CN110605122A - Low-temperature flue gas denitration catalyst and preparation method and application thereof - Google Patents
Low-temperature flue gas denitration catalyst and preparation method and application thereof Download PDFInfo
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
The invention relates to the field of flue gas denitration, and discloses a low-temperature flue gas denitration catalyst, and a preparation method and application thereof. The catalyst comprises a honeycomb ceramic carrier, and an inert coating and an active coating which are sequentially coated on the carrier; the inert coating contains Ti oxide; the active coating contains Fe oxide and Mn oxide. The method comprises the following steps: mixing tetrabutyl titanate with absolute ethyl alcohol to obtain a solution A; mixing water, acetic acid and absolute ethyl alcohol to obtain a solution B; adding the solution A into the solution B to obtain an inert coating liquid; coating the carrier by using an inert coating liquid, and then drying and roasting to obtain the carrier coated with the inert coating; mixing Mn salt, Fe salt, oxalic acid and water to obtain active coating liquid; the carrier coated with the inert coating layer is coated with an active coating layer coating liquid, and then dried and calcined to obtain the catalyst. The ferromanganese low-temperature flue gas denitration honeycomb catalyst disclosed by the invention has excellent denitration performance in the range of 120-300 ℃.
Description
Technical Field
The invention relates to the field of flue gas denitration, and particularly relates to a low-temperature flue gas denitration catalyst and a preparation method and application thereof.
Background
Nitrogen oxides (NOx) are an important atmospheric pollutant, and the main sources thereof are combustion of fossil fuels, emission of exhaust gas from industrial boilers, and emission of exhaust gas from mobile sources such as diesel engines. Acid rain and chemical smog caused by NOx pose an increasing threat to human life. The new emission-limiting standard greatly limits SO2NOx emission limits, SO in industrial boiler combustion exhaust2The concentration is less than 50mg/m3NOx concentration less than 100mg/m3The concentration of NOx discharged in the key area is particularly required to be less than 50mg/m3The treatment of NOx has reached an ever-slow stage.
At present, the catalyst system widely used in industry is V2O5-WO3/TiO2The catalyst system is widely applied to a denitration system of a high-temperature and high-dust arrangement mode of a coal-fired power plant, and the activity temperature window is usually between 350 ℃ and 450 ℃. The temperature of the tail gas discharged by the existing industrial boilers, cement kilns, glass kilns, coking furnaces and the like is often lower than 300 ℃ and even lower than 200 ℃, so that the traditional V is ensured2O5-WO3/TiO2The catalyst system does not function at the exhaust gas temperature; meanwhile, the denitration catalytic system is arranged in a low-temperature and low-dust mode, so that energy consumption is saved, and the service life of the catalyst is prolonged. Therefore, the development of the catalyst with good denitration efficiency in the medium-low temperature wide temperature range (120-300 ℃) is of great significance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides a low-temperature flue gas denitration catalyst, a preparation method and application thereof, wherein the catalyst has good denitration efficiency at the temperature of 120-300 ℃.
In order to achieve the above object, the present invention provides a low-temperature flue gas denitration catalyst, which comprises a honeycomb ceramic carrier, and an inert coating layer and an active coating layer sequentially coated on the carrier;
wherein the inert coating contains an oxide of Ti; the active coating contains an oxide of Fe and an oxide of Mn.
Preferably, the honeycomb ceramic carrier is cordierite.
Preferably, the inert coating further comprises an oxide of Ce.
The second aspect of the present invention also provides a process for preparing a catalyst as described above, which comprises:
(1) mixing tetrabutyl titanate with absolute ethyl alcohol to obtain a solution A; mixing water, acetic acid and absolute ethyl alcohol to obtain a solution B; adding the solution A into the solution B to obtain an inert coating liquid;
(2) carrying out first coating on the honeycomb ceramic carrier by using the inert coating liquid to obtain a honeycomb ceramic carrier coated with an inert coating;
(3) mixing Mn salt, Fe salt, oxalic acid and water to obtain active coating liquid;
(4) and secondly coating the honeycomb ceramic carrier coated with the inert coating by using the active coating liquid to obtain the honeycomb ceramic carrier coated with the inert coating and the active coating.
