CN103787353A - Molecular sieve production apparatus - Google Patents

Abstract

The invention relates to a molecular sieve production apparatus, which comprises a NaY molecular sieve exchange device, a baking furnace, a gas phase ultra-stable reactor and a gas-solid separation device, wherein the gas phase ultra-stable reactor comprises a molecular sieve inlet, a molecular sieve outlet and a silicon tetrachloride inlet. According to the present invention, with the gas phase ultra-stable reactor, the molecular sieve can move to the molecular sieve outlet of the gas phase ultra-stable reactor from the molecular sieve inlet of the gas phase ultra-stable reactor in the case of no requirement of conveying of the molecular sieve through carrier gas, and the molecular sieve and gas phase silicon tetrachloride can be subjected to a contact reaction in the gas phase ultra-stable reactor; and the apparatus can be used for continuous production of the high silicon molecular sieve, and further has characteristics of process simplifying, no requirement of molecular sieve fluidization carrier gas, and substantial silicon tetrachloride consumption reduction.

Description

A kind of equipment of preparing molecular sieve

Technical field

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

Background technology

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

Preparing aspect the molecular sieve of high silica alumina ratio, mainly contain 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) is mainly to use 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 forming in dealumination process ₃affect hydrothermal stability with residual silicofluoride, also pollute the environment.

Hydrothermal method is still the at present industrial method generally adopting, but mend silicon not in time there is dealuminzation in water-heat process after, easily cause lattice to subside, and non-framework aluminum clogged with fragments duct, this has not only affected 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, mends silicon timely, and product crystallization reservation degree is high, Heat stability is good, and 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, after making its water-content lower than 10 % by weight, according to the weight ratio of silicon tetrachloride: Y zeolite=0.1-0.9:1, pass into the silicon tetrachloride gas that dry air carries, at temperature 150-600 ℃, react 10 minutes to 6 hours, after reaction, purge 5 minutes to 2 hours with dry air, remove Na remaining in zeolite with decationized Y sieve water washing ⁺, Cl ^-, Al ³⁺etc. solubility by product.The method molecular sieve maintains static, and uses dry air to carry SiCl ₄, react rear with air purge, unrealized serialization is produced, and 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 balance lattice constant is at least 0.985 with the ratio of initial lattice constant.The preparation method of this zeolite comprises and will contact with silicon tetrachloride containing rare earth Y type zeolite, 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), also comprise an agitator (4) in the inside of reactor (1), a gas-solid separator (5) is installed on air outlet (3), the bore dia of gas-solid separator (5) contained hole and porosity guarantee gas can by and zeolitic solid particle can not pass through, the agitator arm of agitator (4) stretches out outside reactor (1), 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 ℃, 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, the method is generally all long required duration of contact, need a few hours, add charging before reaction and discharging after completion of the reaction, can only carry out once at the most above-mentioned dealumination complement silicon reaction a general day shift, 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 stirring in reactor, 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, in reactor, be difficult to guarantee fully to stir, therefore, adopt the mode of aforesaid reaction vessel, within one day, can obtain at the most the high-silica zeolite of 1200kg.And, in the method for above-mentioned prior art, in order to guarantee the high silicon content of the molecular sieve obtaining, generally all make SiCl ₄excessive far away, excessive SiCl ₄use increased undoubtedly production cost and expenses of environmental protection.On the other hand, aforesaid method all needs very numerous and diverse manual operation, such as: hand charging, manual cleaning and after reaction completes, need long scavenging line etc., 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 serious environmental pollution and serious harm operator's health.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, and the method is included under the carrying of inert carrier gas flow, make molecular sieve with inert carrier gas flow, and with gas phase SiCl ₄under flow state, contact 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 making beating granulation with binding agent, clay and water, obtain 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, can control molecular sieve and SiCl ₄the time of contact, thus can make molecular sieve and SiCl ₄contact reacts in tubular reactor, carry out fully.But the method adopts gas to carry molecular sieve powder material and SiCl ₄the catalytic mode of gas is carried out the super steady reaction of gas phase, for the amount of fluidisation molecular sieve gas must be enough large, and carrier gas and SiCl ₄part by weight can reach 10-250, not so the problem that easily causes device to stop up, increases the amount of gas and causes reaction depth to be difficult to improve, exist that solid materials is carried and the raising of the super steady reaction depth of gas phase between contradiction, in addition, the method needs larger large SiCl in order to reach certain level of response ₄intake, must cause remaining SiCl after the super steady reaction of gas phase ₄amount increase, the harm that has not only 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 with Na type molecular sieve high-silica zeolite, and this device can be used for, by NaY molecular sieve serialization manufacture high-silica zeolite, can reducing the SiCl of gas chemistry legal system for high-silica zeolite ₄consumption.

The invention provides a kind of equipment of 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 for carrying out roasting to the molecular sieve exchanging, 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 for separating the molecular sieve of discharging from the super steady reactor of gas phase with the silicon tetrachloride of unreacted device, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride entrance and molecular sieve outlet, and the molecular sieve that the super steady reactor of described gas phase can make to introduce wherein moves to molecular sieve outlet from molecular sieve entrance in the situation that carrying without carrier gas.

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, and the molecular sieve the roasting that makes to obtain from stoving oven is directly introduced the super steady reactor of gas phase and reacted, and realizes the continuous production of molecular sieve.Without 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, owing to not needing rare gas element delivery of molecules sieve, can be realized easily the super steady reactor of described gas phase 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 that the first drying installation, the first described drying installation are dried in order to the molecular sieve that the molecular sieve filter device after exchange is obtained, then dried molecular sieve is introduced to stoving oven roasting, the molecular sieve after the exchange that also described filtration unit can be obtained is without the roasting of dry directly introducing stoving oven.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 the time preparing according to existing method, generally include crystallization synthetic, crystallization synthetic product is filtered, filter the filtration cakes torrefaction obtaining or do not comprise and be drying to obtain Na type molecular sieve.Conventionally, described equipment also comprises the filtration unit (the present invention claims the first filtration unit) filtering for crystallization synthetic product, preferably the first described filtration unit is belt filter (the present invention is called the first band filter), is called the second drying installation for drying installation the present invention of the first filtration unit filtration cakes torrefaction.The first band filter, interchanger, the second band filter, the second drying installation and stoving oven are communicated with successively, described Na type molecular sieve is once exchanged 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 of preparing molecular sieve, the equipment of preparing molecular sieve that the method utilizes the invention described above to provide, 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 reacted with the silicon tetrachloride of introducing the described super steady reactor of gas phase.

The method of preparing molecular sieve provided by the invention, the molecular sieve that roasting is obtained is incorporated in the super steady reactor of gas phase, in the situation that carrying without carrier gas, make molecular sieve move to the molecular sieve outlet 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 of 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 that the weight ratio before weight and the roasting of molecular sieve after high-temperature roasting (is calcination base content, referring to 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 ℃, the water content of solid content=100%-molecular sieve of molecular sieve.Introduce the SiCl of the super steady reactor of gas phase ₄be preferably 0.01-1, more preferably 0.05-0.60, molecular sieve and gas phase SiCl with the weight ratio of the molecular sieve of introducing the super steady reactor of gas phase ₄contact Temperature be 250-700 ℃, more preferably 300-650 ℃; 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.

