CN113893848A - Anti-toxicity layered granular catalyst and preparation method thereof - Google Patents

Anti-toxicity layered granular catalyst and preparation method thereof Download PDF

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CN113893848A
CN113893848A CN202111268928.4A CN202111268928A CN113893848A CN 113893848 A CN113893848 A CN 113893848A CN 202111268928 A CN202111268928 A CN 202111268928A CN 113893848 A CN113893848 A CN 113893848A
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vocs
pcdd
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龙红明
钱立新
丁龙
魏进超
顾明言
徐辉
杨本涛
陈萍
王光应
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Anhui University of Technology AHUT
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Abstract

The invention discloses an antitoxic layered granular catalyst and a preparation method thereof, relates to the technical field of catalysts, and ensures the catalytic efficiency of the catalyst by forming a coating layer containing pores on the outer layer of a catalyst core containing catalytic active ingredients, SO as to avoid SO2、H2Toxic substances such as O, alkali metals and the like directly contact with the active substances, and have good SO resistance2、H2Poisoning properties of O and alkali metals。

Description

Anti-toxicity layered granular catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an antitoxic layered granular catalyst and a preparation method thereof.
Background
A large amount of volatile organic pollutants (VOCs), dioxin (PCDD/Fs) and CO in industrial coal-fired flue gas enter the atmosphere every year, and serious influence is generated on the global environment. VOCs can cause photochemical smog, greenhouse effect and other environmental problems, dioxin is a highly toxic substance, can cause huge damage to a human body and can cause cancer and malformation, and CO can be combined with hemoglobin to cause biological poisoning and death. The pollutants have certain reducibility, and the perovskite type composite oxide is used as a catalyst, so that the pollutants can be efficiently catalyzed, combusted and degraded. But the general flue gas contains a large amount of SO2、H2O and alkali metals (potassium, sodium) and the like, and the perovskite type composite oxide is easily affected by the substances to cause poisoning, thereby losing the degradation activity. How to improve the water resistance, sulfur resistance and alkali metal resistance of the perovskite type composite oxide becomes a limiting factor of the application of the perovskite type catalyst.
At present, aiming at the anti-poisoning research of the catalyst, the method mainly aims at adjusting the adding proportion of each element in the catalyst in the preparation process of the catalyst, changing the preparation method and adding Sr, Zr and other elements to improve the anti-poisoning performance of the catalyst. Although the modes can improve the anti-poisoning performance of the catalyst, the active site of the prepared catalyst is still exposed in smoke, and the anti-poisoning performance can hardly meet the requirement of actual production.
The applicant has proposed a sulfur-resistant perovskite titanium compound according to Shenliuqian (study on the activity, toxicity resistance and stability of combustion of VOCs catalyzed by perovskite catalysts)The preparation method of the mineral catalyst adopts lanthanum nitrate, strontium nitrate and manganese nitrate to prepare the perovskite metal oxide catalyst, and respectively takes toluene (VOCs substitute), chlorobenzene (PCDD/Fs substitute) and CO as pollutants (toluene concentration is 500 mg/m)3Chlorobenzene concentration 500mg/m3CO concentration 1000mg/m3) The total air flow is 280ml/min, and the air speed ratio is 42000h-1，O2Content 16%, N2The degradation efficiency of the catalyst on VOCs, PCDD/Fs and CO is respectively tested under the laboratory condition of balance gas, and the catalyst is also tested when the catalyst is loaded with 1% of mass fraction K2The degradation characteristics of the O-containing catalyst on the pollutants are tested, and the sulfur resistance (SO in mixed gas) of the 300 ℃ catalyst is also tested2The concentration is 100mg/m3) Water-resistant (H in mixed gas)2O volume fraction 10%) performance. The results of the experiment are shown in table 1. (mode of Activity parameter detection in the following description of the embodiments)
TABLE 1
Figure BDA0003327453130000011
Figure BDA0003327453130000021
From the above results, it is clear that the catalysts known in the literature are specific to poisoning substances such as SO2Resistant to SO2The activity of the product is still more than 80% after 4.5H, but other toxic substances such as H2O、K2O, etc., and the resistance is poor, and the catalyst activity is seriously lowered under the influence of these poisoning substances. The method of only adopting simple element addition can improve a certain anti-poisoning performance of the catalyst, but has great disadvantages. Therefore, it is necessary to prepare a catalyst with high poisoning resistance by other means on the basis of ensuring the activity of the catalyst.
