CN103787353B - A kind of equipment preparing molecular sieve - Google Patents

Abstract

A kind of equipment preparing molecular sieve, comprise: the super steady reactor of NaY molecular sieve switch, stoving oven, gas phase and gas-solid separating device, the super steady reactor of wherein said gas phase comprises molecular sieve entrance, outlet molecular sieve, silicon tetrachloride entrance, the super steady reactor of described gas phase can 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 makes molecular sieve and gas phase silicon tetrachloride contact reacts in the super steady reactor of gas phase.This device may be used for serialization and prepares high-silica zeolite, can simplification of flowsheet, without the need to using the carrier gas of fluidisation molecular sieve, and greatly can reduce the consumption of silicon tetrachloride.

Description

A kind of equipment preparing molecular sieve

Technical field

The present invention relates to a kind of equipment preparing molecular sieve, relate to a kind of equipment and the application thereof that utilize gas chemistry method aluminium extracting and silicon supplementing method production molecular sieve furtherly.

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 silicofluoride method aluminium-eliminating and silicon-replenishing, hydrothermal method and gas chemistry method aluminium-eliminating and silicon-replenishing (the present invention is called the super steady method of gas phase).

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

Hydrothermal 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 active centre, also affects the further raising of its thermostability.

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 treatment 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 purge, 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 conversion unit, this equipment as shown in Figure 1, comprise a reactor (1), an opening for feed (2) and an air outlet (3), an agitator (4) is also comprised in the inside of reactor (1), air 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 agitator arm 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 tetracol phenixin, the silica alumina ratio of the described y-type zeolite containing rare earth is 3-8, lattice constant is 2.45-2.48nm.Obviously, duration 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 mode of operation 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, aforesaid method all needs very numerous and diverse manual operation, such as: hand charging, manual cleaning and need long scavenging 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 operator.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 catalyzer, 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 state, molecular sieve and gas phase SiCl ₄duration 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 ₄contact reacts 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 ₄contact reacts 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 materials conveying and the super steady reaction depth of gas phase, in addition, the method needs larger large SiCl to reach certain level of response 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 technical problem to be solved in the present invention is to provide a kind of device of Na type molecular sieve high-silica zeolite, and this device can be used for preparing high-silica zeolite by NaY molecular sieve continuous prodution, can reduce the SiCl of gas chemistry legal system for high-silica zeolite ₄consumption.

The invention provides a kind of equipment preparing molecular sieve, comprise: Na type molecular sieve switch, stoving oven, the super steady reactor of molecular sieve gas phase and gas-solid separating device, wherein Na type molecular sieve switch is in order to exchange Na type molecular sieve, stoving oven is used for carrying out roasting to exchanged molecular sieve, the super steady reactor of molecular sieve gas phase is in order to carry out gas chemistry dealumination complement silicon reaction (the present invention is also referred to as the super steady reaction of gas phase) to baked molecular sieve, gas-solid separator is used for the molecular sieve of discharging from the super steady reactor of gas phase to be separated with the silicon tetrachloride of unreacted device, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride entrance and outlet molecular sieve, and the super steady reactor of described gas phase can make introducing molecular sieve wherein move to outlet molecular sieve when carrying without carrier gas from molecular sieve entrance.

Preferably, the molecular sieve discharge port of described stoving oven is communicated with the molecular sieve opening for feed of the super steady reactor of described meteorology, makes the molecular sieve after the roasting obtained from stoving oven directly introduce the super steady reactor of gas phase and reacts, realize the continuous seepage of molecular sieve.Without the need to first storing by molecular sieve cooling packing or by molecular sieve, and then intensification feeds intake.The super steady reaction unit of gas phase of the present invention sieves owing to not needing rare gas element delivery of molecules, can realize the super steady reactor of described gas phase easily and be connected with stoving oven.

Described molecular sieve switch can adopt existing molecular sieve switch, comprise the molecular sieve filter device (the present invention is also referred to as the second filtration unit) after interchanger, exchange, wherein can also comprise the first drying installation, the first described drying installation carries out drying in order to the molecular sieve obtained by the molecular sieve filter device after exchange, then dried molecular sieve is introduced stoving oven roasting, the molecular sieve after the exchange that also described filtration unit can be obtained directly introduces stoving oven roasting without drying.Molecular sieve filter device after described exchange is band filter, the present invention is called the second belt filter, owing to using belt filter, can filter continuously, described filtration unit can directly be connected with interchanger, and the second described belt filter can directly be connected with stoving oven.

Because described Na type molecular sieve can be purchased or obtain according to existing method.In time preparing according to existing method, generally include crystallization synthesis, crystallization synthetic product is filtered, filter the filtration cakes torrefaction that obtains or do not comprise and be drying to obtain Na type molecular sieve.Usually, described equipment also comprises the filtration unit (the present invention claims the first filtration unit) filtered for crystallization synthetic product, the first preferably described filtration unit is belt filter (the present invention is called the first band filter), and the drying installation the present invention for the first filtration unit filtration cakes torrefaction is called the second drying installation.First band filter, interchanger, the second band filter, the second drying installation are communicated with successively with stoving oven, make described Na type molecular sieve once be undertaken exchanging and roasting by described device, then enter the super steady reactor of gas phase and carry out aluminium-eliminating and silicon-replenishing reaction.

The present invention also provides a kind of method preparing molecular sieve, the equipment of molecular sieve that what the method utilized the invention described above to provide prepare, comprise: Na type molecular sieve is exchanged in switch, then introduce roasting kiln roasting and the product of roasting after roasting is introduced in the super steady reactor of described gas phase and react with the silicon tetrachloride of the super steady reactor of gas phase described in introducing.

