CN108311134B - Titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas and preparation method thereof - Google Patents
Titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas and preparation method thereof Download PDFInfo
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Abstract
The invention discloses titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas and a preparation method thereof, belonging to the field of carrier coating materials. The invention provides titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, aiming at overcoming the defects of the existing SCR catalyst, and the titanium-tungsten-silicon composite powder is prepared by the following method: pulping metatitanic acid, dispersing, and adding ammonia water to adjust pH to obtain slurry; b. adding ammonia water into metatitanic acid to adjust the pH value, then adding a tungsten source and a silicon source, and heating and preserving heat to obtain a master batch; c. and (3) uniformly mixing the slurry and the master batch, then carrying out filter pressing, and calcining and crushing a filter cake to obtain the catalyst. The invention controls the quality of the raw materials, adjusts the proportion, and is matched with a corresponding preparation process, so that the titanium-tungsten-silicon composite powder not only has higher specific surface area, but also has high-temperature aging resistance and wide catalysis temperature, and the prepared catalyst has the performances of high denitrification efficiency, low drying crack rate and shedding rate, long service life and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of carrier coating materials, and particularly relates to titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas and a preparation method thereof.
Background
Today, modern industry is more developed, people need an environment with fresh air, PM2.5 is an important factor influencing the quality of the air environment, and tail gas emission of coal-fired power plants/large boilers burning heavy oil, diesel vehicles/ships and the like are sources forming PM 2.5; along with the development of the automobile industry in China and the increase of automobile holding capacity, the technology for treating the automobile exhaust also increasingly draws attention of people; nitrogen Oxides (NO) in diesel vehicle/ship exhaustx) Is the main component in treatment and is selectedThe Selective Catalytic Reduction (SCR) denitration technology is widely applied to a denitration system of a coal-fired power plant due to its high efficiency and reliable denitration performance, and is also applied to a denitration technology of diesel engine tail gas of diesel vehicles/ships and the like.
The SCR (selective catalytic reduction) flue gas denitration technology refers to that harmful nitrogen oxides in flue gas are selectively catalytically reduced into clean and harmless nitrogen and water through reducing agents such as ammonia and urea under the action of a catalyst, so that standard emission is realized, and the denitration catalyst is a key and core part for implementing the technology. Typical commercial SCR catalysts are TiO2As a carrier, with V2O5-WO3(MoO3) And noble metal oxides are used as active components. At present, most of vehicle/ship SCR catalysts are prepared by using metal and honeycomb ceramics as carriers and titanium-tungsten-vanadium or titanium-tungsten-molybdenum-vanadium metal oxides as coating materials and active substances. However, since the vehicle/ship SCR catalyst needs to meet special requirements of aging resistance, high strength, low sulfur, high specific surface area and the like at high temperature, the prior vehicle/ship SCR catalyst mostly adopts fully imported carrier and coating materials, and has higher application cost; therefore, the research on the efficient, high-temperature aging resistant and high-strength SCR denitration catalyst carrier and the coating material thereof suitable for the tail gas treatment of the diesel vehicle/ship and the realization of the localization have great practical significance and economic value.
Chinese patent CN101757907 discloses a preparation technology of tungsten-containing titanium dioxide powder of a honeycomb SCR denitration catalyst, the component of which is TiO2-WO3The powder is only suitable for denitration of flue gas of a coal-fired power plant and is not suitable for denitration of tail gas of a mobile source including a diesel vehicle/ship; patent CN103769080 discloses a diesel vehicle tail gas purification SCR catalyst and a preparation method of a carrier coating material, which comprises TiO2-WO3Preparation technology of powder, preparation technology of powder and common SCR catalyst carrier TiO2-WO3The preparation of the powder is the same, and the powder is not specially treated, so that the problem of high-temperature aging resistance of the catalyst cannot be solved; the patent CN103908970 discloses an integral SCR honeycomb catalyst for treating diesel vehicle tail gas and a preparation method thereof, and introduces a preparation technology of SCR catalyst carrier coating material, and components thereofIs ZrO2-TiO2The composite oxide is prepared by precipitation method, and the auxiliary active substance WO3And the active substance vanadium adopts a post-addition method, so the preparation cost is higher.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nano TiO catalyst carrier used for treating tail gas of a diesel vehicle/ship2-WO3-SiO2The composite powder has the advantages of high specific surface area, high surface chemical activity, high temperature aging resistance, high processability and the like of the catalyst for diesel vehicles, has the advantages of high mechanical strength and scouring resistance, and is low in cost and simple in preparation process.
