CN102453519A - Catalytic conversion method for improving product distribution - Google Patents
Catalytic conversion method for improving product distribution Download PDFInfo
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- CN102453519A CN102453519A CN2010105141281A CN201010514128A CN102453519A CN 102453519 A CN102453519 A CN 102453519A CN 2010105141281 A CN2010105141281 A CN 2010105141281A CN 201010514128 A CN201010514128 A CN 201010514128A CN 102453519 A CN102453519 A CN 102453519A
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Abstract
The invention discloses a catalytic conversion method for improving product distribution. The method comprises the following steps of: allowing high-quality raw oil and a thermally regenerative catalyst with lower activity and coarse size distribution to contact on the lower part of a reactor to undergo cracking reaction, performing selective hydrogen transfer reaction and isomerization reaction on the generated oil gas and a carbon-containing catalyst in upstream under a certain reaction environment, separating reaction products, and stripping and regenerating spent catalysts for recycle. By the method, under the condition that the isobutene content in the liquefied gas and the olefin content in gasoline group composition are increased, the dry gas yield and coke are obviously reduced; and the particles of the catalysts are more uniform, so the local temperature distribution is more uniform in the regenerating process, and the breaking tendency of the catalysts is correspondingly reduced.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is to belong to improve the catalysis conversion method that product distributes.
Background technology
Conventional catalytic cracking process is mainly used in production gasoline, and gasoline yield is up to more than the 50 heavy %.Early eighties, unleaded gasoline force catalytic cracking technology to develop to the direction of producing stop bracket gasoline, and for this reason, wide variation have taken place for the processing condition and the catalyst type of catalytic cracking.At process aspect, mainly be the contact efficiency that improves temperature of reaction, shortens the reaction times, improves the reaction severity, suppresses hydrogen transfer reactions and cross cracking reaction and improve riser tube bottom oil gas and catalyzer; Aspect catalyzer, developed USY type zeolite and combined inert base or the catalyzer of active matrix and dissimilar zeolite compound catalyzer.
Though catalytic cracking technology has been obtained above-mentioned progress; Satisfied the requirement of unleaded gasoline, improved the octane value of gasoline, but no matter be through changing processing condition; Also be to use novel zeolite catalyst to improve gasoline octane rating; All be to increase the octane value of gasoline to improve olefin(e) centent in the gasoline component, olefin(e) centent is 35～65 heavy % in the gasoline component at present, and this and RFG differ greatly to the requirement of olefin(e) centent.Olefin(e) centent was higher during liquefied gas was formed, and about about 70 heavy %, wherein butylene is the several times of Trimethylmethane, is difficult to as raw material for alkylation greatly.
ZL99105904.2 discloses a kind of Trimethylmethane and catalysis conversion method that is rich in isoparaffin gasoline produced; Be that one of the entering of the raw oil after the preheating is comprised in the reactor drum of two reaction zones; Contact with the cracking catalyst of heat, the temperature of first reaction zone is that 530～620 ℃, reaction times are 0.5～2.0 second; The temperature of second reaction zone is that 460～530 ℃, reaction times are 2～30 seconds, reaction product isolated, and reclaimable catalyst gets into through stripping and recycles after revivifier burns.Adopt that Trimethylmethane content is 20～40 heavy % in the liquefied gas that method provided by the invention produces; Isoparaffin content during gasoline family forms is 30～45 heavy %; Olefin(e) centent is reduced to below the 30 heavy %, and its RON is 90～93, and motor-method octane number is 80～84.
ZL99105905.0 discloses a kind of catalysis conversion method of producing propylene, Trimethylmethane and being rich in isoparaffin gasoline; Be that one of the entering of the raw oil after the preheating is comprised in the reactor drum of two reaction zones; Contact with the cracking catalyst of heat, the temperature of first reaction zone is that 550～650 ℃, reaction times are 0.5～2.5 second; The temperature of second reaction zone is that 480～550 ℃, reaction times are 2～30 seconds, reaction product isolated, and reclaimable catalyst gets into through stripping and recycles after revivifier burns.The liquefied gas yield that adopts method provided by the invention to produce can reach 25～40 heavy %, and wherein propylene content is about 30 heavy %, and Trimethylmethane content is 20～40 heavy %, and the productive rate of gasoline can reach 35～50 heavy %, and the isoparaffin during gasoline is formed is 30～45 heavy %.