The method preparing molecular sieve provided by the invention, molecular sieve roasting obtained is incorporated 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 ₄contact reacts in the super steady reactor of gas phase.Described catalytic condition comprises: the molecular sieve solid content introducing 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 procedure, 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 residence time 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 ₄contact reacts.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 ₄spatial movement, 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.There is in reactor higher molecular sieve concentration, greatly can reduce the volume of reactor, and owing to not needing the carrier gas introducing delivery of molecules sieve, without gas dilution or carry silicon tetrachloride, the heat that carrier gas is taken away and the purification expense reducing carrier gas greatly can be reduced; Surprisingly, speed of reaction can be accelerated, Reaction time shorten, and can improve the degree of depth of the super steady reaction of gas phase, the homogeneity of product is better in addition.

The method preparing molecular sieve provided by the invention, by molecular sieve and SiCl ₄send into continuously in the super steady reactor of gas phase, by action of gravity and/or provide power to make molecular sieve fully be expelled to gas-solid separator from discharge port 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 materials 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 ₄contact reacts carry out continuously; By controlling mass transport speed or/and the length of reactor, the residence time 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 ₄contact reacts evenly carry out fully in tubular reactor; By using the tubular reactor or regulatory molecule sieve and SiCl that are provided with well heater ₄add-on ratio, can control different temperature of reaction, thus can control differential responses condition and level of response, and then can obtain the zeolite product of different dealumination depth.

Compared with the super steady technique of existing autoclave gas phase, the equipment preparing molecular sieve provided by the invention is in the super steady reaction process of gas phase, the super steady reaction of serialization gas phase can be realized, and operation can all automatization serializations carry out, hand labor intensity is little, and production efficiency is high, product performance 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 mode of operation of break tour, also the high-silica zeolite of 1200kg can be produced every day at the most, and adopt aforesaid device 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.Compare with the super steady reaction process of existing continous way gas phase, the present invention adopts e Foerderanlage reactor can allow the SiCl of molecular sieve and vaporization ₄gas directly contacts in high reaction temperatures 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 times 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 catalyzer 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 5 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 cylindrical shell shown in embodiment 3 and the schematic diagram of weir plate, wherein 7 is weir plate, and 8 is flight, and 1 is body.

Fig. 8 is a kind of novel Zeolite Calciner provided by the invention.

Fig. 9 is a kind of coupling device being communicated with described stoving oven and the super steady reactor of gas phase provided by the invention.

Embodiment

The method preparing molecular sieve 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 molecular sieve, then silicon tetrachloride can be introduced in reactor vaporization in the reactor with liquid phase and react with molecular sieve, but in order to make reaction evenly, is incorporated in the super steady reactor of gas phase after preferred silicon tetrachloride vaporization.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 fluidized-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 e Foerderanlage.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, endless belt conveyor, pipe chain conveyer, worm conveyor, circulation piston handling machinery, 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 an opening for feed, can make molecular sieve and SiCl ₄send in the body of reactor by this opening for feed, 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 stoving oven sieves, and that is, this opening for feed is communicated with stoving oven usually, therefore, preferable case, the super steady reactor of described gas phase also comprises silicon tetrachloride feeding mouth (the second opening for feed), and described silicon tetrachloride feeding mouth is positioned at position adjacent with described molecular sieve opening for feed (the first opening for feed) on body; Described silicon tetrachloride feeding mouth can be in the position of molecular sieve opening for feed upstream, also can be in the position in molecular sieve opening for feed downstream, and preferably, silicon tetrachloride feeding mouth is in the position in molecular sieve opening for feed downstream.Described upstream and downstream is for molecular sieve travel 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 isomorphous substitution 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 equipment preparing molecular sieve provided by the invention, the super steady reactor of described gas phase can be tubular reactor (also claiming tubular reactor), comprise molecular sieve entrance, body, molecular sieve e Foerderanlage and outlet molecular sieve and silicon tetrachloride entrance, or also comprise gas outlet.During use, 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 spiral tube; The cross section of described body can be different shape, and be such as square, circular, Polygons, described body is preferably pipe.

According to the equipment preparing molecular sieve provided by the invention, the super steady reactor of described gas phase can be tubular reactor, the super steady reactor of described tubular type gas phase comprises body, opening for feed and discharge port, and wherein opening for feed and discharge port 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 opening for feed, with silicon tetrachloride contact reacts, the molecular sieve reacting complete discharges reactor from molecular sieve discharge port, 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 or by mechanical transport effect, such as, endless belt conveyor, pipe chain conveyer, worm conveyor, circulation piston handling machinery, 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.Described molecular sieve and gas phase SiCl ₄duration 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 preferably not less than 1, and being 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 the tubular reactor of 5 ~ 130 meters of such as 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 state 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 °.

The body of described tubular reactor 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 or the pipeline of broken line, linear pattern pipeline 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 residence time 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 and/or by mechanical transport 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 handling machinery 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.

Described Na type molecular sieve switch, preferably includes interchanger and the second filter, and described interchanger can for realizing any device that molecular sieve and exchange liquid carry out exchanging.Described interchanger can be swap tank, it is such as container that is circular or grooved, molecular sieve entrance is set at top and exchanges liquid entrance, molecular sieve pulp outlet is set in bottom, the slurries of drawing from outlet introduce the second filter filtration, the exchange area that also can arrange on belt filter, by molecular sieve to be exchanged as on belt filter, with the drip washing of exchange liquid.The described preferred vacuum band-type filter machine of the second filter.Such as described swap tank can be cylindric tank, and can there be conical head bottom.Preferably its aspect ratio ratio of diameter internal diameter (height with) is preferably not less than 1:1, and be such as 1:1 ~ 5:1, the entrance of its molecular sieve entrance and exchange liquid is all arranged at the top of tank, and the outlet of its molecular sieve pulp is arranged on the bottom of tank.The exchange of described NaY molecular sieve can as required, and one or more such as using in ammonium salt (such as ammonium sulfate, ammonium nitrate, ammonium chloride), rare-earth salts (such as rare earth nitrate, rare earth chloride) exchange.Use belt filter, the exchange process of molecular sieve can be made to realize continuous seepage, and realize to the continuous Automatic-feeding of stoving oven.