The technical means adopted by the invention for solving the technical problems is to provide titanium-tungsten-silicon composite powder for diesel vehicle/ship tail gas SCR denitration, which is prepared by the following method:
a. pulping and dispersing metatitanic acid until the mass fraction of metatitanic acid calculated by titanium dioxide is 22-25%, adding ammonia water to adjust the pH, and uniformly stirring to obtain slurry for later use;
b. pulping metatitanic acid, dispersing the metatitanic acid by the mass fraction of 15-20% calculated by titanium dioxide, adding ammonia water to adjust the pH, then adding a tungsten source and a silicon source, and heating and preserving the temperature to obtain a master batch;
c. and c, uniformly mixing the slurry obtained in the step a and the master batch obtained in the step b, performing filter pressing, drying the obtained filter cake, calcining, and crushing the calcined material to obtain the titanium-tungsten-silicon composite powder for SCR denitration of the tail gas of the diesel vehicle/ship.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step a, the mass concentration of metatitanic acid is 25-30%, the content of iron metatitanic acid is less than or equal to 100ppm, and the particle size distribution D50 is 0.8-1.0 μm.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step b, the mass concentration of metatitanic acid is 25-30%, the content of iron metatitanic acid is less than or equal to 100ppm, and the particle size distribution D50 is 0.8-1.0 μm.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, the mass ratio of the usage amount of metatitanic acid in the step a to the usage amount of metatitanic acid in the step b in terms of titanium dioxide is 0.5-1.5: 1.
in the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step a, the adding amount of ammonia water is to adjust the pH value of a system to 7.5-8.8.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step b, the adding amount of ammonia water is adjusted to adjust the pH value of the system to 7.5-8.8.
Wherein, in the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step b, the tungsten source is ammonium paratungstate and WO thereof3The mass content is 88-90%.
Wherein, in the titanium-tungsten-silicon composite powder for SCR denitration of the diesel vehicle/ship tail gas, in the step b, the addition amount of the tungsten source is controlled by WO in the master batch3The mass content is 6-20%.
In the titanium-tungsten-silicon composite powder for diesel vehicle/ship tail gas SCR denitration, in the step b, the silicon source is silica sol; SiO of the silica sol2The mass content is 25-35%, the particle size is 10-20 nm, and the specific surface area is not less than 600m2/g。
Wherein, in the titanium-tungsten-silicon composite powder for SCR denitration of the diesel vehicle/ship tail gas, in the step b, the dosage of the silicon source is controlled by SiO in the master batch2The mass content is 3-7%.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step b, the heating and heat preservation temperature is 70-80 ℃ and the time is 1-3 h.
In the titanium-tungsten-silicon composite powder for SCR denitration of the diesel vehicle/ship tail gas, in the step b, ammonia water is added in the heating and heat preservation process to keep the pH value of the system to be 7.5-8.8.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step a, the concentration of the ammonia water is 18-21%.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, the concentration of the ammonia water in the step b is 18-21%.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step c, the drying temperature is 250-300 ℃, and the drying time is 1.5-2.5 h.
In the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas, in the step c, the calcination is sectional calcination, namely calcination is performed at 350-380 ℃ for 60-120 min, calcination at 480-500 ℃ for 40-80 min and calcination at 580-620 ℃ for 40-80 min.
The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas provided by the invention can be prepared by the method, and comprises the following components in percentage by weight: 84 to 93 percent of titanium dioxide, 3 to 10 percent of tungsten trioxide, 1.5 to 3.5 percent of silicon dioxide, 0.5 to 3.0 percent of sulfate radical and 0.5 to 2.0 percent of water.
The granularity of the titanium-tungsten-silicon composite powder for SCR denitration of the diesel vehicle/ship tail gas provided by the invention is-325 meshes.