ZL99105903.4 discloses a kind of riser reactor that is used for fluidized catalytic conversion; 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 drum both can have been controlled first reaction zone, can make the raw oil of different performance carry out the segmentation cracking again, obtains required purpose product.
These patents have constituted the basic patent of the catalytic cracking process (MIP) of voluminous isoparaffin, and have been widely used just, have been applied to nearly 50 cover CCUs at present, obtain huge economic benefit and social benefit.Although prior art can obtain being rich in the liquefied gas of Trimethylmethane and be rich in isoparaffin gasoline; But to handling the fine catalytically cracked stock; Especially the hydrogenation wax oil causes content of olefin in gasoline on the low side, and the iso-butylene content in the liquefied gas is on the low side; Products distribution is optimized inadequately, and petroleum resources are underused.
Fine particle less than 40 μ m in the size composition of conventional catalytic cracking catalyst is about 20% (volume).Find after deliberation; Though these fine grain catalyzer have higher cracking ability; But the selectivity to dry gas and coke is relatively poor, and in regenerative process, catalyzer is easy to fragmentation more; Therefore the size composition of optimizing catalyzer can improve the selectivity of dry gas and coke and the work-ing life of improving catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of catalysis conversion method that product distributes that improves.
Method provided by the invention is: high quality raw material are oily and activity is lower and hot regenerated catalyst that coarse grain directly distributes contacts the generation cracking reaction in the bottom of reactor drum; The oil gas that generates and the catalyzer that contains charcoal be up, and optionally hydrogen transfer reactions and isomerization reaction take place under the certain reaction environment; Reaction product isolated, reclaimable catalyst recycles after stripping, regeneration.
Method provided by the invention is to comprise in the reactor drum of realizing two types of differential responses at one carrying out; This reactor drum be selected from the equal diameter riser tube, etc. a kind of in linear speed riser tube, reducing riser tube, the fluidized-bed, also can be the compound reactor that constitutes by equal diameter riser tube and fluidized-bed.
Method provided by the invention is such practical implementation:
(1), the high quality raw material of preheating oil get into reactor drum and activity be 35～55 preferred 40～50 and the hot regenerated catalyst that directly distributes of coarse grain contact; 490 ℃～620 ℃ preferred 500 ℃～600 ℃ of temperature of reaction; Preferred 0.8 second～1.5 seconds of 0.5 second～2.0 seconds reaction times, the weight ratio of catalyzer and raw oil (hereinafter to be referred as agent-oil ratio) 3～15: 1 preferred 3～12: under 1 the condition cracking reaction takes place;
(2), the oil gas and the used catalyst that generate be up, 420 ℃～550 ℃ preferred 460 ℃～500 ℃ of temperature of reaction, the reaction times is under preferred 3 seconds～15 seconds the condition optionally hydrogen transfer reactions and isomerization reaction to take place in 2 seconds～30 seconds;
(3), reaction product isolated obtains being rich in the liquefied gas and moderate gasoline and other product of olefin(e) centent of iso-butylene, reclaimable catalyst recycles after stripping gets into the revivifier coke burning regeneration.
The pressure of the said cracking reaction of step (1), the said hydrogen transfer reactions of step (2) and isomerization reaction is 130kPa～450kPa, and the weight ratio of water vapor and raw oil (hereinafter to be referred as WOR) is 0.03～0.3: 1, is preferably 0.05～0.3: 1.
The reactor drum that this method is suitable for can be selected from the equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or the reducing riser tube, also can be the compound reactor that constitutes by equal diameter riser tube and fluidized-bed.
Method provided by the invention can the equal diameter riser tube, etc. carry out in linear speed riser tube or the fluidized-bed reactor, the conventional catalyst cracker in its intermediate diameters riser tube and refinery is identical, waits in the linear speed riser tube fluidic linear speed basic identical.The equal diameter riser tube, etc. the linear speed riser reactor be followed successively by pre lift zone, first reaction zone, second reaction zone from bottom to up; Fluidized-bed reactor is followed successively by first reaction zone, second reaction zone from bottom to up, and the ratio of the height of first reaction zone, second reaction zone is 10～40: 90～60.When use the equal diameter riser tube, etc. when linear speed riser tube or fluidized-bed reactor; Establish one or more cold shocks medium inlet in second reaction zone bottom; And/or in second reaction zone, heat collector being set, the height of heat collector accounts for 50%～90% of the second reaction zone height.Control the temperature and the reaction times of each reaction zone respectively.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from cold shock agent, refrigerative regenerated catalyst and refrigerative half regenerated catalyst.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively; The regenerated catalyst carbon content is below the 0.1 heavy %; Be preferably below the 0.05 heavy %; Half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.