Na type molecular sieve provided by the invention can be purchased, or prepare according to existing method, in time preparing according to existing method, (filter the present invention used is called the first filter to generally include synthesized gel rubber, crystallization and filtration, preferred vacuum band-type filter machine), dry (moisture eliminator the present invention used is called the second moisture eliminator) or moistly obtain Na type molecular sieve.

Described stoving oven is in order to heat molecular sieve, the temperature of molecular sieve and solid content are met the demands, any existing device that can meet described object can be adopted as stoving oven, such as can adopt existing continous way stoving oven, as long as described molecular sieve roasting can be realized, such as rotary calciner, owing to adopting the super steady reactor of gas phase of the present invention to react, can be easy to realize described continous way stoving oven and be communicated with the super steady reaction unit of gas phase.Preferably, described maturing temperature is 200 ~ 650 DEG C, and be preferably 300 ~ 600 DEG C, described roasting time is not less than 0.5 hour usually, such as, be 0.5 ~ 10 hour.

Preferably, the present invention uses a kind of novel stoving oven, as shown in Figure 8, described comprises stoving oven cylindrical shell 2, for heating the heating unit 1 of stoving oven cylindrical shell, this stoving oven cylindrical shell 2 comprises feed end 24, middle cylinder 20 and discharge end 25.Described feed end 24 and described discharge end 25 offer opening for feed 21 and discharge port 22 respectively, the inwall of described middle cylinder 20 is provided with flight 3 and weir plate 4, described flight 3 is preferably acute angle from the molecular sieve entrance of stoving oven to the axis (from molecular sieve entrance to the direction exported) of the direction that outlet molecular sieve extends and middle cylinder 20, and described weir plate 4 is perpendicular to the axis of described middle cylinder 20.Described middle cylinder 20 is for rotating, and described feed end 24 and described discharge end 25 are fixing.During operation, described middle cylinder 20 rotates, and adds the molecular sieve treating roasting from opening for feed 21, then the molecular sieve after discharge port 22 collects roasting, angle between the bearing of trend of described flight 3 and the axial direction of described middle cylinder 20 is acute angle or obtuse angle, and does not contact between adjacent two flights 3.The number that described flight 3 and described weir plate 4 are arranged can be all 1 or multiple.Reference numeral in Fig. 8 is: 1-body of heater; 10-thermostat; 11-thermal insulation layer; 12-heating system; 13-burner hearth; 2-cylindrical shell; 20-middle cylinder; 21-opening for feed; 22-discharge port; 23-connecting steering mechanism; 24-feed end; 25-discharge end; 3-flight; 4-weir plate.Shown in figure 30 ° are the signal of flight and axis angle, the restriction not to described angle.This novel stoving oven, can make the discharging time of molecular sieve more evenly good, be conducive to the direct UNICOM of the super steady reactor with described gas phase.Described middle cylinder can be rotated counterclockwise and also can turn clockwise, discharging all can be made more even, preferably, it is identical along the direction that middle cylinder circumference extends the sense of rotation of described stoving oven makes flight extend from molecular sieve import to outlet molecular sieve direction.

Described stoving oven can be communicated with by molecular sieve line of pipes with the super steady reactor of described gas phase, and the outlet molecular sieve position of stoving oven is higher than stoving oven molecular sieve entry position.In order to make molecular sieve more steady to the process of the super steady reactor inlet of gas phase from stoving oven outlet flow, at least one section of described molecular sieve line of pipes is set to, the axis of described tilting section and the angle of horizontal plane are 35 ~ 75 °, for the ease of controlling the flow of molecular sieve, described connection line also can be provided with valve or flashboard with the size of Molecular regulator sieve transfer passage, when valve or flashboard are set time, described tilting section and the angle of horizontal plane are 55 ~ 65 °, this is convenient to the flow controlling molecular sieve, and by by-pass valve control or flashboard aperture, ensure that molecular sieve flows when making molecular sieve form certain molecular sieve layer above it, play the air-flow of the super steady reactor of isolated gas phase and stoving oven, in time fluctuating, organize gas phase silicon tetrachloride to enter stoving oven.

A kind of described connecting pipeline preferably includes the first vertical section, the second vertical section and tilting section, as shown in Figure 9, first vertical section 511 one end is connected with the outlet molecular sieve of stoving oven, one end is connected with tilting section 513 in addition, other one end of tilting section 513 is connected with one end of the second vertical section 512, and other one section of the second vertical section 512 is sieved into mouth with the molecular sieve of the super steady reactor of gas phase and is communicated with.The axis of described tilting section and the angle of horizontal plane are preferably 30 ~ 80 °.Described connecting pipeline is preferably also provided with flashboard 514, can control the flow of molecular sieve on the one hand, can control the material level of molecular sieve in described connecting pipeline in addition, playing sealing process by arranging flashboard, stops silicon tetrachloride to enter stoving oven.As shown in Figure 9, flashboard moves to upper right side, then flow path increases the flow that can increase molecular sieve or the material level reducing molecular sieve above flashboard, otherwise below is mobile left for flashboard, then can reduce the flow of molecular sieve or improve the material level of molecular sieve above flashboard.

