CN105505441A - Catalytic cracking reaction regeneration method and device - Google Patents

Catalytic cracking reaction regeneration method and device Download PDF

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Publication number
CN105505441A
CN105505441A CN201610002678.2A CN201610002678A CN105505441A CN 105505441 A CN105505441 A CN 105505441A CN 201610002678 A CN201610002678 A CN 201610002678A CN 105505441 A CN105505441 A CN 105505441A
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gas
regenerator
reaction
catalyst
breeding blanket
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CN105505441B (en
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石宝珍
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Priority to PCT/CN2016/111713 priority patent/WO2017118301A1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/10Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst

Abstract

The invention provides a catalytic cracking reaction regeneration method which is applied to the catalytic reaction process of petroleum hydrocarbon raw materials. The method is characterized in that a regeneration device is divided into a burning gas preheating area, a first regeneration region, a second regeneration region and a gas-solid separation region; the burning gas is directly mixed with a regeneration agent in the regeneration device for heat exchange to achieve preheating, and thus NOx generated in the burning process is reduced; the burning gas cools the regeneration agent at the same time, the agent-oil ratio of a reactor is increased, and the distribution of reaction products is improved; meanwhile, an additional low-temperature catalyst is provided for the reactor and can be an agent to be generated or a cooling regeneration agent, the conditions of the reactor are further optimized, and product distribution is controlled.

Description

A kind of catalytic cracking reaction renovation process and device
Technical field
The present invention relates to a kind of chemical field gas-solid catalysis technology, particularly relate to a kind of for petroleum hydrocarbon catalyzed reaction renovation process.
Background technology
Catalytic cracking of petroleum hydrocarbon reaction is the secondary processing technique of crude oil, reacts two reaction process form by raw material reaction and catalyst regeneration.Raw material reaction process generally generates the coke of inlet amount 5.5% ~ 10.0%, and these coke are attached to catalyst surface, blocking catalyst micropore, must make renewing catalyst activity by cyclic char.Catalytic material reaction and catalyst regeneration reaction are all important sport technique segments.
Raw material reaction determines object product, but in plant investment, operation energy consumption, device maintenance cost, catalyst regeneration process occupies main status.
Existing more typical catalyst regeneration techniques comprises two-stage regeneration, adverse current two-stage regeneration technology.Especially the adverse current two-stage regeneration technology of Uop Inc. and the exploitation of Beijing designing institute of China Petrochemical Industry embodies higher efficiency.Uop Inc. and Ashland company disclose its two-phase up-flow regeneration reaction regeneration technology developed jointly in US4299687, and CN97121795.5 discloses a kind of heavy oil fluidized catalyzed conversion eclipsed form two-stage regeneration technology.
Prior art catalyst regeneration process only pays close attention to coke combustion reactions.But coke and burn nitrogen in gas contact reacts process and can generate oxynitride (NOx).Along with the raising of environmental requirement, traditional scheme adopts the discharge of building equipment for denitrifying flue gas control NOx, increases investment, energy consumption and process cost, affects economic benefit.The technology directly reducing combustion reactions process NOx generation in burning process is better approach.
In prior art, the gas (being generally air) that burns of about 190 DEG C come from compressor in catalyst regeneration (burning) reaction process is participated in catalyst coke directly and is burnt reaction.That improves coke burning burns gas temperature, and the temperature reducing combustion zone especially effectively can reduce NOx generation in local " high temperature ".
Arrange in the catalytic cracking process of regenerator water cooler at revivifier, the low-temp recovery agent that in prior art, regenerator water cooler produces returns burns reaction zone, can reduce the temperature of burning reaction, and speed of response is burnt in impact, also just reduces and burns reaction efficiency; The internal circulating load strengthening regenerator is often needed to make up breeding blanket temperature.But the regenerator carbon content looped back is very low, can reduce again the content of combustion zone coke, too increase the energy consumption of catalyst recirculation conveying simultaneously.
In catalytic cracking of petroleum hydrocarbon reaction process, catalyzer is key problem, but in reaction process, the performance of catalyst in reactor and the performance of unreacted procatalyst are different.Example is should be with hydrocarbon compound Catalytic Cracking Unit of Measure, in reaction process, catalyzer can because of green coke, alkaline components and metallic pollution, passivation, the performance of catalyzer in real reaction process is deteriorated gradually, in reactor, especially in tubular reactor, the performance of each site catalysts is different, and the katalysis efficiency played is also different.The reaction conditions such as the temperature of the activity of catalyzer in reaction process, reagent oil ratio or air speed, reaction raw materials and catalyzer and temperature head is all the important factor affecting raw material reaction result in addition, the change of these conditions and control all can change reaction result.
