CN103785437B

CN103785437B - A kind of method preparing catalytic cracking catalyst

Info

Publication number: CN103785437B
Application number: CN201210418185.9A
Authority: CN
Inventors: 许明德; 张蔚琳; 朱玉霞; 田辉平; 周灵萍; 张杰潇
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: 2012-10-26
Filing date: 2012-10-26
Publication date: 2016-01-13
Anticipated expiration: 2032-10-26
Also published as: CN103785437A

Abstract

A kind of method preparing catalytic cracking catalyst, comprise: molecular sieve is incorporated in the super steady reactor of gas phase, molecular sieve is made to move to the outlet molecular sieve of the super steady reactor of gas phase from the molecular sieve entrance of the super steady reactor of gas phase when carrying without carrier gas, and with gas phase silicon tetrachloride haptoreaction in the super steady reactor of gas phase, by reacted molecular sieve washing, mix with matrix pull an oar prepared slarry, spraying dry.The method does not need to use inert carrier gas delivery of molecules sieve, simplification of flowsheet, and save the consumption of carrier gas, reduce the consumption of silicon tetrachloride, the catalyst obtained has excellent catalytic cracking effect.

Description

A kind of method preparing catalytic cracking catalyst

Technical field

The present invention relates to a kind of preparation method of catalytic cracking catalyst.

Background technology

In catalytic cracking catalyst, molecular sieve is a kind of application material widely, and be also very important a kind of component, the performance of molecular sieve has directly had influence on the reactivity worth of catalytic cracking catalyst simultaneously.According to different needs, different modifications can be carried out to reach the requirement of use to molecular sieve.It is required that the molecular sieve of such as high silica alumina ratio is generally considered to catalytic cracking catalyst.

Preparing in the molecular sieve of high silica alumina ratio, mainly containing following several method: ammonium fluosilicate method aluminium-eliminating and silicon-replenishing, hydro-thermal method and gas chemistry method aluminium-eliminating and silicon-replenishing (the present invention is called the super steady method of gas phase).

Ammonium fluosilicate method aluminium-eliminating and silicon-replenishing (also referred to as chemical method aluminium-eliminating and silicon-replenishing) mainly uses ammonium fluosilicate dealumination complement silicon, and the degree of crystallinity of the molecular sieve of acquisition is high, and Si/Al when heat endurance is high, but the indissoluble thing AlF formed in dealumination process ₃affect hydrothermal stability with residual fluosilicate, also pollute the environment.

Hydro-thermal method is still the industrial method generally adopted at present, but mend silicon there is dealuminzation in water-heat process after not in time, easily cause lattice to subside, and non-framework aluminum clogged with fragments duct, this not only have impact on the accessibility in activated centre, also affects the further raising of its heat endurance.

The feature of gas chemistry method aluminium-eliminating and silicon-replenishing is that dealuminzation is even, and mend silicon timely, product crystallization reservation degree is high, and Heat stability is good, duct is unimpeded.CN1121903C discloses a kind of preparation method of rare-earth type high-silicon gamma-zeolite, the method comprises carries out drying process by the y-type zeolite containing rare earth, make its water content lower than after 10 % by weight, according to silicon tetrachloride: the weight ratio of Y zeolite=0.1-0.9:1, pass into the silicon tetrachloride gas that dry air carries, at temperature 150-600 DEG C, react 10 minutes to 6 hours, after reaction, purge 5 minutes to 2 hours with dry air, with Na remaining in decationized Y sieve water washing removing zeolite ⁺, Cl ^-, Al ³⁺deng soluble by-products.The method molecular sieve maintains static, and uses dry air to carry SiCl ₄, reacted rear air and purged, unrealized continuous prodution, yields poorly.

CN1281493C discloses Y type zeolites containing rare-earth and high content of silicon and preparation method thereof, and this zeolite contains rare earth, and the silica alumina ratio of this zeolite is 5-30, and initial lattice constant is 2.430-2.465nm, and the ratio of balance lattice constant and initial lattice constant is at least 0.985.The preparation method of this zeolite comprises and contacting containing rare earth Y type zeolite with silicon tetrachloride, described contact is carried out in a consersion unit, this equipment as shown in Figure 1, comprise a reactor (1), a charging aperture (2) and a gas outlet (3), an agitator (4) is also comprised in the inside of reactor (1), gas outlet (3) is provided with a gas-solid separator (5), the bore dia of gas-solid separator (5) contained hole and porosity ensure gas by and zeolitic solid particle not by, the puddler of agitator (4) stretches out reactor (1) outward, under the stirring of agitator (4), the described y-type zeolite containing rare earth contacts with carbon tetrachloride gas, the temperature of contact is 100-500 DEG C, the time of contact is 5 minutes to 10 hours, be 1:0.05-0.5 containing the y-type zeolite of rare earth and the weight ratio of carbon tetrachloride, the silica alumina ratio of the described y-type zeolite containing rare earth is 3-8, lattice constant is 2.45-2.48nm.Obviously, time of contact needed for the method is general all long, need a few hours, add the charging before reaction and discharging after completion of the reaction, the reaction of above-mentioned dealumination complement silicon can only be carried out once a general day shift at the most, even if adopt the operating type of break tour also can only carry out twice above-mentioned dealumination complement silicon reaction, and owing to needing in reactor to stir, therefore reactor also can not be infinitely great, based on current level, the production capacity that can be used for the maximum reactor of above-mentioned dealumination complement silicon reaction is 600kg, continue augmenting response still, then be difficult in reactor ensure fully to stir, therefore, adopt the mode of aforesaid reaction vessel, the high-silica zeolite of 1200kg within one day, can be obtained at the most.And, in the method for above-mentioned prior art, in order to ensure the high silicon content of the molecular sieve obtained, generally all make SiCl ₄excessive far away, excessive SiCl ₄use add production cost and expenses of environmental protection undoubtedly.On the other hand, said method all needs very numerous and diverse manual operation, such as: hand charging, manual cleaning and need long blow line etc. after completion of the reaction, these not only bring hand labor intensity large, the problem that production efficiency is very low, and, molecular sieve dust when charging and discharging and excessive SiCl ₄also cause the health of serious environmental pollution and serious harm operating personnel.Therefore, the super steady technique of the gas phase of above-mentioned autoclave is difficult to carry out suitability for industrialized production.

CN102049315A discloses a kind of preparation method of catalyst, under the method is included in the carrying of inert carrier gas flow, molecular sieve is flowed with inert carrier gas, and with gas phase SiCl ₄contact under flow regime, molecular sieve and gas phase SiCl ₄time of contact be 10 seconds to 100 minutes, then by gained and gas phase SiCl ₄molecular sieve after contact mixes with binding agent, clay and water pulls an oar and granulation, obtains catalytic cracking catalyst.The preparation method of the catalytic cracking catalyst that this invention provides can realize molecular sieve and SiCl ₄haptoreaction carry out continuously, by controlling the flow velocity of carrier gas and the length of tubular reactor, molecular sieve and SiCl can be controlled ₄the time of contact, thus molecular sieve and SiCl can be made ₄haptoreaction carry out fully in tubular reactor.But the method adopts gas to carry molecular sieve powder material and SiCl ₄the catalytic mode of gas carries out the super steady reaction of gas phase, in order to the amount of fluidisation molecular sieve is sufficiently large, and carrier gas and SiCl ₄part by weight can reach 10-250, not so easily cause the problem that device blocks, increase the amount of gas and cause reaction depth to be difficult to improve, the contradiction between the raising that there is solid material conveying and the super steady reaction depth of gas phase, in addition, the method needs larger large SiCl to reach certain extent of reaction ₄intake, SiCl remaining after the super steady reaction of gas phase must be caused ₄amount increase, the harm not only having increased the weight of environmental pollution is more unfavorable for effective absorption of tail gas.

Summary of the invention

The object of the invention is the critical defect existed for the super steady explained hereafter synthetic zeolite catalysts cracking catalyst of existing continuous gas phase, provide one to reduce SiCl ₄the method preparing catalytic cracking catalyst being suitable for continuous prodution of consumption.

The invention provides a kind of method preparing catalytic cracking catalyst, the method comprises: be incorporated into by molecular sieve in the super steady reactor of gas phase, when carrying without carrier gas, make molecular sieve move to the outlet molecular sieve of the super steady reactor of gas phase from the molecular sieve entrance of the super steady reactor of gas phase, and make molecular sieve and gas phase SiCl ₄haptoreaction in the super steady reactor of gas phase, by after obtained haptoreaction molecular sieve washing, mix with matrix and water pull an oar, granulation.

Described catalytic condition comprises: the solid content introducing the Molecular sieve raw material of the super steady reactor of described gas phase is preferably greater than 98 % by weight (burning decrement is no more than 2 % by weight), the solid content of described molecular sieve is the weight of molecular sieve after high-temperature roasting and (the i.e. calcination base content of the weight ratio before roasting, see RIPP32-90 analytical method, Petrochemical Engineering Analysis method, (RIPP test method), the Yang Cui volume such as surely, Science Press, nineteen ninety), the temperature of roasting is generally 800 DEG C, the water content of the solid content=100%-molecular sieve of molecular sieve.Introduce the SiCl of the super steady reactor of gas phase ₄0.01-1 is preferably, more preferably 0.05-0.60, molecular sieve and gas phase SiCl with the weight ratio of the molecular sieve introducing the super steady reactor of gas phase ₄contact Temperature be 250-700 DEG C, more preferably 300-650 DEG C; The time of staying of molecular sieve in the super steady reactor of gas phase is 10 seconds to 120 minutes, is preferably 1 minute to 60 minutes.