The invention has the beneficial effects that:
the metatitanic acid adopted by the invention is large in specific surface area, and a multistage cyclone classification technology is provided, so that the metatitanic acid product has uniform particle size (D50 is controlled to be 0.8-1.0 mu m), centralized distribution, large specific surface area and excellent binding performance; SiO of silica sol used in the invention2The mass content is 25-35%, the particle size is 10-20 nm, and the silica sol has a larger specific surface area of more than or equal to 600m compared with the conventional silica source white carbon black2TiO produced using silica sol as silicon source/g, stronger adsorbability and higher dispersibility2-WO3-SiO2The composite powder has higher denitration efficiency, better ageing resistance and high temperature resistance and longer service life; meanwhile, as the silica molecular bond in the silica sol has large energy, the noble metal WO can be reduced on the premise of ensuring the mechanical strength and other denitration use performances3The amount of (c); lifting deviceThe curing process for heating and heat preservation can further promote the combination of titanium dioxide, silicon dioxide and tungsten trioxide, so that the combination is firmer, the adsorption and combination capabilities of the produced product are stronger, the falling rate is low, the denitration efficiency is higher, the anti-aging performance is better, and the service life is prolonged; simultaneously, the dosage of the silica sol can be reduced, so that the product is in SiO2The high denitration efficiency can be achieved under the condition of reducing the content, and the purposes of reducing the consumption of noble metals and reducing the production cost are achieved.
The invention provides the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas by controlling the quality of raw materials, adjusting the proportion and matching with a corresponding preparation process, the titanium-tungsten-silicon composite powder has higher specific surface area, high temperature aging resistance and wide catalysis temperature, and the prepared catalyst has the performances of high denitrification efficiency, low drying crack rate and falling rate, long service life and the like, and has wide application prospect.
Detailed Description
Specifically, the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas is prepared by the following method:
a. pulping and dispersing metatitanic acid until the mass fraction of metatitanic acid calculated by titanium dioxide is 22-25%, adding ammonia water to adjust the pH, and uniformly stirring to obtain slurry for later use;
b. pulping metatitanic acid, dispersing by mass percent of 18-20% calculated by titanium dioxide, adding ammonia water to adjust pH, then adding a tungsten source and a silicon source, and heating and preserving heat to obtain a master batch;
c. and c, uniformly mixing the slurry obtained in the step a and the master batch obtained in the step b, performing filter pressing, drying the obtained filter cake, calcining, and crushing the calcined material to obtain the titanium-tungsten-silicon composite powder for SCR denitration of the tail gas of the diesel vehicle/ship.
The mass concentration of the raw material metatitanic acid is 25-30%, the content of iron metatitanic acid is less than or equal to 100ppm, the particle size distribution D50 is 0.8-1.0 μm, and the material can be prepared by the following method:
a. respectively carrying out acidolysis on the titanium slag and the titanium ore, wherein the mass ratio of the titanium slag to the titanium ore is 1.5-2.5: 1, carrying out acidolysis on the titanium slag by using 96.5-98.3 percent sulfuric acid, and carrying out acid hydrolysisThe mass ratio of the titanium slag to the amount of the titanium slag is 1.65-1.75: 1, carrying out acidolysis on titanium ore by using 91.5-93% sulfuric acid, wherein the mass ratio of the acid amount to the titanium ore is 1.45-1.55: 1; curing the titanium slag for 3 to 5 hours after the acidolysis is finished, and curing the titanium slag for 2 to 3 hours after the acidolysis is finished; adding water for leaching after curing, and combining the leaching solutions to obtain a titanium solution; in the titanium solution: in the concentration of TiO2Calculated as 150 +/-5 g/L, Ti3+1.5 +/-0.5 g/L, the F value is 1.8 +/-0.25, the iron-titanium ratio is 0.3 +/-0.05, and the stability is more than or equal to 600 mL;
b. c, filtering the titanium liquid obtained in the step a at 15-55 ℃ to obtain clear titanium liquid (the solid content is less than or equal to 0.03%), concentrating the clear titanium liquid, and controlling the concentration of the concentrated titanium liquid to be TiO2The weight is 200 plus or minus 5 g/L;