Catalytic cracking of petroleum hydrocarbon is greater than C with carbon number 3component be main purpose product, C 2and the product of following small molecules product mainly thermally splitting.Intensified catalytic cracking reacts, and reducing heat cracking reaction is the target that catalytic cracking process is pursued always.In catalytic cracking reaction process, the selection of reaction conditions and control are directly connected to the selectivity of reaction conversion ratio and reactor product.The technology of existing optimization reactive system operation is a lot, for petroleum hydrocarbon raw material catalytic conversion reaction, the mixing temperature control techniques, outlet area rapid separation, chilling termination reaction technology etc. of dry gas pre-lifting technology, employing feed change decanting point and injected media all on reaction result impact obviously, are industrially better applied.In reaction process catalyst performance improvement and control also be vital.
From the seventies in last century, catalytic cracking of petroleum hydrocarbon reaction riser reactor replaces fluidized-bed reactor.Petroleum hydrocarbon raw material catalytic cracking reaction is gas-solid thermo-negative reaction, and reaction raw materials is generally liquid feed, and first liquid raw material needs endothermic gasification, and then gas reactant enters catalyzer micro channel again and carries out catalyzed reaction.The heat of gasification of liquid raw material is provided by regenerated catalyst.The liquid starting material catalyzed reaction of tubular reactor is used all to there are liquid-phase vaporization and gas-phase reaction two processes.By realizing with catalyst exposure heat supply, because gasification is not moment, completes simultaneously, in gasification, more or less there is certain reaction in gasification.The essential advantage of tubular reactor is just the existence of " gradient ", could realize the target improving reaction " impellent " (reactant concn) like this, improve reaction efficiency and selectivity.This is the one of the main reasons being replaced fluidized-bed by riser tube.Petroleum hydrocarbon raw material forms complicated, the raw molecule amount that reactor inlet enters is roughly 300, reactor outlet molecular weight product is roughly 100 or less, and in riser reactor, different positions presents different reactant character and reaction process, also needs different reaction conditionss.As more than atomizing nozzle, initial stage in gas-phase reaction district, the mainly stock oil macromole cracking reaction that stock oil carries out after completing gasification, this process is generally through the reaction times of about 1.0 ~ 1.5 seconds, and the gas-phase reaction district of riser tube latter half then mainly carries out comparatively small molecules such as diesel oil, gasoline, liquefied gas composition and reacts and the reaction such as isomerization, hydrogen transference again.Therefore often whole gas-phase reaction is divided into " cracking reaction district, upgrading reaction zone " etc. again.The temperature difference in liquid-phase vaporization reaction process between catalyzer and raw material and the high temperature of catalyzer all can increase heat cracking reaction, increase C 2following byproduct ratio, affects economic benefit; The temperature of cracking in vapour phase reaction zone, upgrading reaction zone, agent-oil ratio, catalyst activity etc. all cause remarkably influenced to the reaction result of whole reaction zone.
Be catalytically conveted to example with petroleum hydrocarbon raw material, result of study both domestic and external confirms for a long time, and regenerator temperature is high, causes reagent oil ratio lower, and the contact temperature difference between regenerator and reaction raw materials is large, dry gas yied all can be caused high, make a significant impact liquid yield; Along with the carrying out of reaction in riser tube, the activity of catalyzer reduces fast, and riser tube downstream reaction district efficiency reduces, and affects reaction effect.Reduce regenerator temperature, rising agent oil ratio and the activity improving riser tube inner catalyst are the targets always pursued of catalytic cracking unit for many years.
Many technical measures are had in the regenerator reducing reaction raw materials liquid-phase vaporization zone of action and the stock oil temperature difference.For reduction and stock oil first contact temperature problem, the way the most easily expected is " low temperature catalyst in external warmer is introduced riser tube pre lift zone ".Uop Inc. proposes the nineties in last century and the low temperature catalyst in external warmer is sent into the method that riser tube carries pre lift zone in patent US5800697.The patent application of this respect is more, as US6059958, US6558530B1, CN01119805.1, CN1664074A, CN101191067A, CN101191072A etc.
US5800697 discloses a kind of catalytic conversion reaction-renovation process, on revivifier side, cooling catalyst district is set, enter bottom riser reactor and participate in reaction through standpipe, guiding valve, thus make reagent oil ratio become independent variable after entering cooling area heat exchange to optimal temperature from the thermal regenerant of dense bed from outlet.CN101161786A discloses a kind of method for transformation of petroleum hydrocarbon, the water cooler cooling that is regenerated catalyst through of heat turns back to reactor bottom and participates in stock oil and contact and carry out cracking reaction, and reclaimable catalyst is transported to the mixing tank that revivifier carries out the use of coke burning regeneration Posterior circle or partly directly enters reactor bottom after stripping.
The another kind of way reducing stock oil and the regenerator first contact temperature difference is that the temperature of stock oil is improved.CN101144028A discloses a kind of cracking method for hydrocarbon oil, hydrocarbon ils and regenerated catalyst is heated in interchanger, then makes the hydrocarbon ils after heat exchange and the regenerated catalyst after heat exchange contact reacts in the reactor.
