CN109926037A - One kind preparing TiO by titanium-based binder2The method of preformed catalyst carrier - Google Patents
One kind preparing TiO by titanium-based binder2The method of preformed catalyst carrier Download PDFInfo
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Abstract
The present invention provides one kind to prepare high purity Ti O by titanium-based binder2The method of preformed catalyst carrier includes the following steps: the mixture of (1) hydro-thermal process Ti base binder solution and titanium-based molding powder;(2) gelatinizing agent, which is added, makes it be changed into sticky milk, and pulpous state filter cake is filtered to obtain in washing;(3) cake moisture is adjusted by microwave heating, obtains clay shape dough;(4) clay shape dough through kneading, extrusion, roast to obtain TiO2Preformed catalyst carrier.This method increases the bonding action of titanium-based binder by hydro-thermal process, has promoted binder to be uniformly distributed by microwave dehydration, prepared TiO2Shaping carrier has a purity is high, large specific surface area, and intensity is high, and wearability is good, the features such as not losing powder, and can use in the harsh reaction system such as strong acid, highly basic, strong hydrothermal.TiO in shaping carrier2Content >=99wt%, crystal form are anatase or/and rutile-type, axial compression strength >=8MPa, specific surface area >=70m2/ g, average pore size 10-60nm.
Description
Technical field
The present invention relates to the preparation methods and technique of a kind of shaping of catalyst carrier, in particular to one kind by titanium-based
The method that binder prepares TiO2 preformed catalyst carrier.
Background technique
The chemicals provided by modern chemical industry process about 85% is generated by catalytic process, and catalyst is catalysis
The core of technology plays very important effect to the development of catalysis technique.Catalyst is generally by active constituent and carrier two
Part forms, and active component is highly dispersed in carrier.Carrier is the skeleton of catalyst activity component, and shape, compares table at intensity
Stability of the physicochemical properties such as area, pore structure in catalystic converter system determines the service life and economic value of catalyst.
With the development of modern catalysis technique and the continuous expansion of application range, in environmental protection, the fields such as new energy, Aeronautics and Astronautics occur
The new catalystic converter system of some extreme harshnesses, needs catalyst in strong acid, highly basic, high temperature, high pressure, strong hydrothermal reaction system
It uses, common catalyst carrier, such as activity Al2O3, SiO2, TS molecular sieve etc. has been unable to meet requirement.Meanwhile with
Catalytic field research is goed deep into, and the research and development difficulty of new active component is increasing, and it is desirable to pass through research and development energy and active component
The carrier of interaction is generated to improve existing catalyst performance, opens up new catalytic applications.To sum up, high performance carrier materials
Research and development have become the new research hotspot of catalytic field.
People are the study found that TiO2Carrier can keep long-term steady under the conditions of the strong hydrothermal of strong acid, highly basic and high temperature and pressure
It is fixed, and can change the activity and selectivity of catalyst by the way that " strong interaction " occurs with active metal component.For example,
In methanation reaction, TiO is used2Instead of traditional Al2O3Make catalyst carrier, can not only significantly improve catalytic activity, moreover it is possible to
Improve its cryogenic property.TiO is used in claus reaction2Do that catalyst carrier can be subjected to harsh hydro-thermal process and keep high
Activity.In recent years, TiO2It is increasingly valued by people as novel catalyst carrier.But industrial dioxy
Changing titanium products is mostly nanoscale or micron-sized powder, is directly used as catalyst carrier, deposits and be easy to run off in use, with product hardly possible
The problems such as separation, can not directly apply in Industrial Catalysis reaction system.Therefore, people are to titanium dioxide powder forming technique exhibition
Extensive research is opened.
