CN1923971A - Catalytic conversion method capable of increasing propylene yield - Google Patents

Abstract

The invention discloses a catalytic conversing method of increasing production propylene, which comprises the following steps: injecting preheat crude oil in the main elevating pipe of double-elevating reacting regenerating system; contacting with heat catalyst to proceed catalytic cracking reaction; separating production; recycling re-living agent; injecting liquid propylene in the auxiliary elevating pipe; proceeding olefin superposition; cracking and dehydrogenizing the superposition product; separating production; recycling the re-living agent. The catalyst is compound of two catalysts, which contains first cracking catalyst with Y-typed molecular sieve and second cracking catalyst agent with ZSM-5 molecular sieve, transition metal additive and phosphorus additive with the dried weight rate of first and second catalysts at 10-70:30-90.

Description

The catalysis conversion method of propylene enhancing

Technical field

The present invention relates to a kind of under the situation that does not have hydrogen catalytic conversion method of hydrocarbon oil, more particularly, be a kind of the petroleum hydrocarbon catalyzed conversion to be produced the light hydrocarbons product, improve the catalysis conversion method of productivity of propylene simultaneously significantly.

Background technology

Catalytic cracking is one of most important technological process of petroleum refining industry.Conventional catalytic cracking technology mostly adopts isodiametric single riser reactor and reaction-regeneration system flow process.In the riser tube reaction-regeneration system, the stock oil of preheating enters riser reactor through the feed nozzle system, contacts, vaporizes and react with high temperature catalyst (title regenerator) from revivifier.Constantly generate coke in the reaction process and be deposited on catalyst surface and the active centre on, make activity of such catalysts descend the selectivity variation.For this reason, coked catalyst (title spent agent) in time separated with reaction oil gas and enter revivifier carry out coke burning regeneration, and then recycle.Reaction oil gas then enters separation system and isolates light-end products, in the raw material after primary first-order equation unconverted heavy oil can enter once more and carry out cracking reaction in the riser reactor.The general industry riser reactor is about 30～40 meters, about 4～5 meter per seconds of reactor inlet rate of flow of fluid, and along with the carrying out of cracking reaction, the minimizing of product molecular-weight average, about 15～18 meter per seconds of fluid outlet flow velocity, about 1～3 second of total reaction time.

Though the bed reactor that the early stage catalytic cracking process of riser reactor adopts is much superior, but also there is the improved place of many needs, mainly show: (1) riser tube exit catalyst performance sharply descends, and second half section cracking reaction condition is more abominable; (2) for some secondary reaction, the reaction times is too short, thereby has suppressed some secondary reactions useful to quality product; (3) just near piston flow, still there is air-teturning mixed phenomenon from flow pattern in riser reactor; (4) reactor internal reaction condition is more single and fixing, difficultly adapts to current catalytically cracked stock and forms changeablely, and market requirement frequent variations causes complicated situation that products distribution and product property requirement are also changed at any time.For this reason, people constantly improve riser reactor, overcoming these drawbacks, such as:

A kind of two sections tandem riser reactors that are used for catalytic cracking are disclosed among the CN2380297Y.This reactor is made of two identical, connected head-to-tail riser reactors of structure, and each reactor is made up of riser tube, settling vessel, stripping section, inclined tube to be generated, revivifier, regeneration standpipe and regenerator sloped tube.Revivifier wherein can use jointly for the two-stage riser reactor, constitutes the two-way reaction-reprocessing cycle structure of a kind of two-stage riser, a revivifier.A kind of two-stage riser fluid catalytic cracking technology is disclosed among the CN1118539C, its technological process is: enter first section riser tube bottom from the regenerator of revivifier and contact, vaporize and react with stock oil, enter intermediate separator half reclaimable catalyst is separated with oil gas, half reclaimable catalyst returns revivifier and regenerates after gas is carried; The oil gas that goes out from middle separator enters second section riser tube, contacts with thermocatalyst from external warmer, proceeds catalytic cracking reaction.The technical characterstic of this two sections examination riser catalytic crackings is to have improved the average behaviour of catalyzer by oil gas series connection, catalyzer relay, can increase substantially per pass conversion and light-end products yield, improves the catalytic gasoline quality.

Disclosed adaptable multieffect catalyst cracking method among the CN1069054A adopts two independently riser tube and two corresponding settling vessels, uses with a kind of catalyzer, and light petroleum hydrocarbon is reacted under different reaction conditionss with heavy petroleum hydrocarbon.In first riser reactor, the thermocatalyst that light hydrocarbons and revivifier come reacts under 600～700 ℃, the condition of agent-oil ratio 10～40,2～20 seconds residence time, coke on regenerated catalyst 0.1～0.4 heavy %, with yield-increasing gas alkene, improve gasoline octane rating, remove impurity such as sulphur nitrogen, improve gasoline stability, reducing atmosphere is provided, heavy metal contaminants on the catalyzer is carried out passivation, for the cracking reaction of carrying out heavy hydrocarbon in catalyst recirculation to the second riser tube provides favourable condition.Heavy hydrocarbon reacts under conventional riser catalytic cracking reaction conditions.But this method is increased low carbon olefine output both, and passivation is deposited on metal pollutant on the catalyzer to a certain extent again.

In addition, also disclose in other many patents and adopt two riser tubes stock oil of different nature to be carried out the catalyst cracking method of selective cracking.Such as, USP5, disclosed cracking hydrocarbon method adopts duo-lift tube reactor cracking hydrocarbon raw material of different nature in 009,769.Wax oil and residual oil inject first riser tube, cracking under agent-oil ratio 5～10, the condition of 1～4 second residence time; Straight-run spirit, straight run intermediate oil and catalysis heavy petrol inject second riser tube, cracking under agent-oil ratio 3～12, the condition of 1～5 second residence time.Two riser tube ends enter in the same settling vessel, and shared follow-up fractionating system.This response style is mainly used in produces high aromatic hydrocarbons stop bracket gasoline and low-carbon (LC) hydro carbons.USP5,944,982 use duo-lift tube reactor, first riser cracking hydrocarbon feed, the light ends of second riser cracking device.The cracking in first riser tube of hydrocarbon feed and regenerator, cracked product is separated in first cyclone separation system with catalyzer, that the cracked product fractionation obtains is light, weigh two kinds of distillates, lighting end (mainly being gasoline) is injected second riser tube and is reacted once more behind hydrogenation, oil gas separates in second cyclone separation system with catalyzer.

A kind of riser reactor is disclosed among the CN1237477A, this reactor vertically be followed successively by co-axial each other pre lift zone, first reaction zone, enlarged-diameter from bottom to up second reaction zone, reduced outlet area, at the outlet area end one level pipe is arranged.It is different with the processing condition of second reaction zone that this reactor both can optionally have been controlled first reaction zone, can make the stock oil of different performance carry out the segmentation cracking again, obtains required purpose product.Producing Trimethylmethane and being rich in the catalysis conversion method of isoparaffin gasoline based on above-mentioned new texture riser reactor disclosed among the CN1232069A, this method is that the stock oil after the preheating is entered a reducing reactor that comprises two reaction zones, contact with the cracking catalyst of heat, 530～620 ℃ of first reaction zone temperatures, 0.5～2.0 second reaction times; 460～530 ℃ of second reaction zone temperatures, in 2～30 seconds reaction times, after the reaction product isolated, reclaimable catalyst enters through stripping and recycles after revivifier burns.Adopt Trimethylmethane content 20～40 heavy % in the liquefied gas that this method produces, isoparaffin content 30～45 heavy % during gasoline family forms, olefin(e) centent is reduced to below the 30 heavy %, and its research octane number (RON) is 90～93, and motor-method octane number is 80～84.