In addition, the influence factor of catalyzer to reaction not only comprises the catalyst temperature, liquid phase (stock oil) the gasification zone contact temperature difference and the agent-oil ratio that react front pre lift zone, and the cracking in vapour phase reaction zone catalyst activity after stock oil gasification and agent-oil ratio also have material impact to reaction process.
To control and the improvement of catalyst action in each position reaction process in reactor, except to except liquid-phase vaporization district, the improvement of catalyzer in the gas-phase reaction district after to stock oil gasification, the control to the catalyst condition provided also should be comprised.
To sum up, catalyzer enters the condition of reactor and mode is significant to improvement raw material reaction effect, optimizes regeneration and reaction, formed mutually mate, the complete reaction regeneration decorum is more meaningful; Adopt high temperature to burn gas and carry out the discharge index that catalyst regeneration reaction can improve flue gas.
Summary of the invention
Main purpose of the present invention is to provide a kind of catalytic cracking reaction renovation process, be made up of raw material reaction and catalyst regeneration two reactive moieties, comprise catalyst regenerator, tubular reactor, reacting-settler etc., reaction regeneration process is undertaken by clicking step:
1, reaction raw materials enters at reactor different sites, with catalyst exposure and catalyzed dose of heating and gasifying, then reacts; Reaction product enters immediately to be located at and is called first step gas-solid separator and second stage gas-solid separator in settling vessel together with catalyzer after reactor outlet outflow, and realize catalyzer and be separated with gas product, gas product flows out through settling vessel oil gas vent.
2, complete the catalyzer after raw material reaction to enter settling vessel stripping zone and carry out stripping, spent agent after stripping enters bottom the regenerative response district in the middle part of revivifier through inclined tube to be generated, regenerative response is carried out with the gas that burns from below, simultaneously catalyzer and regenerative response gas and and regenerative response generation flue gas together with upwards carry, being separated of gas and catalyzer is realized in revivifier gas solid separation district, gas flows out revivifier from exhanst gas outlet, catalyzer is introduced into the dense phase fluidized bed storage area in revivifier, that delivers to regenerator bottoms from this district through regenerator transfer lime burns gas preheating zone, preheating zone with burn gas and directly mix and make to burn gas heating, self is cooled simultaneously, cooled regenerator enters reactor through regenerator sloped tube from burning gas preheating zone below reaction raw materials entrance.When being provided with regenerator catalyst cooler (also claiming external warmer), catalysts cooler, regenerator catalyst cooler and catalysts cooler catalyst inlet arrange this revivifier dense phase fluidized bed storage area.
3, first part burns gas and burns gas preheating zone in regenerator bottoms and to enter from gas distributor and burn gas preheating zone, directly forms fluidized state contact heat-exchanging, through Perforated plate distributor inflow catalyst breeding blanket on backward by heating with regenerator; Another is set above or below orifice plate between gas preheating zone and catalyst regeneration zones burns gas (main air) and enter pipe and distribution pipe (claiming the second sparger) burning, burn gas by this pipe introduction partial regeneration and enter revivifier; Optimize, second section burn gas above the inner catalyst material level of regenerator preheating zone, burn between gas preheating zone and breeding blanket orifice plate below enter revivifier, the high-temperature gas come with preheating zone mixes, and then enters breeding blanket through orifice plate, participates in burning reaction; Complete the gas-carrying portion catalyzer after burning and carry out full gas solid separation in revivifier gas solid separation district, gas flows out revivifier from exhanst gas outlet.
4, the Valve controlling by regenerator transfer lime is arranged burns catalyst inventory or the material level of gas preheating zone.
5, by burning the change of gas preheating zone catalyzer material level or reserve, and change enter the gas volume that burns burning gas preheating zone can adjustments of gas preheating temperature and regenerator cooling temperature.
According to method of the present invention, be divided in catalyst regenerator housing and be divided into catalyst regeneration reactive moieties up and down, burn gas (generally using air) regenerator section and gas-solid separate part; Circulation orifice plate is set burning between gas preheating zone and catalyst regeneration zones, dense phase fluidized catalyst storage area is set between breeding blanket and gas-solid disengaging zone, be used for for regenerator transfer lime, external warmer (if any) regenerated catalyst is provided; This regenerator storage area can be located at catalyst regeneration zones, also independently can arrange outside breeding blanket; In this regenerator storage area and burn between gas preheating zone and arrange regenerator transfer lime; When needs for revivifier catalyst cooler (external warmer) is set, reaction regeneration agent cooler is set for reactor time, the catalyst inlet of regenerated catalyst water cooler and reaction regeneration agent cooler is also located at this district.
Reactor body is riser tube conversion zone, stock oil gasification zone, catalytic cracking reaction zone is followed successively by stock oil admission port, downstream, catalytic cracking reaction zone arranges settling vessel, arranges gas-solid separator in it, and isolated catalyzer enters stripping stage downwards by gravity; Spent agent after stripping enters revivifier breeding blanket through regeneration standpipe, contacts carry out burning reaction with from the gas that burns burning gas preheating zone below.
