CN1055380A - Use the catalytic pyrolysis of quenching - Google Patents

Abstract

In catalytic cracking method, provide effective quenching to reduce thermo-cracking.In order to increase the product yield, adopt specific quenchant to inject in certain location.In example, quenchant injects oily product in the downstream of rough lumber reactor at once.Quenchant comprises turning oil.

Description

Use the catalytic pyrolysis of quenching

The present invention relates to catalytic pyrolysis, more particularly relate to increase the method for valuable liquid yield in the system of units of catalytic pyrolysis.

The catalytic pyrolysis of oil is the important method of refining that is used for producing gasoline and other hydrocarbon polymer.During catalytic pyrolysis, at the catalytic pyrolysis temperature and pressure with in the presence of catalyzer, make be generally a cut that cuts crude oil be raw material and in reactor cracking to produce more valuable low-molecular-weight hydrocarbon.Gas oil is usually as the raw material in the catalytic pyrolysis.Gas oil feed typically comprises the 55%-80%(volume), boiling spread is about 650 °F (343 ℃) to about 1000 °F (538 ℃) and is less than 1%(weight) RAMS carbon: gas oil.Gas oil feed also typically comprises and is less than the 5%(volume) petroleum naphtha and boiling point be lower than 430 light hydrocarbon, the 10%-30%(volume), boiling spread is about the diesel oil and the kerosene of 430 (221 ℃)-650 (343 ℃), and be less than the 10%(volume), boiling point is higher than 1000 Residual oil, the amount of Residual oil is more or Residual oil added in the gas oil feed sometimes.

In the fluid catalytic cracking unit of routine (FCCU), make from the hot product in the riser reactor and continue in the downstream of vertical tube reactor, to carry out 900 heat scission reactions more than (482 ℃).These heat scission reactions make product degradation and reduce yield and make excessive light gas, and this light gas has usually limited the throughput of catalytic pyrolysis unit inadequately.

In addition, often need make under such as 1025 (552 ℃) or higher high temperature the standing tube reactor running to increase gasoline octane rating and to increase the conversion of oil and Residual oil, this type high temp cracking can increase the generation of ethane and light Fuel gas basically.Combusted gas generant compelling growth can cause the imbalance of refining combustion gases system.It also may limit the ability of these FCCU, and FCCU has the load that not enough gas compression ability is handled growth.Therefore, although encourage to increase the production of gasoline and octane, the temperature of vertical tube also must be lowered sometimes.

Under higher cracking temperature, can produce more unsettled petroleum naphtha and be easy to produce unwanted oxidizing reaction and form gelatinoid.The stabilization of gasoline method that was used for keeping the stability approach of cracking naphtha in the past and was used for keeping containing cracking naphtha comprises: (1) adds the chemical antioxidants such as phenylenediamine or hindered phenol; (2) handle all cleavage methods of control, such as the amount that reduces cracking temperature and/or restriction Residual oil; Perhaps (3) restriction is incorporated into the amount of handling petroleum naphtha in the gasoline.

Regenerator, catalytic pyrolyzing agent, reactant, equipment and method of refining are just like shown in the following United States Patent (USP) in some typical prior art: 2,240,160; 2,382,270; 2,382,382; 2,398,739; 2,398,759; 2,414,002; 2,422,501; 2,425,849; 2,436,927; 2,458,862; 2,669,591; 2,827,422; 2,884,303; 2,901,418; 2,981,676; 2,985,584; 3,004,926; 3,039,953; 3,290,405; 3,338,821; 3,351,548; 3,364,136; 3,513,087; 3,563,911; 3,593,968; 3,661,800; 3,676,519; 3,692,667; 3,838,036; 3,844,973; 3,850,742; 3,886,060; 3,907,661; 3,909,392; 4,043,899; 4,218,300; 4,325,817; 4,331,533; 4,332,674; 4,341,623; 4,341,660; 4,375,021; 4,446,009; 4,478,708; 4,552,645; 4,695,370; 4,764,268; 4,814,067; 4,824,557; 4,859,310; And No. the 83307095.6th, european patent application (publication number: EPO113 180A2), No. 85307242.9 (publication number: EPO180 355A2) and in No. 88309278.5 (publication number: EPO 311 375A1) set forth.These catalytic pyrolyzing agents of the prior art, regenerator, catalyzer, equipment and method of refining have had success in various degree.

Therefore, need provide a kind of improved method and system to increase the stability that the yield of gasoline (petroleum naphtha) in catalytic pyrolysis unit and improvement contain the gasoline (volatile oil) of these petroleum naphthas.

Here provide a kind of reality effective, high effect and have a unit of the improved catalytic cracking method that attractability is arranged economically.

Novel catalytic cracking method and unit comprise such as gas oil, the catalytic pyrolysis of the oil of hydrotreatment and/or the stock oil of the residual dregs of fat.Stock oil is placed the reactor of catalytic pyrolysis unit (FCCU), in the presence of catalyst for cracking to produce a kind of catalytic pyrolysis, flow out the runoff yield of selected oil, after catalytic pyrolysis is finished substantially, make the quenching of product gas from the outside, when catalytic pyrolysis oil from reactor, draw with discharge after just enter the reactor that has quenching pipeline or injector the downstream with the yield that increases petroleum naphtha and gasoline and produce more stable gasoline.Fast quench also obtains required transformation and has selectivity in the coke preparation.

Be preferably, quenching makes the expansion of when vaporization volume be lower than water and steam substantially, and in a preferred form, quenchant comprises cracking in advance or through the hydrocarbon steam of processing with the kind of removing great majority and can react.Necessary is that quenchant should have low heat reactivity.Be very satisfactory through the cracked hydro carbons in advance, because they are lower than the raw material of the original raw material of fresh undressed mistake and hydrotreatment to the reactivity of hot quenching.

The result, quenchant comprises that lightweight gas oil, coking distill out the overhead product of thing (CSD), hydrotreatment or fresh untreated original raw material in kerosene, the coker, such as, virgin gas oil, heavy virgin naphtha, lightweight virgin naphtha, but comprise lightweight cycle oil (LCCO or LCO), heavy cycle oil (HCCO or HCO) or heavy catalytic naphtha (HCN) or their mixture preferably.The boiling point of LCCO is lower than HCCOO, but they have identical vaporization heat approximately.Preferably quenchant comprises the LCOO of molecular weight greater than water.But HCCO also is very useful quenchant, and is more cheap than LCCO.

Usually the quenchant that unsuitable water or water vapour conduct meet the requirements, because they are a lot of in the bright expansion of evaporation, the volume of many reactors accounts for, to the top pipe expansion, cause because of pressure and cause destruction, disturb catalytic environment, disturb the cyclonic separator running inversely and produce a large amount of polluted water that must be purified.In the water vapour quenching, also still require to have excessive water vapour.

Light naphtha (lightweight virgin naphtha, lightweight catalytic naphtha, lightweight coking stone brain etc.) also generally should not be as the quenchant that meets the requirements, because it has occupied too many volume in reactor.In addition, lightweight stone brain is the product that mixes in the gasoline, does not need light naphtha is cracked into the hydro carbons of littler value.

The oil of octaneization (DCO) generally also need not make to conform with the quenchant of requirement, because it has pyrogenic tendency.Catalyzer in DCO also can corrode the pipeline of the wall of internal reactor.

Say that further Residual oil is not also as the quenchant that meets the requirements, because it has pyrogenic tendency and blocks pipeline.

The liquefied hydrocarbon quenchant is more preferred than gaseous state quenchant, and it can obtain the vaporization heat of liquid quenchant.Say so liquid quenchant with the 2%-20%(volume with meeting the requirements), better be the 5%-15%(volume) the flow rate of feed oil liquid quenchant is injected the product steam.Advantageously, quenching has been lowered the temperature of product flow and thermo-cracking can have been reduced to minimum.Quenching has also increased feed oil and has been converted into selected oil and can increases octane in the gasoline.

The gas oil in kerosene, the coking furnace and the overhead product of hydrotreatment are not so good as the good of LCCO and HCCO as quenchant.Liquid nitrogen can be used as useful quenchant, but very expensive and the volumetric expansion that does not meet the requirements arranged.

LCCO and HCCO have very high heat absorption capacity, increase operation, and expending from the practicality, maintenance and the waste treatment that increase operation in fact not.LCCO and HCCO provide good quenchant, and be economical, stable because they can obtain in refining, has low volumetric expansion, provides the heat that can reclaim again to get rid of, and it is few that it forms pyrogenic tendency.Can reduce the amount that forms carbonizing matter with cycle oil.Catalytic pyrolysis also allows Pintsch process and does not lose more valuable hydro carbons and do not damage cyclonic separator inside, ventilation or refractory wall.What meet the requirements is to have reduced the generation of combustion gases basically with the cycle oil quenching.

In method more preferably, by the roughing out in the steam catalyst separator, pyrogenic catalyzer and selected oil content are opened, and making the quenching at once of selected oil is the hydrocarbon product and the hydrocarbon matter hydrocarbon gas of low value to reduce that selected oil is thermally cracked to.What meet the requirements is, the downstream that quenching ties up to riser reactor produces, and steam forms in the exit of the rough lumber cyclonic separator of catalytic pyrolysis unit.It is then more effective and economical to add quenchant after the roughing out at catalyzer from oil in catalytic pyrolysis oil.The required quenchant volume and the energy consumption of pump also can reduce.

In an example of being set forth, adopt quenching in the upstream of separator and stripping tube.A preferred form of this application is that catalytic pyrolysis unit has an extraneous rough lumber cyclonic separator at standing tube reactor with separating between stripping tube, quenchant is injected at once the downstream of steam (product) outlet of extraneous rough lumber cyclonic separator.

In another example, catalytic pyrolysis unit has a separator tube (separator) with inner rough lumber separator＜with quenchant to inject the downstream of separator and near the outlet of inner rough lumber separator steam (product) at once.Inner rough lumber separator comprises inner cyclonic separator or handstand pot type separator.Also available trajectory separator and other inertial separator.

Advantageously, adopt quenching can reduce pyrogenic selectivity, the dilution of separation and stripping tube mutually the part coking can reduce.Expend the coking fallen catalyzer in revivifier, regenerate and to the vertical tube reactor recirculation use.What meet the requirements is that in new quench process, the regeneration temperature of revivifier reduces.Preference pattern is that revivifier is being entirely the CO(carbon monoxide) thus work is at the support combustion gases such as air under the burning, comprise unnecessary carbonizing matter being finished burn on the carbonic acid gas stoichiometry excess of oxygen exist down pyrogenic catalyzer is regenerated that revivifier also can move under portion C O burning.

In this patent application, term " transformation efficiency " is illustrated in the above relative disappearance amount of inlet amount of 430 of boiling points (221 ℃).

In this patent application, term " coking selectivity " expression carbonizing matter must be measured the ratio with conversion product.

Make more detailed explanation and propose claims below in conjunction with accompanying drawing.

Fig. 1 is the schema that has the catalytic pyrolysis unit of external cyclone;

Fig. 2 is the schema that has another catalytic pyrolysis unit of external cyclone;

Fig. 3 is the schema of olein refining part;

Fig. 4 oil purified is the schema of a part in addition;

Fig. 5 is the schema of coking unit;

Fig. 6 is the schema of catalytic pyrolysis unit;

Fig. 7 and 8 is the graphic representations to the product temperature of all quenchant consumptions;

Fig. 9 is the graphic representation of quenchant volume to the product volume;

The graphic representation of Figure 10 and 11 effects of initial quenchant in different catalytic pyrolysis units;

Figure 12 is the catalytic pyrolysis unit's schema that has inner rough lumber separator;

Figure 13 is the mould sectional view that separator is made along the 13-13 line among Figure 12;

Figure 14 has the longitudinal diagram that the amplification that tank switching and quench tube separator done along the 14-14 line is arranged among Figure 15;

Figure 15 is the schema that has the center standing tube reactor and the catalytic pyrolysis unit of the inside rough lumber separator that comprises tank switching;

Figure 16 is the schema that has another catalytic pyrolysis unit of inner rough lumber separator.