Propylene is important Organic Chemicals, and along with the continuous growth to derivative demands such as polypropylene, the whole world rapidly increases the demand of propylene.In some areas, such as China, the propylene market value is far above other lower carbon number hydrocarbons.Catalytic cracking also is to produce the especially important technology of propylene of light olefin except producing light Fuel oil productions such as gasoline, diesel oil.At present, the propylene feedstocks in the whole world about 32% originates from catalytic cracking process.Improve though above technology has been carried out some to riser reactor, overcome many deficiencies of conventional riser reactor, do not consider to excavate to greatest extent the potentiality of catalytic cracking propylene-increasing.

More catalytic cracking unit mainly is the catalyzer that contains the ZSM-5 zeolite by use at present, changes the reaction conditions increase scission reaction degree of depth simultaneously and increases light olefin and productivity of propylene.Such as USP5,318,696, USP5,997,728, CN1034223C, USP6,566,293, USP5,171,921, USP6,080,303, USP5,472,594, USP2002/0049133A1 and CN1465527A etc.

A kind of catalytic cracking process that increases productivity of propylene is disclosed among the USP2002/0003103A1.The near small part gasoline product of this technology enters carries out cracking reaction again in second riser tube, and in the catalyst composition that is adopted except that containing macropore USY zeolite, the mineral binder bond component that also contains mesopore zeolites such as ZSM-5 and have cracking performance.Phosphorous in the mineral binder bond component wherein, its P/A1 ratio is 0.1～10.This technological process is increased low carbon olefine output significantly, particularly increases productivity of propylene.

A kind of two-stage catalytic cracking process of being produced C2～C4 alkene by the heavy hydrocarbon feedstocks selectivity is disclosed among the CN1299403A.This method comprises: in the presence of conventional large pore zeolite catalytic cracking catalyst, in first conversion zone of being made up of catalytic cracking unit heavy feed stock is changed into than low-boiling products.The naphtha fraction than in the low-boiling products that is generated entered by reaction zone, gas carry in second conversion zone that district, catalyst regeneration zones and fractionation zone form, contact the formation crackate with containing the zeolite catalyst of about 10～50 heavy % mean pore sizes less than about 0.7 nanometer under 500～600 ℃ of temperature, wherein productivity of propylene is up to 16.8 heavy %.

Disclose among the CN1423689A and a kind ofly changed into light olefin and naphtha by the turning oil that produces in the catalytic cracking reaction.This method is: the FCC charging is contacted under catalytic cracking condition in the first catalytic cracking stage with cracking catalyst produce crackate; At least a cycle oil fraction in the described crackate is carried out hydrogenation, gained hydrogenation turning oil and cracking catalyst contacted under catalytic cracking condition in the second fluid catalytic cracking stage form second crackate, the catalyzer that wherein was used for for the second cracking stage comprises and contains the catalyzer of aperture more than or equal to the large pore zeolite of 0.7 nanometer between the catalyzer of selecting the shape zeolite containing of about 50～95 heavy % and about 5～50 heavy %.

Disclose a kind of production premium among the CN1490383A and increased production light product and the catalytic conversion process of propylene and device.Wherein the catalytic cracking unit that is provided comprises catalytic conversion reactor, settling vessel and revivifier, wherein catalytic conversion reactor is a kind of series parallel structure of compound reducing, have first riser tube and second riser tube of two parallel connections, the two ends up and down of two riser tubes link with settling vessel and revivifier respectively.First riser tube is prepared section, heavy oil cracking section, is radially constituted than the catalytic conversion stage of heavy oil cracking section expansion and the outlet section that links with settling vessel that radially dwindles than catalytic conversion stage by pre lift zone, reaction respectively from bottom to top.Second riser tube constitutes by recycle stock pre lift zone, recycle stock soaking section, catalytic conversion stage with outlet section that the first riser tube catalytic conversion stage or settling vessel link respectively from bottom to top.Second riser tube also can be and the similar variable-diameter structure of first riser tube.Described catalytic conversion process is: prepare section in the reaction of the first riser tube bottom and inject quenching medium, contact with regenerated catalyst, generate oil gas; Inject in the heavy oil cracking section through the fresh feed oil of preheating, recycle stock and reprocessed oil slurry then inject the second riser tube pre lift zone top, and reactant contacts with regenerator in two riser tubes respectively and carries out cracking reaction, and enters catalytic conversion stage respectively; The oil gas that enters catalytic conversion stage carries out dimolecular reaction, aromizing and isomerization reaction under certain condition and reacts with the sulphur nitrogen transformation; Oil gas and catalyzer converges or carry out gas solid separation, catalyst regeneration respectively in two riser tubes afterwards.This method is compared conventional catalytic cracking, can make the light product yield improve 0～3 percentage point; Content of olefin in gasoline can be reduced to below the 35v%, and extend inductive phase, and the sulphur nitrogen content reduces; Liquid gas propylene content can improve more than 5 percentage points.

A kind of method of producing propylene by catalytic cracking or thermal naphtha material selectivity is disclosed among the CN1383448A.This method is boiling point to be contacted less than the zeolite catalyst of about 0.7 nanometer greater than 180 ℃ carbon raw material and the mean pore size that contains 10～50 heavy % form pre-coked catalyst.In described second district, 500～600 ℃ of temperature, hydrocarbon partial pressure 10～40psia, 1～10 second residence time and agent weight of oil than 4～10 reaction conditions under, petroleum naphtha is contacted with described pre-coked catalyst form crackate, wherein productivity of propylene is up to 16.8 heavy %.

Though above technology is obtaining some progress aspect the increase catalytic cracking productivity of propylene, but all mainly be to rely on the liquefied gas yield that improves catalytic cracking to improve propene yield, owing to be subjected to the restriction of drastic cracking, isomerization, aromizing and hydrogen transfer reactions under the catalytic cracking reaction condition, its limitation that increases catalytic cracking unit propylene selectivity and productive rate is still very big.

Summary of the invention

The objective of the invention is on the basis of existing technology, provide a kind of petroleum hydrocarbon is carried out catalyzed conversion production light hydrocarbons product, can improve the catalysis conversion method of productivity of propylene simultaneously significantly.

Method provided by the invention may further comprise the steps: (1) is injected the stock oil after the preheating in the main riser tube of double lifting leg reaction-regeneration system, contact with the catalyzer of heat and to carry out catalytic cracking reaction, reaction product isolated, reclaimable catalyst recycles after stripping, regeneration; (2) the liquefied gas product that will isolate behind the propylene injects in the subsidiary riser as unstripped gas, contact with the catalyzer of heat, successively carries out alkene oligomerization, superimposed product cracking and dehydrating alkanes reaction, reaction product isolated, and reclaimable catalyst recycles after regenerating; Described catalyzer is two kinds of mixture of catalysts: contain first kind of cracking catalyst of Y zeolite and contain second kind of cracking catalyst of ZSM-5 molecular sieve, the butt weight ratio of first kind of cracking catalyst and second kind of cracking catalyst is 10～70: 30～90; Described second kind of cracking catalyst is made up of the ZSM-5 molecular sieve of 10～65 heavy %, the clay of 0～60 heavy %, the inorganic oxide binder of 15～60 heavy %, the transition metal additives of 0.5～15 heavy % and the phosphorus additive of 2～25 heavy % by butt.Said transition metal additives and phosphorus additive are all in oxide compound.

In the method provided by the invention, described catalyst mixture preferably is made up of first kind of cracking catalyst of 15～55 heavy % and second kind of cracking catalyst of 45～85 heavy % by butt weight.

In the method provided by the invention, described second kind of cracking catalyst, a preferred prescription scheme is to be made up of the ZSM-5 molecular sieve of 20～50 heavy %, the clay of 10～45 heavy %, the inorganic oxide of 25～50 heavy %, the transition metal additives of 1～10 heavy % and the phosphorus additive of 5～15 heavy % by butt weight.

