CN112275279A - Regeneration method of lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst - Google Patents
Regeneration method of lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 238000011069 regeneration method Methods 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims description 64
- 230000001147 anti-toxic effect Effects 0.000 claims description 32
- 230000002401 inhibitory effect Effects 0.000 claims description 27
- 230000001502 supplementing effect Effects 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 14
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 14
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 4
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 27
- 206010027439 Metal poisoning Diseases 0.000 abstract description 24
- 208000008127 lead poisoning Diseases 0.000 abstract description 24
- 238000005245 sintering Methods 0.000 abstract description 13
- 239000003546 flue gas Substances 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000013589 supplement Substances 0.000 abstract description 3
- 239000000571 coke Substances 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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Abstract
The invention aims to provide a regeneration method of a Mn-Ce carbon-based low-temperature denitration catalyst poisoned by lead components in sintering flue gas, which can simply and efficiently remove lead in the denitration catalyst, simultaneously supplement damaged active components and improve the lead poisoning resistance of the regenerated catalyst. The method is simple and convenient to operate, the denitration rate of the regenerated catalyst can be recovered to a level close to that of a fresh catalyst, and the regeneration effect is obvious.
Description
Technical Field
The invention relates to the field of poisoned catalyst regeneration, in particular to a regeneration method of a Mn-Ce carbon-based catalyst for Selective Catalytic Reduction (SCR) denitration of lead poisoning.
Background
Environmental protection is a difficult problem to be solved urgently in the transformation and upgrading process of the steel industry in China. As a typical high energy consumption, high pollution, resource type industry, the atmospheric pollutant emitted by steel enterprises is SO2、NOxDust, heavy metals and dioxins, and the like, and mainly comes from the sintering process. At present, iron and Steel plant dust and SO2Has become mature, mainly resulting from NO in the sintering processx(more than 50 percent) becomes the most urgent pollutant for treatment in steel enterprises. The national ecological environment department issued comments on promoting the implementation of ultra-low emission in the iron and steel industry and comprehensive treatment scheme of atmospheric pollution of industrial furnaces in 5 and 7 months in 2019 respectively, and documents stipulate the process NO of iron and steel sinteringxEmission limit of 50mg/Nm3. At present, NO is the most part of iron and steel enterprises in ChinaxThe emission of the steel sintering furnace is difficult to meet the strict standard of ultralow emission, and the smoke emission of the steel sintering industry faces unprecedented environmental protection pressure.
Based on this, various scholars aim at NO in steel sintering flue gasxAnd (5) researching emission reduction technology. By taking the successful denitration experience of a large coal-fired power plant and the actual conditions of domestic iron and steel enterprises as reference, the Selective Catalytic Reduction (SCR) denitration technology is high in denitration efficiency because the technical core is a catalyst, is easier to design pertinently aiming at the component characteristics of sintering flue gas, has a wide application prospect, and is considered to be one of the most potential technologies for denitration of sintering flue gas of iron and steel plants. Research shows that the catalyst prepared by the Mn-Ce composite oxide loaded by carbon materials (semi-coke, biomass coke, active coke and the like) has the function of SCR denitration at low temperature (sintering flue gas 100-The performance is excellent.
The main substances causing catalyst poisoning in industrial flue gas include alkali metals (K, Na), alkaline earth metals (Ca), heavy metals (Pb, Hg, Zn), arsenic (As), and the like. The sintering flue gas has complex components, and the associated lead content in many coal types and iron ores in China is high, so that the lead in the sintering flue gas is deposited on the surface of the denitration catalyst to cause the catalyst to be poisoned and inactivated, thereby reducing the denitration efficiency of the catalyst. Lead deposition on the catalyst can cause the chemical state of active components on the surface of the catalyst to be changed, and can neutralize the acidity of Lewis acid sites and Bronsted acid sites of the catalyst, thereby causing the catalyst to be poisoned and deactivated. When the denitration activity is reduced to the extent that the denitration requirement of the sintering plant flue gas cannot be met, the catalyst needs to be replaced, and the replacement cost is high. The method has the advantages that the lead-poisoned and inactivated Mn-Ce carbon-based denitration catalyst is regenerated, the denitration activity of the catalyst can be recovered and even improved, the aim of recycling the inactivated catalyst is fulfilled, and the cost for treating the waste catalyst can be saved. Therefore, the regeneration and utilization of the lead-poisoned Mn-Ce carbon-based denitration catalyst have important economic benefits and application prospects.
