CN110694474B - A green and low-cost flue gas mercury removal method - Google Patents
A green and low-cost flue gas mercury removal method Download PDFInfo
- Publication number
- CN110694474B CN110694474B CN201911161899.4A CN201911161899A CN110694474B CN 110694474 B CN110694474 B CN 110694474B CN 201911161899 A CN201911161899 A CN 201911161899A CN 110694474 B CN110694474 B CN 110694474B
- Authority
- CN
- China
- Prior art keywords
- red mud
- flue gas
- montmorillonite
- mercury
- demercuration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 24
- 239000003546 flue gas Substances 0.000 title claims description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052753 mercury Inorganic materials 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 17
- 239000003054 catalyst Substances 0.000 claims description 39
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 31
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 31
- 239000010802 sludge Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000004131 Bayer process Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- -1 hydroxy iron aluminum Chemical compound 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 10
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 8
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 8
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 101150019148 Slc7a3 gene Proteins 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种绿色、低成本的烟气脱汞方法，属于废物综合利用和气体净化领域。本发明的烟气脱汞方法是将烟气通入利用天然矿土和废渣制备的脱汞催化剂的床层中，使得烟气中的Hg0经催化氧化为Hg2+，实现汞的脱除。所述催化剂以成本低廉的天然矿土蒙脱石和工业废弃物赤泥、污泥为原料，有效利用赤泥中含有的Fe、Al、Ti等金属和碱以及污泥中的有机质，具有孔隙率高、比表面积大、金属固载稳定的优势，其比表面积可达178m2/g。本发明的烟气脱汞方法能够在较低温度下实现Hg0的高效氧化，具有极高的工业和环保价值。The invention relates to a green and low-cost method for removing mercury from flue gas, and belongs to the fields of comprehensive utilization of waste and gas purification. The method for removing mercury from flue gas of the present invention is to pass the flue gas into a bed of a mercury removing catalyst prepared by using natural ore and waste residue, so that Hg 0 in the flue gas is catalytically oxidized to Hg 2+ , so as to realize the removal of mercury . The catalyst uses low-cost natural mineral montmorillonite, industrial waste red mud and sludge as raw materials, effectively utilizes metals such as Fe, Al, Ti and other metals and alkalis contained in the red mud and organic matter in the sludge, and has a porosity. It has the advantages of high specific surface area, large specific surface area and stable metal loading, and its specific surface area can reach 178m 2 /g. The flue gas mercury removal method of the invention can realize the efficient oxidation of Hg 0 at a lower temperature, and has extremely high industrial and environmental protection value.
Description
Technical Field
The invention relates to a green and low-cost flue gas demercuration method, and belongs to the field of waste comprehensive utilization and gas purification.
Background
The coal as the most main energy occupies more than 70% of the energy structure in China, and the coal consumed in China every year occupies 31% of the total consumption of raw coal in the world. However, the average mercury content in the coal in China is 0.22mg/kg, which is far higher than the world average mercury content of 0.13 mg/kg. The amount of mercury discharged to the atmosphere in China every year due to coal-fired power stations is 500-700 t, and accounts for about 30% of the total emission amount of the world. Therefore, how to effectively control mercury in coal-fired flue gas has become an urgent problem to be solved.
The catalytic oxidation demercuration technology is to remove Hg in flue gas0Oxidation to easily removed Hg2+The technique of (1). The research on the mercury catalytic oxidation technology at present is mainly for the development of catalysts, and the catalysts can be divided into three categories: SCR catalyst, catalyst using carbon as carrier to load metal, metal and its oxide. The catalysts all adopt pure chemical reagents as raw materials, the preparation cost is high, and how to develop the catalyst which is low in price and can ensure high catalytic oxidation efficiency becomes the key point of research.