In refining process, with pump 12 with unrefined, primary whole crude (oil) is extracted out from ground storage vessel 10 and enter one or more demineralizers 16 to remove the microparticle shape thing (Fig. 3) such as husky, salt and metal from oil by feed-pipe 14.The oil that takes off supersalt enters tube furnace 20 by furnace inlet pipeline 18, is heated to certain temperature at this oil, for example is heated to 750 °F (399 ℃) under the pressure of 125-200psi.Remove from stove with the oil that pump 24 will heat, pump is to primary distillation tower 26 by feed-pipe 25.

Before entering upper end rectifying part or lower end stripping part, make its choosing enter elementary atmospheric distillation tower, the flash zone of tube furnace or crude oil unit 26 oil of heating.Primary tower is worked being lower than under the 60psi preferably.In primary tower, the separating of oil one-tenth wet gas of heating, light naphtha, medium naphtha, heavy naphtha, kerosene, virgin gas oil and elementary Residual oil part.Wet gas, a part of petroleum naphtha and kerosene reflux preferably (recirculation) to the primary tower to improve fractionation rate and efficient.

Wet gas is than discharging by upper end moisture pipeline 28 in the primary tower 26.From primary tower, shift out light naphtha by light naphtha pipe 29.From primary tower, shift out medium naphtha by medium naphtha pipe 30.From primary tower, take out heavy naphtha by heavy naphtha pipe 31.From primary tower, remove the oil and the furnace oil of kerosene and generation jet combustion by kerosene pipeline 32.If desired, part kerosene and/or heavy naphtha can be from 186 chargings of quenching pipeline as quenchant parts (Fig. 1).From primary tower, shift out elementary non-pressurized virgin oil and pump to the 34(Fig. 4 of fluid catalytic cracking unit (FCCU) by elementary perfectly straight oil pipe 33), enter among the FCCU again by catalysis charging hydrotreatment unit sometimes.。

By elementary Residual oil pipe 35 elementary Residual oil is discharged from the bottom of primary tower 26.With pump 36 with the elementary stripper pump in the pipeline 35 to stove 38 and be heated to all 520F(271 according to appointment ℃)-750F(399 ℃) temperature.The elementary Residual oil that will heat by stove drainage conduit 40 is transported to the tube furnace vacuum, the flash distillation section of tower 42 or directly deliver in the FCCU reactor.

Tube furnace vacuum column 42(Fig. 3) works under the 35-50mm mercurypressure scope more fortunately.Water vapour can be injected the bottom part of vacuum column by water vapour pipe 44.In vacuum column, wet gas or vacuum condensate be venting from the vertical wet gas pipe 46 of tower.Heavy and/or lightweight vacuum gas oil shift out and enter the catalysis charging 49(CFHU of hydrotreatment unit from the gas oil pipe 48 at vacuum column middle part) (Fig. 4) or enter the riser type reactor.Vacuum resid is removed (Fig. 3) from the vacuum resid pipe 50 of the bottom of vacuum column 42.Vacuum resid is meant that also typical initial boiling point is near about 1000F(538 ℃) residual oil.

Some Residual oils can by residual property management 52 pumps of FCCU to or be dosed among the FCCU34 (Fig. 4) or Residual oil enters in the residue hydrotreatment unit (RHU) that comprises a series of ebullated beds, expanded bed reactor selected.Also can be fed among the FCCU34 from the lightweight gas oil (LGO) among the RHU by RHU LGO pipe 54.Some resistatess can be by coking residue 58 pumps to coker unit 56.

The 56(Fig. 5 of coker unit) comprises coker or coking bucket 62 and merging tower 64.In coker 62, under the pressure of about 10psig-50psig, be that coking is carried out in about 895 (479 ℃)-915 (491 ℃) vacuum columns bottom in coking temperature.By chute, conduit or pipeline 66 are removed carbonizing matter from coker 62, be transferred to carbonizing matter storage ground with acting on fluid fuel, the steam that coker produces is removed from coker 62 by coker vapour pipe 68 and is passed through (charging) to mixed coking tower 64.In mixed coking tower 64, coking product steam can be divided into coker gas, coker petroleum naphtha, lightweight coker gas oil, coke still distillate (coker distillate and heavy coker gas oil part.Coker gas can be removed from mixing column 64 by coker flue 70.The coker petroleum naphtha can be removed from mixing column 64 from coker petroleum naphtha pipe 72.Coke still distillate (coker distillate) can be by removing in the coke still distillate CSD pipe 73.Lightweight coker gas oil can be by lightweight coker gas oil pipe 74 to remove and to enter among the ECCU34 (Fig. 4) or to enter catalysis charging hydrotreater (CFHU) 49 in the mixing column 64.If desired, part coke still distillate (coker fraction), lightweight coker gas oil and/or coker gas can be from 186 chargings of quenchant pipe as the part quenchants.Heavy coker watt phase oil can be by heavy coker gas oil pipe 76 from mixing column 64(Fig. 5) remove and at cat cracker 34(FCCU) in before the catalytic pyrolysis at catalysis charging hydrotreater (CFHU) 49(Fig. 4) in hydrotreatment.Used hydrogen from hydrogen input be 78 at pressure from normal atmosphere to 2000psia, preferably from 1000psia to 1800psia temperature at 650 °F (343 ℃) to 750(399 ℃) input, in the presence of hydrogenation catalyst, the oil of hydrotreatment is emitted and is sent into cat cracker 34(FCCU from the hydrotreater vomit pipe 80 that adds catalyzer).

Catalytic cracking reaction device 34 among Fig. 1 has a vertical standing tube reactor 104 that has upper end portion 102 and end portion 104.Split and explain catalyzer and feed oil by oneself and mix in the bottom of standing tube reactor 100.Cat-cracker (standing tube reactor) 100 makes the oily catalytic pyrolysis of charging in the presence of catalyst for cracking under the catalytic pyrolysis condition.The catalytic pyrolysis oil vapour that contains the useless coking catalyst of particulate makes the catalyst for cracking coking.

The rough lumber inertial separator that comprises outside rough lumber cyclonic separator 106 is by cyclonic separator inlet pipe 105 link to each other with the upper end of standing tube reactor 100 (Fig. 1).Outside rough lumber cyclonic separator 106 is installed on the same height in upper end portion 102 of standing tube reactor 100.Pyrogenic catalyzer of this rough lumber cyclonic separator and the rough segmentation of catalytic pyrolysis oil.Be to make 92%-98% at least preferably by rough lumber cyclonic separator 106.Pyrogenic catalyzer is removed in the oil.What be installed on external cyclone 106 lower ends is a vertical separator tube or a separator 108.

Separator tube 108(Fig. 1) from catalytic pyrolysis oil, isolates a large amount of residual coking catalysts.Separator tube is worked under 900 (482 ℃)-975 (524 ℃) temperature.There is a dilution phase part 110 separator tube 101 upper ends, this is partly with at least one inner cyclonic separator 112, one and flows out the outlet pipe 113 of product, the dense phase part 114 in lower end, gas is put forward part 116 provides a gas to carry device, therein the evaporable hydro carbons is put forward by gas from pyrogenic catalyzer.Gas is put forward part baffle plate or internals 115.Gas is carried vapour pipe and can be carried device 116 with gas with injector 117 and link to each other.

What extend out from external cyclone 106 upper ends is cyclonic separator outlet pipe 118, and portion of product stream pipe 119(Fig. 1 is provided).Produce stream tube 11 a upper end horizontal component 118 is arranged, vertical intermediate 120, by-level part 122, and prolong vertical component 124,124 provide the two-way intubate of a product stream, and its lower end is by the upper end portion that dilution phase part 110 is connected to dense phase part 114 of going up of separator tube.The two-way intubate 124 of product steam has inner inertial separator, and it has one to be positioned at the middle portion of dilution phase part on the separator tube 108 and the outlet 126 that communicates with it.Produce stream tube 118 a separator tube input channel is provided, it extends between the upper end dilution part 110 of external cyclone 106 and separator tube 108, and links to each other with them and communicate.

The spent catalyst outlet conduit of cyclonic separator, passage and skewed slot provide a two-way intubate 128,128 of catalyzer to extend in the dense phase part in lower end 114 and to put forward part 116 adjacent with the gas of separator tube 108.The two-way intubate 128 of catalyzer has vertical component 130 on, middle oblique angle part 132, declivity angle part 134 and have outlet 137 vertical bidirectional cannula distal end part 136.Can link to each other with last vertical component 130 by tracheae 138.Fluidization stream tube 139 can link to each other with declivity angle part 134.

Revivifier 140(Fig. 1) comprise a regeneration organ pipe 142, it is positioned at separator 108 tops.Revivifier 140 makes the coking catalyst that expends burn substantially and regenerate in the presence of such as the support incendiary oxygen-containing gas of air.Vertically extending lifting conduit 144 is pipelines that the catalyzer that expends rises, this pipeline be from regeneration organ pipe 142 end portion extend out, extend downwards by the middle portion of separator tube 108 dense phase parts 114, it is used for making in the regenerating tube 142 of pyrogenic catalyzer above being transported to from separator tube 108.Litres of air injector 146 be positioned at promote conduit 144 bottoms near be used for injecting air, suct spent catalyst and it be transported in the regeneration organ pipe 142, promote pyrogenic catalyzer burning.Revivifier 142 can have inner cyclonic separator 148 and 150, one upper end dilution phase steam rings 152, top gas stack 154 and lower end dense gas stack mutually ring 156 and pipeline 158.

The regenerated catalyzer is by catalyzer drainage conduit, passage and skewed slot 160(Fig. 1) drain in the placement well and container 162 of top the pressure that 162 lower end part has a random air ring 164 to be set up with payment.Extend a vertical regenerated catalyst standpipe 166 from the lower end of placing well 162 and extend to slide valve 168.The regenerated catalyst pipe 170 of level links to each other with the end portion 104 of vertical reactor 100.Fluidization suspension vapour pipe 171 can be connected on the regenerated catalyst pipe 170 under the slide valve 168.Blowing air pipe 172 can be connected to the middle portion of regenerated catalyst standpipe 166.

Logical vapour pipe 176(Fig. 1) also can receive on the end portion 104 of vertical reactor 100.Nozzle 178(Fig. 1 of injector) can be installed on the lower end part 104 of vertical reactor 100 so that feed oil is injected vertical reactor.In the example of being narrated, be mixed into oil pipe 180 and be connected on nozzle 178 and the fresh oil inlet pipe 33.Recirculation oil pipe 182 can be connected to be mixed on the oil pipe 180 and also communicate with it so that heavy catalytic cycle oil (HCCO), octane carburetion (DCO) and/or pulpous state oil can enter in the vertical reactor 100, mostly be most the 40%(volume), better with the 5%-10%(volume), the fresh feed ratio is in fresh oil inlet pipe 33.The temperature of revivifier reduces about 1 °F to 20 °F by the turning oil quenching.

Catalytic cycle oil quenching injection tube 184 comprises LCCO injection tube and/or HCCO injection tube, it has a vertical catalytic cycle oil injector section 186, its extends downwards to link to each other and pass to mutually with the vertical component 120 of separation vessel input tube 118 light cycle (LC-CO) quenchant and/or heavy catalytic cycle oil (HCCO) quenchant is injected hydrocarbon product, and this reaches after product enters in the vertical reactor 100 in external cyclone 106 downstreams and carried out before product enters separation vessel 108.Quenching make the product heat of steam cracking of catalytic pyrolysis rough segmentation oil reduce to minimum and suppress to be thermally cracked to the hydro carbons of lesser value basically, such as comburant (-rent) gas etc.The turning oil quenchant can stop 75%-90% product oil thermo-cracking and increase the production of the yield of petroleum naphtha with increase gasoline simultaneously.Between cold snap, the oily product vapour temperature of discharging from rough segmentation cyclonic separator 106 has reduced about 30 °F (17 ℃)-200 °F (111 ℃), be about 50 °F (28 ℃)-80 °F (44 ℃) preferably, temperature range is about 900 °F (482 ℃)-930 °F (499 ℃) like this.

The turning oil quenchant has increased feed oil and has transformed and increased gasoline octane to selected oil.The injection ratio of quenchant is the 2%-20%(volume), better be the 5%-15%(volume) the input ratio of charging in the vertical reactor 100.Advantageously form still less carbonizing matter in the dilution phase part 110 of separation vessel 108.Between the turning oil cold snap, also less produce C _2-Fuel gas.