A kind of equipment provided by the invention prepares the workflow of molecular sieve as shown in Figure 2.Synthesis material such as sial directed agents a1 and the sodium aluminate of Na type molecular sieve, the mixture a2 of water glass and sodium hydroxide and water together adds in synthesis reactor 1, crystallization obtains the crystallization synthetic product comprising Na type molecular sieve and synthesis mother liquid, then introduce band filter 21 to filter, the filter cake that filtration obtains adds swap tank 3 and pulls an oar together with exchange liquid such as re chloride, draw the slurries swap tank from the bottom of swap tank simultaneously, introduce band filter 22 to filter, the molecular sieve filter cake introducing that filtration obtains is carried out stoving oven 4 and is carried out roasting, the molecular sieve that temperature is 200-600 DEG C is obtained after roasting, its solid content is not less than 98 % by weight, this molecular sieve gas phase SiCl rear with heating ₄raw material b sends in tubular reactor 5 from molecular sieve opening for feed and silicon tetrachloride feeding mouth respectively, molecular sieve with flowed by e Foerderanlage in tubular reactor 5 and with gas phase SiCl ₄contact, by the well heater being arranged on tube wall and/or inside, tubular reactor 5 is heated, to ensure that temperature of reaction in tubular reactor 5 is for 250-700 DEG C, enters gas-solid separator 6, afterwards in gas-solid separator 6, molecular sieve is deposited in the bottom of gas-solid separator 6, directly or regularly discharge, add washing tank 8 in the lump with water, then filter through band filter 23, obtain high-silica zeolite c, with the unreacted gas phase SiCl of molecular sieving ₄then enter in absorption tower 7 by the outlet at gas-solid separator 6 top, contact with the absorption agent alkali lye in absorption tower 7, tail gas d overflows from alkali lye, discharges, SiCl from the outlet at top, absorption tower 6 ₄then with alkaline reaction, directly or regularly discharge waste water e by outlet at bottom afterwards.

The first concrete embodiment preparing the equipment of molecular sieve provided by the invention, the super steady reactor of described gas phase is 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 times 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, the angle of its axis and horizontal plane is preferably 30-70 °, 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 increase molecular sieve dealumination complement silicon level of response.Molecular sieve entrance and silicon tetrachloride gas inlet 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 times 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 unit 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 negative area 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 times 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 ratio 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 surge 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 section of lower to position under gravity movement, 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 length-to-diameter 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 3 ~ 100:1.

Preferably, the equipment preparing molecular sieve provided by the invention, the second embodiment, the super steady reactor of described gas phase 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, be such as 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 quality product 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 times of molecular sieve in body and be convenient to control molecular sieve, can promote mixing of silicon tetrachloride and molecular sieve, improve and react homogeneity.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 mixture 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 quality product, 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 different 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 cross section), and the width of described flight can be 1/30 ~ 1/10 of pipe diameter internal diameter.Described flight can be installed the various quantity of different 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, volution, waviness, 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 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 level of response 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 arranges described sleeve pipe.

According to the second embodiment preparing the method for molecular sieve 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 flight 11, baffle plate 21, molecular sieve entrance 31, gas phase silicon tetrachloride entrance 41, outlet molecular sieve 51, inner sleeve 61 and pneumatic outlet 71, 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 contact reacts, 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 calorific loss, described gas-solid separator 6 is for collecting and SiCl ₄molecular sieve after gas contact.

The third preferred implementation of equipment preparing molecular sieve provided by the invention, described reactor utilizes power to carry out the conveying of molecular sieve, make molecular sieve mobile in the reactor, described power conveying device can be arbitrary device, as long as can make molecular sieve and gas phase SiCl ₄continuous moving in reactor contact reacts.Device for carrying such as use in circulation piston pusher, pipe chain conveyer, spiral conveyer, tube-shaped belt handling machinery 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.

Mode is the conveying utilizing tube-shaped belt handling machinery to carry out molecular sieve, and described tube-shaped belt handling machinery band conveyor is arranged on airtight tubular reactor inside, molecular sieve and gas phase SiCl ₄entering from the opening for feed on top, tubular reactor one end drops to endless belt conveyor, the discharge port of tubular reactor the other end bottom is transported to by endless belt conveyor, on band conveyor, material can fully react, described endless belt conveyor can be the conventional any transfer roller used, and endless belt conveyor length and width depend on the position of tubular reactor opening for feed and discharge port 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 ° and are such as 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 conveying 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 the 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 discharged 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 pneumatic outlet 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, the concentration of gas blanket silicon tetrachloride can be improved, be conducive to reaction.The gas of being drawn by pneumatic outlet 62 can reclaim silicon tetrachloride after overcooling, and uncooled gas can be emptying after sponging a small amount of silicon tetrachloride wherein carried.Usually, the molecular sieve thickness on conveying 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 handling machinery to carry, described circulation piston handling machinery 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 opening for feed 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 continuously feeding like this.

Utilizing power delivery of molecules to sieve preferably can also use pipe chain conveyer to carry, described pipe chain conveyer comprises drive sprocket, corner sprocket, circumversion chain, material containing chain sheet, circulation transfer lime, opening for feed, discharge port, circumversion chain is sleeved on drive sprocket and corner sprocket, material containing chain sheet is vertically inserted on circumversion chain, circulation transfer lime is sleeved on outside circumversion chain, and drive sprocket, corner sprocket, circumversion chain, material containing chain sheet and circulation transfer lime 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 and molecular sieve substantially identical, the distance of adjacent described material containing chain sheet preferably more than in described reactor body through diameter, be preferably 1/4 ~ 1/2.

In the super steady reactor of described gas phase, spiral conveyer delivery of molecules preferably can also be utilized to sieve, described spiral conveyer includes axle spiral conveyer and shaftless screw handling machinery, wherein shaftless screw handling machinery 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 spiral conveyer to be utilize spiral steel disc to rotate and then pass the continuous conveying equipment of material, this kind of e Foerderanlage can be set to horizontality and also can be set to heeling condition.The pitch of described spiral conveyer does not have particular 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 of the super steady reactor of described gas phase 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 surge is too fast.

