CN106517238B - It is a kind of to prepare equipment and preparation method of the low-Na and high-Si aluminium than Y type molecular sieve - Google Patents
It is a kind of to prepare equipment and preparation method of the low-Na and high-Si aluminium than Y type molecular sieve Download PDFInfo
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- CN106517238B CN106517238B CN201611116722.9A CN201611116722A CN106517238B CN 106517238 B CN106517238 B CN 106517238B CN 201611116722 A CN201611116722 A CN 201611116722A CN 106517238 B CN106517238 B CN 106517238B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
Equipment and preparation method of the low-Na and high-Si aluminium than Y type molecular sieve are prepared the invention discloses a kind of, the equipment includes reactor (1), first feeding channel (2), tapping channel (4), the second feeding channel (3), mixing device (8), reaction component (7), heating device (9), gas-solid separating device (5), regenerative apparatus (10)；It include at least one set of reaction component (7) equally distributed in the middle in the reactor (1), the reaction component (7) includes at least one fluidized bed.When preparing molecular sieve using the equipment, operating process is short, no ammonia and nitrogen pollution, and sewage quantity is few, production cost is low, and reaction controlling is good, and the extent of reaction is high, and product sodium content is low, silica alumina ratio is high, silica alumina ratio is controllable, and product property is uniform, can carry out large-scale continuous be automatically brought into operation.
Description
Technical field
The present invention relates to molecular sieve modified technical field, in particular to low-Na and high-Si aluminium is led than the technology of Y type molecular sieve
Domain.
Background technique
It is well known that reducing Y type molecular sieve sodium content and aluminic acid center density, improving silica alumina ratio, be conducive to improve molecule
The chemical stability and hydrothermal stability of sieve are conducive to improve using molecular sieve as the service life of the catalyst of active component, reduce hydrogen
Transfer activity reduces coke generation.Therefore, how short route, low emission acquisition low-Na and high-Si aluminium are than Y type molecular sieve, to raising
Molecular sieve stability and catalyst performance, reduce environmental pollution, to reduce manufacturing cost most important.
Due to the not aobvious acidity of NaY type molecular sieve, to generate solid acid, it is necessary to introduce polyvalent cation or Hydrogen Proton brilliant
In lattice, in the prior art, drop sodium is carried out to molecular sieve and mainly uses ion exchange, refers to and uses NH4+、RE3+、Mg2+Equal metals
Na in ionic compartmentation molecular sieve+.In order to improve sodium exchange degree, ion exchange-roasting-ion exchange-roasting is mostly used greatly
" two hand over two roastings " technique, can generate waste water, the exhaust gas largely containing heavy metal and ammonia nitrogen during this.
And there are two ways to obtaining high silica alumina ratio Y type molecular sieve: direct synthesis technique and rear modified method.Wherein directly synthesize
It is in alkaline system, NaY molecular sieve silica alumina ratio obtained is difficult more than 6 and sodium oxide content is high；It can according to template agent method
The NaY molecular sieve of direct synthesizing Si-Al ratio 6-20, but template is expensive, high production cost.Therefore people largely use
It is modified method afterwards, i.e., it is next the NaY molecular sieve original powder synthesized under alkaline system to be carried out ion exchange, dealuminzation, the method for dealumination complement silicon
It obtains low-Na and high-Si aluminium and compares Y type molecular sieve.
Use dealuminzation, dealumination complement silicon method come with the method for improving the silica alumina ratio of molecular sieve substantially have hydrothermal dealumination method,
Chemical dealuminization method and gas phase dealumination complement silicon method.
Wherein, hydrothermal dealumination method is to be handled with high-temperature water vapor molecular sieve, and water vapour enters molecular sieve pore passage
Generating Al (OH) x with its skeleton reactive aluminum afterwards makes aluminium atom move out of skeleton, to achieve the purpose that complete molecular sieve dealuminzation.
Chemical dealuminization method, which refers to, to be contacted with inorganic acid or organic acid, metal ion network mixture, fluosilicate etc. with molecular sieve,
Aluminium on framework of molecular sieve is extracted by way of dissolution, complexing, liquid phase same order elements.But above-mentioned processing method
In, fluosilicate liquid phase isomorphous substitution method can generate the harmful villiaumite stray crystal (NH for being difficult to separate4)3AlF6、Na3AlF6, thus shadow
Molecular sieve catalytic performance is rung, also generation waste water containing fluorine, environmental pollution are serious；Other processing methods will lead to molecule sieve skeleton
The avalanche of frame, crystallinity are greatly reduced, and the non-framework aluminum for extracting generation can also block molecular sieve pore passage, to catalytic performance and hydro-thermal
Stability adversely affects.
Gas phase dealumination complement silicon gas phase same order elements owned by France, chemical reaction mechanism are as follows: M1/n[AlO2•(SiO2)x]+SiCl4
→1/nMCln+AlCl3+[(SiO2)x+1], wherein M is metal ion (Beyer, Belenykaja. Studies in
Surface Science and Catalysis, 1980,5:203-210).I.e. by halogen silane gas (such as monochlor(in)ate silicon, two
Silicon chloride, trichlorosilicane, silicon tetrachloride) it is contacted at high temperature with Y type molecular sieve, while deviating from aluminium, silicon is filled into aluminium vacancy
On, the aluminium taken off is escaped in the form of aluminum chloride gas, while aluminium chloride also generates NaAlCl with the sodium effect in molecular sieve4It is multiple
Salt, then by way of washing or acid extracting, can be obtained crystal retention is high, duct is unimpeded, silica alumina ratio be up to 550 Y type point
Son sieve.
CN1382525A discloses a kind of preparation method of rare-earth type high-silicon gamma-zeolite, including water content is lower than 10wt%
NaY molecular sieve according to silicon tetrachloride: NaY=0.1 ~ 0.9:1 weight ratio contact, silicon tetrachloride dry air carrying be passed through
In reactor, in 150-600 DEG C of reaction 10min-6h.After reaction, 5min ~ 2h is purged with dry air, reaction product is with spending
Cationic water washing removes Na remaining in molecular sieve+, C1-, Al3+Equal soluble by-products.Such as the patent and
Described in CN102320621A, in the prior art, gas phase dealumination complement silicon carries out in fixed bed reactors mostly, and sieve particle is solid
It is scheduled on the interlude of reactor, halogen silane gas steady flow over-molecular sieve bed.This method leads to mol sieve beds mass-and heat-transfer
Effect is poor, and reaction is exothermic reaction in addition, is easy to produce hot-spot, causes the property that reaction is uneven, obtains product different；
And react the NaAlCl of generation4Molecular sieve can be bonded blocking, it is inconvenient to cause to load, and is unfavorable for continuous production.