Method provided by the invention also can be carried out in the compound reactor that is made up of equal diameter riser tube and fluidized-bed; The equal diameter riser tube of bottom is first reaction zone; The fluidized-bed on top is second reaction zone, controls the temperature and the reaction times of each reaction zone respectively.Establish one or more cold shocks medium inlet in the bottom of fluidized-bed, and/or in second reaction zone, heat collector is set, the height of heat collector accounts for 50%～90% of the second reaction zone height.Control the temperature and the reaction times of each reaction zone respectively.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from cold shock agent, refrigerative regenerated catalyst and refrigerative half regenerated catalyst.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively; The regenerated catalyst carbon content is below the 0.1 heavy %; Be preferably below the 0.05 heavy %; Half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.
Method provided by the invention can also be carried out in reducing riser reactor (referring to ZL99105903.4); The constitutional features of this reactor drum is as shown in Figure 1: riser reactor vertically be followed successively by co-axial each other pre lift zone a, the first reaction zone b, enlarged-diameter from bottom to up the second reaction zone c, reduced outlet area d, be connected with one section level pipe e at the outlet area end.The combining site of first and second reaction zone is a truncated cone-shaped, and the apex of its longitudinal section isosceles trapezoid is 30 °～80 °; The combining site of second reaction zone and outlet area is a truncated cone-shaped, and the base angle β of its longitudinal section isosceles trapezoid is 45 °～85 °.
The height sum of the pre lift zone of this reactor drum, first reaction zone, second reaction zone, outlet area is the total height of reactor drum, is generally 10 meters～60 meters.
The diameter of pre lift zone is identical with conventional equal diameter riser reactor, is generally 0.02 meter～5 meters, and it highly accounts for 5%～10% of total reactor height.The effect of pre lift zone be promote in advance medium in the presence of regenerated catalyst moved upward and quicken, used identical of used preparatory lifting medium and the equal diameter riser reactor of routine is selected from water vapor or dry gas.
The similar of first reaction zone is in the equal diameter riser reactor of routine; Its diameter can be identical with pre lift zone; Also can be big slightly than pre lift zone, the diameter of first reaction zone and the diameter ratio of pre lift zone are 1.0～2.0: 1, it highly accounts for 10%～30% of total reactor height.Cracking reaction under higher temperature of reaction and agent-oil ratio, residence time (being generally 0.5 second～2.5 seconds) of lacking, mainly takes place in raw oil and catalyzer after this district is mixed.
Second reaction zone is thicker than first reaction zone, and the diameter ratio of its diameter and first reaction zone is 1.5～5.0: 1, and it highly accounts for 30%～60% of total reactor height.Its effect is flow velocity and the temperature of reaction that reduces oil gas and catalyzer.Reduce the method for this district's temperature of reaction; Can inject the cold shock medium from the combining site of this district and first reaction zone; And/or through heat collector being set in this district; Take the part heat away to reduce this district's temperature of reaction, suppress the purpose that secondary cracking reacts, increases isomerization reaction and hydrogen transfer reactions thereby reach.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from cold shock agent, refrigerative regenerated catalyst and refrigerative half regenerated catalyst.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively; The regenerated catalyst carbon content is below the 0.1 heavy %; Be preferably below the 0.05 heavy %; Half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.If heat collector is set, then it highly accounts for 50%～90% of the second reaction zone height.Logistics can be longer in this reaction zone residence time, is 2 seconds～30 seconds.
The similar of outlet area is in the equal diameter riser reactor top exit part of routine, and the diameter ratio of its diameter and first reaction zone is 0.8～1.5: 1, and it highly accounts for 0～20% of total reactor height.Logistics can stop certain hour in this district, to suppress cracking reaction and heat cracking reaction, improves rate of flow of fluid.