The equipment preparing molecular sieve provided by the invention, 4th kind of preferred embodiment, power and gravity can also be used to combine the conveying carrying out molecular sieve in the super steady reactor of described gas phase, 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 residence time in the reactor by controlling mechanical transmission device, control the reaction times 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 conveyer, spiral conveyer, 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 equipment preparing molecular sieve provided by the invention, also comprises gas-solid separation equipment and absorption equipment.Described gas-solid separation equipment is used for reacted molecular sieve to separate from gas phase, is separated with silicon tetrachloride unreacted in gas phase, removes unreacted silicon tetrachloride in molecular sieve as far as possible; The silicon tetrachloride that described absorption equipment is used in the gas after gas solid separation absorbs, and 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 gaseous fraction in reacted mixture enter absorption tower as far as possible, under preferable case, the position that described gas-solid separator is connected with discharge port is higher than the zero position of described taper.Under further preferable case, the position that described gas-solid separator is connected with discharge port is positioned at the middle and upper part of described gas-solid separator, and gas-solid separator is communicated with the resorber that hereafter will describe (or claiming absorption tower) by its open top.

In gas-solid separator, solid molecular sieves and gas delivery, thus obtain high-silica zeolite product.Described gas-solid separator generally comprises opening for feed 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 opening for feed 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 settling time on the other hand.Described reactor and gas-solid separator can be set to micro-negative pressure operation, and the vacuum tightness 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.

In the present invention, the gas of drawing from gas-solid separator pneumatic outlet 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 absorption agent is contained in described absorption tower, for absorbing the SiCl having neither part nor lot in reaction ₄, thus make air reach emission standard.Absorption tower 7 is for absorbing unreacted SiCl ₄, thus make gas-solid separator 6 gas out reach emission standard.Described absorption tower 7 can be the various absorption towers that this area routine uses, as long as can absorb SiCl ₄.General use alkali lye such as aqueous sodium hydroxide solution absorbs SiCl ₄, water also can be used to absorb.Therefore, in the present invention, described absorption tower 7 preferably includes gas inlet and absorption liquid entrance and two outlets, and wherein gas inlet 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 SiCl in expellant gas 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 pneumatic outlet of resorber can connect induced draft fan.

The super steady reactor of gas phase of the present invention also can comprise well heater, to heat the material in reactor.Described well heater can adopt conventional type of heating to realize, described well heater can be various well heater, such as can by electric stove wire, the reactor steam heating/inside reactor coil pipe heating/thermal radiation heating/microwave heating that reactor outer wall is wound around heating zone, reactor outer wall installs heating additional.Under preferable case, in the present invention, described well heater can be arranged in described molecular sieve opening for feed, the heat tape of silicon tetrachloride feeding mouth and tube wall and/or inside, steam jacket, spiral heater one or more.Described interchanger also can adopt conventional heat exchange mode to realize, such as, use water vapor and solid SiCl ₄carry out heat exchange, or carry out heat exchange with other steam heats.Well 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 discharge port each several part temperature from opening for feed.Also can not well 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 well heater is electric heater is such as heat tape or electric stove wire, and described heat tape is many, simultaneously, body is divided into multistage, is wound around a heat tape or electric stove wire respectively at the outer wall of every section of body.So just can respectively at the inside set temperature measuring apparatus 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.

Molecular sieve after roasting is incorporated in the super steady reactor of gas phase by the present invention, and the temperature preferably introducing 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.Described molecular sieve is just from the molecular sieve that stoving oven is discharged, the thermal source that after can utilizing roasting so on the one hand, the high temperature of molecular sieve reacts as dealumination complement silicon, starts dealumination complement silicon reaction, thus save 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.The crystallization synthetic product of drawing from crystallization synthesis reactor 1, cause vacuum band-type filter machine 21 to filter, molecular sieve filter cake is introduced swap tank 3 with according to the ratio of exchange, the exchange liquid introduced in swap tank mixes from the top of swap tank 3, permutoid reaction is carried out in swap tank, draw the slurries containing molecular sieve from the bottom of swap tank simultaneously, cause vacuum band-type filter machine 22 to filter, roasting in stoving oven 4 introduced by molecular sieve filter cake, to obtain temperature be the molecular sieve preferable temperature of 200-600 DEG C is the molecular sieve of 300 ~ 600 DEG C, with the gas phase SiCl obtained after heating ₄raw material b sends in tubular reactor 5 (reactor can arrange or not arrange well heater) respectively, molecular sieve and gas phase SiCl ₄contact reacts in tubular reactor 5, and move to outlet molecular sieve direction, well heater by being arranged on tube wall and/or inside heats tubular reactor 5, to adjust temperature of reaction in tubular reactor 5 for 250-700 DEG C, enter gas-solid separator 6 afterwards, in gas-solid separator 6, the high-silica zeolite be obtained by reacting is deposited in the bottom of gas-solid separator 6, directly or regularly discharge, be incorporated in washing tank 8 and wash, then filter the high-silica zeolite c obtaining silica alumina ratio and improve through vacuum band-type filter machine 23; Unreacted gas phase SiCl ₄then enter in absorption tower 7 by the outlet at gas-solid separator 6 top, contact with the such as alkali lye of the absorption agent in absorption tower 7, tail gas d overflows from alkali lye, discharges, SiCl from the outlet at top, absorption tower 7 ₄then with alkaline reaction, directly or regularly discharge waste water e by outlet at bottom afterwards.

