CN1281718C

CN1281718C - Cracking process for hydrocarbon oil

Info

Publication number: CN1281718C
Application number: CN 200310100431
Authority: CN
Inventors: 龙军; 田辉平; 朱玉霞; 郭瑶庆; 刘宇键; 陈振宇; 许友好; 张久顺; 达志坚; 何鸣元
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2003-10-16
Filing date: 2003-10-16
Publication date: 2006-10-25
Anticipated expiration: 2023-10-16
Also published as: CN1607240A

Abstract

The present invention relates to a hydrocarbon oil cracking method which comprises: hydrocarbon oil contacts a catalyst in a reactor comprising a plurality of reaction zones, the catalyst is a cracking catalyst containing a metal component or is a catalyst mixture containing the cracking catalyst containing a metal component and a cracking catalyst without a metal component existing in a highest oxidation valence state or a reduction valence state, and the content of the metal component measured by an oxide of the metal component in a highest oxidation state is from 0.1 to 30 wt% by using the cracking catalyst containing a metal component as the reference; a part of the regenerated catalyst, or a mixture of a part of the regenerated catalyst and a fresh catalyst contacts a gas atmosphere containing reducing gas, and the catalyst after contacting the gas atmosphere containing a reducing gas contacts the hydrocarbon oil in a first reaction zone and reacts with the hydrocarbon oil; the other part of the regenerated catalyst orderly contacts reaction products obtained in a previous reaction zone and reacts with the reaction products in at least one reaction zone behind the first reaction zone. The method has the advantages of high heavy oil cracking capability and high desulphurizing capability.

Description

A kind of cracking method for hydrocarbon oil

Technical field

The invention relates to a kind of cracking method for hydrocarbon oil.

Background technology

The cracking method of hydrocarbon ils is usually included in the zone of cracking, under the cracking reaction condition, with hydrocarbon ils and a kind of cracking catalyst contact reacts, separate crackate and catalyzer, regenerated in catalyst recirculation to breeding blanket, catalyst recirculation after the near small part regeneration is gone back to the zone of cracking, and the purpose of regenerated catalyst is the cracking activity that keeps catalyzer.

Contain impurity such as Ni-V-Fe in some hydrocarbon ils, impurity such as Ni-V-Fe deposits on the catalyzer of molecular sieve containing in the hydrocarbon ils, can cause catalyst deactivation or influence crackate distributing.For addressing this problem, some cracking method for hydrocarbon oil has added a reduction zone after the breeding blanket.

US4,345,992 disclose a kind of hydrocarbon oil catalytic cracking method, this method is included in the zone of cracking, under the cracking reaction condition, hydrocarbon ils is contacted with a kind of particulate state cracking catalyst, the described cracking catalyst of part is transferred to a breeding blanket continuously,, removes deposition of carbon thing on the catalyzer with the incendiary method in the breeding blanket, catalyzer after the regeneration is transferred to a reduction zone continuously, in the reduction zone, described catalyzer is contacted with a kind of reducing gas, the reductive condition is reduced the foreign metal adverse effect, used a kind of sealing gland in the upstream of reduction zone, to guarantee that the major portion of the reducing gas of consumption does not enter the zone of cracking; Catalyzer after the reduction is transferred to the zone of cracking continuously.Described catalyzer comprises the cracking catalyst of various routines, as contains the cracking catalyst and the amorphous aluminosilicate catalyzer of zeolite.

US4,623,443 disclose a kind of method of hydrogenation of olefins, this method is included in a zone of cracking, under the cracking reaction condition, with a kind of hydro carbons of metallic coating catalyzer cracking after a kind of regeneration, described catalyzer is transferred to a breeding blanket, contact with a kind of oxygen-containing gas, with catalyst regeneration, continuously the catalyzer behind the partial regeneration is transferred to the described zone of cracking, simultaneously, catalyzer after another part regeneration is transferred to a reduction zone, in the reduction zone, described catalyzer is contacted with a kind of reducing gas, the condition of contact makes the metallic reducing on the catalyzer, hydro carbons after the cracking is transferred to a disengaging zone, isolate hydrogen and alkene from crackate in the disengaging zone, a hydrogenation zone, the described hydrogen of near small part and alkene contact with catalyzer after the reduction, make hydrogenation of olefins, described catalyzer is transferred to the breeding blanket.

US4,623,443 also disclose a kind of alkene continously hydrogen adding method, this method is under regeneration condition, a kind of cracking catalyst that is contaminated with metals of inactivation is contacted with a kind of oxygen containing gas, the catalyzer that is contaminated with metals after obtaining regenerating, under reductive condition, the catalyzer that is contaminated with metals after the regeneration is contacted with a kind of reducing gas, obtain the catalyzer that is contaminated with metals after reductive is regenerated, then, at once under hydroconversion condition, the cracking catalyst that is contaminated with metals after the described reductive regeneration is contacted with the mixture of a kind of hydrogen and alkene, to described hydrogenation of olefins.

US4,623,443 also disclose a kind of hydrocarbon conversion processes, this method comprises that (1) is at a reaction zone, under the cracking reaction condition, a kind of hydro carbons that contains metal is contacted with a kind of active catalyst, obtain the catalyzer that is contaminated with metals of crackate and part inactivation; (2) with the catalyst separating that is contaminated with metals of crackate and part inactivation; (3) described crackate is fractionated into hydrogen, alkene and other hydro carbons; (4) under regeneration condition, the cracking catalyst that is contaminated with metals of described part inactivation is contacted the catalyzer that is contaminated with metals after obtaining regenerating with a kind of oxygen containing gas; (5) with the catalyst recirculation that is contaminated with metals after the described regeneration of part to described reaction zone; (6) under reductive condition, the catalyzer that is contaminated with metals after the remaining regeneration is contacted with a kind of reducing gas, obtain the catalyzer that is contaminated with metals after a kind of reductive is regenerated; (7) under hydroconversion condition, the catalyzer that is contaminated with metals after the regeneration of described reductive is contacted the catalyzer that is contaminated with metals after the reductive that obtains alkene behind the hydrogenation and part coking is regenerated with alkene with hydrogen; (8) with the catalyst separating that is contaminated with metals after the reductive regeneration of alkene behind the described hydrogenation and part coking; (9) alkene behind the hydrogenation is recycled to (3) described fractionating system; (10) regenerated in the catalyst recirculation that is contaminated with metals to (4) after the reductive regeneration of part coking.

In recent years, for the consideration of environmental protection, worldwide, the requirement of oil fuel standard is improved constantly.With China is example, and State Quality Supervision Bureau had formulated " motor spirit objectionable impurities control criterion " in 1999, and according to the requirement of this standard, the sulphur content of gasoline product should be less than 800ppm.Europe fuel oil III emission standard has proposed more harsh requirement less than 30ppm to gasoline sulfur.In fact, the sulphur of gasoline product more than 90% comes from FCC gasoline.On the other hand, the heaviness tendency of catalytically cracked material is serious day by day, the proportion of middle-eastern crude in the shared crude oil in Chinese refinery with higher sulfur content is also increasing, therefore, need develop the cracking catalyst with high cracking activity and desulfurization performance and have the cracking method of strong heavy oil cracking ability and sweetening power.

US6,036,847 and patent families EP0,798,362A2 discloses a kind of fluidized catalytic cracking of hydrocarbons method, wherein, and under the condition of described hydrocarbon feed hydrogenation outside not existing, by cracking, and all particles that comprise granules of catalyst are constantly in cracking hydrocarbon district and a catalyst regeneration zones circulation a zone of cracking.Wherein, contain another particle in all particles, this particle has the activity of the cracking hydrocarbon ils lower than granules of catalyst, and described activity is benchmark with the fresh granules.This particle is made up of the inorganic oxide of titanium oxide and a kind of non-oxide titanium basically.The inorganic oxide of described non-oxide titanium contains a kind of Lewis acid, this Lewis acid is selected from following element and compound composition thereof one group: nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and germanium, described Lewis acid loads on the aluminum oxide.Because use this auxiliary agent that contains titanium oxide, crackate FCC sulfur in gasoline content is reduced.

CN1078094C discloses a kind of riser reactor that is used for fluid catalytic cracking, this reactor vertically is followed successively by co-axial each other pre lift zone from bottom to up, second reaction zone of first reaction zone, enlarged-diameter, the outlet area of reduced are connected with one section level pipe at the outlet area end.It is different with the processing condition of second reaction zone that this reactor both can satisfy first reaction zone, can make stock oil of different nature carry out the segmentation cracking again.

CN1076751C discloses a kind of catalysis conversion method of producing Trimethylmethane and being rich in isoparaffin gasoline, the stock oil that is included in preheating enters in the reactor that comprises 2 reaction zones, in the presence of water vapor, contact with the cracking catalyst of heat, carry out once and secondary reaction, the cracking reaction condition comprises that the temperature of first reaction zone is 530-620 ℃, reaction times is 0.5-2 second, the temperature of second reaction zone is 460-530 ℃, reaction times is 2-30 second, reaction product isolated, reclaimable catalyst enters revivifier behind stripping, recycle after burning.

The purpose of this invention is to provide a kind of new cracking method for hydrocarbon oil with strong heavy oil cracking ability and sweetening power.

Method provided by the invention is included in the reactor that comprises a plurality of reaction zones, under the cracking reaction condition, hydrocarbon ils is contacted with a kind of catalyzer, and with reaction product and catalyst separating, the isolated catalyzer of regenerating uses the catalyst recirculation after the regeneration; Wherein, described catalyzer is a kind of cracking catalyst of metallic components, or contain the cracking catalyst of this metallic components and the catalyst mixture of the cracking catalyst of metallic components not, described metal component exists with highest oxidation valence state or reduction valence state, cracking catalyst with described metallic components is a benchmark, oxide compound in the metal component of highest oxidation state, the content of metal component is 0.1-30 weight %, and described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, VIII family base metal, in the rare earth metal one or more; The part of the catalyzer after the part of the catalyzer after the regeneration or the regeneration contacts with a kind of atmosphere that contains reducing gas with the mixture of live catalyst, the described temperature that contacts with the atmosphere that contains reducing gas is 100-900 ℃, the pressure of contact is the 0.1-0.5 MPa, the time of contact was at least 1 second, the consumption that contains the atmosphere of reducing gas is that the cracking catalyst per minute of metallic components per ton is not less than 0.03 cubic metre of reducing gas, will with catalyzer after the atmosphere that contains reducing gas contacts in first reaction zone and described hydrocarbon ils contact reacts; The other part of the catalyzer after the regeneration is at the later reaction zone of at least one first reaction zone, successively the product contact reacts that obtains with last reaction zone.

Method provided by the invention has strong heavy oil cracking ability and sweetening power.

For example, adopting method provided by the invention that hydrocarbon ils is carried out catalytic cracking, is 30 weight % with the MOY zeolite content, and the content of aluminum oxide is 34 weight %, and kaolinic content is 35 weight %, with Co ₂O ₃Meter, cobalt contents is that the cracking catalyst catalytic cracking sulphur content of the metallic components of 1 weight % is 2.0 weight %, boiling range is 329-550 ℃ a vacuum gas oil.In the crackate, heavy oil content has only 4.94 weight %, and gasoline content is up to 48.37 weight %, and coke content has only 4.66 weight %, and the sulphur content of gasoline fraction has only 510 mg/litre.And adopt identical catalyzer, under identical condition, same hydrocarbon ils is carried out catalytic cracking, just the catalyzer after the regeneration not with contain reducing gas and contact, in the crackate, heavy oil content is up to 6.48 weight %, gasoline content has only 45.84 weight %, and coke content is up to 5.62 weight %, and the sulphur content of gasoline fraction is up to 1100 mg/litre.

Again for example, adopting method provided by the invention that hydrocarbon ils is carried out catalytic cracking, is 30 weight % with the MOY zeolite content, and the content of aluminum oxide is 34 weight %, and kaolinic content is 35 weight %, with Co ₂O ₃Meter, cobalt contents is that the cracking catalyst catalytic cracking sulphur content of the metallic components of 1 weight % is 0.07 weight %, initial boiling point is 346 ℃ a vacuum gas oil (being substantially free of the hydrocarbon ils of sulphur).In the crackate, heavy oil content has only 4.52 weight %, and liquefied gas and gasoline content are up to 63.21 weight %, and coke content has only 3.5 weight %.And adopt identical catalyzer, under identical condition, same hydrocarbon ils is carried out catalytic cracking, just the catalyzer after the regeneration is without contacting with described gas mixture, in the crackate, heavy oil content is up to 7.36 weight %, liquefied gas and gasoline content have only 59.21 weight %, and coke content is up to 5.6 weight %.

Again for example, adopt method provided by the invention that hydrocarbon ils is carried out catalytic cracking, with the trade mark is that (sulphur content is 2.0 weight % for the industrial cracking catalyst catalytic cracking decompressed wax oil that contains rare earth of MLC-500, boiling range is 329-550 ℃) content is that 20 weight % and long residuum (initial boiling point is 282 ℃, and sulphur content is 0.13 weight %) content are the mixing oil of 80 weight %.In the crackate, heavy oil content has only 6.91 weight %, and diesel oil content is up to 27.51 weight %, and coke content has only 7.53 weight %, and the sulphur content of gasoline fraction has only 110 mg/litre.And adopt identical catalyzer, under identical condition, same hydrocarbon ils is carried out catalytic cracking, just the catalyzer after the regeneration is without contacting with described gas mixture, in the crackate, heavy oil content is up to 9.88 weight %, diesel oil content has only 22.57 weight %, and coke content is up to 8.53 weight %, and the sulphur content of gasoline fraction is up to 330 mg/litre.

Method provided by the invention can also be according to the market requirement, number by the on-off reaction district, suitably change the operational condition of each reaction zone,, produce different purpose products as conditioned reaction temperature, agent-oil ratio (weight ratio of catalyzer and hydrocarbon ils) and reaction times etc.For example, can improve the temperature of each reaction zone, increase liquefied gas and gasoline content by increasing the number of reaction zone.Can reduce liquefied gas output by the temperature that reduces the later reaction zone of first reaction zone, maximum is produced gasoline and/or diesel oil.

Description of drawings

Fig. 1-the 4th, the schematic flow sheet of method provided by the invention.

Embodiment

One, reduction process

According to method provided by the invention, according to the kind difference of cracking case, described catalyzer can in position or will carry out in catalyst recirculation to a reduction reactor with contacting of the atmosphere that contains reducing gas.When described cracking case is fixed bed, fluidized-bed reactor or moving-burden bed reactor, recycling catalyst not, after catalyzer is directly regenerated in bed, feed the described atmosphere that contains reducing gas again, contact with the atmosphere that contains reducing gas, reach recycling of catalyzer by recycling to be equipped with the reactor of catalyzer after the atmosphere that contains reducing gas contacts.And when cracking case was riser reactor, then with catalyst recirculation to a revivifier regeneration, in catalyst recirculation to a reduction reactor after the regeneration, described catalyzer carried out with contacting in reduction reactor of the atmosphere that contains reducing gas.

The catalyzer that enters reduction reactor can be direct from the catalyzer after the regeneration of revivifier, also can be from the cooling of the process of the catalyzer after the regeneration of revivifier or the catalyzer after the regeneration after heating up.Can directly enter corresponding riser reactor with the catalyzer after the atmosphere that contains reducing gas contacts, also can or heat up through cooling enters corresponding riser reactor again.To the regeneration rear catalyst with the intensification of catalyzer after the atmosphere that contains reducing gas contact with lower the temperature and can adopt existing various device, reach as tube and shell heat exchanger, plate-type heat exchanger, floating coiler heat exhanger and/or hot-blast heater, these heat-exchanger rigs are conventionally known to one of skill in the art.

The temperature that catalyzer contacts with the atmosphere that contains reducing gas can be 100-900 ℃, is preferably 400-700 ℃, and the pressure of contact is the 0.1-0.5 MPa, be preferably the 0.1-0.3 MPa, the time of contact was at least 1 second, was preferably 10 seconds to 1 hour, more preferably 1 minute to 40 minutes.The consumption that contains the atmosphere of reducing gas is that the cracking catalyst per minute kind of metallic components per ton is not less than 0.03 cubic metre of reducing gas, the cracking catalyst per minute 0.05-15 cubic meter reducing gas of preferred metallic components per ton, more preferably the cracking catalyst per minute 1-8 cubic meter reducing gas of metallic components per ton.The described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.

