CN108928833A - The method of modifying and modified molecular screen of molecular sieve and application - Google Patents

Abstract

The present invention relates to molecular sieve preparation field, the method for modifying and modified molecular screen and application, the method for modifying of molecular sieve for disclosing molecular sieve include：NaY molecular sieve is successively carried out to the super steady processing of ion-exchange reactions, hydro-thermal, roasting, the reaction of gas chemistry dealumination complement silicon and gas solid separation, the super steady method for handling and roasting of hydro-thermal makes the molecular sieve temperature after roasting be 350-600 DEG C, and solid content is not less than 98 weight %.Method of modifying process flow provided by the invention is simple, greatly reduces the production energy consumption of high-silica zeolite, modified molecular screen obtained has both high crystallinity and second level pore structure, and has high fever and hydrothermal stability.

Description

The method of modifying and modified molecular screen of molecular sieve and application

Technical field

The present invention relates to molecular sieve preparation fields, method of modifying more particularly to molecular sieve and obtained by this method change Property molecular sieve and application.

Background technique

In catalytic cracking catalyst, molecular sieve is a kind of very widely used material, while being also very important The performance of a kind of component, molecular sieve has directly influenced the reactivity worth of catalytic cracking catalyst.According to different needs, can be with Different modifications is carried out to reach the requirement used to molecular sieve.For example the molecular sieve of high silica alumina ratio is generally believed that it is that catalysis is split It is required to change catalyst.

In terms of the molecular sieve for preparing high silica alumina ratio, it is mainly the following method：Ammonium fluosilicate method aluminium-eliminating and silicon-replenishing, hydro-thermal Method and gas phase chemical method aluminium-eliminating and silicon-replenishing (present invention is known as the super steady method of gas phase).

Ammonium fluosilicate method aluminium-eliminating and silicon-replenishing (also referred to as chemical method aluminium-eliminating and silicon-replenishing) mainly uses ammonium fluosilicate dealumination complement silicon, obtains Molecular sieve crystallinity it is high, Si/Al ratio and thermal stability are high, but the indissoluble object AlF formed in dealumination process₃With remaining fluorine Effects of Silicate hydrothermal stability, also pollutes the environment.

Hydro-thermal method is still the method industrially generallyd use at present, but too late there are silicon is mended after dealuminzation in water-heat process When, easily cause lattice to collapse, and non-framework aluminum clogged with fragments duct, this not only affects the accessibility in activated centre, also shadow Ring further increasing for its thermal stability.

Currently, industrially producing Y-type high-Si zeolite mainly uses hydro-thermal method.NaY zeolite is subjected to multiple rare earth ion friendship It changes and is roasted with multiple high temp, the Y-type high-Si zeolite containing rare earth can be prepared, this is also that prepare Y-type high-Si zeolite the most conventional Method, but hydro-thermal method prepares rare-earth type high-silicon gamma-zeolite and is disadvantageous in that：Due to excessively harsh hydrothermal conditions The structure of zeolite can be destroyed, the very high y-type zeolite of silica alumina ratio cannot be obtained；Though the generation of the outer aluminium of skeleton is to the stabilization for improving zeolite Property and form the outer aluminium of the beneficial but excessive skeleton in new acid site and reduce the selectivity of zeolite；In addition, many de- in zeolite Aluminium hole cannot be filled by the silicon migrated out on skeleton in time, often result in the lattice defect of zeolite, the crystal retention of zeolite It is lower；Therefore, the heat and hydrothermal stability for the Y type zeolites containing rare-earth and high content of silicon that hydro-thermal method is prepared are poor, show that its lattice collapses Temperature of collapsing is low, its crystallinity retention rate and specific surface area retention rate are low after hydrothermal aging.But pore structure study shows water The high-Si Y-type molecular sieve of thermal method preparation has second hole abundant.

In US4584287 and US4429053, NaY zeolite is first then subjected to steam treatment, institute with rare earth ion exchanged Method is stated since the shielding action and support of rare earth ion make relatively difficult, the zeolite of aluminium removing of zeolite during steam treatment Cell parameter before steam treatment increases to 2.465-2.475nm, and after handling is 2.420-2.464nm, reduces structure cell Parameter required temperature is higher (593-733 DEG C).The heavy oil cracking activity of zeolite is not high, and coke selectivity is bad.

In the method that US5340957 and US5206194 is provided, the SiO of raw material NaY zeolite₂/Al₂O₃Than being 6.0, cost compared with It is high.The method is also after NaY is carried out rare earth exchanged, then to carry out hydro-thermal process, equally exist aforementioned US4584287 and The shortcomings that US4429053.

Gas chemistry method is the important side of another kind for preparing silica-rich zeolite that Beyer and Mankui were reported first in 1980 Method.Gas chemistry method generally uses the SiCl under nitrogen protection₄It is reacted at a certain temperature with anhydrous NaY zeolite.Entirely Reaction process makes full use of SiCl₄The external source Si provided is once completed dealuminzation by same order elements and mends pasc reaction.Therefore, It carries out generating hydroxyl hole when dealumination complement silicon reaction under the conditions of NaY zeolite can be effectively avoided existing for the vapor, occur Lattice collapses, and destroys the defect of structure, and so as to prepare high-crystallinity retention rate, the silica alumina ratio of high fever and hydrothermal stability is very High Y-type high-Si zeolite.US4273753, US4438178, CN1382525A, CN1194941A, CN1683244A disclose benefit Use SiCl₄The method of gas chemistry dealuminzation ultrastable.

The characteristics of gas chemistry method aluminium-eliminating and silicon-replenishing is that dealuminzation is uniform, and benefit silicon is timely, and product crystal retention is high, thermal stability Good, duct is unimpeded.

CN1281493C discloses Y type zeolites containing rare-earth and high content of silicon and preparation method thereof, which contains rare earth, and the zeolite Silica alumina ratio be 5-30, initial lattice constant be 2.430-2.465nm, balance lattice constant and initial lattice constant ratio extremely It is less 0.985.The preparation method of the zeolite includes that will contain rare earth Y type zeolite to contact with silicon tetrachloride, and the contact is anti-at one Answer in equipment and carry out, the equipment as shown in Figure 1, include a reaction kettle (1), a feed inlet (2) and a gas outlet (3), Further include a blender (4) in the inside of reaction kettle (1), a gas-solid separator (5), gas-solid are installed on gas outlet (3) The bore dia and porosity of separator (5) contained hole guarantee that gas can cannot pass through by zeolitic solid particle, blender (4) Stirring rod stretch out reaction kettle (1) outside, under the stirring of blender (4), the y-type zeolite and carbon tetrachloride gas containing rare earth Contact, the temperature of contact are 100-500 DEG C, and the time of contact is 5 minutes to 10 hours, y-type zeolite and four chlorinations containing rare earth The weight ratio of carbon is 1：0.05-0.5, the silica alumina ratio of the y-type zeolite containing rare earth are 3-8, lattice constant 2.45- 2.48nm.Obviously, time of contact needed for this method is generally all long, needs a few hours, in addition the charging before reaction and anti- Discharging after answering, a general day shift can only at most carry out primary above-mentioned dealumination complement silicon reaction, even with the work of break tour Industry mode can only also carry out above-mentioned dealumination complement silicon reaction twice, and due to needing to stir in reaction kettle, and reaction kettle is not yet May be infinitely great, based on current level, the production capacity that can be used for the maximum reaction kettle of above-mentioned dealumination complement silicon reaction is 600kg, Continue to increase reaction kettle, then it is difficult to ensure that being sufficiently stirred in reaction kettle, therefore, by the way of aforesaid reaction vessel, one day at most The high-silica zeolite of 1200kg can be obtained.Moreover, in the method for the above-mentioned prior art, in order to guarantee the molecular sieve obtained High silicon content generally all makes SiCl₄It is much excessive, excessive SiCl₄Use undoubtedly increase production cost and expenses of environmental protection. On the other hand, the above method requires very many and diverse manual operation, such as：Hand charging, manual cleaning and reaction complete After need prolonged blow line etc., these not only bring labor intensity big, the very low problem of production efficiency, moreover, Molecular sieve dust and excessive SiCl when charging and discharging₄It also causes serious environmental pollution and seriously endangers operator Health.Therefore, the super steady technique of the gas phase of above-mentioned autoclave is difficult to carry out industrialized production.

CN102049315A discloses a kind of preparation method of catalyst, and this method includes the carrying in inert carrier gas flow Under, flow molecular sieve with inert carrier gas, and with gas phase SiCl₄It is contacted under flow regime, molecular sieve and gas phase SiCl₄'s Time of contact is 10 seconds to 100 minutes, then by gained and gas phase SiCl₄Molecular sieve and binder, clay and water after contact It is mixed with beating and is granulated, obtain catalytic cracking catalyst.The preparation method for the catalytic cracking catalyst that the invention provides can be real Existing molecular sieve and SiCl₄Haptoreaction be carried out continuously, by control carrier gas flow velocity and tubular reactor length, can control Molecular sieve processed and SiCl₄The time of contact, so as to make molecular sieve and SiCl₄Haptoreaction in tubular reactor sufficiently Progress.However this method carries molecular sieve powder material and SiCl using gas₄The catalytic mode of gas carries out gas phase Super steady reaction, must sufficiently large, carrier gas and SiCl in order to fluidize the amount of molecular sieve₄Weight ratio is up to 10-250, not so The problem of be easy to causeing device to block, the amount for increasing gas cause reaction depth to be difficult to improve, there is solid material conveying with Contradiction between the raising of the super steady reaction depth of gas phase, in addition, this method in order to reach certain extent of reaction need it is biggish big SiCl₄Intake, be necessarily caused to pass through remaining SiCl after the super steady reaction of gas phase₄Amount increase, not only aggravated environmental pollution Harm be less useful for effective absorption of tail gas.

In addition, being surely the silicon and framework of molecular sieve under the super steady reaction condition of gas phase in gas phase silicon tetrachloride since gas phase is super In aluminium same order elements effect directly occurs so that dealuminzation carries out simultaneously with benefit silicon, and dealuminzation is uniform, therefore, the crystalline substance of molecular sieve Body structure keeps complete, and crystallinity is high, and the microcellular structure of molecular sieve keeps complete, and the crystallinity of gas phase super stable molecular sieve is high, heat And good hydrothermal stability, still, pore structure study shows that gas phase super stable molecular sieve does not have second hole.However, due to the weight of crude oil Matter and in poor quality need to improve catalytic cracking catalyst to the cracking capability of heavy and inferior raw material as in activity The Y type molecular sieve of the heart has more second hole, good excellent of the active center accessibility of molecular sieve with second level pore structure Point, it directly affects the product distribution and economic benefit of catalytic cracking unit.

As can be seen that needing multiple high temp steam roasting repeatedly dilute with high-Si Y-type molecular sieve prepared by hydro-thermal method merely The molecular sieve of native ion-exchanged, preparation has second hole, and still, content of rare earth is low, crystallinity reservation degree is low, heat and hydro-thermal Stability is low, in addition, since hydro-thermal method preparation process high temperature vapor has biggish destruction to the crystallinity of molecular sieve, Therefore, hydro-thermal method cannot prepare the high-silica zeolite of high-crystallinity and high silica alumina ratio；Vapor phase method can prepare crystallinity height and silicon Aluminium is than very high high-silica zeolite, heat and good hydrothermal stability, still, the microcellular structure of the super stable molecular sieve of vapor phase method preparation Remaining intact does not have second level pore structure.Therefore, hydro-thermal method in the prior art or the performance of the super stable molecular sieve of vapor phase method preparation The needs of current processing heavy oil and poor oil cannot be met well.Therefore, develop it is a kind of have high-crystallinity, high fever and The high-silica zeolite with second level pore structure of hydrothermal stability is the urgent of current catalyzed cracking processing mink cell focus and poor oil It needs.