In the prior art, dust on the surface of the catalyst is removed by adopting a high-pressure gas blowing and ultrasonic cleaning method, a regenerated solution adopts an acetic acid + triethylene tetramine solution, and the denitration efficiency of the regenerated catalyst reaches 95.70%. According to the method, although lead which causes catalyst deactivation is removed through complexation of triethylene tetramine and PbO, the denitration activity of the catalyst is recovered to a certain extent, and the lost active components V and W cannot be supplemented. And the method does not correspondingly improve the antitoxic capability of the catalyst, so that the regenerated catalyst is easy to be deactivated by lead poisoning again in the using process, and the service life of the regenerated catalyst is shortened. In addition, the method mainly aims at lead poisoning inactivation regeneration of the commercial vanadium-based catalyst, and the regeneration effect of the lead poisoning Mn-Ce carbon-based low-temperature denitration catalyst is not ideal.
At present, the research on the inactivation mechanism and the regeneration method of heavy metal lead poisoning is less, and the research on the inactivation mechanism and the regeneration process of lead poisoning has important significance for reducing the operation cost of a denitration system (especially a low-temperature flue gas denitration system). Therefore, it is necessary to develop a lead poisoning regeneration method for Mn-Ce carbon-based low-temperature denitration catalyst. The invention provides a novel regeneration method for a lead-poisoned Mn-Ce carbon-based denitration catalyst, which can simply and efficiently remove lead contained in the poisoned denitration catalyst, simultaneously supplement damaged active ingredients and remarkably improve the lead poisoning resistance of the regenerated catalyst.
Disclosure of Invention
The invention aims to provide a regeneration method of a lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst, which is characterized by comprising the following steps of:
(1) preparing an active supplementary solution and an antitoxic inhibiting solution:
the active supplementary liquid comprises the raw material components of manganese nitrate, cerous nitrate hexahydrate and water;
the antitoxic inhibition liquid is niobium oxalate and water;
mixing the active supplementary liquid and the antitoxic inhibiting liquid uniformly;
according to the technology, active substances Mn and Ce required by the lead poisoning catalyst are supplemented by the active supplementing liquid, and the regenerated catalyst has good lead poisoning resistance by the antitoxic inhibiting liquid.
(2) Cleaning a lead-poisoned Mn-Ce carbon-based denitration catalyst;
(3) putting the lead-poisoned Mn-Ce carbon-based denitration catalyst into the mixture of the active supplementing liquid and the antitoxic inhibiting liquid obtained in the step 1) for dipping;
(4) drying the treated catalyst;
(5) and calcining the dried catalyst in an inert gas atmosphere to obtain the regenerated Mn-Ce carbon-based low-temperature denitration catalyst.
Further, in the step (1), the mixing volume ratio of the activity supplementing liquid to the antitoxic inhibiting liquid is 1: 1; after mixing, the two were mixed by mechanical stirring for 30 min.
Further, in the step (1), the concentrations of the manganese nitrate and the cerous nitrate hexahydrate in the activity supplementing liquid are 1.0-2.0 mol/L.
Further, in the step (1), the concentration of niobium oxalate in the antitoxic inhibition solution is 0.5-1.0 mol/L.