The example of described pure reducing gas comprises hydrogen, carbon monoxide and contains in the hydro carbons of 1-5 carbon atom one or more, preferably includes in hydrogen, carbon monoxide, methane, ethane, propane, butane, pentane and the various isomer thereof one or more.

Described rare gas element refers to not the gas with described composition or metallic compound generation chemical action, as in periodic table of elements zero group gas, nitrogen, the carbonic acid gas one or more.

The described example that contains reducing gas and inert gas atmosphere comprises hydrogen, carbon monoxide, contain in one or more and the rare gas element in the hydro carbons of 1-5 carbon atom one or more mixture or the dry gas in the refinery (as catalytic cracking tail gas, catalytic reforming tail gas, hydrocracking tail gas and delayed coking tail gas etc.).

In the described atmosphere that contains reducing gas, the concentration of reducing gas is not particularly limited.Under the preferable case, in the described atmosphere that contains reducing gas, reducing gas content is at least 10 volume %, more preferably 50 volume %.

Two, cracking reaction-regenerative process

According to method provided by the invention, described reactor comprises a plurality of reaction zones, be followed successively by first reaction zone, second reaction zone, the 3rd reaction zone along the hydrocarbon ils flow direction ... the number of reaction zone can increase or reduce according to different needs, the number of described reaction zone is preferably 2-5, more preferably 2-3.Wherein first reaction zone is a cracking reaction district, and second reaction zone is the secondary reaction district, and later reaction zone is reaction zone repeatedly.

Described reactor can be the reactor of arbitrary form or their combination.Reactor can be one of the reactor with arbitrary form of a plurality of reaction zones as described, or has a combination between the reactor of arbitrary form of a plurality of reaction zones, or have a plurality of reaction zones arbitrary form reactor and have combination between the reactor of single reaction zone, or have the combination between the reactor of single reaction zone.

Say that further described reactor can be riser reactor, fixed-bed reactor, fluidized-bed reactor, moving-burden bed reactor itself or the combination between them.

Preferred reactor is riser reactor or their combination, as common riser reactor, have the riser reactor (the disclosed riser reactor that is used for fluid catalytic cracking of CN1078094C) of a plurality of reaction zones or the combination between above-mentioned each riser reactor.Wherein, common riser reactor, as the equal diameter riser reactor or etc. the linear speed riser reactor can be used as the multi-region reactor and be used for the present invention.

The cracking reaction condition of each reaction zone can be the same or different, and all can be conventional cracking reaction condition.The cracking reaction condition of described routine comprises that temperature of reaction is 350-700 ℃, is preferably 400-650 ℃, and reaction pressure is the 0.1-0.8 MPa, is preferably the 0.1-0.5 MPa, and agent-oil ratio is 1-30, is preferably 2-15.

For example, when reactor is when having the riser reactor of a plurality of reaction zones, can adopt conventional method to adjust the cracking reaction condition of each reaction zone, the feeding temperature that interchanger is set before injecting cold shock agent, reaction zone at needs as the combining site at two adjacent reaction zones, regulates the temperature of the catalyzer that enters respective reaction zones and/or regulates hydrocarbon ils is to regulate the temperature of reaction of each reaction zone.Regulate hydrocarbon oil feed speed and come adjusting reaction time.Described interchanger and cold shock agent are conventionally known to one of skill in the art.For example, the temperature that described adjusting enters the catalyzer of respective reaction zones can adopt and interchanger is set before entering reaction zone reaches, and described interchanger can be tube and shell heat exchanger, plate-type heat exchanger, floating coiler heat exhanger and/or hot-blast heater.

In order to suppress the cracking and the heat cracking reaction excessively in certain reaction zone and riser tube exit, can take gas-solid sharp separation or in the junction of this reaction zone and adjacent last reaction zone, perhaps the junction of last reaction zone and outlet area adds the method for cold shock agent or terminator, and the temperature of this reaction zone or riser reactor outlet area is reduced.Adopt this method can improve product and distribute, improve the content of gasoline and diesel oil.The method of gas-solid sharp separation is referring to EP163978, EP139392, EP564678, US5104517, US5308474.The method that adds the cold shock agent is referring to US5089235, EP593823.Described cold shock agent, terminator can be selected from one or more in raw gasline, gasoline, diesel oil, separation column turning oil, the water.

When described reactor is riser reactor, under the preferable case, the cracking reaction condition of first reaction zone comprises that temperature of reaction is 450-650 ℃, is preferably 480-620 ℃, reaction pressure is the 0.1-0.5 MPa, be preferably the 0.1-0.3 MPa, be 0.4-6 second duration of contact, is preferably 0.8-4 second, agent-oil ratio is 1-30, be preferably 2-15, charging atomized water steam and the pre-total amount that promotes water vapour account for the 1-30 weight % of hydrocarbon ils weight, preferred 2-15 weight %.Here, the agent-oil ratio of a certain reaction zone is the internal circulating load of the catalyzer of this reaction zone in the unit time and the weight ratio that enters the hydrocarbon ils of first reaction zone in the unit time.

The cracking reaction condition of second reaction zone is according to the kind of the kind of catalyzer, hydrocarbon ils, form adjust different with the requirement of character to product.The temperature of reaction of second reaction zone is 470-650 ℃, is preferably 480-580 ℃, and reaction pressure is the 0.1-0.5 MPa, be preferably the 0.1-0.3 MPa, be 1-15 second duration of contact, is preferably 2-10 second, agent-oil ratio be first reaction zone greater than 1 to 3 times, be preferably 1.1-2 doubly.

The reactant of the 3rd reaction zone and later reaction zone thereof is the reaction product that obtains through after the first and second riser reactor crackings, and for avoiding overcracking, its cracking reaction condition should comparatively relax.The cracking reaction condition of the 3rd reaction zone and later reaction zone thereof comprises that temperature of reaction is 450-550 ℃, preferred 470-520 ℃, reaction pressure is the 0.1-0.5 MPa, be preferably the 0.1-0.3 MPa, be 1-4 second duration of contact, be preferably 1-2 second, agent-oil ratio be first reaction zone greater than 1 to 3 times, be preferably 1.1-2 doubly.

The condition of riser reactor outlet area is conventional condition, and these conditions comprise that temperature is 460-590 ℃, are preferably 470-570 ℃, and be 0.1-1 second duration of contact, is preferably 0.1-0.8 second.The condition of riser reactor outlet area is conventionally known to one of skill in the art.

When reactor is fixed-bed reactor, when fluidized-bed reactor or moving-burden bed reactor, described multi-region fixed-bed reactor can be contacted with a plurality of fixed beds, a plurality of fluidized-bed reactor polyphones, a plurality of moving-burden bed reactor polyphones or fixed-bed reactor, the mode of the polyphone between fluidized-bed reactor and the moving-burden bed reactor meets the demands, one of them reactor is exactly a reaction zone, can adopt conventional method to adjust the cracking reaction condition of each reactor (with respect to each reaction zone), adjust the temperature of reaction of each fixed-bed reactor (with respect to each reaction zone) as adopting heating or refrigerative mode.

In general, for fixed bed, fluidized-bed and moving-burden bed reactor, the cracking reaction condition of each reaction zone comprises that temperature of reaction is 350-700 ℃, be preferably 400-650 ℃, reaction pressure is the 0.1-0.8 MPa, is preferably the 0.1-0.5 MPa, and weight hourly space velocity is 1-40 hour ^-1, be preferably 2-30 hour ^-1, agent-oil ratio is 1-30, is preferably 2-15.The cracking reaction condition of first reaction zone and second reaction zone and later reaction zone thereof can be according to the kind of the kind of catalyzer, hydrocarbon ils, form different with the requirement of character to product, in above-mentioned cracking reaction condition and range, the cracking reaction condition of each reaction zone is adjusted respectively.

When cracking case was riser reactor, method provided by the invention can directly utilize existing reaction-regeneration system to finish, and just increased a reduction reactor in existing reaction-regeneration system.The variety of way of described existing reaction-regeneration system rapidly is conventionally known to one of skill in the art, and existing reaction-regeneration system rapidly as described can be different with the arrangement of revivifier according to settling vessel and same high block form, height block form or coaxial-type reaction-regeneration system rapidly that divide.Wherein, riser reactor can be deep into the settling vessel from settling vessel, stripping stage center, also can be the peripheral hardware riser reactor.Wherein said riser reactor comprises any type of riser tube feed nozzle, mixing temperature control techniques, reaction terminating facility etc." residual oil complete processing ", (Li Chunnian writes the 282-338 page or leaf, Sinopec press published in 2002) existing catalytic cracking reaction-regeneration system rapidly is summarized, as the ROCC-V process unit, full grand celebration vacuum residue catalytic (VR-RFCC) process unit, the residual oil fluid catalytic cracking RFCC device of U.S. Dao Daer (Total) company of two-stage regeneration, the atmospheric residue of the employing two-stage regeneration that A Xilan (Ashland) company and UOP develop jointly transforms the RCC process unit, the FCC process unit that burns the pot type highly efficient regeneration of UOP, the mobile type riser reactor catalytic cracking unit that the riser reactor that flexicracking (Flexicracking IIIR) technology of Exxon (Exxon) company relates to combines with bed reactor, one section reverse-flow regenerating unit and super positive flow pattern FCC process unit that heavy oil cracking (HOC) technology of Kellogg (Kellogg) company relates to.Described reaction-regeneration system is not limited to above-mentioned giving an example.

Described revivifier can be single hop regeneration or two-stage regeneration.Described single hop regeneration can be regeneration of turbulent bed single hop or the regeneration of fast bed single hop.Described two-stage regeneration can be the turbulent bed two-stage regeneration, burn jar the two-stage regeneration, fast bed two-stage regeneration or the tubular type that constitute jointly with conventional turbulent bed regenerates.Described turbulent bed two-stage regeneration can be two device adverse current two-stage regenerations, two device cross-flow two-stage regeneration.Described burn jar the two-stage regeneration that constitutes jointly with conventional turbulent bed can be prepositionly burn a jar two-stage regeneration, postposition is burnt a jar two-stage regeneration.Heat collector or external warmer in described revivifier can have as required.Heat collector can be horizontally disposed or vertically arranged bed spiral coil cooling tube in described.Described external warmer can be upflowing, downflow system, back-mixing formula or Pneumatic-control type external warmer." residual oil complete processing ", 282-338 page or leaf (Li Chunnian writes, and Sinopec press published in 2002) is also summed up revivifier.

According to embodiment preferred of the present invention, method provided by the invention is included in the riser reactor that comprises a plurality of reaction zones, under the cracking reaction condition, hydrocarbon ils is contacted with a kind of catalyzer, with reaction product and catalyst separating, the catalyst recirculation that isolated catalyst recirculation to a revivifier will be regenerated after will regenerating is used; Wherein, described catalyzer is a kind of cracking catalyst of metallic components, or the cracking catalyst of this metallic components and the catalyst mixture of the cracking catalyst of metallic components not, described metal component exists with highest oxidation valence state or reduction valence state, cracking catalyst with described metallic components is a benchmark, oxide compound in the metal component of highest oxidation state, the content of metal component is 0.1-30 weight %, and described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, VIII family base metal, in the rare earth metal one or more; Between revivifier and riser reactor, also comprise a reduction reactor, the part of the catalyzer after the part of the catalyzer after the regeneration or the regeneration and the mixture of live catalyst enter reduction reactor, in reduction reactor, contact with a kind of atmosphere that contains reducing gas, the described temperature that contacts with the atmosphere that contains reducing gas is 100-900 ℃, the pressure of contact is the 0.1-0.5 MPa, the time of contact was at least 1 second, the consumption that contains the atmosphere of reducing gas is that the cracking catalyst per minute of metallic components per ton is not less than 0.03 cubic metre of reducing gas, will with catalyst recirculation to the first reaction zone and the described hydrocarbon ils contact reacts after the atmosphere that contains reducing gas contacts; The other part of the catalyzer after the regeneration is circulated to the later reaction zone of at least one first reaction zone, successively the product contact reacts that obtains with last reaction zone.

Below in conjunction with accompanying drawing, some concrete embodiments of the present invention are described.These embodiments are some the representative embodiments in the numerous embodiments of the present invention.Can be according to practical situation, according to these embodiments, the number of the type of reactor design and other equipment, size, shape, parameter and reaction zone.

According to first specific embodiment of the present invention, method provided by the invention can be undertaken by flow process shown in Figure 1.Described reactor is the disclosed riser reactor that is used for fluid catalytic cracking of CN1078094C, this reactor vertically is followed successively by co-axial each other pre lift zone from bottom to up, second reaction zone of first reaction zone, enlarged-diameter, the outlet area of reduced are connected with one section level pipe at the outlet area end.Under the preferable case, the diameter of first reaction zone of this reactor and the ratio of pre lift zone diameter are 1-1.2, and the ratio of the diameter of second reaction zone and first reaction zone diameter is 1.5-5.0, and the ratio of the diameter of outlet area and first reaction zone diameter is 0.8-1.5; The height of pre lift zone accounts for the 5-20% of total reactor height, the height of first reaction zone accounts for the 10-30% of total reactor height, the height of second reaction zone accounts for the 30-60% of total reactor height, the height of outlet area accounts for the 0-20% of total reactor height, first reaction zone and the second reaction zone combining site are round table-like, its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is the 30-80 degree, second reaction zone and outlet area combining site also are round table-like, its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is the 45-85 degree.

Catalyzer after contacting from the atmosphere with containing reducing gas of pipeline 8 enters the pre lift zone of reactor, is advanced into first reaction zone 9 under the pre-lifting water vapor from pipeline 10 drives.Simultaneously, from the hydrocarbon ils after the preheating of pipeline 11 with from the atomized water vapor mixing of pipeline 12, enter first reaction zone 9, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carries out a cracking reaction.Reactant flow continues to go upward to second reaction zone 14, reaction zone 14 with contact from the catalyzer after the regeneration of pipeline 28, carry out secondary reaction, wherein, cooling if desired, can inject the cold shock agent in the junction of first reaction zone 9 and second reaction zone 14 from pipeline 13, the cold shock agent is mixed with reaction mass.Logistics behind the secondary reaction continues up, by outlet area 15, through level pipe 16, enters the settling vessel 17 of separation system, and the cyclonic separator in the settling vessel 17 separates catalyzer with crackate.In order to suppress the cracking and the heat cracking reaction excessively in riser tube exit, can take gas-solid sharp separation or, add terminators through pipeline 29 in outlet area 15 and second reaction zone, 14 junctions, reduce the temperature of reactant flow.Isolated catalyzer enters the stripper 18 of separation system, with water vapor counter current contact from pipeline 19, stripping goes out remaining crackate on the catalyzer, obtain reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 20 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 22 through inclined tube 21 to be generated, in revivifier 22, under regeneration temperature, reclaimable catalyst is contacted with oxygen containing atmosphere from pipeline 23, removes coke wherein, and reacted flue gas is discharged from pipeline 24.The part of the catalyzer after the regeneration enters reduction reactor 3 from pipeline 25, in reduction reactor 3, under reductive condition, catalyzer after catalyzer after the regeneration or the regeneration with contact with the atmosphere that contains reducing gas from the mixture of the live catalyst of storage tank 1 through pipeline 2 from pipeline 4, waste gas is through pipeline 5 discharges.Enter or do not enter interchanger 7 heat exchange with the catalyzer after the atmosphere that contains reducing gas contacts through pipeline 6, the catalyzer after heat exchange or the not heat exchange enters the pre lift zone of reactor.The other part of the catalyzer after the regeneration enters or does not enter interchanger 27 heat exchange through pipeline 26, and the catalyzer after the regeneration after heat exchange or the not heat exchange enters second reaction zone through pipeline 28.When the temperature of reaction that reaches first reaction zone when the temperature in the reduction reactor 3 requires, can directly enter the pre lift zone of reactor without interchanger 7 with catalyzer after reducing gas contacts.When the temperature of the catalyzer after the regeneration of pipeline 26 reached the temperature of reaction requirement of second reaction zone, the catalyzer after the regeneration can directly enter second reaction zone without interchanger 27.

According to second specific embodiment of the present invention, method provided by the invention can be undertaken by flow process shown in Figure 2.Described reactor is the described reactor of first embodiment.