Make quenchant spray out and form the quenchant of quick contact and mix rapidly with one or more injectors that make quenchant atomizing, the mixing of quenchant and volatilize to increase to effectively and be less than 5 seconds like this is to be less than 3 seconds preferably.The most last injection speed of quenchant is that 50-100ft/ (15-30 meter per second) residence time second is 0.1-5 second, better is less than 0.2 second.Can avoid losing quenchant.

High boiling point quenchant medium improves the recovery of energy.The quenchant preheating can be higher than 212 °F (100 ℃) preferably, with the recovery that increases heat and that the loss of heat amount is reduced to is minimum.Quenchant is sprayed into external cyclone vapor outlet port pipe 118 makes product cool off rapidly entering reaction vessel dilution phase front.

In order to obtain optimum, should wait to react-finish and just inject quenchant, be preferably and wait for that pyrogenic granules of catalyst roughing out from catalytic pyrolysis oil product stream back of coming out carries out quenching at once.After isolating catalyzer the amount of required quenchant than catalyst separating before required amount lack.

Unexpected and be surprisingly found out that with the turning oil quenchant and can increase the yield of high value petroleum naphtha and improve the formation and the selectivity of carbonizing matter.

Gas oil except reactor transforms in the rough lumber cyclonic separator that has catalyzer to exist and finishes substantially.Excessive fuel gas product has prolonged the residence time of separation vessel dilution phase part in advance before adding the turning oil quenchant.

The regenerated catalytic cracking catalyst can enter (Fig. 1) in the vertical reactor 100 by regenerated catalyst pipe 170 successively.The new catalyzer that replenishes can add in the revivifier 140.In the FCC vertical reactor, the hydrocarbon raw material evaporation is mixed mutually with thermal cracking catalyst, catalytic material is cracked into more valuable low-molecular-weight hydro carbons.Temperature range in the vertical reactor 100 is about 900 °F (482 ℃)-1200 °F (649 ℃), is from about 950 °F (510 ℃) to about 1040 °F (560 ℃) preferably, and its pressure is that normal atmosphere is to about 50psig.Weight-space velocity scope hourly in the vertical reactor is about 5-200WHSV.Oil vapour flow velocity degree scope in the vertical reactor is about 5ft/ second (1.5 meter per second)-100ft/ second) (30m/ second).

Stable catalyst for cracking includes, but are not limited to these catalyzer that contains silicon-dioxide and/or aluminum oxide (comprising acid type).Catalyst for cracking can contain other such as magnesium oxide or zirconic refractory metal oxides.Catalyst for cracking is the catalyzer that contains crystalline aluminosilicate, zeolite or molecular sieve preferably, and its amount is the lytic activity that can be enough to increase catalyzer, for example in about 1%-50%(weight) between.The silicon-dioxide in the crystalline aluminosilicate and the mol ratio of aluminum oxide were at least 2: 1, and for example 2 to 12: 1, in order to obtain optimum, mol ratio was 4-6 preferably: 1.Usually the crystalline aluminosilicate that is easy to get is a sodium-salt form, this component preferably by hydrogen ion exchange, such as the exchange of the hydrogen precursor of ammonium ion or polyvalent metal ion it is reduced to for example to be less than about 4%(weight or even about 1%(weight).Suitable polyvalent metal comprises calcium, strontium, barium and such as cerium, lanthanum, neodymium rare earth metal and/or the mischmetall of formation naturally.This class crystalline material can keep its vesicular structure under the hot conditions of Preparation of Catalyst, hydrocarbon processing process and catalyst regeneration.Crystalline aluminosilicate has quite little even porous, and the bore dia in its transverse section is 6-20A, is preferably about 10-15A.The catalyst for cracking of silica-alumina has the important proportion of silicon-dioxide, for example, about 60%-90%(weight) silicon-dioxide and about 10%-40%(weight) aluminum oxide, it is fit to mix with crystalline aluminosilicate or be used as catalyst for cracking.The size in other catalyst for cracking and hole also can be used.Catalyst for cracking also can contain or comprise carbon monoxide (CO) combustion improver or for example platinum catalyst catalyzer be increased in the revivifier 140 dense mutually in the burning of carbon monoxide.

Make the sedimental spent catalyst of the inactivation that contains carbonizing matter from separation vessel 108, discharge and promote to get on and add to the bottom that is positioned at top fluidization catalyst regenerator or burner 140 by spent catalyst standpipe 144.Standing tube reactor and revivifier have formed the elementary composition of catalytic pyrolysis unit together.Air is injected into the bottom of revivifier by air injection tube 146 and spent catalyst riser 144.Air injects under certain pressure and fluid and makes the spent catalyst particulate fluidization and upwards enter revivifier, is included in residual carbon (carbonizing matter) perfect combustion in revivifier 140 basically on the granules of catalyst, stays the regenerated catalyzer and can be used in the reactor.The regenerated catalyzer is discharged from revivifier 140 by regenerated catalyst pipe 160 and is fed to standing tube reactor 100 by regenerated catalyst pipe 170 and regenerated catalyst standpipe 172.Combustion tail gas (stack gas) is extracted out from the top of burner 140 by unburned gas pipe or flue gas pipe 154.

As shown in Figure 6, the outflow product of the hydro carbons of catalytic pyrolysis (volatile oil) circulation overcurrent is produced FCC was discharged and was transported in property management 113 from separating purification device 108 tops main separator 190.In FCC fractionator 190, the catalytic pyrolysis hydro carbons comprise oil vapour and flash distillation gas can through fractionation (separation) become hydrocarbon matter hydrocarbon gas, petroleum naphtha, light catalytic cycle oil (＜CCO), the oil (DCO) of heavy catalytic cycle oil (HCCO) and octaneization.The light class gas of lightweight is removed from the FCC fractionator by light gas pipe 192.Petroleum naphtha is removed from the FCC fractionator by petroleum naphtha pipe 194.LCCO removes from the FCC fractionator by light catalytic cycle oil pipe 196.HCCO removes from the FCC fractionation by heavy catalytic cycle oil pipe 198.The octane carburetion is removed from the FCC fractionation by octane carburetion pipe 199, and partial L CCO and/or HCCO can be recycled to turning oil quench tube 184(Fig. 1) and as quenchant.

Interchangeablely be, in main fractionator 402, but oil vapour and flash vapors fractionation (separation) or (a) boiling point be lower than the light hydrocarbon of 430 (221 ℃), (b) light catalytic cycle oil (LCCO) and (c) oil of octaneization (DCO).Light hydrocarbon can be removed from main fractionator and enter in the bucket of separator by the upper end pipeline.In the bucket of separator, light hydrocarbon is separable into (1) humid gas and reaches the C that (2) comprise propane, propylene, butane, butylene and petroleum naphtha ₃Light hydrocarbons material to 430 (221-℃).Wet gas is by discharging in the wet gas pipe on the separator barrel and processing in vapor recovery unit (VRU) again.C ₃From the drainage conduit of separator barrel, discharge and pass through vapor recovery unit (VRU) to 430-(221-℃) material and do further processing.LCCO manages discharge and is used as quenchant part or refining again, processing or sale from the LCCO of main fractionator.Octane carburetion (DCO) can be removed from main fractionator from one or more DCO pipelines and further be used.The pulpous state recirculating oil that comprises octane carburetion (DCO) can be by pump through slurry pipe 182(Fig. 1) and from DCO pipe 199(Fig. 6 of the bottom of main fractionator 190) middle pump to standing tube reactor 100 is used for recirculation.Residual DCO can pass on, and re-uses in refining.

From standing tube reactor 100(Fig. 1) the coking catalyst of the useless inactivation of discharging can carry the gas stripping gas body of part 116 usefulness such as light hydrocarbon gase or steam and propose transpirable hydro carbons at gas.Put forward the spent catalyst pipe 144 of device 116 and enter revivifier 140 through gas by the pyrogenic catalyzer that gas was carried.Air injects to make useless coking catalyst fluidization and carry useless coking catalyst by air injection tube 146 and enters revivifier 140 with the speed of 0.2ft/ second (0.06m/ second)-4ft/ second (1.22 meter per second) through spent catalyst standpipe 144.Be preferably, excessive air is injected revivifier 140 fully the carbonizing matter on the catalyzer is changed into carbonic acid gas and water vapour.Make carbonizing matter change into air capacity on carbonic acid gas and the necessary stoichiometry of water vapour for perfect combustion, air can excessive about 2.5%-25%.

In revivifier 140 (Fig. 1), the burning of carbonizing matter in the presence of air on the catalyzer, catalyzer contains the weight less than 1%(as a result) carbonizing matter.Coking catalyst is contained in the dense phase part of revivifier lower end, and the dilution of revivifier upper end is the bottom of part mutually.Though carbon monoxide mainly be have promote incendiary material dense mutually in burning, the promptly dense CO combustion improver that has mutually, carbon monoxide (CO) the dilution phase with dense mutually in incendivities all.Dense temperature range in mutually is about 1050 °F (566 ℃)-1400 °F (760 ℃).The temperature range of dilution in mutually is about gas (combustion gases) that 1200 (649 ℃)-1510 (821 ℃) pile up and discharges from the flue 154 of the upper end of revivifier 140, makes to pile up gas and be less than 0.2%(2000ppm best) (volume) CO.The major portion of CO burning heat is preferably absorbed by catalyzer and is transferred in the standing tube reactor 100 by regenerated catalyst pipe 170 and vertical tube 166 usefulness regenerated catalysts.

In cat cracker (standing tube reactor) 100, some nonvolatile carbonaceous materials or carbonizing matter are deposited on the catalyst particles.Carbonizing matter comprise generally contain 4-10%(weight), the highly enriched aromatic hydrocarbon of hydrogen.Because carbonizing matter ties up on the catalyzer and constitutes, institute so that the lytic activity of catalyzer and catalyzer the selectivity of generation blended gas and oil is reduced.Remove most of carbonizing matters of catalyzer with a suitable method of property again, catalyzer can recover its initial ability.

The regeneration of catalyzer is by adopting the oxygen-containing gas such as air that the carbonizing matter burning that is deposited on catalyst surface is carried out.The oxygen or the air that need large volume from catalyzer burning coking settling.The carbonizing matter oxidation is characterised in that as the simple method of oxidation of coal and can be represented by following chemical equation:

Reaction formula (a) and (b) under typical catalyst regeneration condition, all can take place, wherein the catalyst temperature scope is about 1050 °F (566 ℃)-1300 °F (704 ℃), and it is gas-solid chemical action when regenerated catalyst is in this temperature range.The effect that temperature raises is that the ratio of coal increases and removes carbon elimination or carbonizing matter more up hill and dale from catalyzer.Because fuel ratio increases, then, may produce phase phase reaction (C) as long as capacity oxygen has the heat of increase when existing emit.The latter's reaction causes by radical and propagates.Further CO is burnt into CO ₂Be an attracting source of heat energy, because reaction (c) is a great thermopositive reaction.

The total 26S Proteasome Structure and Function of the cat cracker (catalytic pyrolysis unit) of Fig. 2 is similar to Fig. 1's, except light catalytic cycle oil (LCCO) quench tube 284 pitch angle are about 15 °-45 °, be 30 ° and different preferably, vertical relatively, the track that can increase quenchant like this can mix it.Regenerator vessel 242 also is installed in the side of separator 208.For easy to understand, the part among Fig. 2, element and composition are all numbered corresponding to part, element and the composition of the catalytic pyrolysis among Fig. 1, except only increasing by 100, i.e. standing tube reactor 200 for example in 200 series, external cyclone 206, separator 208, gas is carried device 216, revivifier 240 etc.The catalytic cracking reaction device comprises standing tube reactor preferably.There are two standing tube reactors in some catalytic pyrolysis units, two rough lumber cyclonic separators, and two slide valves and two vertical tubes, they link to each other with a revivifier and a separator.

Similar among Figure 12 and the general 26S Proteasome Structure and Function of 13 cat cracker (catalytic pyrolysis unit) and Fig. 2, just slightly add inner inertia cyclonic separator except four inner rough lumber inertial separators 306 comprise, it is used for product catalytic pyrolysis oil vapour and discharges the back goes out a large amount of catalyzer with external cyclone rough segmentation from catalytic pyrolysis occasion by horizontal product pipe 305 from vertical reactor 300.Four CCO quenchant injection tubes 384 extend to separator tube (separator) 302 interior dilutions, and partly (district's band) 310 is inner and lucky above inner rough lumber separator tube 306 vapor outlet port 318, after most of pyrogenic catalyzer are removed from oil with inner rough lumber separator 306, comprise that from 384 injections and spraying LCCO and/or HCCO are at the CCO of catalytic pyrolysis oil quenchant.The quenching injection tube can be installed as 15 ° minimum to the oblique angle of 90 ° (levels) relatively vertically quenchant is refluxed back to reduce to.