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 that product that reaction is generated and reclaimable catalyst are delivered to separation system and carry out gas solid separation.Its diameter is confirmed by those skilled in the art as the case may be.The effect of pre lift zone is in the presence of preparatory lifting medium, and the catalyzer after the regeneration is promoted, and gets into first reaction zone.
The high quality raw material oil that this method is suitable for can be the petroleum cuts of different boiling ranges.Specifically, high quality raw material grease separation one or more in atmospheric overhead, gasoline, catalytic gasoline, diesel oil, straight-run gas oil, hydrogenation wax oil.
Two reaction zones in this method can be suitable for the catalyzer of all same types; It both can be the amorphous silicon aluminium catalyzer; It also can be zeolite catalyst; The active ingredient of zeolite catalyst is selected from y-type zeolite, HY type zeolite, ultrastable Y, ZSM-5 series zeolite or has the supersiliceous zeolite of five-membered ring structure, one or more the mixture of arbitrary proportion in the ferrierite, and this zeolite can contain rare earth and/or phosphorus, also can not contain rare earth and phosphorus.
Two reaction zones in this method also can be suitable for dissimilar catalyzer, and dissimilar catalyzer can be particle size different catalyst and/or apparent bulk density different catalyst.Active ingredient is selected dissimilar zeolites respectively for use on particle size different catalyst and/or the apparent bulk density different catalyst; Zeolite is selected from y-type zeolite, HY type zeolite, ultrastable Y, ZSM-5 series zeolite or has the supersiliceous zeolite of five-membered ring structure, one or more the mixture of arbitrary proportion in the ferrierite; This zeolite can contain rare earth and/or phosphorus, also can not contain rare earth and phosphorus.The catalyzer of particulate catalyzer and/or the height apparent bulk density of varying in size can get into different reaction zones respectively; For example; The oarse-grained catalyzer that contains ultrastable Y gets into first reaction zone, increases cracking reaction, and the short grained catalyzer that contains rare earth Y type zeolite gets into second reaction zone; Increase hydrogen transfer reactions; The particle size different catalyst is isolated macrobead and catalyst particle then in same stripper stripping and the regeneration of same revivifier, and catalyst particle gets into second reaction zone through cooling.The particle size different catalyst is between 30～40 microns, to demarcate, and the apparent bulk density different catalyst is with 0.6～0.7g/cm
3Between the boundary.
The size distribution of said catalyzer is that coarse grain directly distributes.The size composition of the catalyzer that said coarse grain directly distributes is: account for all particulate volume ratios less than 40 microns particles and be lower than 10%, be preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
The lower catalyzer of activity that this method is suitable for is meant catalyst activity 35～55, preferred 40～50.It can be measured through measuring method of the prior art: the mat activity test method of company standard RIPP 92-90--catalytic cracking " petrochemical complex analytical procedure (RIPP TP) ", and people such as Yang Cuiding, 1990, hereinafter referred is RIPP 92-90.Said catalyst activity is that its calculation formula is to be lower than gasoline yield+gas yield+coke yield of 204 ℃ in MA=(being lower than gasoline output+gas yield+coke output of 204 ℃ in the product)/charging total amount * 100%=product by light oil microactivity (MA) expression.The appreciation condition of light oil micro-reactor (with reference to RIPP 92-90) is: it is 420～841 microns particle that catalyst breakage is become diameter; Loading amount is 5 grams; Reaction raw materials is that boiling range is 235～337 ℃ a straight distillation light diesel oil, and temperature of reaction is 460 ℃, and weight space velocity is 16 hours
-1, agent-oil ratio is 3.2.
The invention has the advantages that:
If conventional equal diameter riser tube or the fluidized-bed reactor of 1 employing comes embodiment of the present invention, only need to reduce treatment capacity, the prolongation reaction times just can implement.
If 2 adopt the reducing riser reactor; The advantage of this reactor drum is both to have kept higher temperature of reaction and the agent-oil ratio in conventional riser reactor bottom to increase a cracking reaction; Cracking and the heat cracking reaction excessively that suppress the top simultaneously; Under lower temperature of reaction, prolong the reaction times in the reactor drum middle and upper part again, increase isomerization reaction, the hydrogen transfer reactions of alkene.