Disclosure of Invention
Aiming at the technical problem that the perovskite type catalyst is easy to be poisoned in the using process in the prior art, the invention provides the antitoxic layered granular catalyst and the preparation method thereof, and further, the technical problem of how to ensure the catalytic efficiency after adopting antitoxic measures is solved, and the technical problem is improved by forming a coating layer containing pores on the outer layer of the catalyst core containing catalytic active components.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a poison-resistant layered granular catalyst, wherein catalyst particles comprise a catalyst core and a coating layer; wherein the catalyst core comprises a catalytic active component, pores are formed in the coating layer, the catalytic active component in the catalyst core is communicated to the outside of the catalyst particles through the pores, the layered granular catalyst is characterized in that the coating layer containing the pores is formed on the outer layer of the catalyst core containing the catalytic active component, pollutants in flue gas need to pass through the coating layer containing the pores on the outer layer before reaching the catalyst core containing the catalytic active component in the using process of the catalyst, and the pollutants such as SO in the pores are in the pores2、H2Substances such as O, alkali metals and the like which are easy to poison and deactivate the catalyst can be absorbed, so that the possibility of the easy-to-poison condition of the catalyst core is improved; in addition, the coating layer containing pores can also ensure the normal contact of the catalyst core and the flue gas, ensure the catalytic efficiency of the catalyst and avoid SO2、H2Toxic substances such as O, alkali metals and the like directly contact with the active substances, and have good SO resistance2、H2O, alkali metal poisoning property.
Preferably, the catalytically active component of the catalyst core is a perovskite-type catalytically active component; the perovskite-type catalytic active component is easily oxidized with SO2、H2The components in the flue gas such as O, alkali metal and the like are inactivated and are easily absorbed by the coating layer containing pores, SO that the catalyst of the perovskite type catalytic active component can effectively avoid SO under the condition of ensuring better catalytic effect2、H2The influence of O, alkali metals, etc. on the activity of the catalytically active components.
Preferably, the titanium ore type catalytically active component is a perovskite type oxide formed of Ce with Mn and O.
Preferably, the perovskite oxide formed by Ce, Mn and O is a perovskite oxide formed by reacting cerium nitrate with manganese acetate.
Preferably, the molar ratio of Ce to Mn in the catalytic active component is 1 (0.9-1.1).
Preferably, the coating layer comprises titanium-containing oxide and silicon-containing oxide, and TiO is used2With SiO2Phase transition law, TiO at 620 deg.C2Crystal shrinkage and SiO2The crystal expands, gaps appear among the composite metal oxide crystal grains, and a large number of gaps are communicated to form complex reticular pores.
Preferably, the pores are formed in the TiO2With SiO2Between the grains.
Preferably, the particle size of the catalyst core is not greater than 400 mesh.
Preferably, the catalyst particles have a particle size of 40 to 60 mesh.
The layered granular catalyst is prepared by preparing a granular catalyst core containing a catalytic active component, then placing the catalyst core in a system containing a pore component which can be formed by roasting, drying and grinding to obtain the layered granular catalyst.
Drawings
FIG. 1 is a schematic view of the structure of a layered granular catalyst with poison resistance according to the present invention.
FIG. 2 is a schematic structural diagram of a layered particulate catalyst containing graphene.
Description of reference numerals:
100. catalyst particles; 110. a catalyst core; 111. a catalytically active component; 112. graphene;
120. a coating layer; 121. an oxygen storage component; 122. a pore; 123. a titanium-containing oxide; 124. a silicon-containing oxide.
Detailed Description
For a further understanding of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings and examples.
The structure, proportion, size and the like shown in the drawings are only used for matching with the content disclosed in the specification, so that the person skilled in the art can understand and read the description, and the description is not used for limiting the limit condition of the implementation of the invention, so the method has no technical essence, and any structural modification, proportion relation change or size adjustment still falls within the scope of the technical content disclosed by the invention without affecting the effect and the achievable purpose of the invention. Meanwhile, the terms such as "upper", "lower", "left", "right" and "middle" used in the present specification are for clarity of description only, and are not used to limit the implementable scope, and the relative relationship changes or adjustments may be considered to be within the implementable scope of the present invention without substantial technical changes; in addition, the embodiments of the present invention are not independent of each other, but may be combined.
The invention relates to a poison-resistant layered granular catalyst, wherein the particle size of a catalyst particle 100 is 40-60 meshes, and the catalyst particle 100 comprises a catalyst core 110 and a coating layer 120; wherein the particle size of the catalyst core 110 is not greater than 400 meshes, the catalyst core 110 comprises a catalytically active component 111, and the catalytically active component 111 of the catalyst core 110 is a perovskite-type catalytically active component; the perovskite-type catalytic active component is easily oxidized with SO2、H2The components in the flue gas such as O and alkali metals are inactivated and these components are easily absorbed by the coating layer 120 containing the pores 122, but the perovskite-type catalytically active component has a good catalytic effect. More specifically, the titanium ore type catalytic active component may be a perovskite type oxide formed by Ce, Mn and O, the perovskite type oxide formed by Ce, Mn and O is a perovskite type oxide formed by reaction of cerium nitrate and manganese acetate, and the molar ratio of Ce to Mn element in the catalytic active component 111 is 1 (0.9-1.1), preferably, it may be 1: 1.
