CN116688934A - Efficient wet denitration adsorbent and application method thereof - Google Patents
Efficient wet denitration adsorbent and application method thereof Download PDFInfo
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- CN116688934A CN116688934A CN202310629378.7A CN202310629378A CN116688934A CN 116688934 A CN116688934 A CN 116688934A CN 202310629378 A CN202310629378 A CN 202310629378A CN 116688934 A CN116688934 A CN 116688934A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003546 flue gas Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005751 Copper oxide Substances 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 aluminum ions Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- VWWHFOBVDHPEKJ-UHFFFAOYSA-N aluminum ethanol trinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Al+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] VWWHFOBVDHPEKJ-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/018—Natural gas engines
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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
Abstract
The invention relates to a high-efficiency wet denitration adsorbent and an application method thereof, comprising the following steps: adding sodium hydroxide solution and a high-efficiency wet denitration adsorbent into a wet denitration adsorption tower; introducing flue gas from an inlet of the wet denitration adsorption tower; discharging the denitrated gas from the outlet of the wet denitration adsorption tower to finish wet denitration; the high-efficiency wet denitration adsorbent comprises ferric oxide, nickel oxide, copper oxide, cerium oxide and aluminum oxide; iron oxide, nickel oxide, copper oxide and cerium oxide negativeSupported on alumina particles. The beneficial effects of the invention are as follows: ceO of the high-efficiency wet denitration adsorbent provided by the invention 2 The component can strengthen Fe 2 O 3 NOx adsorption capacity of NiO, cuO, and the like.
Description
Technical Field
The invention relates to the field of flue gas treatment, in particular to a high-efficiency wet denitration adsorbent and an application method thereof.
Background
The gas turbine technology is a mature natural gas power generation technology and is widely used in China. The installed scale of the natural gas power generation in 2020 reaches more than 1.1 hundred million kw, and the proportion of the installed scale of the natural gas power generation exceeds 5 percent.
The main components of NOx in the flue gas discharged from the power plant are NO and NO 2 Wherein NO is poorly soluble in water, NO 2 The direct reaction with water releases part of the NO gas. Thus, NO 2 When the content is about 60% of the NOx content, the NOx is most easily absorbed by the absorption tower, and the reaction equation is as follows:
4NO+6NO 2 +9H 2 O 2 +10NaOH＝10NaNO 3 +14H 2 O
the efficiency of NOx removal by wet denitration systems is still limited by the rate of NOx adsorption by the solution in the tower on the flue gas, and therefore a denitration additive is needed to accelerate the adsorption of NOx in the solution in the tower on the flue gas.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a high-efficiency wet denitration adsorbent and an application method thereof.
In a first aspect, a high-efficiency wet denitration adsorbent is provided, which comprises ferric oxide, nickel oxide, copper oxide, cerium oxide and aluminum oxide in mass ratio: (0.01-0.03): (0.01-0.03): (0.01-0.03): (0.005-0.007): iron oxide, nickel oxide, copper oxide and cerium oxide are supported on alumina particles.
In a second aspect, there is provided a method for preparing the efficient wet denitration adsorbent according to the first aspect, including:
step 1, preparing an ethanol solution containing 0.1-0.3mol/L trivalent aluminum ions;
step 2, atomizing the ethanol solution into mist drops with the particle size of 1-10 microns, and fully burning the mist drops through flame to obtain micron alumina particles;
step 3, cleaning the micron alumina particles with dilute hydrochloric acid under ultrasonic treatment, and then washing with water to obtain clean micron alumina particles;
step 4, adding an ethanol solution containing ferric iron, nickel, cupric, tetravalent cerium ions and the clean micron alumina particles into a reaction vessel, and preparing an aqueous solution to obtain a mixed suspension;
step 5, standing the mixed suspension for 3-4 hours at room temperature, and then centrifugally separating to obtain a solid, thereby obtaining an adsorbent precursor;
and step 6, washing and drying the adsorbent precursor with clear water, heating for 1.5-3 hours at the constant temperature of 400-600 ℃ in an air atmosphere, and naturally cooling to room temperature to obtain the high-efficiency wet denitration adsorbent.
Preferably, in the step 1, the ethanol solution containing 0.1-0.3mol/L trivalent aluminum ions is aluminum chloride solution or aluminum nitrate solution.
Preferably, in step 4, the ethanol solution containing ferric ions is ferric chloride solution or ferric nitrate solution.
Preferably, in step 4, the ethanol solution containing divalent nickel ions is a nickel acetate solution.