3, increase more than the 30 heavy % with iso-butylene content in the liquefied gas of method production provided by the invention, it is more than the 30 heavy % that the olefin(e) centent during gasoline family forms rises to.
4, under the situation that olefin(e) centent increased during iso-butylene content and gasoline family formed in liquefied gas, dry gas yied and coke reduce significantly.
5, catalyzer is more even because of particle, thereby partial temperature distribution is also more even in regenerative process, and the catalyst breakage tendency also correspondingly reduces.
Description of drawings
Fig. 1 is the synoptic diagram of novel riser reactor, and a among the figure, b, c, d, e represent pre lift zone, first reaction zone, second reaction zone, outlet area, level pipe respectively.
Fig. 2 is the schematic flow sheet of preferred forms of the present invention.Each numbering explanation is as follows in the accompanying drawing:
1,3,4,6,11,13,17,18 all represents pipeline; 2 is the pre lift zone of riser tube; 5,7 be respectively riser tube first reaction zone, second reaction zone; 8 is the outlet area of riser tube; 9 is settling vessel, and 10 is cyclonic separator, and 12 is stripper, and 14 is inclined tube to be generated, and 15 is revivifier, and 16 is regenerator sloped tube.
Embodiment
The present invention has different embodiment.
One of embodiment:
Bottom at conventional equal diameter riser reactor; The raw oil of preheating contact the generation cracking reaction with active lower and hot regenerated catalyst that coarse grain directly distributes; The oil gas that generates contacts with injection refrigerative regenerated catalyst with used catalyst is up; Isomerization reaction and hydrogen transfer reactions take place thereupon, and reaction back elute gets into settling vessel; Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part gets into this reactor bottom, and another part gets into this reactor drum middle and lower part after lowering the temperature.
Two of embodiment:
Bottom at conventional equal diameter riser reactor; The raw oil of preheating contact the generation cracking reaction with active lower and hot regenerated catalyst that coarse grain directly distributes; The oil gas that generates contacts with refrigerative half regenerated catalyst with injection cold shock agent with used catalyst is up; Isomerization reaction and hydrogen transfer reactions take place thereupon, and reaction back elute gets into settling vessel; Reaction product isolated; Reclaimable catalyst is behind stripping; Get in the two-stage regeneration device and burn, half regenerated catalyst that from first section revivifier, comes out gets into this reactor drum middle and lower part after lowering the temperature, and the regenerated catalyst that from second section revivifier, comes out directly returns this reactor bottom without cooling.
Three of embodiment:
For CCU with conventional riser tube-fluidized-bed reactor; Conventional cracking stock after the preheating gets into lower with activity from the bottom of riser tube and hot regenerated catalyst that coarse grain directly distributes contacts; The oil gas that the reaction back generates goes upward to the top of riser tube; Contact with catalyzer after the cooling and to proceed reaction, reaction back elute entering settling vessel; Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part gets into the bottom of riser tube, and another part gets into the top of riser tube after lowering the temperature.
Four of embodiment:
This embodiment is a preferred forms of the present invention.
For CCU with novel reducing riser reactor; Conventional cracking stock after the preheating gets into lower with activity from the first reaction zone bottom of reactor drum and hot regenerated catalyst that coarse grain directly distributes contacts; Cracking reaction takes place; Catalyzer after the second reaction zone bottom that the oil gas that reaction back generates goes upward to reactor drum and the cooling contact and carries out hydrogen transfer reactions and isomerization reaction, elute entering settling vessel after the reaction; Reaction product isolated, reclaimable catalyst gets into the second reaction zone bottom then through stripping, regeneration.
Method provided by the invention is not limited thereto.
Further specify method provided by the present invention below in conjunction with accompanying drawing, but therefore the present invention does not receive any restriction.
Fig. 2 adopts the reducing riser reactor, improves the flow process of the catalysis conversion method of product distribution, and the shape of equipment and pipeline, size do not receive the restriction of accompanying drawing, but confirm as the case may be.