The outlet of the super steady reactor of gas phase is moved to from the molecular sieve entrance of the super steady reactor of gas phase (being also called for short reactor below) in order to make molecular sieve when carrying without carrier gas, move, with the SiCl in reactor in the process of movement under the effect of mechanical transmission device and/or gravity by making the molecular sieve in the described reactor of introducing ₄haptoreaction.Owing to not introducing the gas carrier being used for fluidisation molecular sieve in reactor, thus make the molecular sieve be in the super steady reactor of gas phase be in close phase state, the bed density of its molecular sieve is higher.Described SiCl ₄preferably be incorporated in the super steady reactor of gas phase after vaporization, molecular sieve is containing SiCl ₄space move, the SiCl of gas phase ₄by diffusion or also by agitaion, enter into the space of sieve particle, and be diffused into further in the hole of sieve particle inside and carry out aluminium-eliminating and silicon-replenishing reaction.Due to molecular sieve continuous moving from the inlet to the outlet in the super steady reactor of gas phase, molecular sieve can be introduced continuously to reactor from the molecular sieve entrance of reactor, draw the super steady reacted molecular sieve of gas phase continuously from the outlet of reactor, thus the production of continuous gas phase super stabilizing can be realized.And owing to not needing the carrier gas introducing delivery of molecules sieve, without gas dilution or carry silicon tetrachloride, greatly can reduce the volume of reactor, and not introduce carrier gas and greatly can reduce the heat that carrier gas is taken away and the purification expense reducing carrier gas.Surprisingly, super stabilizing reaction rate can be accelerated, Reaction time shorten, and can improve the degree of depth of the super steady reaction of gas phase, the uniformity of product is better in addition.

The method preparing catalytic cracking catalyst provided by the invention, by molecular sieve and SiCl ₄send into continuously in the super steady reactor of gas phase, by Action of Gravity Field and/or provide power to make molecular sieve fully be expelled to gas-solid separator from discharging opening again after reaction in tubular reactor, solid is separated in gas-solid separator with gas, gaseous component introduces absorption tower, sponges SiCl excessive on a small quantity ₄after gas can directly discharge, solid material can be drawn separator continuously or be stayed regular drain separator in the separator.As can be seen here, the method preparing molecular sieve provided by the invention can realize molecular sieve and SiCl ₄haptoreaction carry out continuously; By controlling mass transport speed or/and the length of reactor, the time of staying of molecular sieve material in reactor can be controlled, controlling molecular sieve and SiCl ₄the time of contact, thus molecular sieve and SiCl can be made ₄haptoreaction evenly carry out fully in tubular reactor; By using the tubular reactor or regulatory molecule sieve and SiCl that are provided with heater ₄addition ratio, can control different reaction temperatures, thus can control differential responses condition and the extent of reaction, and then can obtain the zeolite product of different dealumination depth.

Compared with the super steady technique of existing autoclave gas phase, method provided by the invention can realize the super steady reaction of serialization gas phase, and operation can all automation serializations carry out, hand labor intensity is little, and production efficiency is high, properties of product are stablized, and the suitability for industrialized production of the super steady technique of molecular sieve serialization gas phase is become a reality.Experiment proves, adopt still reaction method disclosed in CN1281493C, even if adopt the operating type of break tour, also the high-silica zeolite of 1200kg can be produced every day at the most, and adopt the said equipment provided by the invention, the high-silica zeolite can producing 1000kg per hour, the high-silica zeolite of 24000kg can be produced every day, its production efficiency is 20 times of still reaction method disclosed in CN1281493C, and the labor operation intensity of workman also greatly reduces, as can be seen here, the economic benefit of equipment provided by the invention is very significant.Steady technics comparing super with existing continous way gas phase, the present invention adopts conveying device reactor can allow the SiCl of molecular sieve and vaporization ₄gas directly contacts in higher reaction temperature and carries out sufficient dealumination complement silicon reaction, not only efficiently solve the super steady technology Middle molecule sieve pressed powder conveying continuously of existing molecular sieve, contradiction between reaction time and the raising of the super steady reaction depth of gas phase, and, owing to reacting fully between the raising of the degree of depth of the super steady reaction of gas phase and reaction mass, SiCl can be reduced ₄consumption and SiCl remaining after gas-phase reaction can be made ₄amount greatly reduce, be very beneficial for the absorption of tail gas, and then reduce environmental pollution from source.And because the super steady reaction depth of gas phase improves, the Activity and stabill of gas phase super stable molecular sieve is improved further, therefore, the consumption of the molecular sieve in catalyst preparing can be reduced, reduce the cost of catalyst further.

Accompanying drawing explanation

Fig. 1 is the structural representation of the equipment for the preparation of molecular sieve of prior art;

Fig. 2 is the structural representation of the equipment for the preparation of molecular sieve provided by the invention;

The structural representation of the tubular reactor that Fig. 3 provides for embodiment 2;

The schematic diagram of the angle α between tubular reactor 1 axis that Fig. 4 is equipment shown in Fig. 2 and horizontal plane;

The structural representation of the tubular reactor equipment that Fig. 5 provides for embodiment 1;

Fig. 6 is the structural representation of the super steady equipment of gas phase described in embodiment 3.

The flight of A-A cross section that Fig. 7 is body shown in embodiment 3 and the schematic diagram of weir plate; Wherein 7 is weir plate, and 8 is flight, and 1 is body.

Detailed description of the invention

The method preparing catalytic cracking catalyst provided by the invention, molecular sieve is incorporated into continuously in the super steady reactor of gas phase, make molecular sieve move to outlet molecular sieve when carrying without carrier gas continuously from molecular sieve entrance, and contact with the silicon tetrachloride gas in the super steady reactor of gas phase and carry out super stabilizing reaction.In reactor, introduce silicon tetrachloride continuously simultaneously.

Provided by the inventionly prepare in the method for catalytic cracking catalyst, silicon tetrachloride can be introduced in reactor with liquid phase and then vaporizes in the reactor and react with molecular sieve, but in order to make reaction even, be incorporated into after preferred silicon tetrachloride vaporization in the super steady reactor of gas phase.Be incorporated in the super steady reactor of gas phase by the silicon tetrachloride of molecular sieve and vaporization, silicon tetrachloride carries out dealumination complement silicon reaction by stirring and/or diffuse in the space of sieve particle and duct in the reactor.Molecular sieve moves under gravity and/or under the effect of mechanical force, and silicon tetrachloride moves along the direction of molecular sieve movement on the whole and reacts with molecular sieve; Due to the carrying out of the super steady reaction of gas phase, along the direction that molecular sieve moves, silicon tetrachloride concentration in molecular sieve space reduces gradually, when molecular sieve arrives the outlet molecular sieve of reactor, the concentration of the silicon tetrachloride in molecular sieve material has been reduced to very low level, also the silicon tetrachloride namely in molecular sieve material all take part in the super steady reaction of gas phase as effective reactant in the reactor substantially, is thus conducive to the consumption of reduction silicon tetrachloride, raising dealumination complement silicon effect.

In the super steady reactor (being also called for short reactor below) of gas phase described in the present invention, the super steady reaction of described molecular sieve gas phase carries out with fluid bed, moving bed, fixed bed or its form combined.Owing to not using delivery of carrier gas to carry out molecular sieve conveying, the sieve particle concentration thus in the reactor as one of reactant is higher, is moved by the conveying of conveying device.And the present invention directly introduces silicon tetrachloride gas in reactor, and dilute without diluent gas, the concentration as the silicon tetrachloride of another reactant is also higher.In order to realize molecular sieve in the reactor without carrier gas conveying move, mechanical transmission device and/or gravity transfer device can be used in the reactor.Such as, ribbon conveyer, pipe chain conveyor, conveying worm, circulation piston conveyer, tubular type gravity conveyor or their combination can be used, to make molecular sieve from the outlet molecular sieve of the reactor of the molecular sieve entrance movement of reactor.The molecular sieve of discharging from the outlet molecular sieve of the super steady reactor of gas phase is then introduced gas-solid separator and is separated.