In order to make molecular sieve move to the outlet of the super steady reactor of gas phase from the molecular sieve entrance of the super steady reactor of gas phase (being also called for short below reactor) in the situation that carrying without carrier gas, can under the effect of mechanical transmission device and/or gravity, move by the molecular sieve that makes to introduce in described reactor, in mobile process with reactor in SiCl ₄contact reacts.Due to not to introducing the gas carrier gas for fluidisation molecular sieve in reactor, thereby make molecular sieve in the super steady reactor of gas phase in close phase state, the bed density of its molecular sieve is higher.Described SiCl ₄preferably after vaporization, be incorporated in the super steady reactor of gas phase, 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 further diffused 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, can to reactor, introduce molecular sieve continuously from the molecular sieve entrance of reactor, draw continuously the super steady reacted molecular sieve of gas phase from the outlet of reactor, produce thereby can realize continuous gas phase super stabilizing.In reactor, there is higher molecular sieve concentration, can greatly dwindle the volume of reactor, and owing to not needing to introduce the carrier gas of delivery of molecules sieve, without gas dilution or carry silicon tetrachloride, can greatly reduce the heat that carrier gas takes away and the purification expense that reduces carrier gas; Unexpectedly, can accelerate speed of reaction, 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 of preparing molecular sieve provided by the invention, by molecular sieve and SiCl ₄send into continuously in the super steady reactor of gas phase, be expelled to gas-solid separator from discharge port again by action of gravity and/or after providing power that molecular sieve is fully reacted in tubular reactor, solid separates in gas-solid separator with gas, gaseous component is introduced absorption tower, sponges a small amount of excessive SiCl ₄after gas can directly discharge, solid materials can be drawn continuously separator or be stayed in separator regularly drain separator.As can be seen here, the method for 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 can be controlled the residence time of molecular sieve material in reactor, control molecular sieve and SiCl ₄the time of contact, thus can make molecular sieve and SiCl ₄contact reacts in tubular reactor, evenly carry out fully; Be provided with tubular reactor or regulatory molecule sieve and the SiCl of well heater by use ₄add-on ratio, can control different temperature of reaction, thereby can control differential responses condition and level of response, and then can obtain the zeolite product of different dealumination depths.

Compared with the super steady technique of existing autoclave gas phase, the equipment of preparing molecular sieve provided by the invention is in the super steady reaction process of gas phase, can realize the super steady reaction of serialization gas phase, and operation can all automatization serializations carries out, hand labor intensity is little, and production efficiency is high, product performance are stable, and the suitability for industrialized production of the super steady technique of molecular sieve serialization gas phase is become a reality.Experimental results show that, adopt the disclosed still reaction method of CN1281493C, even if adopt the mode of operation of break tour, also can produce at the most the high-silica zeolite of 1200kg every day, and adopt aforesaid device provided by the invention, the high-silica zeolite that can produce 1000kg per hour, can produce the high-silica zeolite of 24000kg every day, its production efficiency is 20 times of the disclosed still reaction method of CN1281493C, and workman's labor operation intensity also greatly reduces, as can be seen here, the economic benefit of equipment provided by the invention is very significant.With the super steady reaction process comparison 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 and carries out sufficient dealumination complement silicon reaction under higher temperature of reaction, not only effectively solve the contradiction between molecular sieve solid powder conveying in the continuous super steady technology of existing molecular sieve, reaction times and the raising of the super steady reaction depth of gas phase, and, due to reaction fully between the raising of the degree of depth of the super steady reaction of gas phase and reaction mass, can reduce SiCl ₄consumption and can make SiCl remaining after gas-phase reaction 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 further improved, therefore, can reduce the consumption of the molecular sieve in catalyzer preparation, further reduce the cost of catalyzer.

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;

Fig. 4 is the schematic diagram of the angle α between tubular reactor 5 axis and the horizontal plane of equipment shown in Fig. 2;

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.

Fig. 7 is the flight of A-A cross section and the schematic diagram of weir plate of cylindrical shell shown in embodiment 3, and 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 described stoving oven and coupling device of the super steady reactor of gas phase of being communicated with provided by the invention.

Embodiment

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

In the method for preparing molecular sieve provided by the invention, silicon tetrachloride can be introduced and in reactor, then in reactor, vaporizes and react with molecular sieve with liquid phase, but in order to make reaction evenly, preferably after silicon tetrachloride vaporization, is incorporated in the super steady reactor of gas phase.The silicon tetrachloride of molecular sieve and vaporization is incorporated in the super steady reactor of gas phase, and in reactor, silicon tetrachloride carries out dealumination complement silicon reaction by stirring and/or diffuse in the space of sieve particle and duct.Molecular sieve moves under action of gravity and/or under the effect of mechanical force, and the direction that silicon tetrachloride moves along molecular sieve is on the whole moved and reacted with molecular sieve; Due to the carrying out of the super steady reaction of gas phase, the direction of moving along molecular sieve, silicon tetrachloride concentration in molecular sieve space reduces gradually, in the time that molecular sieve arrives the molecular sieve outlet of reactor, the concentration of the silicon tetrachloride in molecular sieve material has been reduced to very low level, also be that silicon tetrachloride in molecular sieve material has substantially all participated in the super steady reaction of gas phase as effective reactant in reactor, thereby be conducive to reduce the consumption of silicon tetrachloride, raising dealumination complement silicon effect.In the super steady reactor of gas phase described in the present invention (being also called for short below reactor), the super steady reaction of described molecular sieve gas phase is to carry out with the form of fluidized-bed, moving-bed, fixed bed or its combination.Owing to not using delivery of carrier gas to carry out molecular sieve conveying, thereby in reactor, the sieve particle concentration as one of reactant is higher, moves by the conveying of e Foerderanlage.And the present invention, to directly introducing silicon tetrachloride gas in reactor, dilutes without diluent gas, also higher as the concentration of the silicon tetrachloride of another reactant.In order to realize molecular sieve carrying and moving without carrier gas in reactor, can in reactor, use mechanical transmission device and/or gravity transfer device.For example, can use endless belt conveyor, pipe chain conveyer, worm conveyor, circulation piston handling machinery, tubular type gravity conveyor or their combination, so that the outlet of the molecular sieve of the reactor that molecular sieve moves from the molecular sieve entrance of reactor.The molecular sieve of discharging from the molecular sieve outlet of the super steady reactor of gas phase is introduced gas-solid separator and is separated.

Described reactor can be anyly can meet molecular sieve and gas phase SiCl in the present invention 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 under preferable case dealumination complement silicon of the present invention reaction in tubular reactor, carry out or belt conveying bed bioreactor in carry out.Described reactor comprises molecular sieve entrance, silicon tetrachloride entrance and molecular sieve outlet, wherein silicon tetrachloride can share an entrance with molecular sieve entrance, also can silicon tetrachloride entrance 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 moving.The super steady reactor of gas phase provided by the invention, in the situation that only having an opening for feed, can make molecular sieve and SiCl ₄send into by this opening for feed in the body of reactor, but under preferable case, while production continuously for the ease of industrialization with the coordinating of other devices, described molecular sieve is generally the thermo-molecular sieve from stoving oven, that is to say, this opening for feed is communicated with stoving oven conventionally, therefore, preferable case, the super steady reactor of described gas phase also comprises silicon tetrachloride feeding mouth (the second opening for feed), 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, preferably, the position of silicon tetrachloride feeding mouth in molecular sieve opening for feed downstream.Described upstream and downstream is with respect to molecular sieve for the travel direction in reactor.

For the present invention, because silicon tetrachloride is incorporated into after the super steady reactor of gas phase, do not need carrier gas to carry, thereby in the super steady reactor of described gas phase, the such as air of gas that described gas comprises silicon tetrachloride gas and brought into by molecular sieve.Due to super steady reaction of silicon tetrachloride gas and molecular sieve, silicon can with molecular sieve in aluminium carry out isomorphous substitution reaction and enter into the skeleton structure of molecular sieve, and the aluminium removing can form aluminium-chlorine compound with chlorine, thereby, the super steady reactor of described gas phase can only arrange a material outlet (now the present invention exports also referred to as molecular sieve), and molecular sieve, the gas of being 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 of 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 molecular sieve outlet and silicon tetrachloride entrance, or also comprise gas outlet.When 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 molecular sieve outlet along body, leaves the described super steady reactor of gas phase.Described silicon tetrachloride is incorporated into the super steady reactor of gas phase from silicon tetrachloride entrance, contacts and reacts with molecular sieve.Described body can be to make molecular sieve mobile any type of pipe therein, for example, can be one or more the combination in straight tube, broken line pipe, bend pipe, for example, can be that wherein one section is rectilinear tubes, and other one section is bend pipe or spiral tube; The cross section of described body can be different shape, for example, be square, circular, Polygons, and described body is preferably pipe.