To solve the problems, such as that molecular sieve is easy to stick caked in the reactor, CN1057977C discloses a kind of containing rich silicon ultra stabilization
The preparation method of the carbon monoxide-olefin polymeric of Y zeolite, it includes by the drying and moulding object of NaY zeolite and heat-resistant inorganic oxide by four
Silicon chloride: the contact of molding=0.1-0.8:1 weight ratio, silicon tetrachloride gas are less than the dry behaviour's air of 900ppm by water content and take
Band is passed through in fixed bed reactors, in 150 ~ 550 DEG C of reaction 10min-5h.35 ~ 125 microns of partial size of particle in the molding
The weight ratio of 80% or more, the NaY and heat-resistant inorganic oxide that account for total particle number are 1:0.2 ~ 1, the silica alumina ratio of NaY zeolite is 3 ~
6.Molding good fluidity used in this method avoids the phenomenon that coalescing blocking and blocking, but sieve particle is still solid
It is scheduled in tubular reactor, still remains the disadvantage that mass-and heat-transfer effect is poor, product property is inhomogenous.
System with molecular sieve for preparing is caused molecular sieve paper in patent CN101850239A, then after molecular sieve paper is hot pressed into corrugated shape
It is stacked alternately or rolls up with molecular sieve paper and be built into honeycomb ceramics, be placed in closed container, with nitrogen and silicon tetrachloride gas
Molecular sieve honeycomb body is cleaned repeatedly after reaction, then uses pickling by mixed gas reaction.Through product made from this method
Matter is uniform, avoids molecular sieve bonds blocking problem, but to manufacture molecular sieve paper and honeycomb ceramics, to obtain powder product also
This honeycomb ceramics need to be broken into pieces, increased manufacturing cost and labor intensity.
Patent CN1286721C discloses a kind of gas phase aluminium-eliminating and silicon-replenishing method of molecular sieve, and gas phase dealumination complement silicon is reacted one
It is carried out in the reaction kettle of a band stirring.This method keeps silicon tetrachloride gas and molecular sieve solid particle haptoreaction more uniform,
Avoid between molecular sieve solid particle the phenomenon that being agglomerated into compact massive object, labor intensity can be reduced, can be reduced environment
Pollution significantly reduces production cost.But stirring also brings along the ill effect that molecular sieve is raised with air-flow and taken away, there is also
Production cycle length, stirred-tank reactor cannot infinitely amplify, be difficult to the deficiencies of large-scale continuous production.
Patent CN102049315A, CN102049316A, CN102050459A, CN102050460A, CN102451655A,
In CN102451656A, CN102451657A, CN102451658A, CN102451729A, CN102451730A, gas phase dealuminzation is mended
Pasc reaction be a 50 ~ 95m of root long, 0.1 ~ 1.4m of diameter flat-pushing streaming with being carried out in heat levels tubular reactor, this
It further include outside gas mixer, raw material mixed cell, gas-solid separator, absorption tower, beater.Molecular sieve and gas phase silicon tetrachloride
In a tubular reactor with inert carrier gas flowing and haptoreaction, time of contact 10s-100min, after gas phase dealumination complement silicon
Molecular sieve is mixed with beating and is granulated with binder, clay and water, obtains catalytic cracking catalyst.This method avoids sieve particle
It is viscous glutinous, the haptoreaction that can be realized molecular sieve and silicon tetrachloride is carried out continuously.Additionally by controlling different reaction temperature,
To control differential responses condition and the extent of reaction, and then obtain the zeolite product of different dealumination depths；By controlling carrier gas
Flow velocity and tubular reactor length, the time that molecular sieve is contacted with silicon tetrachloride can be controlled.However this method is in order to reach
The purpose for carrying sieve particle flowing to gas, avoiding sieve particle blocking pipeline, be bound to flow rate of carrier gas to be increased, from
And reaction depth is caused to be difficult to improve, the deficiencies such as product silica alumina ratio is low；In addition to reaction depth, need to increase the logical of silicon tetrachloride
Enter amount, inevitably enlarges the load of exhaust treatment system；And time of contact is controlled by the length of control tubular reactor, increase
, there is inconvenience in actual production in installation area.
Patent CN103769193A, CN103785436A, CN103785437A, CN103785438A, CN103787352A,
In CN103787352A, CN104549445A, above-mentioned gas phase dealumination complement silicon reactor is optimized, haptoreaction is at one
It is carried out in inclined tubular reactor, the tubular reactor can rotate around tube body axis and have weir plate and shovelling plate, molecule
Sieve and gas phase silicon tetrachloride are mobile by mechanical transmission device or gravity in inclined tube in the case where not having to carrier gas conveying.This method
It can be used for serialization and prepare high-silica zeolite, simplification of flowsheet, without using fluidizing the carrier gas of molecular sieve, and can be significantly
The consumption for reducing silicon tetrachloride, can be realized the super steady reaction of serialization gas phase.Additionally by control material conveying speed or/and instead
The length of device is answered, can control residence time of the molecular sieve material in reactor；By using with heating tubular reactor or
Person's regulatory molecule sieve and silicon tetrachloride additional amount, can control different reaction temperatures, reaction condition and the extent of reaction, obtain not
With the zeolite product of dealumination depth.However in this method, the molecular sieve concentration in reactor is high, and bed density is higher, molecule
Sieve is in pipeline and silicon tetrachloride is in close phase state, and mass-and heat-transfer effect is poor, and the property that will lead to product is different；Another party
Face, catalytic gas phase is pure silicon tetrachloride gas, and not by carrier gases dilute, and the silicon tetrachloride of high concentration is directly and molecule
Sieve particle contact, strong dealumination complement silicon reaction destroys crystal form larger, and molecular sieve structure is caused to collapse serious, product crystallinity
It declines to a great extent, and the amount of heat released also is easy to produce hot-spot；And the rotating device of sloped tubular reactor is set
With the molecular sieve conveying device in reactor, equipment manufacturing costs and difficulty of construction are also increased, and silicon tetrachloride is absorbing
It in tower and after alkaline reaction, is discharged directly as waste water, will increase sewage treatment burden, causes the very big destruction to environment.
Summary of the invention
It is an object of the invention to solve above-mentioned prior art defect, it is short to provide a kind of operating process, no ammonia and nitrogen pollution, dirty
Water is few, and structure is simple, and production cost is low, and reaction controlling is good, and the extent of reaction is high, and product sodium content is low, silica alumina ratio is high, sial
Than controllable, product property is uniform, can carry out it is large-scale continuous be automatically brought into operation, high production efficiency be used for Y type molecular sieve system
Standby equipment and the preparation method to match therewith.