According to method of the present invention, revivifier breeding blanket is divided into the first breeding blanket, the second breeding blanket further; First breeding blanket is in bottom, and the second breeding blanket is on the first top, breeding blanket; The each interval in first breeding blanket and the second breeding blanket arranges circulation orifice plate (sparger); The catalyzer of the first breeding blanket and gas are transported to the second breeding blanket through orifice plate simultaneously to be continued to burn; The cone section that the diameter that second coboundary, breeding blanket (catalyzer material level) extends up to revivifier breeding blanket and gas solid separation interval expands gradually; Reduce due to gas flow rate in cone section, the density of catalyzer is increased, and become dense phase fluidized bed, this fluidized-bed becomes regenerator storage area simultaneously; Flue gas gas solid separation district is set above the second breeding blanket; In the second dense phase fluidized bed district, breeding blanket with burn air preheat interval and arrange regenerator transfer lime, the regenerator after burning to be sent into through this regenerator transfer lime and is burnt gas preheating zone by regenerator; Spent agent enters the first breeding blanket; Part is burnt gas (general custom claims main air) and is entered gas preheating zone through gas distribution tube, directly contacts in preheating zone with regenerator, is reproduced agent heating, then enters the first breeding blanket through orifice plate; Regenerator self is cooled while gas is burnt in heating, is burnt the regenerator after gas cooling and enters reactor bottom (generally claiming pre lift zone) from preheating zone through process fluid (generally claiming standpipe).
According to method of the present invention, arrange interior bucket in the cone section below revivifier gas solid separation district, the second breeding blanket is divided into inside and outside Liang Ge district, outskirt becomes regenerator recovery, storage area; The flue gas of the first breeding blanket and catalyzer enter this interior bucket to be continued to burn reaction; This interior bucket is designed to the cylinder of iso-cross-section or cross-sectional area upwards increases gradually, gas flow rate reduces gradually burns reaction zone; Now arrange outward at this interior bucket and burn air shooter and sparger, supplement to this catalyzer storage area and burn gas.
According to method of the present invention, in revivifier cone section and gas-solid disengaging zone housing, the second breeding blanket housing is set, first breeding blanket is directly communicated with the second breeding blanket, second breeding blanket outlet arranges transfer lime, transfer lime outlet arranges gas-solid just separator, breeding blanket and revivifier gas solid separation are separated and is split into two independently parts, the catalyzer in regenerative response district and gas directly export in breeding blanket and carry out preliminary gas solid separation, gas in revivifier gas solid separation district again through the two-stage be located between breeding blanket and revivifier housing revolve point isolate catalyzer after flow out revivifier, catalyzer enter between breeding blanket and revivifier housing catalyzer storage area.
According to method of the present invention, catalyst recirculation pipe is set between regenerator storage area and the first breeding blanket, controls the combustion reaction temperature of the first breeding blanket spent agent.
According to method of the present invention, when catalyst regeneration reaction needed heat-obtaining, draw catalyzer enter catalyst cooler from regenerator storage area, cooled catalyzer directly enters from catalyst tube and burns gas preheating zone.
According to concrete scheme of the present invention, in method of the present invention, the cracking reaction after reactor stripping stage and reactor bottom (pre lift zone) or gasification is intersegmental arranges spent agent return line, controls the temperature of inside reactor, agent-oil ratio and catalyst activity.
According to concrete scheme of the present invention, in method of the present invention, cracking reaction behind the second breeding blanket and reactor bottom (pre lift zone) or gasification is intersegmental arranges reaction regeneration agent cooler and the reaction regeneration agent transfer lime after lowering the temperature, make the regenerator after cooling enter reactor, control the temperature of inside reactor, agent-oil ratio and catalyst activity.
According to specific embodiment of the invention scheme, in method of the present invention, be arranged with the first orifice plate in spent agent entrance in revivifier breeding blanket, revivifier be divided into breeding blanket and gas preheating zone; Described first orifice plate can be porous barrier, also can be other forms of grid distributor, and one of its effect makes the gas (can carry partially catalyzed agent) from preheating zone below grid distributor evenly enter the first breeding blanket on orifice plate by this first grid distributor; Another effect of first orifice plate is separated the regenerator of gas preheating zone and the catalyzer of breeding blanket, prevents regenerator from being carried by air-flow and upwards enter into breeding blanket; Be appreciated that in the present invention, suitably can adjust the setting position of the first grid distributor or control gas preheating zone catalyzer controlling level to control to enter from preheating zone the catalytic amount of the first breeding blanket.In addition, in method of the present invention, can also burn gas as required enter the first breeding blanket by the second gas distributor introducing portion, this gas distributor can above the first orifice plate, also can below the first orifice plate; Preferably, this sparger is arranged below the first orifice plate.
