CN106582490A - Method for preparing microsphere composition - Google Patents
Method for preparing microsphere composition Download PDFInfo
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- CN106582490A CN106582490A CN201510677037.2A CN201510677037A CN106582490A CN 106582490 A CN106582490 A CN 106582490A CN 201510677037 A CN201510677037 A CN 201510677037A CN 106582490 A CN106582490 A CN 106582490A
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Abstract
The invention provides a method for preparing a microsphere composition. The method comprises the following steps: binder dispersion liquid and dispersion liquid of other components of the composition are mixed in a piece of spraying apparatus with a mixing function in order to form composition slurry, and spraying and drying are carried out; wherein, the spraying apparatus with the mixing function comprises a fluid inlet cavity (1) and a nozzle sheet (4), at least two rotary chambers (2) are arranged between the fluid inlet cavity (1) and the nozzle sheet (4), and flow deflectors (3) opened with deflector holes are arranged between different rotary chambers; a fluid inlet cavity (1) is provided with a fluid inlet tube (12), in order to introduce the binder dispersion liquid and dispersion liquid of other components of the composition. The method can improve wear resistance of the microsphere compositions, stabilize pore volume, and stabilize quality of the product.
Description
Technical field
The present invention relates to a kind of method for preparing microspheroidal composition.
Background technology
Microspheric composition such as catalyst, auxiliary agent or adsorbent are typically by being spray-dried system
It is standby.The preparation flow of typical microspheroidal composition is will to be used to prepare several originals of composition
Material mixes uniformly composition slurry liquid in mixing arrangement such as stirred tank, then leads in slurries
Cross fluid delivery pump and be transported to atomising device and be atomized into droplet, droplet drying and moulding in drying tower.
A kind of atomizing type is pressure type atomization, and it passes through high-pressure pump and composition slurries are transported to into pressure
Formula atomizer is atomized, can be dry with adjustable spraying by adjustable spraying pressure and nozzle bore
The average grain diameter and size distribution of dry product.Have product particle equal because press spray is dried
Even property preferably, the characteristics of nozzle cleaning is easy, is widely used in the preparation of microspheroidal composition.
The preparation of such as FCC catalyst, by molecular sieve, water, kaolin and binding agent in mixing kettle
Jing press spray drying after beating is uniform is prepared into the microspheroidal with certain particle size distribution and urges
Catalyst particles.
The content of the invention
Present inventor's research finds, by raw material of different nature after mixing kettle mixing
Spray drying, the catalyst obtained after spray drying forming after some materials mixing or auxiliary agent quality
Bad, such as zinc oxide slurries and acidic oxidation al binder are spray-dried after stirred tank mixing
Made by product abrasion index it is poor；Magnesia slurry and acidic oxidation al binder are in stirred tank
Spray dried products abrasion index is poor after mixing；Molecular sieve pulp and phosphorus aluminium glue are mixed in stirred tank
Spray dried products abrasion index is poor after conjunction, and pore volume easily fluctuates, molecular sieve pulp and silicon
Colloidal sol spray dried products abrasion index after stirred tank mixing is poor, and pore volume easily fluctuates.
One of the technical problem to be solved in the present invention is to provide a kind of microspheroidal composition of preparing
New method.
The invention solves the problems that other technical problem be to provide a kind of device for said method
System.
A kind of method for preparing microspheroidal composition, including：Will bonding agent dispersing liquid and combination
The dispersion liquid of thing other components is mixed to form composition in the spraying apparatus with mixed function
Slurries and spray, be dried；Wherein, the described spraying apparatus with mixed function includes：
Fluid intake chamber and nozzle piece, are provided with least two between fluid intake chamber and nozzle piece
Individual rotating room and at least one flow deflector, any two is provided with one between adjacent rotating room
Flow deflector arranges pod apertures so that described Liang Ge rotating rooms to be separated, on the flow deflector with even
Lead to the adjacent Liang Ge rotating rooms；The side wall of fluid intake chamber arranges at least two fluids and enters
Mouth pipe；At least one fluid inlet tube is used to introduce bonding agent dispersing liquid (abbreviation binding agent entrance
Pipe), at least one fluid inlet tube is used to introduce the dispersion liquid (abbreviation of other components of composition
Other component inlet tubes), the agent dispersing liquid that will bond is drawn by one or more fluid inlet tubes
Enter in fluid intake chamber, by the dispersion liquid of composition other components by one or more with
The different fluid inlet tube of bonding agent dispersing liquid fluid inlet tube is incorporated in fluid intake chamber.
The present invention also provides a kind of preparation facilities of microsphere composition, including bonding agent dispersing liquid is defeated
Other component dispersion liquid conveying devices of device, composition, the spraying with mixed function are sent to set
Standby and drying equipment, the described spraying apparatus with mixed function：Including fluid intake chamber
And nozzle piece, at least two rotating rooms are provided between fluid intake chamber and nozzle piece, no
Flow deflector with pod apertures is set between same rotating room, and described inlet chamber is arranged at least
Two fluid inlet tubes, the agent dispersing liquid conveying device that bonds and the spraying apparatus with mixed function
At least one fluid inlet tube connect with to mixed function spraying apparatus conveying bonding
Agent dispersing liquid, other component dispersion liquid conveying devices of composition and the spraying with mixed function
Equipment is connected with defeated to the spraying apparatus with mixed function with least one with fluid inlet tube
Send the dispersion liquid of other components of composition.Introduce the fluid inlet tube of bonding agent dispersing liquid and introduce
The fluid inlet tube of composition other component dispersion liquids is different.