The CN101342498A TiO that drying is concentrated in a mold2Slurries obtain one by control drying temperature and time
The green body of setting shape, is fired to obtain TiO2Preformed catalyst carrier.The intensity for the shaping carrier that this method obtains is low, wears away
Greatly, picking is serious.This is because TiO2And its forerunner's powder belongs to lean material, binding force is weaker between powder granule,
In no binder, TiO2Powder is difficult to form by compression molding method, extrusion moulding etc..Therefore, people are to TiO2
Powder molding binder expands a large amount of research.By the type for using binder, TiO2The molding of powder can be divided into organic glutinous
Mixture method and inorganic binder method.CN1045763A alkanolamine is made organic to be binder, by extruded moulding method dioxy
It is pelleted substrate that it is body formed, which to change titanium valve,.CN1689702A using sesbania powder, polyvinyl alcohol, carboxymethyl cellulose etc. as
Organic bond, nitric acid solution are peptizing agent, are prepared for molding TiO with extruded moulding method2Carrier.The principle of organic bond method
Be by the way that long-chain macromolecule organic matter is filled between molding powder granule and particle in the gap that is formed, improve particle it
Between bond strength, increase the plasticity of dough, at the same also have concurrently dilution, lubrication and reduce in rub effect, can prepare
The formed body of various shapes such as cylindrical type, Raschig ring type, trifolium-shaped out, and solve the deformation after formed body drying, cracking,
Pulverizing problem.But the major defect of organic bond method is: after formed body is fired, organic bond is removed, and is not only made
Cohesive force is lost between shaping carrier internal particle, a large amount of holes are also generated inside particle, causes to form TiO2Support strength
Low, porosity is big, the easily broken, dusting in transport, filling, use process.Compared with organic bond method, inorganic binder method
TiO can be increased substantially2The intensity of shaping carrier, CN101890376A are inorganic binder, nitric acid solution with boehmite
Peptizing agent is made, TiO is prepared2The intensity of shaping carrier, resulting vehicle is high, and wearability is good, does not lose powder, still, due to intending thin water
Aluminium stone cannot remove in roasting process, can be present in TiO as impurity2In carrier, influence to form TiO2The performance of carrier.
TiO is formed to improve2The purity of carrier solves the pollution problem in forming process, and people, which expand, to be fired
It is changed into TiO2Titanium-based binder research.Patent CN1830548A using potassium titanate and its derivative as inorganic binder,
To TiO2Whisker is formed.But this method expensive raw material price, long preparation period, preparation process is complicated, prepares costly, system
Standby low efficiency.CN1895781A is machine binder with cheap titanyl sulfate, metatitanic acid etc., in order to increase molding dough
Plasticity, and the middle use organic adhesion agents such as cellulose, paraffin, starch simultaneously.Although this method will not introduce impurity, due to
Ti base binder used can not be generated between forming powder granule compared with strong bonding effect and binder it is easy to reunite, carrier after molding
Grain intensity is low, easily loses powder, although improving maturing temperature can increase its intensity, maturing temperature will lead to specific surface area significantly
Decline.
Summary of the invention
For TiO in the prior art2The purity of shaping carrier is low, easily loses powder, and intensity and specific surface area cannot be compatible etc. asks
Topic, the present invention is intended to provide a kind of make shaping assistant using titanium-based binder, high-intensitive, bigger serface, the TiO not lost powder2
The preparation method of shaping carrier.
Technical solution provided by the invention is as follows:
The present invention prepares high purity Ti O by titanium-based binder including one kind2The method of preformed catalyst carrier, according to following
Step operation:
(1) first by hydro-thermal process after the mixture of hydro-thermal process Ti base binder solution and titanium-based molding powder;
(2) gelatinizing agent, which is added, makes it be changed into sticky milk, obtains pulpous state filter cake after washing filtering;
(3) cake moisture is adjusted by microwave heating, obtains clay shape dough;
(4) clay shape dough through kneading, extrusion, roast to obtain TiO2Preformed catalyst carrier.
The Ti base binder of the step (1) refers to one of positive fourth rouge of titanyl sulfate, titanium tetrachloride, metatitanic acid etc., preferably
Titanyl sulfate.
The titanyl sulfate be technical grade sulfuric acid oxygen titanium, be sulfate process titanium dioxide production technology between product.White powder,
Titanyl sulfate content is greater than 90%.
