CN115715984B - Copper-cerium modified CaO for cooperatively removing carbon dioxide and NO based on calcium circulation, and preparation method and application thereof - Google Patents
Copper-cerium modified CaO for cooperatively removing carbon dioxide and NO based on calcium circulation, and preparation method and application thereof Download PDFInfo
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- 239000011575 calcium Substances 0.000 title claims abstract description 72
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 66
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 8
- 239000001569 carbon dioxide Substances 0.000 title description 2
- 239000010949 copper Substances 0.000 claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 18
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000000703 Cerium Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000001351 cycling effect Effects 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical group [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000002265 prevention Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002250 absorbent Substances 0.000 abstract description 5
- 230000002745 absorbent Effects 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 18
- 230000009467 reduction Effects 0.000 description 16
- 230000002195 synergetic effect Effects 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
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- 238000001514 detection method Methods 0.000 description 3
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- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a method for cooperatively removing CO based on calcium circulation 2 And NO, and a preparation method and application thereof, belonging to the technical field of environmental pollutant control and clean combustion. The invention utilizes copper and cerium to modify CaO, takes CaO as a matrix, and dopes cerium and copper in the matrix; the mol ratio of CaO, copper and cerium is 100 (0.8-1.1): 5, and the CaO, copper and cerium are used as denitration catalyst and CO 2 Absorbent, realizing CO in the stage of calcium circulation carbonation 2 The method can effectively reduce the concentration of CO in the tail gas while cooperatively removing NO, the denitration efficiency is up to 99%, and the CO is 2 The trapping efficiency is as high as 83%; the denitration efficiency is high, the economic cost is extremely low, cu-Ce-CaO repeatedly flows in the calcining and carbonating furnace, the catalyst can be repeatedly utilized, and the Cu-Ce-CaO can still efficiently catalyze CO denitration and efficiently trap CO in the residence time even after more than 20 times of calcium circulation 2 。
Description
Technical Field
The invention belongs to the technical field of environmental pollutant control and clean combustion, and in particular relates to a method for removing CO based on calcium circulation in a synergistic manner 2 Copper-cerium modification with NOSexual CaO, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The coal-fired power plant is fossil energy related CO 2 The main source of emission, aiming at CO of coal-fired power plants 2 Emission reduction is a major issue in global carbon emission reduction. The calcium recycling technology, caO recycling calcination/carbonation technology, is currently the most promising for achieving large scale CO 2 One of the trapping technologies has the advantages of high trapping efficiency, low cost, good coupling with a power plant and the like. The calcium cycle comprises two reactors, a carbonator reactor and a calciner reactor, which are fluidized bed reactors. CaCO (CaCO) 3 Calcining in a calciner at 800-950 ℃ and decomposing to generate CO 2 And CaO (as shown in formula (1)), the calciner being powered by fuel combustion; the calcined CaO flows into a carbonator at 600-700 ℃ to absorb CO in the flue gas 2 Generating CaCO 3 (as shown in formula (2)); finally CaCO 3 Returning to the calciner to generate decomposition reaction and release CO 2 And realizes CaO regeneration. CaO circularly flows in the calciner and the carbonator to realize CO 2 Is included in the collection of the liquid. High concentration CO discharged from calciner 2 Can be directly stored or utilized.
CaCO 3 →CaO+CO 2 (1)
CaO+CO 2 →CaCO 3 (2)
CaCO in calciner 3 Decomposition is an endothermic reaction, typically using oxygen-enriched combustion of biomass to power the calciner. When CaO flows out of the calciner after calcination, some unburned biomass coke in the calciner is entrained by CaO and flows into the carbonator where it is mixed with O in the flue gas 2 The reaction takes place to form CO. Is subjected to coke type, entrainment quantity and O in flue gas 2 The concentration effect, the CO concentration in the carbonator is about 0.1-1.2%. The control of the CO concentration can be achieved by controlling the amount of char in the carbonation furnace or other technical means. In addition, NO, one of the main pollutants of coal-fired power plants, is a great hazard to the environment, such as acid rain, photochemical smog, and the like. CO is used as a reducing agent for denitration, so that NH (NH) can be avoided 3 The problems of difficult corrosion to equipment and transportation, low cost and wide sources of CO, and the like, and can reduce the denitration cost of the coal-fired power plant. CaO has catalytic ability to reduce NO by CO, so that in the calcium cycle, caO can realize CO 2 Capturing and catalyzing CO to reduce NO.