Summary of the invention

The purpose of the invention is to overcome high-silica zeolite heat of the existing technology and hydrothermal stability poor, Wu Fajian Have the defect of high crystallinity and second level pore structure, a kind of method of modifying of molecular sieve, modification obtained by this method are provided The application of molecular sieve and the modified molecular screen in catalytic cracking.Method of modifying process flow provided by the invention is simple, greatly The production energy consumption of high-silica zeolite is reduced greatly, modified molecular screen obtained has both high crystallinity and second level pore structure, and And there is high fever and hydrothermal stability.

The present inventor has found in the course of the research, first carries out the super steady place of hydro-thermal to the molecular sieve that ion exchange is crossed Reason, roasting, and controlling the molecular sieve temperature after roasting is 350-600 DEG C (preferably 400-550 DEG C), and solid content is not less than 98 Weight % (preferably not lower than 99 weight %) then carries out the reaction of gas chemistry dealumination complement silicon, not only can be to avoid traditional water The heat and hydrothermal stability for the Y type zeolites containing rare-earth and high content of silicon that thermal method is prepared are poor, the low defect of lattice collapse temperature, Er Qieke To guarantee that modified molecular screen obtained has second hole abundant.

Based on this, the present invention provides a kind of method of modifying of molecular sieve, this method includes：By NaY molecular sieve successively into The super steady processing of row ion-exchange reactions, hydro-thermal, roasting, the reaction of gas chemistry dealumination complement silicon and gas solid separation, the hydro-thermal are super steady The method of processing and roasting makes the molecular sieve temperature after roasting be 350-600 DEG C, and solid content is not less than 98 weight %.

The present invention also provides modified molecular screen made from above-mentioned method of modifying, the hole of the second hole of the modified molecular screen Volume accounts for the 15-22% of total pore volume, and framework si-al ratio is with SiO₂/Al₂O₃Molar ratio computing is 10-15, relative crystallinity 55- 65%.

The present invention also provides application of the above-mentioned modified molecular screen in catalytic cracking.

Using method of the invention under preferable case of the present invention, the super steady processing of the hydro-thermal and roasting are in New-type bifunctional It is carried out on roaster, the modified molecular screen of preparation has both higher crystallinity and second level pore structure, and has higher heat And hydrothermal stability, it is very suitable for preparing catalytic cracking catalyst, prepares catalytic cracking catalyst as active component, It is not only able to improve conversion ratio, yield of light oil and the liquid yield of catalyst, and can reduce the generation of coke, and energy It consumes lower.For example, the catalyst A-1 being prepared using modified molecular screen made from embodiment 1, micro-activity (800,4h) It can achieve 84 weight %, be used for during residual oil cracking, heavy oil conversion rate is up to 75.87 weight %, and light oil is received Rate is up to 75.83 weight %, and total liquid yield is up to 88.56 weight %, and coke selectivity is lower, and comparative example 1 is used to make The catalyst DA-1 that the modified molecular screen obtained is prepared, micro-activity (800,4h) are 81 weight %, are used for heavy oil In cracking process, heavy oil conversion rate is 73.67 weight %, and yield of light oil is 70.84 weight %, and total liquid yield is up to 85.01 weight %, and coke selectivity is higher.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1 is a kind of structural schematic diagram of the difunctional roaster of preferred embodiment of the invention；

Fig. 2 is a kind of structural schematic diagram of the equipment of the modification for molecular sieve of preferred embodiment of the invention；

Fig. 3 is a kind of structural schematic diagram of the super steady reactor of gas phase of preferred embodiment of the invention；

Fig. 4 is the schematic diagram of the angle α between the super steady reactor axis of gas phase and horizontal plane of equipment shown in Fig. 2；

Fig. 5 is a kind of structural schematic diagram of the super steady reactor of gas phase of preferred embodiment of the invention；

Fig. 6 is a kind of structural schematic diagram of the super steady reactor of gas phase of preferred embodiment of the invention；

Fig. 7 is the shovelling plate of the cross section A-A of the super steady reactor of gas phase shown in fig. 6 and the schematic diagram of weir plate；

Fig. 8 is the connection of the connection difunctional roaster and the super steady reactor of gas phase of a kind of preferred embodiment of the invention Device.

Description of symbols

1- furnace body 10- thermostat 11- insulating layer 12- heating layer 13- burner hearth

2- cylinder 20- middle cylinder 21- feed inlet 22- discharge port

23- connecting steering mechanism 24- feed end 25- discharge end 3- shovelling plate 4- weir plate

5- vapor the first open end distributor 51- first through hole 52- the first closed end 53-

6- dry gas distributor the second open end 61- the second through-hole 62- the second closed end 63-

111-NaY Zeolite synthesis reactor the first filter device of 112-

The difunctional roaster of 113-NaY molecular sieve switch 114- the second filter device 115-

The super absorption tower steady reactor 117- gas-solid separating device 120- of 116- gas phase

121- first reactor shovelling plate 122- baffle 123- the first molecular sieve entrance

124- the first silicon tetrachloride entrance 125- the first outlet molecular sieve 126- inner sleeve

127- first gas exports 131- the second molecular sieve entrance 132- the second silicon tetrachloride entrance

The outlet of 133- lace conveying device 134- the second outlet molecular sieve 135- second gas

141- third molecular sieve entrance 142- third silicon tetrachloride entrance 143- reactor tube body

144- molecular sieve arrival end 145- rotatable portion 146- outlet molecular sieve end

147- the first support device 148- the second support device the first shovelling plate of 149-

150- reactor weir plate 151- driving device

511- the first vertical section 512- the second vertical section 513- tilting section 514- flashboard

Specific embodiment

Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The present invention provides a kind of method of modifying of molecular sieve, and this method includes：NaY molecular sieve is successively subjected to ion exchange Reaction, the super steady processing of hydro-thermal, roasting, the reaction of gas chemistry dealumination complement silicon and gas solid separation, the hydro-thermal is super steady to be handled and roasts The method of burning makes the molecular sieve temperature after roasting be 350-600 DEG C, and solid content is not less than 98 weight %.

In the present invention, the solid content of the molecular sieve is the weight before weight and roasting of the molecular sieve after high-temperature roasting Than (i.e. calcination base content, referring to RIPP32-90 analysis method, petrochemical analysis method, (RIPP test method), Yang Cuiding Deng volume, Science Press, nineteen ninety), the temperature of roasting is usually 800 DEG C, solid content=100%- molecular sieve of molecular sieve Water content.

A preferred embodiment of the invention, after the super steady method for handling and roasting of hydro-thermal makes roasting Molecular sieve temperature be 400-550 DEG C, solid content be not less than 99 weight %.It, will be specific using the preferred embodiment of the present invention The molecular sieve of temperature and solid content carries out subsequent gas chemistry dealumination complement silicon reaction and is more advantageous to high obtained crystallinity, heat and hydro-thermal The good molecular sieve of stability.

A preferred embodiment of the invention, the super condition surely handled of the hydro-thermal include：Temperature is 350-480 DEG C, time 0.5-3h, relative to every kilogram of molecular sieve, the dosage of superheated vapour is 0.15-0.45 kilograms, further preferably Ground, temperature are 390-460 DEG C, time 1-2.5h, and relative to every kilogram of molecular sieve, the dosage of superheated vapour is 0.3-0.42 Kilogram.Using the preferred embodiment of the present invention, it is more advantageous to the relative crystallinity for improving modified molecular screen obtained.

In the present invention, the amount of steam refers in the super steady treatment process of hydro-thermal, is passed through reaction unit (roasting Furnace) amount.

In the present invention, the super steady processing of the hydro-thermal refers to the hydro-thermal process more mitigated.

The present invention is wider to the condition range of choice of the roasting, as long as the molecular sieve temperature after roasting is made to be 350- 600 DEG C (preferably 400-550 DEG C), solid content is not less than 98 weight % (preferably not lower than 99 weight %), it is preferable that Molecular sieve after roasting meets requirement of the super steady reaction of subsequent gas phase to material initial reaction temperature.

In accordance with the present invention it is preferred that the condition of the roasting includes：Temperature is 350-550 DEG C, time 0.5-1.5h, It is further preferred that temperature is 400-530 DEG C, time 1-1.5h.

In method provided by the invention, this method can be continous way operation and be also possible to intermittent operation, when described Operation is that continous way operates, it is preferable that the hydro-thermal surpasses the condition surely handled and includes：Temperature is 350-480 DEG C, further preferably It is 390-460 DEG C；Relative to the molecular sieve treating capacity of 1000kg/h, overheated steam intake is 150-400kg/h, further Preferably overheated steam intake is 300-420kg/h.

In method provided by the invention, the roasting is preferably carried out under dry gas circulation condition, when the operation is company Continuous formula operation, it is preferable that relative to the molecular sieve treating capacity of 1000kg/h, dry gas intake is 2-10m³/ h, further preferably For 3.75-10m³/h。

In the present invention, the dry gas refers to dry gas, for example, can be selected from dry air and dry inertia At least one of gas, the inert gas can be various inert gases commonly used in the art, as nitrogen, argon gas and At least one of helium.The preferably described dry gas of the present invention is dry air.

There is no particular limitation to the method that the gas chemistry dealumination complement silicon reacts by the present invention, it is preferable that gas chemistry Dealumination complement silicon reaction method include：By the molecular sieve and silicon tetrachloride gas haptoreaction after the super steady processing of hydro-thermal and roasting.

The present invention is wider to the range of choice of the catalytic condition, it is preferable that the catalytic temperature is 200-650 DEG C, further preferably 350-500 DEG C, the catalytic time are 10-300min, further preferably 30- 90min。

The method provided according to the present invention, it is preferable that the weight of silicon tetrachloride and the molecular sieve after the roasting in terms of butt Compare 0.05-0.2:1, further preferably 0.08-0.2：1.

Using method provided by the invention, the molecular sieve after exchange is subjected to the super steady processing of hydro-thermal and roasting, is then carried out Gas chemistry dealumination complement silicon reaction (preferably in the case where not having to carrier gas conveying), can be substantially reduced the dosage of silicon tetrachloride, Reduce the production cost of molecular sieve.

A preferred embodiment of the invention, the temperature of the silicon tetrachloride gas are 80-100 DEG C.

A preferred embodiment of the invention, the super steady time interval that processing terminate starts to roasting of the hydro-thermal No more than 5min, preferably 1-4min.When this kind of preferred embodiment makes super steady treated the molecular sieve interval of hydro-thermal shorter Between carry out the roasting, be conducive to the recycling of molecular sieve heat after the super steady processing of hydro-thermal, also, do not expose, avoid in air The negative effect of external environment.

A preferred embodiment of the invention, the super steady processing of the hydro-thermal and roasting carry out on same device, As long as the device that can satisfy above-mentioned condition is used equally for the present invention, but in order to further increase the catalytic of catalyst obtained Can and reduce energy consumption as far as possible, preferably described hydro-thermal it is super it is steady handle and roast carried out on difunctional roaster 115, as shown in Figure 1, The difunctional roaster 115 includes furnace body 1 and the cylinder 2 being arranged in the furnace body 1, and the cylinder 2 successively includes charging End 24, middle cylinder 20 and discharge end 25 are moved towards along material, the difunctional roaster 115 further include be successively set on it is described For to the vapor distributor 5 for providing vapor in the cylinder 2 and for being used for being provided in the cylinder 2 in cylinder 2 The dry gas distributor 6 of dry gas as roasting medium.