According to the equipment of 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 is incorporated into moving axially reactor and along body from molecular sieve opening for feed, with silicon tetrachloride contact reacts, the molecular sieve that reacts complete is discharged reactor from molecular sieve discharge port, and the molecular sieve of discharge and unreacted a small amount of silicon tetrachloride enter gas-solid separating device.Can molecular sieve be moved in described tubular reactor by action of gravity or by mechanical transport effect, for example, can use endless belt conveyor, pipe chain conveyer, worm conveyor, circulation piston handling machinery, tubular type gravity conveyor or their combination to make molecular sieve move to molecular sieve outlet 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, for example, can be 4 ~ 39 minutes, and in contact process, can select molecular sieve and gas phase SiCl ₄whether heat, so that molecular sieve and gas phase SiCl ₄the temperature of contact is 250-700 ℃.The present inventor's discovery, the length of described tubular reactor is that 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, more preferably 20-80 rice.The diameter (internal diameter) of described tubular reactor is preferably 0.01-6 rice, and more preferably 0.02-3 rice, is further preferably 0.1-2 rice, for example, can be 0.2 ~ 1.5 meter.Ratio through (diameter) in the length of described body and body is preferably not less than 1, and being preferably is 3 ~ 100:1, for example, can be 10 ~ 100:1.Be that for example 0.1 ~ 1.5 meter, 0.01-1.5 rice, length are 5 ~ 130 meters of for example tubular reactors of 15-130 rice with respect to diameter, 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, molecular sieve and gas phase SiCl both can have been guaranteed ₄by tubular reactor, can guarantee again molecular sieve and gas phase SiCl continuously ₄contact can fully carry out.Adopt method provided by the invention under same dealuminzation degree, can greatly reduce gas phase SiCl ₄consumption.Molecular sieve and the rear SiCl vaporizing of heating ₄under continuous conveying device, contact with flow state.Described body can level or inclination, as long as can make molecular sieve move in body in the situation that carrying without carrier gas, for example the angle of its axis and horizontal plane can be 0 ~ 90 °, for example, 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 can realize molecular sieve and SiCl ₄the sufficient reacting object of carrying out, be convenient to control residence time of molecular sieve.In order further fully to guarantee to realize contact more fully in shorter pipeline, and prevent or reduce and in tubular reactor, react inhomogeneous the second-rate of molecular sieve that cause, described tubular reactor can arrange by action of gravity and/or by mechanical transport effect molecular sieve is moved therein, for example be chosen in tubular reactor inner installation continuous conveying device or utilize gravity that molecular sieve is moved, can solve so the continuous transportation problem of pressed powder, can also improve material reaction total amount, described handling machinery can be arbitrarily continuous conveying device to guarantee 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, any device that described interchanger can exchange for realizing molecular sieve and exchange liquid.Described interchanger can be swap tank, it is for example the container of circle or grooved, molecular sieve entrance and exchange liquid entrance are set at top, molecular sieve pulp outlet is set in bottom, the slurries of drawing from outlet are introduced the second filter and are filtered, the exchange area that also can arrange on belt filter, as on belt filter, uses the drip washing of exchange liquid by molecular sieve to be exchanged.The described preferred vacuum band-type filter machine of the second filter.For example described swap tank can be cylindric tank, and conical head can be arranged at bottom.Preferably its aspect ratio ratio of diameter internal diameter (height with) is preferably not less than 1:1, for example, be 1:1 ~ 5:1, and its molecular sieve entrance and the entrance that exchanges liquid are 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 be as required, for example, use for example, for example, in ammonium salt (ammonium sulfate, ammonium nitrate, ammonium chloride), rare-earth salts (rare earth nitrate, rare earth chloride) one or more to exchange.Use belt filter, can make the exchange process of molecular sieve realize production continuously, and realize to the continuous Automatic-feeding of stoving oven.

Na type molecular sieve provided by the invention can be purchased, or according to existing method preparation, in the 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, preferably vacuum band-type filter machine), dry (moisture eliminator the present invention used is called the second moisture eliminator) or the moist Na of obtaining type molecular sieve.

Described stoving oven is in order to heat molecular sieve, temperature and the solid content of molecular sieve are met the demands, can adopt any existing device that can meet described object as stoving oven, for example can adopt existing continous way stoving oven, as long as can realize described molecular sieve roasting, for example 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 ℃, is preferably 300 ~ 600 ℃, and described roasting time is not less than 0.5 hour conventionally, for example, 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, and this stoving oven cylindrical shell 2 comprises feed end 24, middle cylindrical shell 20 and discharge end 25.On described feed end 24 and described discharge end 25, offer respectively opening for feed 21 and discharge port 22, in the middle of described, on the inwall of cylindrical shell 20, be provided with flight 3 and weir plate 4, axially (direction from molecular sieve entrance to outlet) of the direction that described flight 3 extends to molecular sieve outlet from the molecular sieve entrance of stoving oven and middle cylindrical shell 20 is preferably acute angle, and described weir plate 4 is perpendicular to the axis of cylindrical shell 20 in the middle of described.In the middle of described, cylindrical shell 20 is for rotating, and described feed end 24 and described discharge end 25 are for fixing.When operation, in the middle of described, cylindrical shell 20 rotates, and adds the molecular sieve for the treatment of roasting, then collect the molecular sieve after roasting at discharge port 22 from opening for feed 21, angle between the axial direction of the bearing of trend of described flight 3 and described middle cylindrical shell 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 arrange 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; Cylindrical shell in the middle of 20-; 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, not the restriction to described angle.The stoving oven that this is novel, can make the discharging time of molecular sieve better evenly, is conducive to the direct UNICOM with the super steady reactor of described gas phase.Described middle cylindrical shell can be rotated counterclockwise also and can turn clockwise, all can make discharging more even, preferably, the direction that the sense of rotation of described stoving oven is extended flight extending from molecular sieve import to molecular sieve Way out along middle cylindrical shell circumference is identical.

The super steady reactor of described stoving oven and described gas phase can be communicated with by molecular sieve line of pipes, and the molecular sieve outlet position of stoving oven is higher than stoving oven molecular sieve entry position.In order to make molecular sieve export the process that flows to the super steady reactor inlet of gas phase more steady from stoving oven, 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, on described connection line, also can be provided with valve or the flashboard size with Molecular regulator sieve transfer passage, in the time that valve or flashboard are set, described tilting section and the angle of horizontal plane are 55 ~ 65 °, this is convenient to control the flow of molecular sieve, and can pass through by-pass valve control or flashboard aperture, molecular sieve is formed in the situation of certain molecular sieve layer above it and guarantee that molecular sieve flows, play the air-flow of the isolated super steady reactor of gas phase and stoving oven, in the time of fluctuation, organize gas phase silicon tetrachloride to enter stoving oven.

A kind of described connecting pipeline preferably includes vertically section and tilting section of the first vertical section, second, as shown in Figure 9, first vertical section 511 one end are connected with the molecular sieve outlet of stoving oven, one end is connected with tilting section 513 in addition, other one end of tilting section 513 with second vertically one end of section 512 is connected, second vertically other a section of section 512 be sieved into mouth with the molecular sieve of the super steady reactor of gas phase and be 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 on the one hand the flow of molecular sieve by flashboard is set, and can control in addition the material level of molecular sieve in described connecting pipeline, plays sealing process, stops silicon tetrachloride to enter stoving oven.As shown in Figure 9, flashboard moves to upper right side, and flow path increases the material level that can increase the flow of molecular sieve or reduce flashboard top molecular sieve, otherwise below is mobile left for flashboard, can reduce the flow of molecular sieve or improve the material level of flashboard top molecular sieve.

