CN104549420B - A kind of method for preparing microsphere FCC catalyst - Google Patents
A kind of method for preparing microsphere FCC catalyst Download PDFInfo
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- CN104549420B CN104549420B CN201310516097.7A CN201310516097A CN104549420B CN 104549420 B CN104549420 B CN 104549420B CN 201310516097 A CN201310516097 A CN 201310516097A CN 104549420 B CN104549420 B CN 104549420B
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Abstract
The invention provides a kind of method for preparing microsphere FCC catalyst, the method includes：Molecular sieve, clay, boehmite and acid beating are obtained into catalyst slurry, the catalyst slurry is spray-dried, it is characterised in that before being spray-dried, the viscosity for controlling catalyst slurry is 500 10000 centipoises, and the inlet temperature being spray-dried is 300 450 DEG C.The method of the present invention is obtained in that the microsphere FCC catalyst of high sphericity.And remaining physico-chemical parameter for the microsphere FCC catalyst for obtaining reaches the level that the level of prior art is even above prior art.
Description
Technical field
The present invention relates to a kind of method for preparing microsphere FCC catalyst.
Background technology
Sphericity is an important physical property of FCC catalyst.The sphericity of FCC catalytic cracking catalysts not only affects catalysis
The fluidizing performance of agent, and it is closely related with the anti-wear performance of catalyst.The catalyst of sphericity difference is easy in use
Abrasion.Abrasion produce fine powder run damage, not only can dose consumption also pollute the environment；The fine powder that catalyst abrasion is produced in addition
The equipment such as follow-up cigarette machine may be impacted, it is unfavorable to the long-term operation of catalytic cracking unit.
CN1160436C discloses a kind of catalytic cracking catalyst preparation method, and which is with the viscosity of catalyst slurry as control
The addition of mineral acid when index is to adjust boehmite acidifying, the method can be avoided because of the ripple of boehmite acid consumption
The dynamic fluctuation for causing catalyst strength and pore volume, but Jing tests find that the catalyst spherical degree prepared using the method is poor.
The content of the invention
It is an object of the invention to providing on the basis of existing technology a kind of high sphericity FCC catalyst can be prepared
Method, and except remaining property that can improve the spherical catalyst be outside one's consideration, obtain is substantially suitable with state of the art or more
It is high.
To realize object defined above, the invention provides a kind of method for preparing microsphere FCC catalyst, the method includes：
Molecular sieve, clay, boehmite and acid beating are obtained into catalyst slurry, the catalyst slurry is carried out
It is spray-dried, it is characterised in that before being spray-dried, the viscosity for controlling catalyst slurry is 500-10000 centipoises, and is sprayed
Dry inlet temperature is 300-450 DEG C.
The method of the present invention is obtained in that the microsphere FCC catalyst of high sphericity.And the microsphere FCC catalyst for obtaining
Level of remaining physico-chemical parameter substantially close to the level even above prior art of prior art.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the sectional view of the nozzle according to one embodiment of the present invention；
Fig. 2 is the top view of the nozzle with 2 nozzle entrances according to one embodiment of the present invention；
Fig. 3 is the top view of the nozzle with 6 nozzle entrances according to one embodiment of the present invention.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method for preparing microsphere FCC catalyst, the method includes：
Molecular sieve, clay, boehmite and acid beating are obtained into catalyst slurry, the catalyst slurry is carried out
It is spray-dried, wherein, before being spray-dried, the viscosity for controlling catalyst slurry is 500-10000 centipoises, and be spray-dried
Inlet temperature is 300-450 DEG C.
The method according to the invention, in order to further improve sphericity, before being preferably spray-dried, controls catalyst slurry
The viscosity of liquid is 1000-4000 centipoises, and the inlet temperature being spray-dried is 330-420 DEG C.
In the present invention, to the outlet temperature that is spray-dried without particular/special requirement, can be the conventional selection of this area, for example may be used
Think 100-200 DEG C.
The method according to the invention, the viscosity of catalyst slurry can be adjusted by various tune adhering methods, in order to subtract
Few operation and as far as possible reduction affect remaining factor of the property of catalyst slurry, preferably in pulping process, by adjusting
Section boehmite and sour addition, the solid content of regulation catalyst slurry are to control catalyst slurry as target viscosities.This
It is well known to those skilled in the art, is not described here in detail.
