CN1903434A - Catalyst for modifying faulty gasoline, preparing method and application thereof - Google Patents
Catalyst for modifying faulty gasoline, preparing method and application thereof Download PDFInfo
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- CN1903434A CN1903434A CN 200610048409 CN200610048409A CN1903434A CN 1903434 A CN1903434 A CN 1903434A CN 200610048409 CN200610048409 CN 200610048409 CN 200610048409 A CN200610048409 A CN 200610048409A CN 1903434 A CN1903434 A CN 1903434A
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Abstract
A catalyst for modifying the poor-quality gasoline by removing S from the gasoline is proportionally composed of the Zn and Ti modified molecular sieve, the Zn, Ti and optional RE modified carrier, and adhesive. The process for modifying the poor-quality gasoline features its two steps of reaction.
Description
Technical field
The invention belongs to PETROLEUM PROCESSING hydrocarbon oil refining field, relate to a kind of catalyst for modifying faulty gasoline and preparation method thereof, and the application of this kind catalyst for modifying faulty gasoline in a kind of inferior gasoline upgrading technology.
Background technology
In order to control the pollutant emission of vehicle exhaust, strict restriction has all been made to the olefin(e) centent and the sulfur content of motor petrol by the main developed country in the world.World fuel standard II, III and IV class motor petrol standard-required sulfur content are respectively less than 200 μ g/g, 30 μ g/g and 10 μ g/g, and olefin(e) centent is respectively less than 20v%, 10v% and 10v% (v% represents percentage by volume); Europe III, Europe IV motor petrol discharge standard require content of sulfur in gasoline respectively less than 150 μ g/g and 50 μ g/g, and olefin(e) centent is respectively less than 18v%.The 80m% of China's motor petrol (m% represents percetage by weight) comes catalytic cracking (FCC) technology, so alkene and sulfur content are all higher; Reducing the olefin(e) centent and the sulfur content of catalytically cracked gasoline, is the key that realizes the motor petrol quality upgrading.Improving the inferior patrol method for quality has a lot, utilizes the method for catalytic cracking unit modifying inferior patrol to be divided into two kinds of catalyst technology and technologies.The described combination of molecular sieve with desulfidation of Chinese patent CN1388220A is for a kind of chemical composition is ZnO/TiO
2/ Al
2O
3Oxide on surface coating molecule screen composition, the oxide on surface coating accounts for 2～20m% of combination of molecular sieve gross weight, the acting in conjunction by L acid in the B in molecular sieve acid and the oxide on surface coating removes the sulphur in the gasoline.GraceDavison company develops the D-Prism sulfur prodegradant (referring to the 31st～33 page of " oil Refining Technologies and engineering " 2004 the 3rd phase, " commercial Application of D-Prism sulfur prodegradant "), the D-Prism sulfur prodegradant that adds 10m% in the catalyst can make the sulfur content decline 25m% of FCC gasoline.Akzo Nobel company develops Resolve 750 sulfur prodegradants (referring to the 9th～12 page of " Industrial Catalysis " 2003 the 9th phase, " Aksu company olefine lowering catalyst and sulfur prodegradant are in the application of RFCCU "), Resolve 750 sulfur prodegradants that add 6m% in the catalyst can make the sulfur content decline 10m% of FCC gasoline.The LGSA sulfur prodegradant of domestic development is (referring to the 1st～4 page of " petroleum refining and chemical industry " 2004 the 2nd phase, " the catalytically cracked gasoline sulfur prodegradant is used to process the commercial Application of high content of beary metal raw material "), in catalyst, add 10m%, can make the sulfur content decline 14.6m% of FCC gasoline.Above-mentioned sulfur-lowing catalyst or sulfur prodegradant are all undesirable to the effect that reduces content of sulfur in gasoline.The GOR-Q olefine lowering catalyst is (referring to the 5th～8 page of " petroleum refining and chemical industry " 2002 the 7th phase, " GOR-Q reduces the commercial Application of content of olefin in gasoline catalytic cracking catalyst "), be y-type zeolite and the modification ZRP zeolite of in the FCC catalyst, introducing the oxide surface modification; This catalyst can make the olefin(e) centent of FCC gasoline reduce by 8.68 volume percentage points.Luoyang engineering research institute of petroleum chemical engineering company is main active component with the shape zeolite of selecting of poly-metal deoxide modification, develop LAP and fall alkene auxiliary agent (referring to the 23rd～27 page of " oil refining design " the 9th phase of calendar year 2001, " reducing the commercial Application of the LAP auxiliary agent of catalytic cracking gasoline olefine content "); The LAP auxiliary agent that adds 5～6m% in the catalyst can make the olefin(e) centent of FCC gasoline reduce by 5～8 volume percentage points.
At process aspect, MGD technology has the function that reduces content of olefin in gasoline (referring to the 19th～22 page of " petroleum refining and chemical industry " 2002 the 2nd phase, " Fujian refinery company catalytic cracking unit is used the commerical test of MGD technology ").MGD technology is divided into two sections to conventional FCC master's riser reactor, and hypomere is as the gasoline upgrading conversion zone, and epimere utilizes high agent-oil ratio and high activated catalyst reformulated gasoline as FCC master's riser conversion zone.Will take into account the reaction condition of downstream riser RFCC because of this technology, the amount of gasoline upgrading is limited, and it is limited therefore to fall the alkene amplitude, can make the FCC content of olefin in gasoline reduce by 10～12 volume percentage points.MIP technology is (referring to the 1st～5 page of the 8th phase of " petroleum refining and chemical industry " calendar year 2001, " produce the catalytic cracking new technology MIP of clean gasoline component "), adopt the novel reaction system and the corresponding technological conditions of series connection riser reactor pattern, optionally control cracking reaction, hydrogen transfer reaction and isomerization reaction.The novel reaction system optimization of this technology the primary first-order equation and the secondary response of catalytic cracking, first conversion zone is based on a cracking reaction, second conversion zone mainly increases hydrogen transfer reaction and isomerization reaction, suppresses the secondary cracking reaction.This technology can make 8～15 volume percentage points of content of olefin in gasoline decline, sulfur content decline 20～30m%.The FDFCC technology of Luoyang engineering research institute of petroleum chemical engineering company exploitation is (referring to the 15th～18 page of " oil Refining Technologies and engineering " 2003 the 3rd phase, " commerical test of adaptable multieffect catalytic cracking process technology "), employing one is arranged with the catalytic cracking unit of two riser reactors (heavy oil riser reactor and gasoline rising pipe reactor), two riser reactors all can processed different feedstock oil separately under the optimized reaction condition separately, make full use of the advantage of high activity state catalyst, for the desirable secondary response of gasoline provides independently upgrading space and reaction time fully, avoided influencing each other of gasoline upgrading and residual oil cracking.Because the ratio of gasoline upgrading is unrestricted, the alkene effect of falling of FDFCC technology improves greatly, content of olefin in gasoline 20～40 the volume percentage points that can descend, the sulfur content 25～40m% that descends.It is remarkable that this technology reduces the content of olefin in gasoline effect, but the content of sulfur in gasoline decline scope is limited.
Summary of the invention
Technical problem to be solved by this invention is: adopt existing catalyst or auxiliary agent and existing catalytic cracking process, it is lower that content of sulfur in gasoline reduces amplitude.
For addressing the above problem, the technical solution used in the present invention is: a kind of catalyst for modifying faulty gasoline, modified molecular screen by 5～65m%, the modified support of 20～80m% and the binding agent of 10～20m% are formed, described modified molecular screen is modification REY, REHY, REUSY, USY, ZSM-5, in the β zeolite one or both, molecular sieve modified element is zinc and titanium, described modified support is a modified kaolin, in the boehmite one or both, the support modification element is zinc and titanium, or rare earth, zinc and titanium, described binding agent is an aluminium colloidal sol, Ludox, a kind of or their mixture in the phosphorus aluminium colloidal sol, the element gross weight of modifying element accounts for 0.1～10m% of this kind modified molecular screen gross weight in each modified molecular screen, and modifying element zinc is 0.1～3.0 with the element wt ratio of titanium; The element gross weight of modifying element accounts for 0.1～20m% of this kind modified support gross weight in each modified support, and modifying element zinc is 0.1～3.0 with the element wt ratio of titanium, and rare earth is 0～0.5 with the element wt ratio of zinc and titanium sum.