c. mixing the titanium liquid concentrated in the step b with seed crystals, hydrolyzing, stirring and curing the reaction system at the constant temperature of 94-96 ℃ for 20-40 min, heating to ensure that the reaction system is boiled after curing is finished, and standing at the constant temperature for 20-40 min when the reaction system is changed into steel gray (generally 10-15 min is needed); heating and stirring the reaction system to boil again; keeping the reaction system in a micro-boiling state for 170-190 min under 30-100 mmHg after boiling, and obtaining hydrolyzed metatitanic acid after hydrolysis is finished; the seed crystal is prepared by the following method: heating the seed crystal titanium solution and the sodium hydroxide solution to 88-92 ℃, adding the seed crystal titanium solution into the sodium hydroxide solution twice, adding 1/3 of the total volume of the seed crystal titanium solution for the first time, and finishing the addition within 60-90 seconds; 2/3 of the total volume of the seed crystal titanium liquid is added for the second time, and the addition is finished within 30-50 seconds; the time interval from the first addition to the second addition is 15-25 seconds to form a mixed solution; heating the mixed solution to 95-97 ℃, keeping the temperature and measuring the stability, and obtaining seed crystals when the stability reaches 100-125 mL; the concentration of the seed crystal titanium solution is TiO2The weight is 200 plus or minus 5 g/L; the mass concentration of the sodium hydroxide solution is 8 +/-0.2%; the addition of the sodium hydroxide solution is calculated by NaOH and is used as TiO in the crystal seed titanium solution220-25% of the mass; the concentration of the seed crystal is TiO2Calculated as 148 plus or minus 2.5 g/L; the indexes of the hydrolyzed metatitanic acid are controlled as follows: in the concentration of TiO2Is 165 +/-5 g/L, Ti3+1.5 +/-0.5 g/L, hydrolysis rate of 95.5 +/-0.5 percent and pumping speed of 150 percentPlus or minus 50' and the sedimentation height is 150 plus or minus 25 mm;
d. washing the hydrolyzed metatitanic acid obtained in the step c in a leaf filter, controlling the thickness of an upper piece to be 40-50 mm, controlling the vacuum degree (preferably, the vacuum degree is more than or equal to 0.05MPa and less than or equal to 0.1MPa) at 0.05MPa, and washing for 2-4 h; adding water into the metatitanic acid after water washing for size mixing until the titanium content of the size is TiO2Calculated as 260-300 g/L, and then Ti is added3+And sulfuric acid, controlling the indexes of the bleached pulp: ti3+0.5-2 g/L of free acid (i.e. H)+) 25-60 g/L; rinsing the bleached pulp in a leaf filter, wherein the thickness of a plated piece is required to be 30-40 mm, the vacuum degree is more than or equal to 0.05MPa (preferably, the vacuum degree is more than or equal to 0.05MPa and less than or equal to 0.1MPa), and the rinsing time is 3-5 h, so that the rinsed metatitanic acid is obtained, and the content of iron metatitanic acid is less than or equal to 100 ppm;
f. and D, grading the metatitanic acid qualified by rinsing obtained in the step D by adopting a multistage combined cyclone grading technology (in a slurry state), and controlling the slurry D50 to be 0.8-1.0 mu m to obtain the metatitanic acid serving as the raw material of the invention.
The metatitanic acid adopted by the invention is metatitanic acid with large specific surface area (the specific surface area is 300 +/-50 m)2And/g), a multistage cyclone classification technology is added after combined water washing, so that the metatitanic acid product has uniform particle size (D50 is controlled to be 0.8-1.0 mu m), concentrated distribution, large specific surface area and excellent combination performance.
Tests show that because the titanium tungsten oxide and the silicon dioxide in the titanium-tungsten-silicon composite powder are relatively low in content and less titanium dioxide needs to be combined with the tungsten trioxide and the silicon dioxide, the mass ratio of the used amount of the metatitanic acid in the step a to the used amount of the metatitanic acid in the step b is controlled to be 0.5-1.5: 1, the combination of titanium dioxide, silicon dioxide and tungsten trioxide can be further promoted by heating and curing in the step b, so that the combination is firmer, and the product is made from SiO2The high denitration efficiency can be achieved under the condition of reducing the content, the purposes of reducing the consumption of noble metals and reducing the production cost are achieved, meanwhile, the energy consumption is saved, and the cost is further reduced. The metatitanic acid used in step a and step b of the present invention may be used in the same batch, or in different batches, as long as the quality of the present invention is satisfiedAnd (4) summing the dosage requirement.
In the step a, after pulping and dispersing metatitanic acid, the mass fraction of titanium dioxide is controlled to be 22% -25%, and then ammonia water is added to adjust the pH of the system to 7.5-8.8; in the step b, after pulping and dispersing metatitanic acid, the mass fraction of titanium dioxide is controlled to be 18% -20%, then ammonia water is added to adjust the pH of the system to 7.5-8.8, and in the heating and heat preservation process, the ammonia water is added to keep the pH of the system to 7.5-8.8.