In the present invention, the consumption of each raw material can be based entirely on and be actually needed determination, and the present invention is to which without special
Limit.With the method for the invention it is preferred in terms of the dry weight of catalyst slurry, contain molecular sieve 10- in the catalyst slurry
55 weight %, aluminium oxide 10-40 weight %, clay 15-65 weight %.
In the present invention, to the solid content of catalyst slurry without particular/special requirement, can be the conventional selection of this area, for example may be used
Think 20-50 weight %.
In the present invention, the addition sequence of each material also has no particular limits, but for effective control catalyst slurry
Viscosity, improves sphericity, and preferred molecular sieve was added before clay, and boehmite is added after clay.Therefore, for this
Molecular sieve, clay, boehmite and acid are preferably beaten by invention as follows：Molecular sieve is mixed into shape with water
Into molecular sieve pulp, clay mix homogeneously is subsequently adding, is subsequently adding boehmite and sour mix homogeneously, obtains catalyst slurry
Liquid.
The method according to the invention, in order to improve sphericity, preferably described beating is carried out in the presence of Alumina gel, in order to carry
High sphericity, the preferably solid content of the Alumina gel are 10-40 weight %.
The method according to the invention, when Alumina gel is added, in order to improve sphericity, preferably as follows by molecule
Sieve, clay, boehmite and acid are beaten：Molecular sieve, Alumina gel and water are mixed to form into molecular sieve pulp, Ran Houjia
Enter clay mix homogeneously, be subsequently adding boehmite and sour mix homogeneously, obtain catalyst slurry.
With the method for the invention it is preferred to the molecular sieve be the molecular sieve with FAU structures, with MAZ structures point
One or more in sub- sieve, the molecular sieve with MFI structure, the molecular sieve with BEA structures；Wherein, with FAU structures
Molecular sieve can be one or more in X molecular sieve, Y molecular sieve, SAPO-37 molecular sieves etc.；Molecular sieve with MAZ structures
Can be Omega molecular sieves；Molecular sieve with MFI structure can be ZSM-5 molecular sieve；Molecular sieve with BEA structures can
Think beta-molecular sieve.
For the present invention, preferably the molecular sieve is Y type molecular sieve, ZSM-5 molecular sieve, Omega molecular sieves and beta-molecular sieve
In one or more, more preferably described molecular sieve is Y type molecular sieve and/or ZSM-5 molecular sieve.
The method according to the invention, optional wider range of the species of the clay, clay commonly used in the art are equal
Can be used for the present invention, for the present invention, during preferably the clay is Kaolin, galapectite, meerschaum, tired de- soil and montmorillonite
One or more, the preferably clay is Kaolin.
The method according to the invention, optional wider range of the species of the boehmite are commonly used in the art
Boehmite is used equally to the present invention, and for the present invention, preferably the boehmite is a diaspore, gibbsite and visits
One or more in your stone.
The method according to the invention, optional wider range of the species of the acid, acid commonly used in the art can use
In the present invention, for the present invention, the acid is one or more in hydrochloric acid, nitric acid, phosphoric acid and sulphuric acid.
The present invention can be spray-dried using various spray dryers, and the spray dryer can for example be centrifugation
Formula spray dryer or pressure spray dryer.
The method according to the invention, in order to further improve sphericity, preferably uses the following nozzle with the present invention
Spray dryer is spray-dried.
Therefore, one kind of the invention preferred embodiment, is entered by following nozzle during preferably spray drying
Row spraying, is then dried, as shown in figure 1, the nozzle includes：Nozzle body with cavity, on the nozzle body
It is provided with nozzle entrance 1, spray orifice 4；Wherein, the roof in the cavity of the nozzle body has been downwardly projected conducting element 3, the water conservancy diversion
Space between the inner surface of the outer surface of part 3 and the cavity forms rotating room 2.
In the present invention, in the case where contrary explanation is not made, be related to the description of nozzle, the noun of locality for using as " it is upper and lower,
Left and right, top, bottom " typically refers to upper and lower, left and right shown in refer to the attached drawing, top, bottom；" inside and outside " is referred to relative to each part sheet
The profile of body it is inside and outside.
The method according to the invention, in order to further improve the atomizing effect of nozzle, preferably in vertical direction, the water conservancy diversion
1/10-4/5 of the distance on the bottom of part 3 and the top of spray orifice 4 for cavity height；More preferably in vertical direction, the conducting element 3
Bottom and spray orifice 4 top distance for cavity height 1/5-1/3.
The method according to the invention, in order to further improve the atomizing effect of nozzle, the outer surface of the preferred conducting element 3
With the distance between the inner surface of the cavity for cavity diameter 1/10-2/5.