The ZSM-5 molecular sieve that contains in second kind of cracking catalyst has the MFI structure, and phosphorus and be selected from transition metal modified ZSM-5 molecular sieve preferably, is counted (0～0.3) Na with oxide compound at its anhydrous chemical expression ₂O (0.5～5) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M _xO _y(70～97) SiO ₂, wherein M is selected from Fe, Co or Ni, Fe preferably, and x represents the atomicity of M, y represents to satisfy the required number of M oxidation state; Wherein preferred modified zsm-5 zeolite anhydrous chemical expression is counted (0～0.2) Na with oxide compound ₂O (0.9～3.5) Al ₂O ₃(1.5～7) P ₂O ₅(0.9～10) M _xO _y(82～92) SiO ₂

Said transition metal additives is selected from the additive of one or more metals among Fe, Co and the Ni, preferably Fe additive in second kind of cracking catalyst.

In the method provided by the invention, described first kind of cracking catalyst is made up of the Y zeolite of 10～70 heavy %, the clay of 0～60 heavy %, the inorganic oxide binder of 15～60 heavy % by butt weight, preferably is made up of the Y zeolite of 25～50 heavy %, the clay of 25～50 heavy %, the inorganic oxide binder of 25～50 heavy %.

In first kind of cracking catalyst, contained Y zeolite is various Y type or the HY type molecular sieve that contains or do not contain rare earth, the Y zeolites that contain or do not contain the super-stable Y molecular sieves of rare earth of comprising that generally adopt in the prior art, and the present invention has no particular limits it.

In the method provided by the invention, described clay is conventionally known to one of skill in the art, the present invention has no particular limits it, can be selected from one or more the mixture that comprises in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, the tired clay material that takes off stone, wherein preferred kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired one or more the mixture that takes off in the stone.

In the method provided by the invention, described inorganic oxide binder is conventionally known to one of skill in the art, the present invention has no particular limits it, one or more the mixture that comprises pseudo-boehmite, aluminium colloidal sol, silicon-aluminum sol, water glass, phosphorus aluminium colloidal sol, the mixture of one or more in wherein preferred pseudo-boehmite, aluminium colloidal sol, silicon sol and the phosphorus aluminium colloidal sol.

In the method provided by the invention, described catalyzer can be by molecular sieve, clay, inorganic oxide binder, transition metal additives, and phosphorus additive adopts any method in the existing cracking catalyst technology of preparing comprise spray drying forming to prepare, and the present invention has no particular limits it.

In the method provided by the invention, the transition metal additives in described second kind of cracking catalyst exists with the form of the oxide compound of transition metal, phosphoric acid salt, phosphite, subphosphate, acid phosphate.Transition metal additives can be added the transistion metal compound introducing in any step before the spray drying forming in slurries in second kind of cracking catalyst preparation process, also can be by dipping or chemisorption transistion metal compound behind spray drying forming, roasting is introduced then, preferably introduces before the spray drying forming of catalyst preparation process.

Therefore, described transition metal additives may reside in any position that may exist of catalyzer, as may reside in the inside, duct of zeolite, the surface of zeolite, and may reside in the substrate material, can also be present in simultaneously in the surface and substrate material of inside, duct, zeolite of zeolite.

Wherein, described transistion metal compound is selected from the various mineral compound of transition metal and in the organic compound one or more.Described transistion metal compound can be soluble in water, also can be to be insoluble in water or water-fast compound.The example of transistion metal compound comprises oxide compound, oxyhydroxide, muriate, nitrate, vitriol, the phosphoric acid salt of transistion metal compound, organic compound of transition metal etc.Preferred transistion metal compound is selected from one or more in muriate, nitrate, vitriol and the phosphoric acid salt of Fe, Co, Ni.

When described transition metal additives is introduced in the catalyzer afterwards by spray drying forming, the preparation method comprises floods catalyzer or the chemisorption processing with the aqueous solution that contains transistion metal compound, carry out solid-liquid separation (if necessary), drying and roasting then, wherein the exsiccant temperature is a room temperature to 400 ℃, preferred 100-300 ℃, the temperature of roasting is 400-700 ℃, is preferably 450-650 ℃, roasting time is 0.5-100 hour, is preferably 0.5-10 hour.

In the method provided by the invention, the phosphorus additive in described second kind of cracking catalyst exists with the form of phosphorus compound (as oxide compound, phosphoric acid salt, phosphite, subphosphate, the acid phosphate of phosphorus).Phosphorus additive can add phosphorus compound in slurries before the catalyzer spray drying forming, or be incorporated in the catalyst component by inorganic oxide binder, when containing phosphorus aluminium colloidal sol in the inorganic oxide binder, both brought phosphorus in the roasting rear catalyst component, phosphorus aluminium colloidal sol can play the effect of substrate material and binding agent again, and this part phosphorus also belongs to phosphorus additive of the present invention.Phosphorus additive can also be introduced by roasting behind dipping or the chemisorption phosphorus compound after the catalyzer spray drying forming.

Therefore, described phosphorus additive may reside in any position that may exist in the catalyzer, as may reside in the inside, duct of zeolite, the surface of zeolite, and may reside in the described substrate material, can also be present in simultaneously in the surface and described substrate material of inside, duct, zeolite of zeolite.

Wherein, described phosphorus compound is selected from the various mineral compound of phosphorus and in the organic compound one or more.Described phosphorus compound can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound.The example of phosphorus compound comprises oxide compound, phosphoric acid, phosphoric acid salt, phosphite, hypophosphite, phosphorated organic compound of phosphorus etc.Preferred phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, aluminum phosphate, the phosphorus aluminium colloidal sol.

When described phosphorus additive is introduced in the catalyzer afterwards by spray drying forming in the catalyst preparation process, the preparation method comprises floods the aqueous solution of catalyzer with P contained compound or the chemisorption processing, carry out solid-liquid separation (if necessary), drying and roasting then, wherein the exsiccant temperature is a room temperature to 400 ℃, preferred 100-300 ℃, the temperature of roasting is 400-700 ℃, is preferably 450-650 ℃, roasting time is 0.5-100 hour, is preferably 0.5-10 hour.

In the method provided by the invention, described double lifting leg reaction-regeneration system comprises following equipment: main riser tube, subsidiary riser and shared revivifier, and gas-solid separation equipment.Wherein, main riser tube links to each other with revivifier with the regenerator inlet tube by the spent agent outlet pipe; Subsidiary riser links to each other with revivifier with the regenerator inlet tube by gas-solid separation equipment, links to each other with main riser tube by the spent agent inlet tube.

In the method provided by the invention, described riser tube is the conventional riser reactor of 1.5～30 meter per seconds for empty bed linear speed.The structure of conventional riser reactor is: diameter is 0.2～5 meter, and total height is 10～60 meters, but this structured data does not limit the present invention.

In the method provided by the invention, in main riser tube, the hydrocarbon oil crude material cracking generated products such as gasoline, diesel oil and liquefied gas, further transform the generation propylene by the propylene liquefied gas product that takes off of the near small part of subsidiary riser.

In the method provided by the invention, the effect of main riser tube is macromolecular hydrocarbon oil crude material cracking to be generated products such as gasoline, diesel oil and liquefied gas.Main riser tube can be conventional equal diameter riser reactor, also can be the reducing riser reactor described in the CN1237477A.Its operating method and operational condition also are similar to the reducing riser reactor described in conventional equal diameter riser reactor or the CN1237477A.

In the method provided by the invention, the stock oil that is suitable for can be petroleum cuts, residual oil or the crude oil of different boiling ranges, such as: time processing fraction oil comprises gasoline, diesel oil, decompressed wax oil, residual oil etc.; The mixture of the arbitrary proportion of two or more above-mentioned time processing fraction oil; Be mixed with time processing fraction oil or its mixture of wax tailings, deasphalted oil or other secondary processing fraction oil of 10～30 heavy %; Crude oil.

In the method provided by the invention, operational condition in the described main riser tube is that temperature of reaction is 450～650 ℃, the weight ratio (agent-oil ratio) of preferred 480～600 ℃, catalyzer and raw material is 1～25, preferred 3～20, the reaction times is 0.5～30 second, preferred 1～10 second, reactor pressure (absolute pressure) is 0.1～0.4MPa, preferred 0.15～0.35MPa.