In Figure 12, the dense part in lower end (district's band) 314 and gas that the lower end that vertical output spent catalyst pipe, conduit and skewed slot 328 are attached to inner rough lumber separator 306 makes the spent catalyst of separating drain into separator 306 are carried part (gas is carried device) 316.Extremely inner cyclonic separator 312 is arranged 5 times at the top of separator 308 upper ends dilution phase region band 310.Secondary inner cyclonic separator 312 co-operate of separator tube 308 and rough lumber separator 306 tops are to remove the granules of catalyst (fine powder) that left behind from flowing gas and oil vapour.For easy to understand, the part of cat cracker, element and composition are similar to the numbering of corresponding section among Fig. 2 among Figure 12 and 13, standing tube reactor 300, and inner rough lumber wind separator 306, gas is carried device 316, revivifier 340 etc.

FCCU600 unit is similar with 13 cat cracker to Figure 12, and it is to be to use HCCO to replace LCCO to make the separator quenching that its a main design replenishes change.Select HCCO to replace LCCO to avoid liquid flooding, promptly in fractionator, surpass the performance of LCCO, and improve the heat recuperation of all units, and in the HCCO circulation pump capacity in bigger progress.

HCCO quenchant nozzle is installed into by cooling reaction and brings into play quenching efficient to greatest extent after the HCCO catalyzer enters cyclonic separator.HCCO can make separator cooling 30 (17 ℃) to 200 °F (93 ℃), and situation can be cooled off at least 100 °F (38 ℃) at least preferably.

Similar among the total 26S Proteasome Structure and Function of Figure 14 and 15 cat cracker (catalytic pyrolysis unit) and Figure 12, but vertically extend upwardly to dilution mutually in part (the district's band) 410 differences along separator 408 Z-axises except vertical centre, center standing tube reactor 400.The upper end of standing tube reactor 409 and the inside rough lumber inertial separator 406 coaxial installations that comprise a tank switching.Tank switching 406 has, and open bottom 406a is used for making the coking catalyst of separating to enter dense phase part (district's band) the 414 gentle device parts 416 of putting forward of separator tube 408; The surface of an atresia or flat-top or top ceiling 406b give on the upper end 409 of standing tube reactor 400 restriceted envelope and are providing a bump flat board that steam is hit outside standing tube reactor outlet upper end 409 on the catalyst cupport steam of catalytic pyrolysis oil; The columniform wall 406c in upper end, it extends downwards from top 406b; Middle portion has a cover 406d, and it extends under upper end wall 406c, the cylindrical wall 406e of a lower end, and it is that the open bottom of 406a extends out below the 406d from cover.

Cover 406d(Figure 14 and 15) comprises an outside open skirt shape edge.Cover 406d extends longitudinally to the wall 406f that there is a fork upper end, and it extends from upper end wall 406c, is concentrated into lower end wall 406g downwards, and it is from wall 406f extension downwards and get.The rhombus wall 406f of upper end has relative rectangle discharge opening of a pair of diameter or window 406h, and it allows catalytic pyrolysis oil at oil after rough segmentation is come out from catalyzer, and its mobile product steam can be from middle outlet.

As the catalyzer that carries full catalytic pyrolysis oil upper end 409(Figure 14 and 15 from standing tube reactor 400) go out, it impinges upon the enough momentum on the top 406b of inner rough lumber separator (tank switching) 406, forces that rough segmentation goes out a large amount of useless coking catalysts from catalytic pyrolysis oil.The catalyzer of separating is discharged owing to gravity by the open bottom 406a of tank switching 406.The catalytic pyrolysis oil that rough segmentation is come out from catalyzer is discharged by the window 406h of tank switching 406.

A pair of radially relative horizontal quench tube or injector 484(Figure 14) 410 inside mutually partly (is distinguished and is with) in the dilution that flatly extends into separator tube 408, they also are arranged in it together near window 406h, and their ejections comprise the quenchant in catalytic pyrolysis oil of LCCO and/or HCCO.But quench tube 484 arranged askew become 15 ° to 90 ° (level), and the backflow of the vertical relatively such quenchant of quench tube can reduce to minimum.

Separator tube 408(Figure 15) with at the secondary inner cyclonic separator 412(at separator tube top above rough lumber separator 406) from flowing gas and oil vapour, remove residual coking catalyst particle (fine powder) jointly.For easy to understand, the corresponding section among the part of the catalytic pyrolysis among Figure 14 and 15, element and component and Figure 12, the numbering of element and composition is identical, except being 400 series, for example, standing tube reactor 400, inner rough lumber separator 406, gas is carried device 416, revivifier 440 etc.

The cat cracker (catalytic pyrolysis unit) of Figure 16 is similar to total 26S Proteasome Structure and Function among Figure 12, but is the below that is contained in separator tube (separator) 508 except revivifier 540.For the ease of understanding, the numbering of corresponding section, element and composition among Figure 16 among the part of cat cracker, element and component and Figure 12 is similar, and except being 500 series, for example, vertical reactor 506, gas are carried device 516, revivifier 540 etc.

In some environment, need to adopt fluidized-bed reactor or fluidised catalytic cracking reaction device to replace standing tube reactor.

Embodiment

The following example is used for setting forth practical application of the present invention but in office where face does not limit the scope of the invention.

Embodiment 1 and 2

Similarity method as shown in Figure 1 experimentizes in catalytic pyrolysis unit (Y of unit).The test card Benq plinth situation of embodiment 1.Catalytic pyrolysis among the embodiment 1 carries out the LCCO quenching.Catalytic pyrolysis in embodiment 2 test is that the LCCO quenchant with temporary transient regional control quenching pipeline carries out, and test-results is as follows.LCCO quenching test has produced beyond thought surprising good result, because the petroleum naphtha octane increases 0.2RM/2, transformation efficiency increases the 0.64%(volume), the petroleum naphtha yield increases the 0.5%(volume), heavy catalytic cycle oil-proofness increases.C _2-The gas yield reduces 23%(weight).The degree, output and the quality that generate product during with the catalytic pyrolysis of LCCO quenching all are unhoped-for.The growth that this class forms owing to the LCCO quenching has produced value of the product and has increased widely.

Embodiment 1 embodiment 2 data movement

Difference

The LCCO quenchant, MB/D 0.0 1.5+1.5

Fresh feed, MB/D 24.6 24.7+0.1

Standpipe F 955. 956.+1.

The rough lumber whirlwind 951. 903.-48. of pipeline top

Separator, °F

From separator tube to main fractionating tower 940. 903.-34.

The steam pipeline temperature head, °F

Between standing tube reactor and separator tube 15. 53.+38.

Temperature head, °F

Preheating temperature, °F 437. 435.-2.

HCCO recirculation, B/D 710. 790.+80.

Soup compound recirculation, B/D 700. 700. 0.

The Regenerative beds temperature, °F 1312. 1305.-7.

Transformation efficiency, the %(volume) 69.15 69.79+0.64

Fresh feed character

Gravity 23.9 24.0+0.1

Nitrogen, %(weight) 0.112 0.111-0.001

Sulphur, %(weight) 1.23 1.22-0.01

Gas oil, the %(volume) 97.8 97.6+0.2

Embodiment 1 embodiment 2 data movement

Difference

Transformation efficiency, the %(volume) 69.15 69.79+0.64

TC2-，WT%??3.34??3.11??-0.23

TC3, the Vol%(volume) 10.80 10.90+0.10

C3＝/TC3??0.689??0.693??+0.004

TC4，Vol%??13.19??13.52??+0.33

C4＝/TC4??0.524??0.513??-0.009

IC4/C4 saturated 0.789 0.785-0.004

C5/430，Vol%??51.83??52.33??+0.50

Gasoline mixture

For example, pentane, amylene

LCCO，Vol%??25.54??24.91??-0.63

DCO，Vol%??4.62??4.57??-0.05

Carbonizing matter, Wt% 5.90 6.16+0.26

Recovery volume, Vol% 105.99 106.24+0.24

C5/430

MCL octane 93.7 93.9+0.2

RCL octane 81.4 81.6+0.2

Embodiment 1 embodiment 2 data movement

Difference

LCN

Inductive phase, minutes 25 25 0

RON??94.5??94.5??0

MON??80.2??80.2??0

HCN

Inductive phase 395 615+220

RON??92.9??93.4??+1.6

MON??80.9??81.4??+0.5

Embodiment 3 and 4

Behind the catalyst particles of removing carbonizing matter, carry out small research with kerosene imitation catalytic pyrolysis oil.In embodiment 3 and 4 tests, quenchant speed is 60 Grams Per Hours, and oily product speed is 125 Grams Per Hours.The quenchant of embodiment 3 is HCCO.The quenchant of embodiment 4 is LCCO.The quenching result of HCCO that reports below and LCCO is very similar:

Embodiment 3 embodiment 4

Reactor F 1,095 1100

C2-combustion gases (Wt%)

Isothermal quenching 14 16+

Cooling 10 9 in 20 minutes

Cooling 86 in 60 minutes

Embodiment 5 and 6

Experimentize in another catalytic pyrolysis unit (FCCU500) with similar methods as shown in Figure 2.Embodiment 5 provides the base case that does not adopt LCCO.Embodiment 6 carries out catalytic pyrolysis with the LCCO quenchant.The oil feed rate ratio is 79MBD.The standing tube reactor temperature is 1020 °F (549 ℃).Do not have the LCCO quenchant, the temperature of reactor at separator tube top is lower than 12 of standing tube reactors.Under the 5.6MBDLCCD quenchant, the LCCO quenchant has reduced the generation at the dry gas that is formed by about 16.7%1140MSCFH-980MSCFH with meeting the requirements, fully increased by 4.4% gasoline product, increased about 1% volume recovery from 39.5MBD-41.2MBD.The LCCO quenchant has also reduced the generation of propane, propylene and Trimethylmethane, and working conditions and test-results are as follows:

Embodiment 5 embodiment 6

No quenchant has the LCCO quenchant

LCCO quenchant speed O MBD 5.6MBD

1020 of standpipe temperature (549 ℃) 1020 (549 ℃)

1008 of separator tube tip temperature (542 ℃) 967 (519 ℃)

The temperature head of standpipe and separator tube+12 (7 ℃)+53 (30 ℃)

C _2-4Dry gas 1140MSCFH 980MSCFH

C ₅+ gasoline 39.5MBD 41.2MBD

Recovery volume % 108.9% 109.8%

Embodiment 5 embodiment 6

No quenchant quenchant difference

（wt.%）??（wt.%）??（wt.%）

C _2-Dry gas 4.8 4.0-.8

Propane 2.1 1.8-.3

Propylene 5.7 5.3-.4

Trimethylmethane 3.7 3.5-.2

Normal butane 1.2 1.2-

Butylene 6.8 6.7-

Gasoline 41.2 43.0+1.8

LCO/DCO??29.4??29.3??-

Carbonizing matter 5.1 5.2-

Embodiment 7-9

In with the catalytic pyrolysis unit of turning oil quenchant, further test.In embodiment 7, to shown in Figure 1 similar, the quench tube with a temporary transient local control after coming out in the outside rough lumber cyclonic separator of product from catalytic pyrolysis unit (Y of unit) injects the LCCO quenchant at once.The product back of coming out is injected the LCCO quenchant at once in two outside rough lumber cyclonic separators in embodiment 8 and similar another catalytic pyrolysis unit (FCCU500) shown in Figure 2.In embodiment 9, inject the HCCO quenchant at once to making the product back of coming out in four inner rough lumber cyclones in Figure 12 and the catalytic pyrolysis unit similar shown in 13.Experiment condition is as follows to be reached shown in Figure 10 and 11:

Embodiment 7

Feeding rate 24,700B/D

951 of standpipe output temperatures

Quenchant medium LCCO

1500B/ of quenchant speed (6.1%)

Steam residence time 16SEC in separator

Combustion gases reduction 635M SCFD

K=(635M SCFD)/(24.7M B/D(16 second))=1.61SCF/BBL-Ssc

Embodiment 8

Feeding rate 77,000B/D

1017 of standpipe output temperatures

Quenchant medium LCCO

Quenchant speed 5500B/D(7.1%)

Steam residence time 9sec in separator

Combustion gases reduction 5MM SCFD

K=(5,000M SCFD)/(77M B/D(9 second))=7.21SCF/BBL-Ssc

Embodiment 9

Feeding rate 37,000B/D

980 of stand-pipe output temperature

Quenching medium HCO

Quenchant speed～3000B/D(8.1%)

Steam in the separator tube stagnant from time 13sec

Combustion gases reduction 1.5MM SCFD

K=(1,500M SCFD)/(37M B/D(13 second))=3.12SCF/BBL-Ssc

Embodiment 10-18

Make temperature of reactor rise to 940 °F (504 ℃) or more than, when being higher than 1000 °F (538 ℃), will reduce the oxidative stability of naphtha product and gasoline products especially.Active matrix octane catalyzer (contains overstable-Y zeolite, in zeolite, have or do not have to exchange the rare earth element of zeolite, be supported on the carrier matrix, the lytic activity that it shows and zeolite is irrelevant) also produce a naphtha product and a gasoline that is produced not as rare earth exchanged Y catalyzer and stablize, the Y catalyzer of rare earth exchanged produces the low octane petroleum naphtha of large volume.In addition, the Residual oil that is mingled with in the FCU incoming mixture will reduce naphtha product and stabilization of gasoline.