In the present invention, it is related to the description of the part of nozzle, if no special instructions, internal diameter refers to interior diameter, what external diameter referred to
It is overall diameter, footpath refers to diameter.
In the present invention, the distance between the outer surface of the conducting element 3 and inner surface of the cavity are referred to same
On horizontal line, the distance between point point corresponding with the inner surface of cavity of the outer surface of conducting element 3, preferred conducting element 3
Each point of outer surface is equal with the distance between each corresponding point of the inner surface of cavity.
In order to further improve the atomizing effect of nozzle, one kind of the invention is preferred embodiment, preferably described
Conducting element 3 includes the cylinder being connected and cone, wherein, one end of cylinder is connected to the roof of cavity, wherein, it is connected
Connect and refer to one end of cylinder and engage with the bottom surface of cone, the height ratio of more preferably described cylinder and cone is 0.5-
3:1, preferably 1.5-2:1.
It is of the invention it is a kind of preferred embodiment, the preferred at least partially cylinder of the cavity, the spray
Mouth entrance 1 is communicated with rotating room 2 in tangential direction, so that the nozzle with conducting element has more preferable rectification effect, from
And the atomizing effect of the nozzle of the present invention can be improved.
In the present invention, the nozzle entrance 1 is communicated with rotating room 2 in tangential direction and refers to the nozzle entrance 1 along cutting
It is circular tangent with rotating room 2 to direction.
The method according to the invention, the set location of the spray orifice 4 can be selected according to actual needs, specifically can be with
It is configured according to prior art, for the present invention, the preferably spray orifice 4 is arranged on the bottom of the nozzle body.
The shape of the nozzle body is not particularly limited in the present invention, specifically can be selected according to actual needs
Select, preferred embodiment, preferably the nozzle body includes cylinder and the cone being connected to one kind of the invention,
Roof of the one end of cylinder for nozzle body, wherein, connection is referred to one end of cylinder and is engaged with the bottom surface of cone, more
It is preferred that the height ratio of the cylinder and cone of the nozzle body is 0.5-3:1, preferably 0.6-1:1.
Preferred embodiment, the cavity of the preferably nozzle body includes the cylinder being connected to one kind of the invention
Chamber and conical cavity.
Preferred embodiment, preferably the nozzle body includes cylinder and the circle being connected to one kind of the invention
Cone, the preferably cylindrical cavity are located in the cylinder body, and the conical cavity is located in the circular cone body, more preferably described cylinder
The height ratio of chamber and conical cavity is 0.5-3:1, preferably 0.6-1:1.
In the present invention, the cone and cylinder of the nozzle body can be made of one, it is also possible to make respectively, use
When fit together use.
The method according to the invention, as shown in Figure 1 when the nozzle body includes the cylinder and the cone that are connected,
It is preferred that the spray orifice 4 is formed at the vertex of a cone of the cone of the nozzle body and is connected with the conical cavity.
The method according to the invention, as shown in Figure 1 when the nozzle body includes the cylinder and the cone that are connected,
The nozzle entrance（1）It is arranged on the cylinder of nozzle body and is connected with the cylindrical cavity in tangential direction.It is concrete that position is set
Put can according to it needs to be determined that, the present invention to this without particular/special requirement.
Preferred embodiment, preferably the conducting element 3 includes the circle being connected to one kind of the invention as previously mentioned
Cylinder and cone, the nozzle body include the cylinder being connected and cone, and the cavity of the nozzle body includes phase
The cylindrical cavity and conical cavity of connection, wherein, the cone angle of the cone of the preferred nozzle body, the conducting element（3）Circular cone
The cone angle of body can be each 20 ° -150 ° with the cone angle of the conical cavity, the cone of the cone of more preferably described nozzle body
Angle, the conducting element（3）Cone cone angle it is equal with the cone angle of the conical cavity.
With the method for the invention it is preferred to the diameter of the nozzle entrance 1, the diameter of spray orifice 4 are straight with the cylindrical cavity
The ratio in footpath is 1-8:1-10:20-40.
With the method for the invention it is preferred to the nozzle also includes the part 5 with loudspeaker opening, the loudspeaker of the part 5
Opening is communicated with the spray orifice 4.
Communicated with the spray orifice 4 by making the loudspeaker opening of the part 5 so that be formed with loudspeaker in the outlet of spray orifice
Mouthful, can protect from nozzle spray annular liquid film from surrounding air interference, it is ensured that annular liquid film expand change mist
Little droplet evenly is formed during change, atomizing effect is improve.