In the method provided by the invention, the effect of described service hoisting pipe reactor is that the liquefied gas product of near small part after gas separation equipment is isolated propylene further transforms the generation propylene.The service hoisting pipe reactor vertically is followed successively by co-axial each other first reaction zone, second reaction zone, outlet area and level pipe from bottom to top, and wherein, the ratio of the height of first reaction zone, second reaction zone, outlet area is 10～40: 90～60: 0～25.

Subsidiary riser be the equal diameter riser tube, etc. linear speed riser tube or reducing riser tube.

If subsidiary riser is the reducing riser tube, the diameter ratio of its first reaction zone, second reaction zone, outlet area is 1: 1.5～5.0: 0.8～1.5.

One end of level pipe links to each other with outlet area, and the other end links to each other with settling vessel; When the height of outlet area is 0 to be riser reactor when not having outlet area, and an end of level pipe links to each other with second reaction zone, and the other end links to each other with settling vessel.The effect of level pipe is the product that reaction generates to be delivered to separation system with reclaimable catalyst carry out gas solid separation, and its diameter is definite as the case may be by present technique field personnel.

In the method provided by the invention, the described liquefied gas that removes propylene and promote medium from the subsidiary riser first reaction zone bottom injecting reactor, catalyzer is introduced reactor through the catalyst inlet pipe from the first reaction zone bottom, the catalyzer of introducing reactor from the first reaction zone bottom is a regenerator or/and the reclaimable catalyst of being drawn by main riser tube.

The temperature of reaction of first reaction zone is lower than the temperature of reaction of conventional catalytic cracking in the subsidiary riser, and the light hydrocarbon that helps not containing propylene carries out building-up reactions.Can and promote the temperature of medium by the regulator solution gasification, also can control the temperature of first reaction zone by the catalyst temperature that adjusting enters pre-riser tube.Can in the middle of the catalyst inlet pipe, increase the temperature that cooling tank reduces the catalyzer that enters reactor.

In the method provided by the invention, the temperature of the second reaction zone internal reaction thing gas and catalyzer is higher than the temperature of reaction of conventional catalytic cracking or identical with the temperature of reaction of conventional catalytic cracking in the service hoisting pipe reactor, helps further cracking of superimposed product and dehydrogenating propane and generates propylene.Control the temperature of second reaction zone by constantly replenishing high-temperature regenerated catalyst by the second reaction zone bottom, improve catalyzer cracking reaction activity thereby reach, the superimposed product of cracking carries out the purpose of dehydrogenation reaction.

In the method provided by the invention, described subsidiary riser reactor operating condition is: first reaction zone temperature is 150～450 ℃, preferred 250～400 ℃, reaction times are 0.5～2.0 second, the weight ratio of preferred 1～2.0 second, catalyzer and unstripped gas (agent gas than) is 1～30, preferred 3～21; The temperature of second reaction zone is 450～650 ℃, and preferred 480～600 ℃, reaction times are 3～20 seconds, and preferred 1～10 second, agent gas ratio are 3～60, preferred 5～40; Reactor pressure (absolute pressure) is 0.1～0.4MPa, preferred 0.15～0.35MPa.

In the method provided by the invention, reaction product and reclaimable catalyst can adopt conventional gas-solid separation equipment, separate such as conventional cyclonic separator, and the present invention has no particular limits it.

In the method provided by the invention, can adopt conventional gas fractionation plant to separate such as the conventional gas separation column with the isolating reaction product of reclaimable catalyst, isolate propylene, the present invention has no particular limits it.

In the method provided by the invention, revivifier can adopt conventional catalytic cracking regenerator, and the present invention has no particular limits it.The effect of revivifier is that spent agent is carried out coke burning regeneration, and offers the required heat energy of reaction in the reactor.Its operating method and operational condition also are similar to catalytic cracking regenerators such as routine.The regeneration of catalyzer is exactly that with the process that the coke in the catalyst mixture is burnt, this process is to well known to a person skilled in the art general knowledge in oxygen-containing atmosphere (being generally air).For example, in general, described regeneration temperature is 600～770 ℃, preferred 650～730 ℃." residual oil complete processing ", 282～338 pages (Li Chunnian writes, and Sinopec press published in 2002) summarize existing catalytic cracking reaction-regeneration system rapidly and revivifier.When adopting independent revivifier,, also suitably add cracking catalyst to be generated, residual oil or the solid fuel etc. of high coke content in the revivifier in order to improve the temperature of revivifier in the past.

The advantage that light hydrocarbons provided by the invention is produced propylene is:

When this reaction-regeneration system is used for hydrocarbon oil conversion, the hydrocarbon oil crude material cracking is generated products such as gasoline, diesel oil and liquefied gas by main riser tube, by reinforced low-carbon hydrocarbon building-up reactions, the further scission reaction of superimposed product and the dehydrogenating propane reaction successively under the differential responses condition of differential responses district in the subsidiary riser, liquefied gas product after gas separation system is isolated propylene is further transformed the generation propylene, thereby under the prerequisite that does not increase liquefied gas yield, improve the productive rate of propylene significantly.

The shared revivifier of subsidiary riser and main riser tube, the regenerative operation of subsidiary riser spent agent have also made full use of the heat energy that revivifier produces simultaneously continuously, simply, flexibly.

Description of drawings

Accompanying drawing is the catalysis conversion method schematic flow sheet of propylene enhancing provided by the invention.

Each numbering is described as follows in the accompanying drawing:

I-master's riser tube;

The II-subsidiary riser;

The III-revivifier;

1-stock oil pipeline; 2-subsidiary riser first reaction zone; 3-subsidiary riser second reaction zone; 4-subsidiary riser outlet area; 5-subsidiary riser level pipe; 6,7, the 8-gas-solid separation equipment; 9,10,11-regenerated catalyst pipeline; 12,13-reclaimable catalyst pipeline; 14-unstripped gas pipeline; 15-promotes the medium pipeline; 16-gas is carried vapour line; The 17-gas pipeline.

Below in conjunction with accompanying drawing method provided by the present invention is further described.

(1) pre-lift steam enters from main riser I pre lift zone through pre-lift medium pipeline 15, the regenerated catalyst of heat enters pre lift zone through regenerative agent inlet tube 9, by pre-lift steam regenerated catalyst is promoted, feedstock oil after the preheating and atomizing steam enter from pre lift zone through feedstock oil pipeline 1, mix backward upper motion with the thermocatalytic agent and under certain reaction condition, carry out cracking reaction, after reaction oil gas product and green coke catalyst mixture enter the air lift steam air lift of stripping section via pipeline 16 injections, carry out gas-solid by gas-solid separation equipment 6 and separate. The reclaimable catalyst of part green coke inactivation is divided into two parts, a part enters subsidiary riser the first reaction zone bottom through reclaimable catalyst pipeline 13, another part enters regenerator through reclaimable catalyst pipeline 12 and carries out coke burning regeneration, and the reaction oil gas product goes fractionating column to separate through oil-gas pipeline 17;

(2) mixture of the liquefied gas after the gas piece-rate system removes propylene and lifting medium enters from subsidiary riser II bottom through pipeline 14, the regenerated catalyst of heat enters the bottom of the first reaction zone 2 through regenerated catalyst pipeline 10 (or the spent agent of drawing from main riser is through spent agent inlet tube 13), unstripped gas mixes with the thermocatalytic agent and moves upward, in the first reaction zone, under 150～450 ℃ reaction temperature, carry out building-up reactions, then enter second reaction zone 3, mix with the high-temperature regenerated catalyst from regenerated catalyst pipeline 11, under 450～650 ℃ reaction temperature, carry out cracking and dehydrogenation reaction, product and green coke decaying catalyst mixture enter piece-rate system through outlet 4 and horizontal tube 5, carrying out gas-solid by gas-solid separation equipment 7 separates, the reclaimable catalyst of green coke inactivation enters and carries out coke burning regeneration among the regenerator III, and product is then separated through the oil-gas pipeline 17 body piece-rate system of degassing.