Technical scheme is as follows:
A kind of to prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, which includes reactor (1), and opening is located at reaction
First feeding channel (2) and tapping channel (4) on device (1) top, opening are located at second feeding channel of reactor (1) lower part
(3), it is located at the mixing device (8) of reactor (1) inner lower, is located at reactor (1) internal reaction component (7), to reaction
Device (1) carries out the heating device (9) of heat supply, and the gas-solid separating device (5) being connected with tapping channel (4) one end is uniformly distributed in
Regenerative apparatus (10) in reactor (1)；It include at least one set of reaction group equally distributed in the middle in the reactor (1)
Part (7), the top end of the reaction component (7) is connected with the other end of tapping channel (4), bottom end and mixing device (8)
Top is connected, and the lower part of the mixing device (8) is connected with first feeding channel (2), in the middle part of it and second pan feeding
Channel (3) is connected；The reaction component (7) includes at least one fluidized bed.
Its a kind of preferred embodiment are as follows: the mixing device (8) and first feeding channel (2) pass through first pipe
(101) it is connected, the first pipe (101) is one of the coil pipe or a variety of of vertical or inclined straight tube, downward spiral
Combination.
A variety of group described herein be combined into such as first pipe (101) a part be vertical straight tube, another part be incline
A part of oblique straight pipe or first pipe (101) is vertical straight tube, a part be inclination straight tube, part in addition be spiral to
Under coil pipe as combining form (not exclusively enumerating).
The preferred embodiment can realize that accurately control passes through the first feeding channel when preparing Y type molecular sieve using the equipment
(2) residence time, preheating degree, circulating rate and the circulating pressure for entering the material of mixing device (8), make it and by second
The material that feeding channel (3) enters mixing device (8) carries out optimal mixing, realizes the in-depth and control of the extent of reaction.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: the reactor (1)
Body be selected from one of cylindrical body, cone, cuboid, square, sphere, triangular prism, quadrangular or a variety of groups
It closes.
It is similar as above, a variety of group described herein be combined into such as described reactor (1) be a part be cylindrical body, it is another
A part is the form of composite structure as cone.
Its further be preferably the reactor (1) be upper and lower end be cone or hemisphere, middle part is cylindrical body
Body.It is internal that the preferred embodiment can further improve the spacial distribution density of reaction component (7), balanced reaction device (1)
Stress distribution, improve device load-bearing capability, improve internal components property easy to loading and unloading.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: the reaction component
(7) body of fluidized bed is selected from one of centrum, cylindrical body, sphere or a variety of combinations.
Similar as above, a variety of group described herein is combined into the fluidized bed of such as described reaction component (7) as a part
It is the forms that centrum, another part are composite structure as sphere.
, it is further preferred that it is cone or hemisphere that the fluidized bed, which is upper and lower end, middle part is cylindrical body for it
Body.The preferred embodiment can further improve that raw material is fluidity in fluidized bed, be homogenized point of the raw material in fluidized bed
Cloth adjusts flow path and flow rate of the raw material in fluidized bed, realizes the control to the extent of reaction and product uniformity.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: the gas solid separation
Device (5) is high-temperature-resistant cloth bag dust collector.
It is further preferably high temperature resistant pulsed jet cloth filter.
The optimal technical scheme can realize the separation to material high-efficiency therein is entered on the basis of reducing production cost
With trapping.
Further preferably；The high temperature resistant pulsed jet cloth filter contains high temperature resistance filtration material, such as glass fibre, carbon
One of fiber, polytetrafluoroethylene (PTFE), polyimides are a variety of.
The further preferred embodiment not only may make gas-solid separator 200℃It is run under above hot conditions, and
Particularly suitable for efficiently separating halogen silane gas with sieve particle, it can not pass through, realize efficiently trapping.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: the reactor (1)
Interior includes that from top to bottom equally distributed 3 ~ 5 groups of reaction components (7), every group of reaction component (7) contain 1 ~ 3 concatenated fluidisation
Bed, the fluidized bed that series connection beginning is located in the reaction component (7) of topmost are connected with the tapping channel (4), lowest part it is anti-
The fluidized bed for being located at series connection end in component (7) is answered to be connected with the mixing device (8), remaining reaction component is gone here and there between (7)
Connection, it is 0.003 ~ 33.33 that the diameter height of the fluidized bed, which compares, between each fluidized bed by runner pipe be connected, the runner pipe with it is described
The diameter ratio of fluidized bed is 0.005 ~ 20.
The quantity of fluidized bed can be further ensured that the reaction interval of material in the preferred reaction component (7) and reaction component (7)
Degree, product structure and reduction energy consumption reduce production cost, in without preferred situation, if reaction component (7) was distributed
More, then residence time of the Molecular sieve raw material in reactor (1) is too long, overreact is be easy to cause, to reduce molecular sieve knot
Brilliant degree, while causing that pipeline is too long, the resistance of ducting increases, it could be defeated by reaction product so as to cause the flow for needing to increase carrier gas
The case where sending out reactor generates, and the requirement to power device and the drying plant of carrier gas also just increases.
The shape of fluidized bed in the reactor (1) can be identical or different.It is the multiple in further preferred situation
Fluidized bed shape is identical.
It is also preferred that: the circulation pipe diameter in the reaction component (7) between each fluidized bed is 5 ~ 200mm, described
The diameter of each fluidized bed is 10 ~ 1000mm, is highly 30 ~ 3000mm；In further preferred situation, the diameter of the runner pipe is
10 ~ 150mm, the diameter of each fluidized bed be 20 ~ 800mm, be highly 60 ~ 2000mm, the runner pipe and the fluidized bed
Diameter ratio be 0.01 ~ 7.5, it is 0.01 ~ 13.33 that the diameter height of the fluidized bed, which compares,；In the case of still more preferably, the circulation
The diameter of pipe is 20 ~ 100mm, and the diameter of the fluidized bed is 50 ~ 200mm, is highly 100 ~ 1000mm, the runner pipe and institute
The diameter ratio for stating fluidized bed is 0.03 ~ 3.33, and it is 0.03 ~ 6.67 that the diameter height of the fluidized bed, which compares,.
By above-mentioned several preferred embodiments, may make into the Molecular sieve raw material in reaction component (7) at each position
Different states is presented: in circulation duct, Molecular sieve raw material particle is very fast by carrier gas carrying flowing velocity, swims in gas
Irregular vigorous exercise is done in body, Molecular sieve raw material particle is acutely disturbed and mixed, and suspended, fast bed or strength are presented respectively
Transport status；After it enters fluidized bed, the sudden enlargement of caliber can lead to raw material flow rate and reduce suddenly, and feed particles are in poly-
Formula fluidisation or turbulent bed state.By raw material, the difference of each position flow regime and reciprocal variation in reaction component (7), are avoided
Deposition and damming of the Molecular sieve raw material in runner pipe, avoid reunion of the Molecular sieve raw material in fluidized bed and
It overflows and dissipates, enhance mass transfer, heat-transfer capability, effectively improve reaction depth, sufficiently control product structure.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: the heating device
It (9) is to be heated by one of hot wind, electric heating, steam heating, infrared heating, microwave heating or multiple heating mode
Device.It is further excellent in view of reaction temperature control, convenient degree of operation, heat utilization efficiency and energy-saving and emission-reduction etc. factor
Choosing be the heating device (9) heating method be one or both of hot wind or electric heating, it is even furthermore preferable that
The heating device (9) passes through Hot-blast Heating.The hot wind may be from hot-blast stove, baking flue gas, refinery's heating furnace or reboiler furnace
The industry such as flue gas, boiler smoke are easy to the heat source obtained.
