CN109926037B - Preparation of TiO from titanium-based adhesive2Method for shaping catalyst carrier - Google Patents
Preparation of TiO from titanium-based adhesive2Method for shaping catalyst carrier Download PDFInfo
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Abstract
The invention provides a method for preparing high-purity TiO by using a titanium-based adhesive2A method of forming a catalyst support comprising the steps of: (1) carrying out hydro-thermal treatment on a mixture of the Ti-based adhesive solution and the titanium-based molding powder; (2) adding gelatinizing agent to convert into viscous emulsion, washing, and filtering to obtain slurry-like filter cake; (3) adjusting the water content of the filter cake by microwave heating to obtain a daub-shaped material mass; (4) kneading, extruding and roasting the daub-shaped material groups to obtain TiO2And (4) forming the catalyst carrier. The method increases bonding effect of titanium-based adhesive by hydrothermal treatment, promotes uniform distribution of the adhesive by microwave dehydration, and prepares the TiO2The formed carrier has the characteristics of high purity, large specific surface area, high strength, good wear resistance, no powder falling and the like, and can be used in harsh reaction systems of strong acid, strong alkali, strong hydrothermal reaction and the like. TiO in shaped supports2The content is more than or equal to 99 wt%, the crystal form is anatase or/and rutile, the axial compression strength is more than or equal to 8MPa, and the specific surface area is more than or equal to 70m2(ii)/g, average pore diameter is 10-60 nm.
Description
Technical Field
The invention relates to a preparation method and a process of a catalyst molded carrier, in particular to a method for preparing a TiO2 molded catalyst carrier by using a titanium-based adhesive.
Background
About 85 percent of chemicals provided by modern chemical engineering processes are generated by means of catalytic processes, and a catalyst is the core of catalytic technology and plays a significant role in the development of catalytic technology. The catalyst generally consists of two parts, namely an active component and a carrier, wherein the active component is highly dispersed in the carrier. The carrier is the framework of the active component of the catalyst, and the stability of the physical and chemical properties of the carrier, such as shape, strength, specific surface area, pore structure and the like, in a catalytic reaction system determines the service life and economic value of the catalyst. With the development of modern catalytic technology and the continuous expansion of the application rangeThe method is characterized in that a plurality of extremely harsh new catalytic reaction systems appear in the fields of environmental protection, new energy, aviation, aerospace and the like, and a catalyst is required to be used in a strong acid, strong alkali, high temperature, high pressure and strong hydrothermal reaction system and a common catalyst carrier, such as active Al2O3，SiO2TS molecular sieves and the like, cannot meet the use requirements. Meanwhile, with the research in the field of catalysis, the research and development of new active components become more and more difficult, and people hope to improve the performance of the existing catalyst and develop a new catalytic application field by researching and developing a carrier capable of generating interaction with the active components. In conclusion, the development of high performance carriers has become a new research hotspot in the field of catalysis.
It has been found that TiO2The carrier can keep long-term stability under strong acid, strong base and high-temperature and high-pressure strong hydrothermal conditions, and can change the activity and selectivity of the catalyst through strong interaction with active metal components. For example, in methanation reactions, TiO is used2Replacing the traditional Al2O3As a catalyst carrier, the catalyst not only can obviously improve the catalytic activity, but also can improve the low-temperature performance. Use of TiO in Claus reactions2The catalyst carrier can be subjected to harsh hydrothermal treatment and keeps high activity. In recent years, TiO2The catalyst is increasingly regarded as a novel catalyst carrier. However, most of the titanium dioxide products produced in industry are nano-scale or micron-scale powder, and are directly used as catalyst carriers, so that the titanium dioxide products are easy to run off in use, difficult to separate from the products and the like, and cannot be directly applied to an industrial catalytic reaction system. Therefore, extensive research has been conducted on the technique of forming titanium dioxide powder.