Montmorillonite is a common natural mineral, and in recent years, part of scholars adopt modified montmorillonite for mercury removal. CN105664838A discloses a mercury removal adsorbent of pillared montmorillonite loaded with metal oxide, which has higher thermal stability through the synergistic action between pillared montmorillonite and active componentsQualitative, high demercuration efficiency, low cost, environmental friendliness and great application potential. The research institute of process engineering of Chinese academy of sciences also uses the montmorillonite loaded with manganese for the catalytic oxidation of elemental mercury in flue gas, and the result shows that 4% Mn/montmorillonite shows good mercury removal efficiency and has potential industrial application value (research on the catalytic oxidation of elemental mercury by montmorillonite-loaded manganese catalyst, Wu Ying hong, Chinese outstanding Master thesis). Therefore, the combination of the montmorillonite and the metal oxide can effectively adsorb and catalyze and oxidize Hg in the smoke. The red mud is Al produced in bauxite industry2O3The strong alkaline solid residue generated in the process and the waste alkali liquor in the red mud can cause soil alkalization, swampiness and pollution to surface and underground water sources, and directly harm human health. China is the world with the highest output of alumina and red mud, and in China, each ton of Al2O31-1.6 tons of red mud can be formed during the production, but the utilization rate is less than 15%, so that the comprehensive utilization of the red mud is widely concerned. The red mud mainly comprises iron oxide and hydroxide, aluminum oxide and hydroxide, kaolinite, quartz, calcite, titanium oxide and other substances, and is rich in metal elements. If the metal elements in the red mud can be effectively utilized, the waste is changed into valuable, and the method is one of effective sections for solving the problem of mass accumulation of the red mud in the current national conditions. In addition, the municipal sewage treatment plant can generate a lot of sludge which contains rich organic matters, and the sludge can form sludge carbon with rich pore structures after being carbonized, so that the sludge carbon has good adsorption capacity.
Based on the prior art, the inventor develops a method for preparing the flue gas demercuration catalyst by using natural mineral soil montmorillonite, solid waste red mud and sludge as raw materials through long-term research, and the method is used for flue gas catalytic oxidation demercuration. The obtained catalyst effectively utilizes metal Fe, Al and Ti contained in the red mud and organic matters in alkali and sludge, has low cost, can solve the problems of accumulation of industrial wastes and environmental pollution, can change waste into valuable by applying the catalyst to flue gas demercuration, treats waste by waste, and has wide application prospect.
Disclosure of Invention
The invention aims to provide a green and low-cost flue gas demercuration method, namely, flue gas is introduced into a demercuration catalyst bed layer prepared from natural ore soil and waste residues, so that Hg in the flue gas is removed0Is oxidized into Hg by catalysis2+And mercury removal is realized. The catalyst takes low-cost natural mineral soil montmorillonite and industrial waste red mud and sludge as raw materials, effectively utilizes metals such as Fe, Al, Ti and the like and alkali contained in the red mud to simultaneously carry out pillared modification and loading on the montmorillonite, and then is mixed and carbonized with the sludge to form a porous structure. The catalyst prepared by the invention has the advantages of high porosity, large specific surface area and stable metal immobilization, wherein the specific surface area can reach 178m2Per g, pore volume up to 0.49m3The mercury removal catalyst is applied to flue gas mercury removal, and can realize Hg at a lower temperature0High efficiency oxidation.
Specifically, the green and low-cost flue gas demercuration method comprises the following steps:
introducing the flue gas into a demercuration catalyst bed layer filled with natural ore soil and waste residues to ensure that Hg in the flue gas is removed0Is oxidized into Hg by catalysis2+The mercury removal is realized, the reaction temperature is 150-400 ℃, and the feeding space velocity is 1000-30000h-1；
The preparation method of the demercuration catalyst comprises the following steps:
(1) adding red mud into water with the volume 2-5 times that of the red mud, continuously stirring, filtering, collecting filtrate, and recovering alkali in the red mud, wherein the filtrate is recorded as s 1; adding 0.1-0.8mol/L hydrochloric acid into the obtained red mud, adding acid, and stirring for 0.5-2h to dissolve partial metal Al and Fe in the red mud, wherein the liquid-solid ratio L/S =2-10mL/g, and the obtained suspension is marked as S2;
(2) slowly adding the filtrate S1 into the suspension S2 under continuous stirring, adding the amount of liquid-solid ratio L/S =2-5mL/g, continuously adding water with the volume of 15-20 times that of the filtrate S1, stirring for 1-3h, standing and aging to ensure that dissolved Al and Fe form hydroxyl compounds, and recording the obtained suspension as S3;
(3) adding dried montmorillonite into the suspension s3, wherein the adding amount is 0.5-2 times of the mass of the solid in the suspension, continuously stirring to ensure that hydroxy iron aluminum carries out pillared modification on the montmorillonite, standing for aging, filtering, washing and drying to obtain a mixture of red mud and pillared montmorillonite;
(4) and mixing the mixture of the red mud and the pillared montmorillonite with 10-20wt% of dehydrated dry sludge, roasting and carbonizing at 900 ℃ for 5-10h under a nitrogen atmosphere, and continuously roasting at 500 ℃ for 2-6h under an air atmosphere at 300-.