Flow direction of the hot wind in reactor (1) is from top to bottom that temperature is preferably 500 ~ 600 DEG C, at it
400 ~ 500 DEG C of the pyroreaction section on self-assembling formation top, 200 ~ 400 DEG C of the medium temperature at middle part in reactor during flowing
100 ~ 200 DEG C of low-temp reaction section of conversion zone and lower part.
Further, it is also possible to setting hydraulic barrier or backstop in reactor (1), to extend the hot wind multiple stage fluidized-bed
The interior residence time, to improve heat utilization rate, reduce thermal loss.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: the accumulation of heat dress
Setting (10) is selected from one of heat storage plate, heat-storing sphere, heat accumulation plate or gitter brick or a variety of.
Be uniformly distributed in reactor (1) each position of interior upper, middle and lower regenerative apparatus (10) can pattern it is identical or different.
In order to make entire heat storage absorb heat and release heat more evenly quickly and convenient for handling, further preferred feelings
Under condition, the regenerative apparatus (10) is heat-storing sphere, and is uniformly distributed in the material of the heat-storing sphere at reactor (1) each position of upper, middle and lower
Matter and/or quantity are different, can be made warm from bottom to top in reactor (1) by the difference of unlike material heat-storing sphere thermal diffusion coefficient
Degree is gradually increased, with certain temperature gradient.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: reactor (1) is internal
It further include that at least three assigns the temperature sensing in temperature sensor casing (12), being located at reactor (1) upper, middle and lower portion respectively
Device (11), the temperature sensor (11) are connected with temperature controller.
The temperature controller is preferably 0.1 DEG C of lowest resolution, 0.5 grade of temperature measurement accuracy, control error≤± 1 DEG C.
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: second pan feeding
Channel (3) further includes branch pipe.
The preferred embodiment, which can realize other materials while pass through the second feeding channel (3), to be entered in reactor (1).
It is described to prepare low-Na and high-Si aluminium preferred embodiment more another than the equipment of Y type molecular sieve are as follows: the reactor
(1), the material of the connecting pipe between reaction component (7), mixing device (8) and each component is hydrochloric acid corrosion resistant, resistance to 500 DEG C of height
Adiabator, such as ceramic material, glass fiber material, carbon fibre material, the high temperature alloys such as titanium-based, Ni-based, cobalt-based, or contain
The stainless steel material of Cr, Ni, Ti, Mo.
Method of the low-Na and high-Si aluminium than Y type molecular sieve is prepared the present invention further provides a kind of, passes through any of the above-described kind
It prepares low-Na and high-Si aluminium to be prepared than the equipment of Y type molecular sieve or its preferred embodiment, will directly to synthesize, without chemistry
Or Y type molecular sieve original powder of the water content lower than 2wt% that physical method is modified is passed through first feeding channel using dry carrier gas
(2) in, halogen silane is passed through in second feeding channel (3), the two is uniformly mixed in mixing device (8), laggard
Enter and reacted in reaction component (7), sufficiently enters gas-solid separating device (5) by tapping channel (4) after reaction, in gas solid separation
Device (5) lower end discharge port collects molecular sieve solid particle, uses decationizing water or/and weak acid scrubbing thereafter to get institute is arrived
It states low-Na and high-Si aluminium and compares Y type molecular sieve.
In the above-mentioned methods, the gaseous component in the gas-solid separating device (5) after separation can further be passed through chemical water or
Lye realizes recycling for silicon-aluminium glue body separation and recovery and chemical water or lye through filtering.
A kind of preferred embodiment of the above method are as follows: be passed through tune into the branch pipe (102) of second feeding channel (3)
Become reagent, the modulation reagent is selected from monochloro methane, methylene chloride, chloroform, carbon tetrachloride, phosphorus trichloride, phosphoric
One of phosphorus, phosphorus trifluoride, phosphorus pentafluoride, boron chloride, four chlorinations, two boron are a variety of.
The modulation reagent and halogen silane mass ratio are 0.1 ~ 10:1, which can further modulation produce
Sodium content and silica alumina ratio in product.
In further preferred situation, the modulation reagent is monochloro methane, methylene chloride, chloroform, phosphorus pentachloride, three
One or more of boron chloride.
Another preferred embodiment of above-mentioned preparation method are as follows: the Y type molecular sieve original powder is NaY, the halogen silicon
Alkane is selected from difluoro SiClx, ocratation, a chlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, methyl trichlorosilane, chlorine
One of methyl trichlorosilane is a variety of.
It may further be preferable that the halogen silane is selected from ocratation, dichlorosilane, trichlorosilane, silicon tetrachloride
One of or it is a variety of.
The ability to work of equipment according to the present invention, it is clear that, the Y type molecular sieve original powder can also be for selected from NH4NaY、
NH4Y, one of Y type molecular sieve through being just modified such as HY, REY, USY, REUSY or a variety of.
Another preferred embodiment of above-mentioned preparation method are as follows: the dry carrier gas be selected from air, oxygen, nitrogen,
One of argon gas, helium, phosgene, monosilane are a variety of, and water content is lower than 1000ppm.
It is further preferably: the dry carrier gas is one or both of air or nitrogen.
It is 15 ~ 480min, further preferably 60 ~ 360min that the present invention, which preferably controls the reaction time,.