Further, in the step (2), when the lead-poisoned Mn-Ce carbon-based denitration catalyst is cleaned, preliminarily removing dust and partial lead on the surface of the lead-poisoned Mn-Ce carbon-based denitration catalyst in a high-pressure gas blowing mode, and then carrying out ultrasonic cleaning treatment for 30 min; the pressure of the purge gas is 0.3-0.8MPa, the frequency of the ultrasonic wave is 30-50KHz, and the intensity is 0.3-0.5W/cm2。
Further, in the step (3), the lead-poisoned Mn-Ce carbon-based denitration catalyst is placed in the mixture of the active supplementing liquid and the antitoxic inhibiting liquid obtained in the step 1) to be soaked for 2 hours, and the stirring is carried out once every half hour.
Further, in the step (4), the treated catalyst is dried in a drying oven at 90-110 ℃ for 12 hours.
Further, in the step (5), a vacuum tube furnace is adopted for calcination.
Further, in the step (5), the calcination temperature is 400-500 ℃, and the calcination time is 6 hours.
Compared with the existing lead poisoning catalyst regeneration method, the method has the following advantages:
(1) according to the invention, the regeneration liquid is prepared by mixing the active replenisher and the antitoxic inhibitor, so that the lead-poisoned Mn-Ce carbon-based denitration catalyst can be regenerated, and the regenerated catalyst has good lead poisoning resistance, so that the service life of the regenerated catalyst is prolonged.
(2) According to the invention, lead deposited on the surface of the catalyst is removed by adopting a high-pressure gas purging and ultrasonic cleaning treatment mode, and no new poisoning component is introduced into the Mn-Ce carbon-based denitration catalyst.
(3) The active supplementing liquid can effectively supplement active components Mn and Ce to the catalyst and effectively recover the low-temperature denitration activity of the poisoned catalyst. The niobium oxalate added into the antitoxic inhibiting liquid has good resistance to lead, thereby improving the anti-lead poisoning capability of the regenerated catalyst and prolonging the service life of the regenerated catalyst.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
the test sample is a lead-poisoned Mn-Ce active coke low-temperature denitration catalyst, and the catalyst is prepared by adopting an impregnation method. The lead content is: 0.5 wt%.
(1) Preparing active supplementary liquid and antitoxic inhibiting liquid. The active supplementary liquid comprises the raw materials of manganese nitrate, cerous nitrate hexahydrate and the balance of water. The concentration of the manganese nitrate and the cerous nitrate hexahydrate in the active supplementing liquid is 1.0 mol/L. The antitoxic inhibiting liquid contains niobium oxalate, and the concentration of the niobium oxalate is 0.5 mol/L. Respectively weighing the prepared active supplementing liquid and the antitoxic inhibiting liquid according to the volume ratio of 1:1, mixing, and mechanically stirring for 30min to uniformly mix.
The regeneration steps of the lead poisoning Mn-Ce active coke low-temperature denitration catalyst are as follows:
(2) the lead poisoning Mn-Ce active coke denitration catalyst is subjected to preliminary removal of dust and partial lead on the surface of the catalyst in a high-pressure gas purging mode, and then ultrasonic cleaning treatment is carried out for 30 min. The pressure of the purge gas is 0.3MPa, the frequency of the ultrasonic wave is 30KHz, and the intensity is 0.3W/cm2。
(3) And (3) placing the lead-poisoned Mn-Ce active coke denitration catalyst in the step (1) into an active replenishment solution for dipping regeneration, wherein the dipping time for regeneration is 2 hours, and stirring is carried out once every half an hour.
(4) The regenerated catalyst from step 2 was then dried in a 90 ℃ drying oven for 12 hours.
(5) Putting the catalyst treated in the step 3 into a vacuum tube furnace, N2Calcining for 6 hours at 400 ℃ under protection to obtain the regenerated Mn-Ce carbon-based low-temperature denitration catalyst.
The performance of the denitration catalyst is evaluated, the denitration activity of the lead-poisoned Mn-Ce active coke catalyst is 58.1% at the reaction temperature of 200 ℃, the denitration rate of the regenerated catalyst is 91.5%, and the regeneration effect is obvious.