Pores 122 are formed in the clad 120, and pores 122 are formed through the pores 122So that the catalytically active components 111 in the catalyst core 110 are communicated to the outside of the catalyst particle 100; the formation may be: the cladding layer 120 includes a titanium-containing oxide 123 and a silicon-containing oxide 124 therein, using TiO2With SiO2Phase transition law, TiO at 620 deg.C2Crystal shrinkage and SiO2The crystal expands, gaps appear among the composite metal oxide crystal grains, and a large number of gaps are communicated to form complex reticular pores, wherein the pores 122 are formed in the TiO2With SiO2Between the grains.
The pores 122 allow the catalytically active component 111 in the catalyst core 110 to communicate with the outside of the catalyst particle 100, and the layered granular catalyst is prepared by forming the coating layer 120 having pores on the outer layer of the catalyst core 110 containing the catalytically active component 111, and pollutants in the flue gas pass through the coating layer 120 having pores 122 on the outer layer before reaching the catalyst core 110 containing the catalytically active component 111 during the use of the catalyst, while in the pores 122, such as SO2、H2Substances such as O and alkali metals which easily poison and deactivate the catalyst can be absorbed, so that the possibility of easily poisoning the catalyst core 110 is improved; in addition, the coating layer 120 containing the pores 122 can also ensure the normal contact between the catalyst core 110 and the flue gas, ensure the catalytic efficiency of the catalyst and avoid SO2、H2Toxic substances such as O, alkali metals and the like directly contact with the active substances, and have good SO resistance2、H2O, alkali metal poisoning properties; and the catalyst with strong anti-poisoning performance and high activity can be prepared by using low-price elements, and pollutants such as CO, VOCs, PCDD/Fs and the like can be effectively degraded.
In the preparation process, the concrete preparation steps are as follows:
(1) preparation of perovskite-type composite oxide catalyst core 110
Dissolving cerium-containing salt, manganese-containing salt and citric acid in water, stirring after dissolving, using the dissolved citric acid as a complexing agent to react with metal ions to generate a soluble complex, continuously losing water in the stirring process, converting the soluble complex solution into colloid, stirring into colloid, drying, grinding, and roasting to obtain the perovskite type composite oxide catalyst core 110.
In addition, the cerium-containing salt and the manganese-containing salt are respectively cerium nitrate and manganese acetate; the molar ratio of Ce to Mn in the added cerium nitrate and manganese acetate is 1 (0.9-1.1); the mole number of the citric acid is 1.5-2 times of that of the metal salt, wherein the mole number of the cerium nitrate and the manganese acetate refers to the total mole number of cerium atoms and manganese atoms, the citric acid is a complexing agent of metal ions, if the amount of the citric acid is too small, the metal salt is precipitated, the metal ions cannot be uniformly dispersed, and the uniformity of the catalyst is influenced; if the citric acid is too much, the xerogel is excessive, and the crystal growth of the metal oxide is not facilitated.
In addition, the mass of the deionized water can be 10-15 times of the total amount of the solid, and the solid comprises cerium-containing salt, manganese-containing salt and citric acid; the particle size of the catalyst core 110 obtained by grinding is not more than 400 meshes, when roasting is carried out, the roasting atmosphere is air, the temperature rising speed is 10 ℃/min in the process of from room temperature to 300 +/-10 ℃, after the temperature of 300 +/-10 ℃ is preserved for 0.8 h-1.2 h, the temperature is raised to 1000 +/-20 ℃ at the temperature rising speed of 2 ℃/min, the temperature is preserved for 1.8 h-2.2 h, and furnace cooling is carried out after the temperature preservation is finished;
(2) preparation of the coating layer 120
Dissolving ethyl orthosilicate and tetrabutyl titanate in an organic solvent to form a coating layer 120 mixed solution, adding the catalyst core 110 prepared in the step (1) into the coating layer 120 mixed solution, stirring, and standing to form a gel state to form a catalyst precursor; preparing ethyl orthosilicate and tetrabutyl titanate according to a molar ratio of 1 (8-10); and/or the organic solvent is absolute ethyl alcohol, and the added mass of the absolute ethyl alcohol is 0.8-1.2 times of the sum of the volumes of the ethyl orthosilicate and the tetrabutyl titanate; and/or acetic acid is 0.1-0.15 times of the volume of the absolute ethyl alcohol; adding acetic acid in the process of dissolving ethyl orthosilicate and tetrabutyl titanate in an organic solvent; and/or the volume of the acetic acid is 0.1-0.15 times of that of the organic solvent.
(3) Preparation of the composite catalyst
And (3) drying the catalyst precursor in the step (2), grinding the dried catalyst precursor into powder, and roasting the powder to prepare the composite catalyst, wherein in the roasting process, the temperature is increased at the temperature rise speed of 10 ℃/min, the roasting temperature is 620-650 ℃, and the roasting time is 2-2.5 h.