The part 5 for meeting aforementioned claim may be incorporated for the present invention, and which can be various ways, for example, can be with loudspeaker
Opening truncated cone-shaped part, or while with loudspeaker opening and with the cavity of nozzle body size fit
Protective cover（As shown in Figure 1）, during use by shielding cover on nozzle body, then its loudspeaker opening is communicated i.e. with spray orifice
Can, wherein, and along towards the direction on the outside of spray orifice, the internal diameter of the loudspeaker opening gradually increases.
For the present invention, the preferred bus of loudspeaker opening and the angle of horizontal direction are 10-60 °（It is β angles in Fig. 1）.
For the height of preferably loudspeaker opening of the invention（Or claim depth）For 1/10-2 times of cavity height, more preferably loudspeaker
The height of opening（Or claim depth）For 1/5-2/3 times of cavity height.
For the present invention, 2-20 times for injection diameter of the maximum gauge of preferred loudspeaker opening, more preferably 5-10 times, loudspeaker
1-2 times for injection diameter of the minimum diameter of opening.
The method according to the invention, the number of the nozzle entrance 1 can be selected according to needs, generally 1-10
It is individual.The top view of the nozzle with 2 nozzle entrances that Fig. 2 is provided for the present invention, Fig. 3 are sprayed with 6 for what the present invention was provided
The top view of the nozzle of mouth entrance.
It is of the invention it is a kind of preferred embodiment, a diameter of 1-8mm of the nozzle entrance, the length of nozzle entrance
Degree and diameter ratio are 0.5-5.0；The cavity diameter of nozzle body is 10-40mm；Spray orifice with diameter greater than equal to nozzle entrance
Diameter, a diameter of 2-10mm of spray orifice, the height of spray orifice is 1-8mm；Conducting element includes the cylinder being connected and cone, institute
Cylinder and cone that nozzle body includes being connected are stated, the cavity includes the cylindrical cavity being connected and conical cavity, described
The cone angle of the cone of nozzle body, the cone of the conducting element cone angle it is equal with the cone angle of the conical cavity.
The height of the shell portion of nozzle body is 1.5-15mm, the height 3-15mm of the cone section of nozzle body；Lead
The diameter with diameter greater than spray orifice of the shell portion of stream part, a diameter of 8-30mm of shell portion, the shell portion of conducting element
Height is highly equal with the shell portion of nozzle body, and the height of the cone section of conducting element is less than the cone of nozzle body
The height of section, the height of the cone section of conducting element is 1-10mm；The internal diameter of the shell portion of conducting element is 2-20mm.
By the following examples, the present invention is further illustrated, but content not thereby limiting the invention.
Model DV-S rotating cylinder viscometer of the viscosity of catalyst using the production of Bo Lefei companies of the U.S. in the following example
Determine, condition determination：Rotating speed 6rpm, 25 DEG C of temperature.
In the present invention, sphericity is represented with sphericity index SPHT, refer to the surface area with the spheroid of object same volume
With the ratio of the surface area of object.
Sphericity computing formula is as follows：
Sphericity index SPHT=4 π A2/P2, projected areas of the wherein A for granule, projection girths of the P for granule.
CamsizerXT dynamic digital imaging particles analyser in embodiment and comparative example using Lai Chi companies of Germany is surveyed
The sphericity of examination catalytic cracking catalyst.Dry method is determined, and condition determination is：Sample fast forward rate in feed well specifies for instrument
Maximum vibration speed 60%, sample enter the speed of measurement window be instrument specify the 55% of maximum vibration speed, sample
Product addition is 1.2g.
Water droplet pore volume, abrasion index, apparent bulk density（Heap ratio）Respectively according to《(RIPP is tried Petrochemical Engineering Analysis method
Proved recipe method))) (Yang Cui surely wait compile, Science Press, nineteen ninety publish) in RIPP28-90, RIPP29-90, RIPP31-90
Determine with RIPP92-90 standard methods.