The TiO of the step (1)2Or its hydrate can be selected from the low-quality titanium dioxide of industry, pigment-level titanium dioxide and various
Nano-TiO also can be selected also selected from the intermediate products metatitanic acid of Titanium White Production By Sulfuric Acid Process in industrial titanium dioxide2, mesoporous oxygen
Change titanium whisker etc..
In the step (1), on the basis of the quality for forming powder, the dosage of the Ti base binder is 10-50wt%;
On the basis of the gross mass of solution, the concentration of Ti base binder aqueous solution is that (Ti base binder, forms the matter of powder to 5-15wt%
Amount presses TiO2Quality meter).
The hydro-thermal process of the step (1) carries out in the autoclave with polytetrafluoroethyllining lining, reaction temperature
It is 100-180 DEG C, preferably 120 DEG C, the processing time is 1-10 hours, and preferably 3-10 hours, most preferably 4 hours can be certainly after processing
So it is down to room temperature, it is also possible to water quick cooling, preferably water quenching.
The gelatinizing agent of the step (2) is NH3·H2O, urea, Na2CO3, one of NaHCO3 or a variety of.Gelatinizing agent
Concentration be 10-30wt%;Preferred concentration is 20%.Sticky milk pH range is 3-7 after gelatinization.
The cleaning solution of the step (2) is deionized water, and solid-liquid separation method is suction method or centrifugal separation.
The drying process process of the pulpous state filter cake of the step (3) is carried out under microwave action, and the frequency of microwave is
600-9000MHZ;Power is 100-1000W, adjustable, and a kind of power or multiple power is selected to be used alternatingly in drying process.It is micro-
Wave dry total time is 20-200min, and the microwave time per treatment is no more than 10min, and break time is no more than 10min.
In microwave drying process, within break time, according to the solid content of pulpous state filter cake, stirring may be selected, rubbed with hand
Pinch, roller mediate etc. modes uniform dough, when dough solid content rises to 60-75wt%, stop drying.
After the extruded moulding of step (4), TiO2The shape of preformed catalyst carrier can be cylindrical type, Raschig ring
Ball can be obtained after shaping in type, Round Porous column type, trifolium-shaped, bunge bedstraw herb type or honeycomb ceramic type etc., the carrier after extrusion
The carrier granulars such as type, spherical shape.
The extrusion drying side mode of step (4) is naturally dry to constant weight, and drying time is greater than 48 hours;Also it can choose
Microwave drying, dry power are less than 100W.
The baking modes of step (4) can directly temperature-raising method and process control temperature-raising method, preferable procedure temperature-raising method, heating rate
For 2 DEG C/min, maturing temperature is 500-1000 DEG C, preferably 700-900 DEG C.
TiO in prepared molding2Content >=99wt%, crystal form are anatase or/and rutile-type, average pore size 10-
60nm。
Commercial pigments grade TiO in the present invention2, commercially available nano-TiO2For titanium dioxide pigment [standard No.] GB/T 1706-
2006, production, which produces house, to be had: Jiangsu Hehai Nanometer Technology Co., Ltd., Xuancheng Jingrui New Material Co., Ltd., Dupont
Company etc., this only refers to ratio, but is not limited to these.
Advantages of the present invention: the present invention solves TiO2The specific surface area and intensity of shaping carrier are unable to compatibling problem, press
According to the TiO of the method for the present invention preparation2Axial compression strength >=8MPa of shaping carrier, specific surface area >=70m2/g.The present invention can lead to
It crosses and changes the material powder type of carrier, forms the macro geometry of formula, maturing temperature, carrier etc. to adjust the strong of carrier granular
Degree and specific surface area.
It is poor that the present invention solves Ti base binder viscosity, can not be formed and meet the plasticity walk that moulding process requires, must
TiO must could be prepared by organic bond2Preformed catalyst carrier problem.The present invention passes through hydro-thermal process, Ti base binder
It can be with molding powder TiO2Or the hydroxyl on its hydrate particle surface chemically reacts, and hydroxide is generated between powder granule
Or peroxide, make to bond together by chemical bond between particle, so as to increase substantially the intensity of shaping carrier.This
Different from the non-titanium-based inorganic binder such as boehmite, silica solution, have also different from sesbania powder, polyvinyl alcohol, cellulose etc.