Preferably, the method further comprises a pretreatment step of impregnating the honeycomb ceramic support with a nitric acid solution before coating the honeycomb ceramic support.
Preferably, in the step (1), a Ce salt is added into the solution B.
Preferably, the first coating and the second coating are both dip coatings.
The third aspect of the invention also provides the catalyst and the application of the catalyst prepared by the method in a flue gas denitration system.
Compared with the prior art, the invention has the following beneficial effects:
(1) the components selected in the process are low-toxicity and environment-friendly products, and the process has low cost and good economic and environmental benefits.
(2) The ferromanganese low-temperature flue gas denitration honeycomb catalyst disclosed by the invention has excellent denitration performance in the range of 120-300 ℃, has a wider active temperature window, can be suitable for different flue gas conditions, and has a wider application prospect.
(3) The ferromanganese low-temperature flue gas denitration honeycomb catalyst disclosed by the invention is simple in forming process and has a certain industrial application value.
Drawings
Fig. 1 is a graph showing the sulfur resistance of the flue gas denitration catalyst prepared in example 4.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a low-temperature flue gas denitration catalyst, which comprises a honeycomb ceramic carrier, and an inert coating and an active coating which are sequentially coated on the carrier;
wherein the inert coating contains an oxide of Ti (preferably TiO)2) (ii) a The active coating contains an oxide of Fe (preferably Fe)2O3) And oxides of Mn (preferably MnO)2)。
The term "inert coating" refers to a coating that does not substantially participate in the denitration reaction in the flue gas denitration process. The term "active coating" refers to a coating that is primarily involved in the denitration reaction in a flue gas denitration process.
The inventor of the invention finds in research that the honeycomb ceramics are used as the carrier of the flue gas denitration catalystOn one hand, the preparation process can be effectively simplified, and on the other hand, V is not contained2O5The denitration catalyst as one of the active components can show higher denitration efficiency and sulfur poisoning resistance at low temperature (lower than 300 ℃), and on the other hand, toxicity V is reduced2O5The secondary pollution caused by the method has positive significance in controlling the environmental pollution and the secondary pollution of the catalyst.
Further, the inventors of the present invention have also found in their studies that the denitration efficiency and the sulfur poisoning resistance of the catalyst at low temperatures can be further improved by first coating an inert coating layer containing an oxide of Ti on, for example, a carrier and then coating an active coating layer containing an oxide of Fe and an oxide of Mn thereon.
According to the present invention, the honeycomb ceramic support may be various existing honeycomb ceramic supports, for example, the honeycomb ceramic support may be, but not limited to, cordierite, mullite, aluminum titanate, activated carbon, silicon carbide, activated alumina, zirconia, silicon nitride, cordierite-mullite composite matrix, and cordierite-aluminum titanate composite matrix. According to a preferred embodiment of the present invention, the honeycomb ceramic substrate is cordierite. Wherein cordierite is a silicate mineral, and may also contain Na, K, Ca, Fe, Mn, and H2O。
According to the invention, the contents of the support, inert coating and active coating in the catalyst can be varied within wide limits. According to a preferred embodiment of the present invention, the carrier is present in an amount of 75 to 91 wt% (e.g., may be 75 wt%, 77 wt%, 79 wt%, 81 wt%, 83 wt%, 85 wt%, 87 wt%, 89 wt%, 91 wt%), the inert coating is present in an amount of 5 to 13 wt% (e.g., 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%), and the active coating is present in an amount of 4 to 12 wt% (4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%), based on the total weight of the catalyst. In this preferable range, the low-temperature denitration efficiency of the catalyst can be further improved.
According to the present invention, in the active coating layer, the content of the oxide of Fe and the content of the oxide of Mn may be set according to the contents of the respective components in the denitration catalyst of the related art. According to a preferred embodiment of the present invention, in the active coating layer, a molar ratio of an oxide of Fe in terms of Fe element to an oxide of Mn in terms of Mn element is 1: 0.5 to 1.8, preferably 1:1-1.5, e.g., 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1: 1.5.