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

The concrete embodiment of the first of the equipment of preparing 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 the movement that the body of inclination is convenient to control the reaction times of molecular sieve in body and is convenient to control molecular sieve.Be preferably straight tube, its cross section is preferably circle.Described body is preferably inclination, the angle of its axis and horizontal plane is preferably 30-70 °, this preferred axis and horizontal plane angle, be conducive to control the material level of molecular sieve in 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.Be provided with molecular sieve entrance and silicon tetrachloride gas inlet in compare Gao one end, body position, molecular sieve enters sedimentation under the effect of gravity after body, and mix and contact with silicon tetrachloride gas wherein, and carry out super stabilizing reaction, silicon tetrachloride moves to material outlet (molecular sieve outlet) direction on the whole, and along with the carrying out of reaction reduces gradually along the axial concentration of reactor, discharge reactor to exit, the other end that molecular sieve outlet is arranged on body is compare Di one end, 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 for example set in exit or valve is set by the resistance of controlling exit, control is deposited on the material level of the molecular sieve of bottom, thereby can be controlled at the reaction times of post-depositional molecular sieve.Molecular sieve contacts mixing in the process of sedimentation with silicon tetrachloride, then molecular sieve is deposited in the bottom of body, wherein in the space of molecular sieve and hole, 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 (molecular sieve outlet) and introduce gas-solid separating device, the reacted molecular sieve of super stabilizing is separated with the gas wherein carrying, gas is introduced absorption unit and is absorbed silicon tetrachloride wherein, molecular sieve is collected in the bottom of gas-solid separator, continuous or periodic discharge gas-solid separator.Due to the negative area that is molecular sieve, the top at body, silicon tetrachloride is in gas phase, therefore molecular sieve starts to carry out super stabilizing with silicon tetrachloride and reacts in the process of sedimentation, then be deposited on the bottom of reactor, 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 molecule sieve aperture reacts gradually.By controlling height, the height of settling section and the height of accumulation horizon of reactor, can control the reaction times, so that the silicon tetrachloride in sieve particle space and hole reacts completely as far as possible, because the accumulation horizon forming has higher drag, can prevent that the silicon tetrachloride of introducing is because the larger fluctuation of pressure directly enters in gas-solid separator by molecular sieve accumulation horizon, thereby be conducive to the consumption of the utilization ratio reduction silicon tetrachloride that improves silicon tetrachloride.Therefore in preferred situation, described reactor at least a portion cross section is filled full molecular sieve, can stop because pressure surge causes silicon tetrachloride and directly enter gas-solid separator from material outlet, can reduce reactor size and can guarantee reaction effect.In described reactor, weir plate can also be set.Molecular sieve enters in body from compare Gao one end, position, and silicon tetrachloride also in the inlet tube body of same one end, and contacts the other end motion of molecular sieve along body to body with molecular sieve.In this kind of situation, molecular sieve is deposited in body, and lower one section of movement to position under the effect of gravity, and the gas that has silicon tetrachloride and bring into when introducing molecular sieve in body in the particle voids of molecular sieve, moves with molecular sieve.Wherein molecular sieve exports in compare Di one end, position, can be on the end face of body, and also can be near on the tube wall of end face.Preferably, described reactor body diameter (internal diameter) is 0.1 ~ 2 meter of pipe, 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 for example 1.5 ~ 400:1, more preferably 3 ~ 150:1 is for example 3 ~ 100:1.

Preferably, the equipment of 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 better steadily, improve reaction effect, the body of described tubular reactor is set to rotate, be that part or all of described tubular reactor body can be set to rotate around the axis of body, conventionally rotating part is the more than 20% of reactor tube body length, be for example 20% ~ 100%, also can be 20 ~ 90%.Can increase considerably molecular sieve and SiCl by rotation ₄exposure level, the super stabilizing process of molecular sieve is more steady, and quality product is more stable.In this situation, the location optimization of its molecular sieve material inlet is higher than the position of molecular sieve outlet; Under preferable case, the axis of described body can become with horizontal plane α angle (acute angle), and angle can be 5-90 °, is preferably 5-70 °, for example, can be 10 ~ 20 °, and 20 ~ 50 °, 30 ~ 40 °, 40 ~ 60 ° or 60 ~ 70 °, more preferably 30 ~ 55 °.The body tilting is convenient to control the reaction times of molecular sieve in body and the movement of being convenient to control molecular sieve, can promote mixing of silicon tetrachloride and molecular sieve, improves and reacts homogeneity.The body of described tubular reactor is preferably straight tube.Preferably make molecular sieve and silicon tetrachloride and drift moving.In the time that part or all of body is set to rotate, the velocity of rotation of body is 0.05 ~ 40 rev/min, is preferably 0.5 ~ 25 rev/min and is for example 0.5 ~ 15 rev/min.In the time that body is rotation, body inside can arrange multi-form flight and baffle plate, wherein fully mixture molecular sieve and SiCl of flight and baffle plate ₄, baffle plate also claims weir plate, can prevent that the too fast slip of molecular sieve from causing the huge fluctuation of quality product, avoids part molecular sieve too fast by reactor, flight can promote the mixing of molecular sieve and silicon tetrachloride.Described flight can be that straight line is welded on body inside, parallel with axis, also can be inclination certain angle (angled with respect to axis) welding, can also carry out spiral welded, wave welding and different shape welds, it can be also multiple that described flight can be quantitatively one, a common flight can meet the demands, and preferably 1 ~ 6 (the flight number having for cross section), the width of described flight can be 1/30 ~ 1/10 of pipe diameter internal diameter.The various quantity of different shape can be installed on described flight 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 in body inside, also can inhomogeneously weld, described plate washer can be quantitatively that zero can be also multiple, the width of described baffle plate can be 1/100 ~ 1/10 of the interior warp of pipe diameter, in the object minimizing reactor of baffle plate, molecular sieve slides, for example reduce the speed of lower floor faster than the speed of upside, so that reaction is more even, reduce silicon tetrachloride consumption.Described α angle is preferably 30 ~ 50 °, so both can guarantee that molecular sieve carries in body, is conducive to again stabilized product quality.

In the time that part or all of body is set to rotate, sleeve pipe is preferably also set in described body, be conducive to improve the concentration of silicon tetrachloride in reactor, improve level of response and then reduce the consumption of silicon tetrachloride, promote mass transfer.Described sleeve pipe can be coaxial with described body, can be pipe, and its external diameter is preferably 1/4 ~ 3/4 of the interior warp of pipe diameter.Preferably, described body rotatable portion arranges described sleeve pipe.

According to the second embodiment of the method for preparing 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, molecular sieve outlet 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 the space between silicon tetrachloride entrance 14 and molecular sieve entrance 31 lead-in bushings 61 and the super steady reactor tube walls of gas phase, and contact reacts, wherein flight 11 can make the molecular sieve upset in body, be conducive to mixing of molecular sieve and silicon tetrachloride, baffle plate 21 can stop molecular sieve to glide along reactor tube walls, being conducive to molecular sieve steadily moves, thereby be conducive to prevent the translational speed of the molecular sieve material translational speed of below faster than top molecular sieve, be conducive to stabilized product quality, the introducing of sleeve pipe 61 is reacted molecular sieve in annular space, be conducive to molecular sieves stabilized quality, and be conducive to reduce calorific loss, described gas-solid separator 6 is for collecting and SiCl ₄molecular sieve after gas contact.