The obtained demercuration catalyst takes sludge carbon, pillared montmorillonite, aluminosilicate and the like as carriers, and takes loaded ferric oxide, alumina, titanium oxide and other small amount of metal oxides as active components. Wherein, transition metal oxide iron oxide is used as a main catalytic active component, titanium oxide and other small amount of metal components are used as auxiliary agents, and aluminum oxide can regulate the acidity of the catalyst. Organic matters in the sludge are continuously volatilized in the carbonization process, and the volatilized gas can effectively expand the pores of the catalyst, so that the catalyst forms a loose and porous structure, and the mass transfer is enhanced.
Furthermore, the red mud is Bayer process red mud, and is marked by mass fraction Al2O35-20wt% of Fe2O3The content is 5-35 wt%.
Further, the montmorillonite is acid-pretreated montmorillonite.
Further, the aging in the steps (2) and (3) is carried out at room temperature, and the aging time is 6-10 h.
Further, the air speed of the flue gas is 5000-10000h-1The reaction temperature is 200-300 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the flue gas demercuration catalyst provided by the invention adopts natural minerals and industrial wastes as raw materials, is low in cost, can solve the problems of accumulation of the industrial wastes and environmental pollution, changes waste into valuable, and treats waste with waste; the specific surface area of the obtained catalyst can reach 178m2The preparation method has the advantages of simple preparation process, mild conditions and suitability for large-scale production.
(2) The inventionThe flue gas demercuration method can realize Hg at lower temperature (200-300 ℃), and0high efficiency catalytic oxidation of Hg0The oxidation rate of the mercury removing agent can reach 70-80%, and the mercury removing agent is a green, low-cost and efficient flue gas mercury removing method.
Drawings
FIG. 1 shows N of Cat1, Cat2 and Cat32-adsorption/desorption isotherms; wherein, A is Cat1, B is Cat2, and C is Cat 3.
FIG. 2 shows that Cat1, Cat2 and Cat3 are used for simulating Hg in smoke at different temperatures0Oxidation rate of (c).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Red mud (Bayer process red mud, Al)2O310wt% of Fe2O325 wt%) into water with 4 times volume, continuously stirring and filtering, collecting filtrate, recovering alkali in the red mud, and recording the filtrate as s 1; adding 0.5mol/L hydrochloric acid into the obtained red mud, stirring for 2 hours to dissolve partial metal Al and Fe in the red mud, wherein the liquid-solid ratio of the added acid is L/S =8mL/g, and the obtained suspension is recorded as S2;
(2) slowly adding the filtrate S1 into the suspension S2 under continuous stirring, adding the amount of liquid-solid ratio L/S =4mL/g, continuously adding water with the volume being 20 times that of the filtrate S1, stirring for 2h, standing and aging at room temperature for 8h to ensure that dissolved Al and Fe form hydroxyl compounds, and recording the obtained suspension as S3;
(3) adding dried montmorillonite into the suspension s3, wherein the adding amount is 1 time of the mass of the solid in the suspension, continuously stirring to ensure that hydroxy iron aluminum carries out pillared modification on the montmorillonite, standing and aging for 8 hours at room temperature, filtering, washing and drying to obtain a mixture of red mud and pillared montmorillonite;
(4) and (3) mixing the mixture of the red mud and the pillared montmorillonite with dehydrated and dried sludge with the mass fraction of 18wt%, roasting and carbonizing for 8 hours at 900 ℃ under a nitrogen atmosphere, and continuously roasting for 4 hours at 400 ℃ under an air atmosphere to obtain the demercuration catalyst which is recorded as Cat 1.