Preferably, in step 4, the ethanol solution containing cupric ions is a cupric chloride solution or cupric nitrate solution.
Preferably, in step 4, the ethanol solution containing tetravalent cerium ions is a ceric ammonium nitrate solution.
In a third aspect, there is provided a method for applying the high-efficiency wet denitration adsorbent according to the first aspect, including:
step 1, adding a sodium hydroxide solution and a high-efficiency wet denitration adsorbent into a wet denitration adsorption tower;
step 2, introducing flue gas from an inlet of the wet denitration adsorption tower;
and step 3, discharging the denitrated gas at the outlet of the wet denitration adsorption tower to finish wet denitration.
Preferably, in the step 1, the concentration of the sodium hydroxide solution is 0.1mol/L to 1mol/L.
Preferably, in step 1, the volume-to-mass ratio of the sodium hydroxide solution to the efficient wet denitration adsorbent is (1L): (0.1-1 g).
The beneficial effects of the invention are as follows:
1. the high-efficiency wet denitration adsorbent provided by the invention comprises Al 2 O 3 The components are prepared by adopting a flame synthesis mode, the particle size is smaller, and the particle size distribution is more uniform.
2. CeO of the high-efficiency wet denitration adsorbent provided by the invention 2 The component can strengthen Fe 2 O 3 NOx adsorption capacity of NiO, cuO, and the like.
3. According to the high-efficiency wet denitration adsorbent provided by the invention, adsorbed NOx is carried into the solution for reaction through random movement on the surface of the solution, so that high-efficiency absorption of NOx can be realized.
Drawings
Fig. 1 is a flow chart of a method of applying a high-efficiency wet-process denitration adsorbent.
Detailed Description
The invention is further described below with reference to examples. The following examples are presented only to aid in the understanding of the invention. It should be noted that it will be apparent to those skilled in the art that modifications can be made to the present invention without departing from the principles of the invention, and such modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Example 1:
the embodiment of the invention provides a high-efficiency wet denitration adsorbent, which is an acid gas adsorbent taking NOx as a main adsorption object, and has double functions of physical adsorption and chemical adsorption on NOx.
The adsorbent is prepared from precursors of various metal oxides by the processes of flame synthesis, chemical washing, chemical impregnation, constant-temperature calcination and the like in sequence, and comprises the following components:
step 1, preparing 0.2mol/L aluminum nitrate ethanol solution;
step 2, atomizing the aluminum nitrate ethanol solution, and fully burning the atomized aluminum nitrate ethanol solution by flame to obtain Al with the grain size range of 1-10 microns 2 O 3 Particles;
step 3, cleaning the micron alumina particles with dilute hydrochloric acid under ultrasonic treatment, and then washing with water to obtain clean micron alumina particles;
step 4, fe (NO) 3 ) 3 ·9H 2 O、Ni(CH 3 COO) 2 ·4H 2 O、Cu(NO 3 ) 2 ·3H 2 O、Ce(NH 4 ) 2 (NO 3 ) 6 Fully mixing according to the mass ratio of 9.9:2.1:3.8:1 to obtain mixed powder, and taking 30g of mixed powder and 100g of Al 2 O 3 The particles and 100ml of purified water are fully dissolved under ultrasonic wave;
and 5, standing the mixed suspension for 3 hours at room temperature, separating out solids by using a centrifuge, washing and drying the solids by using clear water, keeping the temperature of 400-600 ℃ for 2 hours in an air atmosphere, and naturally cooling to the room temperature to obtain the adsorbent.
In the efficient wet denitration adsorbent, the weight percentages of the components are shown in table 1:
TABLE 1
| Chemical composition | Weight percent |
| Al 2 O 3 | 94.5wt％ |
| Fe 2 O 3 | 2wt％ |
| NiO | 1wt％ |
| CuO | 2wt％ |
| CeO 2 | 0.5wt％ |
In addition, in the high-efficiency wet denitration adsorbent, the metal oxide is one or more oxides of metals such as Fe, ni, cu, ce, al. The metal oxide can adsorb acid gases in the flue gas, which are mainly NOx, and migrate into the solution.
Example 2:
when the efficient wet denitration adsorbent provided by the invention is used, 50kg of adsorbent is added into every 100 cubic NaOH/H2O2 solution, and NOx in flue gas is adsorbed by circularly spraying the NaOH/H2O2 solution in a wet absorption tower and is removed by chemical reaction. In the process, the adsorbent can be dispersed on the surface of the spray solution liquid drops, so that the trapping of NOx in the flue gas by the liquid drops is enhanced.