Catalyzer after contacting from the atmosphere with containing reducing gas of pipeline 8 enters the pre lift zone of reactor, is advanced into first reaction zone 9 under the pre-lifting water vapor from pipeline 10 drives.Simultaneously, from the hydrocarbon ils after the preheating of pipeline 11 with from the atomized water vapor mixing of pipeline 12, enter first reaction zone 9, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carries out a cracking reaction.Reactant flow continues to go upward to second reaction zone 14, reaction zone 14 with contact from the catalyzer after the regeneration of pipeline 28, carry out secondary reaction, wherein, cooling if desired, can inject the cold shock agent in the junction of first reaction zone 9 and second reaction zone 14 from pipeline 13, the cold shock agent is mixed with reaction mass.Logistics behind the secondary reaction continues up, by outlet area 15, through level pipe 16, enters the settling vessel 17 of separation system, and the cyclonic separator in the settling vessel 17 separates catalyzer with crackate.In order to suppress the cracking and the heat cracking reaction excessively in riser tube exit, can take gas-solid sharp separation or add terminator at outlet area 15 and second reaction zone, 14 junctions through pipeline 29, reduce the temperature of reactant flow.Isolated catalyzer enters the stripper 18 of separation system, with water vapor counter current contact from pipeline 19, stripping goes out remaining crackate on the catalyzer, obtain reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 20 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 22 through inclined tube 21 to be generated, in revivifier 22, under regeneration temperature, reclaimable catalyst is contacted with oxygen containing atmosphere from pipeline 23, removes coke wherein, and reacted flue gas is discharged from pipeline 24.The part of the catalyzer after the regeneration enters gas displacement jar 30 through pipeline 25, in gas displacement jar 30, the part of the catalyzer after the part of the catalyzer after the regeneration or the regeneration and use the oxygen-containing gas of the catalyst entrainment after will regenerating from the rare gas element of pipeline 31 to cement out from the mixture of the live catalyst of storage tank 1 through pipeline 2, gas after the displacement is discharged through pipeline 32, catalyzer through gas displacement enters reduction reactor 3 from pipeline 33, in reduction reactor 3, under reductive condition, described catalyzer contacts with the atmosphere that contains reducing gas from pipeline 4, and waste gas is discharged through pipeline 5.Enter or do not enter interchanger 7 heat exchange with the catalyzer after reducing gas contacts through pipeline 6, the catalyzer after heat exchange or the not heat exchange enters the pre lift zone of reactor.The other part of the catalyzer after the regeneration enters or does not enter interchanger 27 heat exchange through pipeline 26, and the catalyzer after the regeneration after heat exchange or the not heat exchange enters second reaction zone through pipeline 28.The introducing of gas displacement jar 30 can make that entrained oxygen-containing atmosphere is displaced in the regeneration rear catalyst, makes the reduction reaction in reduction jars 3 carry out more fully, and can reduce the consumption of reducing gas.When the temperature of reaction that reaches first reaction zone when the temperature in the reduction reactor 3 requires, can directly enter the pre lift zone of reactor without interchanger 7 with catalyzer after reducing gas contacts.When the temperature of the catalyzer after the regeneration of pipeline 26 reached the temperature of reaction requirement of second reaction zone, the catalyzer after the regeneration can directly enter second reaction zone without interchanger 27.

According to the 3rd specific embodiment of the present invention, method provided by the invention can be undertaken by flow process shown in Figure 3.The flow process of this scheme is identical with first embodiment, just replaces the described reactor of first specific embodiment with common riser reactor.

According to the 4th specific embodiment of the present invention, method provided by the invention can be undertaken by flow process shown in Figure 4.The flow process of this scheme is identical with second embodiment, just replaces second described reactor of specific embodiment with common riser reactor.

Wherein, described common riser reactor can be the common riser reactor of any routine, as the equal diameter riser reactor of routine or etc. the linear speed riser reactor.First reaction zone is lower part of riser reaction zone, second reaction zone is upper part of riser reaction zone, pre lift zone accounts for the 5-20% of riser reaction zone total length, the length of first reaction zone accounts for the 10-30% of riser reaction zone total length, the length of second reaction zone accounts for the 30-60% of riser reaction zone total length, and outlet area accounts for the 0-20% of riser reaction zone total length.

The effect of atomized water steam is to make the hydrocarbon ils atomizing effect better, makes hydrocarbon ils and catalyst mix more even.The consumption of described atomized water steam is conventionally known to one of skill in the art, and in general, atomized water steam accounts for the heavy % of 1-30 of hydrocarbon ils, the heavy % of preferred 2-15.

The effect of atomized water steam is to make the hydrocarbon ils atomizing effect better, makes hydrocarbon ils and catalyst mix more even.The effect that is used as the water vapor of pre-lifting medium is that catalyzer is quickened, and forms density uniform catalyst piston flow at pre lift zone.Described atomized water steam and the pre-consumption that promotes water vapor are conventionally known to one of skill in the art, and in general, atomized water steam and the pre-total amount that promotes water vapor account for the heavy % of 1-30 of hydrocarbon ils, and preferred 2-15 weighs %.

The effect of water stripping steam is that the oil gas that is full of between the granules of catalyst and in the particle hole is cemented out, and improves the oil product productive rate.The consumption that is used for steam stripped water vapor is conventionally known to one of skill in the art.In general, the consumption that is used for steam stripped water vapor accounts for the 0.1-0.8 weight % of catalyst recirculation amount, is preferably 0.2-0.4 weight %.

Wherein, promoting water vapor in advance can be with other pre-medium that promotes, as in refinery dry gas, light paraffins, the light olefin one or more, or one or more and the gas mixture replacement of water vapor in them.

Described oxygen containing atmosphere can be oxygen or any mixed gas that contains oxygen, and oxygen-containing atmosphere commonly used is an air.Described regeneration temperature is conventionally known to one of skill in the art, and in general, described regeneration temperature is 600-770 ℃, preferred 650-730 ℃.

Described rare gas element comprise any not with the gas or the gaseous mixture of catalyst action, as the zero group gas in nitrogen, the periodic table of elements, in the carbonic acid gas one or more.The throughput of described rare gas element is enough to make the entrained oxygen-containing gas of catalyzer to be displaced.In general, the throughput of described rare gas element is a catalyzer per minute 0.01-30 cubic meter per ton, is preferably the 1-15 cubic meter.

Because catalyzer is after circulation after a while, have the little amount of catalyst loss, therefore, the effect of storage tank 1 is to be used for catalyzer regular or that irregular postreaction consumed, the contained metal component of catalyzer in the storage tank 1 can be to go back ortho states, also can be oxidation state.

Three, catalyzer

1, catalyzer and catalyst mixture

According to method provided by the invention, described catalyzer is a kind of cracking catalyst of metallic components, or contains the catalyst mixture of the cracking catalyst of the cracking catalyst of metallic components not and metallic components.Described metal component exists with highest oxidation state or reduction valence state, cracking catalyst with described metallic components is a benchmark, oxide compound in the metal component of highest oxidation state, the content of metal component is 0.1-30 weight %, and described metal component is selected from one or more in the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, group vib metal, VIIB family metal, VIII family base metal, the rare earth metal.With described catalyst mixture is benchmark, and the content of the cracking catalyst of metallic components is at least 0.1 weight %, is preferably at least 1 weight %, more preferably at least 3 weight %, preferably at least 10 weight %.

2, the cracking catalyst of metallic components

(1) cracking catalyst of the metallic components that exists with highest oxidation state

The cracking catalyst of described metallic components comprises one or more in the cracking catalyst of existing metallic components.As metal component, molecular sieve, heat-resistant inorganic oxide matrix as described in containing, contain or not argillaceous, contain or phosphorated not the cracking catalyst that described metal exists with highest oxidation state.Cracking catalyst with described metallic components is a benchmark, and in the oxide compound of highest oxidation state metal, the content of described metal component is 0.1-30 weight %, is preferably 0.5-20 weight %.Other components contents is the content of such catalyzer routine in the cracking catalyst of described metallic components, for conventionally known to one of skill in the art.As with as described in the cracking catalyst of metallic components be benchmark, the content of described molecular sieve is 1-90 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 0-80 weight %, in Vanadium Pentoxide in FLAKES, the content of phosphorus is 0-15 weight %.Under the preferable case, the content of described molecular sieve is 10-60 weight %, and the content of heat-resistant inorganic oxide is 10-50 weight %, and the content of clay is 20-70 weight %, and the content of phosphorus is 0-8 weight %

Described metal component is selected from one or more in the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, group vib metal, VIIB family metal, VIII family base metal, the rare earth metal.

The non-aluminum metal of described IIIA family comprises gallium, indium, thallium.Described IVA family metal comprises germanium, tin, lead.Described VA family metal comprises antimony, bismuth.Described IB family metal comprises copper, silver.Described IIB family metal comprises zinc, cadmium.Described VB family metal comprises vanadium, niobium, tantalum.Described group vib metal comprises chromium, molybdenum, tungsten.Described VIIB family metal comprises manganese, technetium, rhenium.Described VIII family base metal comprises iron, cobalt, nickel.Described rare earth metal is selected from one or more in group of the lanthanides and the actinium series rare earth metal, be preferably in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more, more preferably lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal.Described metal component is preferably one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, lanthanum, cerium, lanthanum rich norium, the cerium-rich mischmetal metal, more preferably one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, cobalt, lanthanum, cerium, lanthanum rich norium or the cerium-rich mischmetal metal.

Described metal component can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.

Described molecular screening is from as the zeolite of active component of cracking catalyst and in the non-zeolite molecular sieve one or more.These zeolites and molecular sieve are conventionally known to one of skill in the art.

Described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth particularly, one or more in the Beta zeolite.

Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as zeolite (as the ZSM-5 zeolite) with MFI structure, in the zeolite with MFI structure (as phosphorous and/or rare earth ZSM-5 zeolite, the zeolite that the disclosed phosphorated of CN1194181A has the MFI structure) of phosphorous and/or rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more.

Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by the molecular sieve of one or more replacements in other element such as phosphorus, titanium, gallium, the germanium.These examples of molecular sieve comprise that the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate, titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, silico-aluminate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more.One or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve particularly.

Under the preferable case, described molecular screening one or more in the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, zeolite, phosphorous and/or rare earth with MFI structure.

Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of cracking catalyst matrix and binder component one or more, as in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide one or more.In preferred aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, magnesium oxide, the calcium oxide one or more.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.

Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.Preferred clay is a kaolin.These clays are conventionally known to one of skill in the art.

Listed the example of the cracking catalyst of some existing metallic components below in non exhaustive mode:

A, the industrial trade mark are the catalyzer that contains rare earth Y type zeolite and ultrastable Y, kaolin, aluminum oxide of HGY-2000R;

B, the industrial trade mark are the catalyzer that contains rare earth Y type zeolite and ultrastable Y, kaolin, aluminum oxide of MLC-500;

C, US5,376,608 disclosed cracking catalyst compositions with desulfidation;

The disclosed desulfurization catalyst of D, CN1281887A;

The disclosed product desulfurization catalyst of E, CN1261618A.

(2) described metal component is with the cracking catalyst of the metallic components of going back ortho states and existing

The cracking catalyst of described metallic components comprises that also metal component wherein is the cracking catalyst of going back ortho states, and this catalyzer is described in detail in the applicant's application number is 03137906.0 Chinese patent application.This catalyzer contains molecular sieve, heat-resistant inorganic oxide, clay and a kind of metal component, wherein, total amount with the cracking catalyst of described metallic components is a benchmark, the content of molecular sieve is 1-90 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 2-80 weight %, metal oxide in described highest oxidation state, the content of metal component is 0.1-30 weight %, described metal component exists with the reduction valence state basically, and it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more.

Described reduction valence state refers to that the average valence of described metal is zeroth order or is higher than zeroth order and is lower than its highest oxidation state.Under the preferable case, the average valence of described metal and the ratio of its highest oxidation state are 0-0.95, and more preferably under the situation, this ratio is 0.1-0.7.

The highest oxidation state of metal described here is meant after abundant oxidation, the highest oxidation state of metal described in the metal oxide of energy stable existence.For example, the highest oxidation state of the non-aluminum metal of periodic table of elements HIA family is generally+3 valencys (as gallium); The highest oxidation state of IVA family metal is generally+4 valencys; The highest oxidation state of VA family metal is generally+5 valencys; The highest oxidation state of IB family metal is generally+divalent (as copper) or+1 valency (as silver); The highest oxidation state of IIB family metal is generally+divalent; The highest oxidation state of VB family metal is generally+5 valencys; The highest oxidation state of group vib metal is generally+6 valencys; The highest oxidation state of VIIB family metal is generally+4 valencys (as manganese) or+7 valencys (as rhenium); The non-noble metal highest oxidation state of VIII family is generally+3 valencys (as iron or cobalt) or+divalent (as nickel).

The method of measuring described metal average valence is as follows:

Accurately take by weighing about 0.4 gram catalyzer, put into the sample pool of TPD/R/O analysis tester, feeding hydrogen content is the hydrogen of 5 volume % and the gas mixture of nitrogen, the flow of hydrogen is 20 ml/min, with the speed of sample pool with 10 ℃/minute, be warming up to 1000 ℃ from room temperature, the catalyzer in the sample pool is carried out temperature programmed reduction(TPR), measure before the reduction respectively and the reduction rear catalyst on the TPR characteristic peak of metal component, calculate the average valence of metal according to following formula:

β _M＝β _M′-2f(A ₁-A)/N

Wherein: β _MBe the average valence of metal component M in the catalyzer, β _{M '}Highest oxidation state for metal component M in the catalyzer; The TPR characteristic peak area of metal M in the A catalyzer that to be metal component M exist with the reduction valence state; The TPR characteristic peak area of metal M in the A1 catalyzer that to be metal component M exist with highest oxidation state; N is the content (unit is mole) of metal component M in the catalyzer; F is a correction factor, and its measuring method is as follows: accurately take by weighing the sample pool that about 6.5 milligrams of CuO put into above-mentioned TPD/R/O analysis tester, under these conditions, measure the TPR characteristic peak area K that CuO is reduced fully ₂, calculate hydrogen-consuming volume (mole) K by the stoichiometric number of reduction reaction ₁, f is the ratio of hydrogen-consuming volume and TPR characteristic peak area, i.e. f=K ₁/ K ₂, the unit of f is a mole/TPR characteristic peak area.

Because therefore the position difference of the TPR characteristic peak of each metal, even contain metal component more than 2 kinds in the catalyzer, also can determine the TPR characteristic peak of each metal.

Described metal component is selected from one or more in the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, group vib metal, VIIB family metal, the VIII family base metal.The non-aluminum metal of described IIIA family comprises gallium, indium, thallium.Described IVA family metal comprises germanium, tin, lead.Described VA family metal comprises antimony, bismuth.Described IB family metal comprises copper, silver.Described II B family metal comprises zinc, cadmium.Described VB family metal comprises vanadium, niobium, tantalum.Described group vib metal comprises chromium, molybdenum, tungsten.Described VIIB family metal comprises manganese, technetium, rhenium.Described VIII family base metal comprises iron, cobalt, nickel.Described metal component is preferably one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel, more preferably one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.

This catalyzer can also contain rare earth metal, and described rare earth metal exists with the form of metal and/or compound.Described rare earth metal can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.Described rare earth metal is selected from one or more in group of the lanthanides and the actinium series rare earth metal, be preferably in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more, more preferably lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal.Total amount with the cracking catalyst of described metallic components is a benchmark, and in oxide compound, described rare earth metal components contents is 0-50 weight %, is preferably 0-15 weight %.

This catalyzer can also contain phosphorus component, and described phosphorus component is with the compound of phosphorus, as the oxide compound and/or the existence of phosphatic form of phosphorus.Described phosphorus component can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.Total amount with the cracking catalyst of described metallic components is a benchmark, and in Vanadium Pentoxide in FLAKES, the content of described phosphorus component is 0-15 weight %, preferred 0-8 weight %.

The selectable scope of kind of the kind of wherein said molecular sieve, the kind of heat-resistant inorganic oxide and clay is identical with scope described in described " catalyzer that metal component exists with oxidation state " part.

This Preparation of catalysts method comprises and will contain the metal component compound, molecular sieve, the composition of heat-resistant inorganic oxide and clay contacts with the atmosphere that contains reducing gas, the temperature of described contact is enough to make the average valence of described metal component to be lower than its highest oxidation state with the time that contacts, described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, each components contents makes in the final catalyzer and contains in the composition, total amount with the cracking catalyst of described metallic components is a benchmark, the molecular sieve of 1-90 weight %, the heat-resistant inorganic oxide of 2-80 weight %, the clay of 2-80 weight % and in the oxide compound of highest oxidation state metal, the metal component of 0.1-30 weight %.

Wherein, the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.