Machine binder, these adhesives cannot promote formationization between substrate material particle by chemically reacting with basis material
Learn bonding.
The present invention solves molding binder pollution problem.The Ti base binder that the present invention uses can be converted into after being fired
Titanium oxide, avoiding to introduce in forming process influences TiO2The non-Ti impurity of performance, can prepare high purity Ti O2Shaping carrier.
Present invention improves TiO2Shaping carrier dusting problems.The present invention is removed more in slurry by method for microwave drying
Remaining moisture, microwave heating is with conventional hot mode the difference is that heating is carried out simultaneously slurry is inside and outside, in week
Under the action of the fast-changing electromagnetic field of phase property, the polarity orientation of the hydrone inside slurry becomes with the variation of external electric field
Change, so as to cause strenuous exercise, the hydrone of strenuous exercise is evenly distributed in binder in basis material, it is therefore prevented that bonding
Agent self-assemble in the drying process and segregation effectively prevent basis material and binder and remove in drying process, from
And shaping carrier particle dusting problems are avoided, increase the intensity of carrier.According to heating, drying mode remove it is more in slurry
Remaining moisture, as heat conduction ecto-entad gradually conducts, the evaporation of water is also pressed in slurry gradually carries out from outside to inside, makes to stick
Mixture generates concentration difference inside slurry, is distributed in the outer layer binder inner layer diffusion of high concentration region, binder is caused to starch
Material is internal to be unevenly distributed, and support strength declines after molding, and matrix powder is easy to fall off.
In conclusion the present invention solves the pollution problem of shaping assistant using Ti base binder, made by hydro-thermal mode
Ti base binder generates chemical adhesive effect between molding powder granule and particle, substantially increases TiO2Shaping carrier it is strong
Degree, solves TiO2The specific surface area and intensity of shaping carrier are unable to compatibling problem, have promoted binder to exist by microwave heating
Being uniformly distributed inside shaping carrier improves the surface area of shaping carrier, improves dusting problems.The present invention provides one kind
High-purity, bigger serface, it is high-intensitive, without the TiO obviously to lose powder2Shaping carrier preparation method.
Specific embodiment
Below with reference to embodiment, the present invention is further described, but these embodiments can not limit the present invention.
TiO of the invention2Content is measured by XRF, Kong Rong, and specific surface area uses N2Physisorphtion measures, and crushing strength is adopted
It is measured with intensity meter.
Embodiment 1
60g titanyl sulfate is added in 600ml water, clear transparent solutions are made it dissolve to obtain at 80 DEG C.Add into solution
Enter 340g metatitanic acid, is vigorously stirred and mixture is transferred in the hydrothermal reaction kettle with tetrafluoroethene liner after forty minutes, 120
DEG C, it is reacted 4 hours under self-generated pressure.Water quenching is cooled to room temperature and uses NH3·H2O tune ph value of mixture is to 7 or so, plastic.
Colloid is separated by solid-liquid separation with suction method, obtains gluey filter cake, washs gluey filter cake nothing into cleaning solution repeatedly with deionized water
Sulfate ion detection.Gluey filter cake after washing is placed on thermal dehydration in micro-wave oven, adjusting microwave rate power is 800W,
Heat altogether 40 minutes, points of 8 times progress, 5 minutes every time, it is adjacent twice between be spaced 3 minutes, obtain solid holdup as 72% clay shape
Dough.Clay shape dough is mediated 30 minutes in kneader, with double screw banded extruder extrusion, extrusion is made after drying to constant weight
Grain.Extrusion after granulation in Muffle furnace by temperature-programmed calcination, 600 DEG C of maturing temperature, constant temperature 4 hours, heating rate 2
DEG C/min, obtain TiO of the invention2Finished particle HT-1.