According to the present invention, the cylinder 2 is this field routine cylinder, and the cylinder 2 includes middle cylinder 20, feed inlet 21, discharge port 22, connecting steering mechanism 23, feed end 24 and discharge end 25.The length of the middle cylinder 20 and the furnace body 1 Equal, and in the inside of the furnace body 1, the feed end 24 and the discharge end 25 are located at the both ends of the middle cylinder 20, The both ends of the furnace body 1 are stretched out without in the inside of the furnace body 1.The feed inlet 21 and the discharge port 22 are provided with respectively On feed end 24 and on discharge end 25, and the further preferred feed inlet 21 is provided with the top of the feed end 24, described Discharge port 22 is provided with the bottom of the discharge end 25.The feed end 24, the discharge end 25 and the middle cylinder 20 3 Section diameter is identical.The middle cylinder 20 be both ends open, and the feed end 24 and the discharge end 25 be it is open at one end, Other end closing.The open at one end of the feed end 24 and the discharge end 25 passes through connecting steering mechanism 23 and the centre Cylinder 20 connects.The connecting steering mechanism 23 guarantees that the feed end 24, the discharge end 25 and the middle cylinder 20 connect Simultaneously No leakage is connect, while being rotated by and the feed end in the connecting steering mechanism 23 of middle cylinder 20 can be made 24 and the discharge end 25 do not rotate.The connecting steering mechanism 23 for example can be the boiler tube disclosed in CN101149214A Turn round transmission system 4.

According to the present invention, the vapor distributor 5 be the cylinder 2 in vapor is provided, as long as therefore can be real The various constructions of existing above-mentioned function may be used as vapor distributor 5 of the invention, under preferable case, the vapor distribution Device 5 is the hollow circular tube shape structure for having the first open end 52 and the first closed end 53, and on the tube wall of the hollow circular tube shape structure Offer first through hole 51.

According to the present invention, first open end 52 and first closed end 53 of the vapor distributor 5 are in institute State the direction placed in cylinder 2, under preferable case, first open end 52 and ipsilateral (the first open end of the feed end 24 52 is close with the feed end 24), first closed end 53 is towards the discharge end 25.

According to the present invention, first open end 52 is connected and fixed on the end face of the feed end 24 and steams as water The entrance of gas.

According to the present invention, the vapor distributor 5 is for directing the inner space that vapor enters the cylinder 2 In, under preferable case, the first through hole 51 opened up on the vapor distributor 5 has multiple, and multiple described first is logical 51 array distribution of hole.

The array distribution is that multiple first through hole 51 extend straight point along the axial direction of the vapor distributor 5 Cloth, and it is equidistant between the through-hole 51, while multiple first through hole 51 are along the circumferential of the vapor distributor 5 Linear and equidistant arranged distribution.

According to the present invention, the shape of the first through hole 51 is unrestricted, under preferable case, can selected from it is for example round, Triangle, square or slit；It is preferably circular.

According to the present invention, the size of the first through hole 51 is unrestricted, as long as being able to satisfy the super steady processing operation of hydro-thermal Condition, under preferable case, the diameter of first through hole 51 is 1-10mm.

According to the present invention, the quantity of the first through hole 51 is unrestricted, as long as being able to satisfy the super steady processing operation of hydro-thermal Condition, under preferable case, the first through hole 51 is distributed as 5-40/m along the circumferential of the vapor distributor 5, Extending direction along the vapor distributor 5 is distributed as 10-50/m；It is preferred that along the circumferential direction of the vapor distributor 5 Be distributed as 10-35/m, the extending direction along the vapor distributor 5 is distributed as 15-45/m.

According to the present invention, according to the needs of the super steady treatment process of molecular sieve water heat, one can be placed in the cylinder 2 Or multiple vapor distributors 5, as long as the amount of vapor needed for molecular sieve carries out the super steady processing of hydro-thermal can be provided, Under preferable case, the quantity for placing the vapor distributor 5 is 1-10；The vapor distributor 5 more preferably placed Quantity be 1.

It according to the present invention, can be inside the cylinder 2 when the vapor distributor 5 is arranged in the cylinder 2 Any place is placed, but in order to provide better vapor and molecular sieve during molecular sieve progress hydro-thermal super steady processing operation Uniformly come into full contact with, under preferable case, multiple vapor distributors 5 being set as in the cylinder 2 water steams The axial direction of gas distributor 5 is axial parallel with the cylinder 2；It is preferred that the vapor distributor 5 be set as with it is described 2 coaxial placement of cylinder.

According to the present invention, in the super steady processing operation of the hydro-thermal of progress molecular sieve, the water of the offer of vapor distributor 5 Vapor volume should be able to meet the requirement of operating condition, and under preferable case, the outer diameter of the vapor distributor 5 is the cylinder 2 The 10%-30% of internal diameter.

According to the present invention, wherein as long as the aqueous vapor distributor 5 is arranged according to aforementioned direction, playing a role be can be realized The purpose of the present invention, for the present invention, it is preferable that the length of the vapor distributor 5 is the length of the cylinder 2 10%-90%.

According to the present invention, the dry gas distributor 6 is to provide dry gas in the cylinder 2, as long as therefore being that by The various constructions for stating function may be used as dry gas distributor of the invention, and under preferable case, the dry gas distributor 6 is to have the The hollow circular tube shape structure of two open ends 62 and the second closed end 63, and second is offered on the tube wall of the hollow circular tube shape structure Through-hole 61.

According to the present invention, second open end 62 and second closed end 63 of the dry gas distributor 6 are described The direction placed in cylinder 2, under preferable case, second open end 62 and ipsilateral (i.e. the second open end of the discharge end 25 62 close to discharge end 25), second closed end 63 is towards the feed end 24.

According to the present invention, second open end 62 is connected and fixed on the end face of the discharge end 25 and as dry gas Entrance.

According to the present invention, the dry gas distributor 6 enters in the inner space of the cylinder 2 for directing dry gas, excellent In the case of choosing, second through-hole 61 opened up on the dry gas distributor 6 has multiple, and multiple second through-hole, 61 arrays Distribution.

The array distribution is that multiple second through-holes 61 extend straight point along the axial direction of the dry gas distributor 6 Cloth, and it is equidistant between second through-hole 61, while multiple second through-holes 61 are along the circumferential direction of the dry gas distributor 6 Also linear and equidistant arranged distribution.

According to the present invention, the shape of second through-hole 61 is unrestricted, under preferable case, can selected from it is for example round, Triangle, square or slit；It is preferably circular.

According to the present invention, the size of second through-hole 61 is unrestricted, as long as it is super surely to molecular sieve object to be able to satisfy gas phase The requirement for expecting degree of drying, under preferable case, the diameter of the second through-hole 61 is 1-10mm.

According to the present invention, the quantity of second through-hole 61 is unrestricted, as long as it is super surely to molecular sieve object to be able to satisfy gas phase The requirement for expecting degree of drying, under preferable case, second through-hole 61 is distributed as along the circumferential of the dry gas distributor 6 5-40/m, the extending direction along the dry gas distributor 6 are distributed as 10-50/m；It is preferred that along the dry gas distributor 6 Circumferential be distributed as 10-35/m, and the extending direction along the dry gas distributor 6 is distributed as 15-45/m.

According to the present invention, according to the needs of molecular sieve roasting process, one or more institutes can be placed in the cylinder 2 Dry gas distributor 6 is stated, as long as the amount of dry gas needed for roasting can be provided, under preferable case, places the dry gas distributor 6 Quantity be 1-10；The quantity for the dry gas distributor 6 more preferably placed is 1.

According to the present invention, can appoint inside the cylinder 2 when the dry gas distributor 6 is arranged in the cylinder 2 It places at meaning, but is come into full contact with to during carrying out baking operation, provide better dry gas and the uniform of molecular sieve, preferably In the case of, the axial direction that is set as the dry gas distributor 6 and institute of each dry gas distributor 6 in the cylinder 2 State the axial parallel of cylinder 2；It is preferred that the dry gas distributor 6 is set as and 2 coaxial placement of cylinder.

According to the present invention, when carrying out the baking operation of molecular sieve, the dry gas amount that the dry gas distributor 6 provides should be able to expire The requirement of sufficient operating condition, under preferable case, the outer diameter of the dry gas distributor 6 is the 10%- of the internal diameter of the cylinder 2 30%.

According to the present invention, wherein as long as the dry gas distributor 6 is arranged according to aforementioned direction, playing a role be can be realized The purpose of the present invention, for the present invention, it is preferable that the length of the dry gas distributor 6 is the 10%- of the length of the cylinder 2 90%.

According to the present invention, wherein preferably, along the axial direction of the cylinder 2, the dry gas distributor 6 and the vapor There are gap between distributor 5, clearance distance is the 1-30% of 2 length of cylinder.

, according to the invention it is preferred to be provided with shovelling plate 3 and weir plate 4 on the inner wall of the middle cylinder 20；The shovelling plate 3 prolongs Stretching the angle between direction and the axial direction of the middle cylinder 20 is acute angle or obtuse angle, and is not contacted between two neighboring shovelling plate 3.

According to the present invention, setting of the shovelling plate 3 in the middle cylinder 20 can there are many forms, as long as can play Overturn the effect of material.When the shovelling plate 3 is arranged in the middle cylinder 20, the shovelling plate 3 not with the intermediate cylinder Body 20 it is axially vertical, but parallel or shape is at a certain angle, it is preferable that the shovelling plate 3 and the middle cylinder 20 formation Certain angle.The extending direction of the shovelling plate 3 is the direction extended since feed inlet 21 to discharge port 22, the intermediate cylinder The axial direction of body 20 refers to the direction from feed inlet 21 to discharge port 22, the extending direction and the middle cylinder 20 of the shovelling plate 3 Axial direction between the angle that is formed be acute angle or obtuse angle, for description of the invention, the corner dimension takes the acute angle to be formed Angle indicate that the preferably described angle is more than or equal to 0 ° and to be less than or equal to 45 °；It is further preferred that the angle is 10-30 °.

According to the present invention, the shovelling plate 3 and the weir plate 4 are provided on the inner wall of the middle cylinder 20.The shovelling plate 3 It is the inner space structure outstanding of the middle cylinder 20 with the weir plate 4.The shovelling plate 3 makes material in the middle cylinder 20 inside forces to stir, and the weir plate 4 prevents material too fast by difunctional roaster 115.

According to the present invention, the shovelling plate 3 be arranged in the middle cylinder 20 position can there are many, under preferable case, The shovelling plate 3 be it is multiple, multiple shovelling plates 3 are along the circumferentially distributed of the middle cylinder 20；It is described circumferentially distributed for equal equal part Cloth or uneven equal distribution, the preferably described shovelling plate 3 are equal distribution along the circumferentially distributed of the middle cylinder 20.

According to the present invention, be arranged in the middle cylinder 20 shovelling plate 3 quantity can have it is multiple, can be wider Selection, can be specifically arranged according to the requirement of roasting in range, and the quantity of the shovelling plate 3 is axial vertical with the middle cylinder 20 On straight arbitrary section, under the quantity of the circumferential one week shovelling plate 3 occurred in section, preferable case, the shovelling plate 3 is along the centre The circumferential distribution number of cylinder 20 is a/all for 1-6, and preferably 2-4/week.

In the case of, according to the invention it is preferred to, each shovelling plate 3 exists along from feed end 24 to the directional spreding of discharge end 25 On the entire middle cylinder 20.I.e. from the position that the middle cylinder 20 is connected with the feed end 24 always in described Between the inner wall of cylinder 20 extend to the position that the middle cylinder 20 is connected with the discharge end 25.

According to the present invention, the shovelling plate 3 has certain length, to realize the purpose of turning over materials, under preferable case, each The ratio of the diameter of the length of the shovelling plate 3 and the middle cylinder 20 is 1-4：1.