The method of the preparation microspheroidal composition that the present invention is provided, it is described with mixed function
Spraying apparatus, including fluid intake chamber, rotating room, flow deflector, and nozzle piece, wherein revolving
Turn room and flow deflector is between fluid intake chamber and nozzle piece, set between different rotating rooms
Flow deflector is equipped with, rotating room is provided between different flow deflectors, the number of rotating room is at least
Two, the number of flow deflector is at least one, the number of rotating room than flow deflector number more than one
It is individual.The described spraying apparatus with mixed function also abbreviation spraying apparatus of the invention, can not only
Atomizing functions are enough realized, and with quick mixed function.
The described spraying apparatus with mixed function, including at least two rotating rooms, any two
The number that a flow deflector, rotating room and flow deflector are provided between individual adjacent rotating room can be with
Determined according to the viscosity and required mixed effect of mixed fluid, increase flow deflector and rotation
The number of room is conducive to improving mixed effect, and high-viscosity fluid can use more rotating rooms
With flow deflector improving mixed effect.Described rotating room is preferably 2-9；Each flow deflector
Each one rotating room of connection in both sides, described flow deflector is preferably 1-8.Different rotations
Separated by flow deflector between room, connected by the pod apertures on flow deflector.Rotating room is at least two
Individual, flow deflector is at least one；If increasing the number of rotating room and flow deflector, flow deflector and
Rotating room increases in pairs, and flow deflector and rotating room are in the described spraying apparatus with mixed function
In be axially arranged alternately.Generally, the number of rotating room than flow deflector number more than one.
Top rotating room is also referred to as apart from the nearest rotating room of fluid intake chamber, apart from fluid intake chamber
Farthest rotating room is also referred to as end rotating room apart from the nearest rotating room of nozzle piece.
The described spraying apparatus with mixed function, described flow deflector is cylindrical sheets
(abbreviation disk), its bottom surface (bottom surface of flow deflector cylinder, also referred to as water conservancy diversion plate plane,
The bottom surface being connected with upstream rotating room is referred to as flow deflector upstream bottom surface or upstream plane, with downstream rotation
The bottom surface for turning room connection is referred to as flow deflector downstream bottom or downstream plane), flow deflector is provided with insertion
The perforate of two bottom surfaces is referred to as pod apertures, to connect the Liang Ge rotating rooms being adjacent (with water conservancy diversion
Piece is joined directly together the Liang Ge rotating rooms for connecing), make the fluid in the rotating room of flow deflector upstream pass through institute
The pod apertures stated enter the rotating room in downstream from the rotating room of upstream.Any one flow deflector it is upper,
Downstream bottom respectively connects a rotating room.Wherein, described upstream and downstream refers to that fluid enters from fluid
The direction of motion of oral chamber to nozzle piece, axially closer to the position of fluid intake chamber
Closer to the position of nozzle piece it is downstream relatively more away from fluid intake chamber for upstream.
If shown in Fig. 1, the left side is upstream, the right is downstream.
In the described spraying apparatus with mixed function, the pod apertures of usual described flow deflector
For circular hole, its cross section (perpendicular to section of water conservancy diversion centerline hole) is circle.Pod apertures
Center line relative to flow deflector inclined bottom surface certain angle, i.e. the center line and water conservancy diversion of pod apertures
The bottom surface out of plumb of piece.Angle (folder of the water conservancy diversion centerline hole and flow deflector upstream plane
Angle represents with β, as shown in figure 3, referred to as pod apertures axially introduced into angle) be 20-70 °, it is excellent
Select 30-60 °.The present invention (crosses water conservancy diversion centerline hole and leads for the pod apertures of flow deflector in radius
The radius of flow upstream plane point of intersection) angle on direction do not have particular/special requirement；Under preferable case,
Water conservancy diversion centerline hole and flow deflector upstream plane point of intersection (as shown in the A points in Fig. 3) with lead
The line segment that the flow upstream plane center of circle (such as the O points in Fig. 3) is formed is (such as the OA in Fig. 3
It is shown) and the water conservancy diversion centerline hole a bit (B in such as Fig. 3 on updrift side extended line
Shown in point) projection (as shown in the C points of Fig. 3) in the plane of flow deflector upstream and water conservancy diversion
The line segment that centerline hole is formed with flow deflector upstream plane point of intersection (as shown in the AC in Fig. 3)
Between angle (represented with α, as shown in figure 3, the present invention be referred to as pod apertures radial direction introduce
Angle) it is 45～135 °, preferably 90～120 °.
The number of the pod apertures on flow deflector can be one or more, preferably several.When leading
When the number of discharge orifice is multiple, each pod apertures is mutually disjointed on flow deflector；It is preferred that feelings
Under condition, the pod apertures are circumferentially uniformly distributed.Described being circumferentially uniformly distributed is to instruct
The intersection point of the center line of flow upstream plane and each pod apertures on same circumference, and in circumference
On be spacedly distributed (the distance between two circumferentially adjacent pod apertures are equal), respectively lead
There is discharge orifice identical tangential direction (each pod apertures is rotated to into same position, its center line
Overlap with same straight line), each pod apertures is enabled flow through into the rotation in flow deflector downstream
Room rotates along identical direction, for example, be and turn clockwise or be rotate counterclockwise.
Under preferable case, the described spraying apparatus with mixed function, described flow deflector is thick
Spend for 1-6mm, preferred 2-4mm；Water conservancy diversion bore dia 1-4mm on the flow deflector, it is excellent
Select 2-3mm；Pod apertures number on the flow deflector is 2-8, preferred 3-6.