According to specific embodiment of the invention scheme, in method of the present invention, in described revivifier breeding blanket, be also provided with on spent agent entrance second orifice plate; Described second orifice plate can be porous barrier, or other forms of grid distributor; The Main Function of the second orifice plate makes the gas of the first breeding blanket and catalyzer evenly enter the second breeding blanket, makes catalyzer active fluidization and the mixing of the second breeding blanket, improves and burn effect; In addition, in method of the present invention, can also burn gas as required enter the second breeding blanket by the 3rd gas distributor introducing portion, this gas distributor can above the second orifice plate, also can below the second orifice plate; Preferably, this sparger is arranged below the second orifice plate.
According to preferred specific embodiments of the present invention, in method of the present invention, to pass into the total amount of burning gas of revivifier for 100%, the amount of burning gas directly passing into gas preheating zone from bottom is about 35% ~ 70%, the amount of burning gas entered from the second sparger is about 30 ~ 60%, and the amount of burning gas entered from the 3rd sparger is about 0 ~ 10%; Each several part gas can be introduced in revivifier respectively by gas distributor, and concrete gas distributor can select the prior art in affiliated field, and the present invention repeats no more.
Effect of the present invention:
Burn gas after revivifier self-preheating again with the coke gasification reaction on catalyzer, form the flue gas that NOx content is low; Burn gas makes regenerator cool simultaneously, for reactor provides low-temp recovery agent, low-temp recovery agent circulation is formed between reactor and revivifier, thermally splitting can be reduced especially gasify and the heat cracking reaction in cracking reaction district, the thermal equilibrium relation of gasification and reaction can be adjusted, realize easily and flexibly reaction each district catalyzer is carried out to multi_control and can reduce energy consumption.
Generally speaking, catalyst reaction renovation process of the present invention is used for petroleum hydrocarbon raw material catalytic cracking process, and regenerative process self, to burning air preheat, realizes high-temperature gas and burns, and reduces NOx emission; Simultaneously for reactor provides the regenerator of low temperature, independently regenerator cooling apparatus is set without the need to providing low-temp recovery agent for reactor; Spent agent or the cracking reaction district of cooled regenerator after reaction raw materials gasification are supplemented and enters reactor, for reactor forms dual catalyst circulation, can according to different positions reaction conditions need different catalysts condition is provided, realize carrying out multi_control to reaction each district catalyzer easily and flexibly.
Of the present invention can see shown in Fig. 1 ~ Fig. 8 for realizing described reaction regeneration method.
Accompanying drawing explanation
Fig. 1: reaction-regeneration section schematic diagram in the catalytic cracking reaction technology of an embodiment of the present invention.
Fig. 2: the catalytic cracking reaction-regeneration section schematic diagram of another way of the present invention.
Fig. 3: the catalytic cracking reaction-regeneration section schematic diagram of another way of the present invention.
Fig. 4: the catalytic cracking reaction-regeneration section schematic diagram of another way of the present invention.
Fig. 5: the catalytic cracking reaction-regeneration section schematic diagram of another way of the present invention.
Fig. 6: the reaction-regeneration section schematic diagram containing revivifier heat-obtaining of the present invention.
Fig. 7: the structural representation of a kind of embodiment of grid distributor between breeding blanket of the present invention.
Fig. 8: the structural representation of the another kind of embodiment of grid distributor between breeding blanket of the present invention.
Number description: 1 reactor; 2 burn gas preheating zone; 3 first catalyst regeneration zones; 4 second catalyst regeneration zones; 5 revivifier gas solid separation districts; 6 settling vessel stripping stages; 7 settling vessel freeboard of fluidized bed; 8 regenerator catalyst cooler; 9 reaction regeneration agent coolers; 11 regenerator inclined tubes; 12 regeneration guiding valves, 13 reactor bottom catalyst section (generally claiming pre-lift); 14,14B reaction raw materials, 14C reaction or extremely cold raw material; 15 reaction raw materials reaction zones; 16 catalyst mix districts; 17, spent agent return port; 18 spent agent return line valves; 19 spent agent return lines; 20 burn gas preheating zone housing; 22 burn gas preheating zone gas distributor; 23 burn flue; 24 low-temp recovery agent outlets; 25 gas preheating zone catalyzer material levels; 26 regenerator spargers; 27 regenerator transfer lime valves; 28 regenerator transfer limes; 29 regenerator transfer limes; 30 first catalyst regeneration zones housings; 31 first orifice plates (multihole distributor); 31B opening; 31C hole cap; 32 combustion gases spargers, 33 burn flue; 34 reclaimable catalyst inclined tube valves; 35 inclined tubes to be generated; 36 reclaimable catalyst spargers; 37 regenerant recycle tube valves; 38 regenerant recycle pipes; 39 regenerant recycle pipes; 40 revivifier cone piece housings; 41 second orifice plates (multihole distributor); 41B opening; 41C hole cap; 41D regenerator storage area grid; 42 gas distributors; 43 flues; 44A, 44B, 44C, 44D regenerator outlet; 45 regenerator storage area catalyzer material levels; 46 second breeding blanket housings, bucket in 46B second breeding blanket; 46C bores section; 47 breeding blanket outlet conduit; 48 gas-solids are separator just; 49 revivifier dense phase fluidized catalyst storage areas; 50 revivifier gas solid separation district housings; 51 revivifier one-level gas-solid separators; 52 revivifier secondary gas-solid separators; 53 collection chambers; 54 burn exhanst gas outlet; 60 settling vessel stripping zone housings; 61 stripping internals; 62 stripping vapour spargers; 63 stripping steam pipes; 64 spent agent outlets; 65 inclined tubes to be generated; 70 settling vessel housings; 71 settling vessel one-level gas-solid separators; 72 settling vessel secondary gas-solid separators; 73 collection chambers; 74 product gas outlet; 81 regenerator catalyst cooler catalyst inlets; 82 regenerator catalyst cooler catalyst outlets; 83 regenerator catalyst cooler outlet valves; 91 reaction regeneration agent cooler catalyst inlets; 92 reaction regeneration agent cooler outlets; 93 reaction regeneration agent cooler outlet valves; 94 low temperature reaction regenerant inlet; 31B, 41B gas and catalyzer rise hole; 31C, 41C grid distributor escutcheon; Gas is burnt in A compression; C catalyst; F flue gas; S steam; G pre-lift medium; O reaction raw materials oil; H burns gas preheating zone catalyzer controlling level.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with drawings and Examples, protection scope of the present invention includes, but are not limited to this.The device structure do not mentioned in detail in the present invention, all can adopt the routine techniques in affiliated field.