Described reactor can be any can meet Middle molecule of the present invention sieve with gas phase SiCl ₄the reactor of contact conditions.The super steady reactor of described gas phase can be tubular reactor or transport bed reactor (moving-burden bed reactor).But dealumination complement silicon reaction of the present invention is carried out or carries out in belt conveying bed bioreactor in tubular reactor under preferable case.Described reactor comprises molecular sieve entrance, silicon tetrachloride entrance and outlet molecular sieve, wherein silicon tetrachloride can share an entrance with molecular sieve entrance, also silicon tetrachloride entrance can be set separately in the position different from molecular sieve entrance, this entrance, preferably near molecular sieve entrance, makes silicon tetrachloride and molecular sieve and drifts dynamic.The super steady reactor of gas phase provided by the invention, when only having a charging aperture, can make molecular sieve and SiCl ₄send in the body of reactor by this charging aperture, but under preferable case, for the ease of during industrialization continuous seepage with the coordinating of other devices, the thermo-molecular that described molecular sieve is generally from roaster sieves, and that is, this charging aperture is communicated with roaster usually, therefore, preferable case, the super steady reactor of described gas phase also comprises silicon tetrachloride feeding mouth (the second charging aperture), and described silicon tetrachloride feeding mouth is positioned at position adjacent with described molecular sieve charging aperture (the first charging aperture) on body; Described silicon tetrachloride feeding mouth can be in the position of molecular sieve charging aperture upstream, also can be in the position in molecular sieve charging aperture downstream, and preferably, silicon tetrachloride feeding mouth is in the position in molecular sieve charging aperture downstream.Described upstream and downstream is for molecular sieve moving direction in the reactor.

For the present invention, after silicon tetrachloride is incorporated into the super steady reactor of gas phase, carrier gas is not needed to carry, thus in the super steady reactor of described gas phase, the gas such as air that described gas comprises silicon tetrachloride gas and brought into by molecular sieve.Because silicon tetrachloride gas and molecular sieve carry out super steady reaction, silicon can carry out same order elements reaction with the aluminium in molecular sieve and enter into the skeleton structure of molecular sieve, and the aluminium removed can form aluminium-chlorine compound with chlorine, thus, the super steady reactor of described gas phase only can arrange a material outlet (now the present invention is also referred to as outlet molecular sieve), and molecular sieve, the gas brought into by molecular sieve and unreacted a small amount of silicon tetrachloride all can leave the super steady reactor of gas phase from this outlet and enter into gas-solid separator.

The method preparing catalytic cracking catalyst provided by the invention, the super steady reactor of described gas phase can be tubular reactor, comprises molecular sieve entrance, body, molecular sieve conveying device and outlet molecular sieve and silicon tetrachloride entrance, or also comprises gas outlet.Described Molecular sieve raw material is incorporated into body from the molecular sieve entrance of the super steady reactor of gas phase, then moves to outlet molecular sieve along body, leaves the super steady reactor of described gas phase.Described silicon tetrachloride is incorporated into the super steady reactor of gas phase from silicon tetrachloride entrance, contacts, react with molecular sieve.Described body can be any type of pipe that can make molecular sieve movement wherein, such as, can be one or more the combination in straight tube, broken line pipe, bend pipe, such as, can be wherein one section be rectilinear tubes, and other one section is bend pipe or helix tube; The cross section of described body can be various shape, and be such as square, circular, polygon, described body is preferably pipe.

According to the method preparing catalytic cracking catalyst provided by the invention, the super steady reactor of described gas phase can be tubular reactor (also claiming tubular reactor), and described tubular reactor comprises body, charging aperture and discharging opening.Wherein charging aperture and discharging opening can lay respectively at the two ends of described body.Wherein molecular sieve to be incorporated into reactor and moving axially along body from molecular sieve charging aperture, with silicon tetrachloride haptoreaction, after reaction, molecular sieve discharges reactor from molecular sieve discharging opening, and molecular sieve and unreacted a small amount of silicon tetrachloride of discharge enter gas-solid separating device.Molecular sieve can be moved in described tubular reactor by Action of Gravity Field or by mechanical conveying effect, such as, ribbon conveyer, pipe chain conveyor, conveying worm, circulation piston conveyer, tubular type gravity conveyor or their combination can be used to make molecular sieve move to outlet molecular sieve from molecular sieve entrance in body.Molecular sieve and gas phase SiCl ₄time of contact be 10 seconds to 120 minutes, preferably 1 ~ 60 minute, such as, can be 4 ~ 39 minutes, and can select molecular sieve and gas phase SiCl in contact process ₄whether heat, to make molecular sieve and gas phase SiCl ₄the temperature of contact is 250-700 DEG C.The present inventor finds, the length of described tubular reactor is 5-200 rice (length of body) is preferably, therefore, the length of the preferred described tubular reactor of the present invention is 5-200 rice, more preferably 7-150 rice, is further preferably 15 ~ 130 meters, is more preferably 20-80 rice.The diameter (internal diameter) of described tubular reactor is preferably 0.01-6 rice, more preferably 0.02-3 rice, is further preferably 0.1-2 rice, such as, can be 0.2 ~ 1.5 meter.The length of described body and the interior ratio through (diameter) of body are not less than 1, preferably 3 ~ 100:1, such as, can be 10 ~ 100:1.Relative to diameter be such as 0.1 ~ 1.5 meter, 0.01-1.5 rice, length is 5 ~ 130 meters, the such as tubular reactor of 15-130 rice, the introduction volume (flow) of molecular sieve is preferably 50-2000kg/ hour, more preferably 100-1500kg/ hour, is further preferably 200-1200kg/ hour.Under these conditions, both molecular sieve and gas phase SiCl can be ensured ₄continually by tubular reactor, molecular sieve and gas phase SiCl can be ensured again ₄contact can fully carry out.Adopt method provided by the invention under same degree of dealumination, greatly can reduce gas phase SiCl ₄consumption.The molecular sieve SiCl that vaporize rear with heating ₄contact with flow regime under continuous conveying device.Described body can level or inclination, as long as molecular sieve can be made to move in body when carrying without carrier gas, the angle of such as its axis and horizontal plane can be 0 ~ 90 °, such as, can be 0 ~ 55 °.

Described body is tubulose, can be linear, also can be the arbitrary shape such as spiral or wave, the present invention preferably uses the pipeline of straight line, linear pattern or broken line type pipeline not only can reduce size and the plant area area of unit scale, reduce difficulty of construction, and molecular sieve and SiCl can be realized ₄the sufficient reacting object of carrying out, be convenient to the time of staying controlling molecular sieve.In order to fully ensure to realize contacting more fully in shorter pipeline further, and prevent from or reduce in tubular reactor, reacting uneven causing the second-rate of molecular sieve, described tubular reactor can be arranged through Action of Gravity Field and/or by mechanical conveying effect, molecular sieve be moved wherein, such as select continuous conveying device is installed in tubular reactor inside or utilizes gravity that molecular sieve is moved, the continus convergence problem of pressed powder can be solved like this, material reaction total amount can also be improved, described conveyer can be that arbitrary continuous conveying device is to ensure molecular sieve and SiCl ₄flowing reactive, the preferred gravity transfer device of the present invention and power conveying device.

As shown in Figure 2, the super steady reaction unit of described gas phase comprises the super steady reactor 1 of gas phase, gas-solid separator 2 and absorber 3, the super steady reactor 1 of described gas phase is provided with molecular sieve entrance a and gas phase silicon tetrachloride entrance b, gas-solid separator 2 is provided with outlet molecular sieve c, the outlet of its top gas is communicated with absorber 3, and absorber 3 is provided with gas vent d in order to discharge the gas after absorbing silicon tetrachloride, and absorbing liquid outlet e is in order to discharge the absorbing liquid absorbing silicon tetrachloride.The molecular sieve that outlet molecular sieve c discharges is introduced washer 4 and is washed, then filter and obtain the molecular sieve after washing, the molecular sieve after this washing through super-dry or without drying, then can introduce pulping device 5, mix with the matrix g introducing pulping device 5 and pull an oar, then introduce granulating system granulation.