Embodiment

The following examples will give further instruction to the present invention, but be not therefore and restriction the present invention.

Among the embodiment and in the Comparative Examples, F ₁～F ₅Five modified zsm-5 zeolite samples are by the disclosed method preparation of CN1465527A, and its anhydrous chemical expression is elementary composition by the x-ray fluorescence spectrometry molecular sieve, obtains through conversion again.

Sample F ₁: 0.04Na ₂O3.57Al ₂O ₃4.0P ₂O ₅2.4Fe ₂O ₃90.49SiO ₂

Sample F ₂: 0.1Na ₂O5.0Al ₂O ₃2.0P ₂O ₅0.9Fe ₂O ₃92SiO ₂

Sample F ₃: 0.03Na ₂O2.2Al ₂O ₃4.9P ₂O ₅2.1Fe ₂O ₃90.8SiO ₂

Sample F ₄: 0.03Na ₂O5.1Al ₂O ₃4.8P ₂O ₅3.6Co ₂O ₃86.5SiO ₂

Sample F ₅: 0.1Na ₂O5.2Al ₂O ₃4.5P ₂O ₅2.0Ni ₂O ₃88.2SiO ₂

Among the embodiment, pseudo-boehmite is Shandong Aluminum Plant's manufacture product, solid content 60 heavy %; The Industrial products that aluminium colloidal sol is produced for the Qilu Petrochemical catalyst plant, Al ₂O ₃Content is 21.5 heavy %; Kaolin is the special-purpose kaolin of cracking catalyst that Suzhou kaolin company produces, solid content 78 heavy %; The Industrial products that water glass is produced for the Qilu Petrochemical catalyst plant, SiO ₂Content 28.9 heavy %, Na ₂O content 8.9 heavy %; The ZRP-5 zeolite is the Industrial products of the conventional MFI structural zeolite of Qilu Petrochemical catalyst plant production, wherein P ₂O ₅2.5 heavy %, degree of crystallinity 85 heavy %, silica alumina ratio 50.

Phosphoric acid, iron trichloride (FeCl ₃.6H ₂O), nickelous nitrate (Ni (NO ₃) ₂.6H ₂O) and Xiao Suangu (Co (NO ₃) ₂.6H ₂O) be chemically pure reagent, be the Beijing Chemical Plant and produce.

The preparation process of second kind of cracking catalyst in embodiment 1～8 explanation method provided by the invention.

Embodiment 1

Phosphorus aluminium colloidal sol preparation: with 1.05 kilograms of pseudo-boehmites (butt) and 3.35 kilograms of decationizing water making beating 30 minutes, stir down and in slurries, add 4.9 kilograms of strong phosphoric acid (chemical pure, phosphoric acid 85 heavy %), be warming up to 70 ℃, under this temperature, reacted 45 minutes then, make water white phosphorus aluminium colloidal sol.P wherein ₂O ₅30.6 heavy %, Al ₂O ₃10.5 heavy %, pH is 1.7.

Get 2.00 kilograms of (butt) F ₁, 1.15 kilograms of (butt) kaolin and 0.65 kilogram of (butt) pseudo-boehmite, add 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of FeCl down ₃.6H ₂The aqueous solution of O (wherein contains 100 gram Fe ₂O ₃), the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 40 heavy %F ₁Zeolite, 23 heavy % kaolin, 27.5 heavy %Al ₂O ₃, 2.0 heavy %Fe additives are (with Fe ₂O ₃Meter) and 7.5 weight % phosphorus additives (with P ₂O ₅Meter) catalyst component B ₁

Embodiment 2

Get 1.84 kilograms of (butt) F ₂Zeolite, 1.33 kilograms of (butt) kaolin and 0.98 kilogram of (butt) pseudo-boehmite add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols were pulled an oar 120 minutes, stir to add 1 liter of FeCl down ₃.6H ₂The aqueous solution of O (wherein contains 250 gram Fe ₂O ₃), the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 36.8 heavy %F ₂Zeolite, 26.6 heavy % kaolin, 31.6 heavy %Al ₂O ₃With 5.0 heavy %Fe additives (with Fe ₂O ₃Meter) microballoon.

Get 1 kilogram of microballoon product (butt), add 10 liters of decationized Y sieve water and 100 gram Secondary ammonium phosphates, stir down and be warming up to 60 ℃, reaction is 20 minutes under this temperature, with dope filtration, drying, then in 500 ℃ of following roastings 2 hours, makes and contains 35 weight %F ₂, 25.3 heavy % kaolin, 30 heavy %Al ₂O ₃, 4.7 heavy %Fe additives are (with Fe ₂O ₃Meter) and 5 weight % phosphorus additives (with P ₂O ₅Meter) catalyst component B ₂

Embodiment 3

Get 2.63 kilograms of (butt) F ₃With 1.24 kilograms of (butt) pseudo-boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of FeCl down ₃.6H ₂The aqueous solution of O (wherein contains 526.5 gram Fe ₂O ₃), the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 52.63 heavy %F ₃, 36.84 heavy %Al ₂O ₃With 10.53 heavy %Fe additives (with Fe ₂O ₃Meter) microballoon.

Get 1 kilogram of microballoon product (butt), add 10 liters of decationized Y sieve water and 105 gram Secondary ammonium phosphates, stir down and be warming up to 60 ℃, in reaction under this temperature after 20 minutes,,, make and contain 50 weight %F then in 500 ℃ of following roastings 2 hours with slurries vacuum filtration, drying ₃, 35 heavy %Al ₂O ₃, 10 heavy %Fe additives are (with Fe ₂O ₃Meter) and 5 weight % phosphorus additives (with P ₂O ₅Meter) catalyst component B ₃

Embodiment 4

The preparation method is with example 1, and that different is the F that uses same amount ₄Replace F ₁, the kaolin consumption is 1.25 kilograms (butts), and with 1 liter of Co (NO ₃) ₂.6H ₂The O aqueous solution (containing 100 gram CoO) replaces FeCl ₃.6H ₂The O aqueous solution makes and contains 35 heavy %F ₄, 28 heavy % kaolin, 27.5 heavy %Al ₂O ₃, the Co additives (in CoO) of 2 heavy % and 7.5 weight % phosphorus additives are (with P ₂O ₅Meter) catalyst component B ₄

Embodiment 5

The preparation method is with example 1, and it is different that different is is F with same amount ₅Replace F ₁, the kaolin consumption is 1.25 kilograms (butts), and with 1 liter of Ni (NO ₃) ₂.6H ₂The O aqueous solution (containing 100 gram NiO) replaces FeCl ₃.6H ₂The O aqueous solution makes and contains 35 heavy %F ₅, 28 heavy % kaolin, 27.5 heavy %Al ₂O ₃, 2 heavy %Ni additives (in NiO) and 7.5 weight % phosphorus additives are (with P ₂O ₅Meter) catalyst component B ₅

Embodiment 6

Get B ₃Kilogram (butt) adds 10 liters of decationized Y sieve water and 157 gram Secondary ammonium phosphates, stirs down and is warming up to 60 ℃, after reacting 20 minutes under this temperature, with slurries vacuum filtration, drying, then in 500 ℃ of following roastings 2 hours, makes and contains 46.25 and weigh %F ₃, 32.38 heavy %Al ₂O ₃, 9.25 heavy %Fe additives are (with Fe ₂O ₃Meter) and 12.12 weight % phosphorus additives (with P ₂O ₅Meter) catalyst component B ₆

Embodiment 7

Get 1.25 kilograms of (butt) F ₂, 1.25 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-boehmite, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of FeCl down ₃.6H ₂The aqueous solution of O (wherein contains 200 gram Fe ₂O ₃), the pH value of regulating slurries with hydrochloric acid soln is 3.0.Mixture is continued 30 fens kinds of making beating, adds 1304 gram Secondary ammonium phosphates, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 25 heavy %F ₂, 25 heavy % kaolin, 30 heavy %Al ₂O ₃, 5 heavy %Fe additives are (with Fe ₂O ₃Meter) and 15 weight % phosphorus additives (with P ₂O ₅Meter) catalyst component B ₇

Embodiment 8

Get 1.75 kilograms of (butt) ZRP-5,1 kilogram of (butt) kaolin and 3.46 kg of water glass, add 5 kilograms of decationized Y sieve water making beating 120 minutes, stir and add 1 liter of FeCl down ₃.6H ₂The aqueous solution of O (wherein contains 750 gram Fe ₂O ₃), the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.With microballoon in 400 ℃ of following roastings 1 hour.