The preparation method of above-mentioned catalyst for modifying faulty gasoline is characterized in that being made up of following steps:
A. molecular sieve modified: molecular sieve REY, REHY, REUSY, USY, ZSM-5 or the β zeolite that will treat modification joins in the zinc solution that the water soluble salt with modifying element zinc is mixed with, heating, stirring, filtration slurries, getting filter cake toasts, mills, sieves, through roasting, make the molecular sieve of zinc modification again; Above-mentioned molecular sieve behind zinc modification is joined in the titanium solution that the water soluble salt with the modifying element titanium is mixed with, heating, stir, filter slurries, get filter cake and toast, mill, sieve,, make the molecular sieve of zinc and titanium modification again through roasting;
During with the various Y zeolite of titanium solution modification behind zinc modification, in the process for preparation of titanium solution, add the complexing agent ethylenediamine tetra-acetic acid identical with the titanium ion molal quantity, dropping ammonia again, the pH value of controlling titanium solution is 2.5～7;
B. support modification: will treat that the carrier kaolin of modification or boehmite join in the zinc solution that the water soluble salt with modifying element zinc is mixed with, heating, stirring, filtration slurries, get filter cake and toast, mill, sieve,, make the carrier of zinc modification again through roasting; Above-mentioned carrier behind zinc modification is joined in the titanium solution that the water soluble salt with the modifying element titanium is mixed with, heating, stir, filter slurries, get filter cake and toast, mill, sieve,, make the carrier of zinc and titanium modification again through roasting;
Or more above-mentioned carrier after zinc and titanium modification is joined in the earth solution that the water soluble salt with the modifying element rare earth is mixed with, heating, stirring, filtration slurries, get filter cake and toast, mill, sieve,, make the carrier of rare earth, zinc and titanium modification again through roasting;
C. shaped catalyst: in deionized water, add binding agent, through one or both molecular sieves of modification, through one or both carriers of modification, add hydrochloric acid again to regulate the pH value of slurries, stir slurries, again through homogeneous, spray-drying, roasting, make catalyst afterwards.
Above-mentioned catalyst for modifying faulty gasoline is applied to inferior gasoline upgrading technology, it is characterized in that this technology comprises following process:
A. enter the bottom of heavy oil riser reactor from the regenerated catalyst of regenerator, contacting the back with the charging of heavy oil riser reactor reacts along the heavy oil riser reactor is up, after reaction finishes, the reaction logistics enters first settler by the top exit of heavy oil riser reactor and carries out catalyst and Oil-gas Separation, isolated heavy oil riser reactor reaction generation oil gas enters fractionating system and carries out fractionation, isolated reclaimable catalyst enters behind stripping at the first settler stripping section and carries out coke burning regeneration in the regenerator, regenerated catalyst part behind the regeneration in-situ regeneration is returned the heavy oil riser reactor, and another part enters the bottom of gasoline rising pipe reactor;
B. the regenerated catalyst that enters the gasoline rising pipe reactor bottom among the process A contacts up reaction of first conversion zone of back along the gasoline rising pipe reactor with the inferior patrol charging, the logistics of reaction afterreaction upwards flows, the bed reactor that enters the hole enlargement structure that is positioned at gasoline rising pipe reactor top of first conversion zone top continues reaction, after reaction in the bed reactor finishes, reactant flows to go up and flows, enter second settler by the top exit of gasoline rising pipe reactor and carry out catalyst and Oil-gas Separation, isolated gasoline rising pipe reactor reaction generation oil gas enters fractionating system and carries out fractionation, and isolated reclaimable catalyst enters behind stripping at the second settler stripping section and carries out coke burning regeneration in the regenerator;
The catalyst that uses in the said process is a catalyst for modifying faulty gasoline of the present invention, the reaction temperature of described gasoline rising pipe reactor first conversion zone is 300～600 ℃, reaction time is 0.7～3.0 second, oil ratio is 2～17, the reaction absolute pressure is 0.15～0.4MPa, and the reaction temperature of bed reactor is 300～600 ℃, and the reaction time is 2.5～10.0 seconds, oil ratio is 2～17, and the reaction absolute pressure is 0.15～0.4MPa.
Adopt the present invention, have following beneficial effect: catalyst for modifying faulty gasoline of the present invention, its modified molecular screen and modified support all contain modifying element.Modified molecular screen has thiophenic sulfur and the alkylating ability of low-molecular olefine in the gasoline of increasing, and has both reduced the olefin(e) centent of gasoline, has reduced the sulfur content of gasoline again, and this a part of sulphur is transferred in the fraction of diesel oil.Therefore carrier has the ability of sulfide in the very strong adsorbed gasoline owing to introduced modifying element; The final condensation of these sulfide is a coke, in regenerative process with the form of sulfur dioxide with fume emission.
The method of introducing modifying element in molecular sieve has a lot, for example ion-exchange, infusion process.What introduce among the CN 1388220A is a kind of face coat oxide process method, and what introduce among the CN 1057408A is a kind of high-temperature process method.Adopt diverse ways, the new position of modifying element in molecular sieve of introducing is just different, and its effect is also inequality.Zinc in the catalyst of the present invention, titanium modified molecular screen adopt immersion process for preparing, with the aqueous solution impregnated zeolite of zinc and titanium.Infusion process is simple, and impregnated molecular sieve is after baking, roasting, and modifying element just deposits and is combined on the molecular sieve, and evenly distributes on molecular sieve, plays the effect of regulating acidic zeolite.Zinc and titanium enter molecular sieve pore passage with ionic species, regulate the ratio of B acid and L acid in molecular sieve by controlling its content, utilize the sulfur content in the synergy reduction gasoline of B acid and L acid.Modifying element finally is to exist with the oxide state, oxide also is to be distributed in equably on the molecular sieve, has so just overcome the adverse effect to catalyst activity that the described oxide on surface coating of CN 1388220A is stopped up molecular sieve pore passage and caused thus greatly owing to particle; Simultaneously, be evenly distributed on titanium oxide (TiO on the molecular sieve
2) can not change fine and close rutile structure into by anatase structured yet, increased the stability that sulphur falls in catalyst.Simultaneously, the distance in B acid and L acid site is nearer, helps the sour acting in conjunction of B acid and L and removes sulphur in the gasoline.Modified support in the catalyst of the present invention also is to adopt immersion process for preparing, and the support modification element is evenly distributed on the carrier.
Catalyst for modifying faulty gasoline of the present invention is applied to inferior gasoline upgrading technology, and this technology is a kind of improved double lift pipe catalytic cracking technology.Principal character is the bed reactor that the hole enlargement structure is set on the top of gasoline rising pipe reactor, thereby the gasoline rising pipe reactor is divided into first conversion zone of bottom and second conversion zone (bed reactor) on top.The inferior patrol charging enters second conversion zone afterwards and continues reaction at first in the reaction of first conversion zone.Very fast because of olefine reaction speed, first conversion zone adopts the relatively short reaction time, makes reactions such as alkene generation hydrogen migration, aromatisation, isomerization and cracking, and the alkene major part in the gasoline is transformed, thereby reduces content of olefin in gasoline.The reaction time that second conversion zone (bed reactor) control is relatively long, so that the thiophene-type sulfide in catalyst and the gasoline fully reacts, sulfide is converted into hydrogen sulfide and from gasoline, removes, thereby reduce the sulfur content of gasoline rising pipe reformulated gasoline that reactor produces.
The inferior gasoline upgrading technology that adopts catalyst for modifying faulty gasoline of the present invention and use this catalyst, can make inferior patrol (particularly sulfur content, the higher catalytically cracked gasoline of olefin(e) centent) when olefin(e) centent keeps descending significantly (with respect to single riser catalytic cracking catalyst of routine and technology, olefin(e) centent reduces by 20～40 volume percentage points), its sulfur content has significantly reduction.Compare with the reformulated gasoline that the catalytic conversion process of the modifying inferior patrol of common double riser fluid catalytic cracking (referring to CN 1401740A) is produced with the employing conventional catalyst, the sulfur content of gasoline rising pipe reformulated gasoline that reactor produces of the present invention can further reduce by 50～75m%, and the full device product distributes good.(sulfur content is for 0.3～0.7m%) the oil refining enterprise, utilizes the present invention can directly production sulfur content to be lower than the motor petrol fuel that meets Europe III emission request that 150 μ g/g, olefin(e) centent are lower than 18v% for the moderate fcc raw material of some processing sulfur content.
The present invention is further detailed explanation below in conjunction with accompanying drawing, the specific embodiment and embodiment.Accompanying drawing, the specific embodiment and embodiment do not limit the scope of protection of present invention.
Description of drawings
Fig. 1 is the double lift pipe catalytic cracking schematic representation of apparatus of modifying inferior patrol of the present invention.
The specific embodiment
Catalyst for modifying faulty gasoline of the present invention is made up of the modified molecular screen of 5～65m%, the modified support of 20～80m% and the binding agent of 10～20m%.Described modified molecular screen is one or both in modification REY, REHY, REUSY, USY, ZSM-5, the β zeolite, and molecular sieve modified element is zinc and titanium.Described modified support is one or both in modified kaolin, the boehmite, and the support modification element is zinc and titanium, or rare earth, zinc and titanium.Described binding agent is a kind of or their mixture in aluminium colloidal sol, Ludox, the phosphorus aluminium colloidal sol.