Embodiment 1
800 grams of water is added toward reactor, the finely dispersed SOY-2 molecular sieves that concentration is 32 weight % are subsequently adding
（The product of Shandong catalyst plant production, is the USY type molecular sieves containing rare earth, RE2O3Content is 2.0 weight %, similarly hereinafter）Serosity
1094 grams, add 476 grams of Alumina gels（Shandong catalyst plant production product, 21 weight % of alumina content, similarly hereinafter）, stirring 15
Minute, add 513 grams of Kaolin（Kaolin of Suzhou Products, 22 weight % of igloss, similarly hereinafter）, it is beaten 1 hour, adds 242
Gram boehmite（Shandong branch company of Chinese Aluminium Co., Ltd product, 38 weight % of igloss, similarly hereinafter）, stir 0.5 little
When, add the concentrated hydrochloric acid of 26 gram of 37 weight % to be acidified 1 hour, the viscosity of analysis of catalyst serosity is 3880 centipoises, then using pressure
Power formula spray dryer（Its nozzle is to be not provided with conducting element and horn mouth with the nozzle difference of embodiment 7 and 8, below
Embodiment it is similar）It it is 400 DEG C in inlet temperature, outlet temperature is spray drying forming under conditions of 100 DEG C, scrubbed drying
Catalyst A is obtained, the sphericity of analysis of catalyst A is 0.936, remaining physico-chemical parameter such as abrasion index, water droplet method pore volume, heap
Than the level that can reach prior art.
Embodiment 2
1000 grams of water is added toward reactor, the finely dispersed SOY-2 molecular sieves that concentration is 32 weight % are subsequently adding
（The product of Shandong catalyst plant production, is the USY type molecular sieves containing rare earth, RE2O3Content is 2.0 weight %, similarly hereinafter）Serosity
1094 grams, add 476 grams of Alumina gels（Shandong catalyst plant production product, 21 weight % of alumina content, similarly hereinafter）, stirring 15
Minute, add 513 grams of Kaolin（Kaolin of Suzhou Products, 22 weight % of igloss, similarly hereinafter）, it is beaten 1 hour, adds 242
Gram boehmite（Shandong branch company of Chinese Aluminium Co., Ltd product, 38 weight % of igloss, similarly hereinafter）, stir 0.5 little
When, the concentrated hydrochloric acid for being subsequently adding 26 gram of 37 weight % is acidified 1 hour, and the viscosity of analysis of catalyst serosity is 1560 centipoises.Then make
With pressure spray dryer in inlet temperature be 420 DEG C, outlet temperature be spray drying forming under conditions of 100 DEG C, Jing washes
Dry catalyst B is washed, the sphericity of analysis of catalyst B is 0.938, remaining physico-chemical parameter such as abrasion index, water droplet method hole
Volume, heap are than the level that can reach prior art.
Embodiment 3
800 grams of water is added toward reactor, the finely dispersed SOY-2 molecular sieves that concentration is 32 weight % are subsequently adding
（The product of Shandong catalyst plant production, is the USY type molecular sieves containing rare earth, RE2O3Content is 2.0 weight %, similarly hereinafter）Serosity
1094 grams, add 381 grams of Alumina gels（Shandong catalyst plant production product, 21 weight % of alumina content, similarly hereinafter）, stirring 15
Minute, add 474 grams of Kaolin（Kaolin of Suzhou Products, 22 weight % of igloss, similarly hereinafter）, it is beaten 1 hour, adds 323
Gram boehmite（Shandong branch company of Chinese Aluminium Co., Ltd product, 38 weight % of igloss, similarly hereinafter）, stir 0.5 little
When, add the concentrated hydrochloric acid of 36 gram of 37 weight % to be acidified 1 hour, 9500 centipoise of viscosity of analysis of catalyst serosity.Then use pressure
Formula spray dryer in inlet temperature be 380 DEG C, outlet temperature be 100 DEG C under conditions of spray drying forming, scrubbed drying
Catalyst C is obtained, the sphericity of analysis of catalyst C is 0.933, remaining physico-chemical parameter such as abrasion index, water droplet method pore volume, heap
Than the level that can reach prior art.
Embodiment 4
Method according to embodiment 3 prepares microsphere FCC catalyst, except for the difference that, will be water, SOY-2 molecular sieve pulps, aluminum molten
Glue, Kaolin, boehmite and concentrated hydrochloric acid are beaten in adding reactor together, and rest materials are with being when spray-dried bar
Part all same, obtains catalyst D, and the sphericity of analysis of catalyst D is 0.930, remaining physico-chemical parameter such as abrasion index, water droplet
Method pore volume, heap are than the level that can reach prior art.
Embodiment 5
Method according to embodiment 3 prepares microsphere FCC catalyst, and except for the difference that, the inlet temperature of spray drying is 450
DEG C, remaining condition all same obtains catalyst E, and the sphericity of analysis of catalyst E is 0.931, and remaining physico-chemical parameter for example weares and teares
Index, water droplet method pore volume, heap are than the level that can reach prior art.