Embodiment 2
70g titanium tetrachloride is added in 400ml water at room temperature, 360g nano-TiO is then added2, will after being vigorously stirred
Mixture is transferred in the hydrothermal reaction kettle with tetrafluoroethene liner, at 150 DEG C, is reacted 4 hours under self-generated pressure.With water urgency
It is cold, it is cooled to room temperature and uses NH3·H2O tune ph value of mixture is to 5 or so, plastic.Colloid is separated by solid-liquid separation with suction method, is obtained
Gluey filter cake washs gluey filter cake chloride ion into cleaning solution repeatedly with deionized water and detects.Gluey filter cake after washing is put
The thermal dehydration in micro-wave oven is set, adjusting microwave rate power is 800W, is heated 40 minutes altogether, point 8 progress, 5 minutes every time, phase
Neighbour is spaced 3 minutes between twice, obtains the clay shape dough that solid holdup is 70%.Clay shape dough is mediated 30 points in kneader
Clock, with double screw banded extruder extrusion, extrusion is granulated after drying to constant weight.Extrusion after granulation passes through temperature programming in Muffle furnace
Roasting, 600 DEG C of maturing temperature, constant temperature 4 hours, 2 DEG C/min of heating rate obtained TiO of the invention2Finished particle HT-2.
Embodiment 3
30g titanyl sulfate is added in 300ml water, clear transparent solutions are made it dissolve to obtain at 80 DEG C.Add into solution
Enter 370g nano-TiO2Whisker is vigorously stirred and mixture is transferred to the hydrothermal reaction kettle with tetrafluoroethene liner after forty minutes
It is interior, at 180 DEG C, reacted 4 hours under self-generated pressure.Water quenching is cooled to room temperature and uses NH3·H2O tune ph value of mixture to 3 a left side
The right side, plastic.Colloid is separated by solid-liquid separation with suction method, obtains gluey filter cake, washs gluey filter cake repeatedly with deionized water to washing
Sulfate radical-free ion in liquid is washed to detect.Gluey filter cake after washing is placed on thermal dehydration in micro-wave oven, adjusts microwave rate function
Rate is 800W, is heated altogether 40 minutes, points of 8 times progress, 5 minutes every time, it is adjacent twice between be spaced 3 minutes, obtaining solid holdup is
73% clay shape dough.Clay shape dough is mediated 30 minutes in kneader, with double screw banded extruder extrusion, extrusion is dried
It is granulated after to constant weight.Extrusion after granulation in Muffle furnace by temperature-programmed calcination, 600 DEG C of maturing temperature, constant temperature 4 hours,
2 DEG C/min of heating rate, obtains TiO of the invention2Finished particle HT-3.
Embodiment 4
20g titanyl sulfate is added in 200ml water, clear transparent solutions are made it dissolve to obtain at 80 DEG C.Add into solution
Enter 380g TiO2Nanotube is vigorously stirred and mixture is transferred in the hydrothermal reaction kettle with tetrafluoroethene liner after forty minutes,
At 120 DEG C, reacted 4 hours under self-generated pressure.Water quenching is cooled to room temperature and uses NH3·H2O tune ph value of mixture to 7 or so,
Plastic.Colloid is separated by solid-liquid separation with suction method, obtains gluey filter cake, washs gluey filter cake repeatedly with deionized water to cleaning solution
Middle sulfate radical-free ion detection.Gluey filter cake after washing is placed on thermal dehydration in micro-wave oven, adjusting microwave rate power is
800W is heated 40 minutes, points of 8 times progress, 5 minutes every time altogether, it is adjacent twice between be spaced 3 minutes, obtain solid holdup as 75%
Clay shape dough.Clay shape dough is mediated 30 minutes in kneader, with double screw banded extruder extrusion, extrusion is dried to constant weight
After be granulated.Extrusion after granulation is by temperature-programmed calcination in Muffle furnace, and 600 DEG C of maturing temperature, constant temperature 4 hours, heating was fast
2 DEG C/min of rate, obtains TiO of the invention2Finished particle HT-4.
Embodiment 5
60g titanyl sulfate is added in 600ml water, clear transparent solutions are made it dissolve to obtain at 80 DEG C.Add into solution
Enter 340g metatitanic acid, is vigorously stirred and mixture is transferred in the hydrothermal reaction kettle with tetrafluoroethene liner after forty minutes, 120
DEG C, it is reacted 4 hours under self-generated pressure.Water quenching is cooled to room temperature and uses NH3·H2O tune ph value of mixture is to 7 or so, plastic.