The equipment preparing molecular sieve provided by the invention may be used for carrying out gas chemistry dealumination complement silicon to various molecular sieve.Described Na type molecular sieve is such as NaY type molecular sieve; (method of crystallization synthesis can adopt existing method to the mixture crystallization of the directed agents of NaY molecular sieve being synthesized, silica-alumina gel and water, such as method disclosed in patent CN101468804B), crystallization product obtains filter cake after filtering, filter cake can be dry or moistly obtain described NaY molecular sieve, then introduces switch and exchange.NaY molecular sieve can obtain the NaY molecular sieve of different exchange degree through ion-exchange.Described exchange can adopt existing method, such as use ammonium salt and or rare-earth salts exchange, one or more in described ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate, described rare-earth salts such as rare earth chloride and/or rare earth nitrate.Such as described NaY molecular sieve can through rare earth exchanged or the Y zeolite obtaining different content of rare earth without rare earth exchanged, and the content of rare earth of described Y zeolite can 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 catalytic cracking catalyst other raw material used and working method can adopt technology well known in the art to carry out.Such as, described with the gross weight of catalytic cracking catalyst for benchmark, the content of molecular sieve 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 aluminum oxide, hydrated aluminum oxide, Alumina gel, silicon sol, silica-alumina gel, silicon-aluminum sol and their precursor, and described clay can be one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.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 and 7 is for illustration of equipment and the method for 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 6 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, discharge port is positioned at the position apart from 1 meter, gas-solid separator top, the aqueous sodium hydroxide solution that concentration is 10 mol/L is filled in absorption tower 7, by tubes connection between absorption tower 7 and gas-solid separator 6, conduit gos deep in aqueous sodium hydroxide solution.

Reactor 5 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 opening for feed 12(molecular sieve opening for feed), at a distance of the downstream of 2 meters, the second opening for feed 22 is set, the upper strata of the ring-type body the other end arranges air-vent 62, and lower floor arranges discharge port 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 endless belt conveyor uses etch-proof metal belt, and metal strip width is no better than ring-type pipe diameter.As shown in Figure 5, molecular sieve enters the body of reactor from the first opening for feed 12 of reactor left upper part, fall on the conveying belt 52 in reactor body upper strata, move right with conveying belt, silicon tetrachloride gas enters in reactor from the second opening for feed 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 speed of reaction also reduces greatly, also air port is cited approvingly from gas outlet 62() draw gas, molecular sieve, then along with conveying belt enters pipe place and conveying belt departs from, discharges the super steady reactor of gas phase by outlet molecular sieve 32 subsequently.Then molecular sieve ingress is turned back to through the body of lower floor with the conveying belt after molecular sieving.

By the temperature from stoving oven 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, sodium oxide content 4.8 % by weight, silicon oxide and the ratio of aluminum oxide be 5.26 times with) and temperature be the SiCl of 90 DEG C ₄gas is sent in the body of tubular reactor continuously by the first opening for feed 12 and the second opening for feed 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 each heating zone in tubular reactor 5 is made to be 400 DEG C, SiCl ₄flow controlled and SiCl by mass flowmeter ₄be 0.25 with the weight ratio of molecular sieve, the inlet amount of molecular sieve is 800kg/ hour, and the residence time of molecular sieve in tubular reactor is 10 minutes.After reaction carries out 1.5 hours, the opening of the molecular sieve in gas-solid separator 6 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 A, its main character is listed in table 1.On conveying 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 conveying belt, the thickness of molecular sieve layer on conveying belt can be controlled.

Embodiment 2

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 6 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, discharge port is positioned at the position apart from 1 meter, gas-solid separator top, the aqueous sodium hydroxide solution that concentration is 10 mol/L is filled in absorption tower 7, by tubes connection between absorption tower 7 and gas-solid separator 6, conduit gos deep in aqueous sodium hydroxide solution.

The tube length of tubular reactor 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 middle 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 opening for feed 31, at a distance of 1.5 meters, the second opening for feed 41 is set, the body the other end arranges discharge port 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, by the temperature from stoving oven 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 of tubular reactor 5 continuously by the first opening for feed 31 and the second opening for feed 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 temperature of tubular reactor 5 outlet molecular sieve is made to be 300 DEG C, SiCl ₄flow controlled and SiCl by mass flowmeter ₄be 0.05 with the weight ratio of molecular sieve, the inlet amount of molecular sieve is 1000kg/ hour, and the residence time of molecular sieve in tubular reactor 5 is 5 minutes.After reaction carries out 1 hour, discharged by the opening of the molecular sieve in gas-solid separator 6 from conical lower portion, pull an oar with decationized Y sieve water afterwards, wash, filter and after 120 DEG C of dryings, obtain high-silica zeolite B, its main character is listed in table 1.

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 inlet end 12, rotatable portion 11 and outlet molecular sieve end 13, molecular sieve inlet 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 inlet 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 exit end 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 osculatory, 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 6 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, discharge port is positioned at the position apart from 1 meter, gas-solid separator top, fill the aqueous sodium hydroxide solution that concentration is 10 mol/L in absorption tower 7, by tubes connection between absorption tower 7 and gas-solid separator 6, conduit gos deep in aqueous sodium hydroxide solution.

By the temperature from stoving oven 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, sodium oxide content 4.8 % by weight, and silicon oxide is 5.26 with the ratio of aluminum oxide) of rare earth and temperature ₄gas is sent in the body of tubular reactor continuously by molecular sieve entrance 5 and gas phase silicon tetrachloride entrance 6 respectively, be wound around electric stove wire at the outer wall of the rotatable portion 11 of body to heat tubular reactor, controlling temperature of reaction is 300 DEG C (reactor outlet molecular sieve temperature), SiCl ₄flow controlled and SiCl by mass flowmeter ₄be 0.08 with the weight ratio of molecular sieve, the inlet amount of molecular sieve is 1000kg/ hour, and the residence time 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 6 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 spiral conveyer or pipe chain conveyer delivery of molecules sieve in the reactor body described in embodiment 2 or 3, 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.

Comparative example 1

Molecular sieve E is prepared according to method disclosed in CN102049315A embodiment 1, molecular sieve used is with the Y zeolite containing rare earth described in embodiment 1, and be divided into every 5 meters and be one section heating zone is set, it is heated, its temperature of reaction and reaction times are 300 DEG C and 5 minutes with embodiment 3, and the ratio of silicon tetrachloride and molecular sieve is 0.3, and inlet amount is 1 ton/hour, obtain molecular sieve E, its character is in table 1.Visible, under same temperature of reaction 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 equipment 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 equipment provided by the invention to obtain, lattice collapse temperature and specific surface 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: pseudo-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 catalyzer 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 catalyzer CC-2.