In the process of research, the inventors of the present invention also found that by adding an oxide of a lanthanide to the inert coating, on one hand, the bonding strength between the active coating and the inert coating can be effectively improved, and on the other hand, the low-temperature denitration efficiency of the catalyst can be further improved.
The content of the oxide of the lanthanide in the inert coating can be selected within wide limits, preferably not more than 8% by weight, preferably not more than 5% by weight, calculated as the lanthanide, based on the total weight of the inert coating.
According to a preferred embodiment of the invention, the oxide of the lanthanide is at least one of an oxide of lanthanum, an oxide of cerium and an oxide of praseodymium, most preferably an oxide of cerium (preferably CeO)2)。
In a second aspect, the present invention provides a process for the preparation of a catalyst as described above, which process comprises:
(1) mixing tetrabutyl titanate with absolute ethyl alcohol to obtain a solution A; mixing water, acetic acid and absolute ethyl alcohol to obtain a solution B; adding the solution A into the solution B to obtain an inert coating liquid;
(2) carrying out first coating on the honeycomb ceramic carrier by using the inert coating liquid to obtain a honeycomb ceramic carrier coated with an inert coating;
(3) mixing Mn salt, Fe salt, oxalic acid and water to obtain active coating liquid;
(4) and secondly coating the honeycomb ceramic carrier coated with the inert coating by using the active coating liquid to obtain the honeycomb ceramic carrier coated with the inert coating and the active coating.
According to the invention, in the step (1), the volume ratio of tetrabutyl titanate to absolute ethyl alcohol can be 1: 1-1.5; the volume ratio of water, acetic acid and absolute ethyl alcohol can be 1:2-2.5: 5-6.
According to the invention, the solution A is added into the solution B preferably slowly, for example, by adopting a dropping method, so that the obtained inert coating liquid has more stable properties, and the coating of the carrier is more facilitated.
According to the invention, where the inert coating of the catalyst preferably contains an oxide of a lanthanide as described above, the process of step (1) also comprises the addition of a salt of a lanthanide to said solution B. Preferably, the lanthanide salt is added in an amount such that its concentration in solution B is not higher than 10% by weight, more preferably not higher than 7.5% by weight.
Preferably, the salt formed by the lanthanide is at least one of a lanthanum salt, a cerium salt and a praseodymium salt.
Preferably, the lanthanum salt is lanthanum nitrate.
Preferably, the cerium salt is cerium nitrate and/or cerium sulfate.
Preferably, the praseodymium salt is praseodymium nitrate.
According to the present invention, in order to further improve the low-temperature denitration efficiency and the sulfur poisoning resistance of the prepared catalyst, the method of the present invention further comprises a step of pretreating the support, and the pretreatment step may comprise: and (3) impregnating the honeycomb ceramic carrier in an acid solution, and then carrying out third drying on the impregnated honeycomb ceramic carrier.
Preferably, the acid solution is a nitric acid solution, a hydrochloric acid solution or a sulfuric acid solution, and most preferably, a nitric acid solution.
Preferably, the time of the impregnation is 0.5 to 2 hours.
Preferably, the third drying conditions include: the temperature is 80-120 ℃ and the time is 4-6 hours.
According to the present invention, in step (2), the inert coating layer coating liquid is preferably applied on the support in an amount such that the content of the inert coating layer in the catalyst is 5 to 13% by weight, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% by weight, based on the total weight of the catalyst.
According to the present invention, the first coating method may adopt the existing coating method, such as but not limited to dip coating, brush coating, spray coating, electrophoretic coating and coprecipitation coating, and the present invention is preferably dip coating.
Wherein the first coating may be divided into a plurality of times.
According to the present invention, preferably, the step (2) further includes the steps of sequentially performing the first drying and the first firing on the honeycomb ceramic support coated with the inert coating layer.
Wherein the conditions of the first drying may include: the temperature is 80-120 ℃ and the time is 10-12 hours.
Wherein the conditions of the first firing may include: 500 ℃ and 600 ℃ for 4-5 hours.