Example 2:
the test sample is a lead-poisoned Mn-Ce active coke low-temperature denitration catalyst, and the catalyst is prepared by adopting an impregnation method. The lead content is: 0.5 wt%.
(1) Preparing active supplementary liquid and antitoxic inhibiting liquid. The active supplementary liquid comprises the raw materials of manganese nitrate, cerous nitrate hexahydrate and the balance of water. The concentration of the manganese nitrate and the cerous nitrate hexahydrate in the active supplementing liquid is 2.0 mol/L. The antitoxic inhibiting liquid contains niobium oxalate, and the concentration of the niobium oxalate is 1.0 mol/L. Respectively weighing the prepared active supplementing liquid and the antitoxic inhibiting liquid according to the volume ratio of 1:1, mixing, and mechanically stirring for 30min to uniformly mix.
The regeneration steps of the lead poisoning Mn-Ce active coke low-temperature denitration catalyst are as follows:
(2) the lead poisoning Mn-Ce active coke denitration catalyst is subjected to preliminary removal of dust and partial lead on the surface of the catalyst in a high-pressure gas purging mode, and then ultrasonic cleaning treatment is carried out for 30 min. The pressure of the purge gas is 0.5MPa, the frequency of the ultrasonic wave is 40KHz, and the intensity is 0.4W/cm2。
(3) And (3) placing the lead-poisoned Mn-Ce active coke denitration catalyst in the step (1) into an active replenishment solution for dipping regeneration, wherein the dipping time for regeneration is 2 hours, and stirring is carried out once every half an hour.
(4) The regenerated catalyst from step 2 was then dried in a drying oven at 100 ℃ for 12 hours.
(5) Putting the catalyst treated in the step 3 into a vacuum tube furnace, N2Calcining for 6 hours at 450 ℃ under protection to obtain the regenerated Mn-Ce carbon-based low-temperature denitration catalyst.
The performance of the denitration catalyst is evaluated, the denitration activity of the lead-poisoned Mn-Ce active coke catalyst is 58.1% at the reaction temperature of 200 ℃, the denitration rate of the regenerated catalyst is 96.3%, and the regeneration effect is obvious.
Example 3:
the test sample is a lead-poisoned Mn-Ce active coke low-temperature denitration catalyst, and the catalyst is prepared by adopting an impregnation method. The lead content is: 0.5 wt%.
(1) Preparing active supplementary liquid and antitoxic inhibiting liquid. The active supplementary liquid comprises the raw materials of manganese nitrate, cerous nitrate hexahydrate and the balance of water. The concentration of the manganese nitrate and the cerous nitrate hexahydrate in the active supplementing liquid is 2.0 mol/L. The antitoxic inhibiting liquid contains niobium oxalate, and the concentration of the niobium oxalate is 1.0 mol/L. Respectively weighing the prepared active supplementing liquid and the antitoxic inhibiting liquid according to the volume ratio of 1:1, mixing, and mechanically stirring for 30min to uniformly mix.
The regeneration steps of the lead poisoning Mn-Ce active coke low-temperature denitration catalyst are as follows:
(2) the lead poisoning Mn-Ce active coke denitration catalyst is subjected to preliminary removal of dust and partial lead on the surface of the catalyst in a high-pressure gas purging mode, and then ultrasonic cleaning treatment is carried out for 30 min. The pressure of the purge gas is 0.8MPa, the frequency of the ultrasonic wave is 50KHz, and the intensity is 0.5W/cm2。
(3) And (3) placing the lead-poisoned Mn-Ce active coke denitration catalyst in the step (1) into an active replenishment solution for dipping regeneration, wherein the dipping time for regeneration is 2 hours, and stirring is carried out once every half an hour.
(4) The regenerated catalyst from step 2 was then dried in a 110 ℃ drying oven for 12 hours.