Drying of concentrated TiO in a mold with CN101342498A2The slurry is dried at a controlled temperature and time to obtain a green body with a certain shape, and the green body is roasted to obtain TiO2And (4) forming the catalyst carrier. The molded carrier obtained by the method has low strength, large abrasion and serious powder falling. This is because TiO2The precursor powder belongs to barren materials, the bonding force between powder particles is weak, and TiO is not used as a binder2The powder is difficult to be extruded by a die pressing forming methodMolding by extrusion molding or the like. Thus, one is dealing with TiO2Powder forming binders have been under considerable investigation. Depending on the type of binder used, TiO2The molding of the powder can be classified into an organic binder method and an inorganic binder method. CN 1045763A uses alkanolamine as organic binder, and titanium dioxide powder is formed into granular catalyst carrier by extrusion molding method. CN1689702A A formed TiO prepared by extrusion molding method using sesbania powder, polyvinyl alcohol, carboxymethyl cellulose and the like as organic binders and nitric acid solution as peptizer2And (3) a carrier. The principle of the organic adhesive method is that long-chain macromolecular organic matters are filled in gaps formed between formed powder particles, so that the bonding strength between the particles is improved, the plasticity of a material mass is increased, and the effects of dilution, lubrication and reduction of internal friction are achieved, so that formed bodies in various shapes such as a cylindrical shape, a Raschig ring shape, a clover shape and the like can be prepared, and the problems of deformation, cracking and pulverization of the formed bodies after drying are solved. However, the main drawbacks of the organic binder method are: after the formed body is roasted, the organic binder is removed, so that not only the adhesive force between the particles in the formed carrier is lost, but also a large number of pores are generated in the particles, and the formed TiO is caused2The carrier has low strength and large porosity, and is easy to break and pulverize during transportation, filling and use. Compared with organic adhesive method, inorganic adhesive method can greatly improve TiO2The strength of the formed carrier is CN101890376A, the pseudo-boehmite is used as an inorganic adhesive, the nitric acid solution is used as a peptizing agent, and the TiO is prepared2The carrier is formed, the obtained carrier has high strength and good wear resistance, and does not fall off powder, but the pseudoboehmite can exist in TiO as impurities because the pseudoboehmite can not be removed in the roasting process2In the support, the shaping of the TiO is effected2The properties of the support.
For improving the shaping of TiO2The purity of the carrier solves the pollution problem in the forming process, and people develop the method for converting the carrier into TiO by roasting2The research of the titanium-based adhesive. Patent CN1830548A uses potassium titanate and its derivatives as inorganic binder for TiO2And forming the whiskers. However, the method has the disadvantages of high raw material price, long preparation period, complex preparation process and high preparation efficiencyHigh preparation cost and low preparation efficiency. CN1895781A uses cheap titanyl sulfate, metatitanic acid, etc. as organic adhesive, and uses cellulose, paraffin, starch, etc. as organic adhesive to increase plasticity of molding material. Although impurities are not introduced in the method, the Ti-based binder cannot generate a strong bonding effect among the formed powder particles, the binder is easy to agglomerate, the strength of the formed carrier particles is low, powder falling is easy, and although the strength can be increased by increasing the roasting temperature, the roasting temperature can cause great reduction of the specific surface area.
Disclosure of Invention
Aiming at TiO in the prior art2The invention aims to provide a TiO forming auxiliary agent which uses a titanium-based adhesive to form a forming auxiliary agent, has high strength and large specific surface area, and does not fall powder2A method for preparing a shaped carrier.
The technical scheme provided by the invention is as follows:
the invention comprises a method for preparing high-purity TiO by using a titanium-based adhesive2A method of forming a catalyst support, comprising the steps of:
(1) firstly, carrying out hydro-thermal treatment on a mixture of Ti-based adhesive solution and titanium-based molding powder;
(2) adding gelatinizing agent to convert into viscous emulsion, washing, and filtering to obtain slurry-like filter cake;
(3) adjusting the water content of the filter cake by microwave heating to obtain a daub-shaped material mass;
(4) kneading, extruding and roasting the daub-shaped material groups to obtain TiO2And (4) forming the catalyst carrier.
The Ti-based binder in the step (1) is one of titanyl sulfate, titanium tetrachloride, n-butyl titanate and the like, and preferably titanyl sulfate.