According to the present invention, the shovelling plate 3 can be arranged along the axial direction of the middle cylinder 20 it is multiple (preferably 0.1-3/ Rice), in the arrangement on 20 inner wall of middle cylinder, each shovelling plate 3 is independently arranged multiple shovelling plates 3, multiple It is mutually not connected between the shovelling plate 3, there is a certain distance between two neighboring shovelling plate 3, it is two neighboring described to copy under preferable case Plate 3 is arranged in parallel, and minimum range apart is 0.1-0.5 times of 3 length of shovelling plate.

According to the present invention, it is distributed multiple shovelling plates 3 on the middle cylinder 20, and forms one in middle cylinder 20 Fixed spatial distribution, under preferable case, multiple shovelling plates 3 are spirally distributed on the whole.

According to the present invention, the shovelling plate 3 is to realize that the purpose for stirring and pushing material can be there are many shape, such as strip Shape, waveform, spiral shape etc., under preferable case, the shovelling plate 3 is strip.

According to the present invention, axial direction distribution of the weir plate 4 along the middle cylinder 20.The weir plate 4 can be annular slab, The periphery of annular slab and the internal diameter of the middle cylinder 20 are almost the same, so that the weir plate 4 and the middle cylinder 20 is interior Wall contact.

According to the present invention, the weir plate 4 can be multiple, and multiple weir plates 4 are distributed along the axial direction of the middle cylinder 20, One or more partitions are axially formed in the middle cylinder 20.The setting of the weir plate 4 can be equalization and be also possible to not Equal distribution, preferably equal distribution.

According to the present invention, the number that the weir plate 4 is arranged is preferably 1-30/10 meters, and more preferably 1-20/10 meters, I.e. every 10 meters of settings 1-30, preferably 1-20, can also be expressed as 0.1-3/rice, and preferably 0.1-2/rice.

According to the present invention, when weir plate 4 is arranged in the middle cylinder 20, the middle cylinder 20 is divided for multistage, institute Stating shovelling plate 3 each can be integrally arranged in the middle cylinder 20, from the middle cylinder 20 and 24 phase of feed end The position of connection extends to the position that the middle cylinder 20 is connected with the discharge end 25；The shovelling plate 3 can also be by weir Plate 4 is divided into multistage, is respectively set in every section, and the shovelling plate 3 in different sections is mutually not connected to；It is preferred that shovelling plate 3 is divided into multistage.It is described Shovelling plate 3 is not in contact with weir plate 4.It is described difunctional to increase movement of the material from the feed inlet 21 to the discharge port 22 Roaster 115 during installation, is installed with the axial direction of the cylinder 2 and horizontal line at 1-5 ° of inclination angle, the charging of when installation End 24 is higher than the discharge end 25.The discharge of material after being conducive to roasting is arranged such.

According to the present invention, the furnace body 1 can be the various furnace bodies of existing roaster, and under preferable case, the furnace body 1 is wrapped Thermostat 10, insulating layer 11, heating layer 12 and burner hearth 13 are included, the furnace in the furnace body 1 is arranged in the middle cylinder 20 In thorax 13.Heating layer 12 is located at the outer layer of heating layer 12, surrounds for the middle cylinder 20 in heating furnace 13, insulating layer 11 The burner hearth 13 of 12 internal layer of heating layer 12 and heating layer, for preventing and reducing the heat loss of entire furnace body 1.

According to the present invention, the heating layer 12 can heat in different ways, such as fuel oil, combustion gas or electric heating side Formula；Preferably Electric heating.

According to the present invention, the thermostat 10 connects the heating layer 12 and maturing temperature measuring cell (not shown), protects Demonstrate,prove the stabilization of maturing temperature.

, not only can be more uniform with the discharging time of molecular sieve using above-mentioned difunctional roaster 115 of the invention, and So that directly progress gas phase is super steady again after the roasting of high temperature dry gas after the super steady processing of hydro-thermal for molecular sieve, it not only can be to avoid The heat and hydrothermal stability for the Y type zeolites containing rare-earth and high content of silicon that conventional hydrothermal method is prepared are poor, the low defect of lattice collapse temperature, And it can guarantee that modified molecular screen obtained has second hole abundant.

The difunctional roaster 115 described in the present invention can rotate counterclockwise, can also rotate clockwise.

The revolving speed of a preferred embodiment of the invention, the difunctional roaster is 0.5-5r/min, into one Step is preferably 1-3r/min.

There is no particular limitation for inlet amount of the present invention to the difunctional roaster, as long as the water can be carried out sufficiently The super steady processing of heat and roasting, it is preferable that the inlet amount of the molecular sieve of the difunctional roaster is 500-1200kg/h, into One step is preferably 600-1000kg/h.

According to the present invention, the difunctional roaster can be connected with induced draught system, it is preferable that so that remaining after reaction Overheated steam and dry gas from difunctional roaster charging extreme direction draw.The present invention does not have the setting of the induced draught system It is special to limit, it can be carried out according to conventional technical means in the art, details are not described herein by the present invention.

As shown in Fig. 2, method of modifying provided by the present invention can carry out on the modified device of molecular sieve, the equipment packet It includes：

NaY molecular sieve switch 113：For being swapped to NaY molecular sieve；

Difunctional roaster 115：For carrying out the super steady processing of hydro-thermal and roasting to exchanged molecular sieve；

The super steady reactor 116 of gas phase：For carrying out gas chemistry dealuminzation benefit to the molecular sieve of the super steady processing of hydro-thermal and roasting Pasc reaction；

Gas-solid separating device 117：For the material being discharged from the super steady reactor of gas phase to be carried out gas solid separation and collected to divide Son sieve.

The method of modifying of the molecular sieve provided according to the present invention, the NaY molecular sieve can be commercially available or according to existing sides Method is prepared, when being prepared according to existing method, generally include synthesized gel rubber, crystallization (existing method can be used in crystallization, such as Method disclosed in CN101468804B) and filtering (the filter present invention used is known as the first filter device 112, and preferably the One filter device 112 is vacuum band-type filter machine), it is optionally dry.Therefore, the modified device of above-mentioned molecular sieve can also include NaY molecular sieve synthesis reactor 111 and the first filter device 112, NaY molecular sieve synthesis reactor 111 and NaY molecular sieve are handed over Changing device 113 is connected to, and in the NaY molecular sieve synthesis reactor 111 and 113 connecting pipeline of NaY molecular sieve switch First filter device 112 is set.

The ion-exchange reactions that the present invention carries out NaY molecular sieve is not particularly limited, can be according to this field routine Method carries out.For example, the ion-exchange reactions that NaY molecular sieve carries out includes：NaY molecular sieve and rare-earth salts and/or ammonium salt is molten Liquid contact carries out ion-exchange reactions, is then successively filtered, washs and optionally dries, and obtains sodium oxide content reduction Y type molecular sieve.It is therefore preferable that the modified device of above-mentioned molecular sieve further includes the second filter device 114, the second filtering dress 114 are set to be arranged on the connecting pipeline of NaY molecular sieve switch 113 and difunctional roaster 115.It is preferred that second filtering Device 114 is band filter.Using band filter, the ion exchange process of NaY molecular sieve can be made to be carried out continuously, and It realizes to the continuous Automatic-feeding of difunctional roaster 115.

, according to the invention it is preferred to which the ion-exchange reactions includes：NaY molecular sieve is contacted with rare-earth salt solution progress from Then sub- exchange reaction is successively filtered, washs and optionally dries, obtains the Y type molecular sieve of sodium oxide content reduction. The present invention is wider to the range of choice of the condition of the ion-exchange reactions, (preferably dilute with rare-earth salt solution to NaY molecular sieve Earth salt aqueous solution) dosage there is no particular limitation, for example, the weight ratio of NaY molecular sieve, rare-earth salts and water can be 1： (0.01-0.2)：(5-15), preferably 1：(0.1-0.2)：(10-15), wherein NaY molecular sieve in terms of butt, rare-earth salts with RE₂O₃Meter.In the present invention, the RE refers to rare earth element.

There is no particular limitation for condition of the present invention to the ion-exchange reactions, for example, the ion-exchange reactions Temperature can be 15-95 DEG C, and the time can be 30-120min, it is preferable that temperature is 65-95 DEG C, time 40-80min.

There is no particular limitation to the mode that the NaY molecular sieve is contacted with rare-earth salts and/or ammonium salt solution by the present invention, example Such as, NaY molecular sieve and water can be formed into slurries, be then added in the slurries rare-earth salts, ammonium salt, rare-earth salts it is water-soluble At least one of liquid and the aqueous solution of ammonium salt.

In the present invention, it is preferred to which the rare-earth salts is rare earth chloride and/or nitric acid rare earth.Rare earth of the present invention can be with For various rare earth metals commonly used in the art, for example, at least one of La, Ce, Pr, Nd and mischmetal.

In the present invention, the ammonium salt can be selected from least one of ammonium sulfate, ammonium nitrate and ammonium chloride.

The purpose of washing in ion-exchange reactions of the present invention be in order to wash away the sodium ion being swapped out, for example, Deionized water or decationized Y sieve water washing can be used.

A preferred embodiment of the invention, modified device of the method for modifying provided by the present invention in molecular sieve Upper progress, the equipment include：Sequentially connected NaY molecular sieve synthesis reactor 111, the first filter device 112, NaY molecular sieve The super steady reactor 116 of switch 113, the second filter device 114, difunctional roaster 115, gas phase, gas-solid separating device 117 And absorption tower 120, the absorption tower 120 are connected to the gaseous phase outlet of the gas-solid separating device 117.

A kind of specific embodiment according to the present invention, the NaY molecule that will be synthesized in NaY molecular sieve synthesis reactor 111 Sieve carries out ion-exchange reactions in NaY molecular sieve switch 113, passes through second after the filtering of the first filter device 112 Filter device 114 filters, and obtained filter cake is sent directly into difunctional roaster 115 and carries out the super steady processing of hydro-thermal and roasting. The difunctional roaster 115 makes the super steady place of hydro-thermal to carry out the super steady processing of hydro-thermal and roasting to exchanged molecular sieve The temperature and solid content (temperature is 350-600 DEG C, and solid content is not less than 98 weight %) of molecular sieve after reason and roasting meet and want It asks.

The molecular sieve that difunctional roaster is discharged preferably is introduced directly into the super steady reactor of gas phase by the present invention, and such one Aspect can mend the heat source of reactive aluminum using the high temperature of molecular sieve after roasting as desiliconization, and reactive aluminum is mended in starting desiliconization, to save The about energy；On the other hand the time of heating molecular sieve can also be saved, to make reaction that can sufficiently carry out in a relatively short period of time.

There is no particular limitation for inlet amount of the present invention to molecular sieve in the gas chemistry dealumination complement silicon reaction process, only It wants sufficiently carry out the gas chemistry dealumination complement silicon reaction, it is preferable that the inlet amount of the molecular sieve is 500- 1200kg/h, further preferably 600-1000kg/h.

A kind of specific embodiment according to the present invention, as shown in Fig. 2, the synthesis material of NaY molecular sieve such as sial is led NaY molecular sieve synthesis reactor 111 is added together with to agent a1 and the mixture a2 of sodium aluminate, sodium metasilicate and sodium hydroxide and water In, crystallization obtain include NaY molecular sieve and synthesis mother liquid crystallization synthetic product, then introduce the first filter device 112 (preferably Vacuum band-type filter machine) be filtered, the filter cake being obtained by filtration with exchange liquid such as ammonium salt solution and/or re chloride one It plays addition NaY molecular sieve switch 113 (such as swap tank) to be beaten, while being drawn in swap tank from the bottom of swap tank Slurries, introduce the second filter device 114 (preferably band filter) and be filtered, the molecular sieve filter cake that is obtained by filtration introduces double Function roaster 115 carries out the super steady processing of hydro-thermal and roasting, obtains molecular sieve after roasting, gas phase after the molecular sieve and heating SiCl₄Raw material b is sent into the super steady reactor 116 of gas phase from molecular sieve feed inlet and silicon tetrachloride feeding mouth respectively, and (preferably tubulose is anti- Answer device) in reacted, molecular sieve in the super steady reactor 116 of gas phase by conveying device flowing and with gas phase SiCl₄Contact, Heater by the way that tube wall and/or inside is arranged in heats tubular reactor, to guarantee in tubular reactor Reaction temperature enters gas-solid separating device 117 later, and in gas-solid separating device 117, molecular sieve is deposited in gas-solid separating device 117 bottom directly or is periodically discharged, obtains high-silica zeolite.Wherein, with the unreacted gas phase SiCl of molecule sieve separation₄ Then entered in absorption tower 120 by the outlet at 117 top of gas-solid separator, is contacted with the absorbent lye in absorption tower 120, tail Gas d is overflowed from lye, is discharged from the outlet at 120 top of absorption tower, SiCl₄Then with alkaline reaction, pass through outlet at bottom later Waste water e directly or is periodically discharged.