Example 1
The specific parameters of the anti-toxicity layered granular catalyst of this example are embodied in the preparation process, which comprises the following steps:
step one, preparing perovskite type composite oxide powder.
(1) Preparing a powder precursor: weighing 0.1mol of cerium nitrate, 0.1mol of manganese acetate and 0.15mol of citric acid, dissolving in 1000ml of deionized water, stirring at the speed of 250r/min at 90 ℃ after completely dissolving, stirring for 4 hours to obtain a mixture which is a ready-made colloid, drying in a drying oven at 105 ℃ for 24 hours to obtain a dried precursor, and grinding the dried precursor powder to obtain precursor powder below 400 meshes;
(2) precursor roasting: roasting the precursor powder in a muffle furnace, heating to 300 ℃ at a heating rate of 10 ℃/min under the air atmosphere, preserving heat for 1h, then heating to 1000 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, and cooling a sample to room temperature along with the furnace after heat preservation is finished;
(3) powder preparation: grinding the powder obtained by roasting to obtain particles (400 meshes) with the size of less than 37 microns;
(4) powder modification: mixing the obtained powder with graphene oxide powder according to a mass ratio of 100: 1, mixing and grinding for 2 hours;
and step two, preparing the layered spherical particle perovskite type catalyst.
(1) Preparing a mixed solution A: dissolving 0.1mol of ethyl orthosilicate and 0.8mol of tetrabutyl titanate in 100ml of absolute ethyl alcohol, adding 15ml of acetic acid to inhibit hydrolysis, adding 55g of the modified powder prepared in the step one into the solution A, and uniformly stirring the components of the solution A by adopting 100HZ ultrasonic oscillation and 250r/min electromagnetic stirring, wherein the treatment time is 30 min;
(2) preparing a mixed solution B: dissolving 55g of cerium nitrate in 25g of acetic acid solution with the concentration of 0.05mol/L to obtain solution B;
(3) preparing a catalyst precursor: adding the solution B into the solution A containing the catalyst core 110 at a dropping speed of 10ml/min, stirring at a stirring speed of 100r/min while dropping, standing for 10h after dropping to obtain colloidal liquid, drying in an oven at 60 ℃ for 12h, and grinding the dried colloid to obtain precursor particles of the 250-doped 425-micron catalyst;
(4) roasting the catalyst: roasting the dried catalyst precursor in a nitrogen protective atmosphere at the heating rate of 10 ℃/min, the roasting temperature of 620 ℃ and the roasting time of 2h to finally obtain the layered spherical particle perovskite catalyst;
step three: catalyst activity detection
A plurality of gas paths are adopted to prepare mixed gas, and the pollutant degradation performance of the catalyst is tested in a temperature programmed furnace. The main process is as follows: the catalyst is placed in a quartz tube with the inner diameter of 5mm, the quartz tube filled with the catalyst is placed in a temperature programmed heating furnace, mixed gas is introduced into the quartz tube, and gas components are detected at a gas inlet and a gas outlet of the quartz tube respectively. The CO content is detected by an ECOM electrochemical flue gas analyzer, and the contents of toluene (VOCs substitute) and chlorobenzene (PCDD/Fs substitute) are detected by hydrogen ion flame chromatography.
When the catalyst is used for catalyzing CO activity detection, the gas distribution component is CO which is 1000mg/m3，O216% of balance gas N2. The catalyst loading is 0.5g, the gas flow rate is 280ml/min, and the air speed ratio is 42000h-1。
When the catalyst is used for catalyzing the activity detection of toluene (VOCs substitutes), the gas distribution component is toluene which is 500mg/m3，O216% of balance gas N2. The catalyst loading is 0.5g, the gas flow rate is 280ml/min, and the air speed ratio is 42000h-1。
When the catalyst is used for catalyzing the activity detection of chlorobenzene (PCDD/Fs substitute), the gas distribution component is toluene which is 500mg/m3，O216% of balance gas N2. The catalyst loading is 0.5g, the gas flow rate is 280ml/min, and the air speed ratio is 42000h-1。
The catalyst activity test temperature is controlled by adopting temperature programming. The temperature range is 100-300 ℃, the temperature difference of the stages is 25 ℃, the heating rate is 10 ℃/min, and after the temperature reaction of each stage is stable for 15min, the tail gas components are detected. The catalyst activity calculation formula is calculated as follows:
Figure BDA0003327453130000071
wherein [ pollutant ]]outIndicates the concentration of the pollutant in the mixed gas after the reaction, [ pollutant ]]inIndicating the mixed gas contaminant concentration prior to reaction.
Step four: catalyst sulfur poisoning resistance detection
When the sulfur resistance of the catalyst is tested, 100mg/m of active detection gas is added3SO of (A)2And controlling the reaction temperature at 200 ℃, detecting the gas components once every 0.5h, continuously testing for 4.5h, and carrying out the catalyst activity calculation method in the same step three.