Refer to shown in Fig. 1 ~ Fig. 5, the device for realizing described reaction regeneration method of the present invention comprises the reactor and revivifier that are set up in parallel, wherein:
Revivifier be used for coke burning regeneration is carried out to the spent agent carrying out autoreactor 1, revivifier is vertical installation, enclosure interior be divided into bottom burn (regeneration) gas preheating zone 2, catalyst regeneration zones and flue gas gas solid separation district 5; Catalyst regeneration divides into the first breeding blanket 3 of bottom and the second breeding blanket 4 of top; Each interval arranges orifice plate 31 or 41, and orifice plate is multi-hole type, and the total area of hole 31B, 41B is by the gas flow rate 12m/s ~ 40m/s passed through, aperture 50mm ~ 200mm; Preheating zone 2 is highly 3.0m ~ 7.0m, is less than 1.2m/s design by gas superficial flow velocity; First scorch region 3 height 8.0m ~ 15.0m, design by gas superficial flow velocity 1.4m/s ~ 2.5m/s, gas solid separation district 5 is less than 0.8m/s design by gas superficial flow velocity; The first breeding blanket is entered between 1.0m/s ~ 4.0m/s above spent agent and the orifice plate between the first breeding blanket and preheating zone 31; Burning (regeneration) gas preheating zone catalyzer material level H is 2.0 ~ 6.0m, and preferred H is 2.5m ~ 3.5m; Cyclone separator 51,52 is adopted to carry out gas solid separation; The internal circulating load of regenerant recycle pipe 38 regenerator is entered the catalytic amount of reactor 1 by regenerator sloped tube 11 0.5 ~ 1.5 times; To lightweight material, when reaction-regeneration system does not need heat-obtaining, spent agent passes through the mixing zone 16 of spent agent return line 19 and return port 17 2.0m ~ 10.0m place Returning reactor 1 above stock oil import, or below stock oil import bottom 2.0m ~ 7.0m place Returning reactor 13, spent agent back amount is entered the catalytic amount of reactor 1 by regenerator sloped tube 11 0.2 ~ 1.0 times.
To the reaction raw materials having surplus heat (needing heat-obtaining), regenerator cooler 9 is set; Its heat-obtaining load is determined by the following method: the regenerator temperature after cooling 500 DEG C ~ 580 DEG C; The flow of catalyzer is determined by 0.2 ~ 1.0 times of the catalytic amount being entered reactor 1 by regenerator sloped tube 11; Regenerator after cooling by the mixing zone 16 of outlet pipe 92 and admission port 93 2.0m ~ 10.0m place Returning reactor 1 above stock oil import, or below stock oil import bottom 2.0m ~ 7.0m place Returning reactor 13.
When arranging regenerator water cooler 8, cooled regenerator is directly entered by regenerator catalyst cooler catalyst outlet 82 and burns gas preheating zone, no longer as routine techniques, enters catalyst regeneration zones; Regenerator water cooler those skilled in the art can complete design.
Settling vessel, settling vessel stripping zone those skilled in the art can complete design; According to above parameter, technician can complete the Application Design of the inventive method; The present invention repeats no more.
Reaction regeneration method of the present invention provides the regenerator of different condition for reactor; Reaction conditions is more optimized; Owing to adopting high-temperature gas reaction, the NOx content in flue gas can be reduced; Realize burning air preheat at revivifier self by the improvement of regenerator configuration, simplify apparatus design, namely reduce investment, also reduce energy consumption; Optimizing materials reaction simultaneously, improves product slates.
Embodiment:
Reaction zone used in the present embodiment catalyzer control and the device of regenerator heat-obtaining method of cooling shown in Figure 3.