The method provided according to the present invention, the structure of steady reactor 116 super to the gas phase is without particular/special requirement, the prior art The super steady reactor of gas phase may be incorporated for the present invention, it is preferable that the super steady reactor 116 of gas phase be WO2014/063445 Disclosed in the super steady reactor of gas phase.

Method in accordance with the invention it is preferred that the method for the gas chemistry dealumination complement silicon reaction includes：Hydro-thermal is super steady Molecular sieve after processing and roasting is introduced into the super steady reactor 116 of gas phase, in the case where not having to carrier gas conveying, keeps hydro-thermal super Molecular sieve after steady processing and roasting is moved to the super steady reactor 116 of gas phase from the molecular sieve entrance of the super steady reactor 116 of gas phase Outlet molecular sieve, and make hydro-thermal it is super it is steady processing and roasting after molecular sieve and silicon tetrachloride gas in the super steady reactor of gas phase Haptoreaction in 116.

According to the present invention, the super steady reactor of the gas phase, which can be, any is able to satisfy molecular sieve and SiCl in the present invention₄Gas The super steady reactor of the gas phase of the contact conditions of body.The super steady reactor of gas phase can be tubular reactor or transport bed reactor (moving-burden bed reactor).But dealumination complement silicon reaction progress or belt conveying in tubular reactor of the present invention under preferable case It is carried out in bed reactor.The reactor includes molecular sieve entrance, silicon tetrachloride entrance and outlet molecular sieve, wherein tetrachloro SiClx can share an entrance with molecular sieve entrance, four chlorinations can also be separately provided in the position different from molecular sieve entrance Silicon entrance, the entrance keep silicon tetrachloride and molecular sieve cocurrent mobile preferably adjacent to molecular sieve entrance.Gas phase provided by the invention is super Steady reactor can make molecular sieve and SiCl in the case where only one feed inlet₄Reactor is sent by the feed inlet In tube body, but under preferable case, for the ease of cooperation when industrialization continuous production with other devices, the molecular sieve is usually Thermo-molecular sieve from roaster, that is to say, that the feed inlet is usually connected to roaster, it is therefore preferable that situation, the gas phase Super steady reactor further includes silicon tetrachloride feeding mouth (second charging aperture), the silicon tetrachloride feeding mouth be located on tube body with it is described The adjacent position of molecular sieve feed inlet (first charging aperture)；The silicon tetrachloride feeding mouth may be at molecular sieve feed inlet upstream Position, also may be at the position in molecular sieve feed inlet downstream, it is preferable that silicon tetrachloride feeding mouth is under molecular sieve feed inlet The position of trip.The upstream and downstream is for molecular sieve moving direction in the reactor.

According to the present invention, the super steady reactor of the gas phase is set as existing with horizontal direction in the specific use process and press from both sides Angle, angle α are 10-80 °, as shown in Figure 4.A preferred embodiment of the invention, gas phase super steady reactor such as Fig. 3 institute Show, the super steady reactor of the gas phase includes：First reactor shovelling plate 121, baffle 122, the first molecular sieve entrance 123, the first tetrachloro SiClx entrance 124, the first outlet molecular sieve 125, inner sleeve 126 and first gas outlet 127, the reactor can also include Tube body rotary drive mechanism (not shown).

Wherein, silicon tetrachloride passes through the first silicon tetrachloride entrance 124 with molecular sieve respectively and the first molecular sieve entrance 123 draws Enter in the gap between inner sleeve 126 and the super steady reactor tube walls of gas phase, and haptoreaction, wherein first reactor shovelling plate 121 can be such that the molecular sieve in tube body overturns, and be conducive to the mixing of molecular sieve and silicon tetrachloride, and baffle 122 can prevent molecule Sieve glides along reactor tube walls, is conducive to molecular sieve and steadily moves, so that the molecular sieve material for being beneficial to prevent lower section is mobile Speed is faster than the movement speed of top molecular sieve, is conducive to stabilized product quality, the introducing of inner sleeve 126 makes molecular sieve in ring It is reacted in gap, is conducive to molecular sieves stabilized quality, and advantageously reduce thermal loss.Its specific configuration and connection relationship It can be defined by aforementioned applications, for known to those skilled in the art, this is not described in detail here.

According to the preferred embodiment of the present invention, the super steady reactor of the gas phase carries out the conveying of molecular sieve using power, Move molecular sieve in the reactor, the reactor is, for example, tubular reactor, and the power conveying device, which can be, appoints The device of meaning, as long as enabling to molecular sieve and gas phase SiCl₄Continuous moving and haptoreaction in reactor.For defeated The device sent is for example using one of circulation piston pusher, pipe chain conveyor, auger conveyor, tube-shaped belt conveyer Or it is a variety of.By using power conveying device, molecular sieve can be made to move in the reactor, the gas in the gap and hole of molecular sieve Body is also moved to the outlet of the super steady reactor of gas phase under the carrying of molecular sieve.

Wherein, a kind of mode is that the conveying of molecular sieve, the tube-shaped belt conveyer are carried out using tube-shaped belt conveyer It is band conveyor to be arranged in inside closed tubular reactor, molecular sieve and gas phase SiCl₄From tubular reactor one end The feed inlet in portion, which enters, to be fallen on belt conveyor, is transported to going out for tubular reactor other end lower part by belt conveyor Material mouth, material can sufficiently be reacted on band conveyor, and the belt conveyor can be conventional use of any defeated Machine is sent, belt conveyor length and width depends on position and the molecular sieve inlet amount of tubular reactor inlet port and outlet port Size.Under preferable case, the thickness of molecular sieve is no more than 20cm, more preferably no more than 10cm on the band conveyor.Make It is sieved with lace conveying device delivery of molecules, the axis of tube body and the angle α of horizontal plane are preferably 0-45 ° for example, 0-25 °.

A kind of reactor sieved using lace conveying device delivery of molecules is as shown in figure 5, Molecular sieve raw material and silicon tetrachloride It is introduced into reactor from the second molecular sieve entrance 131 of one end of reactor and the second silicon tetrachloride entrance 132, molecular sieve is fallen Enter on lace conveying device 133, it is mobile with conveyer belt on lace conveying device 133, it is full of in the gap in face over a molecular sieve Silicon tetrachloride, silicon tetrachloride enter in the duct of molecular sieve and participate in by the gap between diffusing into sieve particle The super stabilizing of aluminium-eliminating and silicon-replenishing reacts, and the molecular sieve after reaction drops into the second outlet molecular sieve of the reactor other end 134 and is discharged instead Answer device.Due to reacting with molecular sieve, along the direction of motion of molecular sieve, the silicon tetrachloride concentration in gas phase is gradually decreased.Wherein The aperture that can control the second outlet molecular sieve 134 is discharged material with certain speed, on the second outlet molecular sieve 134 Portion generates the material accumulation of certain altitude, avoids excessive silicon tetrachloride from being discharged from the second outlet molecular sieve 134, wherein second The air that gas vent 135 is brought into for drawing silicon tetrachloride and molecular sieve from reactor.Squeezing due to silicon tetrachloride in this way Act on out so that with molecular sieve introduce reactor air under the action of silicon tetrachloride, from sieve particle void diffusion to In the gas blanket of top, by extraction overhead gas periodically or non-periodically, the concentration of gas blanket silicon tetrachloride can be improved, have Conducive to reaction.Silicon tetrachloride, uncooled gas can be recycled after supercooling by the gas that second gas outlet 135 is drawn Body can empty after sponging a small amount of silicon tetrachloride wherein carried.In general, the molecular sieve thickness on conveyer belt is not answered It is excessively high, preferably more than 10cm, such as can be no more than 5cm.Its specific configuration and connection relationship can by aforementioned applications It is clear, for known to those skilled in the art, this is not described in detail here.

A preferred embodiment of the invention, the super steady reactor of gas phase is as shown in fig. 6, gas phase super steady reactor Molecular sieve conveying is conveyed by gravity.Reactor includes third molecular sieve entrance 141, third silicon tetrachloride entrance 142, reactor Tube body 143 is straight tube, including molecular sieve arrival end 144, rotatable portion 145 and outlet molecular sieve end 146, molecular sieve arrival end 144 and outlet molecular sieve end 146 by the first support device 147 support, driving device 151 is to drive rotatable portion 145 Axis around reactor tube body 143 rotates, and the second support device 148 is used to support rotatable portion 145.Rotatable portion 145 are provided with the first shovelling plate 149 and reactor weir plate 150, rotatable portion 145 and molecular sieve arrival end 144 and molecular sieve The junction of outlet end 146 is to be flexibly connected, and seal with the external world, and outlet molecular sieve end 146 is arranged in the outlet of molecular sieve On end face, baffle is set on end face, by the size of the adjustable outlet molecular sieve of controllable register, 116 refer to gas in Fig. 6 Mutually super steady reactor 116,117 refers to gas-solid separating device 117.Its specific configuration and connection relationship can by aforementioned applications It is clear, for known to those skilled in the art, this is not described in detail here.

In the present invention, described " first ", " second ", " third " are not constituted merely to distinguish to corresponding component Restriction to above-mentioned component.

Wherein, the section A-A of a preferred embodiment of the invention, the super steady reactor of gas phase shown in fig. 6 is shown It is intended to as shown in Figure 7.

The difunctional roaster and the super steady reactor of gas phase can be defeated by attachment device such as molecular sieve Pipeline is sent to be connected to, the outlet molecular sieve position of difunctional roaster is higher than roaster molecular sieve entry position.In order to make molecular sieve More stable, the attachment device such as molecule during flowing to the super steady reactor inlet of gas phase from the outlet of difunctional roaster At least one section of sieve feed-line is set as tilting, and the axis of the tilting section and the angle of horizontal plane are 35-75 °, in order to just Valve or flashboard are also provided in the flow of control molecular sieve, in the connecting pipeline to adjust the big of molecular sieve transfer passage Small, when valve or flashboard is arranged, the angle of the tilting section and horizontal plane is 55-65 °, this is convenient for control molecular sieve Flow, and can be by control valve or flashboard aperture, the case where making molecular sieve form certain molecular sieve layer above it Lower guarantee molecular sieve flowing, plays the air-flow of isolation gas phase super steady reactor and roaster, prevents to organize gas when fluctuation Phase silicon tetrachloride enters difunctional roaster.

Connecting pipeline (attachment device) described in a kind of preferably includes the first vertical section 511, the second vertical section 512 and inclines Oblique section 513, as shown in figure 8, the discharge end of 511 one end of the first vertical section and roaster connects, other end and tilting section 513 connect It connects, the other end of tilting section 513 is connect with one end of the second vertical section 512, the other end and gas phase of the second vertical section 512 The molecular sieve entrance of super steady reactor is connected to.The axis of the tilting section and the angle of horizontal plane are preferably 30-80 °.Described Connecting pipeline is preferably additionally provided with flashboard 514, on the one hand can control the flow of molecular sieve by setting flashboard, in addition can control Material position of the molecular sieve processed in the connecting pipeline plays sealing process, and silicon tetrachloride is prevented to enter roaster.As shown in figure 8, Flashboard is mobile to upper right side, then flow path increase can increase the flow of molecular sieve or reduce the material position of molecular sieve above flashboard, Otherwise lower section is mobile to the left for flashboard, then it can reduce the flow of molecular sieve or improve the material position of molecular sieve above flashboard.