According to the present invention, quenching is by reducing dilution temperature mutually in the separator tube as much as possible after original rough lumber separating oil vapor product and mixture of catalysts, thereby in fact increased the oxidation and the package stability of naphtha product and gasoline.

The catalytic pyrolysis unit that has or do not have a turning oil quenchant is carried out the oxidisability test.In embodiment 10-13, gas oil enters as shown in Figure 1 similarly uses the quenchant pipeline of temporary transient local control to carry out catalytic pyrolysis in the catalytic pyrolysis unit (Y of unit), if point out, then after coming out, injects product the LCCO quenchant at once from outside rough lumber cyclonic separator.In embodiment 14-16, gas oil oil is fed in as shown in Figure 2 the similar catalytic pyrolysis unit (FCCU500), if point out, then injects the LCCO quenchant from two rough lumber cyclonic separators after product comes out at once.In embodiment 17 and 18, gas oil enters the similar catalytic pyrolysis unit (among the FCCU600) shown in Figure 12 and 13, if point out, then after coming out, injects product quenchant HCCO at once from the rough lumber cyclonic separator of two inside separator (separator tube).Experimental result is as follows:

Dilution phase FCU quenchant is to the FCCU petroleum naphtha

The effect of oxidative stability

Embodiment units of product stream

10 Y heavy catalytic naphtha

11 Y heavy catalytic naphtha

12 Y lightweight catalytic naphtha

13 Y lightweight catalytic naphtha

14??FCCU-500??C5-430

Total catalytic naphtha

15??FCCU-500??C5-430

Total catalytic naphtha

16??FCCU-500??C5-430

Total catalytic naphtha

17 FCCU-600 FCU wild gasolines

-2045 hours

18 FCCU-600 FCU wild gasolines

-2000 hours

Dilution phase FCU quenchant is to the FCCU petroleum naphtha

The effect of oxidative stability

Continuous

Embodiment standpipe output temperature dilution phase temperature quenchant fluid

10 940 940 do not have

11??941??903??LCCO

12 940 940 do not have

13??941??903??LCCO

14 1,019 999 do not have

15??1020??940??LCCO

16??1019??939??LCCO

17 1,020 990 do not have

18??1020??910??HCCO

Dilution phase FCU quenchant is to the FCCU petroleum naphtha

The effect of oxidative stability

Continuous

Feed composition ASTMD-525

The % stability of % hydrotreatment

Embodiment %HVGO gas oil resistates (minute)

10??100??0??0??395

11??100??0??0??615

12??100??0??0??25

13??100??0??0??25

14??72??28??0??200

15??78??22??0??225

16??72??28??0??250

17??52??32??16??75

18??52??32??16??125

The embodiment 10-18 of front has shown the good action of quenching to product stability.

Embodiment 19-48

Carry out further oxidation stability test with the turning oil method of quenching.Inject the LCCO quenchant after coming out in two rough lumber cyclonic separators of product from the catalytic pyrolysis unit similar (FCCU500) at once to Fig. 2.Product to Figure 12 and catalytic pyrolysis unit (FCCU600) similar shown in 13 back of coming out in two inner rough lumber cyclonic separators in the separator (separator tube) inject the HCCO quenchant at once.Catalyst complex system is included among FCCU500 and the FCCU600.The equal temperature of power of standpipe output reflects the charging flow velocity of each unit (FCCU500 and FCCU600) and the cracking temperature of each unit (FCCU500 and FCCU600).Thereby the sampling spot from run-down lines is collected the stability that sample is measured LCN and HCN.ULR and LCN and the HCN fusion handled with the oxidation inhibitor additive.Condition and result are as follows:

Quenching is to containing the unleaded of FCCU product petroleum naphtha

The effect of the oxidative stability of regular grade (ULR) gasoline

The standpipe output temperature

Embodiment F CCU500 FCCU600 power all adds to catalyst complex

In residual percentage ratio

19??970??980??974??4.4

20??973??980??976??4.0

21??980??980??980??4.2

22??980??980??980??4.3

23??980??980??980??4.7

Average 977 980 978 4.3

Limit of error 5-3 0.2

24??980??981??980??4.3

25??983??983??983??4.4

26??975??985??979??4.4

27??985??985??985??4.4

28??985??985??985??4.4

29??985??985??985??4.3

30??985??985??985??4.5

Average 983 984 983 4.4

Limit of error 423 0.1

Quenching is to containing the unleaded of FCCU product petroleum naphtha

The effect of the oxidative stability of regular grade (ULR) gasoline

Total in ULR in ULR in ULR

The catalytic naphtha % of the HCN% LCN% of embodiment

19??50.3??14.5??64.8

20??49.8??19.2??69.0

21??56.5??14.0??70.5

22??58.0??14.7??72.7

23??56.0??9.2??65.2

Average 54.1 14.3 68.4

Limit of error 3.8 3.5 3.4

24??55.3??13.6??68.9

25??55.6??11.3??66.9

26??54.4??9.5??63.9

27??59.3??14.4??73.7

28??54.3??14.7??69.0

29??48.5??17.8??66.3

30??59.0??11.7??70.7

Average 55.2 13.3 68.5

Limit of error 3.6 2.7 3.2

Quenching is to containing the unleaded of FCCU product petroleum naphtha

The effect of the oxidative stability of regular grade (ULR) gasoline

ASTMD-525 in FCCU500 in FCCU600

The HCCO quenching of the LCCO quenching of oxidative stability

Embodiment ULR LCN HCN FCCU500 FCCU600

Whether 19 530 120 225

Whether 20 535 120 195

Whether 21 465 9 000

22 415--whether

23 400--whether

Whether average 469 110 207

Limit of error 63 17 16--

The 24 710 110＞240th, be

25 740 135 105 are

The 26 730 135＞240th, be

The 27 770 105＞300th, be

28 710 105-be

The 29 825 120＞300th, be

30 725--be

Average 744 118-as to be

Limit of error 41 14---

34??1010??1015??1012??6.4

35??1010??1015??1012??5.8

36??1010??1015??1012??5.5

37??1010??1015??1012??5.4

38??1010??1015??1012??5.4

39??1012??1015??1013??5.5

40??1012??1015??1013??5.7

41??1013??1016??1014??5.4

Average 1,011 1,015 1,012 5.8

Limit of error 1 0.2 1 0.5

42??1010??1020??1014??5.3

43??1010??1020??1014??5.3

44??1010??1020??1014??5.8

45??1010??1020??1014??6.0

46??1010??1020??1014??6.0

Quenching is to containing the unleaded of FCCU product petroleum naphtha

The effect of the oxidative stability of regular grade (ULR) gasoline

Total the urging in ULR in ULR in ULR

Embodiment HCN% LCN% fossil cerebrol %

31??56.0??12.3??68.3

32??56.0??12.6??68.6

33??50.0??15.2??65.2

34??52.0??15.7??67.7

35??49.0??14.8??63.8

36??56.0??9.0??65.0

37??55.1??12.5??67.6

38??55.1??12.5??67.6

39??54.7??12.7??67.4

40??56.5??10.5??67.0

41??59.3??13.6??72.9

Average 54.5 12.9 67.3

Limit of error 3.0 2.0 2.4

42??52.8??12.3??65.1

43??52.8??12.3??65.1

44??55.8??8.3??64.1

45??50.0??10.3??60.3

Quenching is to containing the unleaded of FCCU product petroleum naphtha

The effect of the oxidative stability of regular grade (ULR) gasoline

Oxidative stability at FCCU500 at FCCU600

In in

ASTMD-525 LCCO quenchant HCCO quenchant

Embodiment ULR LCN HCN FCCU500 FCCU600

31 415--have or not

32 420＞240＞240 have or not

33 395--have or not

34 330--have or not

35 340--have or not

36 355--have or not

37 335--have or not

38 320--have or not

39 340 90-have or not

40 330 105 75 have or not

41 335 90 135 have or not

Average 335--have or not

Limit of error 36----

42 720 120-have or not

43 720 105＞300 have

44 825 105＞240 have

45 710 105＞240 have

46 710 105＞240 have

Embodiment 49-54

Also reduce the yield of diolefine in the quenching of the downstream of rough lumber cyclonic separator.It is believed that diolefine (molecule that contains two unsaturated C-C keys) has been proved conclusively to be hot tearing product rather than catalytic cracking reaction products, they in pyritous FCCU, form or in FCCU the residence time long and form.By reducing the temperature in the separating area belt, adopt quenching can reduce the yield of diolefine.

C ₄It is harmful that diolefine (divinyl, particularly 1,3 divinyl) is considered in isobutane alkylation unit FCCU butylene class to be continued reaction; They cause acid alkylated catalyst too to dilute.

C ₅Diolefine include but not limited to isopentene, and 1,5-pentadiene and cyclopentadiene, they are considered to undesirable product in the FCCU product stream equally, if C ₅The FCCU product adds in the isobutane alkylation unit, at this C ₅C in the hydrocarbon stream ₅Diolefine can cause the acid alkylated catalyst excess dilution.

Interchangeable is to contain C ₅Can mix in the product gasoline with the FCCU product stream of high-molecular weight diolefine.In gasoline, the diolefine estimation can cause the instability of producing water.The compound reactive behavior height that contains two unsaturated link(age)s, it rapidly and oxygen or other substance reaction form undesirable jelly.

Therefore, need a kind of method that produces diolefine less.Make the quenching of reactor dilution phase will lower the yield of diolefine.It is complicated making the instable chemical reaction of gasoline.It is believed that diolefine is the participant in these reactions, but quenching relates to other molecular compound rather than diolefine then can improve stability if be implemented among the routine 19-48.

Provide the example that quenching reduces the diolefine yield below.C is arranged in the test ₅Diolefine exists.People wish that quenching can change the yield of other diolefine equally.

Split in the catalysis similar and to carry out yield test in the unit (FCCU500) to Fig. 2.From the vapor product pipe that leaves separator tube, obtain total C ₅The sample of-430 naphtha products.

Take out when embodiment 50 and standing tube reactor of sample of 51 are out of service.Other have a standing tube reactor still work, by single outside rough lumber cyclonic separator discharge to the common separation pipe.

Sample among embodiment 49 and the 52-54 takes out when standing tube reactor is worked simultaneously.At once in its rough lumber cyclonic separator downstream LCCO quenching, the material source of quenching is entered in the common separation pipe from the gaseous product of two outside rough lumber cyclonic separators.

The ratio of each standing tube reactor is identical among the embodiment 49,52 and 54, but all separates suitably, and ratio roughly is 50/50.In embodiment 53, the liquidity rate of quenchant is 2500b/d at the A delivery port, and the B delivery port is 4100b/d, and that total is 6600b/d.