An application method of the high-efficiency wet denitration adsorbent is shown in fig. 1, and comprises the following steps:
step 1, adding a sodium hydroxide solution and a high-efficiency wet denitration adsorbent into a wet denitration adsorption tower;
step 2, introducing flue gas from an inlet of the wet denitration adsorption tower;
and step 3, discharging the denitrated gas at the outlet of the wet denitration adsorption tower to finish wet denitration.
In the step 1, the concentration of the sodium hydroxide solution is 0.1mol/L to 1mol/L.
The following is an example of the wet denitration device for removing NOx in the flue gas, which is NO/NO generated by a gas cylinder 2 Air mixture, NO and NO 2 The volume flow ratio of (2) is 4:6, the experimental flue gas flow is 5L/min, the circulating spraying solution amount is 5L, 2.5g of adsorbent is added as an experimental group, and the adsorbent is not added as a control group.
The inlet and outlet NOx concentrations and the calculated NOx removal efficiencies are shown in table 2.
TABLE 2
According to the embodiment, the wet denitration adsorbent can remarkably improve the adsorption rate of the wet denitration device solution on NOx in the flue gas, and improve the removal efficiency of the wet denitration device on NOx.
Claims (10)
1. The efficient wet denitration adsorbent is characterized by comprising ferric oxide, nickel oxide, copper oxide, cerium oxide and aluminum oxide in mass ratio: (0.01-0.03): (0.01-0.03): (0.01-0.03): (0.005-0.007): iron oxide, nickel oxide, copper oxide and cerium oxide are supported on alumina particles.
2. A method for preparing the high-efficiency wet denitration adsorbent as claimed in claim 1, which comprises the steps of:
step 1, preparing an ethanol solution containing 0.1-0.3mol/L trivalent aluminum ions;
step 2, atomizing the ethanol solution into mist drops with the particle size of 1-10 microns, and fully burning the mist drops through flame to obtain micron alumina particles;
step 3, washing the nano alumina particles with dilute hydrochloric acid under ultrasonic treatment, and then washing with water to obtain clean micron alumina particles;
step 4, adding an ethanol solution containing ferric iron, nickel, cupric, tetravalent cerium ions and the clean micron alumina particles into a reaction vessel, and preparing an aqueous solution to obtain a mixed suspension;
step 5, standing the mixed suspension for 3-4 hours at room temperature, and then centrifugally separating to obtain a solid, thereby obtaining an adsorbent precursor;
and step 6, washing and drying the adsorbent precursor with clear water, heating for 1.5-3 hours at the constant temperature of 400-600 ℃ in an air atmosphere, and naturally cooling to room temperature to obtain the high-efficiency wet denitration adsorbent.
3. The method for preparing a high-efficiency wet denitration adsorbent according to claim 2, wherein in the step 1, the ethanol solution containing 0.1-0.3mol/L trivalent aluminum ion is an aluminum chloride solution or an aluminum nitrate solution.
4. The method for preparing a high-efficiency wet denitration adsorbent according to claim 2, wherein in the step 4, the ethanol solution containing ferric ions is ferric chloride solution or ferric nitrate solution.
5. The method for preparing a high-efficiency wet denitration adsorbent according to claim 2, wherein in the step 4, the ethanol solution containing divalent nickel ions is a nickel acetate solution.
6. The method for preparing a high-efficiency wet denitration adsorbent according to claim 2, wherein in the step 4, the ethanol solution containing cupric ions is a cupric chloride solution or a cupric nitrate solution.
7. The method for preparing a high-efficiency wet denitration adsorbent according to claim 2, wherein in the step 4, the ethanol solution containing tetravalent cerium ions is a ceric ammonium nitrate solution.
8. A method of using the high efficiency wet denitration adsorbent as claimed in claim 1, comprising:
step 1, adding a sodium hydroxide solution and a high-efficiency wet denitration adsorbent into a wet denitration adsorption tower;
step 2, introducing flue gas from an inlet of the wet denitration adsorption tower;
and step 3, discharging the denitrated gas at the outlet of the wet denitration adsorption tower to finish wet denitration.
9. The method for applying a high-efficiency wet denitration adsorbent according to claim 8, wherein in the step 1, the concentration of the sodium hydroxide solution is 0.1mol/L to 1mol/L.
10. The method for applying a high-efficiency wet-process denitration adsorbent according to claim 9, wherein in step 1, the volume mass ratio of the sodium hydroxide solution to the high-efficiency wet-process denitration adsorbent is (1L): (0.1-1 g).
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