According to the present invention, in the step (3), in the active coating layer coating solution, the concentrations of the Mn salt, the Fe salt and the oxalic acid may be referred to the concentrations of the Mn salt, the Fe salt and the oxalic acid in the active impregnation solution when the denitration catalyst is prepared according to the prior art. Preferably, in the active coating layer coating liquid of the present invention, the content of the Mn salt is 1.5 to 2.6% by weight, preferably 1.8 to 2.4% by weight, the content of the iron salt is 1 to 1.8% by weight, preferably 1.2 to 1.6% by weight, and the content of the oxalic acid is 5 to 10% by weight, preferably 7 to 9% by weight, in terms of the Mn element.
According to the present invention, preferably, the Mn salt is at least one of manganese nitrate, manganese acetate, and manganese sulfate, and more preferably, manganese nitrate.
According to the present invention, preferably, the Fe salt is at least one of iron nitrate, iron acetate and iron sulfate, and more preferably, iron nitrate.
According to the present invention, preferably, the preparation method of the active ingredient coating liquid includes: dissolving oxalic acid solid in water, then adding iron salt to obtain an oxalic acid solution of the iron salt, fully stirring, adding manganese salt, and fully stirring to obtain the active component coating solution. The amount of the deionized water used in the present invention is not particularly limited, as long as the oxalic acid and the added salt solid can be sufficiently dissolved.
In the invention, researchers of the invention find that metal salt, particularly Fe salt, is easy to hydrolyze in the impregnation process, which has great influence on the uniform distribution of active components on the carrier, therefore, in the invention, oxalic acid is introduced as a complexing agent to prepare the oxalic acid double salt precursor of metal, the hydrolysis of metal ions in the impregnation process is greatly inhibited, and the dispersion degree of the active components on the surface of the carrier is improved.
According to the present invention, in step (4), the amount of the active coating layer coating liquid applied to the inert coating layer-coated honeycomb ceramic support is preferably such that the active coating layer is contained in the catalyst in an amount of 4 to 12 wt%, for example, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, based on the total weight of the catalyst.
According to the present invention, the second coating method may adopt the existing coating method, such as but not limited to dip coating, brush coating, spray coating, electrophoretic coating and coprecipitation coating, and the present invention is preferably dip coating.
Wherein the second coating may be divided into a plurality of times.
According to the present invention, preferably, the step (4) further includes the steps of sequentially performing a second drying and a second firing on the honeycomb ceramic support coated with the inert coating layer and the active coating layer.
Wherein the conditions of the second drying may include: the temperature is 80-120 ℃, and the time is 10-12 hours;
wherein the conditions of the second firing may include: 400 ℃ and 500 ℃ for 4-5 hours.
In a third aspect, the invention provides the catalyst and the application of the catalyst prepared by the method in a flue gas denitration system.
The catalyst provided by the invention can be used for efficiently denitrating in a flue gas environment with the temperature of lower than 300 ℃, and the catalyst provided by the invention is not only suitable for flue gas with the temperature of lower than 300 ℃, but also has high denitrating activity for flue gas with the temperature of above 300 ℃.
According to the invention, the flue gas denitration system can be any flue gas needing denitration, in particular to flue gas with the temperature lower than 300 ℃, for example, a low-temperature flue gas denitration system for industrial boiler flue gas denitration, cement kiln flue gas denitration, coke oven flue gas denitration and the like, or a flue gas denitration system arranged in a low-temperature and low-dust manner.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
method for measuring denitration efficiency (DeNOx (%)) of catalyst:
the catalyst prepared as follows was subjected to catalyst denitration performance evaluation in a micro fixed bed reactor under laboratory simulated flue gas conditions. The simulated smoke conditions are as follows: NH (NH)3Is reducing gas, NO volume fraction is 0.05%, ammonia nitrogen ratio is 1:1, O2Volume fraction of 5%, carrier gas is N2Airspeed of 6000h-1. The gas composition was analyzed using a smoke analyser, model German Testo-350. The test temperatures were 120 deg.C, 140 deg.C, 160 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, 240 deg.C, 260 deg.C, 280 deg.C, and 300 deg.C, respectively.