Obtain following result like this:

The test of no quenchant

The C of cracking temperature fresh feed LCCO fresh feed ₅

Embodiment Temp B/D quenchant diolefine volume

49??1016°F（547℃）??73，500??0??0.21

50??1027°F（553℃）??48，900??0??0.22

51??1027°F（553℃）??48，900??0??0.17

Test with the LCCO quenchant

The C of cracking temperature fresh feed LCCO fresh feed ₅

Embodiment Temp B/D quenchant diolefine volume

52??1009°F（543℃）??80，600??7，000??0.08

53??1019°F（548℃）??76，500??6，600??0.11

54??1020°F（549℃）??74，600??6，300??0.11

Under essentially identical cracking temperature, adopt the LCCO quenching to make C ₅The diolefine yield reduces about 35-50%.

Select quenchant

In order there to be competent heating efficiency to make to cool off cracked oil product effectively that the hot tearing of oily product is counter reduces to minimum and allow recovery of heat carry out in the bottom of fractionator rather than at the top, so the boiling point of quenchant is 125 °F (52 ℃), preferably is at least 430 °F (221 ℃).What meet the requirements is, it is 100%-120% that the molecular weight of quenchant should be higher than 90 total expanding volumes during with the evaporation of restriction quenchant and oily product, oil product volume when being 103%-105% or no quenchant still less preferably, the volumetric expansion that is quenchant should be 0-20% catalytic pyrolysis oil volume, is 3%-5% catalytic pyrolysis oil volume or still less preferably.In addition, 900 °F (482 ℃-1100 °F (593 ℃) down in separator tube dilution phase region band the residence time be 1-30 in second quenchant should be reactionless active and to the hot tearing reactionlessness.Hydro carbons such as the first cracking of LCCO, HCCO, HCN, coker gas oil and coker distillate is well suited for as quenchant, because they are poorer than crossing raw material such as virgin gas oil and virgin naphtha undressed and crossing the reactivity of raw material such as the hydrotreatment that distillate is crossed in the gas oil and the hydrotreatment of hydrotreatment to the reactivity worth of thermo-cracking.In addition, quenchant is that boiling point is lower than 900F(482 ℃ preferably), be gasified totally in can the dilution mutually in separator so that can cool off the catalytic pyrolysis product effectively and avoid the wall and the pipeline coking of refining unit.

What meet the requirements is that quenchant has reduced C ₂The fuel gas product is so that there is than elevated operating temperature catalytic pyrolysis unit.

Table A demonstrates all character of quenchant.LCCO is also included within and takes pump intermediate product reflux in the boiling spread in this patent application, the material that API gravity and molecular weight are similar to LCCO shown in the Table A.

Table A

The character of quenchant

Nominal boiling point nominal API gravity molecular-weight average

430-650 11-30 200-300 of lightweight catalysis

Turning oil (LCCO) (221-343 ℃) average 20 average 215

650-850 2-25 250-350 of heavy catalytic cycle

(HCCO) (343-454 ℃) average 10

300-430 20-50 100-250 of heavy catalysis stone

The average 35-40 of cerebrol (HCN) (149-221 ℃)

500-650 30-35 210-300 of lightweight coker

Average 526 average 34 of gas oil (LCCO)

（260-343℃

Average 274 ℃)

The 430-650 of coke still 30-40 200-250

Average 504 35 average 215 of distillate

（221-343℃）

Average 262 ℃

Kerosene 320-530 °F

Average 400-35-45 150-200

450°F

(160-277 ℃) average 41 175

Average 204-

232℃

The 430-650 of hydrotreatment 35-45 225-265

Average 560 average 39.5 230 of distillate

（221-343℃）

Average 293

Virgin gas oil 650-1000 21-32 300-400

(VGO) (343-538) ℃ average 25 average 350

300-350 40-60 100-250 of heavy straight run

Average 325 50 150 of petroleum naphtha

（149-117℃）

Average 163 ℃

125-175 60-80 70-150 of lightweight virgin naphtha

Average 150 °F 70 125

（LVN）??（52-79℃）

Average 66 ℃

The gas oil 650-1000 of hydrotreatment 24-35 300-400

(343-538 ℃) average 29 average 350

Oily 700-1200-4 and+10 400-600 of octaneization

Average 900 average+2 average 500

（371-649℃）

Average 482 ℃

Residue 1000-1600 0-20 300-1000

(538-871 ℃) average 12 average 700

(H ₂O) 212 °F average 10 18

（100℃）

Quenching comprises a kind of fluid, better is that a kind of liquid is injected catalytic pyrolysis unit, is to be injected into the downstream of rough lumber separator (cyclonic separator) with stopped reaction preferably at once.As a rule, a kind of outstanding quench process:

1) carry out heat scission reaction and produce most economical benefit by reducing valuable product effectively, the heat scission reaction of valuable product is everlasting and is taken place after catalytic pyrolysis is finished substantially.

2) make in the running side effect reduce to minimum.

3) make practicality expend minimum.

Though many fluids can be used as quenchant because quench process is very complicated, the utmost point select the quenchant material and select the utensil of quenchant be remarkable neither be conspicuous.Outstanding on the one hand fluid may then not be accepted on the other hand.

Quench fluid cooling has also been diluted FCC standpipe product and has been reduced the yield of hot product.Fig. 7 and 8 has shown the ability of all quenchant cooled product stream, has promptly shown the relative cooling power of different fluid.The product temperature of quenching is drawn and is represented the effect of quenchant add-on.Before being illustrated in catalyzer rough segmentation is come out from oily product, LCCO/CAT among Fig. 7 just injects LCCO.The quenching additive of representing with per-cent is quench fluid and product steam weight ratio.The thermal capacity of quench fluid and vaporization heat thereof (if liquid) can influence cooling power.Water is very effective, every adding 1%(weight) then cool off 20 °F.Hydro carbons also is effectively, every adding 1%(weight) can cool off 7 °F approximately.Effect relatively poor (add 1%(weight) cooling is 4 °F because water vapour has evaporated) cooled product requires the quench fluid of huge amount before removing catalyzer, because catalyzer is keeping the amount of a large amount of heats and catalyzer very big (oily typically heavy 6 times).Though water provides good cooling, its defective has been offseted this advantage.

Table B

The hot production concentration quenchant C that quenchant is relative ₂Fuel gas

Molecular weight cracking ability concentration reduces %(weight)

Water 18 0.00 0.737 0.263 78.0

Hydrocarbon

Hydrocarbon 106 0.36 0.846 0.154 69.4

Hydrocarbon 114 0.59 0.856 0.144 68.0

Hydrocarbon 130 1.37 0.871 0.129 64.3

Hydrocarbon 201 0.65 0.913 0.087 65.7

Hydrocarbon 216 1.06 0.918 0.082 64.0

Hydrocarbon 245 2.46 0.927 0.073 60.8

Hydrocarbon 339 1.05 0.946 0.054 63.1

Hydrocarbon 365 1.71 0.950 0.050 62.1

Hydrocarbon 414 3.96 0.956 0.044 59.1

Add quenchant liquid the product temperature reduced, thereby and in the dilution standpipe concentration of product reduce fuel gas.The concentration of the residence time of the thermal degradation speed rate apparent temperature of standpipe product (and hydro carbons quenchant) in system, steam and the disturbance reponse (thermo-cracking ability) of material and decide.Reduce the standpipe production concentration and can slow down quench fluid itself owing to underspeeding rather than the standpipe product degradation of producing than the low-heat cracking ability.Table B provides at 1000F(538 ℃) the initial relative volumetric molar concentration of lower standing tube product and will account for the about 15%(weight of product) quench fluid of the various different molecular weights of ratio injects the concentration of quenchant afterwards.In table B and following table, C ₂It is about 13 seconds that the minimizing of fuel gas and hydrocarbon product moment are cooled to 1000 (538 ℃)-900 (482 ℃), residence times.Quench fluid (injection length liquid) is according to the different expanding volume differences that make of molecular weight).Minimum molecular weight expands maximum, thereby has diluted the standpipe product the biglyyest.Table B has assessed C according to laboratory experiment _2-The minimizing of fuel gas, table B also comprises the heat reactivity that quench fluid is relevant.Its C of low-molecular-weight quench liquid is arranged _2-Combustion gases generate minimum, because C _2-Combustion gases have the tendency of thermal destruction, and condition is that quench fluid reply thermo-cracking susceptibility itself is low.

The stability of quenchant is important, and the excessive substituent of unsettled quenching material requirement is that itself also promotes C _2-Generate.Table B comprises all fluidic thermostabilitys.From all quenchant fluidic laboratory tests, measure its thermostability (cracking performance).Value in the table is relevant with the heavy catalytic naphtha, and this petroleum naphtha is very similar to the standpipe product characteristics.Certainly the water of non-hydrocarbons can cracking extremely performance can be used as the index of hydro carbons.Hydrocarbon with low cracking performance has just provided satisfactory performance.

Mixing time also is the factor of a weight in quenching.In the quenchant fluid injected hot product steam, quenchant and product steam must mix as early as possible so that cool off with utmost dispatch.Two kinds of streams undercompoundings will have the extra time to carry out with regard to making thermal response.Inject the quenchant fluid with fog nozzle and can form minimum drop, can disperse soon and evaporate.

Table C is that it shows that mixing time is to reducing the effect of hot product according to the result who the LCCO quenchant is done the experiment gained.

Table C

To LCCO quenchant thirty years of age cooling time to reducing the effect of combustion gases

Product temperature cooling time (second) quenchant product % C _2-Combustion gases

(weight) reduces %

1000°F??1??15??92.4

（538℃）

1000°F??5??15??64.0

（538℃）

1200°F??1??60??92.4

（649℃）

1200°F??5??60??69.5

（649℃）

Steam expanded is an important factor when selecting suitable quenchant.Vaporized quenchant enters the product recovery system, and it must conform to method equipment and can be controlled.The selection of quenchant fluid is improper to cause the outflow of standpipe discharge to be interfered.And hinder catalyzer from the product steam, to separate, and cause that effective running of product fractionator is disturbed, for being disturbed, this class reduces to minimum, when becoming steam, the quenchant fluid should form minimum the expansion to avoid unstable and extreme stress level.Fig. 9 has shown for all quenchant liquid, quenching product flow volume and has been the function of the volume ratio of product stream as quench temperature decline.The LCCO quenchant just injected oily product before the symbol LCCO/CAT among Fig. 9 was illustrated in catalyzer rough segmentation is come out from oily product.Because a large amount of quenchants add to come cooled vapor and the low-molecular-weight large volume gas that produces, so gas, water vapour and propane greatly increase.Water is evaporation expansion basically also.The independent product steam of the volume ratio of the steam of water quenching is big by 20%.This huge expansion may should be avoided in the influence operation event of retroaction ground.On the other hand, liquid hydrocarbon has only almost neutral stereomutation.For liquid hydrocarbon, it is littler than water to be typically the enough high gas volume as a result of molecular weight.By concentrating the refrigerative product expansion of hydrocarbon is cancelled, it is constant that the flow rate of cubing as a result almost keeps.This standard and lower molecular weight cut back steam have formed contrast.

Consumption to quenchant in the practice limits to some extent.If quenchant consumption increase then benefit reduces.Standpipe product temperature is high more benefited also maximum in addition.Table D has set forth this point.In the table each is to the two kind levels of situation corresponding to the adding quenchant.Accompany quenchant can only reduce by 45% C 1000 °F (538 ℃) following pair _2-Yield.Increase by 4 times of quenchants down at 1200 °F (649 ℃) and have to 30% improvement.

Table D

Quenchant and C after the quenching after the quenching before the quenching before the quenching _2-Fuel gas

Time (second) temperature-time (second) temperature charge ratio % reduces %

Quenchant

1 1000 12 950 2.33 71.2 in water

（538℃）??（510℃）

1 1000 12 900 5 99.3+ of water

（538℃）??（482℃）

LCCO??1??1000°F??12??950°F??7??64.0

（538℃）??（510℃）

LCCO??1??1000°F??12??900°F??15??92.4

（538℃）??（482℃）

LCCO??5??1000°F??8??950°F??7??43.9

（538℃）??（510℃）

LCCO??5??1000°F??8??900°F??15??64.0

（538℃）??（482℃）

1 1200 12 1100 5 74.3 in water

（649℃）??（593℃）

1 1200 12 900 20 97.5 in water

（649℃）??（482℃）

LCCO??1??1200°F??12??1100°F??15??67.2

（649℃）??（593℃）

LCCO??1??1200°F??12??900°F??60??92.4

（649℃）??（482℃）

LCCO??5??1200°F??8??1100°F??15??45.8

（649℃）??（593℃）

LCCO??5??1200°F??8??900°F??60??68.5

（649℃）??（482℃）

Coking is another major criterion when the suitable quenchant of decision.The tendency height that forms carbonizing matter is deleterious to the quenchant fluid.The coking settling can limit technical process and can be compelled to stop work, and excessive carbonizing matter may retroaction also influences the thermal equilibrium of unit and uneconomical in the revivifier.On the other hand, the interaction of the catalyzer in the band of dilution zone reduces carbonizing matter in quenchant fluid and the separator tube by making, thereby the selectivity of having improved the unit carbonizing matter is more economical.