Promote steam in advance and get into from riser tube pre lift zone 2 through pipeline 1, the hot regenerated catalyst that activity is lower and coarse grain directly distributes gets into the riser tube pre lift zones through regenerator sloped tube 16 and is promoted by preparatory lifting steam.Raw oil after the preheating gets into from the riser tube pre lift zone through pipeline 4 and atomizing steam from pipeline 3 by a certain percentage, mixes in back entering first reaction zone 5 with the thermocatalyst that coarse grain directly distributes, and carries out cracking reaction under certain conditions.Reactant flow is mixed into second reaction zone 7 with the catalyzer (not marking among the figure) that directly distributes from the cold shock agent and/or the refrigerative coarse grain of pipeline 6; Carry out secondary reaction; Reacted logistics gets into outlet area 8; This reaction zone improves the linear speed of logistics, makes reactant flow get into settling vessel 9, cyclonic separator 10 in the gas solid separation system fast, and reaction product is gone separation system through pipeline 11.The reclaimable catalyst of reaction back band charcoal gets into stripper 12; After from the water vapor stripping of pipeline 13, get into revivifier 15 by inclined tube 14 to be generated; Reclaimable catalyst is coke burning regeneration in from the air of pipeline 17; Flue gas goes out revivifier through pipeline 18, and the hot regenerated catalyst that coarse grain directly distributes returns the riser tube bottom cycle through regenerator sloped tube 16 and uses.
Following embodiment will further specify the present invention, but therefore not limit the present invention.The character of employed raw oil and catalyzer is listed in table 1 and table 2 respectively in embodiment, the Comparative Examples.Catalyzer in the table 2 is produced by China PetroChemical Corporation's Shandong catalyst plant.ZCM-7 catalyzer in the table 2 is through 800 ℃, and 100% water vapor wore out 12 hours and 30 hours respectively, obtains the ZCM-7L and the ZCM-7H of two kinds of different activities levels, and promptly activity is respectively 45 and 67.Again elutriation is carried out in the aging agent of part ZCM-7L, remove fine particle and, obtain the catalyzer that coarse grain directly distributes greater than the particle of 100 μ m, ZCM-7LA, its character is listed in table 2.
Method provided by the invention is adopted in present embodiment explanation, and the catalyzer that uses coarse grain directly to distribute improves the situation of iso-butylene content and content of olefin in gasoline in the liquefied gas on medium-sized reducing riser reactor.
The pre lift zone of reactor drum, first reaction zone, second reaction zone, outlet area total height are 15 meters, and the pre lift zone diameter is 0.025 meter, and it highly is 1.5 meters; First reaction zone diameter is 0.025 meter, and it highly is 4 meters; Second reaction zone diameter is 0.1 meter, and it highly is 6.5 meters; The diameter of outlet area is 0.025 meter, and it highly is 3 meters; The drift angle of the longitudinal section isosceles trapezoid of first and 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 °.
The listed raw oil of the table 1 of preheating gets in this reactor drum; In the presence of water vapor; The catalyzer ZCM-7LA contact reacts listed with the table 2 of heat, the ZCM-7LA catalyst activity is 45, reaction product isolated obtains liquefied gas and gasoline and other product; Reclaimable catalyst gets into revivifier through stripping, and regenerated catalyst recycles after burning.
The operational condition of test, product distribute and the character of gasoline is listed in table 3.
Comparative Examples 1
Adopt type of reactor and operational condition and embodiment 1 identical, used raw material also is the listed raw oil of table 1, and catalyzer also is the catalyzer ZCM-7L of the listed conventional size distribution of table 2, and just this moment, the ZCM-7L catalyst activity was 45.The operational condition of test, product distribute and the character of gasoline is listed in table 3.
Comparative Examples 2
Adopt type of reactor and operational condition and embodiment 1 identical, used raw material also is the listed raw oil of table 1, and catalyzer also is the catalyzer ZCM-7H of the listed conventional size distribution of table 2, and this moment, the ZCM-7H catalyst activity was 67.The operational condition of test, product distribute and the character of gasoline is listed in table 3.
Can find out that from table 3 with respect to embodiment 1, the dry gas yied and the coke yield of Comparative Examples 1 increase significantly.With respect to the Comparative Examples 2 that adopts high reactivity ZCM-7H (being that activity is 67), adopt low activity ZCM-7L (being that activity is 45), the iso-butylene productive rate rises to 2 heavy % by 1.4 heavy %, has increased by 42.86 heavy %, and content of olefin in gasoline rises to 29.3 heavy % by 16.3 heavy %; In addition, liquid yield still increases by 1.2 percentage points.