The described example that contains reducing gas and inert gas atmosphere comprises hydrogen, carbon monoxide, contain in one or more and the rare gas element in the hydro carbons of 1-5 carbon atom one or more mixture or the dry gas in the refinery (as catalytic cracking tail gas, catalytic reforming tail gas, hydrocracking tail gas or delayed coking tail gas etc.).

The temperature of described contact is enough to make the average valence of described metal component and the ratio of its maxivalence attitude to be reduced to 0-0.95 with the time that contacts, and is preferably 0.1-0.7.In general, the temperature of described contact can be 100-900 ℃, is preferably 400-700 ℃, and the time of contact is 0.1 second to 10 hours, is preferably 1 second-5 hours.Described contact can be a Static Contact, and promptly in an airtight container, the atmosphere that will contain reducing gas contacts with described composition.Described contact can be dynamic contact also, is about to the described bed that contains the atmosphere of reducing gas by described composition.The pressure of described contact both can carry out under normal pressure without limits, also can carry out being higher or lower than under the normal pressure.The consumption that contains the atmosphere of reducing gas is that every gram catalyzer per hour is not less than 5 milliliters of reducing gass, and preferred every gram catalyzer per hour is not less than 10 milliliters of reducing gass, and more preferably every gram catalyzer is 100-2000 milliliter reducing gas per hour.

Each components contents preferably makes in the final catalyzer and contains in the composition, in the catalyzer total amount, the molecular sieve of 10-60 weight %, the heat-resistant inorganic oxide of 10-50 weight %, the clay of 20-60 weight % and in the oxide compound of highest oxidation state metal, the metal component of 0.5-20 weight %.

The described composition that contains metal component compound, molecular sieve, heat-resistant inorganic oxide and clay can be the existing cracking catalyst that contains metal component, also can be to introduce the composition that obtains behind the metal component compound in the cracking catalyst of metallic components not.

The existing preparation method who contains the cracking catalyst of metal component is conventionally known to one of skill in the art, here repeats no more.

The method of introducing the metal component compound in the cracking catalyst of metallic components not also be the method for routine.For example, can adopt following method in the cracking catalyst of metallic components not, to introduce metal component, prepare the described composition that contains metal component compound, molecular sieve, heat-resistant inorganic oxide and clay.

One of method

(1) a. is with the precursor and/or the clay of the solution impregnation molecular sieve, the heat-resistant inorganic oxide that contain described metal component compound, heat-resistant inorganic oxide, and is dry or moist then; B. or the solution that will contain described metal component compound mix with the precursor and/or the clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, dry or moist then; C. or with the precursor and/or the clay of described metal component compound and molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide carry out physical mixed; D. or the solution that will contain described metal component compound mix with the precursor and/or the clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, the precipitation agent that adds described metal component compound, described metal component is deposited in the precursor and/or clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, dry or moist then; E. or the solution that will contain described metal component compound mix with the precursor and/or the clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, the slurry preparation that obtains is become colloid, dry or moist then; F. or with the precursor of water-fast described metal component compound and molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide and/or clay and deionized water mix, the slurry preparation that obtains is become colloid, dry or moist then.

(2) will introduce molecular sieve, the heat-resistant inorganic oxide of described metal component compound, the precursor and/or the clay of heat-resistant inorganic oxide, or described mixture, or colloid and deionized water and not molecular sieve, heat-resistant inorganic oxide, the precursor and/or the clay making beating of heat-resistant inorganic oxide of metallic components compound, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, the slurries that drying obtains, roasting or not roasting.

Two of method

Precursor, clay and deionized water making beating with molecular sieve, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, the slurries that drying obtains, roasting or not roasting, then, with the dried solid of the solution impregnation that contains described metal component compound, perhaps the solution with described metal component compound mixes with dried solid, and is dry then, roasting or not roasting.

Three of method

Precursor, clay, deionized water and the making beating of described metal component compound with molecular sieve, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, being prepared into solid content is 10-50 weight %, be preferably the slurries of 20-50 weight %, the slurries that drying obtains, roasting or not roasting.

If also contain rare earth metal component and/or phosphorus component in the catalyzer, can adopt top method separately or introduce rare earth metal component and/or phosphorus component when introducing above-mentioned metal component, just replace the compound of above-mentioned metal component to get final product with rare earth compound and/or phosphorus compound.Described rare earth metal component and/or phosphorus component can also be the y-type zeolite or the overstable gamma zeolite of rare earth and/or phosphorus (as contain) that commercially available molecular sieve itself is had.

Wherein, the drying behind the described introducing metal component compound and the drying means of slurries and condition are conventionally known to one of skill in the art, for example, the exsiccant method can be dry, oven dry, forced air drying, spraying drying.The method of the drying means preferably spray drying of slurries.The exsiccant temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.Roasting condition behind roasting after the described slurry dried and the impregnating metal compound also is conventionally known to one of skill in the art, in general, maturing temperature behind roasting after the described slurry dried and the impregnating metal compound is 400-700 ℃, be preferably 400-650 ℃, roasting time was at least 0.5 hour, be preferably 0.5-100 hour, more preferably 0.5-10 hour.

The precursor of described heat-resistant inorganic oxide refers in described cracking catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminum oxide can be selected from hydrated aluminum oxide (as pseudo-boehmite) and/or aluminium colloidal sol.The precursor of silicon oxide can be selected from silicon sol, one or more in silicon gel and the water glass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of silicon sol and aluminium colloidal sol, one or more in the silica-alumina gel.The precursor of other heat-resistant inorganic oxide can be selected from its oxyhydroxide, as oxyhydroxide, the boric acid of zirconium, titanium, alkaline-earth metal.

Described metal component compound can be water-soluble compound of described metal, also can be to be insoluble in water and/or water-fast compound, as the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, the non-noble metal nitrate of VIII family, muriate, oxyhydroxide, in the oxide compound one or more, particularly gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the nitrate of cobalt, muriate, oxyhydroxide, in the oxide compound one or more.

Described rare earth compound can be water-soluble compound of rare earth metal, also can be to be insoluble in water and/or water-fast compound, as in the muriate of rare earth metal, nitrate, oxyhydroxide, the oxide compound one or more.

Described phosphorus compound can be water-soluble compound of described phosphorus, also can be to be insoluble in water and/or water-fast compound, as phosphoric acid, phosphorous acid, and the oxide compound of the phosphoric acid salt of ammonium, alkali-metal phosphoric acid salt, phosphorus, in the aluminum phosphate one or more.

3, the cracking catalyst of metallic components not

The cracking catalyst of described not metallic components can be any metal-free hydrocarbon cracking catalyzer, and this cracking catalyst is conventionally known to one of skill in the art.As contain molecular sieve, heat-resistant inorganic oxide, contain or not argillaceous, contain or phosphorated hydrocarbon cracking catalyzer not.Wherein, each components contents scope also is conventionally known to one of skill in the art.As the industrial trade mark is the catalyzer that contains ultrastable Y, kaolin, aluminum oxide of ZCM-7.

4, the mixture of catalyzer and auxiliary agent

The described catalyst mixture of method provided by the invention can also contain one or more in the various cracking additives.Described cracking additive can be one or more in ignition dope, sulfur transfer catalyst, the octane enhancing additive.All on the books in former various patents of delivering of these auxiliary agents and the non-patent literature.As CN1034222C, CN 1072109A, the disclosed ignition dope of CN 1089362C, CN 1286134A, CN 1295877A, the disclosed sulfur transfer catalyst of CN 1334316A, CN 1020280C, the disclosed octane enhancing additive of CN1031409C etc.

Four, the scope of application of the present invention

Method provided by the invention is applicable to carries out catalytic cracking to any hydrocarbon ils, to improve the conversion capability of heavy oil, can contain metallic impurity such as Ni-V-Fe in the described hydrocarbon ils.Method provided by the invention be particularly suitable for to metals content impurity less than the sulfur-bearing of 50ppm or not the hydrocarbon ils of sulfur-bearing carry out catalytic cracking.Method provided by the invention especially is suitable for metals content impurity is carried out catalytic cracking less than the hydrocarbon oil containing surphur of 50ppm, improves the ability that removes of gasoline fraction sulphur when improving heavy oil conversion performance.

Described hydrocarbon ils can be crude oil and various fraction, particularly crude oil and boiling range greater than 330 ℃ petroleum cuts.As sulfur-bearing or not long residuum, vacuum residuum, the vacuum gas oil of sulfur-bearing, atmospheric gas oil, straight run gas oil, propane is light/heavy deasphalted oil and coker gas oil and through in the long residuum of hydrotreatment, vacuum residuum, vacuum gas oil, the atmospheric gas oil one or more.

Be riser reactor with described reactor below, the number of reaction zone is 2 and is example, the present invention is elaborated.Use other reactor also to have similar effects, according to the requirement to cracked product, the number of reaction zone can be more.Therefore, can not be interpreted as that the reactor in the method for the invention is a riser reactor, the number of reaction zone only is 2.

Unless stated otherwise, used revivifier is the preposition jar two-stage regeneration device that burns in the example; Described interchanger is tube and shell heat exchanger; The consumption that is used for steam stripped water vapor accounts for 0.4 weight % of catalyst recirculation amount; Used kaolin is that Suzhou kaolin company produces, and its solid content is 76 weight %; Used pseudo-boehmite is that Shandong Zibo 501 factories produce, and its solid content is 62 weight %; Used aluminium colloidal sol is produced its Al for the Shandong catalyst plant ₂O ₃Content is 21 weight %; Used silicon sol is produced its SiO for the Shandong catalyst plant ₂Content is 27 weight %; The compound of metal component is chemical pure.

Embodiment 1

Present embodiment illustrates cracking catalyst of metallic components of the present invention and preparation method thereof.

The cobalt nitrate aqueous solution of kaolin, pseudo-boehmite, concentration 30 weight % is mixed, add deionized water, mix, slowly adding concentration under stirring fast is the hydrochloric acid of 36.5 volume %, regulate the pH value to 2.0 of slurries, (the industrial trade mark is MOY, and lattice constant is 24.59 dusts, Na to add the HY zeolite of phosphorous and rare earth ₂O content is 1.5 weight %, in Vanadium Pentoxide in FLAKES, phosphorus content is 1.2 weight %, rare earth oxide content is 8.5 weight %, and wherein, lanthanum trioxide content is 4.5 weight %, cerium oxide content is 1.1 weight %, other rare earth oxide content is 2.9 weight %, and the Shandong catalyst plant is produced), mix.It is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain.The consumption of kaolin, pseudo-boehmite, MOY zeolite and cobalt nitrate aqueous solution makes kaolin butt weight, Al ₂O ₃, MOY zeolite butt weight and Co ₂O ₃The ratio of weight be 35.0: 34.0: 30.0: 1.0.

With the slurries spraying drying under 150 ℃ temperature that obtains, 550 ℃ of following roastings 1 hour.The catalyzer that obtains is packed in the fixed bed reduction reactor, under 400 ℃ of temperature, feed hydrogen, the feeding amount of hydrogen is 5 milliliters of every gram catalyzer per minutes, make hydrogen contact 0.5 hour with described solid, the temperature of reactor is reduced to room temperature, unload the solid after the reduction, obtain the cracking catalyst C1 of metallic components of the present invention.The ratio of the composition of catalyzer C1 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.Catalyzer is formed by calculating in the table 1, and the content of metal component is in the oxide compound of described metal component highest oxidation state.

Embodiment 2

Method by example 1 prepares catalyzer, and different is, the temperature that described solid contacts with hydrogen is 500 ℃, and be 3 hours duration of contact, obtains the cracking catalyst C2 of metallic components of the present invention.The ratio of the composition of catalyzer C2 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.

Embodiment 3

With concentration is the cobalt nitrate hexahydrate aqueous solution dipping kaolin of 10 weight %, and the weight ratio of the cobalt nitrate hexahydrate aqueous solution and kaolin (butt) is 1: 0.8224,120 ℃ of oven dry, and 600 ℃ of roastings 1 hour obtain containing Co ₂O ₃2.78 the kaolin of weight %.

Method by example 1 prepares catalyzer, and different is with containing Co ₂O ₃2.78 the kaolin of weight % replaces example 1 described kaolin, does not add cobalt nitrate aqueous solution, obtains the cracking catalyst C3 of metallic components of the present invention.The ratio of the composition of catalyzer C3 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.

Example 4

Method by example 1 prepares catalyzer, and different is that the process that in fixed-bed reactor solid is not contacted with hydrogen obtains catalyzer C4.The composition of C4 is listed in the table 1.

Example 5

Method by example 3 prepares catalyzer, and different is that the process that in fixed-bed reactor solid is not contacted with hydrogen obtains catalyzer C5.The composition of C5 is listed in the table 1.

Table 1

Example number	1	2	3	4	5
Example number	1	2	3	4	5	The catalyzer numbering	C1	C2	C3	C4	C5
The molecular sieve kind	MOY	MOY	MOY	MOY	MOY	The catalyzer numbering	C1	C2	C3	C4	C5
The molecular sieve kind	MOY	MOY	MOY	MOY	MOY	Molecular sieve content, weight %	30.0	30.0	30.0	30.0	30.0
The heat-resistant inorganic oxide kind	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃	Molecular sieve content, weight %	30.0	30.0	30.0	30.0	30.0
The heat-resistant inorganic oxide kind	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃	Heat-resistant inorganic oxide content, weight %	34.0	34.0	34.0	34.0	34.0
Clay types	Kaolin	Kaolin	Kaolin	Kaolin	Kaolin	Heat-resistant inorganic oxide content, weight %	34.0	34.0	34.0	34.0	34.0
Clay types	Kaolin	Kaolin	Kaolin	Kaolin	Kaolin	Clay content, weight %	35.0	35.0	35.0	35.0	35.0
The metal component kind	Co	Co	Co	Co	Co	Clay content, weight %	35.0	35.0	35.0	35.0	35.0
The metal component kind	Co	Co	Co	Co	Co	Metal component content, weight %	1.0	1.0	1.0	1.0	1.0
The metal component average valence	+1.5	0	+1.5	+3	+3	Metal component content, weight %	1.0	1.0	1.0	1.0	1.0
The metal component average valence	+1.5	0	+1.5	+3	+3	The ratio of metal component average valence and its maxivalence attitude	0.5	0	0.5	1	1
Metal component distributes	Be evenly distributed in the catalyzer	Be evenly distributed in the catalyzer	Be evenly distributed in the clay	Be evenly distributed in the catalyzer	Be evenly distributed in the clay		0.5	0	0.5	1	1

Embodiment 6

(1) be the zinc nitrate aqueous solution dipping kaolin of 7.0 weight % with concentration, the weight ratio of zinc nitrate aqueous solution and kaolin (butt) is 1: 0.940,120 ℃ of oven dry, and 600 ℃ of roastings 1 hour obtain containing the kaolin of ZnO 3.1 weight %.

(2) with NaY zeolite (Na ₂O content 11 heavy %, silica alumina ratio is 5.6, and the Chang Ling catalyst plant is produced) be that the aqueous ammonium chloride solution of 0.15 mol mixes with concentration, the blended ratio is that every liter of aqueous ammonium chloride solution 20 restrains the NaY zeolites, exchange 1 hour down at 60 ℃, the filter cake after the filtration was 550 ℃ of roastings 2 hours.Again by above-mentioned steps exchange and roasting twice, obtaining sodium oxide content is the HY zeolite of 0.3 weight % with it.

(3) method by example 1 prepares catalyzer, and different is to replace example 1 described kaolin with the kaolin that contains ZnO that (1) prepares, and does not add Xiao Suangu, and the HY zeolite for preparing with (2) replaces MOY; The consumption of the kaolin of the described ZnO of containing, pseudo-boehmite, HY zeolite makes kaolin butt weight, Al ₂O ₃, HY zeolite butt weight and ZnO the ratio of weight be 25.0: 19.2: 55.0: 0.8; Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the consumption of gas mixture is 10 milliliters of every gram catalyzer per minutes, the temperature that described solid contacts with gas mixture is 800 ℃, be 3 hours duration of contact, obtains the cracking catalyst C6 of metallic components of the present invention.The ratio of the composition of catalyzer C6 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Embodiment 7

With concentration is the iron nitrate aqueous solution dipping kaolin of 10 weight %, and the weight ratio of iron nitrate aqueous solution and kaolin (butt) is 1: 1.034,120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain containing Fe ₂O ₃3.1 the kaolin of weight %.