The third preferred implementation of equipment of preparing molecular sieve provided by the invention, described reactor utilizes power to carry out the conveying of molecular sieve, make molecular sieve mobile in reactor, described power conveying device can be to install arbitrarily, as long as can make molecular sieve and gas phase SiCl ₄continuous moving contact reacts in reactor.For delivery of device for example use one or more in circulation piston pusher, pipe chain conveyer, spiral conveyer, tube-shaped belt handling machinery.By using power conveying device, can make molecular sieve move in tubular reactor, the gas in space and the hole of molecular sieve also moves to the outlet of the super steady reactor of gas phase under the carrying of molecular sieve.

Mode is to utilize tube-shaped belt handling machinery to carry out a conveying for molecular sieve, and described tube-shaped belt handling machinery is that band conveyor is arranged on to airtight tubular reactor inside, molecular sieve and gas phase SiCl ₄enter and drop to endless belt conveyor from the opening for feed on top, tubular reactor one end, be transported to the discharge port of tubular reactor the other end bottom by endless belt conveyor, on band conveyor, material can fully react, described endless belt conveyor can be the conventional any transfer roller using, 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 angle α of the axis of body and horizontal plane is preferably 0 ~ 45 ° and is for example 0 ~ 25 °.

A kind of reactor that uses lace conveying device delivery of molecules sieve as shown in Figure 5, molecular sieve raw material and silicon tetrachloride are incorporated into reactor from molecular sieve entrance 12 and the silicon tetrachloride entrance 22 of one end of reactor, molecular sieve falls on lace conveying device 52, on lace conveying device 52, move with conveying belt, in space on molecular sieve, be full of silicon tetrachloride, silicon tetrachloride is by diffusing in the space between sieve particle, and then enter the super stabilizing reaction that participates in aluminium-eliminating and silicon-replenishing in the duct of molecular sieve, 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, produce the solid accumulation of certain altitudes on outlet 32 tops, avoid excessive silicon tetrachloride from exporting 32 discharges, wherein, pneumatic outlet 62 is for drawing the air that silicon tetrachloride and molecular sieve are brought into from reactor.Like this due to the extrusion of silicon tetrachloride, make the air of introducing reactor with molecular sieve under the effect of silicon tetrachloride, gas blanket from sieve particle void diffusion to top, by the regular or irregular top gas of drawing, can improve the concentration of gas blanket silicon tetrachloride, be conducive to reaction.The gas of drawing 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 carrying.Conventionally, the molecular sieve thickness on conveying belt should be not too high, is preferably no more than 10cm, for example, can be to be no more than 5cm.

Utilize power delivery of molecules sieve can also use circulation piston handling machinery to carry, described circulation piston handling machinery is, at airtight tubular reactor, a circulating conveyor being made up of multiple piston pushing rams is set, point two-layer up and down in tubular reactor, upper strata is to provide molecular sieve and gas phase SiCl ₄from the opening for feed on tubular reactor top enters, pushing away proal space by piston rod, lower floor is to provide the space that piston rod self back moves, and forms like this circulating reaction system of a continuously feeding.

Utilize power delivery of molecules 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 the mass transport loop of a sealing.By going out to arrange silicon tetrachloride entrance at molecular sieve entrance, make the direction of motion of silicon tetrachloride substantially identical with molecular sieve, it is interior through diameter that the distance of adjacent described material containing chain sheet is preferably no more than described reactor body, is preferably 1/4 ~ 1/2.

In the super steady reactor of described gas phase, preferably can also utilize spiral conveyer delivery of molecules sieve, described spiral conveyer includes axle spiral conveyer and shaftless spiral conveyer, wherein shaftless spiral conveyer adopts without central axle designs, utilization has the integrated steel spiral pushing material of certain flexibility, thereby it is strong to have anti-entangling, without character such as central shaft interference; Having axle spiral conveyer is the continuous conveying equipment that utilizes the rotation of spiral steel disc and then pass material, and 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 can make molecular sieve move in body, for example, can be 1/100 ~ 1/10 of the interior warp of body.

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

The equipment of preparing molecular sieve provided by the invention, the 4th kind of preferred embodiment, in the super steady reactor of described gas phase, can also use power and gravity to combine the conveying of carrying out molecular sieve, the present invention is called associating mode of movement, in this kind of situation, control the motion of molecular sieve by gravity and mechanical transmission device, can sieve the residence time in reactor by Molecular regulator by controlling mechanical transmission device, control the reaction times of molecular sieve and silicon tetrachloride.Under which, can make the reaction of molecular sieve in tubular reactor 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 of molecular sieve being carried out to aluminium-eliminating and silicon-replenishing, and mechanical transmission device is stressed less, be convenient to control the movement of molecular sieve in reactor, react better even, be conducive to reduce maintenance of equipment.Preferred mechanical transmission device for example circulate piston pusher, pipe chain conveyer, spiral conveyer, band conveyor.Preferably body is set to heeling condition, and the axis of body and the angle of horizontal plane are preferably 25 ~ 55 ℃, can improve the stability of prepared molecular sieve, improves product and distributes.

The equipment of preparing molecular sieve provided by the invention, also comprises gas-solid separation equipment and absorption equipment.Described gas-solid separation equipment, for reacted molecular sieve is separated from gas phase, separates with unreacted silicon tetrachloride in gas phase, removes as far as possible unreacted silicon tetrachloride in molecular sieve; Described absorption equipment absorbs for the silicon tetrachloride of the gas after gas solid separation, can in absorption tower, carry out.The various containers 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, for example, can be cylindric.Further, under preferable case, the bottom of described gas-solid separator is the taper that end has opening.Thereby the molecular sieve obtaining can be discharged from described opening.In order to make the gaseous fraction in reacted mixture enter as far as possible absorption tower and not discharge from above-mentioned opening, under preferable case, the position that described gas-solid separator is connected with discharge port is higher than the zero position of described taper.Further, under 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 below 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 making the sectional area of described gas-solid separator be greater than the cross-sectional area of described tubular reactor body, the sedimentation of the molecular sieve powder material after can realization response under action of gravity, 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, can fully realize like this rapid subsidence of molecular sieve.In order further to guarantee that molecular sieve is fully deposited in gas-solid separator, the present invention also height of preferred described gas-solid separator is not less than 5 meters, for example 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 guarantee so on the one hand the molecular sieve that is deposited in gas-solid separator bottom not to be produced to stirring, can also guarantee on the other hand the more sufficient settling time.Described reactor and gas-solid separator can be set to micro-negative pressure operation, and the vacuum tightness of for example gas-solid separator can be 100Pa ~ 90KPa, preferably 1kpa ~ 80kpa.

Further, under preferable case, described gas-solid separator also comprises bottom solid outlet, separates for discharging the molecular sieve solid obtaining.Further, under preferable case, described gas-solid separator also comprises the valve of opening and closing for controlling described bottom solid outlet, thus can be in good time the molecular sieve solid collected in gas-solid separator is discharged.

In the present invention, the gas of drawing from gas-solid separator pneumatic outlet absorbs to remove the silicon tetrachloride wherein carrying.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 that has neither part nor lot in reaction ₄thereby, make air reach emission standard.Absorption tower 7 is for absorbing unreacted SiCl ₄thereby, make gas-solid separator 6 gas out reach emission standard.Described absorption tower 7 can be the conventional various absorption towers that use, this area, as long as can absorb SiCl ₄.The general alkali lye that uses absorbs SiCl as aqueous sodium hydroxide solution ₄, also can make water 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 guarantee 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, so that the material in reactor is heated.Described well heater can adopt conventional type of heating to realize, described well heater can be various well heaters, for example, can be wound around by reactor outer wall that heating zone, reactor outer wall install the electric stove wire of heating additional, steam heating/inside reactor coil pipe heating/thermal radiation heating/microwave heating for reactor.Under preferable case, in the present invention, described well heater can be arranged on one or more in described molecular sieve opening for feed, silicon tetrachloride feeding mouth and tube wall and/or inner heat tape, steam jacket, spiral heater.Described interchanger also can adopt conventional heat exchange mode to realize, for example, use water vapor and solid SiCl ₄carry out heat exchange, or carry out heat exchange with other steam heats.Well heater is set, can control the temperature of material in tubular reactor, thus the requirement of molecular sieve feeding temperature is reduced, and can be according to the requirement to final aluminium-eliminating and silicon-replenishing molecular sieve, control realizes in tubular reactor identical or different to discharge port each several part temperature from opening for feed.Well heater also can be set, utilize molecular sieve and SiCl ₄reaction heat carry out the regulation and control of reactor content temperature, for example regulatory molecule sieve and SiCl ₄inlet amount ratio, can simplify device flow process.By controlling molecular sieve and gas phase SiCl ₄different Contact Temperatures, and then can obtain the zeolite product of different dealumination depths.