The titanyl sulfate is industrial grade titanyl sulfate and is an intermediate product in the production process of titanium white by a sulfuric acid method. White powder with titanyl sulfate content greater than 90%.
TiO of the step (1)2Or its hydrate can be selected from industrial low-quality titanium dioxide, pigment-grade titanium dioxide and various titanium dioxideIndustrial titanium dioxide, metatitanic acid as intermediate product for sulfuric acid process production of titanium dioxide, and nanometer TiO2Mesoporous titanium oxide whiskers, and the like.
In the step (1), the Ti-based binder is used in an amount of 10-50 wt% based on the mass of the molded powder; the concentration of the aqueous solution of the Ti-based binder is 5-15wt% (based on the total mass of the solution) (the mass of the Ti-based binder and the molding powder is TiO)2Mass meter).
The hydrothermal treatment in the step (1) is carried out in a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction temperature is 100-180 ℃, the preferred temperature is 120 ℃, the treatment time is 1-10 hours, the preferred time is 3-10 hours, the most preferred time is 4 hours, the temperature can be naturally reduced to the room temperature after the treatment, and the treatment can also be carried out by water quenching, the preferred water quenching is carried out.
The gelatinizing agent in the step (2) is NH3·H2O, urea and Na2CO3And NaHCO 3. The concentration of the gelatinizing agent is 10-30 wt%; the preferred concentration is 20%. The pH value of the viscous emulsion after gelling is 3-7.
The washing liquid in the step (2) is deionized water, and the solid-liquid separation method is a suction filtration method or a centrifugal separation method.
The drying treatment process of the slurry-like filter cake in the step (3) is carried out under the action of microwaves, and the frequency of the microwaves is 600-9000 MHZ; the power is 100-. The total time of microwave drying is 20-200min, each microwave treatment time is no more than 10min, and the interruption time is no more than 10 min.
In the microwave drying process, in the discontinuous time, according to the solid content of the slurry-like filter cake, stirring, kneading by hands, kneading by a rolling machine and the like can be selected to homogenize the material mass, and when the solid content of the material mass is increased to 60-75 wt%, the drying is stopped.
After the extrusion molding in the step (4), TiO2The shape of the formed catalyst carrier can be cylindrical, Raschig ring, porous cylindrical, clover or honeycomb ceramic, etc., and the carrier after extrusion can be shaped to obtain pellet, spherical, etc. carrier particlesAnd (4) granulating.
The extruding and drying method in the step (4) is to naturally dry the extruded strip to constant weight, and the drying time is more than 48 hours; optionally, microwave drying with drying power less than 100W is also possible.
The roasting mode in the step (4) can be a direct heating method and a program control heating method, preferably a program heating method, wherein the heating speed is 2 ℃/min, the roasting temperature is 500-.
TiO in the produced shaped article2The content is more than or equal to 99 wt%, the crystal form is anatase or/and rutile, and the average pore diameter is 10-60 nm.
Industrial pigment grade TiO of the invention2Commercially available nano TiO2Is titanium dioxide pigment (Standard No.) GB/T1706-2006, and the production manufacturers have: the references are merely examples, but not limited to, the nano technologies of river and sea, Jiangsu, river and sea, Inc., Xuancheng Jingrui New Material, Inc., DuPont, USA, etc.
The invention has the advantages that: the invention solves the problem of TiO2Problems of incompatibility of the specific surface area and the strength of the shaped support, TiO prepared according to the process of the invention2The axial compression strength of the formed carrier is more than or equal to 8MPa, and the specific surface area is more than or equal to 70m2(ii) in terms of/g. The invention can adjust the strength and specific surface area of the carrier particles by changing the type of the raw material powder of the carrier, the forming formula, the roasting temperature, the macroscopic appearance of the carrier and the like.