Method by example 1 prepares catalyzer, and different is with the above-mentioned Fe of containing ₂O ₃Kaolin replace example 1 described kaolin, do not add Xiao Suangu, replace MOY with the HY zeolite of (2) preparation in the example 4; The described Fe that contains ₂O ₃Kaolin, pseudo-boehmite, the consumption of HY zeolite make kaolin butt weight, Al ₂O ₃, HY zeolite butt weight and Fe ₂O ₃The ratio of weight be 25.0: 19.2: 55.0: 0.8; Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the consumption of gas mixture is 6 milliliters of every gram catalyzer per minutes, the temperature that described solid contacts with gas mixture is 600 ℃, be 0.5 hour duration of contact, obtains the cracking catalyst C7 of metallic components of the present invention.The ratio of the composition of catalyzer C7 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Embodiment 8

With concentration is the copper nitrate aqueous solution dipping kaolin of 20.0 weight % and the mixture of titanium dioxide, the weight ratio of copper nitrate aqueous solution, kaolin (butt) and titanium dioxide is 1: 0.871: 0.0223,120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing the kaolin of CuO 8.68 weight % and the mixture of titanium dioxide.

Method by example 1 prepares catalyzer, and different is replaces example 1 described kaolin with the kaolin of the above-mentioned CuO of containing, does not add Xiao Suangu, and (the industrial trade mark is DASY, and lattice constant is 24.45 dusts, Na with overstable gamma zeolite ₂O content is 1.0 weight %, and the Shandong catalyst plant is produced) replacement MOY; Contain kaolin, the pseudo-boehmite of CuO, the consumption of DASY zeolite makes kaolin butt weight, TiO ₂, Al ₂O ₃, DASY zeolite butt weight and CuO the ratio of weight be 39.0: 1.0: 26.2: 30: 3.8; Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the consumption of gas mixture is 5 milliliters of every gram catalyzer per minutes, the temperature that described solid contacts with gas mixture is 400 ℃, be 0.5 hour duration of contact, obtains the cracking catalyst C8 of metallic components of the present invention.The ratio of the composition of catalyzer C8 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Embodiment 9

With concentration is the manganese nitrate aqueous solution dipping kaolin of 5.0 weight %, and the weight ratio of manganese nitrate aqueous solution and kaolin (butt) is 1: 0.898,120 ℃ of oven dry, and 550 ℃ of roastings 2 hours obtain containing MnO ₂2.63 the kaolin of weight %.

Method by example 1 prepares catalyzer, and different is with the above-mentioned MnO of containing ₂Kaolin replace example 1 described kaolin, do not add Xiao Suangu; (the industrial trade mark is ZRP-1 with the zeolite with MFI structure of DASY zeolite and phosphorous and rare earth, in Vanadium Pentoxide in FLAKES, phosphorus content is 2.0 weight %, rare earth oxide content is 1.0 weight %, wherein, lanthanum trioxide content is 0.53 weight %, and cerium oxide content is 0.13 weight %, other rare earth oxide content is 0.34 weight %, Na ₂O content is less than 0.1 weight %, SiO ₂With Al ₂O ₃Mol ratio be 60, the Shandong catalyst plant is produced) replace MOY; Contain MnO ₂The consumption of kaolin, pseudo-boehmite, DASY zeolite and ZRP-1 zeolite make kaolin butt weight, Al ₂O ₃, DASY zeolite butt weight, ZRP-1 zeolite butt weight and MnO ₂The ratio of weight be 37.0: 27.0: 30.0: 5.0: 1.0.Reductive atmosphere is hydrogen content 80 volume % and the hydrogen of propane content 20 volume % and the gas mixture of propane, the consumption of gas mixture is 7.5 milliliters of every gram catalyzer per minutes, the temperature that described solid contacts with gas mixture is 500 ℃, be 1 hour duration of contact, obtains the cracking catalyst C9 of metallic components of the present invention.The ratio of the composition of catalyzer C9 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Table 2

Example number	6	7	8	9
Example number	6	7	8	9	The catalyzer numbering	C6	C7	C8	C9
The molecular sieve kind	HY	HY	DASY	DASY/ZRP	The catalyzer numbering	C6	C7	C8	C9
The molecular sieve kind	HY	HY	DASY	DASY/ZRP	Molecular sieve content, weight %	55.0	55.0	30.0	35.0
The heat-resistant inorganic oxide kind	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃/TiO2	Al ₂O ₃	Molecular sieve content, weight %	55.0	55.0	30.0	35.0
The heat-resistant inorganic oxide kind	Al ₂O ₃	Al ₂O ₃	Al ₂O ₃/TiO2	Al ₂O ₃	Heat-resistant inorganic oxide content, weight %	19.2	19.2	27.2	27.0
Clay types	Kaolin	Kaolin	Kaolin	Kaolin	Heat-resistant inorganic oxide content, weight %	19.2	19.2	27.2	27.0
Clay types	Kaolin	Kaolin	Kaolin	Kaolin	Clay content, weight %	25.0	25.0	39.0	37.0
The metal component kind	Zn	Fe	Cu	Mn	Clay content, weight %	25.0	25.0	39.0	37.0
The metal component kind	Zn	Fe	Cu	Mn	Metal component content, weight %	0.8	0.8	3.8	1.0
The metal component average valence	+1.4	+2.0	+0.6	+1.5	Metal component content, weight %	0.8	0.8	3.8	1.0
The metal component average valence	+1.4	+2.0	+0.6	+1.5	The ratio of metal component average valence and its maxivalence attitude	0.70	0.67	0.3	0.38
Metal component distributes	Be evenly distributed in the clay	Be evenly distributed in the clay	Be distributed in clay and the heat-resistant inorganic oxide	Be evenly distributed in the clay		0.70	0.67	0.3	0.38

Embodiment 10

With concentration is the ammonium molybdate ((NH of 5.0 weight % ₄) ₆Mo ₇O ₂₄4H ₂O) (solid content is 85.0 weight % for aqueous solution dipping kaolin and diatomite, Shengzhou, Zhejiang Province city China power diatomite factory product) mixture, 120 ℃ of oven dry, and then be the silver nitrate aqueous solution dipping of 2.0 weight % with concentration, 120 ℃ of oven dry, the weight ratio of ammonium molybdate aqueous solution, kaolin (butt), diatomite (butt) and silver nitrate aqueous solution is 1: 0.932: 0.155: 0.747,600 ℃ of roasting 2 hours obtains containing MoO ₃3.58 weight % and Ag ₂The kaolin of O 0.90 weight % and diatomaceous mixture.

Method by example 1 prepares catalyzer, and different is with the above-mentioned MoO of containing ₃And Ag ₂The kaolin of O and diatomite replace example 1 described kaolin, do not add Xiao Suangu, contain MoO ₃And Ag ₂The consumption of the kaolin of O and diatomite, pseudo-boehmite, MOY zeolite makes kaolin and diatomite butt weight, Al ₂O ₃, MOY zeolite butt weight, MoO ₃And Ag ₂The ratio of the weight of O is 32.0: 21.5: 45.0: 1.2: 0.3.Reductive atmosphere is the nitrogen of hydrogen content 50 volume % and mixing of hydrogen, the consumption of gas mixture is 12.5 milliliters of every gram catalyzer per minutes, the temperature that described solid contacts with gas mixture is 650 ℃, and be 1 hour duration of contact, obtains the cracking catalyst C10 of metallic components of the present invention.The ratio of the composition of catalyzer C10 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Embodiment 11

Under agitation, with concentration be the ammonium meta-vanadate (NH of 2.0 weight % ₄VO ₃) aqueous solution dipping kaolin and magnesian mixture, ammonium meta-vanadate (NH ₄VO ₃) aqueous solution, kaolin (butt) and magnesian weight ratio be 1: 1.011: 0.027,120 ℃ of slurries that oven dry obtains, 550 ℃ of roastings 2 hours obtain containing MgO 2.46 weight %, V ₂O ₅1.48 the kaolin of weight %.

The method of example 1 prepares catalyzer, and different is with above-mentioned MgO of containing and V ₂O ₅Kaolin replace example 1 described kaolin, do not add Xiao Suangu, replace the MOY zeolite with DASY zeolite (specification is with example 6); Contain MgO and V ₂O ₅Kaolin, pseudo-boehmite, the consumption of DASY zeolite make kaolinic butt weight, magnesium oxide, Al ₂O ₃, DASY zeolite butt weight and V ₂O ₅The ratio of weight be 39.0: 1.0: 24.4: 35.0: 0.6; The temperature that described solid contacts with hydrogen is 550 ℃, and be 1 hour duration of contact, obtains the cracking catalyst C11 of metallic components of the present invention.The ratio of the composition of catalyzer C11 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Embodiment 12

With concentration is the gallium chloride aqueous solution dipping kaolin of 40 weight % and the mixture of pseudo-boehmite, the weight ratio of the gallium chloride aqueous solution, kaolin (butt) and pseudo-boehmite (butt) is 1: 1.095: 0.314,120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing Ga ₂O ₃13.1 the kaolin of weight % and the mixture of aluminum oxide.

To contain Ga ₂O ₃Kaolin and mixture, silicon sol and the deionized water of aluminum oxide mix, add DASY zeolite and ZRP-1 zeolite again, mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains Ga ₂O ₃Kaolin and mixture, silicon sol, the overstable gamma zeolite of aluminum oxide and the consumption with zeolite of MFI structure make kaolin butt weight, aluminum oxide, silicon oxide, DASY zeolite butt weight ZRP-1 zeolite butt weight and Ga ₂O ₃The ratio of weight be 35.0: 10: 13.2: 30: 5: 6.8.

With the slurries spraying drying under 150 ℃ temperature that obtains, 550 ℃ of following roastings 2 hours.The solid that obtains is packed in the fixed bed reduction reactor, under 600 ℃ of temperature, feed hydrogen, the consumption of hydrogen is 15 milliliters of every gram catalyzer per minutes, make hydrogen contact 2 hours with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain the cracking catalyst C12 of metallic components of the present invention.The ratio of the composition of catalyzer C12 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Embodiment 13

With concentration is the tin protochloride SnCl of 6.0 weight % ₂The aqueous solution, silicon sol and kaolin mix, and the weight ratio of the tin protochloride aqueous solution, silicon sol (butt) and kaolin (butt) is 1: 0.191: 0.954,120 ℃ of oven dry, and 550 ℃ of roastings 3 hours obtain containing SnO ₂4.0 the kaolin of weight % and the mixture of silicon oxide.

To contain SnO ₂Kaolin and mixture, aluminium colloidal sol and the deionized water of silicon oxide mix, add DASY zeolite and ZRP-1 zeolite again, mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains SnO ₂Kaolin and the consumption of mixture, aluminium colloidal sol, DASY zeolite and the ZRP-1 zeolite of silicon oxide make kaolin butt weight, aluminum oxide, silicon oxide, DASY zeolite butt weight, ZRP-1 zeolite butt weight and SnO ₂The ratio of weight be 40.0: 20.0: 8.0: 25: 5: 2.0.With the slurries spraying drying under 150 ℃ temperature that obtains, 550 ℃ of following roastings 2 hours.

The solid that obtains is packed in the fixed bed reduction reactor, under 650 ℃ of temperature, feed hydrogen, the consumption of hydrogen is 5 milliliters of every gram catalyzer per minutes, make hydrogen contact 1 hour with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain the cracking catalyst C13 of metallic components of the present invention.The ratio of the composition of catalyzer C13 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Table 3

Example number	10	11	12	13
Example number	10	11	12	13	The catalyzer numbering	C10	C11	C12	C13
The molecular sieve kind	MOY	DASY	DASY/ZRP-1	DASY/ZRP-1	The catalyzer numbering	C10	C11	C12	C13
The molecular sieve kind	MOY	DASY	DASY/ZRP-1	DASY/ZRP-1	Molecular sieve content, weight %	45.0	35.0	35.0	30.0
The heat-resistant inorganic oxide kind	Al ₂O ₃	Al ₂O ₃/MgO	Al ₂O ₃/SiO ₂	Al ₂O ₃/SiO ₂	Molecular sieve content, weight %	45.0	35.0	35.0	30.0
The heat-resistant inorganic oxide kind	Al ₂O ₃	Al ₂O ₃/MgO	Al ₂O ₃/SiO ₂	Al ₂O ₃/SiO ₂	Heat-resistant inorganic oxide content, weight %	21.5	25.4	23.2	28.0
Clay types	Kaolin/diatomite	Kaolin	Kaolin	Kaolin	Heat-resistant inorganic oxide content, weight %	21.5	25.4	23.2	28.0
Clay types	Kaolin/diatomite	Kaolin	Kaolin	Kaolin	Clay content, weight %	32.0	39.0	35.0	40.0
The metal component kind	Mo/Ag	V	Ga	Sn	Clay content, weight %	32.0	39.0	35.0	40.0
The metal component kind	Mo/Ag	V	Ga	Sn	Metal component content, weight %	1.2/0.3	0.6	6.8	2.0
The metal component average valence	+3.0/0	+2.3	+1.5	+2.2	Metal component content, weight %	1.2/0.3	0.6	6.8	2.0
The metal component average valence	+3.0/0	+2.3	+1.5	+2.2	The ratio of metal component average valence and its maxivalence attitude	0.5/0	0.46	0.5	0.55
Metal component distributes	Be evenly distributed in the clay	Be evenly distributed in clay and the heat-resistant inorganic oxide	Be distributed in clay and the heat-resistant inorganic oxide	Be distributed in clay and the heat-resistant inorganic oxide		0.5/0	0.46	0.5	0.55

Example 14-18

Following example illustrates method provided by the invention.This group example is a main purpose with voluminous gasoline.

Carry out catalytic cracking according to 1# stock oil shown in the flow process his-and-hers watches 4 shown in Figure 1.Catalyst system therefor is respectively the catalyzer C1-C5 of example 1-5 preparation.Described reactor is the disclosed reducing riser reactor of CN1078094C, the height of reactor is 4000 millimeters, the height of pre lift zone is 500 millimeters, interior diameter is 12 millimeters, first reaction zone 9 highly is 1200 millimeters, second reaction zone 14 highly is 1550 millimeters, the interior diameter of first reaction zone 9 is 14 millimeters, the interior diameter of second reaction zone 14 is 22 millimeters, the interior diameter of outlet area 15 is 14 millimeters, highly be 750 millimeters, the combining site of first reaction zone 9 and second reaction zone 14 is round table-like, and its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is 60 degree, second reaction zone 14 also is round table-like with the combining site of outlet area 15, and its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is 60 degree.

Catalyzer after contacting from the atmosphere with containing reducing gas of pipeline 8 enters the pre lift zone of reactor, is advanced into first reaction zone 9 under the pre-lifting water vapor from pipeline 10 drives.Simultaneously, from the hydrocarbon ils after the preheating of pipeline 11 with from the atomized water vapor mixing of pipeline 12, enter first reaction zone 9, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carries out a cracking reaction.Reactant flow continues to go upward to second reaction zone 14, reaction zone 14 with contact from the catalyzer after the regeneration of pipeline 28, carry out secondary reaction.Logistics behind the secondary reaction continues up, by outlet area 15, through level pipe 16, enters the settling vessel 17 of separation system, and the cyclonic separator in the settling vessel 17 separates catalyzer with crackate.Isolated catalyzer enters in the stripper 18, with the water vapor counter current contact from pipeline 19, stripping goes out remaining crackate on the catalyzer, obtains reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 20 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 22 through inclined tube 21 to be generated, in revivifier 22, under regeneration temperature, reclaimable catalyst is contacted with excess air atmosphere from pipeline 23, removes coke wherein, and reacted flue gas is discharged from pipeline 24.The part of the catalyzer after the regeneration enters reduction reactor 3 from pipeline 25, and in reduction reactor 3, under reductive condition, the catalyzer after the regeneration contacts with the atmosphere that contains reducing gas from pipeline 4, and waste gas is discharged through pipeline 5.Enter or do not enter interchanger 7 heat exchange with the catalyzer after reducing gas contacts through pipeline 6, the catalyzer after heat exchange or the not heat exchange enters the pre lift zone of reactor.The other part of the catalyzer after the regeneration enters or does not enter interchanger 27 heat exchange through pipeline 26, and the catalyzer after the regeneration after heat exchange or the not heat exchange enters second reaction zone through pipeline 28.Operational condition is listed in the table 5, and the product composition is listed in the table 6.

Comparative Examples 1 (DB1)

This Comparative Examples explanation reference cracking method for hydrocarbon oil.