The inventors have found that it is currently used in the calcium recycle stage for CO-removal 2 And NO has several drawbacks:
(1) The calcium-based material in the calcium cycle is easy to sinter at high temperature, and the catalytic removal of NO and the capture of CO are caused by the increase of the cycle times 2 The performance is rapidly reduced;
(2) When the CO reduction NO reaction catalyzed by the calcium-based material is insufficient, the concentration of CO in the tail gas exceeds the standard, and environmental pollution is easily caused.
Therefore, there is a need to prepare highly active composite calcium-based absorbents that enhance their synergistic CO removal during calcium cycling 2 And the ability of NO, while reducing the CO concentration in the tail gas.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for cooperatively removing CO based on calcium circulation 2 Copper and cerium modified CaO of NO, preparation method and application thereof, copper and cerium are utilized to modify CaO, and the CaO is used as denitration catalyst and CO 2 Absorbent, realizing CO in the process of calcium circulation carbonation 2 And the high-efficiency synergistic removal of NO, the denitration efficiency is up to 99%, and the CO 2 The trapping efficiency is as high as 83%.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
in one aspect, a CO-removal based on calcium cycling 2 And copper-cerium modified CaO of NO, wherein the copper-cerium modified CaO takes CaO as a matrix, and cerium and copper are doped in the matrix;
the mol ratio of CaO, copper and cerium is 100 (0.8-1.1): 5.
On the other hand, the above-mentioned CO-removal based on the calcium recycle stage 2 And a preparation method of the copper-cerium modified CaO of NO, comprising the following steps:
(1) Adding copper salt and cerium salt into distilled water for dissolution, and stirring in a water bath;
(2) Adding limestone into the solution obtained in the step (1), dipping, and drying to obtain solid particles;
(3) Calcining the solid particles obtained in the step (2) to obtain the CO-removal method based on the calcium circulation stage 2 And copper cerium modified CaO of NO.
In a third aspect, the CO-removal based on calcium cycling as described above 2 And the application of the copper-cerium modified CaO of NO in the prevention and treatment of environmental pollutants, wherein the application is as follows: co-removal based on calcium cycling 2 And copper-cerium modified CaO of NO as a calcium-based material in calcium cycle, CO-removal during calcium cycle 2 And NO.
The beneficial effects of the invention are as follows:
1. the copper-cerium modified CaO based on the calcium circulation and the synergistic removal of CO2 and NO, namely Cu-Ce-CaO, is prepared by adding copper and cerium into a CaO matrix to modify the copper and the cerium, and then is used as a denitration catalyst and CO 2 Adsorbent for realizing CO in flue gas of coal-fired power plant in carbonation reactor of calcium circulation 2 And NO, the denitration efficiency is up to 99%, and the CO is removed simultaneously and efficiently 2 The trapping efficiency is as high as 83%, the denitration efficiency is high, the economic cost is extremely low, the reactor is concentrated, the space utilization rate is high, cu-Ce-CaO repeatedly flows in the calcining and carbonating furnace, and the catalyst can be repeatedly utilized.
The Cu-Ce-CaO of the invention, in the chemical reaction control stage, maintains the concentration of NO at 10ppm (25.2 mg/m as the number of calcium cycle increases from 1 to 20 3 ) The NO removal efficiency is more than 99%, CO 2 The capture efficiency is kept constant (about 80%), and even through more than 20 times of calcium circulation, the Cu-Ce-CaO can efficiently catalyze CO denitration and efficiently capture CO in the residence time 2 。
According to the Cu-Ce-CaO disclosed by the invention, after copper and cerium are added into a CaO matrix for modification, the concentration of CO required by catalyzing CO to reduce NO by using a calcium-based material is reduced, and the concentration of CO in tail gas is greatly reduced. In the chemical reaction control stage, the catalyst is captured by Cu-Ce-CaOThe average concentration of CO in the tail gas is 0.0015%, which shows that Cu-Ce-CaO realizes CO in the carbonation stage 2 And the concentration of CO in the tail gas can be effectively reduced while the NO is removed cooperatively.