Get 1 kilogram of the microballoon (butt) after the above-mentioned roasting, add 10 liters of decationized Y sieve water and 100 gram ammonium chlorides, stir down and be warming up to 60 ℃, after washing 20 minutes under this temperature, the slurries vacuum filtration.By above identical method filter cake is relaundered once, under 120 ℃ of temperature, dry, make and contain 35 heavy %ZRP-5,20 heavy % kaolin, 2.5 heavy %Al ₂O ₃, 20 heavy %SiO ₂, 15 heavy %Fe additives are (with Fe ₂O ₃Meter) and 7.5 weight % phosphorus additives (with P ₂O ₅Meter) catalyst component B ₈

Comparative Examples 1

The explanation of this Comparative Examples contains F ₁, the reference catalyst CB of containing metallic additive and phosphorus additive not ₁And preparation.

Get 2 kilograms of (butt) F ₁, 1.25 kilograms of (butt) kaolin and 1.15 kilograms of (butt) pseudo-boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, add the hydrochloric acid that concentration is 36 heavy % under stirring, the consumption of hydrochloric acid makes that the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 40 heavy %F ₁, 25 heavy % kaolin and 35 heavy %Al ₂O ₃Reference catalyst component CB ₁

Comparative Examples 2

The explanation of this Comparative Examples contains F ₁With phosphorus additive, the reference catalyst CB of containing metallic additive not ₂And preparation.

Get 2 kilograms of (butt) F ₁, 1.25 kilograms of (butt) kaolin and 0.65 kilogram of (butt) pseudo-boehmite, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, add the hydrochloric acid that concentration is 36 heavy % under stirring, the consumption of hydrochloric acid makes that the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 40 heavy %F ₁, 25 heavy % kaolin, 27.5 heavy %Al ₂O ₃With 7.5 heavy % phosphorus additives (with P ₂O ₅Meter) reference catalyst component CB ₂

Comparative Examples 3

The explanation of this Comparative Examples contains F ₁With metal additive, the reference catalyst CB of phosphor-included additive not ₃And preparation.

Get 2 kilograms of (butt) F ₁, 1.25 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-boehmite, add 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of FeCl down ₃.6H ₂The aqueous solution of O (wherein contains 250 gram Fe ₂O ₃), the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating, the slurries that obtain 500 ℃ of temperature ins, are carried out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 40 heavy %F ₁, 25 heavy % kaolin, 30 heavy %Al ₂O ₃, 5 heavy %Fe additives are (with Fe ₂O ₃Meter) reference auxiliary agent CB ₃

Embodiment 9～16

Embodiment 9～16 is an example with the double lifting leg reaction-regeneration system of medium-scale, illustrates by B ₁～B ₈The effect of the catalyst mixture of forming with MLC-500.

The structure of duo-lift tube reactor is: the total height of main riser reactor is 15 meters, and riser tube pre lift zone and conversion zone diameter all are 0.25 meter; First reaction zone of service hoisting pipe reactor, second reaction zone, outlet area total height are 12 meters, and first reaction zone diameter is 0.25 meter, and it highly is 4.4 meters; Second reaction zone diameter is 1 meter, and it highly is 5.2 meters; The diameter of outlet area is 0.25 meter, and it highly is 2.4 meters; The drift angle of the longitudinal section isosceles trapezoid of first, second reaction zone combining site is 45 °; The base angle of the longitudinal section isosceles trapezoid of second reaction zone and outlet area combining site is 60 °.

Catalyst mixture carries out 12 hours burin-in process under 800 ℃, 100% water vapour atmosphere condition.Stock oil character sees Table 1, and catalyst mixture is formed, main operational condition and product distribute sees Table 3, table 4, table 5.

Embodiment 17

Present embodiment is an example with the double lifting leg reaction-regeneration system of medium-scale, illustrates by B ₁The effect of the catalyst mixture of forming with MLC-500.

The structure of duo-lift tube reactor is: the pre lift zone of main riser reactor, first reaction zone, second reaction zone, outlet area total height are 15 meters, and the pre lift zone diameter is 0.25 meter, highly are 1.5 meters; First reaction zone diameter is 0.25 meter, highly is 4 meters; Second reaction zone diameter is 0.5 meter, highly is 6.5 meters; The diameter of outlet area is 0.25 meter, highly is 4 meters; The drift angle of the longitudinal section isosceles trapezoid of first, second reaction zone combining site is 45 °; The base angle of the longitudinal section isosceles trapezoid of second reaction zone and outlet area combining site is 60 °.First reaction zone of service hoisting pipe reactor, second reaction zone, outlet area total height are 12 meters, and first reaction zone diameter is 0.25 meter, and it highly is 4.4 meters; Second reaction zone diameter is 1 meter, and it highly is 5.2 meters; The diameter of outlet area is 0.25 meter, and it highly is 2.4 meters; The drift angle of the longitudinal section isosceles trapezoid of first, second reaction zone combining site is 45 °; The base angle of the longitudinal section isosceles trapezoid of second reaction zone and outlet area combining site is 60 °.

Catalyst mixture carries out 12 hours burin-in process under 800 ℃, 100% water vapour atmosphere condition.Stock oil character sees Table 1, and catalyst mixture is formed, main operational condition and product distribute sees Table 3, table 4, table 5.

Comparative Examples 4～5

Comparative Examples 4～5 is an example with the medium-sized equal diameter riser reactor of routine, and the reaction effect of MLC-500 and CRP-1 is used in explanation respectively.

Catalyzer MLC-500, CRP-1 are the commercial catalysts that China Petrochemical Corp.'s Shandong catalyst plant is produced, and physico-chemical property sees Table 2.

Catalyzer carries out 12 hours burin-in process under 800 ℃, 100% water vapour atmosphere condition.Stock oil character sees Table 1, and operational condition and product distribute and see Table 3.

Comparative Examples 6～10

Present embodiment is an example with the double lifting leg reaction-regeneration system of medium-scale, and reference catalyst mixture (MLC-500, CRP-1, MLC-500+CB are used in explanation respectively ₁, MLC-500+CB ₂, MLC-500+CB ₃) effect.

Reaction unit is with embodiment 9.Catalyzer carries out 12 hours burin-in process under 800 ℃, 100% water vapour atmosphere condition.Stock oil character sees Table 1, and operational condition and product distribute and see Table 3 and table 4.

Comparative Examples 11

This Comparative Examples is an example with the reducing list riser reactor described in the CN1237477A, and the effect that uses reference catalyst CRP-1 is described.

The structure of reducing riser reactor is: the pre lift zone of reactor, first reaction zone, second reaction zone, outlet area total height are 15 meters, and the pre lift zone diameter is 0.25 meter, highly are 1.5 meters; First reaction zone diameter is 0.25 meter, highly is 4 meters; Second reaction zone diameter is 0.5 meter, highly is 6.5 meters; The diameter of outlet area is 0.25 meter, highly is 4 meters; The drift angle of the longitudinal section isosceles trapezoid of first, second reaction zone combining site is 45 °; The base angle of the longitudinal section isosceles trapezoid of second reaction zone and outlet area combining site is 60 °.

Catalyzer carries out 12 hours burin-in process under 800 ℃, 100% water vapour atmosphere condition.Stock oil character sees Table 1, and operational condition and product distribute and see Table 6.