The flow deflector of the described spraying apparatus with mixed function is to the fluid into rotating room
There are dispersion and rectified action, re-mix after the fluid dispersion that rotating room can be made, and in water conservancy diversion
Make rotational flow in the rotating room in piece downstream.
The described spraying apparatus with mixed function, including multiple rotating rooms, multiple rotating rooms
Export from fluid intake chamber to nozzle piece and be arranged in order, water conservancy diversion is passed through between adjacent rotating room
Pod apertures connection on piece, described rotating room is cylindrical space and/or shaping drum.Respectively
The diameter of individual rotating room can be the same or different, and the height of each rotating room can be with identical
Can be with difference.In the case of preferred, each rotating room has identical diameter.Spin chamber diameter
Preferably 10-30mm, more preferably 15-25mm；The length of the rotating room is preferably 3-18mm,
More preferably 5-10mm.
The described spraying apparatus with mixed function, is introduced for mixing by fluid inlet tube
Fluid.Described fluid inlet tube is multiple, to introduce at least two different fluids.
Described fluid inlet tube (also abbreviation inlet tube) may be contained within fluid intake chamber (
Abbreviation inlet chamber) side wall, fluid intake chamber for cylinder, its one end bottom surface closing,
End cap is set, and other end bottom surface is connected with top rotating room.The height of fluid intake chamber
It is to close to distance from the bottom surface of blind end for the height of the part with fluid intake on the wall of side
The distance at the edge of the farthest fluid intake in end, the diameter of fluid intake chamber preferably revolves with top
The diameter for turning room is identical.Fluid inlet tube is tangentially connected with fluid intake chamber, makes fluid edge
Tangential direction into fluid intake chamber.The rotating room for connecing is joined directly together with fluid intake chamber
Referred to as top rotating room, rotating room is cylindrical space or for a shaping drum；Top rotates
In downstream connection flow deflector, flow deflector is that (inclined hole refers to axially bored line with multiple inclined holes for room
With water conservancy diversion plate plane out of plumb) disk, the flow deflector is connected in downstream with other rotating room；
End rotating room is connected in downstream with nozzle piece.The described spraying apparatus with mixed function can
To be provided with least 2 preferred 2-4 fluid inlet tubes according to amount of fluid used, fluid enters
Mouth pipe is tangentially connected with inlet chamber；The diameter (internal diameter) of inlet tube is 2-6mm, preferably
3-5mm.Multiple fluid inlet tubes are distributed along the even circumferential of side wall, preferably in axial location
It is identical, i.e. the distance phase of the same end face of the same rotating room of axial line distance of different fluid inlet tube
Together.
The described spraying apparatus with mixed function, makes material enter from fluid inlet tube and sprays
After equipment, mix through rotating room and flow deflector, then spray from the spray orifice of nozzle piece.Described
Nozzle piece includes nozzle piece inlet cone and spray orifice, nozzle piece inlet cone (cone space)
Bottom surface is connected with end rotating room, and cone top part is connected with spray orifice.The injection diameter of nozzle piece
For 1-4mm, preferred 2-3mm；The spray orifice length of the nozzle piece is 1-5mm, preferred 2-4mm；
The cone angle of the nozzle piece inlet cone is 40-140 °, preferred 60-120 °.Under preferable case,
The basal diameter of nozzle piece inlet cone is identical with the diameter of end rotating room.
The described spraying apparatus each several part with mixed function can be prepared into an entirety,
Can be formed by the Split assembled of each several part.For example can be by fluid intake chamber and adjacent rotation
Turn room as one, it is also possible to by a flow deflector and its one or two adjacent rotating room's system
Integral part, or nozzle entrance chamber part, water conservancy diversion chip part, rotating room are prepared respectively
Part and nozzle chip part, then as required fit together these parts described in obtaining
Spraying apparatus with mixed function.
The microspheroidal preparation method of composition that the present invention is provided, by bonding agent dispersing liquid and formation group
The dispersion liquid of other components of compound is respectively by fluid delivery system such as high-pressure pump or measuring pump
Be transported to the different inlet tubes of spraying apparatus, Jing fluid inlet tubes by tangentially entering in inlet chamber,
Slurries are tentatively mixed in fluid intake chamber and rotating room because high speed rotates, preliminary mixing
Slurries afterwards disperse again again through flow deflector duct, then rotate in rotating room's high speed and enter
One step is well mixed, and at a high speed the slurries being well mixed of rotation form an annular liquid film in spray orifice,
Annular liquid film leaves at a high speed and expand after spray orifice thinning, finally divides uniformly little droplet, little mist
Become microspheroidal composition grain such as catalyst or builder granule after drip-dry is dry.
The microspheroidal preparation method of composition that the present invention is provided, each component is with mixed function
Mixing velocity is fast in spraying apparatus, and good mixing effect, atomizing effect is good, can improve combination produce
The abrasion resistance properties of product.The satisfactory microsphere particle of particle diameter distribution can be obtained.The present invention is carried
For method can save the step of composition slurries are prepared in stirred tank, save stirred tank and throw
Money, shortening prepares boiling range, saves preparation time.The method that the present invention is provided prepares catalyst,
The pore volume that some products can be stablized for example uses Ludox and molecular sieve, molecular sieve and phosphorus aluminium
The pore volume of catalyst prepared by glue.The method that the present invention is provided is particularly suited for preparing binding agent
The unstable microspheroidal composition of property after mixing with other components, it is possible to increase composition it is resistance to
Mill performance, for example can be used for preparation is using phosphorus Alumina gel, Ludox, acidification pseudo-boehmite
The micro-spherical catalyst or auxiliary agent of binding agent or adsorbent.