Example 1
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
(1) And (3) soaking the cut cordierite carrier in a 2 wt% nitric acid solution for 1h, washing the cordierite carrier to be neutral by deionized water, drying the cordierite carrier at 120 ℃ for 5h, and weighing the cordierite carrier for later use.
(2) Measuring 17ml of tetrabutyl titanate and 25ml of absolute ethyl alcohol to prepare solution A; weighing 5ml of deionized water, 12ml of acetic acid and 30ml of absolute ethyl alcohol, and fully stirring to obtain a mixed solution B; and slowly dripping the solution A into the solution B to obtain a clear and transparent coating solution.
(3) And (3) placing the carrier treated in the step (1) into a coating solution for dip coating for 5h, drying at 110 ℃ for 12h, calcining at 550 ℃ for 5h to obtain a carrier loaded with an inert coating, and repeating the step (2) and the step (3) once to obtain the carrier coated with the inert coating for the second time.
(4) Dissolving oxalic acid solid in water, then adding ferric nitrate to obtain an oxalic acid solution of ferric salt, fully stirring, adding manganese nitrate, and fully stirring to obtain the active component coating solution, wherein the content of manganese is 1.8 wt%, the content of iron is 1.2 wt%, and the content of oxalic acid is 8 wt%.
(5) And (4) placing the carrier coated with the inert coating obtained in the step (4) into an active component coating solution for dip coating for 5 hours, drying for 12 hours at 110 ℃, and calcining for 5 hours at 400 ℃ to obtain the ferromanganese low-temperature flue gas denitration honeycomb catalyst.
Wherein, the content of the carrier is 81.27 wt%, the content of the inert coating layer is 12.5 wt%, and the content of the active component is 6.23 wt% based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe calculated as Fe element to the oxide of Mn calculated as Mn element is 1: 1.5.
the denitration efficiency at each temperature of the catalyst is shown in table 1.
Example 2
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
(1) And (3) soaking the cut cordierite carrier in a 2 wt% nitric acid solution for 0.5h, washing the cordierite carrier to be neutral by deionized water, drying the cordierite carrier at 80 ℃ for 6h, and weighing the cordierite carrier for later use.
(2) Measuring 17ml of tetrabutyl titanate and 17ml of absolute ethyl alcohol to prepare solution A; weighing 5ml of deionized water, 10ml of acetic acid and 25ml of absolute ethyl alcohol, and fully stirring to obtain a mixed solution B; and slowly dripping the solution A into the solution B to obtain a clear and transparent coating solution.
(3) And (3) placing the carrier treated in the step (1) into a coating solution for dip coating for 5h, drying at 120 ℃ for 10h, calcining at 500 ℃ for 4.5h to obtain the carrier loaded with the inert coating, and repeating the step (2) and the step (3) twice to obtain the carrier coated with the inert coating for three times.
(4) Dissolving oxalic acid solid in water, then adding ferric nitrate to obtain an oxalic acid solution of ferric salt, fully stirring, adding manganese nitrate, and fully stirring to obtain the active component coating solution, wherein the content of manganese is 2.0 wt%, the content of iron is 1.4 wt%, and the content of oxalic acid is 7 wt%.
(5) And (3) placing the carrier coated with the inert coating obtained in the step (4) into an active component coating solution for dip coating for 5 hours, drying for 10 hours at 80 ℃, and calcining for 4.5 hours at 450 ℃ to obtain the ferromanganese low-temperature flue gas denitration honeycomb catalyst.
Wherein, the content of the carrier is 83.44 wt%, the content of the inert coating layer is 10.33 wt%, and the content of the active component is 6.36 wt% based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe calculated as Fe element to the oxide of Mn calculated as Mn element is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 3
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
(1) And (3) soaking the cut cordierite carrier in a 2 wt% nitric acid solution for 2h, washing the cordierite carrier to be neutral by deionized water, drying the cordierite carrier at 100 ℃ for 4h, and weighing the cordierite carrier for later use.