Comparative Examples 12

This Comparative Examples adopts method provided by the invention, is example with the double lifting leg reaction-regeneration system of medium-scale, and the effect of reference catalyst CRP-1 is described.

Reaction unit is with embodiment 17.Catalyzer carries out 12 hours burin-in process under 800 ℃, 100% water vapour atmosphere condition.Operational condition and product distribute and see Table 6.

Table 1

The stock oil title	Grand celebration VGO+30VR
		Density (20 ℃), gram per centimeter 3	0.8905
Viscosity, millimeter 280 ℃ 100 ℃ of/seconds	39.83 22.13
		Zero pour, ℃	49
Carbon residue, heavy %	2.94
		Elementary composition, heavy % C H S N	86.48 13.18 0.15 0.19
Group composition, heavy % stable hydrocarbon aromatic hydrocarbons gum asphalt	64.5 24.2 11.1 0.2
		Metal content, ppm Ni V Fe	2.9 ＜0.1 3.2
Boiling range, ℃ initial boiling point 50% 63.4%	261 550 565

Table 2

The catalyzer trade names	MLC-500	CRP-1
			Active ingredient	REUSY	ZRP+USY
Chemical constitution, heavy % Al 2O 3 Na 2O	54.1 0.20	54.2 0.03
			Specific surface, m 2/g	252	160
Pore volume (water droplet method), ml/g	0.35	0.26
			Tap density, ml/g	0.69	0.86
Abrasion index, m%/h	1.5	1.2
			*Micro-activity after the burin-in process	65	64

^*The hydrothermal aging condition of catalyzer is 800 ℃, 100% water vapor, 12 hours.

Table 3

Example	Comparative Examples 4	Comparative Examples 5	Comparative Examples 6	Comparative Examples 7	Embodiment 9	Embodiment 10
							Catalyzer	MLC-500	CRP-1	MLC-500	CRP-1	30％ MLC-500 +70％B 1	30％ MLC-500 +70％B 2
Operational condition
							Main riser tube
Temperature of reaction, ℃	500	510	500	510	510	510
							Reaction times, second	3.5	3.5	3.5	3.5	3.5	3.5
Agent-oil ratio	5.0	6.5	5.0	6.5	6.5	6.5
							Water-oil ratio	0.05	0.05	0.05	0.05	0.05	0.05
Subsidiary riser
							One district's temperature, ℃	-	-	300	300	300	300
Two district's temperature, ℃	-	-	550	550	550	550
							Reaction times, second	-	-	6	6	6	6
One district	-	-	1.5	1.5	1.5	1.5
							Two districts	-	-	4	4	4	4
Outlet area	-	-	0.5	0.5	0.5	0.5
							One district agent gas ratio	-	-	10	10	10	10
Two districts agent gas ratio	-	-	30	30	30	30
							Take off propylene liquefied gas freshening amount (stock oil relatively), heavy %	-	-	12.33	19.68	23.02	24.56
Material balance, heavy %:
							Dry gas	1.01	2.20	1.15	2.40	2.50	2.52
Liquefied gas propane propylene butane butylene	17.15 1.83 4.82 3.14 7.36	30.24 1.81 10.56 3.97 13.90	16.51 0.76 8.01 3.84 3.90	31.05 1.22 18.02 4.28 7.53	37.12 1.25 25.56 5.13 5.18	38.79 1.56 23.49 7.15 6.59
							C 5+ gasoline	58.61	39.98	58.92	38.82	36.95	35.73
Diesel oil	11.15	10.59	11.23	10.82	10.18	10.04
							Heavy oil	6.19	11.87	6.18	11.71	7.61	7.23
Coke	5.89	5.12	6.01	5.20	5.64	5.69
							Transformation efficiency, heavy %	82.66	78.54	82.59	77.47	82.21	82.73

Table 4

Example number	Comparative Examples 8	Comparative Examples 9	Comparative Examples 10	Embodiment 11
					Catalyzer	30％MLC-500 +70％CB 1	30％MLC-500 +70％CB 2	30％MLC-500 +70％CB 3	30％MLC-500 +70％B 3
Operational condition
					Main riser tube
Temperature of reaction, ℃	510	510	510	510
					Reaction times, second	3.5	3.5	3.5	3.5
Agent-oil ratio	6.5	6.5	6.5	6.5
					Water-oil ratio	0.05	0.05	0.05	0.05
Subsidiary riser
					One district's temperature, ℃	300	300	300	300
Two district's temperature, ℃	550	550	550	550
					Reaction times, second	6	6	6	6
One district	1.5	1.5	1.5	1.5
					Two districts	4	4	4	4
Outlet area	0.5	0.5	0.5	0.5
					One district agent gas ratio	10	10	10	10
Two districts agent gas ratio	30	30	30	30
					Take off propylene liquefied gas freshening amount (stock oil relatively), heavy %	24.95	23.93	24.17	22.17
Material balance, heavy %:
					Dry gas	2.40	2.31	3.02	2.58
Liquefied gas propane propylene butane butylene	36.31 1.94 20.23 6.54 7.60	36.94 1.68 20.04 7.62 7.20	36.19 1.52 20.42 6.59 7.66	39.53 1.14 28.18 5.74 4.47
					C 5+ gasoline	37.53	37.52	36.09	34.25
Diesel oil	10.27	10.24	10.77	9.91
					Heavy oil	7.90	7.49	7.95	7.54
Coke	5.59	5.50	5.98	5.69
					Transformation efficiency, heavy %	81.83	82.27	81.28	82.55

Table 5

Example number	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16
						Catalyzer	15％ MLC-500 +85％B 4	50％ MLC-500 +50％B 5	30％ MLC-500 +70％B 6	10％ MLC-500 +90％B 7	30％ MLC-500 +70％B 8
Operational condition
						Main riser tube
Temperature of reaction, ℃	520	500	490	550	520
						Reaction times, second	3.5	3.5	3.5	3.5	3.5
Agent-oil ratio	7.0	6.0	6.5	6.5	6.5
						Water-oil ratio	0.05	0.10	0.05	0.0	0.0
Subsidiary riser
						One district's temperature, ℃	350	400	250	300	300
Two district's temperature, ℃	550	580	550	600	500
						Reaction times, second	6	6	6	6	6
One reaction zone	1.5	1.5	1.5	1.5	1.5
						Two reaction zones	4	4	4	4	4
Outlet area	0.5	0.5	0.5	0.5	0.5
						One district agent gas ratio	10	10	10	10	10
Two districts agent gas ratio	30	30	30	30	30
						Take off propylene liquefied gas freshening amount (with respect to stock oil), heavy %	22.18	20.25	23.18	22.37	24.11
Material balance, heavy %:
						Dry gas	2.48	2.31	2.10	2.89	2.21
Liquefied gas propane propylene butane butylene	36.98 1.39 25.94 5.57 4.08	30.39 1.81 21.12 5.21 2.25	37.45 1.21 25.25 5.62 5.37	35.92 1.95 24.34 4.71 4.92	36.69 1.35 24.52 5.19 5.63
						C 5+ gasoline	34.33	42.27	35.56	35.59	37.70
Diesel oil	11.25	12.10	11.31	11.73	10.47
						Heavy oil	9.61	7.14	7.97	8.43	7.31
Coke	5.35	5.79	5.61	5.44	5.62
						Transformation efficiency, heavy %	79.14	80.76	80.72	82.83	82.22