The method preparing catalytic cracking catalyst provided by the invention, the first concrete embodiment, by gravity transfer molecular sieve.Described body is bend pipe or straight tube, and the angle of body axis and horizontal plane is 30 ~ 90 °, and described body is vertical or be obliquely installed, and the body of inclination is convenient to control the reaction time of molecular sieve in body and the movement being convenient to control molecular sieve.Be preferably straight tube, its cross section is preferably circular.Described body is preferably, it can be such as 40-70 ° that the angle of its axis and horizontal plane is preferably 40-80 °, this preferred axis and horizontal plane angle, be conducive to controlling molecular sieve material level in the reactor, and molecular sieve can be discharged, the quality of quiet run, molecular sieves stabilized product and the increase molecular sieve dealumination complement silicon extent of reaction.Molecular sieve entrance and silicon tetrachloride gas access is provided with in one end that body position is higher, molecular sieve enters sedimentation under gravity after body, and contact with silicon tetrachloride gas and vapor permeation wherein, and carry out super stabilizing reaction, silicon tetrachloride moves to material outlet (outlet molecular sieve) direction on the whole, and along with the axial concentration of the carrying out reacted along reactor reduces gradually, discharge reactor to exit, outlet molecular sieve is arranged on the lower one end of the other end of body and body position.In order to reduce the size of reactor, the present invention preferably makes molecular sieve be deposited on the bottom of body and move gradually, reducing, flashboard are such as set in exit by the resistance controlling exit or valve is set, control the material level of the molecular sieve being deposited on bottom, thus the reaction time of molecular sieve after deposit can be controlled.Molecular sieve contacts with silicon tetrachloride and mixes in the process of sedimentation, then molecular sieve is deposited in the bottom of body, wherein in the space and hole of molecular sieve, be mixed with silicon tetrachloride, this part silicon tetrachloride is under the carrying of molecular sieve, along with molecular sieve moves to the outlet of molecular sieve together, and carry out super stabilizing reaction, silicon tetrachloride consumes gradually, then draw body by material outlet (outlet molecular sieve) and introduce gas-solid separating device, the reacted molecular sieve of super stabilizing is separated with the gas wherein carried, gas introduces absorption plant absorption silicon tetrachloride wherein, molecular sieve is collected in the bottom of gas-solid separator, continuous or periodic discharge gas-solid separator.Owing to being the decanting zone of molecular sieve on the top of body, silicon tetrachloride is in gas phase, therefore namely molecular sieve starts to carry out super stabilizing reaction with silicon tetrachloride in the process of sedimentation, then the bottom of reactor is deposited on, Way out to molecular sieve moves, and carry out super stabilizing reaction, along with the movement of molecular sieve, the silicon tetrachloride in its particle voids and molecular sieve pores reacts gradually.By controlling the height of the height of reactor, the height of settling section and accumulation horizon, reaction time can be controlled, react completely to make the silicon tetrachloride be in sieve particle space and hole as far as possible, because the accumulation horizon formed has higher drag, the silicon tetrachloride introduced can be prevented because the larger fluctuation of pressure is directly entered in gas-solid separator by molecular sieve accumulation horizon, thus the utilization rate being conducive to improving silicon tetrachloride reduce the consumption of silicon tetrachloride.Therefore, in preferred situation, described reactor at least partially cross section fills full molecular sieve, can stop because pressure oscillation causes silicon tetrachloride directly to enter gas-solid separator from material outlet, can reduce reactor size and can ensure reaction effect.In described reactor, can also weir plate be set.One end that molecular sieve is higher from position enters in body, and silicon tetrachloride also from the inlet tube body of same one end, and contacts with molecular sieve, the other end motion of molecular sieve along body to body.In that case, molecular sieve is deposited in body, and one end lower to position is under gravity moved, and the gas brought into when having silicon tetrachloride and introduce molecular sieve in the particle voids of molecular sieve in body, moves with molecular sieve.Wherein outlet molecular sieve is in lower one end, position, can on the end face of body, also can on the tube wall near end face.Preferably, described reactor pipe diameter (internal diameter) is 0.1 ~ 2 meter of pipe, be more preferably 0.15 ~ 1.5 meter, the draw ratio (ratio of length and described pipe diameter (interior warp)) of described reactor is greater than 1, be generally 1 ~ 500, be such as 1.5 ~ 400:1, being more preferably 3 ~ 150:1 is such as 10 ~ 100:1.

Preferably, the invention provides the second detailed description of the invention, described reactor is tubular reactor, described tubular reactor utilizes gravity transfer molecular sieve, for the ease of controlling the movement of described molecular sieve in body, make the motion of molecular sieve more steadily good, improve reaction effect, the body of described tubular reactor is set to rotate, part or all of i.e. described tubular reactor body can be set to can rotate around the axis of body, usual rotating part is more than 20% of reactor tube body length, such as, be 20% ~ 100%, also can be 20 ~ 90%.Molecular sieve and SiCl can be increased considerably by rotating ₄exposure level, the super stabilizing process of molecular sieve is more steady, and product quality is more stable.In this situation, the position of its molecular sieve material inlet is preferably higher than the position of outlet molecular sieve; Under preferable case, the axis of described body can become α angle (acute angle) with horizontal plane, angle can be 5-90 °, is preferably 5-70 °, such as, can be 10 ~ 20 °, 20 ~ 50 °, 30 ~ 40 °, 40 ~ 60 ° or 60 ~ 70 °, be more preferably 30 ~ 55 °.The body tilted is convenient to the movement controlling the reaction time of molecular sieve in body and be convenient to control molecular sieve, can promote mixing of silicon tetrachloride and molecular sieve, improve and react uniformity.The body of described tubular reactor is preferably straight tube.Preferably make molecular sieve and silicon tetrachloride and drift dynamic.When part or all of body is set to rotate time, the velocity of rotation of body is 0.05 ~ 40 rev/min, is preferably 0.5 ~ 25 rev/min and is such as 0.5 ~ 15 rev/min.When body be rotate time, tubular body can arrange multi-form flight and baffle plate, and wherein flight and baffle plate can fully mixed material molecular sieve and SiCl ₄, baffle plate also claims weir plate, can prevent the too fast slip of molecular sieve from causing the huge fluctuation of product quality, and avoid moieties sieved fast by reactor, flight can promote the mixing of molecular sieve and silicon tetrachloride.Described flight can be that straight line is welded on tubular body, with axis being parallel, also can be inclination certain angle (angled relative to axis) welding, spiral welded, wave welding and various shape can also be carried out weld, described flight can be quantitatively one also can be multiple, namely a usual flight can meet the demands, preferably 1 ~ 6 (the flight number had for a cross section), the width of described flight is such as 1/30 ~ 1/10 of warp in pipe diameter.Described flight can be installed the various quantity of various shape and can strengthen the little steel plate that molecular sieve stirs, to strengthen stirring, with mass transfer enhancement effect, little steel plate can be one or more in linear pattern, spirality, waveform, circle.Described baffle plate can be that uniform welding is at tubular body, also can unevenly weld, described plate washer can be quantitatively zero also can be multiple, the width of described baffle plate can be such as 1/100 ~ 1/10 of warp in pipe diameter, the object of baffle plate reduces sliding of reactor Middle molecule sieve, such as reduce the speed of speed faster than upside of lower floor, to make reaction evenly, reduce silicon tetrachloride consumption.Described α angle is preferably 30 ~ 50 °, so both can ensure that molecular sieve is carried in body, is conducive to stabilized product quality again.

When part or all of body is set to rotate, in described body, preferably also sleeve pipe is set, is conducive to the concentration improving silicon tetrachloride in reactor, improve the extent of reaction and then reduce the consumption of silicon tetrachloride, promotion mass transfer.Described sleeve pipe can be coaxial with described body, and can be pipe, its external diameter be preferably 1/4 ~ 3/4 of warp in pipe diameter.Preferably, described body rotatable portion is provided with described sleeve pipe.

According to the second detailed description of the invention provided by the invention, a kind of described super steady reactor of gas phase as shown in Figure 3, the super steady reactor of this gas phase comprises: reactor body, molecular sieve entrance 31, gas phase silicon tetrachloride entrance 41, outlet molecular sieve 51, inner sleeve 61 and gas vent 71, arrange reactor flight 11 and baffle plate 21 in reactor body, this reactor can also comprise body rotary drive mechanism (not marking).Silicon tetrachloride and molecular sieve are respectively by silicon tetrachloride entrance 14 and the space between molecular sieve entrance 31 lead-in bushing 61 and the super steady reactor tube walls of gas phase, and haptoreaction, wherein flight 11 can make the molecular sieve in body overturn, be conducive to mixing of molecular sieve and silicon tetrachloride, baffle plate 21 can stop molecular sieve to glide along reactor tube walls, be conducive to molecular sieve steadily movement, thus be conducive to preventing the translational speed of molecular sieve material translational speed faster than top molecular sieve of below, be conducive to stabilized product quality, the introducing of sleeve pipe 61 makes molecular sieve react in annular space, be conducive to molecular sieves stabilized quality, and be conducive to reducing thermal loss, described gas-solid separator 2 is for collecting and SiCl ₄molecular sieve after gas contact.

The third preferred detailed description of the invention provided by the invention, described reactor utilizes power to carry out the conveying of molecular sieve, and molecular sieve is moved in the reactor, and described power conveying device can be arbitrary device, as long as can make molecular sieve and gas phase SiCl ₄continuous moving in reactor haptoreaction.Device for carrying such as use in circulation piston pusher, pipe chain conveyor, auger conveyor, tube-shaped belt conveyer one or more.By using power conveying device, molecular sieve can be made to move in tubular reactor, the gas in the space of molecular sieve and hole also moves to the outlet of the super steady reactor of gas phase under the carrying of molecular sieve.

Make the mode of molecular sieve movement be the conveying utilizing tube-shaped belt conveyer to carry out molecular sieve, described tube-shaped belt conveyer band conveyor is arranged on airtight tubular reactor inside, molecular sieve and gas phase SiCl ₄entering from the charging aperture on top, tubular reactor one end drops to ribbon conveyer, the discharging opening of tubular reactor other end bottom is transported to by ribbon conveyer, on band conveyor, material can fully react, described ribbon conveyer can be the conventional any conveyer used, and ribbon conveyer length and width depend on the position of tubular reactor charging aperture and discharging opening and the size of molecular sieve inlet amount.Under preferable case, on described band conveyor, the thickness of molecular sieve is no more than 20cm, more preferably no more than 10cm.Use lace conveying device delivery of molecules sieve, the axis of body and the angle α of horizontal plane are preferably 0 ~ 45 °, preferably 0 ~ 25 °.