Example 2
The prepared demercuration catalyst Cat1 (0.3 g) is filled in a fixed bed reactor, and simulated flue gas with the composition of 4 percent of O is introduced2，10% CO2，400 ppm SO2，8% H2O, 10 ppm HCl, 200 ppm NO, and N2Balancing gas; by using CO2Hg is used as a carrier0（50μg/m3) Introducing into a reactor at a flow rate of 1L/min and a space velocity of 10000h-1. The mercury oxidation rate was calculated by measuring the reactor outlet mercury content.
Comparative example 1
Using chemical reagent AlCl3、Na2CO3Montmorillonite is subjected to pillared modification and then loaded with Mn by an impregnation method to prepare a 4% Mn/montmorillonite catalyst which is recorded as Cat 2.
Comparative example 2
The addition of sludge and carbonization steps were omitted from the preparation of example 1 and the resulting catalyst was designated Cat 3.
FIG. 1 shows N of Cat1, Cat2 and Cat32Adsorption/desorption isotherms and the pore structure parameters of the catalysts obtained are given in table 1.
TABLE 1
| Catalyst and process for preparing same | Specific surface area (m)2/g） | Pore volume (cm)3/g） |
| Cat1 | 178 | 0.49 |
| Cat2 | 140 | 0.40 |
| Cat3 | 93 | 0.23 |
As can be seen from Table 1, Cat3 without sludge pore-enlarging shows the lowest specific surface, the porosity of the catalyst after sludge carbonization pore-enlarging is greatly improved, and the specific surface can reach 178m2The content of the catalyst is better than that of Mn/montmorillonite of 4 percent, and the invention obtains the oxidation demercuration catalyst with richer pore structures.
FIG. 2 shows Hg for Cat1, Cat2, Cat3 under test conditions0Oxidation rate of (c). As can be seen from the figure, the sludge charring pore-expanded catalyst of the present invention has better Hg than the 4% Mn/montmorillonite and non-pore-expanded catalyst0The highest oxidation rate of the catalyst can reach more than 80 percent. The catalyst has more mass transfer channels and more adsorption sites after being expanded, the probability of contact with catalytic oxidation active components is greatly improved, and meanwhile, the metal components contained in the red mud generate a synergistic promotion effect, so that the catalytic efficiency of the catalyst obtained by the invention is greatly improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (3)
1. A green and low-cost flue gas demercuration method is characterized by comprising the following steps:
introducing the flue gas into a demercuration catalyst bed layer filled with natural ore soil and waste residues to ensure that Hg in the flue gas is removed0Is oxidized into Hg by catalysis2+The mercury removal is realized; the demercuration reaction temperature is 200-300 ℃, the feeding airspeed is 5000-10000h-1；
The preparation method of the demercuration catalyst comprises the following steps:
(1) adding red mud into water with the volume 2-5 times that of the red mud, continuously stirring, filtering, collecting filtrate, and recovering alkali in the red mud, wherein the filtrate is recorded as s 1; adding 0.1-0.8mol/L hydrochloric acid into the obtained red mud, adding acid, and stirring for 0.5-2h to dissolve partial metal Al and Fe in the red mud, wherein the liquid-solid ratio L/S =2-10mL/g, and the obtained suspension is marked as S2;
(2) slowly adding the filtrate S1 into the suspension S2 under continuous stirring, adding the amount of liquid-solid ratio L/S =2-5mL/g, continuously adding water with the volume of 15-20 times that of the filtrate S1, stirring for 1-3h, standing and aging to ensure that dissolved Al and Fe form hydroxyl compounds, and recording the obtained suspension as S3;
(3) adding dried montmorillonite into the suspension s3, wherein the adding amount is 0.5-2 times of the mass of the solid in the suspension, continuously stirring to ensure that hydroxy iron aluminum carries out pillared modification on the montmorillonite, standing for aging, filtering, washing and drying to obtain a mixture of red mud and pillared montmorillonite;
(4) mixing the mixture of the red mud and the pillared montmorillonite with 10-20wt% of dehydrated dry sludge, roasting and carbonizing at 900 ℃ for 5-10h under nitrogen atmosphere and at 500 ℃ under air atmosphere for 2-6h to obtain the demercuration catalyst;
the ageing in the steps (2) and (3) is carried out at room temperature, and the ageing time is 6-10 h.