(5) Putting the catalyst treated in the step 3 into a vacuum tube furnace, N2Calcining for 6 hours at 500 ℃ under protection to obtain the regenerated Mn-Ce carbon-based low-temperature denitration catalyst.
The performance of the denitration catalyst is evaluated, the denitration activity of the lead-poisoned Mn-Ce active coke catalyst is 58.1% at the reaction temperature of 200 ℃, the denitration rate of the regenerated catalyst is 94.1%, and the regeneration effect is obvious.
Example 4:
the test sample is a lead-poisoned Mn-Ce semi-coke low-temperature denitration catalyst, and the catalyst is prepared by adopting an impregnation method. The lead content is: 0.5 wt%.
(1) Preparing active supplementary liquid and antitoxic inhibiting liquid. The active supplementary liquid comprises the raw materials of manganese nitrate, cerous nitrate hexahydrate and the balance of water. The concentration of the manganese nitrate and the cerous nitrate hexahydrate in the active supplementing liquid is 2.0 mol/L. The antitoxic inhibiting liquid contains niobium oxalate, and the concentration of the niobium oxalate is 1.0 mol/L. Respectively weighing the prepared active supplementing liquid and the antitoxic inhibiting liquid according to the volume ratio of 1:1, mixing, and mechanically stirring for 30min to uniformly mix.
The regeneration steps of the lead poisoning Mn-Ce semi-coke low-temperature denitration catalyst are as follows:
(2) the lead poisoning Mn-Ce semi-coke denitration catalyst is subjected to preliminary removal of dust and partial lead on the surface of the catalyst in a high-pressure gas purging mode, and then ultrasonic cleaning treatment is carried out for 30 min. The pressure of the purge gas is 0.8MPa, the frequency of the ultrasonic wave is 50KHz, and the intensity is 0.5W/cm2。
(3) And (3) putting the lead-poisoned Mn-Ce semi-denitration catalyst in the step (1) into an active replenishment solution for dipping regeneration, wherein the dipping time for regeneration is 2 hours, and stirring is carried out once every half an hour.
(4) The regenerated catalyst from step 2 was then dried in a drying oven at 100 ℃ for 12 hours.
(5) Putting the catalyst treated in the step 3 into a vacuum tube furnace, N2Calcining for 6 hours at 450 ℃ under protection to obtain the regenerated Mn-Ce carbon-based low-temperature denitration catalyst.
The performance of the denitration catalyst is evaluated, the denitration activity of the lead-poisoned Mn-Ce semi-coke catalyst is 52.9% at the reaction temperature of 200 ℃, the denitration rate of the regenerated catalyst is 91.4%, and the regeneration effect is obvious.
Example 5:
the test sample is a lead-poisoned Mn-Ce biomass coke low-temperature denitration catalyst, and the catalyst is prepared by adopting an impregnation method. The lead content is: 0.5 wt%.
(1) Preparing active supplementary liquid and antitoxic inhibiting liquid. The active supplementary liquid comprises the raw materials of manganese nitrate, cerous nitrate hexahydrate and the balance of water. The concentration of the manganese nitrate and the cerous nitrate hexahydrate in the active supplementing liquid is 2.0 mol/L. The antitoxic inhibiting liquid contains niobium oxalate, and the concentration of the niobium oxalate is 1.0 mol/L. Respectively weighing the prepared active supplementing liquid and the antitoxic inhibiting liquid according to the volume ratio of 1:1, mixing, and mechanically stirring for 30min to uniformly mix.
The regeneration steps of the lead poisoning Mn-Ce biomass coke low-temperature denitration catalyst are as follows:
(2) the lead poisoning Mn-Ce biomass coke denitration catalyst is subjected to preliminary removal of dust and partial lead on the surface of the catalyst in a high-pressure gas purging mode, and then ultrasonic cleaning treatment is carried out for 30 min. The pressure of the blowing gas is 0.8MPa, and the frequency of the ultrasonic wave is 50KHz, intensity of 0.5W/cm2。
(3) And (3) placing the lead-poisoned Mn-Ce biomass coke denitration catalyst in the step (1) into an active replenishment solution for dipping regeneration, wherein the dipping time for regeneration is 2 hours, and stirring is carried out once every half an hour.