Adopting quenchant to increase practicality expends.Outstanding quenchant liquid can make these expend and reduce to minimum.Expend relevant: the quench fluid of replenish loss, pump quenchant fluid with following situation; Heat recuperation not exclusively and lose; Be used as the requirement of cooling and boiler's water; And addle handled.

Some hydro carbons quenching materials can carry out thermal destruction.C _2-Combustion gases are to produce by degraded.Adopt computer patterns to foretell that the character of all quenching mediums is to C at table E _2-The effect that crude product reduces.The quenchant fluid of degraded product shows can reduce C _2-Combustion gases.

Table E

The quenching materiality is to estimating the effect of use properties

The relative hot tearing quenchant of molecular weight C on average boils _2-Burning gas

Body

Pendulum point ABP concentration of separating ability reduces %

0.825??300??130??1.38??0.129??91.3

0.825??575??245??2.46??0.073??89.5

0.825??800??414??4.00??0.044??88.6

0.93??300??114??0.59??0.144??94.5

0.93??575??216??1.06??0.082??92.4

0.93??800??365??1.72??0.050??91.4

0.99??300??106??0.37??0.154??95.6

0.99??575??201??0.66??0.87??93.4

0.99??800??339??1.06??0.054??92.4

Expending of process water is almost completely uncorrelated as the quenching material with the employing hydrocarbon fluid.When water must be processed water during as quenchant.Adopt finished water to want other expending.It is just contaminated after this method of water process, must handle to satisfy the regulation that control is polluted it.

Recovery of heat also is an important factor when selecting suitable quenchant.A large amount of heats is absorbed by the quenching material.This heat must be reclaimed with a useful form when reality is used the quenchant method.In general, temperature is high more, and then recovery of heat is easy more.Therefore high boiling quenchant recovery of heat is better.In FCC catalytic pyrolysis unit, the thermal accumlation of recovery is in the product fractionator systems.Cryogenic energy typically loses in water coolant in the fractionator.The energy that streams is lower than 212 (100 ℃)-350 (177 ℃) is unrenewable, therefore, since the boiling point of water under normal pressure be 212 °F (100 ℃) and when its condensation the major part energy discharge, so it is bad quenching medium from the energy recovery angle.The fluid that boiling point only is lower than the quenchant temperature of index can have maximum recovery of heat.

Having proposed some among the F at table waits and selects quenchant fluid (the relation with relevant temperature of containing of LCCO, HCLO, HVGO, gas, oil, water.Heat Q ₁, Q ₂, Q ₃, Q ₄Represent that it can absorb heat (a) 625F(329 ℃), more than (b) at 625F(329 ℃) and 475F(246 ℃) between, (c) at 475F(246 ℃) and 325F(163 ℃) between (d) at 325F(163 ℃) and 60F(16 ℃) between.Preferably absorb the material of a large amount of heats (for example Q) at high temperature, (for example Q) is not preferential at the cryogenic absorption heat, and the material among the table F is material (1) HCCO that the quenching medium performance is arranged successively, (2) LCCO, and (3) gas oil is water at last.Maximum limit is 900F(482 ℃ to Q for quenching product temperature and each quenching).At 20psig(238kpa) measured value under the pressure.

Table F

FCCU product, quench fluid and can get the enthalpy of heat

LCCO??HCCO

Temperature can get the heat temperature can get heat

°F??BTU/LB??BTU/LB??°F??BTU/LB??BTU/LB

1,200 866.2 maximum product solubility 1,200 811.5 maximum product temperature

1174??846.9＜＝＝??1174??793.3＜＝＝

1125??810.5??1125??758.9

1050??756.1??1050??707.7

975??703.3??975??657.8

900??652.1??900??609.5

825??602.7??825??562.9

750 555.1 750 433.0＜==liquid

675??508.4??675??384.0

625??417.9??Q1＝234.2??625??353.7??Q1＝255.8

600 372.6＜==liquid 600 338.6

525??325.9??525??295.5

475??296.4??Q2＝121.4??475??268.3??Q2＝85.4

450??2881.7??450??254.7

375??239.9??375??216.4

325??313.8??Q3＝??82.7??325??192.7??Q3＝??75.6

300??200.7??300??180.9

225??164.5??225??148.4

150??131.3??150??119.3

75??101.8??75??94.0

60??95.9??Q4＝??117.9??60??88.9??Q4＝??103.8

32??84.9??32??79.5

Table F(is continuous)

FCCU product, quench fluid and can get the enthalpy of heat

Feed oil

（HVGO）

Gas oil water

Temperature LCCO can get the heat temperature can get heat

°F??BTU/LB??BTU/LB??°F??BTU/LB??BTU/LB

1,200 925.6 maximum product temperature 1,200 1639 maximum product temperature

1174??904.5＜＝＝??1174??1626＜＝＝

1125??864.8??1125??1600

1050??805.3??1050??1500

975??747.2??975??1522

900??678.6??900??1483

825 566.8＜==water 825 1445

750??509.6??750??1408

675??454.5??675??1371

625??419.2??Q1＝??259.4??625??1347??Q1＝??136.15

600??401.5??600??1335

525??350.7??525??1299

475??318.4??Q＝??100.8??475??1275??Q2＝??72

450??302.2??450??1263

375??256.3??375??1227

325??227.5??Q3＝??90.9??325??1203??Q3＝??72

300??213.1??300??1191

225??173.0??225??193

150??136.3??150??118

75 103.5 75 45＜==liquid

60??96.9??Q4＝??130.6??60??20??Q4＝??1175

32??84.7??32??0

The selection of quenching material:

Some quenchant fluids have been assessed among the table G.Different refinings can be with different quench material to satisfy the particular requirement of special occasions.Below in the fluid of Jian Chaing, LCCO the best, HCCO is secondly.Water has serial critical defect.Remaining material reduces successively as the attractability of quenchant.

Table G

The assessment of candidate quenching material

Quenchant water water vapour propane HCN LCCO HCCO

Cooling power E P P A A A

Product dilution E E E A G G

Stability E E E G G G

Volumetric expansion P P P A E E

Coking tendency E E E E G F

Pump/pass on G F F A A A

Recovery of heat P P P F G E

Water P P E E E E

Refuse is got rid of P P E E E E

Keyword:

P: bad F: general A: average G: good E: outstanding

Table G(is continuous)

The assessment of candidate quenching material

(HVGO) hydrotreatment hydrotreatment

Quenchant DCO gas oil kerosene is crossed the LCCO of gas oil

Cooling power A A A A A

Product dilution F F A F A

Stability G A A A A

Volumetric expansion E E E E E

Coking tendency P G E E E

Pump/pass on A A A A A

Recovery of heat E G G G G

Water E E E E E

Refuse is got rid of E E E E E

Keyword:

P: bad F: general A: average G: good E: outstanding

Novel catalytic pyrolysis and method of quenching and advantage of system are:

1. increase value and the quality of product.

2. make valuable hydro carbons recovery rate higher.

3. produce more naphtha and gasoline product.

4. high output

5. the output of product naphtha is better, and oxidation stability is higher.

6. thereby reducing thermal cracking makes the gasoline excessive fragmentation become the possibility of ethane and light Fuel gas to be down to minimum with product degradation.

7. pentadiene component in the reduction naphtha products.

8. produce the low fuel gas of value still less.

9. increase the octane number in naphtha and the final gasoline.

10. economical

11. efficient is high

12. effectively

Although the present invention has set forth some examples, be understood that this technical field personnel are to its all modification of making and alternative then without prejudice to the spirit and scope of the present invention.

Claims (21)

1, a kind of catalytic cracking method is characterized in that it comprises step:

Make feed oil place the reactor of catalytic pyrolysis unit, in the presence of catalyst for cracking, make catalytic pyrolysis produce the catalytic pyrolysis mobile product gas of selected oil; And

Make outside and the downstream part quenchant quenching of described product stream at described reactor, quenchant comprises that at least one is selected from the group of being made up of the distillate of light catalytic cycle oil, heavy catalytic cycle oil, heavy catalytic naphtha, kerosene, coker distillate, lightweight coker gas oil, hydrotreatment, fresh untreated virgin gas oil and fresh untreated virgin naphtha.

2, catalytic cracking method according to claim 1 is characterized in that wherein:

Described feed oil comprises gas oil;

Described quenching comprises the temperature that reduces described product stream again, makes the thermo-cracking of described product stream drop to minimum; And

In the 2%-20% amount suction described product stream of quenchant with every barrel of oil plant oil.

3, catalytic cracking method according to claim 1 is characterized in that wherein:

Described reactor comprises standing tube reactor

Described product steam carries out quenching after described catalytic pyrolysis is finished substantially;

Described quenchant contacts with described product stream, and quenching dosage is the 5%-15% of every barrel of stock oil.

4, a kind of catalytic cracking method is characterized in that it comprises the following steps:

Catalytic pyrolysis stock oil in the presence of catalyst for cracking;

After finishing substantially, described catalytic pyrolysis cools off stock oil that described catalytic pyrolysis crosses so that the amount that described catalytic pyrolysis oil is thermally cracked to fuel gas is reduced to minimum with the hydrocarbon liquids quenchant, the boiling point of hydrocarbon liquids quenchant is higher than water, molecular weight is greater than 90, and volumetric expansion is less than 20% of described catalytic pyrolysis oil volume.

5, catalytic cracking method according to claim 4 is characterized in that wherein:

Described quenchant is an inert to about 482 ℃-593 ℃ hot tearing reaction;

In the reactor of described feed oil by catalytic pyrolysis;

Described quenchant is selected from the group of being made up of the hydrocarbon of the straight run raw material of pre-cracking hydrocarbon, fresh undressed mistake and hydrotreatment;

Described catalytic pyrolysis oil is about 17 ℃-111 ℃ by described quenchant cooling range.

6, catalytic cracking method according to claim 4 is characterized in that wherein:

The cubical expansivity of described quenchant is less than 5%;

Described quenchant has improved the oxidative stability of naphtha products and gasoline;

The essential part boiling point of described quenchant is at least on 221 ℃ and is lower than 482 ℃, volatilization fully basically in dilution mutually.

7, catalytic cracking method according to claim 4 is characterized in that wherein said quenchant is selected from the group of being made up of light catalytic cycle oil, heavy catalytic cycle oil, heavy catalytic naphtha, coker gas oil and coker distillate.

8, catalytic cracking method according to claim 4, it is characterized in that it is included in makes described catalyzer separate from described catalytic pyrolysis oil basically in the rough lumber separator, the rough lumber separator has a vapor outlet port to make product output and near the product delivery port at described rough lumber separator after the separation described quenchant injected in the catalytic pyrolysis oil.

9, a kind of catalytic cracking method is characterized in that it comprises step:

Catalytic pyrolysis stock oil produces selected oil in catalytic pyrolysis unit in the presence of catalyst for cracking, stay pyrogenic catalyzer, catalytic pyrolysis unit comprises that a revivifier and at least one are selected from the catalytic cracking reaction device by standing tube reactor and group that fluidized-bed reactor is formed;

Described pyrogenic catalyzer is separated from described essential oil with the rough lumber separation;

After this make described selected oily quenching be thermally cracked to hydrocarbon product and the light hydrocarbon gas that is worth difference immediately to reduce selected oil widely;

In revivifier, make pyrogenic catalyst regeneration;

Make described regenerated catalyst recycle to described catalytic cracking reaction device.

10, catalytic cracking method according to claim 9 is characterized in that wherein:

Described selected oil is with about 2%-15%(volume) the quenchant of feed oil carry out quenching;

Described quenchant is to be selected from the group of being made up of lightweight circulation, heavy recycle stock, heavy catalytic naphtha and their combination;

Described quenching occurs in the downstream of described standing tube reactor.