The invention solves the problems that Ti-based adhesive has poor viscosity, can not form plastic mud clusters meeting the requirements of a forming process, and can prepare TiO only by virtue of organic adhesive2The problem of forming a catalyst carrier. The Ti-based adhesive can be mixed with the formed powder TiO by hydrothermal treatment2Or the hydroxyl on the surface of the hydrate particles generates chemical reaction, so that hydroxide or peroxide is generated among the powder particles, and the particles can be bonded together through chemical bonds, thereby greatly improving the strength of the formed carrier. The adhesive is different from non-titanium-based inorganic adhesives such as pseudo-boehmite, silica sol and the like and organic adhesives such as sesbania powder, polyvinyl alcohol, cellulose and the like, and the adhesives can not promote the shape among particles of matrix materials through chemical reaction with the matrix materialsForming chemical bonding.
The invention solves the problem of pollution of the forming adhesive. The Ti-based binder used in the invention can be converted into titanium oxide after being roasted, thereby avoiding the introduction of TiO influence in the forming process2non-Ti impurity with performance and capability of preparing high-purity TiO2And (4) forming the carrier.
The invention improves TiO2The problem of powder falling of the formed carrier. The microwave drying method is used for removing redundant water in the slurry, and the microwave heating mode is different from the conventional heating mode in that the heating is carried out simultaneously inside and outside the slurry, under the action of a periodically and rapidly changed electromagnetic field, the polarity orientation of water molecules in the slurry is changed along with the change of an external electric field, so that violent movement is caused, the adhesive is uniformly distributed in the base material by the violently moved water molecules, the spontaneous aggregation and segregation of the adhesive in the drying process are prevented, the base material and the adhesive are effectively prevented from being peeled off in the drying process, the powder falling problem of formed carrier particles is avoided, and the strength of the carrier is improved. If the excessive moisture in the slurry is removed by adopting a heating and drying mode, along with the gradual conduction of heat conduction from outside to inside, the evaporation of the water in the slurry is also carried out from outside to inside, so that the concentration difference of the adhesive is generated in the slurry, and the outer-layer adhesive distributed in a high-concentration area diffuses towards the inner layer, so that the adhesive is unevenly distributed in the slurry, the strength of the formed carrier is reduced, and the matrix powder is easy to fall off.
In conclusion, the Ti-based adhesive is adopted to solve the pollution problem of the forming auxiliary agent, and the Ti-based adhesive generates chemical bonding effect between the forming powder particles in a hydrothermal mode, so that the TiO is greatly improved2The strength of the formed carrier solves the problem of TiO2The specific surface area and the strength of the formed carrier can not be compatible, the uniform distribution of the adhesive in the formed carrier is promoted by microwave heating, the surface area of the formed carrier is increased, and the powder falling problem is improved. The invention provides TiO with high purity, large specific surface area, high strength and no obvious powder falling2A method for preparing a shaped carrier.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
TiO of the invention2The content is determined by XRF, the pore volume and the specific surface area are determined by N2The physical adsorption method is adopted to measure, and the crushing strength is measured by a strength meter.
Example 1
60g of titanyl sulfate was added to 600ml of water and dissolved at 80 ℃ to give a clear and transparent solution. 340g of metatitanic acid was added to the solution, and after vigorously stirring for 40 minutes, the mixture was transferred to a hydrothermal reaction vessel with a tetrafluoroethylene liner and reacted at 120 ℃ under autogenous pressure for 4 hours. Quenching with water, cooling to room temperature, and adding NH3·H2And adjusting the pH value of the mixed solution to about 7 by O, and gelling. And (3) carrying out solid-liquid separation on the colloid by using a suction filtration method to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake by using deionized water until no sulfate ions are detected in the washing liquid. And (3) placing the washed colloidal filter cake into a microwave oven for heating and dehydrating, adjusting the microwave rate power to 800W, heating for 40 minutes totally, and carrying out 8 times, wherein each time is 5 minutes, and the interval between every two adjacent times is 3 minutes, so that the daub-shaped material mass with the solid content of 72% is obtained. Kneading the daub-shaped material mass in a kneader for 30 minutes, extruding the material mass by a double-screw extruder, airing the extruded material mass to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished granules HT-1.