The purpose of controlling the slurry concentration in step a and step b is, on the one hand, to make the TiO compound TiO2、WO3、SiO2The three are fully mixed and uniformly combined, and on the other hand, the SO in the metatitanic acid slurry is ensured4 2-Combined with aqueous ammonia to form (NH)4)2SO4Is convenient to remove SO in the subsequent calcining process4 2-The reason for this is to prevent the catalyst from being poisoned by the S element content, and to maintain the appropriate SO concentration4 2-(0.5% -3.0%) to make SO in the product4 2-By reaction with TiO2Surface coordination with TiO2The chelate bonds are formed between the two, which is beneficial to the maintenance of the material mesopores and the more reasonable distribution of the mesopores, so that the composite powder has very high pore volume and specific surface area, thereby ensuring high catalytic activity; in addition, because the heating and heat preservation treatment is required in the step b, the pulping concentration of the metatitanic acid in the step a and the pulping concentration of the metatitanic acid in the step b need to be controlled respectively, and if the concentration of the slurry in the step a is consistent with that of the slurry in the step b, the content of sulfate radicals in a titanium-tungsten-silicon composite powder product system is low after the calcination treatment, so that the performance of the titanium-tungsten-silicon composite powder product system is affected. The concentration of the ammonia water adopted in the invention is 18-21%.
In the present invention, the tungsten source may be amine secondary tungstate, WO thereof3The mass content is 88-90%, and the addition amount of the tungsten source is WO in the controlled master batch3The mass content is 6-20%; the silicon source can be silica sol, SiO of silica sol2The mass content is 25-35%, the particle size is 10-20 nm, and the silica sol has a larger specific surface area of more than or equal to 600m compared with the conventional silica source white carbon black2A silica sol having a higher adsorptivity and a higher dispersibilityTiO produced as silicon source2-WO3-SiO2The composite powder has higher denitration efficiency, better ageing resistance and high temperature resistance and longer service life; meanwhile, as the silica molecular bond in the silica sol has large energy, the noble metal WO can be reduced on the premise of ensuring the mechanical strength and other denitration use performances3The amount of (c); the dosage of the silicon source is controlled by SiO in the master batch2The mass content is 3-7%.
In the step b, after the tungsten source and the silicon source are added, a heating and heat-preserving curing process is added, the titanium dioxide, the silicon dioxide and the tungsten trioxide can be further promoted to be combined by curing for 1 h-3 h at the temperature of 70-80 ℃, so that the combination is firmer, the produced product has stronger adsorption and combination capacity, low falling rate, higher denitration efficiency, better ageing resistance and longer service life; simultaneously, the dosage of the silica sol can be reduced, so that the product is in SiO2The high denitration efficiency can be achieved under the condition of reducing the content, and the purposes of reducing the consumption of noble metals and reducing the production cost are achieved.
And c, uniformly mixing the slurry obtained in the step a and the master batch obtained in the step b, performing filter pressing, drying the obtained filter cake at 250-300 ℃ for 1.5-2.5 h, calcining, and performing sectional calcination at 350-380 ℃ for 60-120 min, 480-500 ℃ for 40-80 min and 580-620 ℃ for 40-80 min, wherein the calcined material can completely pass through a 325-mesh sieve after being crushed to obtain the titanium-tungsten-silicon composite powder for SCR denitration of the tail gas of the diesel vehicle/ship.
The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas provided by the invention can be prepared by the method, and comprises the following components in percentage by weight: 84 to 93 percent of titanium dioxide, 3 to 10 percent of tungsten trioxide, 1.5 to 3.5 percent of silicon dioxide, 0.5 to 3.0 percent of sulfate radical and 0.5 to 2.0 percent of water.
The present invention is further illustrated by the following test examples and examples, but the scope of the present invention is not limited thereto.
In the embodiment of the invention, the mass concentration of the adopted metatitanic acid is 25-30%, and the iron metatitanic acid containsThe amount is less than or equal to 100ppm, the particle size distribution D50 is 0.8-1.0 μm, and the specific surface area is 300 +/-50 m2(ii)/g; WO in ammonium paratungstate3The mass content is 88-90%; SiO in silica sol225 to 35 percent of mass content, 10 to 20nm of particle size and more than or equal to 600m of specific surface area2(ii)/g; the concentration of ammonia water is 18-21%.