A kind of reactor using lace conveying device delivery of molecules to sieve as shown in Figure 5, Molecular sieve raw material and silicon tetrachloride are incorporated into reactor from the molecular sieve entrance 12 of one end of reactor and silicon tetrachloride entrance 22, molecular sieve falls on lace conveying device 52, lace conveying device 52 moves with conveyer belt, silicon tetrachloride is full of in the space in face over a molecular sieve, silicon tetrachloride is by diffusing in the space between sieve particle, and then in the duct entering molecular sieve, participate in the super stabilizing reaction of aluminium-eliminating and silicon-replenishing, reacted molecular sieve drops into reactor other end outlet 32 and discharges reactor.Owing to reacting with molecular sieve, along the direction of motion of molecular sieve, the silicon tetrachloride concentration in gas phase reduces gradually.Wherein can control the aperture of outlet 32, material is got rid of with certain speed, produces the solid accumulation of certain altitude on outlet 32 top, avoid excessive silicon tetrachloride to discharge from outlet 32, wherein, the air brought into for drawing silicon tetrachloride and molecular sieve from reactor of gas vent 62.Like this due to the extrusion of silicon tetrachloride, make to introduce the air of reactor under the effect of silicon tetrachloride with molecular sieve, from sieve particle void diffusion to the gas blanket of top, by regular or irregular extraction overhead gas, reacting balance can be conducive to and run.The gas of being drawn by gas vent 62 can reclaim silicon tetrachloride after supercooling, and uncooled gas can be emptying after sponging a small amount of silicon tetrachloride wherein carried.Usually, the molecular sieve thickness on conveyer belt should be not too high, preferably more than 10cm, such as, can be no more than 5cm.

Utilizing power delivery of molecules to sieve can also use circulation piston conveyer to carry, described circulation piston conveyer arranges a circulating conveyor be made up of multiple piston pushing ram at airtight tubular reactor, divide two-layer up and down in tubular reactor, upper strata is to provide molecular sieve and gas phase SiCl ₄after the charging aperture on tubular reactor top enters, push proal space by piston rod, lower floor is to provide the space that piston rod self back moves, and forms the circulating reaction system of a continuous feed like this.

Utilizing power delivery of molecules to sieve can also use pipe chain conveyor to carry, described pipe chain conveyor comprises drive sprocket, corner sprocket, circumversion chain, material containing chain sheet, circulation carrier pipe, charging aperture, discharging opening, circumversion chain is sleeved on drive sprocket and corner sprocket, material containing chain sheet is vertically inserted on circumversion chain, circulation carrier pipe is sleeved on outside circumversion chain, and drive sprocket, corner sprocket, circumversion chain, material containing chain sheet and circulation carrier pipe form a closed mass transport loop.By going out to arrange silicon tetrachloride entrance at molecular sieve entrance, make the direction of motion of silicon tetrachloride substantially identical with molecular sieve.Distance between the transporting chain plate of described pipe chain-linked conveyer can be 1:1 ~ 1:100 with the ratio of reaction tube diameter internal diameter, such as, be 1:2 ~ 1:20.

In the super steady reactor of described gas phase, auger conveyor delivery of molecules preferably can also be utilized to sieve, described auger conveyor includes axle auger conveyor and shaftless screw conveyer, wherein shaftless screw conveyer adopts the design of non-stop layer axle, utilize the integrated steel spiral pushing material with certain flexibility, thus there is anti-entangling strong, the character such as non-stop layer axle interference; Have axle auger conveyor to be utilize spiral steel disc to rotate and then pass the continuous conveying equipment of material, this kind of conveying device can be set to level and also can be set to heeling condition.The pitch of described auger conveyor does not have particular/special requirement, as long as molecular sieve can be made to move in body, such as, can be 1/100 ~ 1/10 of warp in body.

Under preferable case, the body that the super steady reactor of described gas phase is is straight tube.Molecular sieve material can be full of the surrounding of body at least one place in reactor, namely at least one place cross section of body is full of molecular sieve, like this, can seal with molecular sieve, make silicon tetrachloride gas be unlikely to flow in gas-solid separating device because of pressure oscillation is too fast.

4th kind of preferred detailed description of the invention provided by the invention, power and gravity can also be used to combine the conveying carrying out molecular sieve, the present invention is called associating mode of movement, in this kind of situation, the motion of molecular sieve is controlled by gravity and mechanical transmission device, can Molecular regulator sieve time of staying in the reactor by controlling mechanical transmission device, control the reaction time of molecular sieve and silicon tetrachloride.Under which, the reaction of molecular sieve in tubular reactor can be made more even, reduce back-mixing, under associating mode of movement, preferred tubular reactor is straight tube reactor, the axis of body and the angle of horizontal plane are preferably 25 ~ 55 °, like this, not only can realize the super steady reaction of gas phase molecular sieve being carried out to aluminium-eliminating and silicon-replenishing, and mechanical transmission device is stressed less, be convenient to control molecular sieve movement in the reactor, react more evenly good, be conducive to reducing maintenance of equipment.Preferred mechanical transmission device such as circulates piston pusher, pipe chain conveyor, auger conveyor, band conveyor.Preferred body is set to heeling condition, and the axis of body and the angle of horizontal plane are preferably 25 ~ 55 DEG C, can improve the stability of prepared molecular sieve, improve product slates.

The method preparing catalytic cracking catalyst provided by the invention, also comprises gas solid separation and absorption process.Described gas solid separation is used for reacted molecular sieve to be separated with silicon tetrachloride unreacted in gas phase, and remove unreacted silicon tetrachloride in molecular sieve as far as possible, gas solid separation can be carried out in gas-solid separator; Described absorption be used for after gas solid separation gas in silicon tetrachloride absorb, can carry out in absorption tower.The various container that can realize above-mentioned gas solid separation object all can be used as gas-solid separator of the present invention, and the present invention to its shape can there is no particular limitation, such as, can be cylindric.Under further preferable case, the bottom of described gas-solid separator is the taper that end has opening.Thus the molecular sieve obtained can be discharged from described opening.Do not discharge from above-mentioned opening to make the gas component in reacted mixture enter absorption tower as far as possible, under preferable case, the position that described gas-solid separator is connected with discharging opening is higher than the original position of described taper.Under further preferable case, the position that described gas-solid separator is connected with discharging opening is positioned at the middle and upper part of described gas-solid separator, and gas-solid separator is communicated with the absorber that hereafter will describe (or claiming absorption tower) by its open top.

In gas-solid separator, solid molecular sieves and gas separaion, thus obtain high-silica zeolite product.Described gas-solid separator generally comprises charging aperture and top gas outlet.One end of described body is communicated with described gas-solid separator, and the sectional area of described gas-solid separator is greater than the cross-sectional area of described tubular reactor body.By the cross-sectional area making the sectional area of described gas-solid separator be greater than described tubular reactor body, can molecular sieve powder material sedimentation under gravity after realization response, thus realize gas solid separation.Further preferable case, the sectional area of described gas-solid separator is 2-10:1 with the ratio of the cross-sectional area of described tubular reactor body, fully can realize the rapid subsidence of molecular sieve like this.In order to ensure that molecular sieve is fully deposited in gas-solid separator further, the height of the present invention's also preferred described gas-solid separator is not less than 5 meters, such as 5-10 rice.Further under preferable case, the charging aperture of described gas-solid separator is positioned at the middle part of described gas-solid separator, can ensure so on the one hand not produce the molecular sieve be deposited in bottom gas-solid separator to stir, and can also ensure the more sufficient sedimentation time on the other hand.Described reactor and gas-solid separator can be set to micro-negative pressure operation, and the vacuum of such as gas-solid separator can be 100Pa ~ 90KPa, preferred 1kpa ~ 80kpa.

Under further preferable case, described gas-solid separator also comprises bottom solid outlet, for discharging the molecular sieve solid being separated and obtaining.Further under preferable case, described gas-solid separator also comprises the valve opened for controlling described bottom solid outlet and close, thus the molecular sieve solid discharge of will collect in gas-solid separator that can be in good time.

The molecular sieve of discharging gas-solid separator washs, described washing can adopt existing method, such as can wash by decationized Y sieve water or deionized water, usual described washing makes sodium oxide content after washing in molecular sieve not higher than 0.5 % by weight, then molecular sieve washing obtained mixes with matrix pulls an oar, by slurries spraying dry.

In the present invention, the gas of drawing from gas-solid separator gas vent carries out absorbing to remove the silicon tetrachloride wherein carried.As shown in Figure 2, described absorption process is preferably carried out in absorption tower, and absorbent is contained in described absorption tower, for absorbing the SiCl having neither part nor lot in reaction ₄, thus make air reach discharge standard.Absorption tower 3 is for absorbing unreacted SiCl ₄, thus make gas-solid separator 2 gas out reach discharge standard.Described absorption tower 3 can be the various absorption towers that this area routine uses, as long as can absorb SiCl ₄.General use alkali lye such as sodium hydrate aqueous solution absorbs SiCl ₄, water also can be used to absorb.Therefore, in the present invention, described absorption tower 3 preferably includes gas access and absorbing liquid entrance and two outlets, and wherein gas access is communicated with gas-solid separator, is preferably placed at the middle and upper part on described absorption tower.Described two outlets lay respectively at top and the bottom on described absorption tower, are respectively used to emission gases and absorb waste liquid.In order to ensure discharge gas in SiCl ₄content is enough low, and under preferable case, described absorption tower is the multiple of series connection.Multiple absorption towers of series connection are to SiCl ₄form multistage absorption.The gas vent of absorber can connect air-introduced machine.