The element gross weight of modifying element accounts for 0.1～10m% of this kind modified molecular screen gross weight in each modified molecular screen, and modifying element zinc is 0.1～3.0 with the element wt ratio of titanium.The element gross weight of modifying element accounts for 0.1～20m% of this kind modified support gross weight in each modified support, and modifying element zinc is 0.1～3.0 with the element wt ratio of titanium, and rare earth is 0～0.5 with the element wt of zinc and titanium sum than [being rare earth: (zinc+titanium)].When the element wt ratio of rare earth and zinc and titanium sum was 0, the support modification element was zinc and titanium, does not contain rare earth element.
Above-mentioned catalyst for modifying faulty gasoline, preferred content of each modifying element and proportioning are as follows: the element gross weight of modifying element accounts for 1～5m% of this kind modified molecular screen gross weight in each modified molecular screen, and modifying element zinc is 0.5～2.0 with the element wt ratio of titanium.The element gross weight of modifying element accounts for 5～10m% of this kind modified support gross weight in each modified support, and modifying element zinc is 0.5～2.0 with the element wt ratio of titanium, and rare earth is 0～0.25 with the element wt ratio of zinc and titanium sum.
Described modified molecular screen is preferably among modification REY, REUSY, the ZSM-5 one or both.Rare earth in the support modification element, preferred lanthanum, cerium.
When catalyst of the present invention is selected two kinds of molecular sieves for use, two kinds of molecular sieve modifications respectively; Two kinds of molecular sieves do not have the restriction of proportioning.When selecting two kinds of carriers for use, two kinds of carrier modifications respectively; Two kinds of carriers do not have the restriction of proportioning.
The preparation method of above-mentioned catalyst for modifying faulty gasoline, be made up of following steps:
A. molecular sieve modified: molecular sieve REY, REHY, REUSY, USY, ZSM-5 or the β zeolite that will treat modification joins in the zinc solution that the water soluble salt with modifying element zinc is mixed with, heating, stirring, filtration slurries, getting filter cake toasts, mills, sieves, through roasting, make the molecular sieve of zinc modification again; Above-mentioned molecular sieve behind zinc modification is joined in the titanium solution that the water soluble salt with the modifying element titanium is mixed with, heating, stir, filter slurries, get filter cake and toast, mill, sieve,, make the molecular sieve of zinc and titanium modification again through roasting;
Heating steps in the above-mentioned steps all is with the slurries heating and be maintained at 60～90 ℃; Whipping step all is to stir slurries 1～3 hour (h); The filter cake baking all is that filter cake was toasted 1～5 hour under 110～130 ℃ of temperature in baking oven; Calcination steps all is in 500～650 ℃ of roasting temperatures 1～5 hour in Muffle furnace.The preferred condition of above-mentioned steps is as follows: heating steps all is with the slurries heating and be maintained at 70～80 ℃; Whipping step all is to stir slurries 1.5～2.5 hours; The filter cake baking all is that filter cake was toasted 3～4 hours under 120 ℃ of temperature in baking oven; Calcination steps all is in 520～600 ℃ of roasting temperatures 3～4 hours in Muffle furnace.
In the above-mentioned steps, during with the various Y zeolites (REY, REHY, REUSY, USY) of titanium solution modification behind zinc modification, in the process for preparation of titanium solution, add the complexing agent ethylenediamine tetra-acetic acid (EDTA) identical with the titanium ion molal quantity, dropping ammonia again, the pH value of control titanium solution is 2.5～7.This be because, with the titanium solution that the water soluble salt of titanium is mixed with, the pH value is less than 1, various Y zeolites crystal structure are with this understanding understood destroyed.Therefore the present invention adopts above-mentioned method, and the pH value of regulating titanium solution is greater than 2.The purpose that adds complexing agent EDTA is the titanium ion (Ti in the complex solution
4+), Ti when next step regulates the pH value with ammoniacal liquor like this
4+Be unlikely to precipitation.Titanium ion is identical with the molal quantity of complexing agent EDTA, i.e. n (Ti
4+): n (complexing agent EDTA)=1, n represents molal quantity.The preferred condition of this step is that by adding complexing agent EDTA dropping ammonia again, the pH value of controlling described titanium solution is 3～4.
B. support modification: will treat that the carrier kaolin of modification or boehmite join in the zinc solution that the water soluble salt with modifying element zinc is mixed with, heating, stirring, filtration slurries, get filter cake and toast, mill, sieve,, make the carrier of zinc modification again through roasting; Above-mentioned carrier behind zinc modification is joined in the titanium solution that the water soluble salt with the modifying element titanium is mixed with, heating, stir, filter slurries, get filter cake and toast, mill, sieve,, make the carrier of zinc and titanium modification again through roasting.
Contain the modification of the carrier of support modification element rare earth, zinc and titanium, be again above-mentioned carrier after zinc and titanium modification to be joined in the earth solution that the water soluble salt with the modifying element rare earth is mixed with, heating, stirring, filtration slurries, getting filter cake toasts, mills, sieves, through roasting, make the carrier of rare earth, zinc and titanium modification again.
Heating steps in the above-mentioned steps all is with the slurries heating and be maintained at 60～90 ℃; Whipping step all is to stir slurries 1～5 hour; The filter cake baking all is that filter cake was toasted 1～5 hour under 100～130 ℃ of temperature in baking oven; Calcination steps all is in 500～650 ℃ of roasting temperatures 1～5 hour in Muffle furnace.The preferred condition of above-mentioned steps is as follows: heating steps all is with the slurries heating and be maintained at 70～80 ℃; Whipping step all is to stir slurries 1.5～4.5 hours; The filter cake baking all is that filter cake was toasted 3～4 hours under 120 ℃ of temperature in baking oven; Calcination steps all is in 520～600 ℃ of roasting temperatures 3～4 hours in Muffle furnace.
C. shaped catalyst: in deionized water, add binding agent, through one or both molecular sieves of modification, through one or both carriers of modification, add hydrochloric acid again to regulate the pH value of slurries.Stir slurries, again through homogeneous, spray-drying, roasting, make catalyst afterwards.Wherein, described binding agent is aluminium colloidal sol, Ludox, phosphorus aluminium colloidal sol, adds wherein one or more in the shaped catalyst step.
In the above-mentioned steps, add hydrochloric acid, make the pH value of slurries be controlled at 2.5～7 to regulate the pH value of described slurries; Stir the slurries step, stirred slurries 1～3 hour; Calcination steps is in 500～650 ℃ of roasting temperatures 1～5 hour in Muffle furnace.The preferred condition of above-mentioned steps is as follows: add hydrochloric acid and make the pH value of slurries be controlled at 3～4, stirring slurries 1.5～2.5 hours, calcination steps in Muffle furnace in 520～600 ℃ of roasting temperatures 3～4 hours.
The modifying element of various molecular sieves of catalyst of the present invention and carrier all derives from the water soluble salt of various modifying elements.The water soluble salt of the various modifying elements described in the above-mentioned catalyst preparation step can be nitrate, chlorate, sulfate, or other water soluble salt.The concentration of the modifying element solution that is mixed with by the water soluble salt of certain modifying element is determined according to the content of this kind modifying element in each modified molecular screen of catalyst and each modified support.The solution of the various modifying elements that relate in catalyst preparation process in addition, is the aqueous solution; In steps A, in the process for preparation of titanium solution, need to add complexing agent EDTA and the pH value of dropping ammonia during with various Y zeolite behind zinc modification of titanium solution modification with the control titanium solution, the solution of remaining various molecular sieve and support modification element is preparation according to a conventional method all, and does not need the pH value (all embodiment herewith) of regulator solution.
Catalyst for modifying faulty gasoline of the present invention is applied to the technology of inferior gasoline upgrading, implements on the double lift pipe catalytic cracking device of modifying inferior patrol of the present invention shown in Figure 1.This device is provided with heavy oil riser reactor 11, first settler 8, regenerator 10, gasoline rising pipe reactor 2 and second settler 5.The bottom of heavy oil riser reactor 11 is provided with heavy oil riser reactor feed entrance 121, and the bottom of gasoline rising pipe reactor 2 is provided with inferior patrol feed entrance 101.The top exit of heavy oil riser reactor 11 is connected with first settler 8, and the bottom is connected with regenerator 10 by first regenerator sloped tube and the first regeneration standpipe.The below that the below of first settler 8 is provided with the first settler stripping section, 9, the first settler stripping sections 9 is provided with first regeneration standpipe, and first regeneration standpipe is connected with regenerator 10.The top exit of gasoline rising pipe reactor 2 is connected with second settler 5, and the bottom is connected with regenerator 10 by second regenerator sloped tube and the second regeneration standpipe.The below that the below of second settler 5 is provided with the second settler stripping section, 3, the second settler stripping sections 3 is provided with second regeneration standpipe and second inclined tube to be generated, and the second settler stripping section 3 is connected with regenerator 10.