The invention has the following advantages:
(1) device structure of the invention is simple, and controllability is high at a lower cost, and equipment heat transfer, mass transfer performances are good, heat
It is evenly distributed, consersion unit internal stress is balanced, and product quality, performance, the shape that can be fully ensured that are uniform；
(2) equipment of the invention can realize the accurate control to the extent of reaction under easy structure, former to each reaction
The carry out optimized control for expecting mutual rate, time of contact, circulation, the product structure made is stable, quality is high；
(3) energy consumption is relatively low during use for equipment of the invention, good product dispersibility, soilless sticking, knot
The appearance of block using raising quality, reduces cost, energy-saving and emission-reduction；
(4) general not with NH in preparation method of the invention4NaY、NH4Y, the pre- modified molecular screen of HY, REY are raw material, and
Be directly to synthesize and without the modified high sodium low silica-alumina ratio NaY molecular sieve original powder of chemically or physically method as raw material, without into
The pre- modification of row, but by continuous multi-stage fluidized bed reactor a step complete molecular sieve removing sodium and dealumination complement silicon it is anti-
It answers, low-Na and high-Si aluminium is made than Y type molecular sieve, simplifies preparation flow of the low-Na and high-Si aluminium than Y type molecular sieve, reduce system
Standby cost, avoids the ammonia and nitrogen pollution in traditional preparation process, realizes ammonia nitrogen zero-emission, and it is negative to significantly reduce sewage treatment
Load；
(5) raw material is in good fluidisation state in reactor in preparation method of the invention, is come into full contact with halogen silane,
The product structure regularity made is high；
(6) molecular screen primary powder described in preparation method of the invention enters mixing device (8) by the first feeding channel (2)
In the process, it can adequately be preheated in mixing device (8), the process for eliminating the additional heat in roaster shortens
Production cycle, reduce energy consumption and labour cost；
(7) dry carrier gas used in preparation method of the invention in addition to delivery of molecules sieve, dilute the halogen silane and
Outside modulation reagent, the heat released when reaction can also be taken away, with the hair for maintaining system thermal balance, preventing hot-spot situation
It is raw；
(8) in preparation method of the invention, good, the isolated gas phase of the separation of gas-solid separating device (5), trapping effect
After component is passed through chemical water or lye absorption, absorbing liquid further can be realized into silicon-aluminium glue body separation and recovery and change through filtering
Recycling for water or lye is learned, gained silicon-aluminium glue body is as the silicon source and silicon source for synthesizing NaY type molecular sieve, thus maximum limit
Degree reaction raw materials are utilized, saved resource to the maximum extent, reduce to the maximum extent environmental pollution and wastewater treatment at
This；
(9) preparation of the invention is carried out in inside reactor, and reactor is other than providing reaction compartment, special shape
Body also have the function of it is firm, bearing, protection internal component and dispersive stress outside, it is often more important that, with reaction component (7),
The collective effects such as heating device (9), regenerative apparatus (10) and feeding channel, naturally form one from bottom to top temperature gradually mention
The high, thermal environment with certain temperature gradient, avoid Molecular sieve raw material and halogen silane gas in react the initial stage i.e. compared with
It is carried out under high-temperature, so that molecular sieve structure serious, product crystallinity of collapsing be caused to decline to a great extent, after product sodium content height etc.
Fruit；
(10) quantity of the interior fluidized bed of reaction component (7) of the present invention, diameter, the diameter etc. of runner pipe has between each fluidized bed
Good regulation and control effect, can be effectively controlled the quality and stability of product；
(11) present invention can control the flow rate of carrier gas, the halogen silane and modulation reagent feeds speed, reaction temperature
To control residence time and reaction depth of the molecular sieve in continuous multi-stage fluidized bed reactor (1), realization zeolite product
Sodium content and silica alumina ratio it is controllable；Extend residence time of the halogen silane gas in reaction component (7), makes the halogen
Plain silane gas is fully utilized, to save raw material, reduction production cost and vent gas treatment load, reduce environmental pollution；
(12) in preparation method of the invention, in order to realize the mesh of further regulatory molecule sieve product sodium content and silica alumina ratio
, it can also be by the branch pipe (102) of the second feeding-passage (3), into the halogen silane gas, injection only serves drop sodium dealuminzation
The modulation reagent of effect.
Detailed description of the invention
Fig. 1 is that a kind of low-Na and high-Si aluminium that is used to prepare provided by the invention shows than the overall structure of the equipment of Y type molecular sieve
It is intended to；
Fig. 2 is the cross section schematic top plan view of reactor (1) main body in equipment described in Fig. 1 or Fig. 4；
Fig. 3 is the schematic diagram of the temperature Staged cotrol system of reactor (1) in equipment shown in Fig. 1；
Fig. 4 is that another kind provided by the invention is used to prepare overall structure of the low-Na and high-Si aluminium than the equipment of Y type molecular sieve
Schematic diagram；
Fig. 5 is the schematic diagram of the temperature Staged cotrol system of reactor (1) in equipment shown in Fig. 4.
Specific embodiment
In specific embodiment part, first chatted to after herein in embodiment using to prepare low-Na and high-Si aluminium ratio Y type point
The equipment of son sieve is described in detail, as follows:
The present invention uses following facilities and equipments:
A kind of to prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, the equipment includes reactor 1, and opening is located at reaction
First feeding channel 2 and tapping channel 4 on 1 top of device, opening are located at the second feeding channel 3 of 1 lower part of reactor, are located at reaction
The mixing device 8 of 1 inner lower of device, the reaction component 7 inside reactor 1 carry out the heating device of heat supply to reactor 1
9, the gas-solid separating device 5 being connected with 4 one end of tapping channel, the regenerative apparatus 10 being uniformly distributed in reactor 1；The reaction
It include at least one set of reaction component 7 equally distributed in the middle, the top end and tapping channel 4 of the reaction component 7 in device 1
The other end be connected, bottom end is connected with the top of mixing device 8, the lower part of the mixing device 8 and first pan feeding lead to
Road 2 is connected, its middle part is connected with second feeding channel 3；The reaction component 7 includes at least one fluidized bed.
The body of the reactor 1 is selected from cylindrical body, cone, cuboid, square, ball in preferred embodiments
One of body, triangular prism, quadrangular or a variety of combinations, particularly preferred reactor 1 are that upper and lower end is cone or hemisphere
Body, middle part is the body of cylindrical body, wherein upper and lower end is as shown in Fig. 1 for the reactor of cone, cross-sectional plan view
As shown in Fig. 2, upper and lower end is that hemispheroidal reactor is as shown in Fig. 4.
The fluidized bed of the reaction component 7 is preferably one of centrum, cylindrical body, sphere or a variety of combinations.
The gas-solid separating device 5 is preferably high-temperature-resistant cloth bag dust collector.
From top to bottom equally distributed 3 ~ 5 groups of reaction components 7, every group of reaction component 7 is preferably included in the reactor 1 to contain
Have 1 ~ 3 concatenated fluidized bed, be located in the reaction component 7 of topmost series connection beginning fluidized bed and 4 phase of tapping channel
Even, the fluidized bed that series connection end is located in the reaction component 7 of lowest part is connected with the mixing device 8, between remaining reaction component 7
It connects, as shown in attached drawing 1 or attached drawing 4, it is 0.003 ~ 33.33 that the diameter height of the fluidized bed, which compares, passes through stream between each fluidized bed
Siphunculus is connected, and the diameter ratio of the runner pipe and the fluidized bed is 0.005 ~ 20.
Second feeding channel 3 may also include branch pipe.
The mixing device 8 is preferably connected by first pipe 101 with first feeding channel 2, the first pipe
It 101 is vertical or inclined straight tube, one of the coil pipe of downward spiral or a variety of combinations, it is further preferably described
First pipe is inclined straight tube, as shown in attached drawing 1 or attached drawing 4.
