention.
As shown in Figure 4 renovation process of the present invention and device thereof adopt eclipsed form two-stage regeneration system, comprise two fluid bed regenerator of arranged superposed, burn the inside that carrier pipe 7 all is arranged on two fluid bed regenerator.The flow sequence of renovation process be the first fluidized bed 6 in the bottom, second fluid bed 12 is on top, two-stage regeneration sets up flue 4,19 and attached guiding valve or butterfly valve separately.
Accompanying drawing 5 is for being arranged in juxtaposition, and first fluidized bed regenerator 6 and second fluid bed regenerator, 12 height are arranged in juxtaposition.Burn carrier pipe 7 and all be arranged on the outside of two fluid bed regenerator.
The oxygen regeneration gas that contains that catalyst regeneration process needs is entered by main air duct 8, through distributor pipe of cardinal wind (or distribution grid) 9, enters the first fluidized bed 6 bottoms.The coke catalyst that contains that enters through catalyst transport pipeline 1 enters catalyst dispenser 18, contains the top that the coke catalyst evenly enters the catalyst first fluidized bed 20 (one section regeneration) dense bed 17 with described.Catalyst from top to bottom, oxygen-containing gas is counter current contacting from bottom to top, burns reaction.In the first fluidized bed, contain the coke reclaimable catalyst after oxidation, can remove the part of coke amount, in the oxygen gas that produces in the regenerative process, contain CO
2, H
2O, O
2And trace amounts of CO, emit a large amount of heats simultaneously, this is a main thermal source of keeping temperature in the first fluidized bed.
Above the first fluidized bed, be provided with conventional dilute phase settling section and cyclone separator (not shown), reclaim the part catalyst that is carried out the first fluidized bed 20 dense beds 17 by flue gas, through the cyclone dip-leg (not shown), return the second fluid bed dense bed 2.Regenerated flue gas enters smoke energy recovering system through regenerated flue gas pipeline 19.
The partial regeneration catalyst of the described first fluidized bed is entered catalyst dispenser 10 through burning carrier pipe 7 from bottom to top with promoting medium 16 (be generally air, Fig. 4 does not draw); Described partial regeneration catalyst is evenly entered the top of catalyst second fluid bed 12 (two sections regeneration) dense bed 2, catalyst from top to bottom, oxygen-containing gas is counter current contacting from bottom to top, proceeds to burn reaction.The oxygen regeneration gas that contains of the second regenerating catalyst in fluidized bed process need is entered by main air duct 3, through distributor pipe of cardinal wind (or distribution grid) 16, enters the bottom of the second fluid bed dense bed 2 of regenerator.
Above second fluid bed, be provided with conventional dilute phase settling section and cyclone separator (not shown), reclaim the part catalyst that is carried out second fluid bed, 12 dense beds 2 by flue gas, through the cyclone dip-leg (not shown), return the second fluid bed dense bed 2.Regenerated flue gas enters smoke energy recovering system through regenerated flue gas pipeline 4.
Regenerated catalyst is installed in second fluid bed is extracted out the facility (not shown), guiding also carries regenerated catalyst to arrive reactor through regenerated catalyst 15.
Required oxygen-containing gas in the catalyst regeneration process is normally through the cheap air of overcompression.
In catalyst, can also add and promote the CO oxidation conversion to become CO
2Combustion adjuvant.It not only can improve the heat energy utilization rate of regenerative process, also can alleviate in the regenerated flue gas CO effectively to the pollution of atmosphere.
When burning liberated heat in the regenerative process greater than reaction during needed heat, can also be provided with interior or/and external warmer, so that control the requirement of catalyst regeneration process and course of reaction effectively to temperature.
The operating condition of above-mentioned regenerating unit is: the gas superficial velocity of the first fluidized bed: 0.3～10m/s, reaction bed temperature: 630～800 ℃; Burn the gas superficial velocity of carrier pipe: 0.3～30m/s, reaction bed temperature: 630～800 ℃; Second fluidized bed gas superficial linear vilocity: 0.1～3.0m/s, reaction bed temperature: 630～800 ℃.
Be preferably: the gas superficial velocity 0.5～5m/s of the first fluidized bed, reaction bed temperature 650-750 ℃; Burn the gas superficial velocity 2～15m/s of carrier pipe, reaction bed temperature 680-750 ℃; The second fluidized bed gas superficial linear vilocity, 0.5～2.0m/s, reaction bed temperature: 650～750 ℃.
The catalyst that enters the above-mentioned regenerating unit first fluidized bed can be from 1,2 or the reclaimable catalyst of a plurality of settler stripping sections or their mixture, enter after the reclaimable catalyst of 2 or a plurality of settler stripping sections can mix, also can enter separately respectively; The regenerated catalyst or the incomplete regen-eration catalyst that also can be any carbon content behind the coke burning regeneration comprise regenerated catalyst, half regenerated catalyst etc. or their mixture.
Example 1
On treating capacity 1.0Mt/a riser fluid catalytic cracking,, catalyst is regenerated according to the renovation process that the present invention proposes.Reactive moieties feedstock oil is the miscella (weight ratio 80: 20) of vacuum distillate and decompression residuum, miscella proportion 0.875, Con. carbon～2.0%.