Example 1
a. Weighing 10Kg metatitanic acid (according to TiO)2In terms of the weight percentage, dividing the mixture into two parts, adding one part of the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 23%, adding ammonia water to adjust the pH value to 7.93, and uniformly stirring to obtain slurry for later use;
b. adding the other part of the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 20%, adding ammonia water to adjust the pH to 7.91, adding 1.1kg of Ammonium Paratungstate (APT) and 1.1kg of silica sol into the slurry, heating to 75 ℃ and preserving heat for 2 hours, and adding ammonia water to keep the pH of the system at 7.5-8.8 in the heating and heat preserving process to obtain a master batch;
c. and mixing and stirring the slurry and the master batch uniformly, performing filter pressing to obtain a blocky filter cake, drying the filter cake at 250 ℃ for 2h, calcining the filter cake in a rotary kiln for 1.5h at 350-380 ℃, calcining the filter cake for 1h at 480-500 ℃ and calcining the filter cake for 1h at 580-620 ℃, and crushing the calcined kiln falling material obtained by calcination by using a shear type rotor mill (325 meshes of all pass after crushing) to prepare powdery titanium dioxide-tungsten trioxide-silicon dioxide composite powder (namely the titanium-tungsten-silicon composite powder for diesel vehicle/ship tail gas SCR denitration).
Example 2
a. Weighing 10Kg metatitanic acid (according to TiO)2In terms of the weight percentage, dividing into two parts, adding one part into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 23%, adding ammonia water to adjust the pH value to 7.76, and uniformly stirring to obtain slurry for later use;
b. adding the other part of the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 18%, adding ammonia water to adjust the pH to 7.84, adding 1.1kg of Ammonium Paratungstate (APT) and 0.52kg of silica sol into the slurry, heating to 75 ℃ and preserving heat for 2 hours, and adding ammonia water to keep the pH of the system at 7.5-8.8 in the heating and heat preserving process to obtain a master batch;
c. and mixing and stirring the slurry and the master batch uniformly, performing filter pressing to obtain a blocky filter cake, drying the filter cake at 250 ℃ for 2h, calcining the filter cake in a rotary kiln for 1.5h at 350-380 ℃, calcining at 480-500 ℃ for 1h, and calcining at 580-620 ℃ for 1h, and crushing the calcined kiln falling material obtained by calcining by using a shear type rotor mill (325 meshes of all pass after crushing) to prepare the powdery titanium dioxide-tungsten trioxide-silicon dioxide composite powder.
Example 3
a. Weighing 10Kg metatitanic acid (according to TiO)2In terms of the weight percentage, dividing into two parts, adding one part into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 23%, adding ammonia water to adjust the pH value to 8.53, and uniformly stirring to obtain slurry for later use;
b. adding the other part of the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 18%, adding ammonia water to adjust the pH value to 8.49, adding 0.4kg of Ammonium Paratungstate (APT) and 1.1kg of silica sol into the slurry, heating to 75 ℃, keeping the temperature for 2 hours, and adding ammonia water to keep the pH value of the system to be 7.5-8.8 in the heating and heat-preserving process to obtain a master batch;
c. and mixing and stirring the slurry and the master batch uniformly, performing filter pressing to obtain a blocky filter cake, drying the filter cake at 250 ℃ for 2h, calcining the filter cake in a rotary kiln at 350-380 ℃ for 1.5h, at 480-500 ℃ for 1h and at 600-630 ℃ for 1h, crushing the calcined kiln falling material obtained by calcination by using a shear type rotor mill (the crushed material passes through 325 meshes completely), and preparing the powdery titanium dioxide-tungsten trioxide-silicon dioxide composite powder.
Example 4
a. Weighing 10Kg metatitanic acid (according to TiO)2In terms of the weight percentage, dividing into two parts, adding one part into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 23%, adding ammonia water to adjust the pH value to 8.36, and uniformly stirring to obtain slurry for later use;
b. adding the other part of the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 18%, adding ammonia water to adjust the pH value to 8.29, adding 0.95kg of Ammonium Paratungstate (APT) and 1kg of silica sol into the slurry, heating to 75 ℃, keeping the temperature for 2 hours, and adding ammonia water to keep the pH value of the system to be 7.5-8.8 in the heating and heat-preserving process to obtain a master batch;
c. and mixing and stirring the slurry and the master batch uniformly, performing filter pressing to obtain a blocky filter cake, drying the filter cake at 250 ℃ for 2h, calcining the filter cake in a rotary kiln for 1.5h at 350-380 ℃, calcining at 480-500 ℃ for 1h, and calcining at 580-620 ℃ for 1h, and crushing the calcined kiln falling material obtained by calcining by using a shear type rotor mill (325 meshes of all pass after crushing) to prepare the powdery titanium dioxide-tungsten trioxide-silicon dioxide composite powder.