The super steady reactor of gas phase of the present invention also can comprise heater, to heat the material in reactor.Described heater can adopt conventional mode of heating to realize, described heater can be various heater, such as can by electric furnace heating wire, the reactor Steam Heating/inside reactor coil pipe heating/heat radiation heating/heating using microwave that reactor outer wall is wound around heating tape, reactor outer wall installs heating additional.Under preferable case, in the present invention, described heater can be arranged in described molecular sieve charging aperture, the heat tape of silicon tetrachloride feeding mouth and tube wall and/or inside, steam jacket, spiral heater one or more.Described heat exchanger also can adopt conventional heat exchange mode to realize, such as, use water vapour and solid SiCl ₄carry out heat exchange, or carry out heat exchange with other steam heats.Heater is set, the temperature of material in tubular reactor can be controlled, thus the requirement of molecular sieve feeding temperature is reduced, and can according to the requirement to final aluminium-eliminating and silicon-replenishing molecular sieve, control realization tubular reactor is interior identical or different to discharging opening each several part temperature from charging aperture.Also can not heater be set, utilizes molecular sieve and SiCl ₄reaction heat carry out the regulation and control of reactor content temperature, such as regulatory molecule sieve and SiCl ₄inlet amount ratio, device flow process can be simplified.By controlling molecular sieve and gas phase SiCl ₄different Contact Temperatures, and then the zeolite product that can obtain different dealumination depth.

In order to the temperature in tubular reactor can be controlled more accurately, under preferable case, described heater is electric heater is such as heat tape or electric furnace heating wire, and described heat tape is many, simultaneously, body is divided into multistage, is wound around a heat tape or electric furnace heating wire respectively at the outer wall of every section of body.So just can respectively at the inside set temperature measurement mechanism of body, the temperature requirement reacted according to aluminium-eliminating and silicon-replenishing and temperature measuring equipment record the actual temperature of this section of body, by controlling the heat tape electric current and the voltage that are wrapped in every section of tube wall, realize controlling the temperature in every section of body.Such as, the length of every section of body can be 2-20 rice, is preferably 2-8 rice.

To molecular sieve and gas phase SiCl ₄contact Temperature control, can to the temperature of molecular sieve and the gas phase SiCl entering reactor ₄temperature without any requirement, can be molecular sieve and the gas phase SiCl of arbitrary temp ₄.In order to enable reaction at molecular sieve and gas phase SiCl ₄carry out fast after contact, the temperature that the present invention preferably introduces the described molecular sieve of the super steady reactor of described gas phase is 200-600 DEG C, SiCl ₄temperature be 60-150 DEG C.Because the temperature of the molecular sieve after roasting is generally more than 300 DEG C, therefore the temperature of above-mentioned molecular sieve can obtain by being combined with roaster by reactor when reacting and starting, that is, under preferable case, described molecular sieve is just from the molecular sieve that roaster is discharged, the thermal source that after such one side can utilize roasting, the high temperature of molecular sieve reacts as dealumination complement silicon, starts dealumination complement silicon reaction, thus economize energy; The time of heating molecular sieve can also be saved on the other hand, thus reaction can fully be carried out in the short period of time.

Below in conjunction with Fig. 2, method provided by the invention is described further.Temperature is gas phase SiCl after the molecular sieve a of 200-600 DEG C and heat exchange ₄raw material b sends in tubular reactor 1 (reactor can arrange or not arrange heater) respectively, molecular sieve and gas phase SiCl ₄haptoreaction in tubular reactor 1, and move to outlet molecular sieve direction, heater by being arranged on tube wall and/or inside heats tubular reactor 1, to adjust reaction temperature in tubular reactor 1 for 250-700 DEG C, enter gas-solid separator 2 afterwards, in gas-solid separator 2, the high-silica zeolite c be obtained by reacting is deposited in the bottom of gas-solid separator 2, directly or regularly discharge, introduce washer 4 to wash, then introducing filtration and drying system 6 carry out filtering and drying, then pulping device 5 is introduced, pull an oar with the matrix g introducing pulping device 5 is mixed, then nodulizer such as spray dryer granulation is introduced, unreacted gas phase SiCl ₄then enter in absorption tower 3 by the outlet at gas-solid separator 2 top, contact with the such as alkali lye of the absorbent in absorption tower 3, tail gas d overflows from alkali lye, discharges, SiCl from the outlet at top, absorption tower 3 ₄then with alkaline reaction, directly or regularly discharge waste water e by outlet at bottom afterwards.

The method preparing molecular sieve provided by the invention may be used for carrying out gas phase dealumination complement silicon to various molecular sieve, and such as described molecular sieve can be Y zeolite, and the content of rare earth of described Y zeolite can be 0 ~ 18 % by weight, silica alumina ratio (SiO ₂/ Al ₂o ₃mol ratio) can be 4 ~ 6.

The molecular sieve that method provided by the invention obtains can be used for preparing catalytic cracking catalyst, prepares other raw materials such as catalytic cracking catalyst matrix used and method of operating can adopt technology well known in the art to carry out.Described matrix such as conventional do in binding agent prepared by catalytic cracking catalyst, clay one or more.Such as, described with the gross weight of catalytic cracking catalyst for benchmark, the content of molecular sieve described in the catalyst obtained is 5-50 % by weight, and with the content of oxide basis binding agent for 0.5-50 % by weight, the content of clay is 5-90 % by weight.Described binding agent can be one or more in aluminium oxide, hydrated alumina, Alumina gel, Ludox, silica-alumina gel, silicon-aluminum sol and their precursor, and described clay can be one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite.The method of described making beating and granulation all can adopt the making beating of this area routine use and the method for granulation, and the present invention does not repeat them here.

The following examples will be further described the present invention, but not thereby limiting the invention.

Embodiment 1-3 is for illustration of the method preparing molecular sieve provided by the invention.

Embodiment 1

The molecular sieve gas phase shown in stainless steel construction drawing 2 that the industrial trade mark that thickness is 3 millimeters is NiCr18Ti is used to mend silicon equipment, wherein the top of gas-solid separator 2 is diameter is 6 meters, height is 14 meters cylindrical, bottom is for having opening taper, cone angle is 45 °, and opening part is provided with valve, discharging opening is positioned at the position apart from 1 meter, gas-solid separator top, the sodium hydrate aqueous solution that concentration is 10 mol/L is filled in absorption tower 3, by tubes connection between absorption tower 3 and gas-solid separator 2, conduit gos deep in sodium hydrate aqueous solution.

Reactor 1 is tubular reactor, it as shown in Figure 5, body total length 80 meters, pipe diameter 0.8 meter, the body of reactor makes ring-type, reactor comprises upper strata straight-tube portion and lower floor's straight-tube portion, levels straight tube level is installed, axis and horizontal plane angle are 0 °, on, the two ends of lower floor's straight tube are communicated with bend pipe respectively, each bend pipe is semicircle, the length of each bend pipe is 6 meters, levels straight-tube portion is 34 meters, thus make body on the whole circlewise, band conveyor 52 is placed on ring-type tubular body, the upper strata of ring-type body one end arranges the first charging aperture 12(molecular sieve charging aperture), at a distance of the downstream of 2 meters, the second charging aperture 22 is set, the upper strata of the ring-type body other end arranges air-vent 62, and lower floor arranges discharging opening 32, and air-vent 62 connects a gas-solid separator, prevents molecular sieve from losing from air-vent.Molecular sieve is carried on belt conveyor, and ribbon conveyer uses etch-proof metal belt, and metal tape width is no better than ring-type pipe diameter.As shown in Figure 5, molecular sieve enters the body of reactor from the first charging aperture 12 of reactor left upper part, fall on the conveyer belt 52 in reactor body upper strata, move right with conveyer belt, silicon tetrachloride gas enters in reactor from the second charging aperture and silicon tetrachloride feeding mouth 22, flow in direction on the whole to gas outlet 62, in the process of movement, the super stabilizing that silicon tetrachloride gas and molecular sieve carry out aluminium-eliminating and silicon-replenishing reacts, concentration reduces gradually, when arriving gas outlet 62 place, silicon tetrachloride concentration in gas phase is reduced to very low, aluminium-eliminating and silicon-replenishing reaction rate also reduces greatly, also air port is cited approvingly from gas outlet 62() draw gas, molecular sieve, then along with conveyer belt enters pipe bent position and conveyer belt departs from, discharges the super steady reactor of gas phase by outlet molecular sieve 32 subsequently.Conveyer belt after being separated with molecular sieve is then turned back to molecular sieve porch through the body of lower floor.