Description of the drawings
(sectional view, section is excessively described for a kind of spraying apparatus front view for providing of the invention for Fig. 1
The center line of spraying apparatus, the F-F sections of Fig. 2).Wherein 1 be fluid intake chamber, 12
For fluid inlet tube, 2 is rotating room, and 3 is flow deflector, and 4 is nozzle piece.Fluid intake chamber
Dashed circle at 1 illustrates another fluid intake position in the axial direction, corresponding to Fig. 2
1 in fluid inlet tube 122.The dotted line of flow deflector 3 illustrates pod apertures (from flow deflector side
The invisible outline line of the pod apertures of the view that face is seen).
The view of the spraying apparatus part that Fig. 2 is provided for Fig. 1 of the present invention.Wherein 1 sets for spraying
The left view of standby inlet chamber part, 121 and 122 is fluid inlet tube, and 2 is portion of rotating room
The left view of part, the part 21 between two circles is rotation locular wall；3 are water conservancy diversion chip part
Left view, 31 is part (the dashed circle signal rotation that flow deflector edge is contacted with rotation locular wall
The internal face of locular wall and the intersection of flow deflector), 4 is the left view of nozzle chip part.
Fig. 3 is the blowing angle schematic diagram (stereogram) of pod apertures on flow deflector.Wherein, put down
Face OAC is the upstream plane of flow deflector, and DO is the axis of flow deflector, and O is flow deflector axis
With the intersection point of flow deflector upstream plane, A is water conservancy diversion centerline hole (axis) and flow deflector upstream
The intersection point on surface, BA for pod apertures center line updrift side extended line (B be the line
On a bit), flow direction of the fluid in pod apertures is BA directions, and AC is leading for BA
Projection in the plane of flow upstream, α is ∠ OAC, and α is defined as the radial direction of pod apertures and introduces angle,
β be ∠ BAC, β be defined as pod apertures axially introduced into angle.
A kind of schematic flow sheet of the microsphere composition preparation system that Fig. 4 is provided for the present invention, B1
For first fluid high-pressure pump, B2 is second fluid high-pressure pump, and B1 and B2 is respectively used to conveying
The dispersion liquid of bonding agent dispersing liquid and composition other components, A is drying tower, and A1 is drying
Tower hot wind inlet, A2 is drying tower air outlet, and A3 is the outlet of composition microballoon, and A4 is spray
Mist equipment and its fixing equipment, the spraying apparatus of A4 is in drying tower A.
Specific embodiment
The method of the preparation microspheroidal composition that the present invention is provided, described other components of composition
Active component is generally included, optionally including carrier component and/or adjuvant component.Described group
Compound other components such as molecular sieve, clay, magnesia, zinc oxide, the compound of iron, nickel
Compound, alumina powder, silicon oxide powder in one or more.By composition other
Prepared by component become one or more dispersion liquid, and each dispersion liquid passes through a fluid or multiple
Fluid is introduced into pipe and is incorporated in the described spraying apparatus with quick mixed function.Described is viscous
(also referred to as phosphorus aluminium glues for knot agent such as silica binder, alumina binder, aluminum phosphate binder
Knot agent) in one or more.
Compared with prior art, the present invention does not have to the dispersion liquid of prepared composition other components
There is particular/special requirement, the contents on dry basis of the dispersion liquid of composition other components generally described in each
It is, for example, 15～45 weight % for 5～50 weight %；The dispersion liquid of the composition other components
For solution or slurries, typically at least a kind of is the slurries containing solid particle, when composition other
When the dispersion liquid of component is the slurries containing solid particle, generally wherein the diameter of solid particle is put down
Particle diameter is less than 5 microns, and for example, 2～5 microns, the D90 of particle size distribution is usual
Less than 20 microns (diameter particle sizes), for example, 3～15 microns.Described binding agent dispersion
Liquid does not have particular/special requirement, example with the binding agent dispersion phase ratio of existing microsphere composition preparation method
The contents on dry basis of binding agent in agent dispersing liquid that such as bonds is 5～40 weight %, preferably 5～30 weights
Amount %, for example, 10～25 weight %.Described bonding agent dispersing liquid such as Ludox, phosphorus aluminium
In colloidal sol, acidic oxidation al binder colloid such as acidification pseudo-boehmite and/or Alumina gel
One or more.
The method of the preparation microspheroidal composition that the present invention is provided, first will be used to prepare microspheroidal group
The raw material of compound is prepared at least two fluids, then by least two described fluids from difference
Fluid inlet tube be incorporated in the described spraying apparatus with mixed function and be well mixed shape
Spray into composition slurries and by described composition slurries, atomization forms droplet, set in drying
Standby middle drying forms microspheric composition grain, and one of which fluid is bonding agent dispersing liquid,
Referred to as first fluid, the composition in addition to binding agent other components are prepared and become at least one stream
Body, such as including the dispersion of one or more in active component, carrier component and adjuvant component
Liquid.Bonding agent dispersing liquid is introduced into pipe and is incorporated in fluid intake chamber by one or more fluids,
Other components of composition can make one or more dispersion liquid, and every kind of dispersion liquid can pass through
One or more fluid inlet tubes are incorporated in fluid intake chamber.For example can make containing activity
The dispersion liquid of component, the dispersion liquid containing carrier, the dispersion liquid containing adjuvant component, containing active component,
The dispersion liquid of two or more in carrier and auxiliary agent, then by prepared different dispersion liquids
It is incorporated in fluid intake chamber by fluid inlet tube.A kind of embodiment, by binding agent with
The bonding agent dispersing liquid that water is formed as a kind of fluid, by positioned at fluid intake chamber side wall
One fluid inlet tube is incorporated in fluid intake chamber, and by composition, other components are formed with water
Dispersion liquid as a kind of fluid, by a fluid intake positioned at fluid intake chamber side wall
Pipe is incorporated in fluid intake chamber, and two kinds of fluids are entered after mixing in fluid intake chamber and begun
End rotating room, then through flow deflector and other rotating rooms, eventually passes through nozzle piece ejection, enters
Enter in drying equipment.