2. The method for preparing the copper-cerium modified CaO by using the impregnation method has the advantages of simple modification process, easy industrial application and good industrial application prospect.
3. The Cu-Ce-CaO of the invention catalyzes CO generated in the CO denitration process 2 Can be absorbed by Cu-Ce-CaO in the carbonator without generating additional CO 2 Emission is a denitration technology with zero carbon emission. Simultaneously, the CO generated in the calcium circulation is recycled, so that the problem of CO emission in tail gas of a carbonator is solved, and CO in coal-fired flue gas is realized in the same reactor 2 And NO removal, realizes simultaneous removal of various pollutants, and has good application prospect in environmental pollutant control.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic illustration of the CO-removal based on calcium cycling in accordance with example 1 of the present invention 2 And a preparation process flow diagram of the NO copper cerium modified CaO;
FIG. 2 is a graph showing the effect of Cu/Ce/Ca molar ratio on the synergistic removal of NO by Cu-Ce-CaO in Experimental example 1 of the present invention;
FIG. 3 is a graph showing the CO removal by CO-CaO CO-Cu-Ce in accordance with the molar ratio of Cu/Ce/Ca in Experimental example 1 of the present invention 2 Is a function of (1);
FIG. 4 shows the effect of calcium cycle number on the synergistic removal of NO by Cu-Ce-CaO in Experimental example 2 of the present invention;
FIG. 5 is a graph showing the CO removal of Cu-Ce-CaO by the calcium cycle number in Experimental example 2 of the present invention 2 Is a function of (1);
FIG. 6 is a graph showing the comparison of CO concentration in the tail gas of the synergistic removal of NO/CO2 by Cu-Ce-CaO and Ce-CaO;
FIG. 7 is an XPS spectrum of Ce3d in Cu-Ce-CaO of Experimental example 4 of the present invention;
FIG. 8 is an XPS spectrum of Cu2p in Cu-Ce-CaO of experimental example 4 of the present invention;
FIG. 9 is a CO-TPR chart of Cu-Ce-CaO and Ce-CaO in experimental example 5 of the present invention;
FIG. 10 is an EPR spectrum of Cu-Ce-CaO and Ce-CaO in experimental example 6 of the present invention;
FIG. 11 is a TEM image of Cu-Ce-CaO in Experimental example 7 of the present invention: wherein a is a TEM image of Cu-Ce-CaO, b is an HRTEM image of Cu-Ce-CaO, c is an HAADF-STEM image of Cu-Ce-CaO, and d-h is an EDS map corresponding to each element.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In view of the fact that the calcium-based material in the calcium circulation in the prior art is easy to sinter at high temperature, the catalytic removal of NO and the capture of CO are caused along with the increase of the circulation times 2 The invention provides a method for cooperatively removing CO based on calcium circulation, which is used for solving the problems that the performance is rapidly reduced, the concentration of CO in tail gas exceeds the standard and environmental pollution is easy to cause when the catalytic CO reduction NO reaction is insufficient 2 And NO copper cerium modified CaO, and a preparation method and application thereof.
In an exemplary embodiment of the invention, a method for CO-removal based on calcium cycling is provided 2 And copper-cerium modified CaO of NO, wherein the copper-cerium modified CaO takes CaO as a matrix, and cerium and copper are doped in the matrix;
the mol ratio of CaO, copper and cerium is 100 (0.8-1.1): 5.
In some examples of this embodiment of the present invention,copper doped in the matrix as CuO/CuO 2 In the form of CeO 2 Is present in the form of (c).