Example 2
70g of titanium tetrachloride were added to 400ml of water at room temperature, and then 360g of nano TiO was added2After vigorous stirring, the mixture was transferred to a hydrothermal reaction kettle with a tetrafluoroethylene liner and reacted at 150 ℃ under autogenous pressure for 4 hours. Quenching with water, cooling to room temperature, and adding NH3·H2And adjusting the pH value of the mixed solution to about 5 by O, and gelling. And (3) carrying out solid-liquid separation on the colloid by using a suction filtration method to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake by using deionized water until chloride ions in the washing liquid are detected. Placing the washed colloidal filter cake in a microwave oven for heating and dehydrating, adjusting the microwave power to 800W, heating for 40 minutes totally, and performing for 8 times, each time for 5 minutes, and two adjacent filter cakesThe interval between the times is 3 minutes, and the daub-shaped material mass with the solid content of 70 percent is obtained. Kneading the daub-shaped material mass in a kneader for 30 minutes, extruding the material mass by a double-screw extruder, airing the extruded material mass to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished granules HT-2.
Example 3
30g of titanyl sulfate was added to 300ml of water and dissolved at 80 ℃ to give a clear and transparent solution. 370g of nano TiO was added to the solution2The whisker is stirred vigorously for 40 minutes, and then the mixture is transferred into a hydrothermal reaction kettle with a tetrafluoroethylene lining and reacted for 4 hours at 180 ℃ under autogenous pressure. Quenching with water, cooling to room temperature, and adding NH3·H2And adjusting the pH value of the mixed solution to about 3 by O, and gelling. And (3) carrying out solid-liquid separation on the colloid by using a suction filtration method to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake by using deionized water until no sulfate ions are detected in the washing liquid. And (3) placing the washed colloidal filter cake into a microwave oven for heating and dehydrating, adjusting the microwave power to 800W, heating for 40 minutes totally, and carrying out 8 times, wherein each time is 5 minutes, and the interval between every two adjacent times is 3 minutes, so that the daub-shaped material mass with the solid content of 73% is obtained. Kneading the daub-shaped material mass in a kneader for 30 minutes, extruding the material mass by a double-screw extruder, airing the extruded material mass to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished granules HT-3.
Example 4
20g of titanyl sulfate was added to 200ml of water and dissolved at 80 ℃ to give a clear and transparent solution. 380g TiO was added to the solution2The nanotube is stirred vigorously for 40 minutes, and then the mixture is transferred into a hydrothermal reaction kettle with a tetrafluoroethylene lining and reacted for 4 hours at the temperature of 120 ℃ under the autogenous pressure. Quenching with water, cooling to room temperature, and adding NH3·H2And adjusting the pH value of the mixed solution to about 7 by O, and gelling. And (3) carrying out solid-liquid separation on the colloid by using a suction filtration method to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake by using deionized water until no sulfate ions are detected in the washing liquid. HandleAnd (3) placing the washed colloidal filter cake in a microwave oven for heating and dehydrating, adjusting the microwave power to 800W, heating for 40 minutes totally, and carrying out 8 times, 5 minutes each time, and 3 minutes between every two adjacent times to obtain the daub-shaped material mass with the solid content of 75%. Kneading the daub-shaped material mass in a kneader for 30 minutes, extruding the material mass by a double-screw extruder, airing the extruded material mass to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished granules HT-4.
Example 5
60g of titanyl sulfate was added to 600ml of water and dissolved at 80 ℃ to give a clear and transparent solution. 340g of metatitanic acid was added to the solution, and after vigorously stirring for 40 minutes, the mixture was transferred to a hydrothermal reaction vessel with a tetrafluoroethylene liner and reacted at 120 ℃ under autogenous pressure for 4 hours. Quenching with water, cooling to room temperature, and adding NH3·H2And adjusting the pH value of the mixed solution to about 7 by O, and gelling. And (3) carrying out solid-liquid separation on the colloid by using a suction filtration method to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake by using deionized water until no sulfate ions are detected in the washing liquid. And (3) placing the washed colloidal filter cake into a microwave oven for heating and dehydrating, adjusting the microwave rate power to be 500W, heating for 60 minutes totally, and carrying out 10 times, wherein each time is 6 minutes, and the interval between every two adjacent times is 3 minutes, so that the daub-shaped material mass with the solid content of 71% is obtained. Kneading the daub-shaped material mass in a kneader for 30 minutes, extruding the material mass by a double-screw extruder, airing the extruded material mass to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished granules HT-5.