11, a kind of catalytic cracking method is characterized in that it comprises step:

The fluid foods stream that the catalytic pyrolysis that the catalytic pyrolysis feed oil is produced contain the selected oil of catalyzer in the reactor of catalytic pyrolysis unit in the presence of catalyst for cracking is crossed;

Described catalyzer is separated from described selected oil basically;

Make selected oily quenching with quenchant in the upstream portion of described outside rough lumber separator downstream and described separator tube, quenchant comprises that at least one is selected from by light catalytic cycle oil, heavy catalytic cycle oil, heavy catalytic naphtha, kerosene, coker distillate, lightweight coker gas oil, hydrotreatment and crosses the group that distillate, fresh untreated virgin gas oil and fresh untreated virgin naphtha are formed;

Described quenchant is to account for every barrel of stock oil 2%-20%(volume) amount inject this streams.

12, a kind of catalytic cracking method is characterized in that it comprises step:

The oil that comprises the basic desalination of crude oil;

The crude oil of the described desalination of heating in stove;

With the crude oil pump of described heating to the primary distillation tower;

Heating in crude oil in the described primary distillation tower is separated into the streams of petroleum naphtha, elementary gas oil and the thick Residual oil of thick level.

With elementary thick stripper pump to the tube furnace vacuum column;

In described tube furnace vacuum column, make described elementary thick Residual oil be separated into wet gas stream, heavy gas oil and vacuum resid;

The stock oil that will comprise described elementary gas oil is transported to from described primary distillation tower in the standing tube reactor of vertical elongated of catalytic pyrolysis unit;

Fresh and regenerated crystallization catalyst for cracking are added in the described standing tube reactor;

Flowing in the selected mobile product that in described standing tube reactor, makes feed oil contain the catalytic pyrolysis oil of spent catalyst through the catalytic pyrolysis generation under the catalyst for cracking condition in the presence of the catalyst for cracking;

In described standing tube reactor downstream one outside rough lumber separator is arranged, among this, do roughing out a large amount of described useless coking catalysts are separated from described product steam described coking catalyst;

From described external separator, export the back at described product steam and become minimum with turning oil quenchant injection product gas so that the hot tearing of described product stream becomes to be worth the hydrocarbon of difference at once, thereby increased the yield of petroleum naphtha jointly, promptly fundamentally increased the formation of gasoline, described quenchant comprises and is selected from the group of being made up of light catalytic cycle oil and heavy catalytic cycle oil that described quenchant is with every barrel of feed oil 5%-15%(volume) amount injects product stream;

The product circulation of described quenching is transported in the dilution mutually of separator tube upper end;

Dilution at described separator tube is separated a large amount of residual useless pyrogenic catalyst fines in an inner cyclonic separator in the part mutually at least from the product stream of quenching;

Putting forward part at the gas of described separator tube puts forward volatile hydrocarbon gas from described pyrogenic catalyzer;

The coking catalyst of carrying through described gas then enters in the revivifier of described catalytic pyrolysis unit;

Air is injected revivifier;

In the presence of air, in described revivifier, the carbonizing matter on the spent catalyst burnt substantially and makes it regeneration;

Make the regenerated catalyst recycle to described standing tube reactor;

In fractionator, cracked oil is separated into light hydrocarbon gase, catalytic naphtha, comprises the lightweight catalytic cycle and catalytic cycle oil octane oil;

Externally have the quenchant injection tube to exist between cyclonic separator and described fluidized-bed reactor, the catalytic cycle oil of recirculation from the separator to the injection tube in as described quenchant.

13, catalytic pyrolysis unit is characterized in that it comprises;

A standing tube reactor that vertically prolongs with the mobile product stream of the elaboration that produces catalytic pyrolysis, stays pyrogenic catalyzer as catalytic pyrolysis feed oil in the presence of catalyst for cracking, and described standing tube reactor has a upper end portion and end portion;

An outside rough lumber separator that links to each other and communicate with the upper end portion of described standing tube reactor, be positioned at its height of standing tube reactor upper end portion as described position close with the top of described standing tube reactor and that carry with the similar liter that the top of standing tube reactor stands away, it is used for making described coking catalyst to separate from catalytic pyrolysis;

A vertical separator tube is used for making a large amount of residual coking catalysts to separate from described catalytic pyrolysis oil, described separator tube has a upper end dilution phase region band that has at least one inner separator, and a dense phase region band in lower end and the gas that has gas to carry device are put forward part;

The product pipe extends out between the upper end of described external separator and described pipe dilution phase part and is attached thereto;

Useless catalyst tube extends out and is attached thereto in the dense part in the lower end of described external separator and separator tube;

Revivifier comprises a tubular container, be used for transporting coking catalyst to vertically carrying of revivifier stretches pipeline, stretches the identical air injector of pipeline and be used for injecting air promoting described pyrogenic catalyzer burning with described carrying, and a regenerated catalyst pipe that links to each other with described standing tube reactor is used for regenerated catalyst is transported in the described standing tube reactor; And

The turning oil quenchant injection tube that links to each other and communicate with described input tube, it is used for and will derives in the external separator of described catalytic pyrolysis oil from standing tube reactor top, and from catalyzer after the roughing out but the quenchant that will comprise catalytic cycle oil before entering separator tube injects described catalytic pyrolysis oil with yield that increases petroleum naphtha and the thermo-cracking that reduces described oily product steam greatly, the described turning oil quenchant system that comprises is selected from the group of being made up of light catalytic cycle oil and heavy catalytic cycle oil, and described turning oil quenchant pipe comprises that vertical substantially light cycle injector is used for that described quenchant is injected input unit substantially vertically downward or it mixes with described product to increase described quenchant mutually with become 15 °-45 ° pitch angle with reference to vertical line.

14, a kind of catalytic cracking method is characterized in that it comprises the following steps:

The catalytic pyrolysis feed oil comprises the streams of catalytic pyrolysis effluent of the selected oil of catalyzer with generation in the presence of catalyst for cracking in the reactor of catalytic pyrolysis unit;

Described catalyzer is separated from described selected oil, and described rough lumber separator comprises the inertial separator that is selected from by inertia cyclonic separator and tank switching group that separator is formed;

In described separator tube, make selected oily quenching in the downstream of described inner rough lumber separator with quenchant, quenchant comprises that at least one is selected from the group of being made up of the virgin gas oil and the fresh untreated virgin naphtha of light catalytic cycle oil, heavy catalytic cycle oil, heavy catalytic naphtha, kerosene, coker distillate, lightweight coker gas oil, the distillate of hydrotreatment, fresh undressed mistake, and described quenchant injects described steam with the 2%-20% amount of every barrel of feed oil.

15, a kind of catalytic cracking method is characterized in that it comprises the following steps:

Comprise that crude oil is basic desalination oil;

The crude oil of the described desalination of heating in stove;

With described heating in crude oil pump to the primary distillation tower;

In described primary distillation tower, heating in crude oil is separated into the streams of elementary gas oil of petroleum naphtha and elementary Residual oil;

With described elementary stripper pump to the tube furnace vacuum column;

In described tube furnace vacuum column, make described elementary Residual oil be separated into wet gas, heavy gas oil and vacuum resid;

The feed oil that will comprise Residual oil is transported to the standing tube reactor that vertically extends in the catalytic pyrolysis unit from the primary distillation tower;

The fresh regenerated crystallization catalyst for cracking that reaches is added in the standing tube reactor;

The streams that makes described stock oil catalytic pyrolysis contain the mobile product of catalytic pyrolysis olein choosing of useless coking catalyst with generation in the presence of the described catalyst for cracking under the catalytic pyrolysis condition is arranged in described standing tube reactor;

In the inside rough lumber separator of separator tube dilution phase part a large amount of described useless coking catalysts are separated from described product steam, this separator is in the downstream of described standing tube reactor, and it comes out the rough segmentation from described product steam of described coking catalyst;

In flowing separator internally, described product comes out that the back injects that the turning oil quenchant makes described product stream quenching at once so that described product heat of steam is cleaved into the low value hydrocarbon is kept to minimum and increases the yield of petroleum naphtha jointly, and increasing gasoline greatly produces, described quenchant comprises and being selected from by light catalytic cycle oil and heavy group that catalytic cycle oil is formed that described quenchant is with about 5%-15%(volume of every barrel of feed oil) amount inject;

In the described dilution phase part of described separator tube, from described quenching product stream, isolate a large amount of residual spent catalyst fine powders at least one inner cyclone;

Carry part gas from pyrogenic catalyzer at the gas of described separator tube and propose volatile hydrocarbon;

The coking catalyst that described gas was carried is transported in the revivifier in the unit of described catalytic pyrolysis;

Air is injected described revivifier;

Carbonizing matter on the spent catalyst is burnt substantially and make catalyst regeneration; Regenerated catalyst is recycled in the standing tube reactor; And

Described quenching catalytic pyrolysis oil is fractionated into light hydrocarbon gas through a separator, catalytic naphtha, catalytic cycle oil it comprise the light catalytic cycle oil octaneization oil and;

Urge turning oil to be recycled to from the lightweight in the described fractionator and be used as described quenchant in the separator.

16,, it is characterized in that it comprises some Residual oils are added in the described standing tube reactor part as feed oil to comprise the quenchant part of heavy catalytic cycle oil according to claim 12 or 15 described catalytic cracking methods.

17,, it is characterized in that wherein light catalytic cycle oil is injected in the described feed oil as described quenchant one to small part according to claim 12 or 15 described catalytic cracking methods.

18, catalytic cracking method according to claim 15 is characterized in that wherein:

Described separation comprises that the mobile product stream that makes to come out impinges upon on the top board of tank switching separator from described standing tube reactor, make its bottom opening place through described tank switching separator discharge the catalyzer that separated, at least one window of the logical tank switching separator products export of the catalytic pyrolysis that separated oil is discharged;

Described quenching sprays into described turning oil near being included in described tank switching separator window.

19, a kind of catalytic pyrolysis unit is characterized in that it comprises:

One is vertically extended standing tube reactor, and it with the mobile product stream that the olein that produces catalytic pyrolysis selects, stays coking catalyst as catalytic pyrolysis stock oil in the presence of catalyst for cracking, and described standing tube reactor has a upper end portion and end portion;

A vertical separator tube, it links to each other with described standing tube reactor, it is used for isolating a large amount of coking catalysts from described catalytic pyrolysis oil, described separator tube has a upper end that has at least one inner cyclonic separator to dilute the phase region band, and a dense phase region band in lower end and the gas that has gas to carry device are put forward part;

An inner rough lumber separator, it is arranged in the dilution phase region band of described separator tube, be used for making the rough segmentation from described catalytic pyrolysis oil of described coking catalyst to come out, described inner rough lumber separator defines a steam orifice as oil export and the catalyst outlet of an end parts is arranged;

Revivifier comprises tubular container, vertically extends riser tubing is to be used for coking catalyst is transported to the described revivifier from described separator tube, air injector communicates with riser tubing and is used for injecting air and promotes pyrogenic catalyzer burning, and the regenerated catalyst pipe that links to each other with described standing tube reactor is used for regenerated catalyst is transported in the described standing tube reactor;

At least one turning oil injection tube that is used for quenching extend into the inside of described separator tube and basically with the oil export alignment of described inner rough lumber separator be used for described catalytic pyrolysis oil that oil output place at described inner rough lumber separator makes rough segmentation fall catalyzer go out the back inject comprise turning oil quenchant to increase the yield of petroleum naphtha, and reduce the thermo-cracking of oily product stream substantially, the described quenchant that comprises turning oil is selected from the group that oily light catalytic cycle oil and heavy catalytic cycle oil are formed.

20, catalytic pyrolysis unit according to claim 19 is characterized in that wherein said turning oil quenchant pipe with respect to what stretch out and vertically becomes 15 ° of-90 ° of oblique angles with reference to pipe from separator tube, can make described quenchant quantity of reflux reduce to minimum so basically.

21, catalytic pyrolysis unit according to claim 19, it is characterized in that wherein said revivifier is positioned at the separator tube below, described catalytic pyrolysis unit comprises the pipeline of basic horizontal, and it is that the standing tube reactor top is linked to each other with described inner rough lumber cyclone.

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