(2) Measuring 17ml of tetrabutyl titanate and 20ml of absolute ethyl alcohol to prepare solution A; weighing 5ml of deionized water, 11ml of acetic acid and 28ml of absolute ethyl alcohol, and fully stirring to obtain a mixed solution B; and slowly dripping the solution A into the solution B to obtain a clear and transparent coating solution.
(3) And (3) placing the carrier treated in the step (1) into a coating solution for dip coating for 5h, drying at 80 ℃ for 11h, calcining at 600 ℃ for 4h to obtain a carrier loaded with an inert coating, and repeating the step (2) and the step (3) once to obtain the carrier coated with the inert coating for the second time.
(4) Dissolving oxalic acid solid in water, then adding ferric nitrate to obtain an oxalic acid solution of ferric salt, fully stirring, adding manganese nitrate, and fully stirring to obtain the active component coating solution, wherein the content of manganese is 2.4 wt%, the content of iron is 1.6 wt%, and the content of oxalic acid is 9 wt%.
(5) And (3) placing the carrier coated with the inert coating obtained in the step (4) into an active component coating solution for dip coating for 5 hours, drying for 11 hours at 120 ℃, and calcining for 4 hours at 500 ℃ to obtain the ferromanganese low-temperature flue gas denitration honeycomb catalyst.
Wherein, the content of the carrier is 82.61 wt%, the content of the inert coating layer is 10.03 wt%, and the content of the active component is 7.36 wt% based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe calculated as Fe element to the oxide of Mn calculated as Mn element is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 4
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that 2g of cerium nitrate was further added to the preparation of the solution B in the step (2).
Wherein the content of the carrier is 81.49 wt%, the content of the inert coating layer is 10.7 wt%, and the content of the active component is 7.81 wt%, based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe, calculated as Fe element, to the oxide of Mn, calculated as Mn element, is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 5
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that 3g of cerium nitrate was further added to the preparation of the solution a in the step (2).
Wherein, the content of the carrier is 82.31 wt%, the content of the inert coating layer is 10.2 wt%, and the content of the active component is 7.49 wt% based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe calculated as Fe element to the oxide of Mn calculated as Mn element is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 6
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that 2g of lanthanum nitrate was further added to the preparation of the solution B in the step (2).
Wherein the content of the carrier is 82.19 wt%, the content of the inert coating layer is 10.27 wt%, and the content of the active component is 7.54 wt%, based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe, calculated as Fe element, to the oxide of Mn, calculated as Mn element, is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 7
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in accordance with the method of example 3, except that the cordierite pretreatment step of step (1) was not included.
Wherein the content of the carrier is 85.37 wt%, the content of the inert coating layer is 9.27 wt%, and the content of the active component is 5.36 wt%, based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe, calculated as Fe element, to the oxide of Mn, calculated as Mn element, is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 8
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that cordierite was pretreated with 2% by weight of hydrochloric acid in the step (1).
Wherein the content of the carrier is 84.75 wt%, the content of the inert coating layer is 9.58 wt%, and the content of the active component is 5.67 wt%, based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of an oxide of Fe, calculated as an Fe element, to an oxide of Mn, calculated as an Mn element, is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 9
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in accordance with the method of example 3, except that in step (1), cordierite was replaced with mullite.
Wherein, the content of the carrier is 85.9 wt%, the content of the inert coating layer is 9.02 wt%, and the content of the active component is 5.08 wt%, based on the whole mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe calculated as Fe element to the oxide of Mn calculated as Mn element is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Example 10
This example is used to illustrate the low-temperature flue gas denitration catalyst provided by the present invention and the preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that in steps (3) and (5), the coating was a coprecipitation coating.
Wherein the content of the carrier is 83.03 wt%, the content of the inert coating layer is 12.6 wt%, and the content of the active component is 4.37 wt%, based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of the oxide of Fe, calculated as Fe element, to the oxide of Mn, calculated as Mn element, is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Comparative example 1
The comparative example is used for explaining a reference low-temperature flue gas denitration catalyst and a preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that the application of the inert coating layer was not included, and the application of the active coating layer was directly carried out.