The method of the preparation microspheroidal composition that the present invention is provided, described composition can include
The composition of the binding agent of in terms of butt 5～90 weight % and in terms of butt 10～95 weight %
Other components, for example, can include that in terms of butt 5～40 weight % binding agents and butt count 60～95
The composition of weight % other components.Described composition can be catalytic cracking catalyst or urge
Change cracking additive, adsorbent such as gasoline desulfurization S-ZORB adsorbents, described active component
Can be cracking active component, auxiliary agent active component and adsorption activity component.Described catalysis is split
Change auxiliary agent such as catalytic cracking sulfur transfer additive, de- NOx auxiliary agents, propylene enhancing auxiliary agent or gold
Category passivator.
A kind of method of the preparation microspheroidal composition that the present invention is provided, embodiment is described
Composition is catalytic cracking catalyst or assistant for calalytic cracking, described catalytic cracking catalyst or
Assistant for calalytic cracking generally includes active component, binding agent and optional carrier such as clay.One
Embodiment is planted, in terms of butt, the catalytic cracking catalyst or assistant for calalytic cracking include
The binding agent of 5～40 weight %, (cracking active component is helped the active component of 10～60 weight %
Agent active component) and 0～60 weight % clay.Described binding agent such as silica binder,
One or more in alumina binder, phosphorus al binder, described bonding agent dispersing liquid example
One or more such as in Ludox, phosphorus Alumina gel or acidic oxidation al binder, described acid
Property alumina binder is, for example, Alumina gel and/or acidification pseudo-boehmite.Described catalysis is split
Change catalyst or assistant for calalytic cracking active component be selected from molecular sieve, magnesium aluminate spinel,
One or more in activated alumina, mesoporous silica-alumina materials.The clay such as kaolin,
One kind in halloysite, rectorite, diatomite, montmorillonite, bentonite, sepiolite or
Person is several.Described catalytic cracking catalyst or assistant for calalytic cracking can also contain modified component
(or claiming adjuvant component), its content is typically not greater than 15 weight %, for example, 0.1～10 weight %.
In described modified component such as iron oxide, magnesia, rare earth oxide, cobalt oxide, nickel oxide
One or more.
A kind of method of the preparation microspheroidal composition that the present invention is provided, embodiment is described
Composition is adsorbent, described adsorbent generally include active component (adsorption activity component),
Binding agent, optional carrier and optional adjuvant component.In terms of butt, described adsorbent
Including 10～80 weight % adsorption activity components, the binding agent of 20～90 weight %, 0～40 weight %
Carrier and 0～10 weight % adjuvant component.Described bonding agent dispersing liquid is, for example, acidity
One or more in alumina binder, Ludox, phosphorus Alumina gel, described adsorption activity
Component is, for example, one or more in zinc oxide, magnesia, molecular sieve.Described carrier example
As in clay, silica, aluminum oxide, silica-alumina, titanium oxide and zirconium oxide
One or more, described adjuvant component such as cobalt and/or nickel.Wherein adjuvant component can be
Spray drying is previously introduced in composition slurries can also be passed through after spray drying forming
Dipping or the mode for precipitating are incorporated in microsphere adsorbing agent.
The solid that butt of the present invention is material to be obtained after 1 hour in 800 DEG C of roastings is produced
Thing.
The method of the preparation microspheroidal composition that the present invention is provided, to described with mixed function
The pressure of spraying apparatus be not particularly limited, the composition that spray drying should generally formed
The particle diameter distribution of particle meets use requirement, the average grain of diameter of the particle of such as microsphere composition
Footpath between 60～80 microns, for catalytic cracking catalyst or assistant for calalytic cracking or adsorbent
For, particle of the preferred diameter particle size less than 149 microns is accounted for more than 90 volumes %,
Particle of the diameter particle size less than 20 microns is accounted for below 4 volumes %, and diameter particle size is less than
40 microns of particle is accounted for below 20 volumes.
The method of the preparation microspheroidal composition that the present invention is provided, by the dry of the spraying apparatus
Base mass flow is preferably 0.2～1 ton hour.Under preferable case, bond agent dispersing liquid and combination
The contents on dry basis of the composition slurries that thing other component dispersion liquids are mixed to form is 5～45 weight %.
The method of the preparations microspheroidal composition that the present invention is provided, described bonding agent dispersing liquid with
The dispersion liquid of composition other components is in described spraying apparatus (the application with mixed function
In also abbreviation spraying apparatus) in the time of staying (the also referred to as time of staying of each component or composition
The time of staying) be typically smaller than 1 minute.The component of composition is formed from into described tool
Have the spraying apparatus of mixed function to leave the described spraying apparatus with mixed function when
Between be less than 1 minute.The described time of staying for example can for 0.001 second～10 seconds or
0.005～0.5 second, or 0.01～0.1 second.