Be provided with the bed reactor 4 of hole enlargement structure on the top of gasoline rising pipe reactor 2.Bed reactor 4 comprises a cylindrical drum, and the top of cylindrical drum and bottom are connected with gasoline rising pipe reactor 2 by conical section respectively.The common liner insulating and wearing-resistant lining of the conical section of the cylindrical drum of bed reactor 4 and cylindrical drum top and bottom.Referring to Fig. 1, the conical section of bed reactor 4 cylindrical drums bottoms links to each other with gasoline rising pipe reactor 2, and to be interfaced to pipeline section between inferior patrol feed entrance 101 centers be that the bed reactor 4 of first conversion zone, 201, the first conversion zones, 201 tops of gasoline rising pipe reactor 2 is second conversion zone of gasoline rising pipe reactor 2.The interface that the conical section of bed reactor 4 cylindrical drums bottom links to each other with gasoline rising pipe reactor 2 is the top exit of first conversion zone 201, is again the bottom inlet of bed reactor 4.The length l of above-mentioned first conversion zone 201 (that is the conical section of bed reactor 4 cylindrical drums bottoms link to each other with gasoline rising pipe reactor 2 be interfaced to vertical range between inferior patrol feed entrance 101 centers) is generally 15～35 meters (m), the inside diameter D of bed reactor 4 cylindrical drums is generally 2.0～6.0 with the ratio of the inner diameter d of gasoline rising pipe reactor 2 first conversion zones 201, and the length L of bed reactor 4 is generally 1/15～1/4 of gasoline rising pipe reactor 2 total lengths.The length l of first conversion zone 201 is preferably 20～30 meters, the inside diameter D of bed reactor 4 cylindrical drums is preferably 2.5～5.0 with the ratio of the inner diameter d of gasoline rising pipe reactor 2 first conversion zones 201, and the length L of bed reactor 4 is preferably 1/10～1/5 of gasoline rising pipe reactor 2 total lengths.Two conical section of bed reactor 4 cylindrical drum tops and bottom only play transition, are connected effect, no concrete structure dimensional requirement.The total length of gasoline rising pipe reactor 2 is meant from inferior patrol feed entrance 101 centers to the length between the thick cyclone inlet of gasoline rising pipe reactor 2 top exits.The pipeline section that gasoline rising pipe reactor 2 is positioned at bed reactor 4 tops mainly be for the reactant stream of bed reactor 4 by, enter second settler 5, do not react basically in this section pipeline section.Device of the present invention is a kind of improved double lifting leg adaptable multieffect catalytic cracking unit, only is that with the difference of common double riser fluid catalytic cracking (shown in CN 1401740A) top of its gasoline rising pipe reactor is provided with the bed reactor of hole enlargement structure; All the other structures of device are identical with the common double riser fluid catalytic cracking then, therefore only carried out briefly bright.
Catalyst for modifying faulty gasoline of the present invention is applied to the technology of inferior gasoline upgrading, implements on double lift pipe catalytic cracking device shown in Figure 1; This technology comprises following process:
A. enter the bottom of heavy oil riser reactor 11 from the regenerated catalyst of regenerator 10 through the first regeneration standpipe and first regenerator sloped tube, contact afterwards along heavy oil riser reactor 11 up reactions with the heavy oil riser reactor charging 12 that enters by heavy oil riser reactor feed entrance 121.After reaction finished, the reaction logistics entered first settler 8 by the top exit of heavy oil riser reactor 11 and carries out catalyst and Oil-gas Separation; Isolated heavy oil riser reactor reaction generation oil gas 7 enters fractionating system and carries out fractionation, and isolated reclaimable catalyst regenerator 10 in carries out coke burning regeneration through the water vapour stripping after first regeneration standpipe enters at the first settler stripping section 9.Regenerated catalyst part in the regenerator 10 after the regeneration is returned heavy oil riser reactor 11, and another part enters the bottom of gasoline rising pipe reactor 2 through the second regeneration standpipe and second regenerator sloped tube;
B. the regenerated catalyst that enters gasoline rising pipe reactor 2 bottoms among the process A contacts first conversion zone, 201 up reactions of back along gasoline rising pipe reactor 2 with the inferior patrol charging 1 that is entered by inferior patrol feed entrance 101, the logistics of reaction afterreaction upwards flows, and the bed reactor 4 that enters the hole enlargement structure that is positioned at gasoline rising pipe reactor 2 tops of first conversion zone, 201 tops continues reaction.After reactions in the bed reactor 4 finished, reactant flowed to go up and flows, and entered second settler 5 by the top exit of gasoline rising pipe reactor 2 and carried out catalyst and Oil-gas Separation; Isolated gasoline rising pipe reactor reaction generation oil gas 6 enters fractionating system and carries out fractionation, and isolated reclaimable catalyst regenerator 10 in carries out coke burning regeneration through the water vapour stripping after second regeneration standpipe and second inclined tube to be generated enter at the second settler stripping section 3.
The catalyst that uses in the said process is a catalyst for modifying faulty gasoline of the present invention.The reaction temperature of described first conversion zone 201 is generally 300～600 ℃, and the reaction time is generally 0.7～3.0 second (s), and oil ratio is generally 2～17, and the reaction absolute pressure is generally 0.15～0.4MPa; The reaction temperature of bed reactor 4 is generally 300～600 ℃, and the reaction time was generally 2.5～10.0 seconds, and oil ratio is generally 2～17, and the reaction absolute pressure is generally 0.15～0.4MPa.Wherein, the reaction temperature of first conversion zone 201 is meant the top exit temperature of first conversion zone, and the oil ratio of first conversion zone 201 is the ratio of weight internal circulating load with the weight flow of inferior patrol charging of the first conversion zone inner catalyst.The reaction temperature of bed reactor 4 is meant the mean temperature of bed reactor inner catalyst bed, and the oil ratio of bed reactor 4 is the ratio of weight internal circulating load with the weight flow of inferior patrol charging of bed reactor inner catalyst.
Above-mentioned first conversion zone 201 and bed reactor 4 preferred reaction conditions are as follows: the reaction temperature of first conversion zone 201 is 400～500 ℃, and the reaction time is 1.0～2.5 seconds, and oil ratio is 4～12, and the reaction absolute pressure is 0.2～0.35MPa; The reaction temperature of bed reactor 4 is 400～500 ℃, and the reaction time is 3.5～8.0 seconds, and oil ratio is 4～12, and the reaction absolute pressure is 0.2～0.35MPa.
In the said process, the reaction condition of heavy oil riser reactor 11 is conventional catalytic cracking condition, and its key reaction condition is generally as follows: reaction temperature is 450～600 ℃, and the reaction time is 0.5～5 second, oil ratio is 3～10, and the reaction absolute pressure is 0.15～0.4MPa.Wherein, the reaction temperature of heavy oil riser reactor 11 is meant the top exit temperature of heavy oil riser reactor, the attach most importance to ratio of weight internal circulating load with the weight flow of heavy oil riser reactor charging of oil riser catalyst in reactor of the oil ratio of heavy oil riser reactor.The present invention, heavy oil riser reactor charging 12 comprises: reduced crude, decompression residuum, straight-run gas oil, wax tailings, shale oil, artificial oil, crude oil, coal tar, recycle oil, slurry oil, deasphalted oil.
Reclaimable catalyst from heavy oil riser reactor 11 and gasoline rising pipe reactor 2 enters regenerator 10 at the first settler stripping section 9 and the second settler stripping section 3 respectively behind the water vapour stripping, carry out coke burning regeneration in regenerator 10 under conventional catalytic cracking catalyst regeneration condition; Regeneration temperature generally is controlled at 650～750 ℃, and the phosphorus content of regenerated catalyst is generally 0.02～0.2m%, and micro-activity is generally 55～70.Regenerated catalyst after the regeneration returns heavy oil riser reactor 11 more respectively and gasoline rising pipe reactor 2 participates in reaction, realizes recycling of catalyst.
The present invention mainly is that structure and the operation to gasoline rising pipe reactor in the double lift pipe catalytic cracking device improves.All the other as structure, operation and the operating condition of heavy oil riser reactor 11, regenerator 10, first settler 8 and critical pieces such as the first settler stripping section 9, second settler 5 and the second settler stripping section 3 all with the common double riser fluid catalytic cracking in identical; Those of ordinary skill in the art is very clearly to the operation and the control procedure of these parts, and the present invention selects for use without limits its operating condition, has also only carried out briefly bright.
The inferior patrol charging 1 of gasoline rising pipe reactor 2 of the present invention, can be the gasoline that double lift pipe catalytic cracking device heavy oil riser reactor of the present invention 11 itself is produced, also can be external or the high-sulfur produced of other device, the inferior patrol of high olefin content.Said inferior patrol charging 1 comprises catalytically cracked gasoline, catalytic cracking heavy petrol, thermal cracking and pressure gasoline and heavy petrol, coker gasoline and gasoline such as coking heavy petrol, cracking ethylene preparation gasoline; The sulfur content of inferior patrol charging is generally 500～1000 μ g/g, and olefin(e) centent is generally 35～65v%.