In order to control more accurately the temperature in tubular reactor, under preferable case, described well heater is that electric heater is for example heat tape or electric stove wire, and described heat tape is many, simultaneously, body is divided into multistage, is wound around respectively a heat tape or electric stove wire at the outer wall of every section of body.So just can be respectively at the inside of body set temperature measuring apparatus, the temperature requirement reacting according to aluminium-eliminating and silicon-replenishing and temperature measuring equipment record the actual temperature of this section of body, be wrapped in heat tape electric current and the voltage of every section of tube wall by control, realize the temperature control in every section of body.For example, the length of every section of body can be 2-20 rice, is preferably 2-8 rice.

The present invention is incorporated into the molecular sieve after roasting in the super steady reactor of gas phase, and the temperature of preferably introducing the described molecular sieve of the super steady reactor of described gas phase is 200-600 ℃, SiCl ₄temperature be 60-150 ℃.Described molecular sieve is the molecular sieve of just discharging from stoving oven, can utilize so on the one hand the high temperature of molecular sieve after roasting as the thermal source of dealumination complement silicon reaction, start dealumination complement silicon and react, thus save energy; Can also save on the other hand the time of heating molecular sieve, thereby reaction can fully be carried out in the short period of time.

Below in conjunction with Fig. 2, method provided by the invention is further narrated.The crystallization synthetic product of drawing from crystallization synthesis reactor 1, causing vacuum band-type filter machine 21 filters, molecular sieve filter cake is introduced swap tank 3 and is mixed with the exchange liquid of introducing in swap tank according to exchange ratio from the top of swap tank 3, in swap tank, carry out permutoid reaction, draw the slurries containing molecular sieve from the bottom of swap tank simultaneously, causing vacuum band-type filter machine 22 filters, molecular sieve filter cake is introduced roasting in stoving oven 4, the preferred temperature of molecular sieve that obtains temperature and be 200-600 ℃ is the molecular sieve of 300 ~ 600 ℃, with the gas phase SiCl obtaining after heating ₄raw material b sends into respectively in tubular reactor 5 (reactor can arrange or not arrange well heater), molecular sieve and gas phase SiCl ₄in the interior contact reacts of tubular reactor 5, and move to molecular sieve Way out, can heat tubular reactor 5 by the well heater that is arranged on tube wall and/or inside, to adjust temperature of reaction in tubular reactor 5 as 250-700 ℃, enter afterwards gas-solid separator 6, in gas-solid separator 6, the high-silica zeolite that reaction obtains is deposited in the bottom of gas-solid separator 6, directly or regularly discharge, be incorporated in washing tank 8 and wash, then filter and to obtain the high-silica zeolite c that silica alumina ratio has improved through vacuum band-type filter machine 23; Unreacted gas phase SiCl ₄enter in absorption tower 7 by the outlet at gas-solid separator 6 tops, contact with for example alkali lye of absorption agent in absorption tower 7, tail gas d overflows from alkali lye, discharges SiCl from the outlet at 7 tops, absorption tower ₄, with alkaline reaction, directly or regularly discharge waste water e by outlet at bottom afterwards.

The equipment of preparing molecular sieve provided by the invention can be for carrying out gas chemistry dealumination complement silicon to various molecular sieves.Described Na type molecular sieve is for example NaY type molecular sieve; (the synthetic method of crystallization can adopt existing method to the mixture crystallization of directed agents, silica-alumina gel and the water that NaY Zeolite synthesis is used, the for example disclosed method of patent CN101468804B), crystallization product obtains filter cake after filtering, filter cake can be dried or moistly obtain described NaY molecular sieve, then introduces switch exchange.NaY molecular sieve can obtain the NaY molecular sieve of different exchange degrees through ion-exchange.Described exchange can adopt existing method, for example use ammonium salt and or rare-earth salts exchange, one or more in described ammonium salt for example ammonium chloride, ammonium nitrate, ammonium sulfate, for example rare earth chloride of described rare-earth salts and/or rare earth nitrate.For example described NaY molecular sieve can or obtain the Y zeolite of different content of rare earth through rare earth exchanged 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 and can adopt technology well known in the art to carry out.For example, the described gross weight take catalytic cracking catalyst is benchmark, and the content of molecular sieve is 5-50 % by weight, and take the content of oxide compound binding agent as 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, aluminium colloidal sol, 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 conventional making beating using in this area 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 illustrating equipment and the method for preparing molecular sieve provided by the invention.

Embodiment 1

Used thickness is that the industrial trade mark of 3 millimeters is NiCr18Ti the molecular sieve gas phase shown in stainless steel construction drawing 2 is mended silicon equipment, wherein the top of gas-solid separator 6 is that diameter is that 6 meters, height are 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 apart from gas-solid separator top the position of 1 meter, in absorption tower 7, fill the aqueous sodium hydroxide solution that concentration is 10 mol/L, between absorption tower 7 and gas-solid separator 6, connect by conduit, conduit gos deep in aqueous sodium hydroxide solution.

Reactor 5 is tubular reactor, it as shown in Figure 5, 80 meters of body total lengths, 0.8 meter of pipe diameter, the body of reactor is made 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, thereby make body on the whole circlewise, band conveyor 52 is placed on ring-type body inside, the upper strata of ring-type body one end arranges the first opening for feed 12(molecular sieve opening for feed), downstream at a distance of 2 meters arranges the second opening for feed 22, 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 that molecular sieve from losing from air-vent.Molecular sieve is carried on belt conveyor, and what endless belt conveyor used is 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 first opening for feed 12 on reactor left end top, fall on the conveying belt 52 in reactor body upper strata, move right with conveying belt, silicon tetrachloride gas is that silicon tetrachloride feeding mouth 22 enters in reactor from the second opening for feed, flow to the direction of gas outlet 62 on the whole, in mobile process, silicon tetrachloride gas reacts with the super stabilizing that molecular sieve carries out aluminium-eliminating and silicon-replenishing, concentration reduces gradually, in the time 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, from gas outlet, 62(also cites approvingly air port) draw gas, molecular sieve, along with conveying belt enters pipe place and conveying belt departs from, exports 32 by molecular sieve subsequently and discharges the super steady reactor of gas phase.Be turned back to molecular sieve ingress through the body of lower floor with the conveying belt after molecular sieving.

By the temperature from stoving oven be 350 ℃ containing the Y zeolite of 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 ℃ 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, 10 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 5 interior each heating zones be 400 ℃, SiCl ₄flow by mass flowmeter control and SiCl ₄with the weight ratio of molecular sieve be 0.25, the inlet amount of molecular sieve is 800kg/ hour, the residence time of molecular sieve in tubular reactor is 10 minutes.Reaction was carried out after 1.5 hours, and the molecular sieve in gas-solid separator 6 is discharged from the opening of conical lower portion, pulled an oar, washs, filtered afterwards and after 120 ℃ of oven dry, obtain high-silica zeolite A with decationized Y sieve water, and its main character is listed in table 1.The about 2cm of molecular sieve thickness on conveying belt.In order to make the thickness of molecular sieve be unlikely to too high and inhomogeneous, can reactor body in mounting limit plate, by controlling the distance of limiting plate distance from bottom conveying belt, can control the thickness of molecular sieve layer on conveying belt.