Certain produces 150 × 10 per year 4the catalytic cracking unit of petroleum hydrocarbon of t/a, reaction regeneration is arranged in juxtaposition, and burns gas preheating zone 2 and adopts fluidized-bed form, and the first breeding blanket 3 adopts circulating fluidized bed form, second breeding blanket 4 is arranged on the revivifier Zhui Duan district between the first breeding blanket 3 and gas-solid disengaging zone 5, adopts fluidized-bed form; Burn gas preheating zone, the first breeding blanket is seen, the first orifice plate grid distributor 31 and the second orifice plate grid distributor 41 is set respectively between the second breeding blanket; Reactor 1 is riser tube form; Arrange reaction regeneration agent cooler 9, reaction regeneration agent cooler 9 produces middle pressure steam, and reaction regeneration agent cooler 9 adopts and carries steam trap pattern, and steam trap is connected directly between on reaction regeneration agent cooler 9, and diameter is identical with regenerator cooler; Catalyzer after the cooling of reaction regeneration agent cooler enters reactor above stock oil, sees the following form in concrete in-position; The gas volume participating in burning air preheat is 52% of total amount, and gas is total amount 48% for burning of sending into the first breeding blanket, and this gas distributor and transfer lime are located at below the second orifice plate; Second breeding blanket no longer supplements burns gas; The comparative example reaction conditions of reaction mass and embodiment and original technology sees the following form.
The anti-plant bulk again of the embodiment of the present invention and crude oil technology comparative example sees the following form.
Embodiment and original technology comparative example reactor product forecast of distribution see the following form.

Claims (10)

1. a catalytic cracking reaction renovation process, be made up of raw material reaction and catalyst regeneration two reactive moieties, comprise catalyst regenerator, tubular reactor, reacting-settler etc., reaction regeneration process clicks step and carries out:
1., reaction raw materials enters reactor at reactor different sites, with catalyst exposure and catalyzed dose of heating and gasifying, then reacts; Reaction product is called first step gas-solid separator in settling vessel and second stage gas-solid separator from entering immediately to be located at after reactor outlet flows out together with catalyzer, and realize catalyzer and be separated with gas product, gas product flows out through settling vessel oil gas vent;
2., complete the catalyzer after raw material reaction to enter settling vessel stripping zone and carry out stripping, spent agent after stripping enters bottom the regenerative response district in the middle part of revivifier through inclined tube to be generated, regenerative response (be also called for short and burn) is carried out with from the gas that burns after the preheating of below, upwards carry together with the flue gas that catalyzer and regenerative response gas and regenerative response produce simultaneously, being separated of gas and catalyzer is realized in revivifier gas solid separation district, isolated catalyzer is introduced into the dense phase fluidized catalyst storage area in revivifier, that delivers to regenerator bottoms from this district through regenerator transfer lime burns gas preheating zone, burning gas preheating zone and burning gas and directly mix and make to burn gas heating, catalyzer self is cooled simultaneously, cooled regenerator enters reactor through regenerator sloped tube from burning gas preheating zone below reaction raw materials entrance, contacts under the effect of pre-lift medium with reaction raw materials, when being provided with regenerator catalyst cooler (also claiming external warmer), catalysts cooler, regenerator catalyst cooler and catalysts cooler catalyst inlet arrange this revivifier dense phase fluidized bed storage area,
3., first part burns gas (also claiming main air) and burns gas preheating zone in regenerator bottoms and enter burn gas preheating zone from gas distributor (also claiming the first gas distributor), directly form fluidized state contact heat-exchanging with regenerator, gas heated backward on through Perforated plate distributor (also claiming the first orifice plate) inflow catalyst breeding blanket; Burn gas and enter pipe and gas distributor (claiming the second gas distributor) burning to arrange above or below the orifice plate between gas preheating zone and catalyst regeneration zones, introduce second section by this sparger and regenerate and burn gas (also claiming main air) and enter revivifier; Optimize, second section burn gas above the inner catalyst material level of regenerator preheating zone, burn between gas preheating zone and breeding blanket orifice plate below enter revivifier, the high-temperature gas come with preheating zone mixes, and then enters breeding blanket through orifice plate, participates in burning reaction; Complete the gas-carrying portion catalyzer after burning and carry out full gas solid separation in revivifier gas solid separation district, gas flows out revivifier from exhanst gas outlet;
4., from revivifier dense phase fluidized catalyst storage area regenerator transfer lime draw regenerator feeding and burn gas preheating zone, burnt catalyst inventory or the material level of gas preheating zone by the Valve controlling that regenerator transfer lime is arranged;
5., by burning the change of gas preheating zone catalyzer material level or reserve, and change enter the gas volume that burns burning gas preheating zone can adjustments of gas preheating temperature and regenerator cooling temperature;
According to method of the present invention, be divided into gas solid separation part, catalyst regeneration reactive moieties in catalyst regenerator housing up and down, burn gas (generally using air) regenerator section; Circulation orifice plate is set burning between gas preheating zone and catalyst regeneration zones, in the cone section below revivifier gas solid separation district, dense phase fluidized catalyst storage area is set, be used for for regenerator transfer lime, external warmer (if any) regenerated catalyst is provided; This regenerator storage area can be located at catalyst regeneration zones, also independently can arrange outside breeding blanket; In this regenerator storage area and burn between gas preheating zone and arrange regenerator transfer lime; When needs for revivifier catalyst cooler (external warmer) is set, reaction regeneration agent cooler is set for reactor time, the catalyst inlet of regenerated catalyst water cooler and reaction regeneration agent cooler is also located at this district; Reactor body is riser tube conversion zone, stock oil gasification zone, catalytic cracking reaction zone is followed successively by stock oil admission port, downstream, catalytic cracking reaction zone (top) arranges settling vessel, arrange reactor product gas-solid separator in it, isolated catalyzer enters stripping stage downwards by gravity; Spent agent after stripping enters revivifier breeding blanket through regeneration standpipe, contacts carry out burning reaction with from the gas that burns burning gas preheating zone below.