In some examples of this embodiment, the molar ratio of CaO, copper, and cerium is 100:1:5.
In another exemplary embodiment of the present invention, the CO-removal based on the calcium recycle stage described above is provided 2 And a preparation method of the copper-cerium modified CaO of NO, comprising the following steps:
(1) Adding copper salt and cerium salt into distilled water for dissolution, and stirring in a water bath;
(2) Adding limestone into the solution obtained in the step (1), dipping, and drying to obtain solid particles;
(3) Calcining the solid particles obtained in the step (2) to obtain the CO-removal method based on the calcium circulation stage 2 And copper cerium modified CaO of NO.
In some examples of this embodiment, in (1), the copper salt is a soluble copper salt, preferably copper acetate, and the cerium salt is a soluble cerium salt, preferably cerium acetate.
In some examples of this embodiment, in (1), the water bath is at a temperature of 55-65 ℃, preferably 60 ℃;
the stirring time is 30 to 60 minutes, preferably 45 minutes.
In some examples of this embodiment, in (2), the drying, drying conditions are: drying at 75-95deg.C for 10-15 hr, preferably at 80deg.C for 12 hr.
In some examples of this embodiment, in (3), the calcining is performed under the following conditions: calcining at 900-1000deg.C in air atmosphere for 10-20min;
preferably, the calcination conditions are: calcining at 950 deg.c in air atmosphere for 15min.
In some examples of this embodiment, in (3), the calcined material is screened to a particle size in the range of 0.125-0.180 mm.
In a third exemplary embodiment of the present invention, the above-described CO-removal based on calcium recycling is provided 2 And the application of the copper-cerium modified CaO of NO in the prevention and treatment of environmental pollutants, wherein the application is as follows: based on calcium circulation and co-removalCO 2 And copper-cerium modified CaO of NO are used as a calcium-based material in the calcium circulation, and CO2 and NO are removed cooperatively in the calcium circulation process.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
Based on calcium circulation is desorption CO in coordination 2 Copper-cerium modified CaO with NO
The preparation method comprises the following steps: calcium carbonate, copper acetate, cerium acetate, distilled water
The preparation method comprises the following steps:
(1) Adding 0.59g of copper acetate and 4.76g of cerium acetate into 30mL of distilled water for dissolution, and stirring for 45min in a water bath at 60 ℃;
(2) Adding 30g of limestone into the stirred solution for soaking, and drying at 80 ℃ for 12 hours to obtain solid particles;
(3) Calcining the particles for 15min in an air atmosphere at 950 ℃ to obtain the copper-cerium modified CaO.
The preparation process flow of the embodiment is shown in figure 1, and final copper-cerium modified CaO is obtained by impregnating and loading copper, cerium additives and calcining at high temperature, wherein the molar ratio of Cu/Ce/CaO is 1:5:100.
Example 2
Based on calcium circulation is desorption CO in coordination 2 Copper-cerium modified CaO with NO
The difference from example 1 is that the Cu/Ce/CaO molar ratio is 0.8:5:100.
Example 3
Based on calcium circulation is desorption CO in coordination 2 Copper-cerium modified CaO with NO
The difference from example 1 is that the Cu/Ce/CaO molar ratio is 0.9:5:100.
Example 4
Based on calcium circulation is desorption CO in coordination 2 Copper-cerium modified CaO with NO
The difference from example 1 is that the Cu/Ce/CaO molar ratio is 1.1:5:100.
Comparative example 1
Based on calcium circulationCo-removal of CO 2 And cerium modified CaO of NO
The difference from example 1 is that Cu is not contained and the Ce/CaO molar ratio is 5:100.
Experimental example 1
On a bubbling fluidized bed reactor, the Cu-Ce-CaO was subjected to synergistic NO/CO removal by different Cu/Ce/CaO molar ratios in examples 1-4 2 Is a function of (a) and (b).