Method by example 18 is carried out catalytic cracking to same stock oil and catalyzer, and different is that the catalyzer that enters reduction reactor 3 does not contact with reducing gas, does not promptly feed the atmosphere that contains reducing gas from pipeline 4.Operational condition is listed in the table 5, and the product composition is listed in the table 6.

Table 4

The stock oil numbering	1#	2#	3#
The stock oil numbering	1#	2#	3#	The stock oil title	Vacuum gas oil	Long residuum	Vacuum gas oil
Density (20 ℃), gram per centimeter ³	0.9154	0.8906	0.873	The stock oil title	Vacuum gas oil	Long residuum	Vacuum gas oil
Density (20 ℃), gram per centimeter ³	0.9154	0.8906	0.873	Viscosity, millimeter ²/ second
50℃	34.14	-	-	Viscosity, millimeter ²/ second
50℃	34.14	-	-	100℃	6.96	24.84	8.04
Bituminous matter, weight %	0.0	0.8	0.0	100℃	6.96	24.84	8.04
Bituminous matter, weight %	0.0	0.8	0.0	Conradson carbon residue, weight %	0.18	4.3	0.15
S, weight %	2.0	0.13	0.07	Conradson carbon residue, weight %	0.18	4.3	0.15
S, weight %	2.0	0.13	0.07	Boiling range, ℃
IBP	329	282	346	Boiling range, ℃
IBP	329	282	346	10％	378	370	411
50％	436	553	462	10％	378	370	411
50％	436	553	462	90％	501	-	523
95％	518	-	-	90％	501	-	523
95％	518	-	-	FBP	550	-	546

Table 5

Example number		14	15	16	17	18	DB1
Example number		14	15	16	17	18	DB1	The catalyzer numbering		C1	C2	C3	C4	C5	C5
Temperature, ℃	First reaction zone 9	520	520	610	525	525	525	The catalyzer numbering		C1	C2	C3	C4	C5	C5
	First reaction zone 9	520	520	610	525	525	525	Second reaction zone 14	500	500	570	505	500	500
	Outlet area 15	480	480	550	485	480	480	Second reaction zone 14	500	500	570	505	500	500
	Outlet area 15	480	480	550	485	480	480	Pressure, MPa	First reaction zone 9	0.15	0.18	0.15	0.18	0.18	0.18
Second reaction zone 14	0.13	0.15	0.13	0.15	0.15	0.15			First reaction zone 9	0.15	0.18	0.15	0.18	0.18	0.18
Second reaction zone 14	0.13	0.15	0.13	0.15	0.15	0.15	Duration of contact, second		First reaction zone 9	2.0	1.2	0.8	1.2	1.0	1.0
Second reaction zone 14	6.5	6.7	6	6.7	6.5	6.5			First reaction zone 9	2.0	1.2	0.8	1.2	1.0	1.0
Second reaction zone 14	6.5	6.7	6	6.7	6.5	6.5		Outlet area 15	0.3	0.3	0.3	0.5	0.5	0.5
Agent-oil ratio	First reaction zone 9	4.5	5.0	4.0	6.0	6.0		Outlet area 15	0.3	0.3	0.3	0.5	0.5	0.5	6.0
	First reaction zone 9	4.5	5.0	4.0	6.0	6.0	The agent-oil ratio of second reaction zone 14 is multiples of first reaction zone 9	1.33	1.4	1.2	1.1	1.2	1.2		6.0
	Temperature in the revivifier 22, ℃		690	690	690	690		1.33	1.4	1.2	1.1	1.2	1.2	700	700
Reduction reactor 3	Temperature in the revivifier 22, ℃		690	690	690	690	Temperature, ℃	600	600	600	680	650	-	700	700
	Time, minute	30	20	10	20	20	Temperature, ℃	600	600	600	680	650	-	-
	Time, minute	30	20	10	20	20	Pressure, MPa	0.13	0.13	0.13	0.13	0.13	-	-
	The atmosphere that contains reducing gas	Hydrogen	Hydrogen	Hydrogen	Hydrogen	Hydrogen	Pressure, MPa	0.13	0.13	0.13	0.13	0.13	-	-
	The atmosphere that contains reducing gas	Hydrogen	Hydrogen	Hydrogen	Hydrogen	Hydrogen	The atmosphere consumption that contains reducing gas, cubic meter/ton/minute	7	7	7	7	7	-	-
	Atomized water steam and the pre-total amount that promotes water vapor account for the percentage ratio of hydrocarbon ils, weight %		8	8	10	10		7	7	7	7	7	-	5	5
Whether enter interchanger 7 heat exchange			8	8	10	10	Be	Be	Not	Be	Be	Be		5	5
Whether enter interchanger 7 heat exchange		Whether enter interchanger 27 heat exchange		Be	Be	Be	Be	Be	Not	Be	Be	Be	Be	Be	Be

Table 6

Example number	14	15	16	17	18	DB1
Example number	14	15	16	17	18	DB1	The catalyzer numbering	C1	C2	C3	C4	C5	C5
Product is formed, weight %							The catalyzer numbering	C1	C2	C3	C4	C5	C5
Product is formed, weight %							Dry gas	3.93	3.86	4.56	4.02	3.91	4.36
Liquefied gas	13.49	13.62	13.97	13.41	13.24	13.14	Dry gas	3.93	3.86	4.56	4.02	3.91	4.36
Liquefied gas	13.49	13.62	13.97	13.41	13.24	13.14	Gasoline	49.38	49.47	49.82	48.98	48.37	45.84
Diesel oil	24.57	24.42	23.06	24.56	24.83	24.49	Gasoline	49.38	49.47	49.82	48.98	48.37	45.84
Diesel oil	24.57	24.42	23.06	24.56	24.83	24.49	Heavy oil	4.21	4.48	3.55	4.47	4.94	6.48
Coke	4.36	4.05	4.99	4.48	4.66	5.62	Heavy oil	4.21	4.48	3.55	4.47	4.94	6.48
Coke	4.36	4.05	4.99	4.48	4.66	5.62	Loss	0.06	0.1	0.05	0.08	0.05	0.07
Gasoline sulfure content, mg/litre	330	310	320	500	510	1100	Loss	0.06	0.1	0.05	0.08	0.05	0.07

From the result of table 6 as can be seen, compare with adopting the reference method, adopt method provided by the invention that the hydrocarbon ils of sulfur-bearing is carried out catalytic cracking, gasoline content obviously improves in the crackate, and heavy oil and coke content obviously descend, and the sulphur content of gasoline reduces significantly.This illustrates that method provided by the invention has stronger heavy oil cracking ability and sweetening power, is fit to voluminous gasoline.

Example 19-23

Following example illustrates method provided by the invention.This group example is a main purpose with voluminous liquefied gas and gasoline.

Carry out catalytic cracking according to 3# stock oil shown in the mode his-and-hers watches 4 shown in Figure 2.Catalyst system therefor is respectively the catalyzer C1-C5 of example 1-5 preparation.Described reactor is the described reactor of example 14-18.

Catalyzer after contacting from the atmosphere with containing reducing gas of pipeline 8 enters the pre lift zone of reactor, is advanced into first reaction zone 9 under the pre-lifting water vapor from pipeline 10 drives.Simultaneously, from the hydrocarbon ils after the preheating of pipeline 11 with from the atomized water vapor mixing of pipeline 12, enter first reaction zone 9, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carries out a cracking reaction.Reactant flow continues to go upward to second reaction zone 14, reaction zone 14 with contact from the catalyzer after the regeneration of pipeline 28, carry out secondary reaction.Logistics behind the secondary reaction continues up, by outlet area 15, through level pipe 16, enters the settling vessel 17 of separation system, and the cyclonic separator in the settling vessel 17 separates catalyzer with crackate.Isolated catalyzer enters in the stripper 18, with the water vapor counter current contact from pipeline 19, stripping goes out remaining crackate on the catalyzer, obtains reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 20 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 22 through inclined tube 21 to be generated, in revivifier 22, under regeneration temperature, reclaimable catalyst is contacted with excess air from pipeline 23, removes coke wherein, and reacted flue gas is discharged from pipeline 24.The part of the catalyzer after the regeneration enters gas displacement jar 30 through pipeline 25, in gas displacement jar 30, the oxygen-containing gas of the catalyst entrainment after the part of the catalyzer after the regeneration is used and will be regenerated from the nitrogen of pipeline 31 cements out, gas after the displacement is discharged through pipeline 32, catalyzer through gas displacement enters reduction reactor 3 from pipeline 33, in reduction reactor 3, under reductive condition, described catalyzer contacts with the atmosphere that contains reducing gas from pipeline 4, and waste gas is discharged through pipeline 5.Enter or do not enter interchanger 7 heat exchange with the catalyzer after reducing gas contacts through pipeline 6, the catalyzer after heat exchange or the not heat exchange enters the pre lift zone of reactor.The other part of the catalyzer after the regeneration enters or does not enter interchanger 27 heat exchange through pipeline 26, and the catalyzer after the regeneration after heat exchange or the not heat exchange enters second reaction zone through pipeline 28.Operational condition is listed in the table 7, and the product composition is listed in the table 8.

Comparative Examples 2 (DB2)

Method by example 21 is carried out catalytic cracking to same stock oil and catalyzer, and different is that the catalyzer that enters reduction reactor 3 does not contact with the atmosphere that contains reducing gas, does not promptly feed the atmosphere that contains reducing gas from pipeline 4.Operational condition is listed in the table 7, and the product composition is listed in the table 8.

Table 7

Example number		19	20	21	DB2	22	23
Example number		19	20	21	DB2	22	23	The catalyzer numbering		C1	C2	C3	C3	C4	C5
Temperature, ℃	First reaction zone 9	570	515	515	515	525	525	The catalyzer numbering		C1	C2	C3	C3	C4	C5
	First reaction zone 9	570	515	515	515	525	525	Second reaction zone 14	555	490	500	500	495	495
	Outlet area 15	530	480	480	480	485	485	Second reaction zone 14	555	490	500	500	495	495
	Outlet area 15	530	480	480	480	485	485	Pressure, MPa	First reaction zone 9	0.18	0.18	0.20	0.20	0.25	0.25
Second reaction zone 14	0.15	0.17	0.17	0.17	0.23	0.23			First reaction zone 9	0.18	0.18	0.20	0.20	0.25	0.25
Second reaction zone 14	0.15	0.17	0.17	0.17	0.23	0.23	Duration of contact, second		First reaction zone 9	1.5	1.5	1.5	1.5	1.0	1.0
Second reaction zone 14	5.3	6.6	6.6	6.6	6.2	6.2			First reaction zone 9	1.5	1.5	1.5	1.5	1.0	1.0
Second reaction zone 14	5.3	6.6	6.6	6.6	6.2	6.2		Outlet area 15	0.5	0.5	0.3	0.3	0.3	0.3
Agent-oil ratio	First reaction zone 9	5.0	4.5	5.0	5.0	5.5		Outlet area 15	0.5	0.5	0.3	0.3	0.3	0.3	5.5
	First reaction zone 9	5.0	4.5	5.0	5.0	5.5	The agent-oil ratio of second reaction zone 14 is multiples of first reaction zone 9	1.3	1.3	1.2	1.2	1.17	1.18		5.5
	Temperature in the revivifier 22, ℃		680	680	680	680		1.3	1.3	1.2	1.2	1.17	1.18	700	700
Reduction reactor 3	Temperature in the revivifier 22, ℃		680	680	680	680	Temperature, ℃	680	620	650	-	600	600	700	700
	Time, minute	10	20	20	-	30	Temperature, ℃	680	620	650	-	600	600	30
	Time, minute	10	20	20	-	30	Pressure, MPa	0.13	0.17	0.16	-	0.23	0.25	30
	The atmosphere that contains reducing gas	50％H ₂+ 50％CO	50％H ₂+ 50％CO	50％H ₂+ 50％CO	-	50％H ₂+ 50％CO	Pressure, MPa	0.13	0.17	0.16	-	0.23	0.25	50％H ₂+ 50％CO
	The atmosphere that contains reducing gas	50％H ₂+ 50％CO	50％H ₂+ 50％CO	50％H ₂+ 50％CO	-	50％H ₂+ 50％CO	The atmosphere consumption that contains reducing gas, cubic meter/ton/minute	5.5	4.0	5	-	5.5	5.5	50％H ₂+ 50％CO
	Nitrogen use level, cubic meter/ton/minute		4	12	8	-		5.5	4.0	5	-	5.5	5.5	6	6
Atomized water steam and the pre-total amount that promotes water vapor account for the percentage ratio of hydrocarbon ils, weight %			4	12	8	-	5	5	8	8	10	10		6	6
		Whether enter interchanger 7 heat exchange		Be	Be	Be	5	5	8	8	10	10	Be	Be	Be
Whether enter interchanger 27 heat exchange		Whether enter interchanger 7 heat exchange		Be	Be	Be	Be	Be	Be	Be	Be	Be	Be	Be	Be

Table 8

Example number	19	20	21	DB2	22	23
Example number	19	20	21	DB2	22	23	The catalyzer numbering	C1	C2	C3	C3	C4	C5
Product is formed, weight %							The catalyzer numbering	C1	C2	C3	C3	C4	C5
Product is formed, weight %							Dry gas	4.92	4.57	4.23	3.72	4.16	3.94
Liquefied gas	13.93	13.82	13.69	12.94	13.79	12.47	Dry gas	4.92	4.57	4.23	3.72	4.16	3.94
Liquefied gas	13.93	13.82	13.69	12.94	13.79	12.47	Gasoline	49.96	49.75	49.52	46.27	49.71	49.37
Diesel oil	23.01	24.12	24.46	24.02	24.59	24.78	Gasoline	49.96	49.75	49.52	46.27	49.71	49.37
Diesel oil	23.01	24.12	24.46	24.02	24.59	24.78	Heavy oil	3.75	4.15	4.52	7.36	4.05	5.31
Coke	4.35	3.49	3.5	5.6	3.64	4.06	Heavy oil	3.75	4.15	4.52	7.36	4.05	5.31
Coke	4.35	3.49	3.5	5.6	3.64	4.06	Loss	0.08	0.1	0.08	0.09	0.06	0.07

From the result of table 8 as can be seen, compare with adopting the reference method, adopt method provided by the invention that the hydrocarbon ils of sulfur-bearing is not carried out catalytic cracking, liquefied gas and gasoline content obviously improve in the crackate, and heavy oil and coke content obviously descend.This illustrates that method provided by the invention is suitable for the not catalytic cracking of hydrocarbon oil containing surphur equally, and method provided by the invention has stronger heavy oil cracking ability, is fit to voluminous liquefied gas and gasoline.

Example 24-27

Following example illustrates method provided by the invention.This group example is main purpose with the high-yield diesel oil.

According to flow process his-and-hers watches shown in Figure 34 listed 2# stock oil content is that 50 weight % and 1# stock oil content are that the mixing oil of 50 weight % carries out catalytic cracking.Catalyst system therefor is respectively the catalyzer C6-C9 of example 6-9 preparation.Described interchanger 7 is a hot-blast heater.Described reactor is conventional equal diameter riser reactor, the height of reactor is 4000 millimeters, the height of pre lift zone is 500 millimeters, interior diameter is 14 millimeters, first reaction zone 11 highly is 1200 millimeters, second reaction zone 12 highly is 1550 millimeters, the interior diameter of first reaction zone and second reaction zone is 20 millimeters, the interior diameter of outlet area is 14 millimeters, highly be 750 millimeters, under pipeline 28 and the reactor interface is first reaction zone 9, is second reaction zone 14 on pipeline 28 and the reactor interface, is outlet area 15 on pipeline 29 and the reactor interface.