Embodiment 6
1200 grams of water is added toward reactor, the finely dispersed SOY-2 molecular sieves that concentration is 32 weight % are subsequently adding
（The product of Shandong catalyst plant production, is the USY type molecular sieves containing rare earth, RE2O3Content is 2.0 weight %, similarly hereinafter）Serosity
1094 grams, add 381 grams of Alumina gels（Shandong catalyst plant production product, 21 weight % of alumina content, similarly hereinafter）, stirring 15
Minute, add 474 grams of Kaolin（Kaolin of Suzhou Products, 22 weight % of igloss, similarly hereinafter）, it is beaten 1 hour, adds 323
Gram boehmite（Shandong branch company of Chinese Aluminium Co., Ltd product, 38 weight % of igloss, similarly hereinafter）, stir 0.5 little
When, add the concentrated hydrochloric acid of 30 gram of 37 weight % to be acidified 1 hour, 3200 centipoise of viscosity of analysis of catalyst serosity.Then use pressure
Formula spray dryer in inlet temperature be 380 DEG C, outlet temperature be 100 DEG C under conditions of spray drying forming, scrubbed drying
Obtain catalyst F, the sphericity of analysis of catalyst F is 0.936, remaining physico-chemical parameter for example abrasion index, water droplet method pore volume,
Heap is than the level that can reach prior art.
Embodiment 7
According to the method for embodiment 3, microsphere FCC catalyst is prepared, except for the difference that, following 1# used in spray-drying process
Nozzle is sprayed, remaining condition all same：
As shown in figure 1,1# nozzles include：With loudspeaker opening and with anti-with the cavity of nozzle body size fit
Shield（As shown in Figure 1）, its loudspeaker opening communicated with spray orifice（The axis of loudspeaker opening is overlapped with the axis of spray orifice, loudspeaker
The height of opening for cavity height 1/5）The bus of loudspeaker opening is 45 ° with horizontal angle, and the maximum of loudspeaker opening is straight
5 times for injection diameter of footpath, 2 times for injection diameter of minimum diameter；Nozzle body with cavity, the nozzle body include
The cylinder being connected and cone, the cavity include the cylindrical cavity being connected and conical cavity, arrange on the nozzle body
There are 2 equally distributed nozzle entrances（The a diameter of 1.8mm of nozzle entrance, length 3.0mm of nozzle entrance）With 1 spray orifice（Spray
A diameter of 2mm in hole, the height of spray orifice is 3mm）, nozzle entrance communicated with rotating room in tangential direction；Spray orifice is arranged on nozzle
At the vertex of a cone of the cone of main body, the conducting element includes the cylinder being connected and cone, the cone angle of conical cavity, nozzle master
The cone angle of the cone of body is equal with the cone angle of the cone of conducting element, the height of the shell portion of conducting element and the height of cylindrical cavity
Degree is equal to be 6mm, and the height of conical cavity is 6mm, and the height of conducting element cone section is 3mm, the shell portion of conducting element
A diameter of 12mm, the internal diameter of cylindrical cavity is 18mm；
Fig. 2 shows the top view of nozzle；
Catalyst G is obtained, the sphericity of analysis of catalyst G is 0.944, remaining physico-chemical parameter such as abrasion index, water droplet
Method pore volume, heap are than the level that can reach prior art.
Embodiment 8
According to the method for embodiment 3, microsphere FCC catalyst is prepared, except for the difference that, following 2# used in spray-drying process
Nozzle is sprayed, remaining condition all same：
As shown in figure 1,2# nozzles include：With loudspeaker opening and with anti-with the cavity of nozzle body size fit
Shield（As shown in Figure 1）, its loudspeaker opening communicated with spray orifice（The axis of loudspeaker opening is overlapped with the axis of spray orifice, loudspeaker
The height of opening for cavity height 1/2）, the bus of loudspeaker opening is 60 ° with horizontal angle, and the maximum of loudspeaker opening is straight
8 times for injection diameter of footpath, 1 times for injection diameter of minimum diameter；Nozzle body with cavity, the nozzle body include
The cylinder being connected and cone, the cavity include the cylindrical cavity being connected and conical cavity, arrange on the nozzle body
There are 6 equally distributed nozzle entrances（The a diameter of 2.8mm of nozzle entrance, the length of nozzle entrance is 3.5mm）With 1 spray orifice
（A diameter of 3mm of spray orifice, the height of spray orifice is 4mm）, nozzle entrance communicated with rotating room in tangential direction；Spray orifice is arranged on spray
At the vertex of a cone of the cone of mouth main body, the conducting element includes the cylinder being connected and cone, the cone angle of conical cavity, nozzle
The cone angle of the cone of main body is equal with the cone angle of the cone of conducting element, height and the cylindrical cavity of the shell portion of conducting element
Highly equal to be 6mm, the height of conical cavity is 8mm, and the height of conducting element cone section is 4mm, the shell portion of conducting element
A diameter of 14mm, the internal diameter of cylindrical cavity is 20mm；
Fig. 3 shows the top view of nozzle；
Catalyst H is obtained, the sphericity of analysis of catalyst H is 0.943, remaining physico-chemical parameter such as abrasion index, water droplet
Method pore volume, heap are than the level that can reach prior art.