Colloid is separated by solid-liquid separation with suction method, obtains gluey filter cake, washs gluey filter cake nothing into cleaning solution repeatedly with deionized water
Sulfate ion detection.Gluey filter cake after washing is placed on thermal dehydration in micro-wave oven, adjusting microwave rate power is 500W,
Heat altogether 60 minutes, points of 10 times progress, 6 minutes every time, it is adjacent twice between be spaced 3 minutes, obtain solid holdup as 71% clay
Shape dough.Clay shape dough is mediated 30 minutes in kneader, with double screw banded extruder extrusion, extrusion is made after drying to constant weight
Grain.Extrusion after granulation in Muffle furnace by temperature-programmed calcination, 600 DEG C of maturing temperature, constant temperature 4 hours, heating rate 2
DEG C/min, obtain TiO of the invention2Finished particle HT-5.
Embodiment 6
60g titanyl sulfate is added in 600ml water, clear transparent solutions are made it dissolve to obtain at 80 DEG C.Add into solution
Enter 340g metatitanic acid, is vigorously stirred and mixture is transferred in the hydrothermal reaction kettle with tetrafluoroethene liner after forty minutes, 120
DEG C, it is reacted 4 hours under self-generated pressure.Water quenching is cooled to room temperature and uses NH3·H2O tune ph value of mixture is to 7 or so, plastic.
Colloid is separated by solid-liquid separation with suction method, obtains gluey filter cake, washs gluey filter cake nothing into cleaning solution repeatedly with deionized water
Sulfate ion detection.Gluey filter cake after washing is placed on thermal dehydration in micro-wave oven, adjusting microwave rate power is 200W,
Heat altogether 120 minutes, points of 10 times progress, 12 minutes every time, it is adjacent twice between be spaced 3 minutes, obtain clay shape dough.Clay
Shape dough is mediated 30 minutes in kneader, and with double screw banded extruder extrusion, extrusion is granulated after drying to constant weight.Squeezing after granulation
Item is by temperature-programmed calcination in Muffle furnace, and 600 DEG C of maturing temperature, constant temperature 4 hours, 2 DEG C/min of heating rate obtained this hair
Bright TiO2Finished particle HT-6.
Comparative example 1
60g titanyl sulfate is added in 600ml water, clear transparent solutions are made it dissolve to obtain at 80 DEG C.Add into solution
Enter 340g metatitanic acid, is vigorously stirred 40 minutes.NH is used after cooling down to room temperature3·H2O tune ph value of mixture is to 7 or so, plastic.
Colloid is separated by solid-liquid separation with suction method, obtains gluey filter cake, washs gluey filter cake nothing into cleaning solution repeatedly with deionized water
Sulfate ion detection.Gluey filter cake after washing is placed thermal dehydration 20 minutes in an oven, obtains clay shape dough.Glue
Pureed dough is mediated 30 minutes in kneader, and with double screw banded extruder extrusion, extrusion is granulated after drying to constant weight.After granulation
Extrusion, by temperature-programmed calcination, 600 DEG C of maturing temperature, constant temperature 4 hours, 2 DEG C/min of heating rate, obtains this in Muffle furnace
The TiO of invention2Finished particle BT-1.
Comparative example 1
60g titanyl sulfate is added in 600ml water, clear transparent solutions are made it dissolve to obtain at 80 DEG C.Add into solution
Enter 340g metatitanic acid, is vigorously stirred 40 minutes.NH is used after cooling down to room temperature3·H2O tune ph value of mixture is to 7 or so, plastic.