Example 5
a. Weighing 10Kg metatitanic acid (according to TiO)2In terms of the weight percentage, dividing into two parts, adding one part into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 25%, adding ammonia water to adjust the pH value to 8.31, and uniformly stirring to obtain slurry for later use;
b. adding the other part of the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 20%, adding ammonia water to adjust the pH to 8.37, adding 0.65kg of Ammonium Paratungstate (APT) and 1kg of silica sol into the slurry, heating to 75 ℃ and preserving heat for 2 hours, and adding ammonia water to keep the pH of the system at 7.5-8.8 in the heating and preserving heat process to obtain a master batch;
c. and mixing and stirring the slurry and the master batch uniformly, performing filter pressing to obtain a blocky filter cake, drying the filter cake at 250 ℃ for 2h, calcining the filter cake in a rotary kiln for 1.5h at 350-380 ℃, calcining at 480-500 ℃ for 1h, and calcining at 580-620 ℃ for 1h, and crushing the calcined kiln falling material obtained by calcining by using a shear type rotor mill (325 meshes of all pass after crushing) to prepare the powdery titanium dioxide-tungsten trioxide-silicon dioxide composite powder.
Example 6
a. Weighing 10Kg metatitanic acid (according to TiO)2Calculated), divided into two parts, one part is added into a reactor with a stirring device, deionized water is added, and the mixture is pulped and dispersed to be oxidized by dioxideAdding ammonia water to adjust the pH to 8.31, and uniformly stirring to obtain slurry for later use, wherein the mass fraction of titanium is 25%;
b. adding the other part of the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 20%, adding ammonia water to adjust the pH to 8.37, adding 1.3kg of Ammonium Paratungstate (APT) and 0.52kg of silica sol into the slurry, heating to 75 ℃ and preserving heat for 2 hours, and adding ammonia water to keep the pH of the system at 7.5-8.8 in the heating and heat preserving process to obtain a master batch;
c. and mixing and stirring the slurry and the master batch uniformly, performing filter pressing to obtain a blocky filter cake, drying the filter cake at 250 ℃ for 2h, calcining the filter cake in a rotary kiln for 1.5h at 350-380 ℃, calcining at 480-500 ℃ for 1h and calcining at 600-640 ℃ for 1h, and crushing the calcined kiln falling material obtained by calcining by using a shear type rotor mill (325 meshes of all pass after crushing) to prepare the powdery titanium dioxide-tungsten trioxide-silicon dioxide composite powder.
Comparative example 1
Metatitanic acid and a tungsten source are the same as those in example 5, 0.35kg of white carbon black is selected as a silicon source to replace 1kg of silica sol in example 5, and the titanium dioxide-tungsten trioxide-silicon dioxide composite powder is prepared by the same preparation method as in example 5.
Comparative example 2
The metatitanic acid, the tungsten source and the silicon source are the same as those in the embodiment 5, the preparation method comprises the steps of pulping metatitanic acid, adjusting the pH value, adding the tungsten source and the silicon source, performing filter pressing, calcining and crushing to obtain the titanium dioxide-tungsten trioxide-silicon dioxide composite powder, and the specific operation is as follows:
weighing 10Kg metatitanic acid (according to TiO)2Adding the mixture into a reactor with a stirring device, adding deionized water, pulping and dispersing until the mass fraction of titanium dioxide is 20%, adding ammonia water to make the pH of the system be 8.41, adding 0.65kg of Ammonium Paratungstate (APT) and 1kg of silica sol into the slurry, performing filter pressing to obtain a blocky filter cake, drying the filter cake at 250 ℃ for 2 hours, calcining the blocky filter cake in a rotary kiln at 350-380 ℃ for 1.5 hours, 480-500 ℃ for 1 hour and 580-620 ℃ for 1 hour, grinding the calcined kiln falling material obtained by calcination by using a shear type rotor mill (325 meshes are passed after grinding) to prepare powdery titanium dioxide-tungsten trioxide-dioxideSilicon composite powder.