2. method as claimed in claim 1, it is characterized in that, revivifier breeding blanket is divided into the first breeding blanket, the second breeding blanket further; First breeding blanket is in bottom; Circulation orifice plate (also claiming the second orifice plate) is set between the first breeding blanket and the second breeding blanket; The catalyzer of the first breeding blanket and gas are transported to the second breeding blanket through orifice plate simultaneously to be continued to burn; The cone section that the diameter that second coboundary, breeding blanket (catalyzer material level) extends up to revivifier breeding blanket and gas solid separation interval expands gradually; Reduce gradually due to gas flow rate in cone section, the density of catalyzer is increased, and become dense phase fluidized bed, this fluidized-bed becomes regenerator storage area simultaneously.
3. method as described in claim 1 and 2, is characterized in that, arranges bucket in being connected with breeding blanket, below, the second breeding blanket is divided into inside and outside Liang Ge district in the cone section below revivifier gas solid separation district, and outskirt becomes regenerator recovery, storage area; The flue gas of the first breeding blanket and catalyzer enter this interior bucket inside to be continued to burn reaction; This interior bucket is designed to the cylinder of iso-cross-section or cross-sectional area upwards increases gradually, gas flow rate reduces gradually burns reaction zone; Now arrange outward at this interior bucket and burn air shooter and sparger (also claiming the 3rd sparger), supplement to this catalyzer storage area and burn gas.
4. method as claimed in claim 1, it is characterized in that, in revivifier cone section and gas-solid disengaging zone housing, the second breeding blanket housing is set, first breeding blanket is directly communicated with the second breeding blanket, the second breeding blanket outlet diminishing cone section of setting area and transfer lime, transfer lime outlet arranges flue gas gas-solid just separator; This second breeding blanket housing makes the second breeding blanket separate into two independently spaces with revivifier gas solid separation district, catalyzer storage area, the catalyzer in regenerative response district and gas directly breeding blanket outlet carry out preliminary gas solid separation, catalyzer enter between breeding blanket and revivifier housing catalyzer storage area.
5. method as claimed in claim 1, is characterized in that, arrange catalyst recirculation pipe between regenerator storage area and the first breeding blanket, control the combustion reaction temperature of the first breeding blanket spent agent.
6. method as claimed in claim 1, it is characterized in that, when catalyst regeneration reaction needed heat-obtaining, draw catalyzer enter catalyst cooler from regenerator storage area, cooled catalyzer directly enters from catalyst tube and burns gas preheating zone.
7. method as claimed in claim 2, is characterized in that, supplements burn gas (also claiming the 3rd sparger) to the second breeding blanket; Optimize, this burns below the orifice plate of gas between the first breeding blanket and the second breeding blanket and enters revivifier.
8. method as claimed in claim 1, is characterized in that, the cracking reaction after reactor stripping stage and reactor bottom (pre lift zone) or gasification is intersegmental arranges spent agent return line, controls the temperature of inside reactor, agent-oil ratio and catalyst activity.
9. method as claimed in claim 1, it is characterized in that, cracking reaction behind revivifier close item fluid catalyst storage area and reactor bottom (pre lift zone) or gasification is intersegmental arranges reaction regeneration agent cooler and the reaction regeneration agent transfer lime after lowering the temperature, make the regenerator after the cooling of regenerator cooler enter reactor, control the temperature of inside reactor, agent-oil ratio and catalyst activity.
10. method as claimed in claim 1, it is characterized in that, to pass into the total amount of burning gas of revivifier for 100%, directly passing into the amount of burning gas of burning gas preheating zone from bottom is about 35% ~ 85%, makes the gas void tower flow velocity burning gas preheating zone at 0.3m/s ~ 1.0m/s; The amount of burning gas entered from the second sparger is about 30 ~ 60%, and the amount of burning gas entered from the 3rd sparger is about 0 ~ 10%; Each several part gas can be introduced in revivifier respectively by gas distributor.
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