By the temperature from roaster be 350 DEG C the Y zeolite containing rare earth (solid content 98.5 % by weight, content of rare earth is 15.0 % by weight, silica alumina ratio 5.26, sodium oxide content 4.8 % by weight, lower with) and temperature be the SiCl of 90 DEG C ₄gas is sent in the body of tubular reactor 1 continuously by the first charging aperture 12 and the second charging aperture 22 respectively, the ring-type body of tubular reactor is divided into 10 sections simultaneously, every segment length 10 meters, outer wall on every section of body is wound around a heat tape and heats tubular reactor, the temperature of in tubular reactor 1 each section is made to be 400 DEG C, SiCl ₄flow controlled and SiCl by mass flowmenter ₄be 0.25 with the weight ratio of molecular sieve, the inlet amount of molecular sieve is 800kg/ hour, and the time of staying of molecular sieve in tubular reactor 1 is 10 minutes.After reaction carries out 1.5 hours, the opening of the molecular sieve in gas-solid separator 2 from conical lower portion is discharged, pull an oar with decationized Y sieve water afterwards, wash, filter and after drying in 120 DEG C of baking ovens, obtain high-silica zeolite A, its main character is listed in table 1.On conveyer belt, molecular sieve thickness is about 2cm.In order to make the thickness of molecular sieve be unlikely to too high and uneven, can mounting limit plate in reactor body, by controlling the distance of limiting plate distance from bottom conveyer belt, the thickness of molecular sieve layer on conveyer belt can be controlled.

Embodiment 2

The tube length of tubular reactor 1 60 meters, for straight tube, body reactor axis and horizontal plane angle at 45 °, pipe diameter (internal diameter) 1 meter, gravity is utilized to carry as shown in Figure 3, body tilts 45 °, the end face distance that molecular sieve entrance center distance and position is higher is 1 meter, silicon tetrachloride entrance is 2.5 meters apart from the distance of this end face, (this rotating part total length is 53 meters to body mid portion, distance entrance one end end face 4 meters) rotate with the speed of 5r/min, the rotatable partial interior of body arranges three pieces of flights 11, the width of flight is 5cm, be parallel to body axis, it is vertical with the section of tube wall intersection with crossing, and weld two pieces of weir plates 21 at inboard wall of tube body simultaneously, wherein first piece of weir plate is 30 meters apart from the end face of molecular sieve entrance one section, and second piece of weir plate is apart from this end face 55 meters, distance other end is about 5 meters, two pieces of weir plates are toroidal, are highly 8cm, perpendicular to body axis.Body one end arranges charging aperture 31, at a distance of 1.5 meters, the second charging aperture 41 is set, the body other end arranges discharging opening 51 and air-vent 71, in the middle of body, a heat insulation cylinder 61 is also set, its external diameter (diameter) is 60cm, length is identical with tube length, is used for reducing the loss of heat, and the super steady reaction of gas phase is evenly carried out.

Shown in Fig. 3, to be the Y zeolite (solid content 98.5 % by weight, content of rare earth is 15.0 % by weight, silica alumina ratio 5.26, sodium oxide content 4.8 % by weight) containing rare earth of 300 DEG C and temperature by the temperature from roaster the be SiCl of 80 DEG C ₄gas is sent in the body of tubular reactor 1 continuously by the first charging aperture 31 and the second charging aperture 41 respectively, the body of tubular reactor is divided into 12 sections simultaneously, every segment length 5 meters, outer wall on every section of body is wound around a heat tape and heats tubular reactor, the reaction temperature of tubular reactor 1 is made to be 300 DEG C (outlet molecular sieve place temperature), SiCl ₄flow controlled and SiCl by mass flowmenter ₄be 0.05 with the weight ratio of molecular sieve, the inlet amount of molecular sieve is 1000kg/ hour, and the time of staying of molecular sieve in tubular reactor 1 is 5 minutes.After reaction carries out 1 hour, the opening of the molecular sieve in gas-solid separator 2 from conical lower portion is discharged, pull an oar with decationized Y sieve water afterwards, wash, filter and after drying at 120 DEG C, obtain high-silica zeolite B, its main character is listed in table 1.

With auger conveyor or pipe chain conveyor delivery of molecules sieve in the reactor body described in embodiment 2, do not arrange described heat insulation cylinder 61 in body, described body rotates or does not rotate, and can reach same reaction effect.In its body, described weir plate and flight are not set.

Embodiment 3

As shown in Figure 6, the molecular sieve conveying of the super steady reactor of gas phase relies on gravity transfer to the super steady reaction unit of gas phase.Reactor comprises molecular sieve entrance 5, gas phase silicon tetrachloride entrance 6, the body 1 of reactor is straight tube, comprise molecular sieve arrival end 12, rotatable portion 11 and outlet molecular sieve end 13, molecular sieve arrival end 12 and outlet molecular sieve end 13 are supported by bracing or strutting arrangement 9, drive unit 3 rotates around the axis of body 1 in order to drive rotatable portion 11, and bracing or strutting arrangement 2 is for supporting rotatable portion 11.Rotatable portion is provided with flight 8 and weir plate 7, the junction of rotatable portion 11 and molecular sieve arrival end 12 and outlet molecular sieve end 13 is for being flexibly connected, and seal with the external world, the outlet of molecular sieve is arranged on the end face of the port of export 13, end face arranges baffle plate, can the size of Molecular regulator sieve outlet by controllable register;

A kind of embodiment, body is circular straighttube, wherein tube length 12 meters, the length of rotatable portion 11 is 9 meters, the length of molecular sieve feed end 12 is 1.8 meters, the length of molecular sieve discharge end 13 is 1.2 meters, body 1 diameter (internal diameter) 0.8 meter, body axis and horizontal plane angle are 35 °, the rotatable portion 11 of body 1 rotates with the speed of 5r/min, tubular body arranges three pieces of flights 7, flight height is 5cm, flight parallels to the axis setting, and perpendicular to crossing the tube wall tangent plane of flight and tube wall contact wire, two pieces of weir plates 7 are welded at inboard wall of tube body, its plate face is perpendicular to the axis of body 1, be highly 6cm, the distance of one piece of weir plate distance molecular sieve entrance one end end face is 3 meters, other one piece of weir plate is 6 meters apart from the distance of aforementioned weir plate, wherein Fig. 7 is the schematic diagram in A-A cross section in Fig. 6.

Reactor tube body axis becomes 55 ° with horizontal plane angle, pipe diameter (internal diameter) 0.5 meter, the top of gas-solid separator 2 is diameter is 6 meters, height is 14 meters cylindrical, bottom is for having opening taper, and cone angle is 45 °, and opening part is provided with valve, discharging opening is positioned at the position apart from 1 meter, gas-solid separator top, fill the sodium hydrate aqueous solution that concentration is 10 mol/L in absorption tower 3, by tubes connection between absorption tower 3 and gas-solid separator 2, conduit gos deep in sodium hydrate aqueous solution.

By the temperature from roaster be 300 DEG C be the SiCl of 80 DEG C containing the Y zeolite (solid content 98.5 % by weight, content of rare earth is 15.0 % by weight, silica alumina ratio 5.26, sodium oxide content 4.8 % by weight) of rare earth and temperature ₄gas is sent in the body 1 of tubular reactor continuously by molecular sieve entrance 5 and gas phase silicon tetrachloride entrance 6 respectively, be wound around electric furnace heating wire at the outer wall of the rotatable portion 11 of body to heat tubular reactor, controlling reaction temperature is 300 DEG C (reactor outlet molecular sieve temperature), SiCl ₄flow controlled and SiCl by mass flowmenter ₄be 0.08 with the weight ratio of molecular sieve, the inlet amount of molecular sieve is 1000kg/ hour, and the time of staying of molecular sieve in tubular reactor is 5 minutes.After reaction carries out 1 hour, the opening of the molecular sieve in gas-solid separator 2 from conical lower portion is discharged, pull an oar with decationized Y sieve water afterwards, wash, filter and after drying at 120 DEG C, obtain high-silica zeolite C, its main character is listed in table 1.

With auger conveyor or pipe chain conveyor delivery of molecules sieve in the reactor body described in embodiment 3, described heat insulation cylinder 61 is not set in body, described body rotates or does not rotate, better reaction effect can be reached, without the need to arranging described weir plate and flight in its body, the angle of body axis and horizontal plane is 0 ~ 70 °.

Comparative example 1

Molecular sieve E is prepared according to method disclosed in CN102049315A embodiment 1, and be divided into every 5 meters and be one section heating tape is set, it is heated, its reaction temperature and reaction time are 300 DEG C and 5 minutes with embodiment 3, the ratio of silicon tetrachloride and molecular sieve is 0.3, inlet amount is 1 ton/hour, obtains molecular sieve E, and its character is in table 1.Visible, under same reaction temperature and time, the present invention can obtain better dealuminzation effect, greatly saves silicon tetrachloride consumption.

Comparative example 2

The silicon tetrachloride of comparative example 1 and the weight ratio of molecular sieve are adjusted to 0.16, obtain molecular sieve and be designated as F, its character is in table 1.

Table 1

From the results shown in Table 1, compared with industrial REY, the framework si-al ratio of the molecular sieve adopting method provided by the invention to obtain and SiO ₂/ Al ₂o ₃mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition, from the results shown in Table 1, compared with industrial REY, the relative crystallinity of the molecular sieve adopting method provided by the invention to obtain, lattice collapse temperature and specific area significantly improve, sodium oxide content obviously reduces, and shows the excellent performance of the molecular sieve that equipment provided by the invention obtains.

Embodiment 4-6

For illustration of the high-silica zeolite Kaolinite Preparation of Catalyst adopting embodiment 1-3 obtained.