Example 6
60g of titanyl sulfate was added to 600ml of water and dissolved at 80 ℃ to give a clear and transparent solution. 340g of metatitanic acid was added to the solution, and after vigorously stirring for 40 minutes, the mixture was transferred to a hydrothermal reaction vessel with a tetrafluoroethylene liner and reacted at 120 ℃ under autogenous pressure for 4 hours. Quenching with water, cooling to room temperature, and adding NH3·H2And adjusting the pH value of the mixed solution to about 7 by O, and gelling. Filtering the colloid by suction filtrationAnd (3) carrying out solid-liquid separation to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake with deionized water until no sulfate ions are detected in a washing liquid. And (3) placing the washed colloidal filter cake in a microwave oven for heating and dehydrating, adjusting the microwave rate power to 200W, heating for 120 minutes totally, performing 10 times, each time for 12 minutes, and performing 3 minutes interval between every two adjacent times to obtain the daub-shaped material mass. Kneading the daub-shaped material mass in a kneader for 30 minutes, extruding the material mass by a double-screw extruder, airing the extruded material mass to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished granules HT-6.
Comparative example 1
60g of titanyl sulfate was added to 600ml of water and dissolved at 80 ℃ to give a clear and transparent solution. 340g of metatitanic acid was added to the solution and stirred vigorously for 40 minutes. Cooling to room temperature and then adding NH3·H2And adjusting the pH value of the mixed solution to about 7 by O, and gelling. And (3) carrying out solid-liquid separation on the colloid by using a suction filtration method to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake by using deionized water until no sulfate ions are detected in the washing liquid. And (4) placing the washed colloidal filter cake in an oven, heating and dehydrating for 20 minutes to obtain a daub-shaped material mass. Kneading the daub-shaped material mass in a kneader for 30 minutes, extruding the material mass by a double-screw extruder, airing the extruded material mass to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished product of the granules BT-1.
Comparative example 1
60g of titanyl sulfate was added to 600ml of water and dissolved at 80 ℃ to give a clear and transparent solution. 340g of metatitanic acid was added to the solution and stirred vigorously for 40 minutes. Cooling to room temperature and then adding NH3·H2And adjusting the pH value of the mixed solution to about 7 by O, and gelling. And (3) carrying out solid-liquid separation on the colloid by using a suction filtration method to obtain a colloidal filter cake, and repeatedly washing the colloidal filter cake by using deionized water until no sulfate ions are detected in the washing liquid. And (4) placing the washed colloidal filter cake in an oven, heating and dehydrating for 20 minutes to obtain a daub-shaped material mass. Kneading the puddle-like dough in a kneader for 30 minutes, extruding the dough into strips by a twin-screw extruderExtruding with a machine, airing to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished product of the granules BT-1.
Comparative example 2
20g of pseudo-boehmite and 80g of metatitanic acid are uniformly mixed, 23g of 9% dilute nitric acid is added, and after stirring, kneading is carried out for 15 minutes in a kneader, so as to obtain the daub-shaped dough. Extruding the mixture by a double-screw extruder, airing the extruded mixture to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished product of the granules BT-2.
Comparative example 3
85g of metatitanic acid, 10g of methylcellulose and 5g of starch are uniformly mixed, 23g of 9% dilute nitric acid is added, and after stirring, kneading is carried out in a kneader for 15 minutes, so as to obtain the daub-shaped dough. Extruding the mixture by a double-screw extruder, airing the extruded mixture to constant weight, and granulating. The extruded strips after granulation are roasted in a muffle furnace by temperature programming, the roasting temperature is 600 ℃, the temperature is kept for 4 hours, and the heating rate is 2 ℃/min, so that the TiO of the invention is obtained2Finished product of the granules BT-3.