2. The method according to claim 1, wherein the red mud is bayer process red mud, in mass fraction, Al2O35-20wt% of Fe2O3The content is 5-35 wt%.
3. The method of claim 1, wherein the montmorillonite is acid pretreated montmorillonite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911161899.4A CN110694474B (en) | 2019-11-25 | 2019-11-25 | A green and low-cost flue gas mercury removal method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911161899.4A CN110694474B (en) | 2019-11-25 | 2019-11-25 | A green and low-cost flue gas mercury removal method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110694474A CN110694474A (en) | 2020-01-17 |
| CN110694474B true CN110694474B (en) | 2021-05-18 |
Family
ID=69206665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911161899.4A Active CN110694474B (en) | 2019-11-25 | 2019-11-25 | A green and low-cost flue gas mercury removal method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110694474B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415850A (en) * | 1993-02-24 | 1995-05-16 | The Research Foundation Of State Univeristy Of New York | Pillared interlayered clay catalysts for the selective reduction of nitrogen oxides with ammonia |
| CN102698753A (en) * | 2012-05-15 | 2012-10-03 | 中国科学院过程工程研究所 | Catalyst for mercury oxidation and preparation method and purpose thereof |
| CN102872871A (en) * | 2012-09-20 | 2013-01-16 | 广东电网公司电力科学研究院 | Catalytic agent for catalytic oxidation of elemental mercury in coal-fired flue gas and preparation method thereof |
| CN103127905A (en) * | 2011-12-01 | 2013-06-05 | 孟宪清 | Preparative technique for bentonite particles |
| WO2016175706A1 (en) * | 2015-04-30 | 2016-11-03 | Nanyang Technological University | A pillared clay catalyst |
| CN107537492A (en) * | 2017-10-24 | 2018-01-05 | 中国科学院过程工程研究所 | A kind of method that iron system denitrating catalyst is directly prepared by the activation of red mud soda acid |
| CN108686651A (en) * | 2018-05-30 | 2018-10-23 | 临沂大学 | A kind of catalyst and its preparation method and application of flue gas denitration demercuration simultaneously |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7763566B2 (en) * | 2006-03-23 | 2010-07-27 | J.I. Enterprises, Inc. | Method and composition for sorbing toxic substances |
| US9295939B2 (en) * | 2008-04-06 | 2016-03-29 | Innosepra Llc | Carbon dioxide recovery |
| ES2395507B1 (en) * | 2011-06-03 | 2013-12-19 | Nanobiomatters Research & Development, S.L. | NANOCOMPOSED MATERIALS BASED ON METAL OXIDES WITH MULTIFUNCTIONAL PROPERTIES |
| US10449492B2 (en) * | 2014-05-30 | 2019-10-22 | Ada Carbon Solutions, Llc | Catalytically enhanced compositions for efficient removal of contaminants in flue gas streams |
-
2019
- 2019-11-25 CN CN201911161899.4A patent/CN110694474B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415850A (en) * | 1993-02-24 | 1995-05-16 | The Research Foundation Of State Univeristy Of New York | Pillared interlayered clay catalysts for the selective reduction of nitrogen oxides with ammonia |
| CN103127905A (en) * | 2011-12-01 | 2013-06-05 | 孟宪清 | Preparative technique for bentonite particles |
| CN102698753A (en) * | 2012-05-15 | 2012-10-03 | 中国科学院过程工程研究所 | Catalyst for mercury oxidation and preparation method and purpose thereof |
| CN102872871A (en) * | 2012-09-20 | 2013-01-16 | 广东电网公司电力科学研究院 | Catalytic agent for catalytic oxidation of elemental mercury in coal-fired flue gas and preparation method thereof |
| WO2016175706A1 (en) * | 2015-04-30 | 2016-11-03 | Nanyang Technological University | A pillared clay catalyst |
| CN107537492A (en) * | 2017-10-24 | 2018-01-05 | 中国科学院过程工程研究所 | A kind of method that iron system denitrating catalyst is directly prepared by the activation of red mud soda acid |
| CN108686651A (en) * | 2018-05-30 | 2018-10-23 | 临沂大学 | A kind of catalyst and its preparation method and application of flue gas denitration demercuration simultaneously |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110694474A (en) | 2020-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107213787A (en) | A kind of desulfurizing agent and preparation method thereof | |