Embodiment 9
Method according to embodiment 8 prepares catalyst, and except for the difference that, the nozzle for using is not provided with anti-with loudspeaker opening
Shield, remaining parameter all same obtain catalyst I, and the sphericity of catalyst I is 0.938, and remaining physico-chemical parameter for example weares and teares and refers to
Number, water droplet method pore volume, heap are than the level that can reach prior art.
Comparative example 1
This comparative example is to prepare catalyst according to the method for CN1160436C.
500 grams of water is added toward reactor, the finely dispersed SOY-2 molecular sieves that concentration is 32 weight % are subsequently adding
（The product of Shandong catalyst plant production, is the USY type molecular sieves containing rare earth, RE2O3Content is 2.0 weight %, similarly hereinafter）Serosity
1094 grams, add 381 grams of Alumina gels（Shandong catalyst plant production product, 21 weight % of alumina content, similarly hereinafter）, stirring 15
Minute, add 474 grams of Kaolin（Kaolin of Suzhou Products, 22 weight % of igloss, similarly hereinafter）, it is beaten 1 hour, adds 323
Gram boehmite（Shandong branch company of Chinese Aluminium Co., Ltd product, 38 weight % of igloss, similarly hereinafter）, stir 0.5 little
When, add the concentrated hydrochloric acid of 49 gram of 37 weight % to be acidified 1 hour, 85000 centipoise of viscosity of analysis of catalyst serosity.Then using pressure
Power formula spray dryer is 550 DEG C in inlet temperature, and outlet temperature is spray drying forming under conditions of 100 DEG C, scrubbed dry
Dry to obtain catalyst M1, the sphericity of analysis of catalyst M1 is 0.913.
Comparative example 2
According to the method for comparative example 1, the inlet temperature for not being both spray drying is 380 DEG C, and remaining condition all same must be urged
Agent M2, the sphericity of analysis of catalyst M2 is 0.915.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as which is without prejudice to this
The thought of invention, which should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of method for preparing microsphere FCC catalyst, the method include：
Molecular sieve, clay, boehmite and acid beating are obtained into catalyst slurry, the catalyst slurry is sprayed
It is dried, it is characterised in that before being spray-dried, the viscosity for controlling catalyst slurry is 500-10000 centipoises, and is spray-dried
Inlet temperature be 300-450 DEG C；
Wherein, sprayed by nozzle in spray-drying process, be then dried, the nozzle is included：With cavity
Nozzle body, is provided with nozzle entrance (1), spray orifice (4) on the nozzle body；Wherein, in the cavity of the nozzle body
Roof has been downwardly projected conducting element (3), and the space between the inner surface of the outer surface and the cavity of the conducting element (3) forms rotation
Turn room (2)；
At least partially cylinder of the cavity, the nozzle entrance (1) are communicated with rotating room (2) in tangential direction.
2. method according to claim 1, wherein, before being spray-dried, the viscosity for controlling catalyst slurry is 1000-
4000 centipoises, and the inlet temperature being spray-dried is 330-420 DEG C.
3. method according to claim 1 and 2, wherein, in terms of the dry weight of catalyst slurry, contain in the catalyst slurry
There are molecular sieve 10-55 weight %, aluminium oxide 10-40 weight %, clay 15-65 weight %.
4. method according to claim 1 and 2, wherein, as follows by molecular sieve, clay, boehmite and
Acid is beaten：
Molecular sieve and water are mixed to form into molecular sieve pulp, clay mix homogeneously is subsequently adding, be subsequently adding boehmite and
Sour mix homogeneously, obtains catalyst slurry.
5. method according to claim 1 and 2, wherein, the beating is carried out in the presence of Alumina gel, the Alumina gel
Solid content is 10-40 weight %.