Table 6

Example number	Example 17	Comparative Examples 11	Comparative Examples 12
				Catalyzer	30％MLC-500 +70％B 1	CRP-1	CRP-1
Operational condition
				Main riser tube
Temperature of reaction, ℃	-	-
				One reaction zone	510	510	510
Two reaction zones	490	490	490
				Reaction times, second	6	6	6
Agent-oil ratio	6.5	6.5	6.5
				Water-oil ratio	0.05	0.05	0.05
Subsidiary riser
				One district's temperature, ℃	300	-	300
Two district's temperature, ℃	550	-	550
				Reaction times, second	6	-	6
One reaction zone	1.5	-	1.5
				Two reaction zones	4	-	4
Outlet area	0.5	-	0.5
				One district agent gas ratio	10	-	10
Two districts agent gas ratio	30	-	30
				Take off propylene liquefied gas freshening amount (with respect to stock oil), heavy %	21.03	-	22.13
Material balance, heavy %:
				Dry gas	2.20	2.20	2.10
Liquefied gas propane propylene butane butylene	37.38 2.49 24.79 6.02 4.08	33.41 2.68 11.23 6.31 13.19	33.46 1.89 19.35 6.57 5.65
				C 5+ gasoline	34.67	38.66	38.61
Diesel oil	10.71	10.65	10.62
				Heavy oil	9.85	9.94	9.97
Coke	5.19	5.14	5.24
				Transformation efficiency, heavy %	79.44	79.41	79.41

Claims (22)

1. the catalysis conversion method of propylene enhancing, it is characterized in that this method may further comprise the steps: (1) is injected the stock oil after the preheating in the main riser tube of double lifting leg reaction-regeneration system, contact with the catalyzer of heat and to carry out catalytic cracking reaction, reaction product isolated, reclaimable catalyst recycles after stripping, regeneration; (2) the liquefied gas product that will isolate behind the propylene injects in the subsidiary riser as unstripped gas, contact with the catalyzer of heat, successively carries out alkene oligomerization, superimposed product cracking and dehydrating alkanes reaction, reaction product isolated, and reclaimable catalyst recycles after regenerating; Described catalyzer is two kinds of mixture of catalysts: contain first kind of cracking catalyst of Y zeolite and contain second kind of cracking catalyst of ZSM-5 molecular sieve, the butt weight ratio of first kind of cracking catalyst and second kind of cracking catalyst is 10～70: 30～90; Described second kind of cracking catalyst is made up of the ZSM-5 molecular sieve of 10～65 heavy %, the clay of 0～60 heavy %, the inorganic oxide binder of 15～60 heavy %, the transition metal additives of 0.5～15 heavy % and the phosphorus additive of 2～25 heavy % by butt, and said transition metal additives and phosphorus additive are all in oxide compound.

2. method according to claim 1 is characterized in that in the described catalyst mixture that the butt weight ratio of first kind of cracking catalyst and second kind of cracking catalyst is 15～55: 45～85.

3. in accordance with the method for claim 1, it is characterized in that described second kind of cracking catalyst be made up of the clay of the ZSM-5 molecular sieve of 20～50 heavy %, 10～45 heavy %, the inorganic oxide binder of 25～50 heavy %, the transition metal additives of 1～10 heavy % and the phosphorus additives of 5～15 heavy % by butt.

4. in accordance with the method for claim 1, it is characterized in that described transition metal additives is one or more metal additives that are selected among Fe, Co and the Ni.

5. in accordance with the method for claim 4, it is characterized in that described transition metal additives is the Fe additive.

6. in accordance with the method for claim 1, it is characterized in that described ZSM-5 molecular sieve through phosphorus be selected from the metal-modified of Fe, Co or Ni, its anhydrous chemical expression, count (0～0.3) Na with oxide compound ₂O (0.5～5) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M _xO _y(70～97) SiO ₂, x wherein represents the atomicity of M, y represents to satisfy the required number of M oxidation state.

7. in accordance with the method for claim 6, it is characterized in that the anhydrous chemical expression of described modified zsm-5 zeolite, count (0～0.2) Na with oxide compound ₂O (0.9～3.5) Al ₂O ₃(1.5～7) P ₂O ₅(0.9～10) M _xO _y(82～92) SiO ₂

8. in accordance with the method for claim 6, it is characterized in that described modified zsm-5 zeolite is through phosphorus and Fe modification.

9. method according to claim 1 is characterized in that described first kind of cracking catalyst by butt, is made up of the Y zeolite of 10～70 heavy %, the clay of 0～60 heavy %, the inorganic oxide binder of 15～60 heavy %.

10. method according to claim 9 is characterized in that described first kind of cracking catalyst, is made up of the Y zeolite of 25～50 heavy %, the clay of 25～50 heavy %, the inorganic oxide binder of 25～50 heavy %.

11. method according to claim 9 is characterized in that described Y zeolite is Y type or the HY type molecular sieve that contains or do not contain rare earth, the super-stable Y molecular sieves that contains or do not contain rare earth.

12., it is characterized in that described clay is selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired one or more the mixture that takes off in the stone according to claim 1 or 9 described methods.

13., it is characterized in that described inorganic oxide is selected from one or more the mixture in aluminum oxide, silicon oxide, amorphous aluminum silicide, the phosphorus aluminium colloidal sol according to claim 1 or 9 described methods.

14. method according to claim 1, it is characterized in that described double lifting leg reaction-regeneration system comprises following equipment: main riser tube, service hoisting pipe reactor and shared revivifier, and gas-solid separation equipment, wherein, main riser tube links to each other with revivifier with the regenerator inlet tube by the spent agent outlet pipe; Subsidiary riser links to each other with revivifier with the regenerator inlet tube by gas-solid separation equipment, links to each other with main riser tube by the spent agent inlet tube.

15. method according to claim 1 or 14, the structure that it is characterized in that described subsidiary riser is: vertically be followed successively by co-axial each other first reaction zone, second reaction zone, outlet area and level pipe from bottom to top, link to each other with settling vessel by level pipe at the outlet area end, the first reaction zone bottom is connected the catalyst inlet pipe with the second reaction zone bottom.

16., it is characterized in that the catalyzer by first reaction zone bottom introducing reactor is that regenerated catalyst is or/and by the reclaimable catalyst of drawing in the main riser tube, the catalyzer of being introduced by the second reaction zone bottom is a regenerated catalyst according to the method for claim 15.

17., it is characterized in that the aspect ratio of described subsidiary riser first reaction zone, second reaction zone and outlet area is 10～40: 90～60: 0～25 according to the method for claim 15.

18. according to the method for claim 1 or 14, it is characterized in that described subsidiary riser be the equal diameter riser tube, etc. linear speed riser tube or reducing riser tube.

19., it is characterized in that first reaction zone, second reaction zone of described reducing riser tube, the diameter ratio of outlet area are 1: 1.5～5.0: 0.8～1.5 according to the method for claim 18.

20. method according to claim 1, it is characterized in that operational condition is: main riser reactor temperature of reaction is that the weight ratio of 450～650 ℃, catalyzer and stock oil is 1～25, reaction times is 0.5～30 second, and main riser tube internal reaction absolute pressure is 0.1～0.4MPa; Service hoisting pipe reactor first reaction zone temperature is that 150～450 ℃, reaction times are that the weight ratio of 0.5～2.0 second, catalyzer and unstripped gas is 1～30, the temperature of second reaction zone is that 450～650 ℃, reaction times are that the weight ratio of 3～20 seconds, catalyzer and unstripped gas is 3～60, and service hoisting inner reaction tube absolute pressure is 0.1～0.4MPa.

21. according to the method for claim 20, it is characterized in that operational condition is: main riser reactor temperature of reaction is 480～600 ℃; The weight ratio of catalyzer and stock oil is 3～20, and the reaction times is 1～10 second, and main riser tube internal reaction absolute pressure is 0.15～0.35MPa; Service hoisting pipe reactor first reaction zone temperature is that 250～400 ℃, reaction times are that the weight ratio of 1～2.0 second, catalyzer and unstripped gas is 3～21, the temperature of second reaction zone is that 480～600 ℃, reaction times are that the weight ratio of 3～10 seconds, catalyzer and unstripped gas is 5～40, and service hoisting inner reaction tube absolute pressure is 0.15～0.35MPa.

22., it is characterized in that described stock oil is petroleum fractions, residual oil or the crude oil of different boiling ranges according to the method for claim 1.

Images