The present invention will be further explained with reference to the examples below:
Analysis method used in each embodiment includes: BET specific surface area using low temperature nitrogen determination of adsorption method, and standard is
GB/T5816-1995；Crystallinity, lattice constant are measured using X-ray diffraction method, and standard is respectively ASTM D3906-2003
(2013) ,ASTM D3942-2003(2013)；(Zhu Chao, Qiao Chensheng, Wang Qiuying wait the Lanzhou big to temperature failure temperature reference literature
Learn journal, 1995,04:127-132.) it is measured using thermogravimetry；Framework si-al ratio reference literature (Peng Piao petroleum journal
(PETROLEUM PROCESSING), 1996,03:103-109.) it is measured using solid-state nuclear magnetic resonance method；Chemical composition reference literature (Wang Zhanqin, Qi
Gui Hong, Zhang Yinguang analysis and testing technology and instrument, 2009,02:118-123.) use X fluorescence spectrum assay.
Embodiment 1
The reactor 1, reaction component 7 is made with the stainless steel of the industrial trade mark 06Cr18Ni11Ti with a thickness of 4mm
Connecting pipe between fluidized bed, mixing device 8 and each component, then it is assembled into the facilities and equipments as described in attached drawing 1 ~ 2, wherein gas-solid
Separator 5 is high temperature resistant pulsed jet cloth filter, using glass fibre corrosion-resistant and high-temperature resistant filtrate；1 shape of reactor is upper
The cylindrical body of lower band cone end socket is provided with the pipeline communicated with reactor 1 on cone end socket up and down, uses for heating
The circulation of hot wind；Reaction component 7 is three groups, and every group contains three fluidized beds, each fluidized bed identical, upper band hemispherical head for shape
The cylindrical body of lower band cone end socket, each fluidized bed diameter are 200mm, are highly 600mm, connecting pipe diameter between each fluidized bed
For 50mm；8 shape of mixing device is up and down with the cylindrical body of hemispherical head, and diameter 400mm is highly 600mm, mixing device
The pipeline connected between 8 lower parts and the first feeding channel 2 is inclined straight tube；Heating device 9 by self-heating wind furnace Lai Hot-blast Heating,
Hot wind is flowed from top to bottom direction in reactor 1, and reactor 1 is entered together with hot wind also plays cooling effect all the way
Cold air, be respectively arranged with regulating valve in two gas circuits, form temperature Staged cotrol system as shown in Fig. 3 with temperature controller
System；Regenerative apparatus 10 is heat-storing sphere, and the Zirconium corundum heat-storing sphere of Φ 10mm, Φ 20mm are filled in lower part respectively in reactor 1
The ceramic heat-storing sphere of corundum mullite rock heat-storing sphere and Φ 30mm；The PT100 that temperature sensor 11 is three A grades of accuracy class
Thermal resistance, and it is uniformly distributed in the upper middle lower part of continuous multi-stage fluidized bed reactor 1, it is corresponding with three PT100 thermal resistances
Three temperature sensor casings 12 in intercalation reaction device 1 or geometric center position of the fluidized bed of reaction component 7 in the horizontal direction,
Three PT100 thermal resistances being inserted into three temperature sensor casings 12 intelligently may be used with three TCW-32B type dual outputs respectively
Temperature controller (manufacture of Shanghai Guo Long instrument and meter Co., Ltd) is programmed to be connected；
It, will be on continuous multi-stage fluidized bed reactor 1 with 500 DEG C of hot winds using temperature Staged cotrol system shown in Fig. 3
Portion is warming up to 400 DEG C and constant temperature, and being during which continually fed into water content lower than 200ppm, temperature by the first feeding channel 2 is room temperature
Dry air purging, displacement apparatus after constant temperature 90min, will be contained with water content lower than 200ppm, the dry air that temperature is room temperature
NaY molecular sieve original powder (its property as shown in table 1) of the water lower than 2wt% is conveyed into mixing device 8 by the first feeding channel 2, with
Uniform from the silicon tetrachloride gas mixing of the second feeding channel 3, wherein silicon tetrachloride is during being sent to mixing device 8
By thermal evaporation, additional amount is silicon tetrachloride: molecular screen primary powder=1:0.71 in terms of butt by mass；After mixing
NaY molecular sieve original powder is conveyed into reaction component 7 and carries out haptoreaction by gas, and the flow of mixed gas can make NaY molecular sieve former
Powder stops 60min in continuous multi-stage fluidized bed reactor 1；Molecular sieve is delivered to gas-solid by tapping channel 4 sufficiently after reaction
Separator 5, wherein gaseous component is passed through in chemical water, realizes that the separation of silica gel and alumine hydroxide colloid is returned after absorbing liquid filtering
It receives, the circulation of chemical water, molecular sieve solid particle is after 5 lower end discharge port of gas-solid separating device is drawn off with 20 times of weight, 70 DEG C
It is filtered after decationizing water washing 90min, dries 12h after Washing of Filter Cake to no Cl at 110 DEG C, obtain low-Na and high-Si aluminium ratio Y
Type molecular sieve, is denoted as G-1, and main character is as shown in table 2.