Step five: catalyst anti-water poisoning detection
When the catalyst is used for water resistance test, H with the volume fraction of 10 percent is added into activity detection gas2And O, controlling the reaction temperature at 200 ℃, detecting the gas components once every 0.5 hour, continuously testing for 4.5 hours, and performing the catalyst activity calculation method in the same step three.
Step six: catalyst anti-alkalosis detection
During the test of the catalyst for resisting alkali poisoning, potassium nitrate is dissolved in deionized water, the potassium nitrate is converted into potassium oxide, and the mass ratio of the potassium oxide to the catalyst is 1: 100, adding the catalyst into the solution, heating and stirring the catalyst at 80 ℃, and roasting the potassium nitrate-loaded catalyst for 4 hours at 400 ℃ in air after the liquid is stirred to be dry to obtain the potassium poisoning catalyst. And (5) detecting the activity of the poisoned catalyst in the same way as the third step. The results are reported in table 2.
TABLE 2
Figure BDA0003327453130000072
Figure BDA0003327453130000081
Example 2
This example is used as a reference experiment, and the experimental procedure of this comparative example is the same as that of example 1, except that: the powder modification (4) in step one was not used, and all the steps of step two were not used. The results are reported in Table 3 as the basis for the later experiments.
TABLE 3
Figure BDA0003327453130000082
Example 3
The experimental procedure of this example is the same as example 1, except that: the powder modification of the step (4) in the step one is not adopted, and cerium nitrate is not added in the preparation of the mixed solution B of the step (2) in the step two. The results are reported in table 4.
TABLE 4
Figure BDA0003327453130000083
Figure BDA0003327453130000091
Example 4
The experimental procedure of this example is the same as example 1, except that: the modified powder prepared in the first step is not adopted, and the modified powder is not added in the preparation of the mixed solution A in the second step (1). The results are reported in table 5.
TABLE 5
Figure BDA0003327453130000092
Figure BDA0003327453130000101
Example 5
The experimental procedure of this example is the same as example 1, except that: in step one, the powder is not modified. The results are reported in table 6.
TABLE 6
Figure BDA0003327453130000102
Example 6
The experimental procedure of this example is the same as example 1, except that: and in the second step, cerium nitrate is not added for modification during preparation of the mixed solution B in the step (2). The results are reported in table 7.
TABLE 7
Figure BDA0003327453130000111
Comparative example 2
The experimental procedure of this comparative example was the same as example 1 except that: in the step two, when the mixed solution A is prepared in the step (1), tetrabutyl titanate is replaced by equal amount of ethyl orthosilicate. The results are reported in Table 8.
TABLE 8
Figure BDA0003327453130000112
Figure BDA0003327453130000121
Comparative example 3
The experimental procedure of this comparative example was the same as example 1 except that: in the step two, when the mixed solution A is prepared in the step (1), the ethyl orthosilicate is replaced by tetrabutyl titanate with the same quantity. The results are reported in Table 9.
TABLE 9
Figure BDA0003327453130000122
By performing comparative analysis on the experimental data, the following conclusions can be obtained:
(1) through the experiments of example 1 and example 2, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 2 are all 100% at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 2 are 50%, 42% and 65%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 2 is 62, 63 and 72 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 2 is 45 percent, 38 percent and 45 percent; it can thus be seen that the core particles prepared by the present invention have good activity but poor resistance to poisoning.
(2) Through the experiments of example 1 and example 3, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 3 are 85%, 86% and 100% at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 3 are 80%, 85% and 100%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 3 is 95, 91 and 100 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 3 is 85, 85 and 100 percent; therefore, no graphene oxide exists on the surface of the core particles of the catalyst, and no CeO exists in the wrapping layer2The activity of the catalyst towards contaminants is reduced.
(3) Through the experiments of example 1 and example 4, it can be found that the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs of example 4 are all 100% at 175 DEG CThe basic activity of CO is respectively 25%, 15% and 30%; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 4 are 20%, 18% and 28%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 4 is 50, 35 and 48 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 4 is 40, 30 and 43 percent; therefore, the catalyst does not contain core particles and graphene oxide, and the activity of the catalyst is obviously reduced.
(4) Through the experiments of example 1 and example 5, the basic activities of VOCs, PCDD/Fs and CO of example 1 are respectively 80%, 85% and 100% at 150 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 5 are respectively 78%, 80% and 100% at 150 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 80%, 82% and 95% at 150 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 5 are 76%, 78% and 100%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98%, 96% and 96% at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 5 is 95%, 91% and 100%; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 5 is 92, 90 and 100 percent; therefore, graphene oxide is not contained in the catalyst, and the basic activity of the catalyst on VOCs and PCDD/Fs is reduced.