The Catalytic Cracking Performance test of catalyzer.

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, catalyzer loading amount is 5.0g, temperature of reaction is 460 DEG C, and stock oil is the huge port solar oil 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%

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

Wherein, transformation efficiency=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/transformation efficiency

The Catalytic Cracking Performance of the catalyzer 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 catalyzer obtained by equipment provided by the invention, compared with REY molecular sieve catalyst, pore volume and the specific surface area of gained catalyzer obviously increase, and micro-activity significantly improves.Compared with the catalyzer that the method for carrying with existing carrier gas obtains, performance is not deteriorated.

Table 3

Table 4

Catalyzer	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
						Transformation efficiency, % 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, the molecular sieve obtained by equipment provided by the invention is adopted to be that catalyzer prepared by active ingredient has higher transformation efficiency, higher yield of light oil and liquid yield, lower coke selectivity.

Embodiment 7

By NaY molecular sieve (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry provides, silica alumina ratio 4.95, sodium oxide content 13.5, relative crystallinity 85%), according to RE ₂o ₃: molecular sieve: described NaY molecular sieve and re chloride are introduced in swap tank and exchanged by the part by weight of water=0.18:1:100, exchange temperature is 75 DEG C, swap time is 1 hour, described slurries are filtered on belt filter, it is dry that moisture eliminator sent into by filter cake after filtration, stoving oven roasting introduced by dried molecular sieve, the outlet molecular sieve of stoving oven is communicated with the molecular sieve entrance of the super steady reactor of gas phase, linking device wherein as shown in Figure 9, comprising three sections, 511 vertical settings are communicated with the outlet molecular sieve of stoving oven, 511 sections are vertically arranged, be communicated with the molecular sieve entrance of the super steady reactor of gas phase, the axis of pipeline 513 and the angle of horizontal plane are 60 ° of connection lines 511 and pipeline 512, 514 is flashboard, the axes normal of itself and pipeline 513, flashboard 514 can move with the size controlling pipeline 513 molecular sieve path on pipeline 513 cross section, flashboard 514 and pipeline 513 junction sealing material make to seal with the external world in 513 pipes, 511, 512, 513 pipes being diameter internal diameter 600mm.

The super steady reactor of gas phase adopts the super steady reactor of gas phase described in embodiment 2, and reaction conditions is with embodiment 2.The gas phase super stable molecular sieve obtained is designated as D.Its physico-chemical property is in table 1.

Stoving oven used as shown in Figure 8, the inwall of middle cylinder 20 arranges flight 3 and weir plate 4.The diameter of whole cylindrical shell 2 is 1m, and the length of whole cylindrical shell 2 is 7m, and wherein feed end 24 and the respective length of discharge end 25 are 0.5m, and the length of middle cylinder 20 is 6m.Weir plate 4 is annular plate, be straightened be welded on middle cylinder 20 inwall on, the height of weir plate 4 is 10cm, thickness is 5mm, weir plate 4 totally two pieces, by middle cylinder 20 trisection long for 6m, first piece in the position axially extending 2m along middle cylinder 20 from middle cylinder 20 and feed end 24 junction to discharge end 25 direction, the position continuing to extend to 4m is second piece; By on the inwall of three sections of middle cylinder 20 of weir plate 4 decile, at every section, flight 3 is set, flight 3 is long strip shape, the length direction of flight 3 becomes 30 ° of angles with the axis of middle cylinder 20, flight 3 be straightened be welded on middle cylinder 20 inwall on, be highly 10cm, thickness is 5mm, by on the inwall of three sections of middle cylinder 20 of weir plate 4 decile, be 3 in the quantity of the flight 3 of every section of equalization of the circumference along middle cylinder 20 setting.Middle cylinder 20 is set to rotate under the drive of rotating mechanism 23.Wherein the Way out along the turning direction of middle cylinder 20 from the Way in of molecular sieve to molecular sieve of flight 3 extends.

Whole stoving oven tilts 1 ° to place relative to sea line with the axial of cylindrical shell 2, and opening for feed 21 is high, and discharge port 22 is low.

Stoving oven heating is reached maturing temperature 400 DEG C, rotation middle cylinder its turning direction of 20(and flight are from molecular sieve entrance to outlet molecular sieve, the direction circumferentially extended is identical), to treat that the opening for feed 21 of the Y zeolite of roasting from cylindrical shell 2 joins cylindrical shell 2 continuously, treat that the Y zeolite of roasting enters in middle cylinder 20 under the rotary action of middle cylinder 20 and carry out roasting.Y zeolite after roasting is collected at discharge port 22 place of stoving oven cylindrical shell 2.Under setting middle cylinder 20 rotating speed 1.8rpm condition, roasting time is 1 hour.The solid content of stoving oven outlet molecular sieve is greater than 98.5 % by weight, and molecular sieve temperature is 310 DEG C

Test shows that this stoving oven has better discharging homogeneity.Test method is as follows: join in above-mentioned stoving oven by 50 kilograms of materials, then molecular sieve is collected in the outlet of stoving oven, can find, the discharging time of described molecular sieve is between 56 ~ 64 minutes, the molecular sieve of 100% can be collected, and adopt the stoving oven of the same size of flight and axis being parallel, material divides three times out, first time was at 25 ~ 29 minutes, load accounts for 10% of total load, second time was at 40 ~ 44 minutes, load accounts for 30% of total load, third time was at 52 ~ 60 minutes, load accounts for 60% of total load, visible described stoving oven discharging evenly, this is conducive to reducing stoving oven volume.