Catalyzer after contacting from the atmosphere with containing reducing gas of pipeline 8 enters the pre lift zone of reactor, is advanced into first reaction zone 9 under the pre-lifting water vapor from pipeline 10 drives.Simultaneously, from the hydrocarbon ils after the preheating of pipeline 11 with from the atomized water vapor mixing of pipeline 12, enter first reaction zone 9, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carries out a cracking reaction.Inject the cold shock agent in the junction of first reaction zone 9 and second reaction zone 14 (is 1800 millimeters places apart from the riser reactor bottom level) from pipeline 13, the cold shock agent is that boiling range is 121-250 ℃ a normal temperature raw gasline, and the consumption of cold shock agent makes reactant flow be reduced to the listed temperature of table 9 in the temperature of reaction of second reaction zone 14.Reactant flow continues uply to be mixed into second reaction zone 14 with the cold shock agent, reaction zone 14 with contact from the catalyzer after the regeneration of pipeline 28, carry out secondary reaction.Logistics behind the secondary reaction continues up, by outlet area 15, through level pipe 16, enters the settling vessel 17 of separation system, and the cyclonic separator in the settling vessel 17 separates catalyzer with crackate.Isolated catalyzer enters in the stripper 18, with the water vapor counter current contact from pipeline 19, stripping goes out remaining crackate on the catalyzer, obtains reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 20 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 22 through inclined tube 21 to be generated, in revivifier 22, under regeneration temperature, reclaimable catalyst is contacted with excess air atmosphere from pipeline 23, removes coke wherein, and reacted flue gas is discharged from pipeline 24.The part of the catalyzer after the regeneration enters reduction reactor 3 from pipeline 25, and in reduction reactor 3, under reductive condition, the part of the catalyzer after the regeneration contacts with the atmosphere that contains reducing gas from pipeline 4, and waste gas is discharged through pipeline 5.Enter or do not enter interchanger 7 heat exchange with the catalyzer after reducing gas contacts through pipeline 6, the catalyzer after heat exchange or the not heat exchange enters the pre lift zone of reactor.The other part of the catalyzer after the regeneration enters or does not enter interchanger 27 heat exchange through pipeline 26, and the catalyzer after the regeneration after heat exchange or the not heat exchange enters second reaction zone through pipeline 28.Operational condition is listed in the table 9, and the product composition is listed in the table 10.

Table 9

Example number		24	25	26	27
Example number		24	25	26	27	The catalyzer numbering		C6	C7	C8	C9
Temperature, ℃	First reaction zone 9	520	525	525	525	The catalyzer numbering		C6	C7	C8	C9
	First reaction zone 9	520	525	525	525	Second reaction zone 14	490	495	495	495
	Outlet area 15	475	470	470	470	Second reaction zone 14	490	495	495	495
	Outlet area 15	475	470	470	470	Pressure, MPa	First reaction zone 9	0.25	0.25	0.25	0.25
Second reaction zone 14	0.20	0.20	0.20	0.20			First reaction zone 9	0.25	0.25	0.25	0.25
Second reaction zone 14	0.20	0.20	0.20	0.20	Duration of contact, second		First reaction zone 9	3.0	1.0	0.8	1.2
Second reaction zone 14	6.6	6.0	6.0	6.3			First reaction zone 9	3.0	1.0	0.8	1.2
Second reaction zone 14	6.6	6.0	6.0	6.3		Outlet area 15	0.5	0.3	0.3	0.3
Agent-oil ratio	First reaction zone 9	5.5	5.5	5.0		Outlet area 15	0.5	0.3	0.3	0.3	6.0
	First reaction zone 9	5.5	5.5	5.0	The agent-oil ratio of second reaction zone 14 is multiples of first reaction zone 9	1.2	1.18	1.18	1.17		6.0
	Temperature in the revivifier 22, ℃		650	700		1.2	1.18	1.18	1.17	680	680
Reductive condition	Temperature in the revivifier 22, ℃		650	700	Temperature, ℃	500	480	450	500	680	680
	Time, minute	20	3	1	Temperature, ℃	500	480	450	500	30
	Time, minute	20	3	1	Pressure, MPa	0.23	0.23	0.23	0.23	30
	The atmosphere that contains reducing gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	Pressure, MPa	0.23	0.23	0.23	0.23	50％H ₂+ 50% dry gas
	The atmosphere that contains reducing gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	The atmosphere consumption that contains reducing gas, cubic meter/ton/minute	7	8	8	7	50％H ₂+ 50% dry gas
	Atomized water steam and the pre-total amount that promotes water vapor account for the percentage ratio of hydrocarbon ils, weight %		8	5		7	8	8	7	5	8
Whether enter interchanger 7 heat exchange			8	5	Be	Be	Be	Be		5	8
Whether enter interchanger 7 heat exchange		Whether enter interchanger 27 heat exchange		Be	Be	Be	Be	Be	Be	Be	Be

Table 10

Example number	24	25	26	27
Example number	24	25	26	27	The catalyzer numbering	C6	C7	C8	C9
Product is formed, weight %					The catalyzer numbering	C6	C7	C8	C9
Product is formed, weight %					Dry gas	3.57	3.36	3.96	3.43
Liquefied gas	13.38	13.57	13.35	13.21	Dry gas	3.57	3.36	3.96	3.43
Liquefied gas	13.38	13.57	13.35	13.21	Gasoline	42.72	42.46	42.63	42.98
Diesel oil	26.82	26.14	26.27	26.42	Gasoline	42.72	42.46	42.63	42.98
Diesel oil	26.82	26.14	26.27	26.42	Heavy oil	6.19	6.58	6.19	6.82
Coke	7.27	7.8	7.49	7.04	Heavy oil	6.19	6.58	6.19	6.82
Coke	7.27	7.8	7.49	7.04	Loss	0.05	0.09	0.11	0.1
Gasoline sulfure content, mg/litre	260	220	180	330	Loss	0.05	0.09	0.11	0.1

Example 28-31

Following example illustrates method provided by the invention.

Carry out catalytic cracking according to mode his-and-hers watches shown in Figure 44 listed 2# stock oils.Catalyst system therefor is respectively the catalyzer C10-C13 of example 10-13 preparation.Described reactor is identical with the described reactor of example 24-27.

Catalyzer after contacting from the atmosphere with containing reducing gas of pipeline 8 enters the pre lift zone of reactor, is advanced into first reaction zone 9 under the pre-lifting water vapor from pipeline 10 drives.Simultaneously, from the hydrocarbon ils after the preheating of pipeline 11 with from the atomized water vapor mixing of pipeline 12, enter first reaction zone 9, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carries out a cracking reaction.Inject the cold shock agent in the junction of first reaction zone 9 and second reaction zone 14 (is 1800 millimeters places apart from the riser reactor bottom level) from pipeline 13, the cold shock agent is that boiling range is 121-250 ℃ a normal temperature raw gasline, and the consumption of cold shock agent makes reactant flow be reduced to the listed temperature of table 11 in the temperature of reaction of second reaction zone 14.Reactant flow continues up, mix with the cold shock agent, enter second reaction zone 14, reaction zone 14 with contact from the catalyzer after the regeneration of pipeline 28, carry out secondary reaction, add terminator through pipeline 29 in the junction of second reaction zone and outlet area (is 3400 millimeters places apart from the riser reactor bottom level).Terminator is that boiling range is 121-250 ℃ a normal temperature raw gasline, and the amount of adding makes the temperature of outlet area be reduced to the temperature of the shown oral region of table 11.Logistics behind the secondary reaction continues up, mixes with terminator, by outlet area 15, through level pipe 16, enters the settling vessel 17 of separation system.Cyclonic separator in the settling vessel 17 separates catalyzer with crackate, isolated catalyzer enters in the stripper 18, with water vapor counter current contact from pipeline 19, stripping goes out remaining crackate on the catalyzer, obtain reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 20 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 22 through inclined tube 21 to be generated, in revivifier 22, under regeneration temperature, reclaimable catalyst is contacted with excess air from pipeline 23, removes coke wherein, and reacted flue gas is discharged from pipeline 24.The part of the catalyzer after the regeneration enters gas displacement jar 30 through pipeline 25, in gas displacement jar 30, use the part of the catalyzer after will regenerating from the helium of pipeline 31 and be equivalent to cementing out from the oxygen-containing gas that the mixture of the live catalyst of storage tank 1 carries of regenerated catalyst 5 weight % through pipeline 2, gas after the displacement is discharged through pipeline 32, catalyzer through gas displacement enters reduction reactor 3 from pipeline 33, in reduction reactor 3, under reductive condition, described catalyzer contacts with the atmosphere that contains reducing gas from pipeline 4, and waste gas is discharged through pipeline 5.Enter or do not enter interchanger 7 heat exchange with the catalyzer after reducing gas contacts through pipeline 6, the catalyzer after heat exchange or the not heat exchange enters the pre lift zone of reactor.The other part of the catalyzer after the regeneration enters or does not enter interchanger 27 heat exchange through pipeline 26, and the catalyzer after the regeneration after heat exchange or the not heat exchange enters second reaction zone through pipeline 28.Operational condition is listed in the table 11, and the product composition is listed in the table 12.

Table 11

Example number		28	29	30	31
Example number		28	29	30	31	The catalyzer numbering		C10	C11	C12	C13
Temperature, ℃	First reaction zone 9	525	525	525	525	The catalyzer numbering		C10	C11	C12	C13
	First reaction zone 9	525	525	525	525	Second reaction zone 14	490	490	490	490
	Outlet area 15	470	470	470	470	Second reaction zone 14	490	490	490	490
	Outlet area 15	470	470	470	470	Pressure, MPa	First reaction zone 11	0.15	0.15	0.15	0.15
Second reaction zone 14	0.13	0.13	0.13	0.13			First reaction zone 11	0.15	0.15	0.15	0.15
Second reaction zone 14	0.13	0.13	0.13	0.13	Duration of contact, second		First reaction zone 11	0.7	0.7	0.7	0.7
Second reaction zone 14	6.1	6.1	6.1	6.1			First reaction zone 11	0.7	0.7	0.7	0.7
Second reaction zone 14	6.1	6.1	6.1	6.1		Outlet area 15	0.3	0.3	0.3	0.3
Agent-oil ratio	First reaction zone 11	9.5	6	5.5		Outlet area 15	0.3	0.3	0.3	0.3	6
	First reaction zone 11	9.5	6	5.5	The agent-oil ratio of second reaction zone 14 is multiples of first reaction zone 9	1.18	1.17	1.18	1.17		6
	Temperature in the revivifier 22, ℃		680	700		1.18	1.17	1.18	1.17	700	700
Reduction reactor 3	Temperature in the revivifier 22, ℃		680	700	Temperature, ℃	520	650	650	650	700	700
	Time, minute	20	20	20	Temperature, ℃	520	650	650	650	20
	Time, minute	20	20	20	Pressure, MPa	0.12	0.12	0.12	0.12	20
	The atmosphere that contains reducing gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	Pressure, MPa	0.12	0.12	0.12	0.12	50％H ₂+ 50% dry gas
	The atmosphere that contains reducing gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	50％H ₂+ 50% dry gas	The atmosphere consumption that contains reducing gas, cubic meter/ton/minute	5	6	6	6	50％H ₂+ 50% dry gas
	The helium consumption, cubic meter/ton/minute		8	3		5	6	6	6	3	3
Atomized water steam and the pre-total amount that promotes water vapor account for the percentage ratio of hydrocarbon ils, weight %			8	3	8	10	10	10		3	3
		Whether enter interchanger 7 heat exchange		Not	8	10	10	10	Be	Be	Be
Whether enter interchanger 27 heat exchange		Whether enter interchanger 7 heat exchange		Not	Be	Be	Be	Be	Be	Be	Be

Table 12

Example number	28	29	30	31
Example number	28	29	30	31	The catalyzer numbering	C10	C11	C12	C13
Product is formed, weight %					The catalyzer numbering	C10	C11	C12	C13
Product is formed, weight %					Dry gas	3.12	3.15	3.34	3.32
Liquefied gas	12.04	11.49	11.39	11.73	Dry gas	3.12	3.15	3.34	3.32
Liquefied gas	12.04	11.49	11.39	11.73	Gasoline	42.15	42.17	42.08	42.63
Diesel oil	25.58	25.47	26.27	25.94	Gasoline	42.15	42.17	42.08	42.63
Diesel oil	25.58	25.47	26.27	25.94	Heavy oil	8.09	8.42	8.23	8.23
Coke	8.95	9.19	8.62	8.05	Heavy oil	8.09	8.42	8.23	8.23
Coke	8.95	9.19	8.62	8.05	Loss	0.07	0.11	0.07	0.1
Gasoline sulfure content, mg/litre	70	100	80	60	Loss	0.07	0.11	0.07	0.1

Example 32-35

Following example illustrates method provided by the invention.This group example is purpose with the high-yield diesel oil.

According to flow process his-and-hers watches shown in Figure 24 listed 1# stock oil content is 20 weight %, and 2# stock oil content is that the mixing oil of 80 weight % carries out catalytic cracking.Described reactor is the disclosed reducing riser reactor of CN1078094C.The total height of this reactor is 15 meters, the height of pre lift zone is 1.5 meters, diameter is 0.25 meter, the height of first reaction zone 9 is 4 meters, the diameter of first reaction zone 9 is 0.25 meter, the height of second reaction zone 14 is 6.5 meters, the diameter of second reaction zone 14 is 0.5 meter, the diameter of outlet area is 0.25 meter, the outlet area height is 3 meters, the apex angle of the profile isosceles trapezoid of first reaction zone and the second reaction zone combining site is 45 degree, and the base angle β of the profile isosceles trapezoid of second reaction zone and outlet area combining site is 45 degree.

Catalyst system therefor is respectively (1) C14, and C14 is that the trade mark is the commercial catalysts of MLC-500, and this catalyzer contains rare earth oxide, ultra-steady Y molecular sieve, and aluminum oxide, kaolin, the content of rare earth oxide are 3.2 weight %; (2) C15, C15 is that the trade mark is the commercial catalysts of CR022, this catalyzer contains phosphorous and hydrogen Y molecular sieve, ultra-steady Y molecular sieve, the zeolite with MFI structure, aluminum oxide, kaolin rare earth, and the content of rare earth oxide is 3.0 weight %, and the content of Vanadium Pentoxide in FLAKES is 1.0 weight %; (3) C16, C16 is that content is that the trade mark of 95 weight % is the catalyst mixture of the catalyzer C1 of the commercial catalysts of HGY-2000R and example 1 preparation that content is 5 weight %, the described trade mark is Y zeolite, the ultra-steady Y molecular sieve that the commercial catalysts of HGY-2000R contains rare earth, aluminum oxide, kaolin, the content of rare earth oxide are 2.1 weight %; (4) C17, C17 is that content is that the trade mark of 85 weight % is the mixture of the catalyzer C5 of the commercial catalysts of GOR-II and example 5 preparations that content is 15 weight %, the trade mark is that the commercial catalysts of GOR-II contains Y zeolite, the ultra-steady Y molecular sieve of rare earth, the zeolite with MFI structure, aluminum oxide, kaolin, the content of rare earth oxide are 2.5 weight %.

Catalyzer after contacting from the atmosphere with containing reducing gas of pipeline 8 enters the pre lift zone of reactor, is advanced into first reaction zone 9 under the pre-lifting water vapor from pipeline 10 drives.Simultaneously, from the hydrocarbon ils after the preheating of pipeline 11 with from the atomized water vapor mixing of pipeline 12, enter first reaction zone 9, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carries out a cracking reaction.Inject the cold shock agent in the junction of first reaction zone 9 and second reaction zone 14 (is 6.2 meters apart from the riser reactor bottom level) from pipeline 13, the cold shock agent is that boiling range is 121-250 ℃ a normal temperature raw gasline, and the consumption of cold shock agent makes reactant flow be reduced to the listed temperature of table 13 in the temperature of reaction of second reaction zone 14.Reactant flow continues to go upward to second reaction zone 14, reaction zone 14 with contact from the catalyzer after the regeneration of pipeline 28, carry out secondary reaction, inject terminator in the junction of second reaction zone 14 and outlet area 15 (is 12.3 meters apart from the riser reactor bottom level) from pipeline 29, terminator is that boiling range is 121-250 ℃ a normal temperature raw gasline, and the consumption of terminator makes reactant flow be reduced to the listed temperature of table 13 in the temperature of reaction of outlet area 15.Logistics continuation behind the secondary reaction is up to be mixed with terminator, by outlet area 15, through level pipe 16, enters the settling vessel 17 of separation system, and the cyclonic separator in the settling vessel 17 separates catalyzer with crackate.Isolated catalyzer enters in the stripper 18, with the water vapor counter current contact from pipeline 19, stripping goes out remaining crackate on the catalyzer, obtains reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 20 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 22 through inclined tube 21 to be generated, in revivifier 22, under regeneration temperature, reclaimable catalyst is contacted with excess air from pipeline 23, removes coke wherein, and reacted flue gas is discharged from pipeline 24.The part of the catalyzer after the regeneration enters gas displacement jar 30 through pipeline 25, in gas displacement jar 30, the oxygen-containing gas of the catalyst entrainment after the part of the catalyzer after the regeneration is used and will be regenerated from the nitrogen of pipeline 31 cements out, gas after the displacement is discharged through pipeline 32, catalyzer through gas displacement enters reduction reactor 3 from pipeline 33, in reduction reactor 3, under reductive condition, described catalyzer contacts with the atmosphere that contains reducing gas from pipeline 4, and waste gas is discharged through pipeline 5.Enter or do not enter interchanger 7 heat exchange with the catalyzer after reducing gas contacts through pipeline 6, the catalyzer after heat exchange or the not heat exchange enters the pre lift zone of reactor.The other part of the catalyzer after the regeneration enters or does not enter interchanger 27 heat exchange through pipeline 26, and the catalyzer after the regeneration after heat exchange or the not heat exchange enters second reaction zone through pipeline 28.Operational condition is listed in the table 13, and the product composition is listed in the table 14.