Conditions are as follows: a fluidized bed reactor; the mass of the Cu-Ce-CaO prepared in examples 1-4 was 16g each; the fluidization number is 2; synergistic removal conditions: 650 ℃,0.05% O 2 /2000ppmCO/1000ppmNO/15％CO 2 /N 2 。
To investigate the effect of the Cu-Ce-CaO stable catalytic stage on CO denitration, the calcined Cu-Ce-CaO was calcined at 2000ppm CO/N 2 The pretreatment in the atmosphere is carried out for about 3min and then the synergistic NO/CO removal is carried out 2 Is a test of (a). The detection results are shown in fig. 2 and 3, wherein fig. 2 is a curve of NO concentration in tail gas and time, and fig. 3 is CO in tail gas 2 Concentration versus time.
As shown in fig. 2, when the Cu/Ce/Ca molar ratio is increased from 0.8:5:100 to 1:5:100, η is controlled during the carbonation kinetics NO From 85% to 99% (t=730 s). The Cu/Ce/Ca mole ratio in the Cu-Ce-CaO is improved, so that the active sites for catalyzing the CO to catalyze the denitration are increased, and the CO denitration is promoted.
As shown in FIG. 3, as the Cu/Ce/Ca molar ratio increases from 0.8:5:100 to 1.1:5:100, CO in the Cu-Ce-CaO carbonation kinetics control stage 2 Concentration change is not great, eta CO2 Is maintained at about 83%. And when the Cu/Ce/Ca molar ratio is further increased to 1.1:5:100, the eta of the kinetic control stage is controlled NO Down to 82%. Further increases in Cu content in Cu-Ce-CaO lead to reduced denitration performance because Cu blocks a portion of the channels, hindering CO, NO and CO 2 Diffusion in Cu-Ce-CaO has an adverse effect on catalytic CO denitration. In general, the positive effect of additives on CO denitration can counteract the negative effects of these blockages. However, when the Cu-Ce-CaO molar ratio exceeds 1.1:5:100, the negative effect is more serious, which is η NO The reason for the drop.
To achieve efficient CO 2 Trapping and CO denitration, a suitable Cu/Ce/CaO molar ratio is 1:5:100.
Experimental example 2
The CO-removal of NO/CO from Cu-Ce-CaO was investigated on the bubbling fluidized bed reactor mentioned in Experimental example 1 using the Cu-Ce-CaO of example 1 for the number of calcination/carbonation cycles 2 Is a function of (a) and (b).
Conditions are as follows: the fluidized bed reactor has the mass of Cu-Ce-CaO of 16g, the fluidization number of 2 and the synergistic removal condition: 650 ℃,0.05% O 2 /2000ppmCO/1000ppmNO/15％CO 2 /N 2 。
In the calcium cycle, the calcium-based absorbent is circulated repeatedly in the carbonator and calciner. To investigate the effect of the Cu-Ce-CaO stable catalytic stage on CO denitration, the calcined Cu-Ce-CaO was calcined at 2000ppm CO/N 2 The pretreatment in the atmosphere is carried out for about 3min and then the synergistic NO/CO removal is carried out 2 Is a test of (a). The detection results are shown in fig. 4 and 5, wherein fig. 4 is a graph of NO concentration in tail gas and time, and fig. 5 is CO in tail gas 2 Concentration versus time.
As shown in FIG. 4, in the chemical reaction control stage, the NO concentration was maintained at 10ppm (25.2 mg/m as the number of cycles was increased from 1 to 20 3 ) In the following, the corresponding NO removal efficiency reaches more than 99%. Cu-Ce-CaO has excellent catalytic activity on CO to reduce NO in 20 cycles. In addition, according to the emission standard of the Chinese atmospheric pollutants, the NOx emission of the coal-fired boiler of the power plant is less than 100mg/m 3 Thus the NO concentration of the exhaust gas meets the regulations.