Claims (28)

1. prepare the equipment of molecular sieve for one kind, comprise: Na type molecular sieve switch, the super steady reactor of stoving oven, molecular sieve gas phase and gas-solid separating device, wherein Na type molecular sieve switch is in order to exchange Na type molecular sieve, stoving oven is used for carrying out roasting to exchanged molecular sieve, the super steady reactor of molecular sieve gas phase is in order to carry out the reaction of gas chemistry dealumination complement silicon to baked molecular sieve, and gas-solid separator is used for the molecular sieve of discharging from the super steady reactor of gas phase to be separated with unreacted silicon tetrachloride; The super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride entrance and outlet molecular sieve, and the super steady reactor of described gas phase can make that introducing molecular sieve is wherein mobile under the effect of mechanical transmission device and/or gravity makes molecular sieve move to outlet molecular sieve when carrying without carrier gas from molecular sieve entrance.

2. according to the equipment preparing molecular sieve according to claim 1, it is characterized in that, the described outlet moving to gas phase super steady reactor when carrying without carrier gas from the molecular sieve entrance of the super steady reactor of gas phase, uses endless belt conveyor, pipe chain conveyer, worm conveyor, circulation piston handling machinery, tubular type gravity conveyor or one or more combination in them.

3. according to the equipment preparing molecular sieve according to claim 1, it is characterized in that, the super steady reactor of described gas phase comprises molecular sieve import, silicon tetrachloride import, reactor body and outlet molecular sieve, and the position of molecular sieve import is higher than described outlet molecular sieve position.

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

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

6. according to the equipment preparing molecular sieve according to claim 5, it is characterized in that, the axis of described reactor body and the angle of horizontal plane are 40 ~ 80 °.

7. according to the equipment preparing molecular sieve according to claim 1, it is characterized in that, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride entrance, reactor body, outlet molecular sieve, and being set at least partially of reactor body can rotate around the axis of body.

8. according to the equipment preparing molecular sieve according to claim 7, it is characterized in that, the super steady reactor body of described gas phase is straight tube, and can rotating around body axis at least partially of described body, velocity of rotation is 0.05 ~ 40 rev/min.

9. according to the equipment preparing molecular sieve according to claim 7, it is characterized in that, the part that the super steady reactor of described gas phase can rotate around body axis comprises weir plate and flight.

10. according to the equipment preparing molecular sieve according to claim 7, it is characterized in that, the angle of described body and horizontal plane is 5 ~ 80 °.

11., according to the equipment preparing molecular sieve according to claim 7, is characterized in that, have sleeve pipe in described reactor body, contact reacts in described molecular sieve and the silicon tetrachloride annular space between body and sleeve pipe.

12., according to the equipment preparing molecular sieve according to claim 11, is characterized in that, described sleeve outer is 1/4 ~ 3/4 with the ratio of described reactor internal diameter of tube body.

13. according to the equipment preparing molecular sieve according to claim 1, it is characterized in that, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride entrance, reactor body and outlet molecular sieve, be provided with mechanical transmission device in described reactor body, described mechanical transmission device is one or more in endless belt conveyor, piston transfer roller, pipe chain conveyer or worm conveyor.

14., according to the equipment preparing molecular sieve according to claim 13, is characterized in that, described reactor tube body axis and the angle of horizontal plane are 0 ~ 70 °.

15., according to the equipment preparing molecular sieve according to claim 14, is characterized in that, described reactor body and the angle of horizontal plane are 25 ~ 55 °.

16., according to the equipment preparing molecular sieve according to claim 1, is characterized in that, described reactor is tubular reactor, and the tube length of described reactor is 5 ~ 200 meters, through being 0.1 ~ 6 meter in pipe diameter.

17., according to the equipment preparing molecular sieve according to claim 16, is characterized in that, the pipe diameter internal diameter of described reactor is 0.2 ~ 1.5 meter.

18., according to the equipment preparing molecular sieve described in any one of claim 1 ~ 17, is characterized in that, the length of described reactor is 3 ~ 100:1 with the ratio of diameter internal diameter.

19. according to the equipment preparing molecular sieve according to claim 1, it is characterized in that, described stoving oven comprises stoving oven cylindrical shell, for heating the heating unit of stoving oven cylindrical shell, the middle cylinder that described stoving oven cylindrical shell comprises opening for feed, discharge port and is between opening for feed and discharge port, is provided with weir plate and flight in described middle cylinder.

20., according to the equipment preparing molecular sieve according to claim 19, is characterized in that, the angle in the direction that described flight extends and described stoving oven tubular axis direction is acute angle or obtuse angle.

21., according to the equipment preparing molecular sieve according to claim 20, is characterized in that, described angle is greater than 0 ° and is less than 45 °.

22. according to equipment according to claim 1, and described Na type molecular sieve switch comprises interchanger, the second band filter, or also comprises the first moisture eliminator; Described interchanger is used for Na type molecular sieve and exchange ion to exchange, and the second described band filter is used for exchanging mother liquor and the molecular sieving after exchanging; The first described moisture eliminator is used for molecular sieve drying after the exchange that obtained by the second belt filter.

23., according to the equipment preparing molecular sieve according to claim 8, is characterized in that, velocity of rotation is 0.1 ~ 15 rev/min.

24. 1 kinds of methods preparing molecular sieve, is characterized in that, comprise Na type molecular sieve is introduced preparing in the equipment of molecular sieve described in any one of claim 1 ~ 23 carrying out modification.

25., according to the method preparing molecular sieve according to claim 24, is characterized in that, in the super steady reactor of described gas phase, and 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 times of the super steady reactor of described gas phase.

26., according to the method preparing molecular sieve according to claim 24, is characterized in that, the maturing temperature of described stoving oven is 300 ~ 500 DEG C.

27., according to the method preparing molecular sieve according to claim 24, is characterized in that, in described switching equipment, the exchange ion exchanged for Na type molecular sieve is one or more in rare earth ion, ammonium ion.

28., according to the method preparing molecular sieve according to claim 24, is characterized in that, the feeding quantity of described Na type molecular sieve is 50-2000kg/ hour.