Embodiment 2

Used thickness is that the industrial trade mark of 3 millimeters is NiCr18Ti the molecular sieve gas phase shown in stainless steel construction drawing 2 is mended silicon equipment, wherein the top of gas-solid separator 6 is that diameter is that 6 meters, height are 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 apart from gas-solid separator top the position of 1 meter, in absorption tower 7, fill the aqueous sodium hydroxide solution that concentration is 10 mol/L, between absorption tower 7 and gas-solid separator 6, connect by conduit, conduit gos deep in aqueous sodium hydroxide solution.

60 meters of the body length of tubular reactor, for straight tube, body reactor axis and horizontal plane angle are at 45 °, 1 meter of pipe diameter (internal diameter), utilize as shown in Figure 3 gravity to carry, 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, apart from 4 meters of entrance one end end faces) be rotated with the speed of 5r/min, the rotatable partial interior of body arranges three 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 simultaneously at two weir plates 21 of inboard wall of tube body welding, wherein first weir plate is 30 meters apart from the end face of one section of molecular sieve entrance, second weir plate is apart from 55 meters of this end faces, it is approximately 5 meters apart from other end, two 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, a heat insulation cylinder 61 is also set in the middle of body, its external diameter (diameter) is 60cm, length is identical with body 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 ℃ be the SiCl of 80 ℃ 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, 5 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, making the temperature of tubular reactor 5 molecular sieve outlets is 300 ℃, SiCl ₄flow by mass flowmeter control and SiCl ₄with the weight ratio of molecular sieve be 0.05, the inlet amount of molecular sieve is 1000kg/ hour, the residence time of molecular sieve in tubular reactor 5 is 5 minutes.Reaction was carried out after 1 hour, the molecular sieve in gas-solid separator 6 is discharged from the opening of conical lower portion, afterwards with the making beating of decationized Y sieve water, washing, filter and 120 ℃ dry after, obtain high-silica zeolite B, its main character is listed in table 1.

Embodiment 3

The super steady reaction unit of gas phase as shown in Figure 6, carry and rely on gravity transfer by the molecular sieve of the super steady reactor 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 molecular sieve exit end 13, molecular sieve inlet end 12 and molecular sieve exit end 13 support by bracing or strutting arrangement 9, drive unit 3 is in order to drive the axis rotation of rotatable portion 11 around body 1, 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 molecular sieve exit 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, baffle plate is set on end face, size that can Molecular regulator sieve outlet by controllable register;

A kind of embodiment, body is circular straighttube, 12 meters of its middle tube body length, 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, 0.8 meter of body 1 diameter (internal diameter), body axis and horizontal plane angle are 35 °, the rotatable portion 11 of body 1 is rotated with the speed of 5r/min, body inside arranges three flights 7, flight height is 5cm, the flight setting of paralleling to the axis, and perpendicular to the tube wall tangent plane of crossing flight and tube wall osculatory, at two weir plates 7 of inboard wall of tube body welding, its plate face is perpendicular to the axis of body 1, be highly 6cm, a weir plate is 3 meters apart from the distance of molecular sieve entrance one end end face, the distance of the aforementioned weir plate of other weir plate distance is 6 meters, 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, 0.5 meter of pipe diameter (internal diameter), the top of gas-solid separator 6 is that diameter is that 6 meters, height are 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 apart from gas-solid separator top the position of 1 meter, in absorption tower 7, fill the aqueous sodium hydroxide solution that concentration is 10 mol/L, between absorption tower 7 and gas-solid separator 6, connect by conduit, conduit gos deep in aqueous sodium hydroxide solution.

By the temperature from stoving oven be 300 ℃ be the SiCl of 80 ℃ containing the Y zeolite of 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 is 5.26 with the ratio of aluminum oxide) 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, being wound around electric stove wire at the outer wall of the rotatable portion 11 of body heats tubular reactor, controlling temperature of reaction is 300 ℃ (reactor molecular sieve temperature outs), SiCl ₄flow by mass flowmeter control and SiCl ₄with the weight ratio of molecular sieve be 0.08, the inlet amount of molecular sieve is 1000kg/ hour, the residence time of molecular sieve in tubular reactor is 5 minutes.Reaction was carried out after 1 hour, and the molecular sieve in gas-solid separator 6 is discharged from the opening of conical lower portion, pulled an oar, washs, filtered afterwards and after 120 ℃ of oven dry, obtain high-silica zeolite C with decationized Y sieve water, and its main character is listed in table 1.

In the reactor body described in embodiment 2 or 3, with spiral conveyer or pipe chain conveyer delivery of molecules sieve, described heat insulation cylinder 61 is not set in body, described body rotates or does not rotate, and can reach same reaction effect.Described weir plate and flight are not set in its body.

Comparative example 1

Prepare molecular sieve E according to the disclosed method of CN102049315A embodiment 1, molecular sieve used is with the Y zeolite containing rare earth described in embodiment 1, and being divided into every 5 meters is one section heating zone is set, it is heated, its temperature of reaction and reaction times are 300 ℃ 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 weight ratio of the silicon tetrachloride of comparative example 1 and molecular sieve is adjusted into 0.16, obtains 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, adopting the framework si-al ratio of the molecular sieve that equipment provided by the invention makes is 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, adopt relative crystallinity, lattice avalanche temperature and the specific surface area of the molecular sieve that equipment provided by the invention makes obviously to improve, sodium oxide content obviously reduces, and shows the excellent performance of the molecular sieve that equipment provided by the invention makes.

Embodiment 4-6

For the high-silica zeolite Kaolinite Preparation of Catalyst that adopts embodiment 1-3 to make is described.

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

Comparative example 3

Adopt according to the method described above industrial REY type molecular sieve catalyzer, industry REY type molecular sieve is to be 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 catalyzer is counted 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, different is that molecular sieve used is molecular sieve E, obtains catalyzer CC-2.

The Catalytic Cracking Performance test of catalyzer.

Light oil microactivity is evaluated: adopt the standard method of RIPP92-90 (to see the 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 ℃, and stock oil is the huge port solar oil of boiling range 235-337 ℃, and product composition is by gas chromatographic analysis, calculate light oil microactivity according to product composition, result is in table 2.

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

Heavy oil cracking performance evaluation condition: catalyzer is first at 800 ℃, 100% steam aging 12 hours, then fixed fluidized bed at ACE() device is upper evaluates, and stock oil mixes three heavy oil (character is in table 3) for force, 500 ℃ of temperature of reaction, 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 that respectively prepared by Evaluation operation example 4-6 and comparative example 3,4 according to the method described above, the results are shown in table 4.

Table 2

From the results shown in Table 2, while adopting the molecular sieve catalyzer being made 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 obviously improves.Compared with the existing catalyzer obtaining by the method that carrier gas is carried, performance does not have variation.

Table 3

Table 4

Catalyzer	A-1	A-2	A-3	CC-1	CC-2
						Product distributes, % 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, adopting the molecular sieve being made by equipment provided by the invention is 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: the part by weight of molecular sieve: water=0.18:1:100 will exchange in described NaY molecular sieve and re chloride introducing swap tank, exchange temperature is 75 ℃, be 1 hour swap time, described slurries are filtered on belt filter, it is dry that filter cake after filtration is sent into moisture eliminator, dried molecular sieve is introduced stoving oven roasting, the molecular sieve outlet 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 with the molecular sieve outlet of stoving oven are communicated with, 511 sections vertically arrange, 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, it is vertical with the axis of pipeline 513, flashboard 514 can move the size to control pipeline 513 molecular sieve paths on pipeline 513 cross sections, flashboard 514 makes to seal with the external world in 513 pipes with sealing material with pipeline 513 junctions, 511, 512, 513 are the pipe of 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 obtaining is designated as D.Its physico-chemical property is in table 1.