According to (material butt) molecular sieve: kaolin: boehmite: the part by weight of Alumina gel=38:30:22:10 is by above-mentioned mixing of materials, making beating, and then spraying dry at 450 DEG C, obtains spherical catalyst Cracking catalyst.High-silica zeolite A, B and C that molecular sieve selects embodiment 1-3 obtained respectively, obtain catalyst A-1, A-2 and A-3 respectively, its main character is listed in table 2.

Comparative example 3

Adopt industrial REY type molecular sieve catalyst according to the method described above, industry REY type molecular sieve obtained through twice rare earth exchanged and bakes to burn the article by NaY molecular sieve, its main character is listed in table 1, and gained catalyst gauge is reference catalyst CC-1, and its main character is listed in table 2.

Comparative example 4

According to the method Kaolinite Preparation of Catalyst of embodiment 6, be molecular sieve E unlike molecular sieve used, obtain catalyst CC-2.

The Catalytic Cracking Performance test of catalyst.

Light oil microactivity is evaluated: adopt the standard method of RIPP92-90 (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes) light oil microactivity of assess sample, catalyst loading amount is 5.0g, reaction temperature is 460 DEG C, and feedstock oil is the huge port light diesel fuel of boiling range 235-337 DEG C, and product composition is by gas chromatographic analysis, calculate light oil microactivity according to product composition, result in table 2.

Light oil microactivity (MA)=(lower than the gasoline production+gas yield+coke output of 216 DEG C in product)/charging total amount × 100%

Residual oil cracking performance evaluation condition: catalyst is first at 800 DEG C, 100% steam aging 12 hours, then fixed fluidized bed at ACE() device to be evaluated, feedstock oil is military mixed three heavy oil (character is in table 3), and reaction temperature 500 DEG C, agent weight of oil ratio is 4.

Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield

Yield of light oil=yield of gasoline+diesel yield

Liquid yield=liquefied gas+gasoline+diesel oil

Coke selectivity=coke yield/conversion ratio

The Catalytic Cracking Performance of the catalyst of Evaluation operation example 4-6 and comparative example 3,4 preparation respectively, the results are shown in table 4 according to the method described above.

Table 2

From the results shown in Table 2, when adopting the molecular sieve catalyst obtained by method provided by the invention, compared with REY molecular sieve catalyst, pore volume and the specific area of gained catalyst obviously increase, and micro-activity significantly improves.Compared with the catalyst that the method for carrying with existing carrier gas obtains, performance is not deteriorated, even better.

Table 3

Table 4

Catalyst	A-1	A-2	A-3	CC-1	CC-2
						Product slates, % by weight
Dry gas	1.03	1.05	1.04	1.23	1.18
						Liquefied gas	12.08	12.69	12.21	13.01	14.29
Coke	5.28	5.09	5.11	5.75	5.44
						Gasoline	56.88	57.22	56.48	47.17	52.76
Diesel oil	18.79	18.01	18.67	19.91	17.95
						Heavy oil	5.94	5.94	6.49	12.93	8.38
Add up to	100	100	100	100	100
						Conversion ratio, % by weight	75.27	76.05	74.84	67.16	73.67
Coke selectivity, % by weight	7.01	6.69	6.83	8.56	7.38
						Yield of light oil, % by weight	75.67	75.23	75.15	67.08	70.71
Liquefied gas+gasoline+diesel oil, % by weight	87.75	87.92	87.36	80.09	85

From the results shown in Table 4, compared with reference catalyst CC-1, adopt, by catalyst provided by the invention, there is higher conversion ratio, higher yield of light oil and liquid yield, lower coke selectivity.Compared with CC-2, the inventive method is when silicon tetrachloride consumption significantly reduces, and the catalyst obtained has higher yield of light oil and liquid yield.

Claims

1. prepare the method for catalytic cracking catalyst for one kind, the method comprises: be incorporated into by molecular sieve in the super steady reactor of gas phase, make molecular sieve move to the outlet molecular sieve of the super steady reactor of gas phase from the molecular sieve entrance of the super steady reactor of gas phase when carrying without carrier gas, and with gas phase SiCl ₄haptoreaction in the super steady reactor of gas phase, washs reacted molecular sieve, mix with matrix pull an oar, granulation; Wherein by making the molecular sieve in the super steady reactor of the described gas phase of introducing move under the effect of mechanical transmission device and/or gravity, realize making molecular sieve move to the outlet molecular sieve of the super steady reactor of gas phase from the molecular sieve entrance of the super steady reactor of gas phase when carrying without carrier gas; The super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride import, reactor body and outlet molecular sieve, and the angle of described reactor tube body axis and horizontal plane is 0 ~ 90 °.

2. in accordance with the method for claim 1, it is characterized in that, in the super steady reactor of described gas phase, molecular sieve and gas phase SiCl ₄the temperature of contact is 250-700 DEG C, and described molecular sieve is 10 seconds to 100 minutes in the reaction time of the super steady reactor of described gas phase.

3. in accordance with the method for claim 1, it is characterized in that, the described molecular sieve that makes when carrying without carrier gas moves to the outlet of the super steady reactor of gas phase from the molecular sieve entrance of the super steady reactor of gas phase, realizes by using ribbon conveyer, pipe chain conveyor, conveying worm, circulation piston conveyer, tubular type gravity conveyor or combination multiple in them.

4. in accordance with the method for claim 1, it is characterized in that, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride import, reactor body and outlet molecular sieve, and the position of molecular sieve entrance is higher than described outlet molecular sieve position.

5. according to the method described in claim 1 or 4, it is characterized in that, described molecular sieve and silicon tetrachloride share material inlet, or molecular sieve entrance and silicon tetrachloride import are in same one end of the super steady reactor of described gas phase.

6. in accordance with the method for claim 4, it is characterized in that, the length of described reactor body is 3 ~ 100:1 with the ratio of reactor pipe diameter internal diameter.

7. in accordance with the method for claim 1, it is characterized in that, the super steady reactor of described gas phase is by molecular sieve entrance, silicon tetrachloride import, reactor body and outlet molecular sieve composition, described reactor tube body axis and the angle of horizontal plane are 30 ~ 90 °, molecular sieve entrance is in higher one end, described reactor tube body position, outlet molecular sieve is positioned at lower one end, described reactor tube body position, outlet molecular sieve is communicated with gas-solid separating device, the distance of silicon tetrachloride import and molecular sieve entrance is greater than the distance of silicon tetrachloride import and outlet molecular sieve, described molecular sieve relies on the effect of gravity to move in the reactor.

8. in accordance with the method for claim 7, it is characterized in that, the angle of described reactor tube body axis and horizontal plane is 40 ~ 80 °.

9. in accordance with the method for claim 1, it is characterized in that, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride import, reactor body and outlet molecular sieve, and being set at least partially of reactor body can be rotated around the axis of body.

10. in accordance with the method for claim 9, it is characterized in that, described reactor body is straight tube, and can rotating around reactor tube body axis at least partially of described reactor body, velocity of rotation is 0.05 ~ 40 rev/min.

11. in accordance with the method for claim 9, it is characterized in that, the part that the super steady reactor of described gas phase can rotate around reactor tube body axis comprises weir plate and flight.

12. in accordance with the method for claim 9, it is characterized in that, the angle of described reactor tube body axis and horizontal plane is 5 ~ 80 °.

13., according to the method described in any one of claim 9 ~ 12, is characterized in that, have sleeve pipe in described reactor body, haptoreaction in described molecular sieve and the annular space of silicon tetrachloride between reactor body and sleeve pipe.

14. in accordance with the method for claim 13, it is characterized in that, described sleeve outer is 1/4 ~ 3/4 with the ratio of described reactor internal diameter of tube body.

15. in accordance with the method for claim 1, it is characterized in that, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride import, reactor body and outlet molecular sieve, be provided with mechanical transmission device in described reactor body, described mechanical transmission device can make molecular sieve move to outlet molecular sieve from the molecular sieve entrance of the super steady reactor of gas phase.

16. in accordance with the method for claim 15, it is characterized in that, described mechanical transmission device is one or more in ribbon conveyer, piston conveyer, pipe chain conveyor or conveying worm.

17., according to the method described in claim 15 or 16, is characterized in that, described reactor tube body axis and the angle of horizontal plane are 0 ~ 70 °.

18. in accordance with the method for claim 17, it is characterized in that, described reactor tube body axis and the angle of horizontal plane are 25 ~ 55 °.

19. in accordance with the method for claim 1, it is characterized in that, the super steady reactor of described gas phase is tubular reactor, it comprises molecular sieve entrance, silicon tetrachloride import, reactor body and outlet molecular sieve, described reactor tube body length is 5 ~ 200 meters, and reactor pipe diameter internal diameter is 0.1 ~ 6 meter.

20. in accordance with the method for claim 19, it is characterized in that, described reactor pipe diameter internal diameter is 0.2 ~ 1.5 meter.

21., according to the method described in claim 1 or 20, is characterized in that, the flow of molecular sieve is 50-2000kg/ hour.

22. in accordance with the method for claim 10, it is characterized in that, described velocity of rotation is 0.1 ~ 15 rev/min.