As shown in FIG. 5, CO at the Cu-Ce-CaO chemical reaction control stage 2 The capture efficiency remained constant (about 80%). Although the number of cycles versus eta for the dynamics control phase CO2 And eta NO The effect is not great but the duration of the chemical reaction control phase drops from 700 seconds to 200 seconds as the number of cycles increases from 1 to 20. The decay of the duration of the carbonation kinetics control phase slows as the number of calcium cycles increases. Considering only the short residence time of the sample in the carbonator, it is speculated that Cu-Ce-CaO can efficiently catalyze CO denitration in the residence time even after more than 20 calcium cyclesAnd high efficiency CO capture 2 。
Experimental example 3
The Cu-Ce-CaO of example 1 and the Ce-CaO of comparative example 1 were investigated for the synergistic NO/CO removal on a bubbling fluidized bed reactor as mentioned in experimental example 1 2 Concentration of CO in the tail gas.
Conditions are as follows: fluidized bed reactors, the Cu-Ce-CaO of example 1 and the Ce-CaO of comparative example 1 are respectively used as calcium-based absorbent, the mass is 16g respectively, the fluidization number is 2, and the Cu-Ce-CaO is cooperatively removed: 650 ℃,0.05% O 2 /2000ppm CO/1000ppm NO/15％CO 2 /N 2 The Ce-CaO synergistic removal conditions are as follows: 650 ℃,0.05% O 2 /2500ppm CO/700ppm NO/15％CO 2 /N 2 。
In order to explore the influence of stable catalytic stages of Ce-CaO and Cu-Ce-CaO on CO denitration, the calcined Ce-CaO and Cu-Ce-CaO are respectively in 2000ppm CO/N 2 The pretreatment in the atmosphere is carried out for about 3min and then the synergistic NO/CO removal is carried out 2 Is a test of (a). The detection results are shown in FIG. 6.
Under the experimental conditions shown in fig. 6, the duration of the Ce-CaO chemical reaction control phase is 0 to 700s. In the chemical reaction control stage, the average concentration of CO in the Ce-CaO tail gas is 0.058%, which is about 38.67 times that of Cu-Ce-CaO (0.0015%). This shows that Cu-Ce-CaO can effectively reduce the concentration of CO in tail gas while realizing the CO-removal of CO2 and NO in the carbonation stage. In addition, the CO concentration in the Cu-Ce-CaO exhaust gas remains stable, while the CO concentration in the Ce-CaO exhaust gas increases sharply. Clearly, cu-Ce-CaO has a greater effect on reducing the concentration of CO in the exhaust than Ce-CaO.
Experimental example 4
The Cu-Ce-CaO obtained in example 1 was investigated at 2000ppm CO/N 2 The atmosphere was pre-treated for about 3min and the X-ray photoelectron spectroscopy was not pre-treated.
Conditions are as follows: cu-Ce-CaO prepared in example 1 2 Reduction pretreatment: 950 ℃,2000ppm CO/N 2 3min. FIGS. 7 and 8 show XPS patterns of Cu-Ce-CaO obtained in example 1, where Ce3d is shown in FIG. 7 and Cu2p is shown in FIG. 8.
As can be seen from FIG. 7, 6 characteristic peaks, u, are observed in the Ce3d spectra of both samples 1 、u 2 V and v 3 Corresponding to Ce 4+ ，u 3 And v 2 Corresponding to Ce 3+ The two valence states coexist due to the low energy required for interconversion. For Cu2p before and after the sample reduction in FIG. 8, cu2p 1/2 At 952eV and Cu2p 3/2 The peaks at 932eV are respectively typical of Cu 2+ And Cu + . The impregnated copper is therefore mainly Cu 2+ And Cu + . In addition, the formation of Cu species with lower chemical valences will further enhance the catalytic ability of the sample.
Comprehensive analysis can show that v1, v2, and u2 of Ce3d and Cu2p of Cu2p in the sample after CO reduction 1/2 And Cu2p 3/2 Is shifted to higher binding energies. This suggests that the interactions between Ce, cu and CaO are enhanced, resulting in charge imbalance. Thus, the Cu-Ce-CaO oxidizing ability is improved, and its catalytic ability to reduce NO by CO is enhanced.