Table 1
| The raw oil numbering | A |
| The raw oil title | The hydrogenation wax oil |
| Density (20 ℃), kilogram/rice 3 | 899.3 |
| Kinematic viscosity, millimeter 2/ second | |
| ?80℃ | 16.22 |
| ?100℃ | 9.29 |
| Carbon residue, heavy % | 0.30 |
| Condensation point, ℃ | 44 |
| Basic nitrogen, ppm | 293 |
| Total nitrogen, heavy % | 0.08 |
| Sulphur, heavy % | 0.12 |
| Carbon, heavy % | 87.01 |
| Hydrogen, heavy % | 12.85 |
| Boiling range, ℃ | |
| Over point | 284 |
| ?10％ | 394 |
| ?30％ | 433 |
| ?50％ | 463 |
| ?70％ | 495 |
| ?90％ | / |
| Final boiling point | / |
Table 2
| The catalyzer numbering | A | B | C |
| Trade names | ZCM-7L | ZCM-7H | ZCM-7LA |
| The particle diameter type | Conventional particle diameter | Conventional particle diameter | The coarse grain footpath |
| Zeolite type | USY | USY | USY |
| Chemical constitution, heavy % | |||
| Aluminum oxide | 46.4 | 46.4 | 46.1 |
| Sodium oxide | 0.22 | 0.22 | 0.22 |
| Red stone | 0.32 | 0.32 | 0.30 |
| Apparent density, kilogram/rice 3 | 600 | 600 | 600 |
| Pore volume, milliliter/gram | 0.32 | 0.32 | 0.30 |
| Specific surface area, rice 2/ gram | 217 | 217 | 209 |
| Size composition, heavy % | |||
| 0～40 micron | 16.1 | 16.1 | 7.2 |
| 40～80 microns | 54.1 | 54.1 | 78.4 |
| ＞80 microns | 29.8 | 29.8 | 14.4 |
Table 3
| |
Comparative Examples 1 | Comparative Examples 2 | |
| Catalyst activity | 45 | 45 | 67 |
| Temperature of reaction, ℃ | |||
| First reaction zone | 550 | 550 | 550 |
| Second reaction zone | 500 | 500 | 500 |
| The residence time, second | 5.5 | 5.5 | 5.5 |
| First reaction zone | 2.0 | 2.0 | 2.0 |
| Second reaction zone | 3.5 | 3.5 | 3.5 |
| Agent-oil ratio | 5.0 | 5.0 | 5.0 |
| WOR | 0.1 | 0.1 | 0.1 |
| Product distributes, heavy % | |||
| Dry gas | 1.3 | 1.4 | 1.8 |
| Liquefied gas | 17.1 | 17.3 | 17.5 |
| Iso-butylene wherein | 2.1 | 2.0 | 1.4 |
| Gasoline | 55.0 | 55.0 | 56.0 |
| Diesel oil | 18.2 | 17.8 | 15.4 |
| Heavy oil | 6.2 | 6.0 | 5.6 |
| Coke | 2.3 | 2.5 | 3.7 |
| Add up to | 90.3 | 90.1 | 88.9 |
| Liquid yield, heavy % | |||
| Octane value | 91.2 | 91.0 | 90.6 |
| RON | 80.8 | 80.7 | 80.5 |
| MON | |||
| Boiling range, ℃ | 38～200 | 38～200 | 37～200 |
| Over point～do | |||
| Group composition, heavy % | |||
| Alkane | 40.3 | 40.5 | 50.6 |
| Naphthenic hydrocarbon | 7.2 | 7.3 | 8.2 |
| Alkene | 29.8 | 29.3 | 16.3 |
| Aromatic hydrocarbons | 22.7 | 22.9 | 24.9 |
Claims (13)
1. improve the catalysis conversion method that product distributes; It is characterized in that high quality raw material are oily and activity is lower and hot regenerated catalyst that coarse grain directly distributes contacts the generation cracking reaction in the bottom of reactor drum; The oil gas that generates and the catalyzer that contains charcoal be up, and optionally hydrogen transfer reactions and isomerization reaction take place under the certain reaction environment; Reaction product isolated, reclaimable catalyst recycles after stripping, regeneration.