Colloid is separated by solid-liquid separation with suction method, obtains gluey filter cake, washs gluey filter cake nothing into cleaning solution repeatedly with deionized water
Sulfate ion detection.Gluey filter cake after washing is placed thermal dehydration 20 minutes in an oven, obtains clay shape dough.Glue
Pureed dough is mediated 30 minutes in kneader, and with double screw banded extruder extrusion, extrusion is granulated after drying to constant weight.After granulation
Extrusion, by temperature-programmed calcination, 600 DEG C of maturing temperature, constant temperature 4 hours, 2 DEG C/min of heating rate, obtains this in Muffle furnace
The TiO of invention2Finished particle BT-1.
Comparative example 2
20g boehmite is uniformly mixed with 80g metatitanic acid, 9% dust technology 23g is added, in kneader after stirring
It is middle to mediate 15 minutes, obtain clay shape dough.With double screw banded extruder extrusion, extrusion is granulated after drying to constant weight.Squeezing after granulation
Item is by temperature-programmed calcination in Muffle furnace, and 600 DEG C of maturing temperature, constant temperature 4 hours, 2 DEG C/min of heating rate obtained this hair
Bright TiO2Finished particle BT-2.
Comparative example 3
By 85g metatitanic acid, 10g methylcellulose, 5g starch is uniformly mixed, and 9% dust technology 23g is added, after stirring
It is mediated 15 minutes in kneader, obtains clay shape dough.With double screw banded extruder extrusion, extrusion is granulated after drying to constant weight.It is granulated
Extrusion afterwards is by temperature-programmed calcination in Muffle furnace, and 600 DEG C of maturing temperature, constant temperature 4 hours, 2 DEG C/min of heating rate was obtained
To TiO of the invention2Finished particle BT-3.
The performance of sample obtained by 1 embodiment of table and comparative example
This method increases the bonding action of titanium-based binder by hydro-thermal process, has promoted binder by microwave dehydration
It is uniformly distributed, prepared TiO2Shaping carrier has purity is high, and large specific surface area, intensity is high, the spies such as wearability is good, does not lose powder
Point can use in the harsh reaction system such as strong acid, highly basic, strong hydrothermal.TiO in shaping carrier2Content >=99wt%, crystal form are
Anatase or/and rutile-type, axial compression strength >=8MPa, specific surface area >=70m2/ g, average pore size 10-60nm.
Claims (10)
1. a kind of prepare TiO by titanium-based binder2The method of preformed catalyst carrier, characterized by the following steps:
(1) first by hydro-thermal process after the mixture of Ti base binder solution and titanium-based molding powder;
(2) gelatinizing agent, which is added, makes it be changed into sticky milk, obtains pulpous state filter cake after washing filtering;
(3) cake moisture is adjusted by microwave heating, obtains clay shape dough;
(4) clay shape dough through kneading, extrusion, roast to obtain TiO2Preformed catalyst carrier.
2. preparation method as described in claim 1, it is characterised in that: the Ti base binder refer to titanyl sulfate, titanium tetrachloride,
One of positive fourth rouge of metatitanic acid etc. is a variety of, preferably sulfuric acid oxygen titanium.
3. preparation method as described in claim 1, it is characterised in that: the base molded powder of Ti refers to TiO2Or/and its hydrate,
TiO2For commercial pigments grade TiO2, commercially available nano-TiO2, mesoporous TiO2Whisker, TiO2One of nanotube is a variety of, and crystal form can
For Detitanium-ore-type or rutile-type;TiO2Hydrate refers to the intermediate products metatitanic acid of Titanium White Production By Sulfuric Acid Process.
4. the preparation method as described in claim 1-3, it is characterised in that: described on the basis of the quality of titanium-based molding powder
The dosage of Ti base binder is 10-50wt%;On the basis of the gross mass of the solution of titanium-based molding powder, Ti base binder is water-soluble
The concentration of liquid is that (Ti base binder forms the quality of powder by TiO to 5-15wt%2Quality meter).
5. preparation method as described in claim 1, it is characterised in that: hydro-thermal process is to react in hydrothermal reaction kettle, temperature
It is 100-180 DEG C, preferably 120 DEG C, the processing time is 1-10 hours, most preferably 4 hours.