Detection of components, properties and application performance of composite powder
The components and property tests of the titanium dioxide-tungsten trioxide-silicon dioxide composite powder prepared in examples 1 to 6 and comparative examples 1 to 2 are shown in table 1, and the specific data are as follows:
TABLE 1 detection of titanium tungsten silicon composite powder composition and Properties
As can be seen from the data in Table 1, the product prepared by adopting the silica sol as the silicon source and adjusting the process parameters has better aging resistance, and the specific surface area, the aging resistance area and other performance indexes of the product can be ensured under the condition that the contents of silicon dioxide and tungsten trioxide are relatively low.
The titanium dioxide-tungsten trioxide-silicon dioxide composite powder prepared in the examples 1-6 and the comparative examples 1-2 is smeared by the same coating process to prepare a catalyst, and then the application performance detection is carried out, and the results are shown in table 2.
TABLE 2 application Performance test
As can be seen from the data in Table 2, the titanium-tungsten-silicon composite powder of the invention has high denitrification rate, low drying crack rate and low shedding rate.
Claims (9)
1. Titanium tungsten silicon composite powder for diesel vehicle/ship tail gas SCR denitration is characterized in that: the preparation method comprises the following steps:
a. pulping and dispersing metatitanic acid until the mass fraction of metatitanic acid calculated by titanium dioxide is 22-25%, adding ammonia water to adjust the pH, and uniformly stirring to obtain slurry for later use;
b. pulping metatitanic acid, dispersing the metatitanic acid by mass percent of 15-20% calculated by titanium dioxide, adding ammonia water to adjust the pH, then adding a tungsten source and a silicon source, and heating and preserving heat to obtain a master batch;
c. uniformly mixing the slurry obtained in the step a and the master batch obtained in the step b, performing pressure filtration, drying the obtained filter cake, calcining, and crushing the calcined material to obtain the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas;
the mass ratio of the using amount of the metatitanic acid in the step a to the using amount of the metatitanic acid in the step b in terms of titanium dioxide is 0.5-1.5: 1;
in the step b, the silicon source is silica sol; SiO of the silica sol2The mass content is 25-35%, the particle size is 10-20 nm, and the specific surface area is not less than 600m2/g；
In the step b, the heating and heat preservation temperature is 70-80 ℃, and the time is 1-3 h; and in the step b, adding ammonia water to keep the pH of the system at 7.5-8.8 in the heating and heat preservation process.
2. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in claim 1, wherein: in the step a and the step b, the mass concentration of the metatitanic acid is 25-30%, the content of iron metatitanic acid is less than or equal to 100ppm, and the particle size distribution D50 is 0.8-1.0 μm.
3. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in claim 1, wherein: in the step a, the adding amount of the ammonia water is to adjust the pH value of the system to 7.5-8.8; in the step b, the adding amount of the ammonia water is to adjust the pH value of the system to 7.5-8.8.
4. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in claim 1, wherein: in step b, the tungsten source is ammonium paratungstate, WO thereof3The mass content is 88-90%; the addition amount of the tungsten source is WO in the controlled master batch3The mass content is 6-20%.
5. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in claim 1, wherein: in the step b, the dosage of the silicon source is controlled by SiO in the master batch2The mass content is 3% -7%% 。
6. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in any one of claims 1 to 5, wherein: in the step a and the step b, the concentration of the ammonia water is 18-21%.
7. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in claim 1, wherein: in the step c, the drying temperature is 250-300 ℃, and the drying time is 1.5-2.5 h; the calcination is sectional calcination, namely calcination is carried out at 350-380 ℃ for 60-120 min, at 480-500 ℃ for 40-80 min, and at 580-620 ℃ for 40-80 min.
8. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in any one of claims 1 to 5 or 7, wherein: the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas comprises the following components in percentage by weight: 84-93% of titanium dioxide, 3-10% of tungsten trioxide, 1.5-3.5% of silicon dioxide, 0.5-3.0% of sulfate radical and 0.5-2.0% of water.
9. The titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas as defined in claim 6, wherein: the titanium-tungsten-silicon composite powder for SCR denitration of diesel vehicle/ship tail gas comprises the following components in percentage by weight: 84-93% of titanium dioxide, 3-10% of tungsten trioxide, 1.5-3.5% of silicon dioxide, 0.5-3.0% of sulfate radical and 0.5-2.0% of water.
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