Embodiment
Following examples 1～embodiment 20 is about catalyst for modifying faulty gasoline of the present invention and preparation thereof; Comprise molecular sieve modified (embodiment 1～embodiment 5), support modification (embodiment 6～embodiment 11), shaped catalyst (embodiment 12～embodiment 20).
Get 3000 gram REY (RE
2O
3Content 15m%, Chang Ling catalyst plant produce, and following examples are herewith) join the Zn (NO that 4000 ml concns are 0.006M
3)
2(Zn (NO in the solution
3)
2Solution Zn (NO
3)
26H
2The O preparation, Zn (NO
3)
26H
2The purity of O is 99m%, and rich Dihua worker Co., Ltd produces by Tianjin, and following examples are herewith), measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 1.5 hours in 70 ℃.Filter slurries, get filter cake in baking oven in 110 ℃ of bakings 1.5 hours, mill afterwards, sieve, again in Muffle furnace in 500 ℃ of roastings 5 hours.In 1000 ml deionized water, add 24 gram TiCl
4(TiCl
4Purity be 48m%, Tian Jinshisu village chemical reagent factory produces, following examples are herewith), add 17.5 gram EDTA (ethylenediamine tetra-acetic acid, Changzhou three honeybee chemical industry Co., Ltds produce, following examples herewith), stirs 15 minutes to dissolving fully; Dropping ammonia (concentration 26m%, chemical reagent factory in Luoyang City's produces, following examples are herewith) 148 grams, and drip deionized water and make liquor capacity reach 2000 milliliters, measuring the pH value is 2.5; This solution is the TiCl that 2000 ml concns are 0.03M
4Solution.Get above-mentioned REY molecular sieve 3000 gram after the Zn modification, the TiCl that to join above-mentioned 2000 ml concns be 0.03M
4Carry out modification in the solution, measure slurry pH value=3.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 3 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 130 ℃ of bakings 4 hours, mill afterwards, sieve, again in Muffle furnace in 520 ℃ of roastings 4.5 hours.REY molecular sieve after the modification is standby; Its zinc content is 0.05m%, and Ti content is 0.1m%.The modification REY molecular sieve of present embodiment is called for short A modified molecular screen, i.e. A-REY.
Get 3000 gram REY and join the Zn (NO that 4000 ml concns are 0.24M
3)
2In the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 3 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 110 ℃ of bakings 5 hours, mill afterwards, sieve, again in Muffle furnace in 600 ℃ of roastings 1.5 hours.In 500 ml deionized water, add 515 gram TiCl
4, add 380 gram EDTA, stir 15 minutes to dissolving fully; Dropping ammonia 512 grams drip deionized water and make liquor capacity reach 2000 milliliters, and measuring the pH value is 3; This solution is the TiCl that 2000 ml concns are 0.65M
4Solution.Get above-mentioned REY molecular sieve 3000 gram after the Zn modification, the TiCl that to join above-mentioned 2000 ml concns be 0.65M
4Carry out modification in the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 1.5 hours in 90 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 2.5 hours, mill afterwards, sieve, again in Muffle furnace in 580 ℃ of roastings 2 hours.REY molecular sieve after the modification is standby; Its zinc content is 2m%, and Ti content is 2m%.The modification REY molecular sieve of present embodiment is called for short B modified molecular screen, i.e. B-REY.
Get 3000 gram USY (production of Chang Ling catalyst plant) and join the Zn (NO that 4000 ml concns are 0.6M
3)
2In the solution, measure slurry pH value=3.5.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 60 ℃.Filter slurries, get filter cake in baking oven in 110 ℃ of bakings 2 hours, mill afterwards, sieve, again in Muffle furnace in 650 ℃ of roastings 1 hour.In 400 ml deionized water, add 633 gram TiCl
4, add 467 gram EDTA, stir 15 minutes to dissolving fully; Dropping ammonia 745 grams drip deionized water and make liquor capacity reach 2000 milliliters, and measuring the pH value is 3; This solution is the TiCl that 2000 ml concns are 0.8M
4Solution.Get above-mentioned USY molecular sieve 3000 gram after the Zn modification, the TiCl that to join above-mentioned 2000 ml concns be 0.8M
4Carry out modification in the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.USY molecular sieve after the modification is standby; Its zinc content is 4.9m%, and Ti content is 2.5m%.The modification USY molecular sieve of present embodiment is called for short C modified molecular screen, i.e. C-USY.
Get 3000 gram REUSY (RE
2O
3Content 6m%, the Chang Ling catalyst plant is produced) join the Zn (NO that 4000 ml concns are 0.12M
3)
2In the solution, measure slurry pH value=3.5.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 90 ℃.Filter slurries, get filter cake in baking oven in 115 ℃ of bakings 1.5 hours, mill afterwards, sieve, again in Muffle furnace in 570 ℃ of roastings 1.5 hours.In 1200 ml deionized water, add 1544 gram TiCl
4, add 1139 gram EDTA, stir 15 minutes to dissolving fully; Dropping ammonia 1300 grams drip deionized water and make liquor capacity reach 4000 milliliters, and measuring the pH value is 3; This solution is the TiCl that 4000 ml concns are 0.98M
4Solution.Get above-mentioned REUSY molecular sieve 3000 gram after the Zn modification, the TiCl that to join above-mentioned 4000 ml concns be 0.98M
4Carry out modification in the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 1 hour in 90 ℃.Filter slurries, get filter cake in baking oven in 125 ℃ of bakings 1.5 hours, mill afterwards, sieve, again in Muffle furnace in 500 ℃ of roastings 5 hours.REUSY molecular sieve after the modification is standby; Its zinc content is 1m%, and Ti content is 5.7m%.The modification REUSY molecular sieve of present embodiment is called for short D modified molecular screen, i.e. D-REUSY.
Get 3000 gram ZSM-5 (University Of Tianjin produces, sial atomic ratio=38) and join the Zn (NO that 4000 ml concns are 0.72M
3)
2In the solution, measure slurry pH value=3.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 90 ℃.Filter slurries, get filter cake in baking oven in 130 ℃ of bakings 2 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Get above-mentioned ZSM-5 molecular sieve 3000 grams after the Zn modification, join the TiCl that 2000 ml concns are 0.98M
4Carry out modification in the solution, measure slurry pH value＜1.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 3.5 hours in 75 ℃.Filter slurries, get filter cake in baking oven in 110 ℃ of bakings 3.5 hours, mill afterwards, sieve, again in Muffle furnace in 560 ℃ of roastings 4.5 hours.ZSM-5 molecular sieve after the modification is standby; Its zinc content is 5.8m%, and Ti content is 3m%.The modified zsm-5 zeolite of present embodiment is called for short E modified molecular screen, i.e. E-ZSM-5.
Get 3000 gram kaolin (China Kaolin Co., Ltd produces, and following examples herewith) and join the Zn (NO that 4000 ml concns are 0.06M
3)
2In the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 4 hours in 70 ℃.Filter slurries, get filter cake in baking oven in 100 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Get above-mentioned kaolin 3000 grams after the Zn modification, join the TiCl that 2000 ml concns are 0.06M
4Carry out modification in the solution, measure slurry pH value=1.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 125 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Kaolin after the modification is standby; Its zinc content is 0.5m%, and Ti content is 0.2m%.The modified kaolin of present embodiment is called for short A modified kaolin, i.e. A-clay.
Get 3000 gram kaolin and join the Zn (NO that 4000 ml concns are 0.6M
3)
2In the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Get above-mentioned kaolin 3000 grams after the Zn modification, join the TiCl that 2000 ml concns are 1.7M
4Carry out modification in the solution, measure slurry pH value＜1.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Kaolin after the modification is standby; Its zinc content is 4.9m%, and Ti content is 5m%.The modified kaolin of present embodiment is called for short B modified kaolin, i.e. B-clay.
Get 3000 gram kaolin and join the Zn (NO that 4000 ml concns are 0.6M
3)
2In the solution, measure slurry pH value=3.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 5 hours in 90 ℃.Filter slurries, get filter cake in baking oven in 110 ℃ of bakings 2.5 hours, mill afterwards, sieve, again in Muffle furnace in 600 ℃ of roastings 1 hour.Get above-mentioned kaolin 3000 grams after the Zn modification, join the TiCl that 2000 ml concns are 3.5M
4Carry out modification in the solution, measure slurry pH value＜1.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2 hours in 90 ℃.Filter slurries, get filter cake in baking oven in 130 ℃ of bakings 1 hour, mill afterwards, sieve, again in Muffle furnace in 500 ℃ of roastings 2.5 hours.Get above-mentioned kaolin 3000 grams after Zn and Ti modification, joining 2000 ml concns is the La (NO of 0.22M
2)
3Carry out modification (La (NO in the solution
2)
3Produced by Shanghai chemical reagent factory, following examples are herewith), measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 3.5 hours in 70 ℃.Filter slurries, get filter cake in baking oven in 100 ℃ of bakings 5 hours, mill afterwards, sieve, again in Muffle furnace in 650 ℃ of roastings 1.5 hours.Kaolin after the modification is standby; Its zinc content is 4.9m%, and Ti content is 9.4m%, and lanthanum content is 2m%.The modified kaolin of present embodiment is called for short C modified kaolin, i.e. C-clay.