The method of the preparation microspheroidal composition that the present invention is provided, composition slurries leave spraying and set
Standby rear entrance drying equipment is atomized to form droplet and be dried, and obtains composition grain.The group for obtaining
Polymer beads can be processed further, for example dipping, washing etc..It is dried and further processes
Method is existing method, and the present invention is without particular/special requirement.Such as dry medium can be high temperature
Flue gas, dry exhaust temperature can be 120～220 DEG C.
The present invention is further illustrated for the following examples, but does not therefore limit this
Bright content.
The abrasion index of catalyst is marked using enterprise of Research Institute of Petro-Chemical Engineering in following Examples
Quasi- Q/SH3360 208-2012 (measure of catalytic cracking catalyst abrasion index) method is determined.
Size distribution (is urged using Research Institute of Petro-Chemical Engineering company standard Q/SH3360 210-2011
The measure laser particle size method of agent size distribution) method analysis.Pore volume adopts petrochemical industry
Research institute company standard Q/SH3360 206-2011 (the measure water droplets of catalyst pore volume
Method) method measure.
Embodiment 1
The The concrete specification of spraying apparatus A is：There are 2 fluid inlet tubes, in fluid feeding cavity
It is symmetrical by symmetry axis of axis on the wall of room side, fluid inlet tube tangentially with fluid feeding cavity
Room is connected；Fluid intake pipe diameter (internal diameter) is 4.0mm；Fluid intake chamber is highly
6mm, a diameter of 18mm；There are 4 rotating rooms, each spin chamber diameter is 18mm, length
Spend for 6mm；There are 3 flow deflectors, each flow deflector thickness 2.5mm；On each flow deflector
Pod apertures number be 6, pod apertures are uniformly distributed on flow deflector, each water conservancy diversion bore dia
2.0mm, water conservancy diversion centerline hole is 50 ° with the angle (axially introduced into angle beta) of water conservancy diversion plate plane,
It is 120 ° radially to introduce angle α, the intersection point of water conservancy diversion centerline hole and flow deflector upstream plane with lead
The distance of flow axis is 7mm.The injection diameter of nozzle piece is 2.5mm, and spray orifice length is
3.0mm, the cone angle of nozzle piece inlet cone is 90 °, and inlet cone basal diameter is 18mm.
Slurries (the average grain of magnesia that the magnesia of weight % of solid content 30 and water are formed
Footpath is 3.5 microns, and D90 is 15 microns) and weight % of solid content 12 the acidifying thin water aluminium of plan
(hydrochloric acid is acidified stone slurries, and HCl is 0.15), by 1 with the mol ratio of aluminum oxide:2.5 quality
Flow proportional is respectively delivered to two fluid inlet tubes of spraying apparatus A by high-pressure pump, then
Into the fluid intake chamber of spraying apparatus B, nozzle piece spraying is eventually passed, inlet chamber
Pressure is 10MPa, and as 500kg/ hours, bond the combination logistics capacity counted with butt agent dispersing liquid
The time of staying with the dispersion liquid of composition other components in spraying apparatus A is less than 1 second.
Composition A1 is obtained after spray drying, the abrasion index of analysed composition A1 is 1.8, hole body
Product is 0.33mL/g.The diameter average grain diameter of resulting composition microballoon is 72 μm, diameter grain
Footpath accounts for 92 volumes % less than 149 microns, and less than 20 microns 1.8 volumes % are accounted for, and is less than
40 microns account for 15 volumes %.
Embodiment 2
The The concrete specification of spraying apparatus B is：There are 2 fluid inlet tubes, along inlet chamber
The even circumferential distribution of side wall, tangential and fluid intake of the fluid inlet tube along fluid intake chamber
Chamber is connected；Fluid inlet diameter (internal diameter) is 4.0mm；Fluid intake chamber is highly
6mm, a diameter of 18mm, there is 3 rotating rooms, and each spin chamber diameter is 18mm,
The length of each rotating room is 8mm；There are 2 flow deflectors, each flow deflector thickness is
3mm, the pod apertures number on each flow deflector is 4, and each water conservancy diversion bore dia is
2.5mm, is circumferentially uniformly distributed on flow deflector, water conservancy diversion centerline hole and water conservancy diversion plate plane
Angle (β angles) be 40 °, α angles are 100 °, water conservancy diversion centerline hole and flow deflector upstream
The intersection point of plane is 7.5mm apart from the distance of flow deflector axis.The injection diameter of nozzle piece is
2.8mm, spray orifice length is 2.5mm, and the cone angle of nozzle piece inlet cone is 100 °, approach cone
Body basal diameter is 18mm.
By the magnesia slurry of weight % of solid content 30, (slurries that magnesia and water are formed, put down
Particle diameter is 3.5 microns, and D90 is 15 microns) and the acidifying plan of weight % of solid content 10 it is thin
Diaspore slurries (slurries formed by boehmite, hydrochloric acid and water, HCl and aluminum oxide
Mol ratio (i.e. sour aluminum ratio) is 0.15), by 1:3 mass flow ratio is distinguished by high-pressure pump
The two entrances pipe of spraying apparatus B is transported to, subsequently into spraying apparatus B mixed atomizings.
The pressure of inlet chamber is 12MPa, the combination logistics capacity counted with butt as 600kg/ hours,
During stop of the dispersion liquid of bonding agent dispersing liquid and composition other components in spraying apparatus B
Between be less than 1 second.Composition B1, the abrasion index of analysed composition B1 are obtained after spray drying
For 2.1, pore volume is 0.33mL/g.The diameter particle size of composition B1 is 71 μm, diameter grain
Footpath accounts for 93 volumes % less than 149 microns, and less than 20 microns 1.9 volumes % are accounted for, and is less than
40 microns account for 16 volumes %.