Experimental example 5
FIG. 9 is a CO-TPR spectrum of Cu-Ce-CaO of example 1 and Ce-CaO of comparative example 1. As can be seen from the figure, cu-Ce-CaO has 3 TPR peaks overlapping each other at 407 ℃,467 ℃ and 602 ℃, respectively. Oxygen adsorbed on the surface of the material can be reduced by CO at a lower temperature, and lattice oxygen can only be reduced by CO at a high temperature. The high temperature reduction peak in the figure should be the reduction peak of lattice oxygen of the material. Lattice oxygen can be generally classified into 3 types as to its position in the material lattice: i.e., surface layer, sublayer and deep lattice oxygen. The surface lattice oxygen can be directly contacted with CO, and the surface lattice oxygen is reduced firstly in the reduction process; secondly, the oxygen vacancies are left after the surface lattice oxygen is reduced, the oxygen of the sub-layer lattice can diffuse to the surface oxygen vacancies at a certain temperature, and the lattice oxygen of the sub-layer is reduced by CO after moving to the surface; the deep lattice oxygen reduction process is similar to the sub-layer lattice oxygen, except that it is more difficult to perform. According to the above analysis, the reduction peak of Cu-Ce-CaO at 407℃should be the reduction peak of surface lattice oxygen, and the reduction peaks at 467℃and 602℃should be the reduction peak of sub-layer or deeper lattice oxygen. The Ce-CaO situation is similar.
The peak area of lattice oxygen of the surface layer of Cu-Ce-CaO is larger than that of Ce-CaO, and the amount of lattice oxygen in the deep layer of the material is relatively reduced due to the dispersion effect of Cu. Simultaneously, three reduction peaks of Cu-Ce-CaO are homogeneously shifted at a lower temperature. This suggests that the lattice oxygen of Cu-Ce-CaO can migrate to the surface under milder conditions, promoting the formation of oxygen vacancies. The analysis shows that the addition of copper and cerium salts greatly improves the number of oxygen vacancies in the surface layer of the material and increases the catalytic sites, so that Cu-Ce-CaO can be catalyzed more efficiently under the condition of low CO/NO concentration ratio.
Experimental example 6
FIG. 10 shows EPR spectra of Cu-Ce-CaO obtained in example 1 and Ce-CaO of comparative example 1. As can be seen from the graph, the signal intensity at g=2.003 is different in the two materials, cu-Ce-CaO>Ce-CaO. The addition of copper and cerium salts increases the oxygen vacancies of the material, and the increase of the oxygen vacancies can reduce O 2- Which is advantageous for increasing the catalytic activity of the material in catalyzing the CO reduction NO reaction during the carbonation stage of the calcium cycle. In addition, O 2- Diffusion on the surface and bulk of the material favors CO 3 2- Is beneficial to the absorption of CO by CaO 2 。
Experimental example 7
FIG. 11 is a TEM image of Cu-Ce-CaO obtained in example 1, wherein a is a TEM image of Cu-Ce-CaO, b is a HRTEM image of Cu-Ce-CaO, c is a HAADF-STEM image of Cu-Ce-CaO, and d-h is an EDS map corresponding to each element.
As can be seen from the figure, the 0.32nm lattice spacing in the HRTEM images corresponds to CeO, respectively 2 The exposed (111) crystal plane, the lattice spacing of 0.21nm corresponds to the Cu (111) crystal plane. White dotted line in figure and Cu/CeO in partial enlarged view 2 Lattice overlap occurs, indicating Cu doping to CeO under sample preparation atmosphere 2 In the crystal lattice, cu is then anchored in CeO by Cu-Ce interactions 2 Is a kind of medium. The formation of this structure is advantageous for increasing its catalytic activity in catalyzing the CO reduction NO reaction during the carbonation stage of the calcium cycle. As can be seen from FIG. 11 (d-h), the EDS patterns of Ca, cu, ce and O elements have almost the same distribution pattern, indicating that the Ca, cu, ce and O components are uniformly distributed. The results indicate that well-mixed adsorbents and catalysts are formed in the materialAnd (3) a chemical agent.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. Co-removal based on calcium cycling 2 And the application of the copper-cerium modified CaO of NO in the prevention and treatment of environmental pollutants, which is characterized in that: co-removal based on calcium cycling 2 And copper-cerium modified CaO of NO as a calcium-based material in calcium cycle, CO-removal during calcium cycle 2 And NO;
the copper-cerium modified CaO takes CaO as a matrix, and cerium and copper are doped in the matrix; the mol ratio of CaO, copper and cerium is 100:0.8-1.1:5; copper doped in the matrix as CuO/CuO 2 In the form of CeO 2 In the form of (2);
the CO-removal of CO based on calcium cycling 2 And a preparation method of the copper-cerium modified CaO of NO, comprising the following steps:
(1) Adding copper salt and cerium salt into distilled water for dissolution, and stirring in a water bath;
(2) Adding limestone into the solution obtained in the step (1), dipping, and drying to obtain solid particles;
(3) Calcining the solid particles obtained in the step (2) to obtain the CO-removal method based on the calcium circulation stage 2 And copper cerium modified CaO of NO.