TABLE 1 Properties of samples obtained in examples and comparative examples
The method increases bonding effect of titanium-based adhesive by hydrothermal treatment, promotes uniform distribution of the adhesive by microwave dehydration, and prepares the TiO2The formed carrier has the characteristics of high purity, large specific surface area, high strength, good wear resistance, no powder falling and the like, and can be used in harsh reaction systems of strong acid, strong alkali, strong hydrothermal reaction and the like. TiO in shaped supports2The content is more than or equal to 99 wt%, the crystal form is anatase or/and rutile, the axial compression strength is more than or equal to 8MPa, and the specific surface area is more than or equal to 70m2(ii)/g, average pore diameter is 10-60 nm.
Claims (11)
1. Titanium-based adhesivePreparation of TiO by mixture2A method for molding a catalyst carrier, characterized by comprising the steps of:
(1) firstly, carrying out hydro-thermal treatment on a mixture of Ti-based adhesive solution and titanium-based molding powder;
(2) adding gelatinizing agent to convert into viscous emulsion, washing, and filtering to obtain slurry-like filter cake;
(3) adjusting the water content of the filter cake by microwave heating to obtain a daub-shaped material mass;
(4) kneading, extruding and roasting the daub-shaped material groups to obtain TiO2Forming a catalyst carrier;
the reaction temperature of the hydrothermal treatment is 100-180 ℃, and the treatment time is 1-10 hours;
the Ti-based adhesive is one or more than two of titanyl sulfate, titanium tetrachloride and n-butyl titanate;
the Ti-based molding powder refers to TiO2Or/and hydrates thereof, TiO2Is industrial pigment grade TiO2Commercially available nano TiO2Mesoporous TiO22Whisker, TiO2One or more of the nanotubes, wherein the crystal form is anatase type or rutile type; TiO22The hydrate refers to the metatitanic acid which is an intermediate product for producing titanium dioxide by a sulfuric acid method.
2. The method of claim 1, wherein the Ti-based binder is titanyl sulfate.
3. The method according to any one of claims 1-2, wherein the amount of the Ti-based binder is 10-50 wt% based on the mass of the titanium-based molding powder; based on the total mass of the solution of the titanium-based molding powder, the concentration of the aqueous solution of the Ti-based adhesive is 5 to 15 weight percent, and the mass of the Ti-based adhesive and the molding powder are all TiO2And (4) measuring the mass.
4. The method according to claim 1, wherein the hydrothermal treatment is carried out in a hydrothermal reaction vessel at 120 ℃ for 4 hours.
5. The method of claim 4, wherein the hydrothermal reaction kettle is lined with polytetrafluoroethylene.
6. The method of claim 1, wherein the gelling agent is NH3•H2O, urea and Na2CO3、NaHCO3One or more than two of them, the concentration of the gelatinizing agent is 10-30 wt%; the pH value of the gelatinized viscous emulsion is 3-7.
7. The method of claim 6, wherein the gelling agent is selected at a concentration of 20%.
8. The method as claimed in claim 1, wherein the frequency of the microwave used is 600-9000MHz, the power is 100-1000W, the method is continuously adjustable, one or more powers are selected for alternate use in the drying process, the processing time of the microwave is not more than 10min each time, the interruption time is not more than 10min, and the microwave drying is performed until the solid content of the material mass is 50-75 wt%.
9. The method of claim 1, wherein: TiO22The shape of the formed catalyst carrier is cylindrical, Raschig ring, porous cylindrical, clover or honeycomb ceramic, and the carrier after extrusion is shaped to obtain pellet or spherical carrier particle.
10. The method as set forth in claim 1, wherein the calcination temperature is 500-1000 ℃, the calcination mode is a direct temperature raising method or a programmed temperature raising method, and the temperature raising speed is 2 ℃/min.
11. The method as claimed in claim 10, wherein the calcination temperature is 700-900 ℃, and the calcination manner is a temperature programmed method.
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Citations (5)
| 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 |
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| KR101789296B1 (en) * | 2015-07-02 | 2017-11-21 | 서울시립대학교 산학협력단 | Method for preparing titanium dioxide photocatalyst dopped silver and photocatalyst prepared thereby |
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Patent Citations (5)
| 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 |
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