Embodiment 2
The reactor 1 is made with the stainless steel that the industrial trade mark with a thickness of 4mm is 022Cr17Ni12Mo2, with a thickness of
The industrial trade mark of 4mm is made between the fluidized bed, mixing device 8 and each component of the reaction component 7 for the titanium alloy of IMI550 to be connected
Adapter tube road, then it is assembled into attached equipment shown in Fig. 4, wherein the cross-sectional view of continuous multi-stage fluidized bed reactor 1 is for example attached
Shown in Fig. 2, the gas-solid separating device 5 is high temperature resistant pulsed jet cloth filter, using polyimides corrosion-resistant and high-temperature resistant filtrate；
1 shape of reactor is up and down to be provided on upper and lower hemispheres shape end socket and to communicate with reactor 1 with the cylindrical body of hemispherical head
Pipeline, for heating the circulation of hot wind；Reaction component 7 be three groups, every group contain three fluidized beds, each fluidized bed be shape it is identical,
Up and down with the cylindrical body of hemispherical head, it is highly 500mm, connecting pipe is straight between each fluidized bed that each fluidized bed diameter, which is 150mm,
Diameter is 40mm；With the cylindrical body with conical end socket under hemispherical on, diameter 300mm is highly 8 shape of mixing device
400mm, the pipeline connected between 8 lower part of mixing device and the first feeding channel 2 are inclined straight tube；Heating device 9 is roasting cigarette
Gas heating, baking flue gas are flowed from top to lower curtate direction in reactor 1, and going back for reactor 1 is entered together with baking flue gas
There is the cold air for playing cooling effect all the way, be respectively arranged with regulating valve in two gas circuits, is formed as shown in Fig. 5 with temperature controller
Temperature Staged cotrol system；Regenerative apparatus 10 is heat-storing sphere, and the filling situation in reactor 1 are as follows: is distinguished in upper middle lower part
Fill the ceramic heat-storing sphere of the Zirconium corundum heat-storing sphere of Φ 10mm, the corundum mullite rock heat-storing sphere of Φ 20mm, Φ 30mm；Temperature
Sensor 11 is three S type thermocouples, and is uniformly distributed in the upper middle lower part of continuous multi-stage fluidized bed reactor 1, with three S
The corresponding three temperature sensor casings 12 of type thermocouple fluidized bed in intercalation reaction device 1 or reaction component 7 in the horizontal direction
Geometric center position, three S type thermocouples being inserted into three temperature sensor casings 12 are double with three TCW-32B types respectively
Intelligent programmable temperature controller (manufacture of Shanghai Guo Long instrument and meter Co., Ltd) is exported to be connected；
Come into operation temperature Staged cotrol system shown in fig. 5, with 550 DEG C of baking flue gas by continuous multi-stage fluidized bed reactor
1 top is warming up to 450 DEG C and constant temperature, and being during which continually fed into water content lower than 150ppm, temperature by the first feeding channel 2 is room temperature
Dry air purging, displacement apparatus will lower than 150ppm, the drying nitrogen that temperature is room temperature with water content after constant temperature 60min
NaY molecular sieve original powder (its property be shown in Table 1) of the water content lower than 1.5wt% is conveyed into mixing device 8 by the first feeding channel 2, with
It is uniformly mixed from the trichlorosilane gas of the second feeding channel 3, trichlorosilane is squeezed into the second pan feeding with corrosion-resistant magnetic drive pump and led to
Behind road 3, by thermal evaporation during being sent to mixing device 8, and according to trichlorosilane: NaY molecular sieve original powder in terms of butt=
The weight ratio of 1:0.62 is fed, and NaY molecular sieve original powder is conveyed into after reaction component 7 and carries out haptoreaction by mixed gas, is mixed
The flow of gas makes NaY molecular sieve original powder stop 120min in continuous multi-stage fluidized bed reactor 1, sufficiently molecule after reaction
Sieve drains into gas-solid separating device 5 by tapping channel 4, and gaseous component is passed through chemical water, and silica gel and hydrogen are realized after absorbing liquid is filtered
Separation and recovery, the circulation of chemical water of alumina gel, molecular sieve solid particle are drawn off in 5 lower end discharge port of gas-solid separating device
Afterwards with being filtered after 15 times of weight, 80 DEG C of decationizing water washing 60min, 9h is dried after Washing of Filter Cake to no Cl at 130 DEG C, is obtained
To low-Na and high-Si aluminium than Y type molecular sieve, it is denoted as G-2, main character is shown in Table 2.
Embodiment 3
With the fluidized bed that the industrial trade mark with a thickness of 4mm is reactor 1, reaction component 7 described in the titanium alloy of IMI550, mix
Expect connecting pipe between device 8 and each component, be then assembled into equipment as shown in Fig. 1, wherein the cross section of reactor 1 is overlooked and shown
It is intended to as shown in attached drawing 2, wherein gas-solid separating device 5 is high temperature resistant pulsed jet cloth filter, is filtered using carbon fibre high temperature resistant
Material；1 shape of reactor is the cylindrical body up and down with conical end socket, is provided with and 1 phase of reactor on cone end socket up and down
Logical pipeline, for heating the circulation of hot wind；Reaction component 7 is three groups, and every group contains three fluidized beds, and each fluidized bed is shape phase
Together, with the cylindrical body with conical end socket under hemispherical on, it is highly 400mm that each fluidized bed diameter, which is 100mm, each fluidized bed
Between connecting pipe diameter be 30mm；8 shape of mixing device is up and down with the cylindrical body of hemispherical head, and diameter 200mm is highly
350mm, the pipeline connected between 8 lower part of mixing device and the first feeding channel 2 are inclined straight tube；Heating device 9 is boiler smoke
Gas heating, boiler smoke are flowed from top to lower curtate direction in reactor 1, and going back for reactor 1 is entered together with boiler smoke
There is the cold air for playing cooling effect all the way, be respectively arranged with regulating valve in two gas circuits, forms temperature as shown in Figure 3 with temperature controller
Spend Staged cotrol system；Regenerative apparatus 10 is heat-storing sphere, and wherein 1 upper middle lower part of reactor is filled with Φ 20mm Zirconium corundum respectively
Heat-storing sphere, Φ 30mm corundum mullite rock heat-storing sphere, Φ 40mm ceramic heat-storing sphere；Temperature sensor 11 is three R type thermocouples,
And it is uniformly distributed in the upper middle lower part of reactor 1, three temperature sensor casings 12 corresponding with three R type thermocouples are along level
The geometric center position of fluidized bed in direction intercalation reaction device 1 or reaction component 7, is inserted into three temperature sensor casings 12
Three R type thermocouples respectively with three TCW-32B type dual output Intelligent programmable temperature controller (Shanghai state dragon instrument and meters
Co., Ltd's manufacture) it is connected；
Come into operation temperature Staged cotrol system shown in Fig. 3, and 1 top of reactor is warming up to 500 DEG C with 600 DEG C of boiler smokes
And constant temperature, during which by the first feeding channel 2 be continually fed into water content lower than 100ppm, temperature be room temperature dry air purging,
Water content after constant temperature 30min, is lower than 1wt% lower than 100ppm, the drying nitrogen that temperature is room temperature with water content by displacement apparatus
NaY molecular sieve original powder (property is shown in Table 1) mixing device 8 is conveyed by the first feeding channel 2, and from the second feeding channel 3
Come dichlorosilane gas be uniformly mixed, it is mixed being sent to after dichlorosilane squeezes into the second feeding channel 3 with corrosion-resistant canned motor pump
Expect during device 8 by thermal evaporation, and according to dichlorosilane: NaY molecular sieve original powder=1:0.53 weight ratio in terms of butt
NaY molecular sieve original powder is conveyed into reaction component 7 and carries out haptoreaction by charging, mixed gas, and the flow of mixed gas makes NaY points
Son sieve original powder stops 240min in continuous multi-stage fluidized bed reactor 1, and sufficiently molecular sieve is drained by tapping channel 4 after reaction
Gas-solid separating device 5, gaseous component is passed through chemical water, realizes that the separation of silica gel and alumine hydroxide colloid is returned after absorbing liquid is filtered
It receives, the circulation of chemical water, molecular sieve solid particle is after 5 lower end discharge port of gas-solid separating device is drawn off with 10 times of weight, 90 DEG C
It is filtered after decationizing water washing 90min, dries 6h after Washing of Filter Cake to no Cl at 140 DEG C, obtain low-Na and high-Si aluminium ratio Y type
Molecular sieve, is denoted as G-3, and main character is shown in Table 2.