(4) The regenerated catalyst from step 2 was then dried in a drying oven at 100 ℃ for 12 hours.
(5) Putting the catalyst treated in the step 3 into a vacuum tube furnace, N2Calcining for 6 hours at 450 ℃ under protection to obtain the regenerated Mn-Ce carbon-based low-temperature denitration catalyst.
The performance of the denitration catalyst is evaluated, the denitration activity of the lead-poisoned Mn-Ce biomass coke catalyst is 56.2% at the reaction temperature of 200 ℃, the denitration rate of the regenerated catalyst is 94.9%, and the regeneration effect is obvious.
Claims (9)
1. A regeneration method of a lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst is characterized by comprising the following steps:
(1) preparing the active supplementary liquid and the antitoxic inhibiting liquid:
the active supplementary liquid comprises the raw material components of manganese nitrate, cerous nitrate hexahydrate and water;
the antitoxic inhibition liquid is niobium oxalate and water;
mixing the active supplementary liquid and the antitoxic inhibiting liquid uniformly;
(2) cleaning a lead-poisoned Mn-Ce carbon-based denitration catalyst;
(3) putting the lead-poisoned Mn-Ce carbon-based denitration catalyst into the mixture of the active supplementing liquid and the antitoxic inhibiting liquid obtained in the step 1) for dipping;
(4) drying the treated catalyst;
(5) and calcining the dried catalyst in an inert gas atmosphere to obtain the regenerated Mn-Ce carbon-based low-temperature denitration catalyst.
2. The regeneration method of the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst as claimed in claim 1, wherein the regeneration method comprises the following steps:
in the step (1), the activity supplementing liquid and the antitoxic inhibiting liquid are mixed and then are stirred mechanically for 30min to be mixed uniformly.
3. The regeneration method of the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst as claimed in claim 1, wherein the regeneration method comprises the following steps:
in the step (1), the concentrations of the manganese nitrate and the cerous nitrate hexahydrate in the active supplementing liquid are 1.0-2.0 mol/L.
4. The regeneration method of the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst as claimed in claim 1, wherein the regeneration method comprises the following steps: in the step (2), when the lead-poisoned Mn-Ce carbon-based denitration catalyst is cleaned, dust and partial lead on the surface of the catalyst are preliminarily removed by the lead-poisoned Mn-Ce carbon-based denitration catalyst in a high-pressure gas blowing mode.
5. The regeneration method of the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst as claimed in claim 1, wherein the regeneration method comprises the following steps: in the step (2), ultrasonic cleaning is adopted for 30 min; the pressure of the purge gas is 0.3-0.8MPa, the frequency of the ultrasonic wave is 30-50KHz, and the intensity is 0.3-0.5W/cm2。
6. The regeneration method of the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst as claimed in claim 1, wherein the regeneration method comprises the following steps: in the step (3), the lead-poisoned Mn-Ce carbon-based denitration catalyst is placed in the mixture of the active supplementing liquid and the antitoxic inhibiting liquid obtained in the step 1) to be soaked for 2 hours, and the stirring is carried out once every half hour.
7. The regeneration method of the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst as claimed in claim 1, wherein the regeneration method comprises the following steps: in the step (4), the treated catalyst is placed in a drying oven for drying.
8. The regeneration method of the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst as claimed in claim 1, wherein the regeneration method comprises the following steps: and (5) calcining by adopting a vacuum tube furnace.
9. The method for regenerating the lead-poisoned Mn-Ce carbon-based SCR low-temperature denitration catalyst 5 as claimed in claim 1, wherein the method comprises the following steps: in the step (5), the calcination temperature is 400-500 ℃, and the calcination time is 6 hours.
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