Embodiment 3
By the Ludox (pH value is 2.5) and solid content of weight % of dioxide-containing silica 10
(the weight ratio of kaolin and molecular sieve is the molecular sieve and kaolin slurry of 35 weight % in slurries
1：1), by 1:1 mass flow ratio is respectively delivered to the two of spraying apparatus A by high-pressure pump
Individual inlet tube, subsequently into spraying apparatus A mixed atomizings, the pressure of inlet chamber is 9MPa,
, as 400kg/ hours, composition each component is in spraying apparatus for the combination logistics capacity counted with butt
The time of staying is less than 1 second.Cracking catalyst A3 is obtained after spray drying, cracking catalysis are analyzed
The abrasion index of agent A3 is 1.3, and pore volume is 0.35mL/g, and the average grain diameter of product is (straight
Footpath) it is 69 μm, diameter particle size accounts for 94 volumes % less than 149 microns, less than 20 microns
Account for volume 2.2%, account for 18 volumes % less than 40 microns.
Embodiment 4
Spraying apparatus reference implementation example 2, except for the difference that rotating room is two, and flow deflector is 1.
Method according to embodiment 2 prepares composition, and the abrasion index of resulting composition is 2.5, hole
Volume is 0.34mL/g.69 microns of average grain diameter, diameter particle size accounts for 92 less than 149 microns
Volume %, less than 20 microns volume 2.4% is accounted for, and less than 40 microns 18 volumes % are accounted for.
Comparative example 1
By the magnesia slurry of weight % of solid content 30, (slurries that magnesia and water are formed, put down
Particle diameter is 3.5 microns, and the D90 of particle diameter (diameter) distribution is 15 microns) and solid content
Acidification pseudo-boehmite slurries (the slurry formed by boehmite, hydrochloric acid and water of 10 weight %
Liquid, HCl is 0.15 with the mol ratio of aluminum oxide (i.e. sour aluminum ratio)), by 1:3 mass ratio
Example mixing, stirring makes to be well mixed for 30 minutes, then will mix gained slurries by high-pressure pump
Slurries are transported to conventional atomizer (a diameter of 2.5mm of spray orifice), obtain after spray drying
Composition DC1, the abrasion index of analysis of catalyst DC1 is 5.8, and pore volume is 0.48mL/g.
The average grain diameter of product is 68 μm.
Comparative example 2
By the Ludox (with embodiment 3) and solid content 35% of weight % of dioxide-containing silica 10
Molecular sieve and kaolin slurry (with embodiment 3), by 1:1 mass flow ratio is dosed into
It is beaten 30 minutes in stirred tank, makes to be well mixed, mixed serum is prepared into, then by high pressure
Mixed serum is transported to conventional atomizer (a diameter of 2.5mm of spray orifice) by pump, and spraying is dry
Catalyst DC2 is obtained after dry, the abrasion index of analysis of catalyst DC2 is 3.5, and pore volume is
0.43mL/g.The average grain diameter of product is 69 μm.
The method of comparative example 2, every a hour grab sample once, takes 8 samples, surveys
Metering-orifice volume, maximum is 0.45mL/g, and mean value is 0.43mL/g, and minimum of a value is 0.35
ML/g, extreme difference 0.1mL/g.And the method for embodiment 3, every a hour grab sample one
It is secondary, 8 samples are obtained, pore volume is measured, maximum is 0.37mL/g, and mean value is
0.35mL/g, minimum of a value is 0.33mL/g, extreme difference 0.04mL/g.Visual contrast example 2 is sprayed
Metapore volume fluctuation is dried than larger, it is seen then that the inventive method can be with stable prod pore volume.
Claims (21)
1. a kind of preparation method of microsphere composition, including：Will bonding agent dispersing liquid and combination
The dispersion liquid of thing other components is mixed to form group in the spraying apparatus with mixed function
Compound slurries and spray, be dried；Wherein, the described spraying with mixed function
Equipment includes：Fluid intake chamber (1) and nozzle piece (4), in fluid intake chamber
(1) at least two rotating rooms (2) are provided with and nozzle piece (4) between, it is different
Flow deflector (3) is provided between rotating room, pod apertures are set on the flow deflector (3)
To connect coupled Liang Ge rotating rooms；Fluid intake chamber (1) is arranged at least
Two fluid inlet tubes (12), at least one fluid inlet tube is used to introduce binding agent point
Dispersion liquid, at least one fluid inlet tube is used to introduce the dispersion liquid of other components of composition.
2. the method for preparing microsphere composition according to claim 1, it is characterised in that
Described rotating room is 2-9, and described flow deflector is 1-8, rotating room
Count one more than the number than flow deflector.
3. the method for preparing microsphere composition according to claim 1, it is characterised in that
Described flow deflector is disk, the center line of the pod apertures and flow deflector upstream plane
Angle β be 20-70 °, the pod apertures number on each described flow deflector is 2-8,
Pod apertures are circumferentially uniformly distributed on water conservancy diversion plate plane.
4. the method for preparing microsphere composition according to claim 3, it is characterised in that
It is 45～135 ° that the radial direction of the pod apertures introduces angle α；Described radial direction introduces angle
Any point of the water conservancy diversion centerline hole on the extended line of updrift side is flat in flow deflector upstream
The line of the projection in face and water conservancy diversion centerline hole and the intersection point of flow deflector upstream plane, with
And intersection point and the center of circle of upstream plane of the water conservancy diversion centerline hole with flow deflector upstream plane
Angle between connecting line.