Wherein the content of the carrier is 99.2 wt% and the content of the active component is 0.8 wt% based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of an oxide of Fe calculated as an Fe element to an oxide of Mn calculated as an Mn element is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
Comparative example 2
The comparative example is used for explaining a reference low-temperature flue gas denitration catalyst and a preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that the inert coating layer coating solution was prepared by directly mixing tetrabutyl titanate, absolute ethyl alcohol, water and acetic acid, with the result that the inert coating layer coating solution could not be prepared.
Comparative example 3
The comparative example is used for explaining a reference low-temperature flue gas denitration catalyst and a preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was carried out in the same manner as in example 3, except that the inert coating layer coating solution was prepared by adding the solution B to the solution a, so that the inert coating layer coating solution could not be prepared.
Comparative example 4
The comparative example is used for explaining a reference low-temperature flue gas denitration catalyst and a preparation method thereof
The preparation of the low-temperature flue gas denitration catalyst was performed in the same manner as in example 3, except that the prepared inert coating layer coating solution and active coating layer coating solution were mixed to prepare a mixed coating solution, and then the support was dip-coated.
Wherein the content of the carrier is 97.3 wt% and the content of the active component is 2.7 wt% based on the entire mass of the catalyst, and in the active coating layer, the molar ratio of an oxide of Fe calculated as an Fe element to an oxide of Mn calculated as an Mn element is 1: 1.5.
the denitration efficiency of the catalyst at each temperature is shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst prepared by the method disclosed by the invention has better denitration efficiency within a wide temperature range of 120-300 ℃, and the denitration efficiency of the catalyst is continuously improved along with the improvement of the content of the loaded active component. The catalyst prepared in the examples 3-6 can maintain almost 100% of denitration efficiency in a low temperature section (120 ℃ C. and 240 ℃ C.), and can maintain more than 97% of denitration efficiency in a wide temperature range of 120 ℃ C. and 300 ℃ C. Furthermore, comparing examples 4-10 with example 3, it can be seen that the effect of adding the lanthanide preferably, the cerium salt more preferably, and the solution B more preferably is superior, and the effect of the catalyst obtained by pretreating the carrier preferably with nitric acid, preferably with cordierite as the carrier, preferably with cordierite coated by impregnation is superior.
Determination of Sulfur poisoning resistance
The sulfur resistance of the catalysts of the examples and comparative examples was evaluated in a mini-fixed bed reactor under laboratory simulated flue gas conditions. The simulated smoke conditions are as follows: NH (NH)3Is reducing gas, NO volume fraction is 0.05%, ammonia nitrogen ratio is 1:1, O2Volume fraction 5%, SO2The concentration is 300mg/m3Or 600mg/m3The carrier gas is N2Airspeed of 6000h-1. The gas composition was analyzed using a smoke analyser, model German Testo-350. The test temperature was 180 ℃.
The results show that at 300mg/m3SO2At concentration, the catalyst of the exampleHas better sulfur resistance, and keeps better denitration efficiency for a longer time, but the catalyst of the comparative example does not have the property. At 600mg/m3SO2The sulfur resistance of the catalyst was reduced at the concentration, and a certain poisoning phenomenon occurred, wherein the test result of the sulfur resistance of the catalyst of example 4 is shown in fig. 1. As the catalyst prepared by the process is mainly applied to a denitration reactor which is industrially arranged behind a desulfurization device, SO is generated under actual conditions2The concentration is far lower than 300mg/m3Therefore, the catalyst prepared by the process has better application prospect in industry.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A low-temperature flue gas denitration catalyst is characterized by comprising a honeycomb ceramic carrier, and an inert coating and an active coating which are sequentially coated on the carrier;
wherein the inert coating contains an oxide of Ti; the active coating contains an oxide of Fe and an oxide of Mn.
2. The catalyst of claim 1, wherein the honeycomb ceramic support is selected from the group consisting of cordierite, mullite, aluminum titanate, activated carbon, silicon carbide, activated alumina, zirconia, silicon nitride, a cordierite-mullite composite matrix, and a cordierite-aluminum titanate composite matrix.