Get 3000 gram kaolin and join the Zn (NO that 4000 ml concns are 1.3M
3)
2In the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Get above-mentioned kaolin 3000 grams after the Zn modification, join the TiCl that 2000 ml concns are 1.6M
4Carry out modification in the solution, measure slurry pH value＜1.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Get above-mentioned kaolin 3000 grams after Zn and Ti modification, joining 2000 ml concns is the La (NO of 0.44M
2)
3Carry out modification in the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Kaolin after the modification is standby; Its zinc content is 9.9m%, and Ti content is 4.7m%, and lanthanum content is 3.9m%.The modified kaolin of present embodiment is called for short D modified kaolin, i.e. D-clay.
Get 3000 gram boehmites (Aluminum group in Shandong produces, and following examples herewith) and join the Zn (NO that 4000 ml concns are 0.96M
3)
2In the solution, measure slurry pH value=3.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 1.5 hours in 85 ℃.Filter slurries, get filter cake in baking oven in 125 ℃ of bakings 1.5 hours, mill afterwards, sieve, again in Muffle furnace in 580 ℃ of roastings 2 hours.Get above-mentioned boehmite 3000 grams after the Zn modification, join the TiCl that 2000 ml concns are 0.98M
4Carry out modification in the solution, measure slurry pH value＜1.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Boehmite after the modification is standby; Its zinc content is 7.6m%, and Ti content is 3m%.The modification boehmite of present embodiment is called for short A boehmite, i.e. A-Al
2O
3
Get 3000 gram boehmites and join the Zn (NO that 4000 ml concns are 0.48M
3)
2In the solution, measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Get above-mentioned boehmite 3000 grams after the Zn modification, join the TiCl that 2000 ml concns are 4.2M
4Carry out modification in the solution, measure slurry pH value＜1.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Get above-mentioned boehmite 3000 grams after Zn and Ti modification, joining 2000 ml concns is the Ce (NO of 0.55M
2)
3Carry out modification (Ce (NO in the solution
2)
3Produce by Shanghai chemical reagent factory), measure slurry pH value=4.The heating slurries, and the temperature maintenance that makes slurries stirred slurries 2.5 hours in 80 ℃.Filter slurries, get filter cake in baking oven in 120 ℃ of bakings 3 hours, mill afterwards, sieve, again in Muffle furnace in 550 ℃ of roastings 2.5 hours.Boehmite after the modification is standby; Its zinc content is 4m%, and Ti content is 10.8m%, and cerium content is 4.8m%.The modification boehmite of present embodiment is called for short B boehmite, i.e. B-Al
2O
3
Add 1500 gram aluminium colloidal sol (laboratory self-control, pH value=3, Al in the 4500 gram deionized waters
2O
3Content 20m%, following examples are herewith), add 1000 gram A-REY molecular sieves, add 367 gram A-clay, add 50 gram concentrated hydrochloric acids (concentration is 37m%, is produced by Luoyang City's chemical reagent factory, and following examples are herewith), measure slurry pH value=3.Stirred slurries 2 hours, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 650 ℃ of roastings 2 hours, promptly obtain catalyst a.Press butt and calculate, contain the 60m%A-REY molecular sieve, 22m%A-clay and 18m% aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 13
Add 1667 gram aluminium colloidal sols in the 4500 gram deionized waters, add 1000 gram B-REY molecular sieves, add 888 gram B-clay, add 45 gram concentrated hydrochloric acids, measure slurry pH value=3.5.Stirred slurries 3 hours, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 500 ℃ of roastings 5 hours, promptly obtain catalyst b.Press butt and calculate, contain the 45m%B-REY molecular sieve, 40m%B-clay and 15m% aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 14
Add 1667 gram aluminium colloidal sols in the 4500 gram deionized waters, add 1000 gram C-USY molecular sieves, add 2000 gram C-clay, add 55 gram concentrated hydrochloric acids, measure slurry pH value=2.5.Stirred slurries 3 hours, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 520 ℃ of roastings 3.5 hours, promptly obtain catalyst c.Press butt and calculate, contain the 30m%C-USY molecular sieve, 60m%C-clay and 10m% aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 15
(phosphorus aluminium colloidal sol is the laboratory self-control, pH value=2.8, Al to add 1250 gram aluminium colloidal sols and 625 gram phosphorus aluminium colloidal sols in the 4500 gram deionized waters
2O
3Content 10m%, P
2O
5Content 30m%, following examples are herewith), add 1000 gram D-REUSY molecular sieves, add 3500 gram D-clay, add 30 gram concentrated hydrochloric acids, measure slurry pH value=6.5.Stirred slurries 1 hour, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 600 ℃ of roastings 4 hours, promptly obtain catalyst d.Press butt and calculate, contain the 20m%D-REUSY molecular sieve, 70m%D-clay, 5m% aluminium colloidal sol and 5m% phosphorus aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 16
Add 833 gram aluminium colloidal sols in the 4500 gram deionized waters, add 500 gram B-REY molecular sieves and 500 gram E-ZSM-5 molecular sieves, add 167 gram A-clay and 333 gram A-Al
2O
3, add 50 gram concentrated hydrochloric acids, measure slurry pH value=3.Stirred slurries 2 hours, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 550 ℃ of roastings 2.5 hours, promptly obtain catalyst e.Press butt and calculate, contain 30m%B-REY molecular sieve and 30m%E-ZSM-5 molecular sieve respectively, 10m%A-clay, 20m%A-Al
2O
3With 10m% aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 17
Add 2000 gram aluminium colloidal sols in the 4500 gram deionized waters, add 1000 gram D-REUSY molecular sieves, add 1200 gram C-clay and 1400 gram B-Al
2O
3, add 60 gram concentrated hydrochloric acids, measure slurry pH value=2.5.Stirred slurries 3 hours, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 550 ℃ of roastings 2.5 hours, promptly obtain catalyst f.Press butt and calculate, contain the 25m%D-REUSY molecular sieve, 30m%C-clay, 35m%B-Al
2O
3With 10m% aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 18
Add 1444 gram aluminium colloidal sols and 111 gram phosphorus aluminium colloidal sols in the 4500 gram deionized waters, add 1000 gram C-USY molecular sieves, add 888 gram A-Al
2O
3, add 50 gram concentrated hydrochloric acids, measure slurry pH value=3.Stirred slurries 1 hour, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 550 ℃ of roastings 2.5 hours, promptly obtain catalyst g.Press butt and calculate, contain the 45m%C-USY molecular sieve, 40m%A-Al
2O
3, 13m% aluminium colloidal sol, 2m% phosphorus aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 19
Add 833 gram aluminium colloidal sols and 417 gram phosphorus aluminium colloidal sols in the 4500 gram deionized waters, add 500 gram B-REY molecular sieves and 833 gram E-ZSM-5 molecular sieves, add 1000 gram D-clay and 667 gram B-Al
2O
3, add 50 gram concentrated hydrochloric acids, measure slurry pH value=3.Stirred slurries 2 hours, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 550 ℃ of roastings 2.5 hours, promptly obtain catalyst h.Press butt and calculate, contain 15m%B-REY molecular sieve and 25m%E-ZSM-5 molecular sieve, 20m%B-Al
2O
3, 30m%D-clay, 5m% aluminium colloidal sol, 5m% phosphorus aluminium colloidal sol.Main physical character sees Table 1.
Embodiment 20
Add 1300 gram aluminium colloidal sols and 100 gram phosphorus aluminium colloidal sols in the 4500 gram deionized waters, add 100 gram C-USY molecular sieves, add 800 gram D-clay and 800 gram A-Al
2O
3, add 50 gram concentrated hydrochloric acids, measure slurry pH value=3.Stirred slurries 2 hours, slurries are through homogeneous, spray-drying afterwards, again in Muffle furnace in 550 ℃ of roastings 2.5 hours, promptly obtain catalyst i.Press butt and calculate, contain the 5m%C-USY molecular sieve, 40m%A-Al
2O
3, 40m%D-clay, 13m% aluminium colloidal sol, 2m% phosphorus aluminium colloidal sol.Main physical character sees Table 1.
Following examples 21～embodiment 29 is the situations that are applied to inferior gasoline upgrading technology about the catalyst of the present invention's preparation on double lift pipe catalytic cracking device shown in Figure 1, gives Comparative Examples 1 simultaneously.Embodiment 21～embodiment 29 uses catalyst a, b, c, d, e, f, g, h, i respectively, and Comparative Examples 1 is used conventional catalytic cracking fresh catalyst MLC-500.Above-mentioned catalyst is all standby after 10 hours at 100% water vapour, 800 ℃ of following hydrothermal treatment consists.