6. method according to claim 5, wherein, as follows by molecular sieve, Alumina gel, clay, boehmite
And acid is beaten：
Molecular sieve, Alumina gel and water are mixed to form into molecular sieve pulp, clay mix homogeneously is subsequently adding, the thin water of plan is subsequently adding
Aluminum stone and sour mix homogeneously, obtain catalyst slurry.
7. method according to claim 1 and 2, wherein, the molecular sieve is the molecular sieve with FAU structures, with MAZ
One or more in the molecular sieve of structure, the molecular sieve with MFI structure, the molecular sieve with BEA structures；The clay is
One or more in Kaolin, galapectite, meerschaum, rectorite and montmorillonite；The boehmite be a diaspore, three
One or more in diaspore and Baeyer stone；The acid is one or more in hydrochloric acid, nitric acid, phosphoric acid and sulphuric acid.
8. method according to claim 7, wherein, the molecular sieve is Y type molecular sieve and/or ZSM-5 molecular sieve, described
Clay is Kaolin, and the boehmite is one or more in a diaspore, gibbsite and Baeyer stone.
9. method according to claim 1, wherein, in vertical direction, bottom and the spray orifice (4) of the conducting element (3)
1/10-4/5 of the distance on top for cavity height.
10. method according to claim 9, wherein, in vertical direction, bottom and the spray orifice (4) of the conducting element (3)
1/5-1/3 of the distance on top for cavity height.
11. methods according to claim 1, wherein, the outer surface of the conducting element (3) and the inner surface of the cavity it
Between distance for cavity diameter 1/10-2/5.
12. methods according to claim 1, wherein, the conducting element (3) including the cylinder and cone being connected,
Wherein, an end of cylinder is connected to the roof of the cavity.
13. methods according to claim 12, wherein, the height ratio of the cylinder and cone of the conducting element (3) is
0.5-3:1。
14. methods according to claim 1, wherein, the spray orifice (4) is arranged on the bottom of the nozzle body.
15. methods according to claim 1, wherein, the nozzle body includes the cylinder being connected and cone, institute
Cylindrical cavity and conical cavity that cavity includes being connected are stated, the cylindrical cavity is located in the cylinder body, and the conical cavity is located at institute
State in circular cone body, the height ratio of the cylindrical cavity and conical cavity is 0.5-3:1.
16. methods according to claim 15, wherein, the spray orifice (4) is formed in the cone of the nozzle body
Connect with the conical cavity at the vertex of a cone, the nozzle entrance (1) is arranged on the cylinder of the nozzle body and the cylinder
Chamber connects in tangential direction.
17. methods according to claim 15, wherein, the conducting element (3) including the cylinder and cone being connected,
Wherein, one end of cylinder is connected to the roof of cavity；The cone angle of the cone of the nozzle body, the conducting element (3)
The cone angle of cone is equal with the cone angle of the conical cavity.
18. methods according to claim 15, wherein, the diameter of the nozzle entrance (1), the diameter of spray orifice (4) and institute
The ratio for stating the diameter of cylindrical cavity is 1-8:1-10:20-40.
19. methods according to claim 1, wherein, the nozzle also includes the part with loudspeaker opening (5), described
The loudspeaker opening of part (5) is communicated with the spray orifice (4).
20. methods according to claim 19, wherein, the height of the loudspeaker opening is 1/10-2 times of cavity height,
The bus of loudspeaker opening and the angle of horizontal direction are 10-60 °, and edge is towards the direction on the outside of spray orifice, the loudspeaker opening
Diameter gradually increases.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246515A (en) * | 1998-09-03 | 2000-03-08 | 中国石油化工集团公司 | Process for preparing catalyst for catalytic cracking |
| CN101829592A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Preparation method of high-solid content fluid catalytic cracking catalyst |
| CN102039228A (en) * | 2009-10-16 | 2011-05-04 | 韩铁夫 | Rotary annular-seam spray nozzle and spraying device thereof |
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2013
- 2013-10-28 CN CN201310516097.7A patent/CN104549420B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246515A (en) * | 1998-09-03 | 2000-03-08 | 中国石油化工集团公司 | Process for preparing catalyst for catalytic cracking |
| CN101829592A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Preparation method of high-solid content fluid catalytic cracking catalyst |
| CN102039228A (en) * | 2009-10-16 | 2011-05-04 | 韩铁夫 | Rotary annular-seam spray nozzle and spraying device thereof |
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