3. The process of claim 1 or 2, wherein the support is present in an amount of 75 to 91 wt.%, the inert coating is present in an amount of 5 to 13 wt.%, and the active coating is present in an amount of 4 to 12 wt.%, based on the total weight of the catalyst; and is
In the active coating layer, the molar ratio of an oxide of Fe in terms of Fe element to an oxide of Mn in terms of Mn element is 1: 0.5-1.8.
4. The catalyst of any one of claims 1-3, wherein the inert coating further comprises an oxide of a lanthanide;
preferably, the content of oxide of lanthanide element calculated as lanthanide element is not higher than 8% by weight, based on the total weight of said inert coating;
preferably, the oxide of the lanthanoid is at least one of an oxide of lanthanum, an oxide of cerium, and an oxide of praseodymium.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, characterized in that it comprises:
(1) mixing tetrabutyl titanate with absolute ethyl alcohol to obtain a solution A; mixing water, acetic acid and absolute ethyl alcohol to obtain a solution B; adding the solution A into the solution B to obtain an inert coating liquid;
(2) carrying out first coating on the honeycomb ceramic carrier by using the inert coating liquid to obtain a honeycomb ceramic carrier coated with an inert coating;
(3) mixing Mn salt, Fe salt, oxalic acid and water to obtain active coating liquid;
(4) and secondly coating the honeycomb ceramic carrier coated with the inert coating by using the active coating liquid to obtain the honeycomb ceramic carrier coated with the inert coating and the active coating.
6. The method of claim 5, wherein prior to coating the honeycomb ceramic support, the method further comprises pretreating the honeycomb ceramic support, the pretreating comprising:
dipping the honeycomb ceramic carrier in acid liquor, and then carrying out third drying on the dipped honeycomb ceramic carrier;
preferably, the third drying conditions include: the temperature is 80-120 ℃ and the time is 4-6 hours.
7. The process according to claim 5 or 6, wherein in step (1), the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 1-1.5; the volume ratio of the water to the acetic acid to the absolute ethyl alcohol is 1:2-2.5: 5-6.
8. The method according to any one of claims 5 to 7, wherein in step (1), further comprising adding a salt of a lanthanide to solution B;
preferably, the lanthanide salt is added in such an amount that its concentration in solution B is not higher than 10% by weight;
preferably, the salt formed by the lanthanide is at least one of lanthanum salt, cerium salt and praseodymium salt;
preferably, the lanthanum salt is lanthanum nitrate; the cerium salt is cerium nitrate and/or cerium sulfate; the praseodymium salt is praseodymium nitrate.
9. The method according to any one of claims 5 to 8, wherein in the step (3), the Mn salt, the Fe salt and the oxalic acid are added in amounts such that, in the active coating liquid, the content of the Mn salt is 1.5 to 2.6% by weight in terms of Mn element, the content of the iron salt is 1 to 1.8% by weight in terms of Fe element, and the content of the oxalic acid is 5 to 10% by weight;
preferably, the Mn salt is at least one of manganese nitrate, manganese acetate and manganese sulfate, and the Fe salt is at least one of iron nitrate, iron acetate and iron sulfate.
10. The method of claim 5, wherein the first and second applications are each independently selected from dip coating, brush coating, spray coating, electrocoat coating, and co-precipitate coating.
11. The method according to claim 5, wherein the step (2) further comprises the steps of sequentially performing a first drying and a first firing on the honeycomb ceramic carrier coated with the inert coating, and the conditions of the first drying comprise: the temperature is 80-120 ℃, and the time is 10-12 hours; the conditions of the first firing include: 500 ℃ and 600 ℃ for 4-5 hours;
preferably, the step (4) further comprises the steps of sequentially performing a second drying and a second firing on the honeycomb ceramic carrier coated with the inert coating layer and the active coating layer, wherein the second drying conditions include: the temperature is 80-120 ℃, and the time is 10-12 hours; the conditions of the second roasting include: 400 ℃ and 500 ℃ for 4-5 hours.
12. Use of the catalyst of any one of claims 1 to 4 and the catalyst prepared by the method of any one of claims 5 to 11 in a flue gas denitration system.
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