(5) Through the experiments of example 1 and example 6, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 6 are 85%, 86% and 90% at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 6 are 82% and 83%,90 percent; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 6 is 96 percent, 96 percent and 96 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98%, 96% and 96% at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 6 is 98%, 98% and 100%; it can be seen that no CeO is added to the catalyst coating2The basic activity of the catalyst is greatly reduced.
(6) Through experiments of example 1 and comparative example 2, it can be found that basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and basic activities of VOCs, PCDD/Fs and CO of comparative example 2 are 95%, 96% and 100% at 175 ℃; catalyst in K2After O poisoning, the VOCs, PCDD/Fs and CO degrading activities of example 1 at 175 ℃ were 95%, 95% and 100%, while the VOCs, PCDD/Fs and CO degrading activities of comparative example 2 were 95%, 95% and 100%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in comparative example 2 is 84, 84 and 84 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in comparative example 2 is 95, 91 and 100 percent; it can be seen that no TiO is added to the catalyst coating2The anti-activity is reduced, and the water resistance is obviously reduced.
(7) Through experiments of example 1 and comparative example 3, it can be found that at 175 ℃, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100%, and at 175 ℃, the basic activities of VOCs, PCDD/Fs and CO of comparative example 3 are all 100%; catalyst in K2After O poisoning, the VOCs, PCDD/Fs and CO degrading activities of example 1 at 175 ℃ are 95%, 95% and 100%, while the VOCs, PCDD/Fs and CO degrading activities of comparative example 3 are 55%, 60% and 80%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in comparative example 3 is 96, 96 and 100 percent; in the sulfur resistance test, the VOCs, PCDD/Fs and CO activities of example 1 were 98, 96 and 96% at 4.5h, while the comparative examplesThe corresponding activities of the VOCs, PCDD/Fs and CO of example 3 are 95%, 95% and 100%; it can be seen that SiO was not added to the catalyst2The anti-alkali poisoning performance of the catalyst is greatly reduced.
The invention is prepared by mixing perovskite CeMnO3The composite oxide particles are used as the catalyst core, and the anti-poisoning substance is coated on the outer layer of the core, thereby avoiding CeMnO3Composite oxide and SO2、H2O、K2And due to direct contact of toxic substances such as O and the like, the prepared catalyst has good resistance to various toxic substances.
The invention leads the SiO coated outside to be coated by changing the thermodynamic condition2With TiO2The crystal transformation is generated, so that a net structure is generated on the catalyst wrapping layer, the pollutants in the flue gas have better contact with the anti-poisoning substances, the pollutants are prevented from entering the inner core of the catalyst, and the anti-poisoning performance of the catalyst is improved. By thermodynamic calculation, externally wrapped SiO2At 573 ℃, a phase transition of beta quartz → alpha quartz occurs, and the process is SiO2Volume expansion occurs with an expansion rate of about 0.82%, while the outer coating of TiO2At 600 ℃ an anatase → rutile phase transition occurs, a process which TiO2The density of the crystal form is increased, the volume is shrunk, the two phase changes can occur simultaneously at the temperature adopted by the invention, and a complex reticular pore canal can be formed on the wrapping layer, which is beneficial to the contact of poisoning substances and anti-poisoning substances.
The invention passes through SiO in the wrapping layer2With TiO2Realize water resistance, sulfur resistance and alkali poisoning resistance. TiO 22With SiO2Hydroxylation easily occurs in the presence of water, and the Ti-O structure is converted into Ti-OH, the Si-O structure is converted into Si-OH, and in addition, TiO2The specific surface area is large, and the coating layer is easy to combine with water in gas, so that the coating layer structure has good water resistance, and-H in Ti-OH and Si-OH is easy to replace alkali metal, so that the Ti-OH and the Si-OH are converted into Ti-O-K and Si-O-K, wherein the Si-OH structure has strong capability of replacing alkali metal elements, and good alkali metal resistance can be realized. SiO 22Belongs to acidic oxides, which are used for SO in mixed gas2With exclusive actionWith, SO2The adsorption property of the coating layer is poor, and the product contains H in the catalytic reaction process2O, hydroxylates Ti-O and Si-O, a process with SO2Adsorption process, having a competitive relationship, in SiO2Rejection and H2In competition for O, SO2Difficult to enter the core of the catalyst and has better sulfur resistance in the macroscopic view.
The invention enhances pollutant adsorption by enhancing chemical adsorption and physical adsorption. Perovskite type CeMnO3The composite oxide has small specific surface area and poor pollutant adsorption, and is prepared by perovskite CeMnO3The composite oxide particle core and the graphene oxide are ground to enable the graphene oxide to be tightly combined with the particle core, large PI bonds are arranged in the graphene oxide distributed on the surface of the particle core, the chemical adsorption effect of the composite oxide core on organic pollutants VOCs and PCDD/Fs can be enhanced, and meanwhile, TiO is wrapped on the outer layer of the core2So that the specific surface area of the catalyst is greatly increased, and the pollutant adsorption is further improved.