Embodiment 4
A branch pipe is opened again at the second feeding channel 3 in equipment described in embodiment 1, using in addition to passing through second
Feeding channel 3 is passed through outside this process of modulation reagent boron chloride while silicon tetrachloride is added by the branch pipe, other steps
With embodiment 1, identical method prepares low-Na and high-Si aluminium than Y type molecular sieve, the modulation reagent boron chloride and tetrachloro with parameter
SiClx is fed by the weight ratio of 5:1, and obtained low-Na and high-Si aluminium is denoted as G-4 than Y type molecular sieve, and main character is shown in Table 2.
Embodiment 5
It will be gone in embodiment 1 by the molecular sieve solid particle use that 5 lower end discharge port of gas-solid separating device draws off discharge
It is 15 according still further to liquid-solid ratio after cationic water washing filtering, Washing of Filter Cake to no Cl, the lemon for the use of concentration being 0.05mol/L
Acid solution washs the filter cake 30min at 90 DEG C, filters thereafter, and washing to filtrate pH=7 obtains low-Na and high-Si aluminium after dry
Than Y type molecular sieve, it is denoted as G-5, main character is shown in Table 2.
Table 1
Table 2
By table 1, table 2 data it can be seen from compared with industrial comparative sample, using low-Na and high-Si aluminium ratio provided by the invention
Molecular sieve sodium content prepared by Y type molecular sieve Preparation equipment is extremely low, and framework of molecular sieve silica alumina ratio greatly improves, and molecular sieve is opposite
Crystallinity retention rate is high, and lattice constant is substantially shunk, and temperature failure temperature greatly improves, and molecular sieve specific surface area is also mentioned
Height illustrates that pore-creating effect is obvious, and above data shows provided by the invention a kind of to prepare low-Na and high-Si aluminium setting than Y type molecular sieve
Standby prepared molecular sieve performance is excellent.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that those skilled in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will fall in principle disclosed in the present application
Within scope and spirit.
Claims (10)
1. a kind of prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: the equipment includes reactor (1), is opened
Mouth is located at first feeding channel (2) and tapping channel (4) on reactor (1) top, and opening is located at the second of reactor (1) lower part
Feeding channel (3) is located at the mixing device (8) of reactor (1) inner lower, is located at reactor (1) internal reaction component
(7), to the heating device (9) of reactor (1) progress heat supply, the gas-solid separating device (5) being connected with tapping channel (4) one end,
The regenerative apparatus (10) being uniformly distributed in reactor (1)；It include at least one set of uniform in the middle point in the reactor (1)
The reaction component (7) of cloth, the top end of the reaction component (7) is connected with the other end of tapping channel (4), bottom end and mixing
The top of device (8) is connected, the lower part of the mixing device (8) is connected with first feeding channel (2), in the middle part of it with it is described
Second feeding channel (3) is connected；The reaction component (7) includes at least one fluidized bed.
2. according to claim 1 prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: the reaction
The body of device (1) is selected from one of cylindrical body, cone, cuboid, square, sphere, triangular prism, quadrangular or a variety of
Combination.
3. according to claim 1 prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: the reaction
The body of the fluidized bed of component (7) is selected from one of centrum, cylindrical body, sphere or a variety of combinations.
4. according to claim 1 prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: the gas-solid
Separator (5) is high-temperature-resistant cloth bag dust collector.
5. according to claim 1 prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: the reaction
It include that from top to bottom equally distributed 3 ~ 5 groups of reaction components (7), every group of reaction component (7) are concatenated containing 1 ~ 3 in device (1)
Fluidized bed, the fluidized bed that series connection beginning is located in the reaction component (7) of topmost are connected with the tapping channel (4), lowest part
Reaction component (7) in be located at series connection end fluidized bed be connected with the mixing device (8), between remaining reaction component (7) into
Row series connection, it is 0.003 ~ 33.33 that the diameter height of the fluidized bed, which compares, between each fluidized bed by runner pipe be connected, the runner pipe with
The diameter ratio of the fluidized bed is 0.005 ~ 20.
6. according to claim 1 prepare equipment of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: described second
Feeding channel (3) further includes branch pipe.
7. a kind of prepare method of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: use any one of claim 1 ~ 6
The equipment preparation will be synthesized directly, is former without Y type molecular sieve of the modified water content of chemically or physically method lower than 2wt%
Powder is conveyed into first feeding channel (2) using dry carrier gas, and halogen silane is passed through second feeding channel (3)
In, the two is uniformly mixed in mixing device (8), enters in reaction component (7) reacted thereafter, sufficiently by discharging after reaction
Channel (4) enters gas-solid separating device (5), collects molecular sieve solid particle in gas-solid separating device (5) lower end discharge port, thereafter
Compare Y type molecular sieve using decationizing water or/and weak acid scrubbing to get to the low-Na and high-Si aluminium.
8. according to claim 7 prepare method of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: to described
Modulation reagent is passed through in the branch pipe of two feeding channels (3), the modulation reagent is selected from monochloro methane, methylene chloride, three chloromethanes
One of alkane, carbon tetrachloride, phosphorus trichloride, phosphorus pentachloride, phosphorus trifluoride, phosphorus pentafluoride, boron chloride, four chlorinations, two boron or
It is a variety of.
9. according to claim 7 prepare method of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: the Y type point
Son sieve original powder is NaY molecular sieve original powder, and the halogen silane is selected from difluoro SiClx, ocratation, a chlorosilane, dichloro silicon
One of alkane, trichlorosilane, silicon tetrachloride, methyl trichlorosilane, Chloromethyltrichlorosilane are a variety of.
10. according to claim 7 prepare method of the low-Na and high-Si aluminium than Y type molecular sieve, it is characterised in that: the drying
Carrier gas is selected from one of air, oxygen, nitrogen, argon gas, helium or a variety of, and water content is lower than 1000ppm.
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| CN111686684B (en) * | 2020-06-23 | 2023-04-18 | 萍乡市华顺环保化工填料有限公司 | III type efficient molecular sieve automatic production line |
| CN111977664B (en) * | 2020-08-21 | 2022-02-01 | 山东荣创催化新材料有限公司 | Molecular sieve material modification treatment equipment and use method thereof |
| CN112758952B (en) * | 2020-12-31 | 2022-12-30 | 中海油天津化工研究设计院有限公司 | High-silica-alumina-ratio Y molecular sieve with hierarchical pore structure and preparation method thereof |
| CN117209171B (en) * | 2023-09-15 | 2024-03-26 | 杭州宏鑫钙业有限公司 | Method for preparing calcium oxide |
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