| CN101293170A (en) | A kind of composite material sulfur dioxide desulfurizer and preparation method thereof | |
| CN103111264B (en) | The preparation method of a kind of ionic liquid and the two modification bacterium slag active carbon of metal and application | |
| CN106881019A (en) | A kind of method that utilization red mud and activated carbon thermal activation prepare desulfurizing agent | |
| CN110893312A (en) | Novel high-efficiency desulfurizer and preparation method thereof | |
| CN102836621A (en) | Flue gas desulfurizing agent and preparation method thereof | |
| CN101804344A (en) | Manganese/carbon nanotube denitrification catalytic reduction catalyst and preparation method thereof | |
| CN105536886A (en) | Regeneration method of arsenic poisoning denitration catalyst | |
| WO2023016311A1 (en) | Sludge-ash-modified titanium oxide-biochar composite photocatalyst, preparation method therefor and application thereof | |
| Jiang et al. | Simultaneous removal of hydrogen sulfide and ammonia in the gas phase: a review | |
| CN107159088B (en) | Mercury-containing material with lasting adsorption performance | |
| CN110833830B (en) | A method for preparing mercury removal catalyst by utilizing natural ore and waste residue | |
| CN110694474B (en) | A green and low-cost flue gas mercury removal method | |
| CN204395780U (en) | A kind of combined desulfurization and denitration fluidized bed plant based on active carbon and low temperature catalyst | |
| CN104368323B (en) | Carbon-based catalyst for desulfurization and denitrification as well as preparation method and application of catalyst | |
| CN111111619A (en) | Efficient adsorbent for treating volatile organic compounds in coal chemical production process | |
| CN103691448B (en) | The preparation method of magnetic sludge base ozone catalyst and application | |
| CN115770571A (en) | Copper-based catalyst-loaded sludge activated carbon and preparation method and application thereof | |
| CN101767041A (en) | Preparation method of flue gas denitration catalyst | |
| CN112547046B (en) | Preparation method of environment-friendly denitration catalyst based on vanadium-titanium slag | |
| CN111348976A (en) | A method for preparing multi-element compound fertilizer from waste activated carbon after flue gas desulfurization and denitrification | |
| CN114259980A (en) | Method for preparing heavy metal adsorption stabilizer by using entrained flow bed gasified fine ash | |
| CN114471044A (en) | Efficient purification method of active coke flue gas | |
| CN1579614A (en) | Method for preparing active carbon base material SO2 adsorbent | |
| CN101766945B (en) | Dry-process integrating method for purifying smoke and system used therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210427 Address after: 201-206, floor 2, Kangya Dongyuan property building, Yexu Town, Taizhou pharmaceutical high tech Industrial Development Zone, Jiangsu Province Applicant after: Taizhou Qingrun Environmental Protection Technology Co.,Ltd. Address before: No. 15-1, group 8, Yongfeng Village, Yexu Town, medical high tech Zone, Taizhou City, Jiangsu Province Applicant before: Xu Shumin |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230626 Address after: Room 112, Building 1, No. 2, Naxian Street, Liangzhu Street, Yuhang District, Hangzhou City, Zhejiang Province, 311100 Patentee after: Hangzhou Lvyuan New Materials Co.,Ltd. Address before: 225300 201-206, 2nd floor, Kangya Dongyuan property building, Yexu Town, Taizhou pharmaceutical hi tech Industrial Development Zone, Jiangsu Province (settled in Jiangsu Heqi business secretary Co., Ltd. - 3) Patentee before: Taizhou Qingrun Environmental Protection Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20241125 Address after: First Floor, Building 2, No. 20 Sanxing Road, Renhe Street, Yuhang District, Hangzhou City, Zhejiang Province 310000 Patentee after: Hangzhou hanglian Lubricating Oil Co.,Ltd. Country or region after: China Address before: Room 112, Building 1, No. 2, Naxian Street, Liangzhu Street, Yuhang District, Hangzhou City, Zhejiang Province, 311100 Patentee before: Hangzhou Lvyuan New Materials Co.,Ltd. Country or region before: China |