The method provided according to the present invention, it is preferable that it is super steady that molecular sieve and silicon tetrachloride gas are continually fed into gas phase In reactor 116, again from gas after reacting molecular sieve sufficiently in tubular reactor by gravity and/or offer power Mutually the molecular sieve discharge port of super steady reactor 116 is expelled in gas-solid separating device 117.

Heretofore described gas solid separation is used to separate the molecular sieve after the super steady reaction of gas phase from gas phase, with gas Unreacted silicon tetrachloride separation in phase, as far as possible unreacted silicon tetrachloride in removing molecular sieve.Solid and gas of the present invention It can be separated in gas-solid separating device 117, gaseous component introduces absorption tower 120, and the absorption tower 120 is used for gas solid separation Silicon tetrachloride in gas afterwards absorbs.The aqueous solution that lye such as sodium hydroxide generally can be used absorbs silicon tetrachloride, can also To use water to be absorbed.Therefore, in the present invention, the absorption tower 120 preferably includes gas access, absorbing liquid entrance and two Outlet, wherein gas access is connected to gas-solid separating device 117, is preferably placed at the middle and upper part on the absorption tower 120.It is described two Outlet is located at the top and bottom on the absorption tower 120, is respectively used to discharge gas and absorbs waste liquid.In order to guarantee to be discharged Gas in SiCl₄Content is sufficiently low, and under preferable case, the absorption tower is concatenated multiple.Concatenated multiple absorption towers pair SiCl₄Form multistage absorption.The gas vent on absorption tower 120 can connect air-introduced machine.

Gas after sponging a small amount of excessive silicon tetrachloride by absorption tower 120 can direct emission, solid material can It is periodically discharged with continuously drawing gas-solid separating device 117 or staying in gas-solid separating device 117.Pass through control material conveying speed The length of degree or/and the super steady reactor 116 of gas phase, can control stop of the molecular sieve material in the super steady reactor 116 of gas phase Time, the time that control molecular sieve is contacted with silicon tetrachloride, so as to make the haptoreaction of molecular sieve and silicon tetrachloride in gas Mutually uniformly adequately carried out in super steady reactor 116 (preferably tubular reactor)；By using the gas phase of setting having heaters Super steady reactor 116 or regulatory molecule sieve and silicon tetrachloride additional amount ratio, can control different reaction temperatures, so as to To control differential responses condition and the extent of reaction, and then the zeolite product of available different dealumination depths.

In the present invention, the various containers that can be realized above-mentioned gas solid separation purpose can be used as the present invention, the present invention couple There is no particular limitation for its shape, such as can be cylindric.In further preferred situation, the gas-solid separating device 117 Bottom is the taper that end has opening, so that the molecular sieve obtained can be discharged from the opening.It is mixed after reaction in order to make It closes the gas component in object and enters absorption tower 120 as far as possible without being discharged from above-mentioned opening, under preferable case, the gas solid separation The position that device 117 is connect with discharge port is higher than the initial position of the taper.In further preferred situation, the gas solid separation The position that device 117 is connect with discharge port is located at the middle and upper part of the gas-solid separating device 117, and gas-solid separating device 117 passes through Its top opening is connected to absorption tower 120.

The method provided according to the present invention, steady reactor 116 super to the gas phase, gas-solid separating device 117 and absorption The specific structure of tower 120 is not particularly limited, and specific configuration and connection relationship can be defined by aforementioned applications, is ability Field technique personnel are known, and this is not described in detail here.

The method provided according to the present invention, it is preferable that this method further includes：The molecular sieve and the exhaustion of yang that gas solid separation is obtained Ionized water mashing, washing, filtering and drying obtain products molecule sieve.

The mashing, washing, filtering and dry method can use method commonly used in the art, and the present invention exists This is repeated no more.

Molecular sieve after ion-exchange reactions is carried out the super steady processing of hydro-thermal to method provided by the invention and roasting (obtains Molecular sieve temperature is 350-600 DEG C, and solid content is not less than 98 weight %), it is gentle then to carry out the reaction of gas chemistry dealumination complement silicon Gu separation, modified molecular screen obtained are high compared with high-Si Y-type molecular sieve crystallinity reservation degree prepared by conventional hydrothermal method, heat and hydro-thermal Stability is high, has second level pore structure abundant compared with the high-Si Y-type molecular sieve of vapor phase method preparation.

Therefore, the present invention also provides modified molecular screen made from above-mentioned method of modifying, the second hole of the molecular sieve Pore volume accounts for the 15-22% of total pore volume, and framework si-al ratio is with SiO_2/Al₂O₃Molar ratio computing is 10-15, and relative crystallinity is 55-65%.

In the present invention, the aperture of the second hole is 2nm-100nm.The measuring method of the pore volume of the second hole is such as Under：According to RIPP 151-90 standard method《Petrochemical egineering analysis method (RIPP test methods)》(Yang Cui is surely equal to be compiled, and science goes out Version society, nineteen ninety publish) total pore volume that molecular sieve is determined according to adsorption isotherm, then make from adsorption isotherm according to T Figure method determines the micro pore volume of molecular sieve, and total pore volume is subtracted micro pore volume and obtains second level pore volume.

The molecular sieve provided according to the present invention, it is preferable that the lattice constant of the molecular sieve is 2.440nm-2.455nm.

The molecular sieve provided according to the present invention, it is preferable that the lattice collapse temperature of the molecular sieve is not less than 1050 DEG C, preferably Not less than 1058 DEG C, for example, 1058 DEG C -1062 DEG C.

The molecular sieve provided according to the present invention, it is preferable that the specific surface area of the molecular sieve is 640-680m²/ g, for example, 650-675m²/g。

The molecular sieve provided according to the present invention, it is preferable that the total pore volume of the molecular sieve is 0.35-0.39mL/g, such as For 0.35-0.37mL/g.

In the present invention, the lattice constant, relative crystallinity are measured by x-ray powder diffraction (XRD), specifically, Using RIPP 145-90, RIPP 146-90 standard method (see《Petrochemical analysis method》(RIPP test method) Yang Cuiding Deng volume, Science Press, nineteen ninety is published) measurement.

Framework si-al ratio is calculated by following formula and is obtained：

SiO₂/Al₂O₃=(2.5858-a₀)×2/(a₀-2.4191)

Wherein, a₀For lattice constant, unit nm.

In the present invention, the lattice collapse temperature of molecular sieve is measured by differential thermal analysis (DTA), and laboratory apparatus uses the U.S. The Dupont1600 thermal analyzer of E.I.Du Pont Company, experiment condition include：Using air as carrier gas, flow 140mL/min, heating speed Rate is 10 DEG C/min.

In the present invention, the specific surface area of molecular sieve refers to BET specific surface area, using Micromeritics company ASAP2400 static state n2 absorption apparatus, sample vacuumize degassing 4h under the conditions of 1.33Pa, 300 DEG C, then connect at 77K with liquid nitrogen Touching, isothermal adsorption, desorption measure adsorption and desorption thermoisopleth, calculate specific surface area using BET formula.

The present invention also provides application of the above-mentioned molecular sieve in catalytic cracking.Molecular sieve provided by the invention has high knot Brilliant degree, high fever and hydrothermal stability, and there is second level pore structure abundant, it is highly suitable for oil product in catalytic cracking process Processing.

Below by embodiment, the invention will be further described, but the content being not intended to limit the present invention.

In following embodiment and comparative example, NaY molecular sieve (also referred to as NaY zeolite) is neat by Sinopec catalyst Co., Ltd Shandong branch company provides, and sodium oxide content is 13.5 weight %, framework si-al ratio (SiO₂/Al₂O₃Molar ratio) it is 4.6, lattice constant For 2.470nm, relative crystallinity 90%.

Rare-earth salts (RE (NO₃)₃) provided by Beijing Chemical Plant；RE(NO₃)₃For mischmetal, the La containing 33 weight % (NO₃)₃With the Ce (NO of 67 weight %₃)₃。

Second level pore volume, total pore volume, specific surface area, lattice constant, relative crystallinity, the lattice collapse temperature of molecular sieve Measuring method with framework si-al ratio is as described above, details are not described herein.

The content of sodium oxide molybdena and rare earth oxide is measured using X-ray fluorescence spectra (XRF) method in molecular sieve, wherein X-ray Fluorescence spectrum (XRF) method uses Rigaku electric machine industry Co., Ltd. 3271E type Xray fluorescence spectrometer, using Rh target, It is measured under conditions of electric current 50mA, voltage 50kV.

Embodiment 1

Method of modifying provided in this embodiment the modification of molecular sieve as shown in Figure 2 equipment (NaY molecular sieve be it is commercially available, Therefore NaY molecular sieve synthesis reactor 111 and the first filter device 112 is not used) on carry out.Wherein,

(1) in NaY molecular sieve switch 113, by 3000kg NaY molecular sieve (in terms of butt) and decationized Y sieve water Then RE (NO is added in mixing₃)₃(earth solution concentration is with RE for solution₂O₃It is calculated as 335g/L), wherein NaY molecular sieve is (with butt Meter), rare-earth salts is (with RE₂O₃Meter) and water dosage weight ratio be 1：0.18：15, in NaY molecular sieve switch 113 into Row ion-exchange reactions, the temperature of ion-exchange reactions are 95 DEG C, time 50min, and the molecular sieve pulp that exchange is completed passes through It crosses second filter device 114 (band filter) filtration washing and obtains filter cake.

(2) filter cake of step (1) is sent directly into difunctional roaster 115 and carries out the super steady processing of hydro-thermal and roasting, such as Fig. 1 Shown, the difunctional roaster includes furnace body 1 (including thermostat 10, insulating layer 11, heating layer 12 and burner hearth 13) and setting Cylinder 2 in the burner hearth 13, the internal diameter of entire cylinder 2 are 1.3m, and the length of entire cylinder 2 is 25m, wherein feed end 24 It is 0.5m with the respective length of discharge end 25, the length of middle cylinder 20 is 24m.Vapor point is internally provided in cylinder 2 Cloth device 5 and a dry gas distributor 6.Vapor distributor 5 and dry gas distributor 6 are that outer diameter is 20cm, and internal diameter is 19cm's Round tube, coaxial with cylinder 2, the length of vapor distributor 5 is 18.2m, and the length of dry gas distributor 6 is 6.5m, steam point There are gap, clearance distance 0.3m between cloth device 5 and dry gas distributor 6.It welds first open end 52 of vapor distributor 5 It is fixed on the end face of feed end 24, the first closed end 53 is towards discharge end 25.Multiple first through hole on vapor distributor 5 51 be in array distribution.First through hole 51 is the round hole of diameter 5mm, along vapor distributor 5 axial linear extension and between waiting Away from being distributed as 30/m；Circumferential equidistantly distributed along vapor distributor 5 is 6/week.Second opening of dry gas distributor 6 End 62 is weldingly fixed on the end face of discharge end 25, and the second closed end 63 is towards feed end 24.Multiple on dry gas distributor 6 Two through-holes 61 are in array distribution.Second through-hole 61 be diameter 3mm round hole, along dry gas distributor 6 axial linear extension and Equidistantly distributed is 40/m；Circumferential equidistantly distributed along dry gas distributor 6 is 9/week.It is set on the inner wall of middle cylinder 20 Set shovelling plate 3 and weir plate 4.Shovelling plate 3 is strip, and shovelling plate 3 is started setting up from middle cylinder 20 and the junction of feed end 24, shovelling plate Angle is formed between 3 extending direction and the axial direction of middle cylinder 20, the angle is 30 °.Shovelling plate 3 is along the middle cylinder 20 Circumferential distribution number be 4/week, shovelling plate 3 is along the axial equidistantly distributed of the middle cylinder 20, and number is 8, is copied The length of plate 3 is 2 times of the diameter of middle cylinder 20, and the minimum range of the two neighboring shovelling plate 3 (being arranged in parallel) apart is 0.2 times of 3 length of shovelling plate.Weir plate 4 is annular slab, along the axial equidistantly distributed of middle cylinder 20, axially adjacent two One weir plate 4 is set between a shovelling plate 3, weir plate 4 is straightened on the inner wall for being welded on middle cylinder 20, weir plate 4 with a thickness of 5mm, shovelling plate 3 are not contacted with weir plate 4.Middle cylinder 20 is set as rotating.Entire roaster is inclined with the axial direction of cylinder 2 with horizontal line Oblique 1 ° of placement.Feed end 24 is higher than discharge end 25.