Embodiment 21
On the present invention's double lift pipe catalytic cracking experimental rig shown in Figure 1, test.Heavy oil riser reactor processing northern Suzhou mixing heavy oil, treating capacity is 30 kg/day; The inferior patrol charging of the gasoline rising pipe reactor gasoline that the oil riser reactor is produced of attaching most importance to, treating capacity is 15 kg/day.Catalyst system therefor is the catalyst a after hydrothermal aging is handled, and micro-activity is 67.
The physical property of catalyst a is listed in table 1, the main character of northern Suzhou mixing heavy oil is listed in table 2, the key reaction condition of heavy oil riser reactor and gasoline rising pipe reactor is listed in table 3, and the product of gasoline rising pipe reactor distributes and the main character of reformulated gasoline is listed in table 4; Sulfur content, octane number and the olefin(e) centent data of the charging of gasoline rising pipe reactor inferior patrol have been listed in the table 4 simultaneously in.In all embodiments, the key reaction condition of gasoline rising pipe reactor all is meant the main operating condition of its first conversion zone and bed reactor.
Comparative Examples 1
On common double lift pipe catalytic cracking experimental rig, carry out contrast test.Apparatus structure is referring to patent CN1401740A.Heavy oil riser reactor processing northern Suzhou mixing heavy oil, treating capacity is 30 kg/day; The inferior patrol charging of the gasoline rising pipe reactor gasoline that the oil riser reactor is produced of attaching most importance to, treating capacity is 15 kg/day.Catalyst system therefor is the MLC-500 catalytic cracking catalyst of the routine after hydrothermal aging is handled, and micro-activity is 63.
The main character of northern Suzhou mixing heavy oil is listed in table 2, and the key reaction condition of heavy oil riser reactor and gasoline rising pipe reactor is listed in table 3, and the product of gasoline rising pipe reactor distributes and the main character of reformulated gasoline is listed in table 4; Sulfur content, octane number and the olefin(e) centent data of the charging of gasoline rising pipe reactor inferior patrol have been listed in the table 4 simultaneously in.
In table 3 Comparative Examples 1, gasoline rising pipe reactor reaction temperature is meant the top exit temperature of gasoline rising pipe reactor, and gasoline rising pipe reactor oil ratio is the ratio of weight internal circulating load with the weight flow of the inferior patrol charging of gasoline rising pipe reactor of gasoline rising pipe catalyst in reactor.
Embodiment 22～embodiment 29
Embodiment 22～embodiment 29 uses catalyst b, c, d, e, f, g, h, i after hydrothermal aging is handled respectively, and micro-activity is respectively 65,66, and 52,65,58,63,57,56.The physical property of catalyst b, c, d, e, f, g, h, i is listed in table 1, the main character of northern Suzhou mixing heavy oil is listed in table 2, the key reaction condition of heavy oil riser reactor and gasoline rising pipe reactor is listed in table 3, and the product of gasoline rising pipe reactor distributes and the main character of reformulated gasoline is listed in table 4; Sulfur content, octane number and the olefin(e) centent data of each embodiment gasoline rising pipe reactor inferior patrol charging have been listed in the table 4 simultaneously in.
Charging that the used experimental rig of embodiment 22～embodiment 29, heavy oil riser reactor and gasoline rising pipe reactor are processed and treating capacity all with embodiment 21 in identical.
The data of embodiment 21～embodiment 29 and Comparative Examples 1 in the comparison sheet 4, as can be seen, the olefin(e) centent and the Comparative Examples 1 of gasoline rising pipe reformulated gasoline that reactor produces of the present invention are more or less the same, all below 18v%.And its sulfur content is than Comparative Examples 1 decline 50～75m%; Below 150 μ g/g, meet Europe III gasoline standard in sulfur content under some reaction condition.
Table 1 catalyst embodiment sample physical property
| Project | Embodiment |
| 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | |
| The catalyst title | a | b | c | d | e | f | g | h | i |
| Pore volume/mlg -1 | 0.27 | 0.25 | 0.19 | 0.17 | 0.25 | 0.24 | 0.25 | 0.22 | 0.16 |
| Specific area/m 2·g -1 | 252 | 236 | 187 | 143 | 251 | 197 | 241 | 189 | 142 |
| Bulk density/gml -1 | 0.76 | 0.77 | 0.82 | 0.83 | 0.75 | 0.74 | 0.75 | 0.73 | 0.75 |
| Abrasion index/m%h -1 | 1.48 | 1.65 | 1.54 | 1.43 | 1.62 | 1.72 | 1.62 | 1.75 | 1.76 |
| Micro-activity (with 100% water vapour at 800 ℃ of following hydrothermal treatment consists 4h) | 82 | 78 | 78 | 65 | 80 | 72 | 77 | 70 | 68 |
| Distribution of particles/v% | |||||||||
| 0～40μm | 18.2 | 18.7 | 19.2 | 18.7 | 19.1 | 18.9 | 18.6 | 19.1 | 18.7 |
| 0～149μm | 92.3 | 91.6 | 90.3 | 91.6 | 92.1 | 91.3 | 91.5 | 90.7 | 91.0 |
| Average grain diameter/μ m | 80.1 | 80.2 | 80.1 | 80.3 | 80.0 | 80.2 | 80.1 | 80.3 | 80.1 |
The main character of table 2 northern Suzhou mixing heavy oil
| Feedstock oil | Northern Suzhou mixing heavy oil |
| Density/20 ℃, kgm -3 | 915.8 |
| Carbon residue/m% | 6.85 |
| Molecular weight | 508 |
| Group composition/m% | |
| Saturated hydrocarbons | 51.2 |
| Aromatic hydrocarbon | 27.5 |
| Colloid+asphalitine | 21.3 |
| Element is formed | |
| Carbon/m% | 86.58 |
| Hydrogen/m% | 12.65 |
| Sulphur/μ gg -1 | 5828 |
| Nitrogen/μ gg -1 | 1640 |
| Nickel/μ gg -1 | 8.8 |
| Vanadium/μ gg -1 | 1.1 |
| Iron/μ gg -1 | 4.0 |
| Sodium/μ gg -1 | 2.2 |
The key reaction condition of table 3 heavy oil riser reactor and gasoline rising pipe reactor
| Project | Comparative Examples 1 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 |
| Catalyst | MLC-500 | a | b | c | d | e | f | g | h | i |
| Gasoline rising pipe reactor reaction temperature/℃ | 450 | / | / | / | / | / | / | / | / | / |
| Gasoline rising pipe reactor reaction time/s | 1.8 | / | / | / | / | / | / | / | / | / |
| Gasoline rising pipe reactor oil ratio | 5.1 | / | / | / | / | / | / | / | / | / |
| Gasoline rising pipe reactor reaction absolute pressure/MPa | 0.28 | / | / | / | / | / | / | / | / | / |
| Heavy oil riser reactor reaction temperature/℃ | 510 | 510 | 510 | 510 | 510 | 510 | 510 | 510 | 510 | 510 |
| Heavy oil riser reactor reaction time/s | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 |
| Heavy oil riser reactor oil ratio | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 |
| Heavy oil riser reactor reaction absolute pressure/MPa | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 |
| The gasoline rising pipe reactor first conversion zone reaction temperature/℃ | / | 450 | 460 | 470 | 480 | 490 | 500 | 510 | 520 | 530 |
| Gasoline rising pipe reactor first conversion zone reaction time/s | / | 1.8 | 1.8 | 1.7 | 1.7 | 1.6 | 1.5 | 1.5 | 1.4 | 1.3 |
| The gasoline rising pipe reactor first conversion zone oil ratio | / | 5.1 | 5.6 | 6.5 | 7.4 | 8.1 | 9.3 | 10.2 | 10.9 | 11.5 |
| Project | Comparative Examples 1 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 |
| Gasoline rising pipe reactor first conversion zone reaction absolute pressure/MPa | / | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 |
| Gasoline rising pipe reactor second conversion zone (bed reactor) reaction temperature/℃ | / | 430 | 440 | 450 | 460 | 470 | 480 | 490 | 500 | 510 |
| Gasoline rising pipe conversion zone second conversion zone (bed reactor) reaction time/s | / | 6.0 | 6.0 | 5.9 | 5.7 | 5.6 | 5.1 | 4.7 | 4.5 | 4.0 |
| Gasoline rising pipe reactor second conversion zone (bed reactor) oil ratio | / | 5.1 | 5.6 | 6.5 | 7.4 | 8.1 | 9.3 | 10.2 | 10.9 | 11.5 |
| Gasoline rising pipe reactor second conversion zone (bed reactor) reaction absolute pressure/MPa | / | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 | 0.26 |
Annotate: this page table is last page table 3 continuous tables.