Comparative Examples 4 (DB4)

Following Comparative Examples explanation reference cracking method for hydrocarbon oil.

Method by example 35 is carried out catalytic cracking to same stock oil, and different is that the catalyzer that enters reduction reactor 3 does not contact with the atmosphere that contains reducing gas, does not promptly feed the atmosphere that contains reducing gas from pipeline 4.Operational condition is listed in the table 13, and the product composition is listed in the table 14.

Table 13

Example number		32	DB3	33	34	35	DB4
Example number		32	DB3	33	34	35	DB4	The catalyzer numbering		C14	C14	C15	C16	C17	C17
Temperature, ℃	First reaction zone 9	520	520	520	520	520	520	The catalyzer numbering		C14	C14	C15	C16	C17	C17
	First reaction zone 9	520	520	520	520	520	520	Second reaction zone 14	495	495	495	495	495	495
	Outlet area 15	475	475	475	475	475	475	Second reaction zone 14	495	495	495	495	495	495
	Outlet area 15	475	475	475	475	475	475	Pressure, MPa	First reaction zone 9	0.15	0.15	0.15	0.15	0.15	0.15
Second reaction zone 14	0.13	0.13	0.13	0.13	0.13	0.13			First reaction zone 9	0.15	0.15	0.15	0.15	0.15	0.15
Second reaction zone 14	0.13	0.13	0.13	0.13	0.13	0.13	Duration of contact, second		First reaction zone 9	1.0	1.0	0.8	0.8	1.0	1.0
Second reaction zone 14	6.5	6.5	6.2	6.2	6.5	6.5			First reaction zone 9	1.0	1.0	0.8	0.8	1.0	1.0
Second reaction zone 14	6.5	6.5	6.2	6.2	6.5	6.5		Outlet area 15	0.5	0.5	0.5	0.5	0.5	0.5
Agent-oil ratio	First reaction zone 9	4.0	4.0	5.0	5.0	6.0		Outlet area 15	0.5	0.5	0.5	0.5	0.5	0.5	6.0
	First reaction zone 9	4.0	4.0	5.0	5.0	6.0	The agent-oil ratio of second reaction zone 14 is multiples of first reaction zone 9	1.18	1.18	1.2	1.2	1.17	1.17		6.0
	Temperature in the revivifier 22, ℃		650	650	680	680		1.18	1.18	1.2	1.2	1.17	1.17	690	690
Reduction reactor 3	Temperature in the revivifier 22, ℃		650	650	680	680	Temperature, ℃	520	-	520	520	700	-	690	690
	Time, minute	30	-	20	20	5	Temperature, ℃	520	-	520	520	700	-	-
	Time, minute	30	-	20	20	5	Pressure, MPa	0.12	-	0.12	0.12	0.12	-	-
	The atmosphere that contains reducing gas	50％H2+ 50％CO	-	50％H2+ 50％CO	70％H2+ 30％CO	70％H2+ 30％CO	Pressure, MPa	0.12	-	0.12	0.12	0.12	-	-
	The atmosphere that contains reducing gas	50％H2+ 50％CO	-	50％H2+ 50％CO	70％H2+ 30％CO	70％H2+ 30％CO	The atmosphere consumption that contains reducing gas, cubic meter/ton/minute	5	-	6	6	6	-	-
	Nitrogen use level, cubic meter/ton/minute		8	-	3	3		5	-	6	6	6	-	3	-
Atomized water steam and the pre-total amount that promotes water vapor account for the percentage ratio of hydrocarbon ils, weight %			8	-	3	3	8	8	8	8	10	10		3	-
		Whether enter interchanger 7 heat exchange		Not	Be	Not	8	8	8	8	10	10	Not	Be	Be
Whether enter interchanger 27 heat exchange		Whether enter interchanger 7 heat exchange		Not	Be	Not	Be	Be	Be	Be	Be	Be	Not	Be	Be

Table 14

Example number	32	DB3	33	34	35	DB4
Example number	32	DB3	33	34	35	DB4	The catalyzer numbering	C14	C14	C15	C16	C17	C17
Product is formed, weight %							The catalyzer numbering	C14	C14	C15	C16	C17	C17
Product is formed, weight %							Dry gas	3.38	3.86	3.32	3.34	3.93	3.46
Liquefied gas	12.84	12.72	12.54	12.58	12.27	11.85	Dry gas	3.38	3.86	3.32	3.34	3.93	3.46
Liquefied gas	12.84	12.72	12.54	12.58	12.27	11.85	Gasoline	41.78	42.38	42.17	41.42	41.32	41.47
Diesel oil	27.51	22.57	27.31	27.93	27.89	22.86	Gasoline	41.78	42.38	42.17	41.42	41.32	41.47
Diesel oil	27.51	22.57	27.31	27.93	27.89	22.86	Heavy oil	6.91	9.88	6.92	7.03	6.76	11.29
Coke	7.53	8.53	7.65	7.6	7.77	9.02	Heavy oil	6.91	9.88	6.92	7.03	6.76	11.29
Coke	7.53	8.53	7.65	7.6	7.77	9.02	Loss	0.05	0.06	0.09	0.1	0.06	0.05
Gasoline sulfure content, mg/litre	110	330	100	90	120	360	Loss	0.05	0.06	0.09	0.1	0.06	0.05

From the result of table 14 as can be seen, compare with the reference method without reduction process, adopt method provided by the invention that the hydrocarbon ils of sulfur-bearing is carried out catalytic cracking, diesel oil content obviously improves in the crackate, heavy oil and coke content obviously descend, and the sulphur content of gasoline reduces significantly.This further specifies method provided by the invention and has stronger heavy oil cracking ability and sweetening power, is fit to high-yield diesel oil.

Claims

1. cracking method for hydrocarbon oil, this method is included in the reactor that comprises a plurality of reaction zones, under the cracking reaction condition, hydrocarbon ils is contacted with a kind of catalyzer, with reaction product and catalyst separating, the isolated catalyzer of regenerating, catalyst recirculation after the regeneration is used, it is characterized in that, described catalyzer is a kind of cracking catalyst of metallic components or contains the cracking catalyst of this metallic components and the catalyst mixture of the cracking catalyst of metallic components not, described metal component exists with highest oxidation valence state or reduction valence state, cracking catalyst with described metallic components is a benchmark, oxide compound in the metal component of highest oxidation state, the content of metal component is 0.1-30 weight %, and described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, VIII family base metal, in the rare earth metal one or more; The part of the catalyzer after the part of the catalyzer after the regeneration or the regeneration contacts with a kind of atmosphere that contains reducing gas with the mixture of live catalyst, the described temperature that contacts with the atmosphere that contains reducing gas is 100-900 ℃, the pressure of contact is the 0.1-0.5 MPa, the time of contact was at least 1 second, the consumption that contains the atmosphere of reducing gas is that the cracking catalyst per minute of metallic components per ton is not less than 0.03 cubic metre of reducing gas, will with catalyzer after the atmosphere that contains reducing gas contacts in first reaction zone and described hydrocarbon ils contact reacts; The other part of the catalyzer after the regeneration is at the later reaction zone of at least one first reaction zone, successively the product contact reacts that obtains with last reaction zone.

2. method according to claim 1 is characterized in that, described reactor is riser reactor, fixed-bed reactor, fluidized-bed reactor, moving-burden bed reactor itself or the combination between them.

3. method according to claim 1 is characterized in that, described cracking reaction condition comprises that temperature of reaction is 350-700 ℃, and reaction pressure is the 0.1-0.8 MPa, and agent-oil ratio is 1-30.

4. method according to claim 3 is characterized in that, described cracking reaction condition comprises that temperature of reaction is 400-650 ℃, and reaction pressure is the 0.1-0.5 MPa, and agent-oil ratio is 2-15.

5. method according to claim 1, it is characterized in that, this method is included in the riser reactor that comprises a plurality of reaction zones, under the cracking reaction condition, hydrocarbon ils is contacted with a kind of catalyzer, with reaction product and catalyst separating,, the catalyst recirculation after the regeneration is used the revivifier regeneration of isolated catalyst recirculation to; Wherein, described catalyzer is a kind of cracking catalyst of metallic components, or the cracking catalyst of this metallic components and the catalyst mixture of the cracking catalyst of metallic components not, described metal component exists with highest oxidation valence state or reduction valence state, cracking catalyst with described metallic components is a benchmark, oxide compound in the metal component of highest oxidation state, the content of metal component is 0.1-30 weight %, and described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, VIII family base metal, in the rare earth metal one or more; Between revivifier and riser reactor, also comprise a reduction reactor, the part of the catalyzer after the part of the catalyzer after the regeneration or the regeneration and the mixture of live catalyst enter reduction reactor, in reduction reactor, contact with a kind of atmosphere that contains reducing gas, the described temperature that contacts with the atmosphere that contains reducing gas is 100-900 ℃, the pressure of contact is the 0.1-0.5 MPa, the time of contact was at least 1 second, the consumption that contains the atmosphere of reducing gas is that the cracking catalyst per minute of metallic components per ton is not less than 0.03 cubic metre of reducing gas, will with catalyst recirculation to the first reaction zone and the described hydrocarbon ils contact reacts after the atmosphere that contains reducing gas contacts; The other part of the catalyzer after the regeneration is circulated to the later reaction zone of at least one first reaction zone, successively the product contact reacts that obtains with last reaction zone.

6. method according to claim 5 is characterized in that, the cracking reaction condition of first reaction zone comprises that temperature of reaction is 450-650 ℃, and reaction pressure is the 0.1-0.5 MPa, and be 0.4-6 second duration of contact, and agent-oil ratio is 1-30; The cracking reaction condition of second reaction zone comprises that temperature of reaction is 470-650 ℃, and reaction pressure is the 0.1-0.5 MPa, and be 1-15 second duration of contact, agent-oil ratio be first reaction zone greater than 1 to 3 times; The cracking reaction condition of the 3rd reaction zone and later reaction zone thereof comprises that temperature of reaction is 450-550 ℃, and reaction pressure is the 0.1-0.5 MPa, and be 1-4 second duration of contact, agent-oil ratio be first reaction zone greater than 1 to 3 times; The condition of riser reactor outlet area comprises that temperature is 460-590 ℃, and be 0.1-1 second duration of contact.

7. method according to claim 6 is characterized in that, the cracking reaction condition of first reaction zone comprises that temperature of reaction is 490-620 ℃, and reaction pressure is the 0.1-0.3 MPa, and be 0.8-4 second duration of contact, and agent-oil ratio is 2-15; The cracking reaction condition of second reaction zone comprises that temperature of reaction is 480-580 ℃, and reaction pressure is the 0.1-0.3 MPa, and be 2-10 second duration of contact, and agent-oil ratio is 1.1-2 a times of first reaction zone; The anti-reaction conditions of cracking of the 3rd reaction zone and later reaction zone thereof comprises that temperature of reaction is 470-520 ℃, and reaction pressure is the 0.1-0.3 MPa, and be 1-2 second duration of contact, agent-oil ratio be first reaction zone 1.1-2 doubly; The condition of riser reactor outlet area comprises that temperature is 470-570 ℃, and be 0.1-0.8 second duration of contact.

8. method according to claim 1 or 5 is characterized in that, the number of described reaction zone is 2-3.

9. method according to claim 1 or 5, it is characterized in that, the temperature that catalyzer contacts with the atmosphere that contains reducing gas is 400-700 ℃, the time of contact is 10 seconds to 1 hour, the consumption that contains the atmosphere of reducing gas is the cracking catalyst per minute 0.05-15 cubic meter reducing gas of metallic components per ton, the pressure that catalyzer contacts with the atmosphere that contains reducing gas is the 0.1-0.3 MPa, and the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.

10. method according to claim 9 is characterized in that, described pure reducing gas comprises hydrogen, carbon monoxide and contains in the hydro carbons of 1-5 carbon atom one or more; Described contain reducing gas and inert gas atmosphere comprise hydrogen, carbon monoxide, contain in one or more and the rare gas element in the hydro carbons of 1-5 carbon atom one or more mixture or the dry gas in the refinery.

11. method according to claim 9 is characterized in that, described rare gas element refers to one or more in periodic table of elements zero group gas, nitrogen, the carbonic acid gas.

12. method according to claim 9 is characterized in that, in the described atmosphere that contains reducing gas, the content of reducing gas is at least 10 volume %.

13. method is characterized in that according to claim 1 or 5, is benchmark with described catalyst mixture, the content of the cracking catalyst of metallic components is at least 0.1 weight %.

14. method according to claim 13 is characterized in that, is benchmark with described catalyst mixture, the content of the cracking catalyst of metallic components is at least 1 weight %.

15. method according to claim 1 or 5, it is characterized in that, the cracking catalyst of described metallic components is for containing described metal component, molecular sieve, heat-resistant inorganic oxide matrix, contain or not argillaceous, contain or phosphorated not the cracking catalyst that described metal exists with highest oxidation state; Cracking catalyst with described metallic components is a benchmark, oxide compound in the highest oxidation state metal, the content of described metal component is 0.1-30 weight %, the content of described molecular sieve is 1-90 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 0-80 weight %, and in Vanadium Pentoxide in FLAKES, the content of phosphorus is 0-15 weight %.

16. method according to claim 15, it is characterized in that, cracking catalyst with described metallic components is a benchmark, oxide compound in the highest oxidation state metal, the content of described metal component is 0.5-20 weight %, and the content of described molecular sieve is 10-60 weight %, and the content of heat-resistant inorganic oxide is 10-50 weight %, the content of clay is 20-70 weight %, and the content of phosphorus is 0-8 weight %.

17. method according to claim 15, it is characterized in that described metal component is selected from one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, lanthanum, cerium, lanthanum rich norium, the cerium-rich mischmetal metal.

18. method according to claim 15, it is characterized in that described molecular screening one or more in the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, zeolite, phosphorous and/or rare earth with MFI structure.

19. method according to claim 15 is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide.

20. method according to claim 15 is characterized in that, described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.

21. method according to claim 1 or 5, it is characterized in that, the cracking catalyst of described metallic components contains molecular sieve, heat-resistant inorganic oxide, clay and a kind of metal component, total amount with the cracking catalyst of described metallic components is a benchmark, the content of molecular sieve is 1-90 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 2-80 weight %, metal oxide in described highest oxidation state, the content of metal component is 0.1-30 weight %, described metal component exists with the reduction valence state basically, and it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more.

22. method according to claim 21 is characterized in that, the average valence of described metal and the ratio of its highest oxidation state are 0-0.95.

23. method according to claim 22 is characterized in that, the ratio 0.1-0.7 of the average valence of described metal and its highest oxidation state.

24. method according to claim 21 is characterized in that, described metal component is selected from one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel.

25. method according to claim 21, it is characterized in that, this catalyzer also contains rare earth metal, described rare earth metal exists with the form of metal and/or compound, total amount with the cracking catalyst of described metallic components is a benchmark, in oxide compound, described rare earth metal components contents is no more than 50 weight %.

26. method according to claim 25 is characterized in that, is benchmark with the total amount of the cracking catalyst of described metallic components, in oxide compound, described rare earth metal components contents is no more than 15 weight %.

27. method according to claim 21 is characterized in that, this catalyzer also contains phosphorus component, and in Vanadium Pentoxide in FLAKES, the content of described phosphorus component is no more than 15 weight %.

28. method according to claim 21, it is characterized in that described molecular screening one or more in the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, zeolite, phosphorous and/or rare earth with MFI structure.

29. method according to claim 21 is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide.

30. method according to claim 21 is characterized in that, described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.

31. method is characterized in that according to claim 1 or 5, described hydrocarbon ils is a metals content impurity less than the sulfur-bearing of 50ppm or hydrocarbon oil containing surphur not.

32. method according to claim 31 is characterized in that, described hydrocarbon ils is the hydrocarbon oil containing surphur of metals content impurity less than 50ppm.