2. according to the method for claim 1, it is characterized in that said high quality raw material grease separation one or more in atmospheric overhead, gasoline, catalytic gasoline, diesel oil, straight-run gas oil, hydrogenation wax oil.
3. according to the method for claim 1, it is characterized in that the lower hot regenerated catalyst activity of said activity is 35～55.
4. according to the method for claim 3, it is characterized in that the lower hot regenerated catalyst activity of said activity is 40～50.
5. according to the method for claim 1; The size composition that it is characterized in that the catalyzer that said coarse grain directly distributes is: account for all particulate volume ratios less than 40 microns particles and be lower than 10%; Account for all particulate volume ratios greater than 80 microns particles and be lower than 15%, all the other are 40～80 microns particle.
6. according to the method for claim 5; The size composition that it is characterized in that the catalyzer that said coarse grain directly distributes is: account for all particulate volume ratios less than 40 microns particles and be lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and be lower than 10%, all the other are 40～80 microns particle.
7. according to the method for claim 1, it is characterized in that said cracking reaction condition is: 490 ℃～620 ℃ of temperature of reaction, 0.5 second～2.0 seconds reaction times, the weight ratio 3～15: 1 of catalyzer and raw oil.
8. according to the method for claim 7, it is characterized in that said cracking reaction condition is: 500 ℃～600 ℃ of temperature of reaction, 0.8 second～1.5 seconds reaction times, the weight ratio 3～12: 1 of catalyzer and raw oil.
9. according to the method for claim 1, it is characterized in that said hydrogen transfer reactions and isomerization reaction condition are: 420 ℃～550 ℃ of temperature of reaction, the reaction times is 2 seconds～30 seconds.
10. according to the method for claim 7, it is characterized in that said hydrogen transfer reactions and isomerization reaction condition are: 460 ℃～500 ℃ of temperature of reaction, the reaction times is 3 seconds～15 seconds.
11. according to the method for claim 1, it is characterized in that the pressure of said cracking reaction, hydrogen transfer reactions and isomerization reaction is 130kPa～450kPa, the weight ratio of water vapor and raw oil is 0.03～0.3: 1.
12. according to the method for claim 1, it is characterized in that said reactor drum be selected from the equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or the reducing riser tube, or the compound reactor that constitutes by equal diameter riser tube and fluidized-bed.
13. method according to claim 12; It is characterized in that said reducing riser tube 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; Be connected with one section level pipe at the outlet area end, wherein the diameter ratio of the diameter of second reaction zone and first reaction zone is 1.5～5.0: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109666506A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of method of hydrogenated oil catalytic pyrolysis |
| CN115161060A (en) * | 2021-04-02 | 2022-10-11 | 上海河图工程股份有限公司 | Catalytic cracking method and device for producing more low-carbon olefins |
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|---|---|---|---|---|
| CN1232069A (en) * | 1999-04-23 | 1999-10-20 | 中国石油化工集团公司 | Method for catalytic conversion to prepare isobutane and isoalkane-enriched gasoline |
| CN101469274A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for producing high-octane petrol |
| US20100213102A1 (en) * | 2007-08-09 | 2010-08-26 | China Petroleum & Chemical Corporation | catalytic conversion process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1232069A (en) * | 1999-04-23 | 1999-10-20 | 中国石油化工集团公司 | Method for catalytic conversion to prepare isobutane and isoalkane-enriched gasoline |
| US20100213102A1 (en) * | 2007-08-09 | 2010-08-26 | China Petroleum & Chemical Corporation | catalytic conversion process |
| CN101469274A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for producing high-octane petrol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109666506A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of method of hydrogenated oil catalytic pyrolysis |
| CN109666506B (en) * | 2017-10-16 | 2020-12-04 | 中国石油化工股份有限公司 | Method for catalytic cracking of hydrogenated oil |
| CN115161060A (en) * | 2021-04-02 | 2022-10-11 | 上海河图工程股份有限公司 | Catalytic cracking method and device for producing more low-carbon olefins |
| CN115161060B (en) * | 2021-04-02 | 2024-02-27 | 上海河图工程股份有限公司 | Catalytic cracking method and device for high-yield low-carbon olefin |
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