2. Use according to claim 1, wherein the molar ratio of CaO, copper and cerium is 100:1:5.
3. The use according to claim 1, wherein in (1) the copper salt is a soluble copper salt and the cerium salt is a soluble cerium salt.
4. The use according to claim 3, wherein in (1) the copper salt is copper acetate and the cerium salt is cerium acetate.
5. The use according to claim 1, wherein in (1), the water bath is at a temperature of 55-65 ℃ and the stirring is carried out for a period of 30-60 minutes.
6. The use according to claim 5, wherein in (1) the water bath is at a temperature of 60 ℃; the stirring time is 45 minutes.
7. The use according to claim 1, wherein in (2), the drying conditions are: drying at 75-95deg.C for 10-15 hr.
8. The use according to claim 7, wherein in (2) the drying is carried out at 80 ℃ for 12 hours.
9. The use according to claim 1, wherein in (3), the calcination is performed under the following conditions: calcining at 900-1000deg.C in air atmosphere for 10-20min.
10. The use according to claim 9, wherein in (3) the calcination is carried out under an air atmosphere at 950 ℃ for 15min.
11. The use according to claim 1, wherein in (3) the calcined material is screened to a particle size in the range of 0.125-0.180 mm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225760A (en) * | 2011-03-22 | 2011-10-26 | 华北水利水电学院 | Coal combustion CO2 capturing method and device based on metal oxide-CaCO3 absorbent |
| CN105944528A (en) * | 2016-05-13 | 2016-09-21 | 东南大学 | Device and method for capturing CO2 in flue gas by using Ca/Cu-based composite particles |
| CN107376826A (en) * | 2017-08-29 | 2017-11-24 | 武汉凯迪工程技术研究总院有限公司 | Calcium oxide-based high temperature CO2Adsorbent and preparation method thereof |
| CN108302523A (en) * | 2018-01-08 | 2018-07-20 | 东南大学 | A kind of composite absorber cycle capture CO with hydration reactor2Device and method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225760A (en) * | 2011-03-22 | 2011-10-26 | 华北水利水电学院 | Coal combustion CO2 capturing method and device based on metal oxide-CaCO3 absorbent |
| CN105944528A (en) * | 2016-05-13 | 2016-09-21 | 东南大学 | Device and method for capturing CO2 in flue gas by using Ca/Cu-based composite particles |
| CN107376826A (en) * | 2017-08-29 | 2017-11-24 | 武汉凯迪工程技术研究总院有限公司 | Calcium oxide-based high temperature CO2Adsorbent and preparation method thereof |
| CN108302523A (en) * | 2018-01-08 | 2018-07-20 | 东南大学 | A kind of composite absorber cycle capture CO with hydration reactor2Device and method |
Non-Patent Citations (1)
| Title |
|---|
| "Double-exchange-induced effective increased CO2 capture of CaO by doping bimetallic oxides with variable valence state";Hongxia Guo等;Chemical Engineering Journal;第433卷;摘要，第2.1节，第1页左栏第1段，第2.3节 * |
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