The revolving speed of difunctional roaster is 1.2r/min, and the inlet amount of molecular sieve is 800kg/h.Water in difunctional roaster The super temperature surely handled of heat is 450 DEG C, is passed through the overheated steam that temperature is 450 DEG C, overheated steam by vapor distributor 5 Intake be 300kg/h, the maturing temperature of furnace zone is 480 DEG C, be passed through temperature be 480 DEG C, intake 3m³The drying of/h Air roasts molecular sieve as dry gas, obtain mitigate hydro-thermal it is super it is steady handle and roast high temperature Y type molecular sieve (Gu 99.5 weight % of content, temperature are 480 DEG C, RE₂O₃Content is 13.5 weight %, 4.5 weight % of sodium oxide content).

(3) the high temperature Y type molecular sieve that step (2) obtains is passed through into molecule with silicon tetrachloride gas at a temperature of 90 °C respectively It is sieved into mouth and silicon tetrachloride entrance enters in tubular reactor (tubular reactor disclosed in embodiment 2 in WO2014/063445) Carry out the reaction of gas chemistry dealumination complement silicon.A heat tape is wound by the outer wall on tube body to add tubular reactor Heat, control reaction temperature are 480 DEG C (reactor outlet molecular sieve temperature), SiCl₄Flow by mass flowmenter control and SiCl₄Weight ratio with molecular sieve (in terms of butt) is 0.05, and the inlet amount of molecular sieve is 800kg/h, and molecular sieve is anti-in tubular type Answering the residence time in device is 20min, and the super steady obtained molecular sieve that reacts of gas phase enters gas-solid separating device 117, is deposited in gas The bottom of solid separation device 117, the top of gas-solid separating device 117 be diameter be 6 meters, a height of 14 meters of cylinder, lower part is End has the taper of opening, and cone angle is 45 °, and opening is provided with valve, after reaction carries out 1h, in gas-solid separating device 117 Molecular sieve be discharged from the opening of conical lower portion, later with the mashing of decationized Y sieve water, washing, filtering and at 120 DEG C it is dry after To molecular sieve SZ-1, main character is listed in Table 1 below.The gaseous phase outlet of gas-solid separating device 117 is connect with absorption tower 120, with The unreacted gas phase SiCl of molecule sieve separation₄Entered in absorption tower 120 by the gaseous phase outlet at 117 top of gas-solid separating device (fill the sodium hydrate aqueous solution that concentration is 10 mol/Ls in absorption tower 120, absorption tower 120 and gas-solid separating device 117 it Between connected by conduit, conduit gos deep into sodium hydrate aqueous solution) contacted instead with the sodium hydrate aqueous solution in absorption tower 120 It answers.

Embodiment 2

(1) in NaY molecular sieve switch 113, by 4000kg NaY molecular sieve (in terms of butt) and decationized Y sieve water Then RE (NO is added in mixing₃)₃(earth solution concentration is with RE for solution₂O₃It is calculated as 335g/L), wherein NaY molecular sieve is (with butt Meter), rare-earth salts is (with RE₂O₃Meter) and water dosage weight ratio be 1：0.18：12, in NaY molecular sieve switch 113 into Row ion-exchange reactions, the temperature of ion-exchange reactions are 90 DEG C, time 60min, and the molecular sieve pulp that exchange is completed passes through It crosses second filter device 114 (band filter) filtration washing and obtains filter cake.

(2) filter cake of step (1) is sent directly into difunctional roaster 115 and carries out the super steady processing of hydro-thermal and roasting, double function Can difunctional roaster disclosed in roaster 115 and embodiment 1 the difference is that, entire roaster is with the axis of cylinder 2 1.3 ° of placements are tilted to horizontal line, the second through-hole 61 is the round hole of diameter 4mm, and the axial straight line along dry gas distributor 6 prolongs It stretches and equidistantly distributed is 30/m；Circumferentially distributed along dry gas distributor 6 is 5/week.

The revolving speed of difunctional roaster is 1.5r/min, and the inlet amount of molecular sieve is 900kg/h.Water in difunctional roaster The super temperature surely handled of heat is 400 DEG C, is passed through the overheated steam that temperature is 400 DEG C, overheated steam by vapor distributor 5 Intake be 350kg/h, the maturing temperature of furnace zone is 420 DEG C, be passed through temperature be 420 DEG C, intake 5m³The drying of/h Air roasts molecular sieve as dry gas, obtain mitigate hydro-thermal it is super it is steady handle and roast high temperature Y type molecular sieve (Gu 99.5 weight % of content, temperature are 400 DEG C, RE₂O₃Content is 13.5 weight %, 4.5 weight % of sodium oxide content).

(3) the silicon tetrachloride gas that high temperature Y type molecular sieve and temperature that step (2) obtains are 95 DEG C is passed through into molecule respectively It is sieved into mouth and silicon tetrachloride entrance enters in tubular reactor (tubular reactor disclosed in embodiment 1 in WO2014/063445) Carry out the reaction of gas chemistry dealumination complement silicon.A heat tape is wound by the outer wall on tube body to add tubular reactor Heat, control reaction temperature are 420 DEG C (reactor outlet molecular sieve temperature), SiCl₄Flow by mass flowmenter control and SiCl₄Weight ratio with molecular sieve (in terms of butt) is 0.2, and the inlet amount of molecular sieve is 900kg/h, and molecular sieve is in pipe reaction Residence time in device is 10min, and the super steady obtained molecular sieve that reacts of gas phase enters gas-solid separating device 117 (with 1 phase of embodiment Together), after reaction carries out 1.5h, molecular sieve in gas-solid separating device 117 is discharged from the opening of conical lower portion, later and the exhaustion of yang from Sub- water mashing, washing, filtering simultaneously obtain molecular sieve SZ-2 after 120 DEG C of dryings, and main character is listed in Table 1 below.With molecular sieve The unreacted gas phase SiCl of separation₄Carry out absorption same as Example 1.

Embodiment 3

(1) in NaY molecular sieve switch 113, by 2000kg NaY molecular sieve (in terms of butt) and decationized Y sieve water Then RE (NO is added in mixing₃)₃(earth solution concentration is with RE for solution₂O₃It is calculated as 335g/L), wherein NaY molecular sieve is (with butt Meter), rare-earth salts is (with RE₂O₃Meter) and water dosage weight ratio be 1：0.19：12, in NaY molecular sieve switch 113 into Row ion-exchange reactions, the temperature of ion-exchange reactions are 95 DEG C, time 50min, and the molecular sieve pulp that exchange is completed passes through It crosses second filter device 114 (band filter) filtration washing and obtains filter cake.

(2) filter cake of step (1) is sent directly into difunctional roaster 115 and carries out the super steady processing of hydro-thermal and roasting, double function Can difunctional roaster disclosed in roaster 115 and embodiment 1 the difference is that, entire roaster is with the axis of cylinder 2 3 ° of placements are tilted to horizontal line, first through hole 51 is the round hole of 3 diameter mm, and the axial straight line along vapor distributor 5 prolongs It stretches and equidistantly distributed is 40/m；Circumferentially distributed along vapor distributor 5 is 8/week.

The revolving speed of difunctional roaster is 1r/min, and the inlet amount of molecular sieve is 700kg/h.Hydro-thermal in difunctional roaster The super temperature surely handled is 400 DEG C, is passed through the overheated steam that temperature is 400 DEG C by vapor distributor 5, overheated steam Intake is 300kg/h, and the maturing temperature of furnace zone is 400 DEG C, be passed through temperature be 400 DEG C, intake 7m³/ h's is dry empty Gas roasts molecular sieve as dry gas, obtain mitigate hydro-thermal it is super it is steady handle and roast high temperature Y type molecular sieve (admittedly contain 99.5 weight % are measured, temperature is 400 DEG C, RE₂O₃Content is 15 weight %, 4 weight % of sodium oxide content).

(3) the silicon tetrachloride gas that high temperature Y type molecular sieve and temperature that step (2) obtains are 85 DEG C is passed through into molecule respectively It is sieved into mouth and silicon tetrachloride entrance enters tubular reactor (the super steady reaction of gas phase disclosed in embodiment 3 in WO2014/063445 Device) in carry out the reaction of gas chemistry dealumination complement silicon.It is anti-to tubular type that electric furnace heating wire is wound by the outer wall of the rotatable portion in tube body Device is answered to be heated, control reaction temperature is 400 DEG C (reactor outlet molecular sieve end temperature), SiCl₄Flow by quality stream Meter control and SiCl₄Weight ratio with molecular sieve (in terms of butt) is 0.09, and the inlet amount of molecular sieve is 700kg/h, molecule Sieving the residence time in tubular reactor is 5min, and the super steady obtained molecular sieve that reacts of gas phase enters gas-solid separating device 117 (same as Example 1), after reaction carries out 1h, the molecular sieve in gas-solid separating device 117 is discharged from the opening of conical lower portion, it It is beaten afterwards with decationized Y sieve water, washing, filters and obtain molecular sieve SZ-3 after dry at 120 DEG C, main character is listed in table 1 In.With the unreacted gas phase SiCl of molecule sieve separation₄Carry out absorption same as Example 1.

Embodiment 4

According to the method for modifying of embodiment 1, the difference is that, the super temperature surely handled of hydro-thermal is 500 DEG C in step (2), by Vapor distributor 5 is passed through the overheated steam that temperature is 500 DEG C, obtains molecular sieve SZ-4, main character is listed in Table 1 below.

Comparative example 1

Molecular sieve (the weight of its silicon tetrachloride and molecular sieve is prepared according to method disclosed in CN102049315A embodiment 1 Than for 0.3), unlike, it is 350 DEG C by the temperature from roaster in CN102049315A embodiment 1 in terms of butt REY molecular sieve such as replaces at the high temperature Y type molecular sieve that step (2) obtains in the embodiment of the present invention 3 of quality, and in tube body 13 Outer wall winding electric furnace heating wire tubular reactor is heated, control reaction temperature be 400 DEG C, obtain molecular sieve DZ-1, lead Property is wanted to be listed in Table 1 below.

Table 1

From the results shown in Table 1, using the framework silicon of modified molecular screen made from method of modifying provided by the invention Aluminium is than being SiO₂/Al₂O₃Molar ratio greatly improves, and second hole pore volume significantly increases, and shows super using same or similar gas phase Steady reactor and the super steady reaction condition of gas phase carry out the super steady processing of hydro-thermal and roasting by using difunctional roaster, not only The zeolite product of high silica alumina ratio can be obtained, moreover, obtained high-silica zeolite has more second hole.In addition, from table 1 Result can be seen that compared with comparative example, collapsed using the lattice of modified molecular screen made from method of modifying provided by the invention Temperature of collapsing significantly improves, and sodium oxide content is substantially reduced, and shows that the present invention provides modified molecular screen made from method of modifying and has Higher thermal stability, has excellent performance.