The product distribution of table 4 gasoline rising pipe reactor and the main character of reformulated gasoline
| Project | Comparative Examples 1 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 |
| Product distribution/m% | ||||||||||
| Dry gas | 3.9 | 3.8 | 3.9 | 3.9 | 4.0 | 4.0 | 4.1 | 4.2 | 4.3 | 4.3 |
| Liquefied gas | 14.6 | 15.0 | 15.6 | 16.2 | 16.7 | 17.1 | 17.5 | 18.0 | 18.9 | 20.1 |
| Gasoline | 39.1 | 38.8 | 38.5 | 37.9 | 37.2 | 36.3 | 35.5 | 34.8 | 34.0 | 32.6 |
| Diesel oil | 24.7 | 24.9 | 25.3 | 25.1 | 24.5 | 24.6 | 24.8 | 25.5 | 25.3 | 25.6 |
| Heavy oil | 9.0 | 8.9 | 8.1 | 8.2 | 8.8 | 9.4 | 9.5 | 8.6 | 8.7 | 8.5 |
| Coke | 8.4 | 8.3 | 8.3 | 8.4 | 8.5 | 8.3 | 8.3 | 8.6 | 8.5 | 8.6 |
| Loss | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| The main character of gasoline rising pipe reactor inferior patrol charging | ||||||||||
| Sulfur content/μ gg -1 | 625 | 467 | 470 | 452 | 440 | 446 | 425 | 420 | 415 | 413 |
| Octane number (RON) | 90.7 | 90.7 | 90.8 | 90.8 | 90.9 | 91.0 | 90.8 | 90.6 | 90.7 | 90.8 |
| Olefin(e) centent/v% | 52.1 | 50.6 | 49.3 | 50.0 | 51.0 | 49.8 | 50.0 | 51.2 | 49.9 | 50.7 |
| The main character of gasoline rising pipe reformulated gasoline that reactor produces | ||||||||||
| Sulfur content/μ gg -1 | 450 | 210 | 195 | 186 | 185 | 162 | 153 | 150 | 125 | 115 |
| Octane number (RON) | 91.1 | 91.2 | 91.4 | 91.4 | 91.7 | 91.8 | 92.0 | 92.3 | 92.6 | 93.0 |
| Olefin(e) centent/v% | 15.6 | 13.5 | 12.6 | 13.3 | 13.0 | 12.0 | 11.5 | 11.0 | 10.2 | 9.3 |
Claims (6)
1, a kind of catalyst for modifying faulty gasoline, modified molecular screen by 5～65m%, the modified support of 20～80m% and the binding agent of 10～20m% are formed, described modified molecular screen is modification REY, REHY, REUSY, USY, ZSM-5, in the β zeolite one or both, molecular sieve modified element is zinc and titanium, described modified support is a modified kaolin, in the boehmite one or both, the support modification element is zinc and titanium, or rare earth, zinc and titanium, described binding agent is an aluminium colloidal sol, Ludox, a kind of or their mixture in the phosphorus aluminium colloidal sol, the element gross weight of modifying element accounts for 0.1～10m% of this kind modified molecular screen gross weight in each modified molecular screen, and modifying element zinc is 0.1～3.0 with the element wt ratio of titanium; The element gross weight of modifying element accounts for 0.1～20m% of this kind modified support gross weight in each modified support, and modifying element zinc is 0.1～3.0 with the element wt ratio of titanium, and rare earth is 0～0.5 with the element wt ratio of zinc and titanium sum.
2, catalyst for modifying faulty gasoline according to claim 1 is characterized in that: the element gross weight of modifying element accounts for 1～5m% of this kind modified molecular screen gross weight in each modified molecular screen, and modifying element zinc is 0.5～2.0 with the element wt ratio of titanium; The element gross weight of modifying element accounts for 5～10m% of this kind modified support gross weight in each modified support, and modifying element zinc is 0.5～2.0 with the element wt ratio of titanium, and rare earth is 0～0.25 with the element wt ratio of zinc and titanium sum.
3, the preparation method of the described catalyst for modifying faulty gasoline of claim 1 is characterized in that being made up of following steps:
A. molecular sieve modified: molecular sieve REY, REHY, REUSY, USY, ZSM-5 or the β zeolite that will treat modification joins in the zinc solution that the water soluble salt with modifying element zinc is mixed with, heating, stirring, filtration slurries, getting filter cake toasts, mills, sieves, through roasting, make the molecular sieve of zinc modification again; Above-mentioned molecular sieve behind zinc modification is joined in the titanium solution that the water soluble salt with the modifying element titanium is mixed with, heating, stir, filter slurries, get filter cake and toast, mill, sieve,, make the molecular sieve of zinc and titanium modification again through roasting;
During with the various Y zeolite of titanium solution modification behind zinc modification, in the process for preparation of titanium solution, add the complexing agent ethylenediamine tetra-acetic acid identical with the titanium ion molal quantity, dropping ammonia again, the pH value of controlling titanium solution is 2.5～7;
B. support modification: will treat that the carrier kaolin of modification or boehmite join in the zinc solution that the water soluble salt with modifying element zinc is mixed with, heating, stirring, filtration slurries, get filter cake and toast, mill, sieve,, make the carrier of zinc modification again through roasting; Above-mentioned carrier behind zinc modification is joined in the titanium solution that the water soluble salt with the modifying element titanium is mixed with, heating, stir, filter slurries, get filter cake and toast, mill, sieve,, make the carrier of zinc and titanium modification again through roasting;
Or more above-mentioned carrier after zinc and titanium modification is joined in the earth solution that the water soluble salt with the modifying element rare earth is mixed with, heating, stirring, filtration slurries, get filter cake and toast, mill, sieve,, make the carrier of rare earth, zinc and titanium modification again through roasting;
C. shaped catalyst: in deionized water, add binding agent, through one or both molecular sieves of modification, through one or both carriers of modification, add hydrochloric acid again to regulate the pH value of slurries, stir slurries, again through homogeneous, spray-drying, roasting, make catalyst afterwards.
4, according to the preparation method of the described catalyst for modifying faulty gasoline of claim 3, it is characterized in that: during with various Y zeolite behind zinc modification of titanium solution modification, the pH value of controlling described titanium solution is 3～4 in the described steps A.
5, the described catalyst for modifying faulty gasoline of claim 1 is applied to inferior gasoline upgrading technology, it is characterized in that this technology comprises following process:
A. enter the bottom of heavy oil riser reactor (11) from the regenerated catalyst of regenerator (10), contact the back along up reaction of heavy oil riser reactor (11) with heavy oil riser reactor charging (12), after reaction finishes, the reaction logistics enters first settler (8) by the top exit of heavy oil riser reactor (11) and carries out catalyst and Oil-gas Separation, isolated heavy oil riser reactor reaction generation oil gas (7) enters fractionating system and carries out fractionation, isolated reclaimable catalyst enters behind stripping in the regenerator (10) at the first settler stripping section (9) and carries out coke burning regeneration, regenerated catalyst part in the regenerator (10) after the regeneration is returned heavy oil riser reactor (11), and another part enters the bottom of gasoline rising pipe reactor (2);
B. the regenerated catalyst that enters gasoline rising pipe reactor (2) bottom among the process A contacts up reaction of first conversion zone (201) of back along gasoline rising pipe reactor (2) with inferior patrol charging (1), the logistics of reaction afterreaction upwards flows, the bed reactor (4) that enters the hole enlargement structure that is positioned at gasoline rising pipe reactor (2) top of first conversion zone (201) top continues reaction, after reaction in the bed reactor (4) finishes, reactant flows to go up and flows, enter second settler (5) by the top exit of gasoline rising pipe reactor (2) and carry out catalyst and Oil-gas Separation, isolated gasoline rising pipe reactor reaction generation oil gas (6) enters fractionating system and carries out fractionation, and isolated reclaimable catalyst enters behind stripping in the regenerator (10) at the second settler stripping section (3) and carries out coke burning regeneration;
The catalyst that uses in the said process is claim 1 or 2 described catalyst for modifying faulty gasoline, the reaction temperature of described gasoline rising pipe reactor first conversion zone (201) is 300～600 ℃, reaction time is 0.7～3.0 second, oil ratio is 2～17, the reaction absolute pressure is 0.15～0.4MPa, and the reaction temperature of bed reactor (4) is 300～600 ℃, and the reaction time is 2.5～10.0 seconds, oil ratio is 2～17, and the reaction absolute pressure is 0.15～0.4MPa.
6, inferior gasoline upgrading technology according to claim 5, it is characterized in that: the reaction temperature of described gasoline rising pipe reactor first conversion zone (201) is 400～500 ℃, reaction time is 1.0～2.5 seconds, oil ratio is 4～12, the reaction absolute pressure is 0.2～0.35MPa, and the reaction temperature of bed reactor (4) is 400～500 ℃, and the reaction time is 3.5～8.0 seconds, oil ratio is 4～12, and the reaction absolute pressure is 0.2～0.35MPa.
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