The invention enhances the oxidation performance of the catalyst to pollutants through a surface active oxygen transfer channel. Catalytic oxidation of pollutants is a non-closed cyclic process requiring constant consumption of oxygen, CeMnO3The composite oxide can oxidize pollutants by consuming oxygen in crystal lattices or absorbing oxygen on the surfaces of the consumed crystals, but the gaseous oxygen in the gas flow is difficult to supplement the consumed oxygen for the composite oxide due to a certain wrapping effect on particle cores. In the invention through CeO2And an oxygen transfer channel is constructed, and the oxygen supply of the composite oxide is enhanced. CeO in the wrapping layer2And CeMnO3CeO in composite oxides2Can be connected with the O in the gas through a Ce-O-Ce structure2Can be fully contacted with O2Converted into surface adsorbed oxygen (O) with high activity2 2-、O-、O2-) Oxygen ions passing through CeO2The lattice can be transferred to CeMnO from the outside3The composite oxide core participates in catalytic reaction, and oxygen ions introduced through the oxygen transfer channel have stronger reactivity.
Example 7
The experimental procedure of this comparative example was the same as example 1 except that: and (4) roasting the catalyst in the second step at the roasting temperature of 550 ℃. The results are reported in Table 10.
Watch 10
Figure BDA0003327453130000161
Example 8
The experimental procedure of this comparative example was the same as example 1 except that: and in the second step (4), when the catalyst is roasted, the roasting temperature is 590 ℃. The results are reported in Table 11.
TABLE 11
Figure BDA0003327453130000162
Figure BDA0003327453130000171
Example 9
The experimental procedure of this comparative example was the same as example 1 except that: and (4) roasting the catalyst in the second step at 800 ℃. The results are reported in table 12.
TABLE 12
Figure BDA0003327453130000172
Figure BDA0003327453130000181
Example 10
The experimental procedure of this comparative example was the same as example 1 except that: and in the step two, when the catalyst in the step (4) is roasted, the roasting time is 4 hours. The results are reported in Table 13.
Watch 13
Figure BDA0003327453130000182
Example 11
The experimental procedure of this example is the same as example 1, except that: in the second step (1), when the mixed solution A was prepared, the mass of the added modified powder was 25g, and the results of the experiment are shown in Table 14.
TABLE 14
Figure BDA0003327453130000183
Figure BDA0003327453130000191
Example 12
The experimental procedure of this example is the same as example 1, except that: in the second step (1), when the mixed solution A was prepared, the mass of the added modified powder was 100g, and the results of the experiment are shown in Table 15.
Watch 15
Figure BDA0003327453130000192
Figure BDA0003327453130000201
Example 13
The experimental procedure of this example is the same as example 1, except that: when the powder is prepared in the step (3), the powder particles are 200-300 meshes, and the experimental results are recorded in the table 16.
TABLE 16
Figure BDA0003327453130000202
(1) By implementingThe experiments of example 1 and example 7 show that the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of comparative example 7 are 84%, 85% and 88% at 175 ℃; catalyst in K2After O poisoning, the VOCs, PCDD/Fs and CO degrading activities of example 1 at 175 ℃ are 95%, 95% and 100%, while the VOCs, PCDD/Fs and CO degrading activities of comparative example 7 are 83%, 83% and 86%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in comparative example 7 is 92, 98 and 100 percent; in the sulfur resistance test, the activity of VOCs, PCDD/Fs and CO in example 1 is 92, 96 and 100 percent at 4.5h, while the activity of VOCs, PCDD/Fs and CO in comparative example 7 is 90, 93 and 93 percent; it can be seen that the firing temperature is lower than SiO2With TiO2Crystal transformation temperature, SiO2Not expanded, TiO2The shrinkage is not generated, which is not beneficial to the formation of the pore channels of the wrapping layer and leads to the reduction of the activity of the catalyst.
(2) Through the experiments of example 1 and example 8, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 8 are respectively 88%, 88% and 89% at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 8 are 85%, 86% and 88%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 8 is 91, 90 and 95 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 8 is 90, 93 and 99 percent; it can be seen that the firing temperature is higher than SiO2Phase transition temperature lower than TiO2The phase transition temperature and the incomplete formation of the pore canal of the wrapping layer lead to the reduction of the activity of the catalyst.
(3) Through experiments of example 1 and example 9, it can be found that the VOCs, PCDD/Fs, CO basis of example 1 is at 175 deg.CThe activity is 100 percent, and the basic activity of the VOCs, PCDD/Fs and CO in example 9 is 100 percent at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 9 are 88%, 95% and 98%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 9 is 94, 93 and 95 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 9 is 85, 85 and 95 percent; it can be seen that the firing temperature exceeds SiO2Phase transition temperature and TiO2The phase transition temperature is about 200 ℃, and the pore canal size of the coating layer is too large, so that the catalytic poisoning resistance is reduced.