Test example 1

This test example is used to illustrate the Catalytic Cracking Performance of catalyst made of molecular sieve provided by the invention.

The preparation of catalyst：By boehmite (Al₂O₃Content is 62 weight %, Shandong Aluminum Plant), deionized water and hydrochloric acid Plastic cans stirring to pulp is added in (36 weight %), and beating time is 1 hour, and pulper slurry temperature is 20 DEG C；Again by above-mentioned implementation Stirring to pulp in plastic cans is added in modified molecular screen made from example and comparative example, and beating time is 3 hours, and pulper slurry temperature is 30℃；Again by kaolin (Law Firm Suzhou Jiangsu) and Aluminum sol (Al₂O₃Content is 22 weight %, Shandong Aluminum Plant) it is added in plastic cans and beats Starch plastic, molecular sieve (in terms of butt)：Kaolin：Boehmite is (with Al₂O₃Meter)：Aluminum sol is (with Al₂O₃Meter) weight ratio It is 32：36：22：10, hydrochloric acid：Boehmite is (with Al₂O₃Meter) weight ratio be 0.26：1, gelation time is 8 hours, plastic Temperature is 30 DEG C, obtains plastic product.Then plastic product is conveyed into spray drying tower, is 450 DEG C in spray inlet temperature Lower spray drying granulation molding, outlet temperature are 200 DEG C, and atomisation pressure 8MPa, the catalytic cracking after being spray-dried is urged Agent microballoon is roasted using obtained catalytic cracking catalyst microballoon as being put into roaster to calcining matter, and maturing temperature is 500 DEG C, calcining time 3h, the catalytic cracking catalyst microballoon after roasting presses water and catalytic cracking catalyst microspheres weight ratio again It is 8：1 is washed, and wash temperature is 50 DEG C, and wash time is 1 hour, is then filtered, the catalysis obtained after filtering is split Change catalyst microspheres and carry out pneumatic conveying drying again, dry temperature is 150 DEG C, and the time is 1.5 hours, obtains catalytic cracking catalysis Agent.Molecular sieve select respectively modified molecular screen SZ-1, SZ-2, SZ-3 and SZ-4 made from embodiment 1-4 (obtain catalyst A-1, A-2, A-3 and A-4) and comparative example 1 made from modified molecular screen DZ-1 (obtain catalyst DA-1), main character is listed in table In 2.

Catalyst Determination of Physical Property Parameters：

Pore volume and specific area measuring, method be RIPP151-90 standard method (see《Petrochemical analysis method》 (RIPP test method), Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes)；Abrasion index and apparent bulk density measurement, method For RIPP 29-90 standard method (see《Petrochemical analysis method》(RIPP test method), Yang Cui delimits the organizational structure, Science Press, Nineteen ninety publishes).

The Catalytic Cracking Performance of catalyst is tested：

Light oil microactivity evaluation：Using RIPP92-90 standard method (see《Petrochemical analysis method》(RIPP examination Proved recipe method) Yang Cui is surely equal compiles, Science Press, nineteen ninety publishes) light oil microactivity of evaluation sample, catalyst loading is 5.0g, reaction temperature are 460 DEG C, and the huge port light diesel fuel that feedstock oil is 235-337 DEG C of boiling range, product composition is by gas-chromatography point Analysis calculates light oil microactivity according to product composition, and the results are shown in Table 2.

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

Heavy oil cracking performance evaluation condition：Catalyst is first at 800 DEG C, 100% steam aging 12 hours, then in ACE It is evaluated on (fixed fluidized bed) device, the property of heavy oil feedstock oil is shown in Table 3, and 500 DEG C of reaction temperature, agent oil weight ratio is 4, heavy oil The results are shown in Table 4 for cracking performance.

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

Yield of light oil=yield of gasoline+diesel yield

Total liquid yield=yield of liquefied gas+yield of gasoline+diesel yield

Coke selectivity=coking yield/conversion ratio

Table 2

Catalyst number	A-1	A-2	A-3	A-4	DA-1
						Molecular sieve number	SZ-1	SZ-2	SZ-3	SZ-4	DZ-1
Al2O3Content/weight %	48.6	48.9	49.1	48.7	49.5
						Na2O content/weight %	0.06	0.04	0.05	0.08	0.14
Pore volume/(mLg-1)	0.42	0.43	0.42	0.39	0.40
						Specific surface area/(m2·g)	292	281	285	280	280
Abrasion index/(%h-1)	0.9	0.9	1.0	1.1	1.5
						Apparent bulk density/(gmL-1)	0.74	0.75	0.75	0.74	0.73
Micro-activity (800,4h)/%	84	83	82	81	80

From the results shown in Table 2, when using system with molecular sieve for preparing provided by the present invention for catalyst, with comparative catalyst DA-1 is compared, and the pore volume of catalyst increases, and sodium oxide content reduces, and micro-activity improves.

Table 3

Table 4

Catalyst number	A-1	A-2	A-3	A-4	DA-1
						Product distribution, weight %
Dry gas	1.04	1.01	1.03	1.09	1.17
						Liquefied gas	12.73	12.41	12.38	12.65	14.17
Coke	4.78	5.08	4.85	5.54	5.44
						Gasoline	57.32	56.97	56.58	54.4	52.89
Diesel oil	18.51	18.99	18.97	18.51	17.95
						Heavy oil	5.62	5.54	6.19	7.81	8.38
It is total	100	100	100	100	100
						Conversion ratio, weight %	75.87	75.47	74.84	73.68	73.67
Coke selectivity, weight %	6.30	6.73	6.48	7.18	7.38
						Yield of light oil, weight %	75.83	75.96	75.55	72.91	70.84
Total liquid yield, weight %	88.56	88.37	87.93	85.56	85.01

From the results shown in Table 4, compared with reference catalyst DA-1, using method of modifying system provided by the present invention The modified molecular screen obtained is the catalyst heavy oil conversion rate with higher of active component preparation, higher liquid yield and lightweight Oil yield, coke selectivity are lower.

Claims (14)

1. a kind of method of modifying of molecular sieve, this method include：NaY molecular sieve is successively subjected to ion-exchange reactions, hydro-thermal surpasses Surely processing, roasting, the reaction of gas chemistry dealumination complement silicon and gas solid separation, the super steady method for handling and roasting of hydro-thermal make Molecular sieve temperature after roasting is 350-600 DEG C, and solid content is not less than 98 weight %.

2. method of modifying according to claim 1, wherein the super steady method for handling and roasting of hydro-thermal to roast Molecular sieve temperature afterwards is 400-550 DEG C, and solid content is not less than 99 weight %.

3. method of modifying according to claim 1 or 2, wherein the hydro-thermal surpasses the condition surely handled and includes：Temperature is 350-480 DEG C, time 0.5-3h, relative to every kilogram of molecular sieve, the dosage of superheated vapour is 0.15-0.45 kilograms；

Preferably, the condition of the roasting includes：Temperature is 350-550 DEG C, time 0.5-1.5h.

4. method of modifying described in any one of -3 according to claim 1, wherein the hydro-thermal is super, and steady processing terminate to roasting The time interval of beginning is not more than 5min, preferably 1-4min.

5. method of modifying described in any one of -4 according to claim 1, wherein the super steady processing of the hydro-thermal and roasting are double Function roaster carries out on (115), and the difunctional roaster (115) includes furnace body (1) and is arranged in the furnace body (1) Cylinder (2), the cylinder (2) successively include feed end (24), middle cylinder (20) and discharge end (25), are moved towards along material, institute Stating difunctional roaster (115) further includes being successively set in the cylinder (2) for offer vapor in the cylinder (2) Vapor distributor (5) and for providing for the dry gas distributor as the dry gas for roasting medium in the cylinder (2) (6)。

6. method of modifying according to claim 5, wherein the vapor distributor (5) is to have the first open end (52) With the hollow circular tube shape structure of the first closed end (53), and first through hole is offered on the tube wall of the hollow circular tube shape structure (51), first open end (52) and the feed end (24) are ipsilateral, and first closed end (53) is towards the discharge end (25), the first through hole (51) has multiple, and multiple first through hole (51) are in array distribution；

Preferably, the quantity of the vapor distributor (5) is 1-10；

Preferably, each vapor distributor (5) is set as the vapor distributor (5) in the cylinder (2) Axial direction and the cylinder (2) it is axial parallel；

Preferably, the outer diameter of the vapor distributor (5) is the 10%-30% of the internal diameter of the cylinder (2)；

Preferably, the length of the vapor distributor (5) is the 10%-90% of the length of the cylinder (2).

7. method of modifying according to claim 6, wherein the first through hole (51) is along the vapor distributor (5) Circumferential be distributed as 5-40/m；Extending direction along the vapor distributor (5) is distributed as 10-50/m；

Preferably, the diameter of the first through hole (51) is 1-10mm.

8. method of modifying according to claim 5, wherein the dry gas distributor (6) be have the second open end (62) and The hollow circular tube shape structure of second closed end (63), and the second through-hole (61) are offered on the tube wall of the hollow circular tube shape structure, Second open end (62) and the discharge end (25) are ipsilateral, and second closed end (63) is towards the feed end (24)； Second through-hole (61) have it is multiple, and multiple second through-holes (61) be in array distribution；

Preferably, the quantity of the dry gas distributor (6) is 1-10；

Preferably, the axis that is set as the dry gas distributor (6) of each dry gas distributor (6) in the cylinder (2) It is axial parallel with the cylinder (2) to direction；

Preferably, the outer diameter of the dry gas distributor (6) is the 10%-30% of the internal diameter of the cylinder (2)；

Preferably, the length of the dry gas distributor (6) is the 10%-90% of the length of the cylinder (2).

9. method of modifying according to claim 8, wherein second through-hole (61) is along the dry gas distributor (6) Circumferential is distributed as 5-40/m；Extending direction along the dry gas distributor (6) is distributed as 10-50/m；

Preferably, the diameter of second through-hole (61) is 1-10mm.

10. the method for modifying according to any one of claim 5-9, wherein

Axial direction along the cylinder (2), there are gap between the dry gas distributor (6) and the vapor distributor (5), Stand-off distance is from the 1-30% for the cylinder (2) length.

11. the method for modifying according to any one of claim 5-10, wherein

Shovelling plate (3) and weir plate (4) are provided on the inner wall of the middle cylinder (20)；

Angle between the extending direction of the shovelling plate (3) and the axial direction of the middle cylinder (20) is acute angle or obtuse angle, wherein The shovelling plate (3) is multiple, and multiple shovelling plates (3), along the circumferentially distributed of the middle cylinder (20), distribution number is 1-6 A/week, and do not contacted between two neighboring shovelling plate (3)；

The weir plate (4) is multiple, and multiple weir plates (4) are distributed number along the axial direction distribution of the middle cylinder (20) It is 1-30/10 meters.

12. method of modifying described in any one of -11 according to claim 1, wherein

Gas chemistry dealumination complement silicon reaction method include：By the molecular sieve and silicon tetrachloride gas haptoreaction after roasting；

Preferably, the catalytic temperature is 200-650 DEG C, and the catalytic time is 10-300min；

Preferably, the weight ratio 0.05-0.2 of silicon tetrachloride and the molecular sieve after the roasting in terms of butt:1.

13. modified molecular screen made from method of modifying described in any one of claim 1-12, the modified molecular screen The pore volume of second hole accounts for the 15-22% of total pore volume, and framework si-al ratio is with SiO₂/Al₂O₃Molar ratio computing is 10-15, opposite to tie Brilliant degree is 55-65%.

14. application of the modified molecular screen described in claim 13 in catalytic cracking.