6. preparation method as claimed in claim 5, it is characterised in that: hydrothermal reaction kettle has polytetrafluoroethyllining lining.
7. preparation method as described in claim 1, it is characterised in that: selected gelatinizing agent is NH3·H2O, urea, Na2CO3、、
One of NaHCO3 or two kinds or more, the concentration of gelatinizing agent are 10-30wt%;Preferred concentration is 20%;Sticky cream after gelatinization
Shape object pH range is 3-7.
8. preparation method as described in claim 1, it is characterised in that: the frequency of used microwave is 600-9000MHZ, power
It for 100-1000W, is continuously adjusted, selects a kind of power or multiple power to be used alternatingly in drying process, when microwave is per treatment
Between be no more than 10min, break time be no more than 10min, microwave drying to dough solid holdup be 50-75wt% until.
9. as described in claim 1, it is characterised in that: TiO2The shape of preformed catalyst carrier can be cylindrical type, Raschig ring
Ball can be obtained after shaping in type, Round Porous column type, trifolium-shaped, bunge bedstraw herb type or honeycomb ceramic type etc., the carrier after extrusion
The carrier granulars such as type, spherical shape.
10. as described in claim 1, it is characterised in that: maturing temperature be 500-1000 DEG C, preferably 700-900 DEG C, baking modes
It can be direct temperature-raising method and programmed temperature method, preferable procedure temperature-raising method, heating rate is 2 DEG C/min.
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CN111337753A (en) * | 2020-03-16 | 2020-06-26 | 昆明理工大学 | Method for adjusting dielectric constant of high-calcium magnesium titanium concentrate under microwave heating condition |
CN112691692A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1095309A (en) * | 1994-02-21 | 1994-11-23 | 中国石化齐鲁石油化工公司 | Novel hydrolytic catalyst of carbonyl sulfur |
CN1895781A (en) * | 2005-07-12 | 2007-01-17 | 沈阳化工研究院 | Preparation of multi-component titanium-based catalyst carrier |
CN101342498A (en) * | 2008-08-15 | 2009-01-14 | 天津大学 | Titanium dioxide nano-tube support with macroscopical shape and preparation method thereof |
CN101513620A (en) * | 2009-04-07 | 2009-08-26 | 南京大学 | Preparation method for titanium dioxide group catalyst carrier |
CN102476827A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing TiO2 powder with large pore volume |
KR20170005275A (en) * | 2015-07-02 | 2017-01-12 | 서울시립대학교 산학협력단 | Method for preparing titanium dioxide photocatalyst dopped silver and photocatalyst prepared thereby |
-
2017
- 2017-12-15 CN CN201711350715.XA patent/CN109926037B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1095309A (en) * | 1994-02-21 | 1994-11-23 | 中国石化齐鲁石油化工公司 | Novel hydrolytic catalyst of carbonyl sulfur |
CN1895781A (en) * | 2005-07-12 | 2007-01-17 | 沈阳化工研究院 | Preparation of multi-component titanium-based catalyst carrier |
CN101342498A (en) * | 2008-08-15 | 2009-01-14 | 天津大学 | Titanium dioxide nano-tube support with macroscopical shape and preparation method thereof |
CN101513620A (en) * | 2009-04-07 | 2009-08-26 | 南京大学 | Preparation method for titanium dioxide group catalyst carrier |
CN102476827A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing TiO2 powder with large pore volume |
KR20170005275A (en) * | 2015-07-02 | 2017-01-12 | 서울시립대학교 산학협력단 | Method for preparing titanium dioxide photocatalyst dopped silver and photocatalyst prepared thereby |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112691692A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
CN111337753A (en) * | 2020-03-16 | 2020-06-26 | 昆明理工大学 | Method for adjusting dielectric constant of high-calcium magnesium titanium concentrate under microwave heating condition |
CN111337753B (en) * | 2020-03-16 | 2021-07-30 | 昆明理工大学 | Method for adjusting dielectric constant of high-calcium magnesium titanium concentrate under microwave heating condition |
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