Stoving oven used as shown in Figure 8, arranges flight 3 and weir plate 4 on the inwall of middle cylindrical shell 20.The diameter of whole cylindrical shell 2 is 1m, and the length of whole cylindrical shell 2 is 7m, wherein feed end 24 and discharge end 25 separately length be 0.5m, the length of middle cylindrical shell 20 is 6m.Weir plate 4 is annular plate, be straightened on the inwall of cylindrical shell 20 in the middle of being welded on, the height of weir plate 4 is 10cm, thickness is 5mm, totally two of weir plates 4, by middle cylindrical shell 20 trisections long 6m, first along middle cylindrical shell 20 axially from middle cylindrical shell 20 and the position of feed end 24 junctions to discharge end 25 directions extension 2m, the position of continuing to extend to 4m is second; On by the inwall of three sections of middle cylindrical shells 20 of weir plate 4 deciles, at every section, flight 3 is set, flight 3 is long strip shape, on the length direction of flight 3 with middle cylindrical shell 20 axial become 30 ° of angles, in the middle of flight 3 is straightened and is welded on, on the inwall of cylindrical shell 20, be highly 10cm, thickness is 5mm, on by the inwall of three sections of middle cylindrical shells 20 of weir plate 4 deciles, the quantity of the flight 3 arranging in the circumferential equalization of every section of middle cylindrical shell 20 in edge is 3.Middle cylindrical shell 20 is set to rotate under the drive of rotating mechanism 23.Wherein the turning direction along middle cylindrical shell 20 of flight 3 is extended to the Way out of molecular sieve from the Way in of molecular sieve.

Whole stoving oven with cylindrical shell 2 axially with respect to sea line tilt 1 ° of placement, opening for feed 21 height, discharge port 22 is low.

Stoving oven heating is reached to 400 ℃ of maturing temperatures, in the middle of rotating, cylindrical shell its turning direction of 20(and flight export to molecular sieve from molecular sieve entrance, the direction of extending along circumference is identical), the Y zeolite for the treatment of roasting is joined cylindrical shell 2 continuously from the opening for feed 21 of cylindrical shell 2, in the middle of the Y zeolite for the treatment of roasting enters under the rotary action of middle cylindrical shell 20, in cylindrical shell 20, carry out roasting.The Y zeolite after roasting is collected at discharge port 22 places at stoving oven cylindrical shell 2.In the middle of setting, under cylindrical shell 20 rotating speed 1.8rpm conditions, 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 ℃

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

Claims (27)

1. prepare the equipment of molecular sieve for one kind, 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 for carrying out roasting to the molecular sieve exchanging, the super steady reactor of molecular sieve gas phase is in order to baked molecular sieve is carried out to the reaction of gas chemistry dealumination complement silicon, and gas-solid separator is for separating the molecular sieve of discharging from the super steady reactor of gas phase with the silicon tetrachloride of unreacted device; The super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride entrance and molecular sieve outlet, and the molecular sieve that the super steady reactor of described gas phase can make to introduce wherein moves to molecular sieve outlet from molecular sieve entrance in the situation that carrying without carrier gas.

2. according to the equipment of preparing molecular sieve claimed in claim 1, it is characterized in that, in described situation of carrying without carrier gas, move to the outlet of the super steady reactor of gas phase from the molecular sieve entrance of the super steady reactor of gas phase, use 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 of preparing molecular sieve claimed in 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 molecular sieve outlet, and the position of molecular sieve import is higher than described molecular sieve outlet position.

4. according to the equipment of preparing molecular sieve described in claim 1 or 3, it is characterized in that, described molecular sieve and silicon tetrachloride share material inlet, or molecular sieve import and silicon tetrachloride import same one end in the super steady reactor of described gas phase.

5. according to the equipment of preparing molecular sieve claimed in 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, molecular sieve outlet composition, described reactor body and the angle of horizontal plane are 30 ~ 90 °, the entrance of molecular sieve is in compare Gao one end, described body position, divide subexit to be positioned at compare Di one end, described body position, molecular sieve outlet 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 molecular sieve outlet, described molecular sieve relies on the effect of gravity to move in reactor.

6. according to the equipment of preparing molecular sieve claimed in 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 of preparing molecular sieve claimed in claim 1, it is characterized in that, the super steady reactor of described gas phase comprises molecular sieve entrance, silicon tetrachloride entrance, reactor body, molecular sieve outlet, and at least a portion of reactor body is set to can be around the axis rotation of body.

8. according to the equipment of preparing molecular sieve described in claim 1 or 7 any one, it is characterized in that, the super steady reactor body of described gas phase is straight tube, and at least a portion of described body can be rotated around body axis, velocity of rotation is 0.05 ~ 40 rev/min, preferably 0.1 ~ 15 rev/min.

9. according to the equipment of preparing molecular sieve described in claim 1 or 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 of preparing molecular sieve claimed in claim 7, it is characterized in that, the angle of described body and horizontal plane is 5 ~ 80 °.

11. according to the equipment of preparing molecular sieve described in claim 7 ~ 10 any one, it is characterized in that, in described reactor body, has sleeve pipe, contact reacts in described molecular sieve and the silicon tetrachloride annular space between body and sleeve pipe.

12. according to the equipment of preparing molecular sieve described in claim 11, it is characterized in that, in described sleeve pipe external diameter and described reactor body, the ratio of warp is 1/4 ~/3/4.

13. according to the equipment of preparing molecular sieve claimed in 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 molecular sieve outlet, in described reactor body, be provided with mechanical transmission device, 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 of preparing molecular sieve described in claim 13, it is characterized in that, described reactor tube body axis and the angle of horizontal plane are 0 ~ 70 °.

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

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

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

18. according to the equipment of preparing molecular sieve described in claim 1 ~ 18 any one, it 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 of preparing molecular sieve claimed in 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, described stoving oven cylindrical shell comprises opening for feed, discharge port and the middle cylindrical shell between opening for feed and discharge port, in described middle cylindrical shell, is provided with weir plate and flight.

20. according to the equipment of preparing molecular sieve described in claim 21, it is characterized in that, the direction that described flight extends and the angle of described stoving oven tubular axis direction are acute angle or obtuse angle.

21. according to the equipment of preparing molecular sieve described in claim 22, it is characterized in that, angle be greater than 0 ° and be less than 45 °.

22. according to equipment claimed in 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 for Na type molecular sieve and exchange ion are exchanged, and the second described band filter is for the molecular sieving by exchange mother liquor and after exchanging; The first described moisture eliminator is for molecular sieve drying after the exchange that the second belt filter is obtained.

Prepare the method for molecular sieve for 23. 1 kinds, it is characterized in that, comprise and will in the device of preparing molecular sieve described in Na type molecular sieve introducing claim 1 ~ 22 any one, carry out modification.

24. according to the method for preparing molecular sieve described in claim 23, it is characterized in that, and in the super steady reactor of described gas phase, molecular sieve and gas phase SiCl ₄the temperature of contact is 250-700 ℃, and described molecular sieve is 10 seconds to 100 minutes in the reaction times of the super steady reactor of described gas phase.

25. according to the method for preparing molecular sieve described in claim 23, it is characterized in that, the maturing temperature of described stoving oven is 300 ~ 500 ℃.

26. according to the method for preparing molecular sieve described in claim 23, it is characterized in that, in described switching equipment, the exchange ion exchanging for Na type molecular sieve is one or more of rare earth ion, ammonium ion.

27. according to the method for preparing molecular sieve described in claim 23, it is characterized in that, the feeding quantity of described Na type molecular sieve is 50-2000kg/ hour.

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