5. the method for preparing microsphere composition according to claim 3, it is characterised in that
The water conservancy diversion centerline hole is 30-60 ° with the angle β of flow deflector upstream plane.
6. the method for preparing microsphere composition according to claim 4, it is characterised in that,
It is 90～120 ° that the radial direction of the pod apertures introduces angle α.
7. the method for preparing microsphere composition according to claim 1, it is characterised in that
The flow deflector thickness 1-6mm；The a diameter of 1-4mm of pod apertures on the flow deflector.
8. the method for preparing microsphere composition according to claim 7, it is characterised in that
The flow deflector thickness is 2-4mm.
9. the method for preparing microsphere composition according to claim 7 or 8, its feature exists
In a diameter of 2-3mm of the pod apertures.
10. the method for preparing microsphere composition according to claim 1, it is characterised in that
The fluid intake chamber (1) is cylindric, fluid intake chamber one end bottom surface end
Lid closing, other end bottom surface is connected with top rotating room, described fluid intake
Pipe (12) is arranged on the side wall of fluid intake chamber (1).
11. methods for preparing microsphere composition according to claim 10, it is characterised in that
The number of described fluid inlet tube (12) is 2-4, along in inlet chamber
Wall even circumferential is distributed, and fluid inlet tube is tangentially connected with fluid intake room, makes to draw
The fluid for entering fluid inlet chamber circumferentially rotates into after fluid intake chamber.
12. methods for preparing microsphere composition according to claim 11, it is characterised in that
A diameter of 2-6mm of fluid inlet tube or 3-5mm.
13. methods for preparing microsphere composition according to claim 1, it is characterised in that
Described rotating room is cylinder, and the spin chamber diameter is 10-30mm, preferably
15-25mm；The length of the rotating room is 3-18mm, preferred 5-10mm.
14. methods for preparing microsphere composition according to claim 1, it is characterised in that
The nozzle piece includes spray orifice and nozzle piece inlet cone, the bottom of nozzle piece inlet cone
Face connects with end rotating room, and the top of inlet cone connects with spray orifice, injection diameter
For the preferred 2-3mm of 1-4mm；The spray orifice length of the nozzle piece is 1-5mm, excellent
Select 2-4mm；The cone angle of the nozzle piece inlet cone is 40-140 °, preferred 60-120 °.
15. methods for preparing microspheroidal composition according to claim 1, it is characterised in that
The dispersion liquid of described bonding agent dispersing liquid and composition other components has in described
The time of staying in the spraying apparatus of mixed function is less than 1 minute.
16. methods for preparing microspheroidal composition according to claim 1, it is characterised in that
The contents on dry basis of binding agent is 5～40 weight % in described bonding agent dispersing liquid, described
The contents on dry basis of composition other component dispersion liquids be 5～50 weight %.
17. methods for preparing microspheroidal composition according to claim 1, it is characterised in that
The D90 of particle diameter distribution is in other component dispersion liquids of described composition
3～20 microns, average grain diameter is 2～5 microns.
18. methods for preparing microsphere composition according to claim 1, it is characterised in that
Described bonding agent dispersing liquid is Ludox, Alumina gel, acidification pseudo-boehmite, phosphorus
Alumina gel；Other components of described composition are active component and optional vehicle group
Divide and/or adjuvant component.
19. methods for preparing microsphere composition according to claim 1, it is characterised in that
Described microsphere composition is catalytic cracking catalyst or assistant for calalytic cracking, with microballoon
On the basis of the butt weight of composition, described catalytic cracking catalyst is included with butt
Meter 5～40 weight % binding agent, the active component of in terms of butt 10～60 weight % and
The clay of in terms of butt 0～60 weight %；Described bonding agent dispersing liquid be Ludox,
One or more in phosphorus aluminium glue, acidic oxidation al binder, described active component
For one kind in molecular sieve, magnesium aluminate spinel, activated alumina, silica-alumina material or many
Kind.
20. methods for preparing microspheroidal composition according to claim 1, it is characterised in that
Described microspheroidal composition is adsorbent, and in terms of butt, described adsorbent includes
The binding agent of 10～80 weight % adsorption activity components and 20～90 weight %, described is viscous
Knot agent dispersing liquid be acidic oxidation al binder, Ludox, phosphorus aluminium glue in one kind or
Various, described adsorption activity component is in zinc oxide, magnesia, molecular sieve
Plant or various.
A kind of 21. preparation facilities of microsphere composition, including bonding agent dispersing liquid conveying device, group
Other component dispersion liquid conveying devices of compound, the spraying apparatus with mixed function and
Drier, the described spraying apparatus with mixed function：Including fluid intake chamber
(1), and nozzle piece (4), fluid intake chamber (1) and nozzle piece (4) it
Between be provided with least two rotating rooms (2), between different rotating rooms arrange have lead
The flow deflector (3) of discharge orifice, described fluid intake chamber (1) arranges at least two and flows
Body inlet tube (12), the agent dispersing liquid conveying device that bonds and the spraying with mixed function
The fluid inlet tube of equipment is connected with to the conveying bonding of the spraying apparatus with mixed function
Agent dispersing liquid, other component dispersion liquid conveying devices of composition with have mixed function
Spraying apparatus fluid inlet tube connect with defeated to the spraying apparatus with mixed function
Send other component dispersion liquids of composition.
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| CN114433012A (en) * | 2020-11-06 | 2022-05-06 | 中国石油化工股份有限公司 | Forming method of molecular sieve adsorbent, molecular sieve adsorbent prepared by forming method and application of molecular sieve adsorbent |
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