Adopt eclipsed form two-stage regeneration of the present invention system as shown in Figure 1, comprise two fluid bed regenerator of arranged superposed, the flow sequence of renovation process be the first fluidized bed 6 in the bottom, second fluid bed 12 is on top, two-stage regeneration has only a flue.
Main operating condition of catalyst regeneration part and result list table 1 in.
Main operating condition of table 1 catalyst regeneration part and result
| Project | Unit | The present invention | Remarks |
| Regeneration pressure | MPa (cutting off) | ??0.32 | |
| The first class bed tempertaure | ??℃ | ??700 | |
| Second fluidized-bed temperature | ??℃ | ??725 | |
| First fluidized bed gas superficial linear speed | ??m/s | ??2.60 | |
| The apparent linear speed of second fluidized bed gas | ??m/s | ??1.05 | |
| The total amount of burnt of regenerator | ??kg/h | ??7150 | |
| The regenerator catalyst inventory | ??t | ??88.0 | |
| Regenerated catalyst contains the charcoal rate | ??w％ | ??0.02 | |
| Reclaimable catalyst contains the charcoal rate | ??w％ | ??1.32 | |
Claims (7)
1. the renovation process of a fluidized catalytic cracking catalyst is characterized in that: the catalyst that 1) contains coke at first in the catalyst first fluidized bed, under the oxidizing condition of coke, burns reaction; 2) catalyst and the flue gas from first fluidized bed partial regeneration enters catalyst dispenser through burning carrier pipe together and on flowing to; 3) evenly enter the top of catalyst second fluid bed from the partial regeneration catalyst of described catalyst dispenser, catalyst from top to bottom, oxygen-containing gas is counter current contacting from bottom to top, proceed to burn reaction, 4) the second fluid bed regenerated flue gas separates the catalyst carry after the regenerated flue gas pipeline, entering smoke energy recovering system, 5) a part of high-temperature regenerated catalyst returns or do not return the described first fluidized bed by described second fluid bed;
The described catalyst that contains coke is to be catalyst or the contact agent or the burnt grain of any carbon content; The catalyst that enters the described first fluidized bed is from 1,2 or the reclaimable catalyst of a plurality of settler stripping sections or their mixture, and the reclaimable catalyst of 2 or a plurality of settler stripping sections enters or enters separately respectively after mixing; Or the regenerated catalyst of any carbon content behind the coke burning regeneration or incomplete regen-eration catalyst comprise regenerated catalyst, half regenerated catalyst etc. or their mixture.
2. the renovation process of a kind of fluidized catalytic cracking catalyst as claimed in claim 1 is characterized in that the dense bed and the dilute phase of the regeneration of second fluid bed is same diameter, or/and be different-diameter; The dense bed of second fluid bed is cone or Rotary-table, or/and be the cylinder identical with the dilute phase diameter, or/and be two cylinders with the dilute phase different-diameter, described two cylinders are with cone or Rotary-table transition.
3. in accordance with the method for claim 1, the gas superficial velocity that it is characterized in that the described first fluidized bed is 0.3～10m/s, and reaction bed temperature is 630～800 ℃; Described gas superficial velocity of burning carrier pipe is 0.3～30m/s, and reaction bed temperature is 630～800 ℃; The described second fluidized bed gas superficial linear vilocity is 0.1～3.0m/s, and reaction bed temperature is 630～800 ℃.
4. in accordance with the method for claim 3, the gas superficial velocity that it is characterized in that the described first fluidized bed is 0.5～5m/s, and reaction bed temperature is 650-750 ℃; Described gas superficial velocity of burning carrier pipe is 2～15m/s, and reaction bed temperature is 680-750 ℃; The described second fluidized bed gas superficial linear vilocity is 0.5～2.0m/s, and reaction bed temperature is 650～750 ℃.
5. according to the described method of claim 1-4, it is characterized in that independent use; Perhaps two regenerating units are used in combination, perhaps be used in combination with other forms of catalyst regeneration equipment, comprise as second regenerator, adopt the flue gas shunting flow process that smoke catalytic agent piece-rate system is set respectively, perhaps be provided with respectively or shared smoke energy recovering system.
6. according to the described method of claim 1-4, it is characterized in that being applied to various reaction regeneration forms, comprise the fluidized catalytic cracker of coaxial-type or block form; Perhaps be used for other gas-solid fluidization reaction burning process and comprise residual oil preliminary treatment, methyl alcohol system ethene, fluid coking or flexicoking.
7. the catalyst regeneration device that adopts of the described method of claim 1-4.
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| CN102371137A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Reaction device for converting methanol or dimethyl ether into light olefins |
| CN103055961A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst regeneration method with characteristic of emission reduction |
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| CN103055961A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst regeneration method with characteristic of emission reduction |
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| CN103157479B (en) * | 2011-12-16 | 2014-12-17 | 山东辰昊化工有限公司 | Regeneration method of vanadium-containing waste catalytic cracking balance agent |
| CN105461497A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Two-stage regenerating reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol and/or dimethyl ether and reaction method for two-stage regenerating reaction device |
| CN110719810A (en) * | 2017-07-04 | 2020-01-21 | 特殊设计和工程局卡塔利扎托尔股份公司 | Catalyst distributor for dehydrogenation reactors with fluidized bed |
| US10464872B1 (en) | 2018-07-31 | 2019-11-05 | Greatpoint Energy, Inc. | Catalytic gasification to produce methanol |
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