(4) Through the experiments of example 1 and example 10, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 10 are all 100% at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 10 are 95%, 96% and 96%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 10 is 92, 91 and 92 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 10 is 92, 91 and 92 percent; it can be seen that the calcination time is twice that of example 1, the crystal growth time of the wrapping layer is sufficient, and the sizes of the crystal pore channels are too large, so that the catalytic poisoning resistance is reduced.
(5) Through the experiments of example 1 and example 11, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 11 are 95%, 98% and 100% at 175 ℃; catalyst in K2After O poisoning, example 1 was run at 175 deg.CThe degradation activity of VOCs, PCDD/Fs and CO is 95%, 95% and 100%, while that of the VOCs, PCDD/Fs and CO in example 11 is 93%, 96% and 100%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 11 is 95, 100 and 100 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 11 is 90, 90 and 95 percent; from this, it can be seen that when the amount of the core particles added was 50% of that of example 1, the catalyst activity was lowered.
(6) Through the experiments of example 1 and example 12, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 12 are all 100% at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 12 are 89%, 92% and 98%; in a water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 95, 99 and 100 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 12 is 89, 89 and 96 percent; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 12 is 84, 85 and 91 percent; it can be seen that when the amount of the core particles added is 200% of that of example 1, the coating layer is thinner than the core particles, and the catalyst poisoning resistance is remarkably lowered.
(7) Through the experiments of example 1 and example 13, the basic activities of VOCs, PCDD/Fs and CO of example 1 are all 100% at 175 ℃, and the basic activities of VOCs, PCDD/Fs and CO of example 12 are all 100% at 175 ℃; catalyst in K2After O poisoning, the degradation activities of VOCs, PCDD/Fs and CO in example 1 are 95%, 95% and 100% at 175 ℃, while the degradation activities of VOCs, PCDD/Fs and CO in example 12 are 88%, 90% and 98%; in the water-resistant experiment, the activity of VOCs, PCDD/Fs and CO in example 1 was 95, 99 and 100% at 4.5h, while that of VOCs, PCDD/Fs in example 12,The corresponding activities of CO are 86%, 86% and 96%; in the sulfur resistance experiment, the activity of VOCs, PCDD/Fs and CO in example 1 is 98, 96 and 96 percent at 4.5h, while the corresponding activity of VOCs, PCDD/Fs and CO in example 12 is 84, 85 and 91 percent; it can be seen that, when the size of the added amount of the core particles is between 200 and 300 meshes, the particle size is larger than that of the example 1, the coating layer is thinner than the core particles, and the anti-poisoning performance of the catalyst is obviously reduced.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.

Claims (10)

1. A layered particulate catalyst resistant to poisoning, characterized in that the catalyst particles (100) comprise a catalyst core (110) and a coating layer (120); wherein the catalyst core (110) comprises a catalytically active component (111), and pores (122) are formed in the coating layer (120), and the catalytically active component (111) in the catalyst core (110) is communicated to the outside of the catalyst particles (100) through the pores (122).
2. A poison-resistant layered particulate catalyst according to claim 1, characterised in that the catalytically active component (111) of the catalyst core (110) is a perovskite type catalytically active component.
3. The poison-resistant layered particulate catalyst of claim 2 wherein the titania-type catalytically active component is a perovskite-type oxide of Ce with Mn and O.
4. The poison-resistant layered particulate catalyst of claim 3 wherein the perovskite oxide of Ce with Mn and O is a perovskite oxide formed by the reaction of cerium nitrate with manganese acetate.
5. The poison-resistant layered granular catalyst according to claim 3, wherein the molar ratio of Ce to Mn in the catalytically active component (111) is 1 (0.9-1.1).
6. A layered particulate catalyst as claimed in claim 1, characterised in that the coating layer (120) comprises a titanium-containing oxide (123) and a silicon-containing oxide (124).
7. A layered particulate catalyst as claimed in claim 5, characterised in that the pores (122) are formed in the TiO2With SiO2Between the grains.
8. A layered particulate catalyst as claimed in claim 1, characterised in that the particle size of the catalyst core (110) is not greater than 400 mesh.
9. A layered particulate catalyst resistant to toxicity according to claim 1, characterized in that the catalyst particles (100) have a particle size of 40 to 60 mesh.
10. A method for preparing an antitoxic layered granular catalyst, characterized in that the layered granular catalyst is the layered granular catalyst according to any one of claims 1 to 9, and in the preparation process, a granular catalyst core (110) containing a catalytic active component (111) is prepared, then the catalyst core (110) is placed in a system containing a component which can form pores (122) after being calcined, and the catalyst is calcined, dried and ground to obtain the layered granular catalyst.
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