CN115155523A - Composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and preparation method and application thereof - Google Patents
Composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and preparation method and application thereof Download PDFInfo
- Publication number
- CN115155523A CN115155523A CN202210871195.1A CN202210871195A CN115155523A CN 115155523 A CN115155523 A CN 115155523A CN 202210871195 A CN202210871195 A CN 202210871195A CN 115155523 A CN115155523 A CN 115155523A
- Authority
- CN
- China
- Prior art keywords
- flue gas
- adsorption catalyst
- composite adsorption
- sulfur dioxide
- removing mercury
- 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.)
- Pending
Links
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003546 flue gas Substances 0.000 title claims abstract description 40
- 229910000474 mercury oxide Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 229920000620 organic polymer Polymers 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 238000001354 calcination Methods 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004890 Hydrophobing Agent Substances 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- -1 polytetrafluoroethylene, perfluoroethylene propylene Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 17
- 230000023556 desulfurization Effects 0.000 abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000004898 kneading Methods 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- 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
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of environmental protection, and particularly relates to a composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas, and a preparation method and application thereof. When the honeycomb composite adsorption catalyst is prepared, the modifier is used for increasing the adsorption capacity of the composite adsorption catalyst on mercury in flue gas, and the hydrophobic property of the organic polymer is used for reducing the surface wettability of the composite adsorption catalyst and treating SO in the flue gas 2 Sulfuric acid droplets generated by oxidation are discharged to the surface of the composite adsorption catalyst, so that self-cleaning and regeneration in the composite adsorption catalyst are improved, the high synergistic demercuration and desulfurization efficiency is kept for a long time, and the service life of the composite adsorption catalyst is prolonged.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas, and a preparation method and application thereof.
Background
Along with the implementation of the ultra-low emission modification of industrial flue gas such as coal-fired power plants, dust and SO in industrial flue gas in China 2 The emission reduction of conventional pollutants such as NOx and the like obtains obvious results, and meanwhile, the key points of the emission reduction of the pollution are gradually shifted to Hg and SO 3 And treating unconventional pollutants. For example, 8 months in 2017, the international mercury convention entitled "water guarantee about mercury" is officially signed in China, and industrial flue gas mercury emission reduction actions in key industries such as coal-fired power plants, industrial boilers, cement, metal smelting, garbage incineration and the like are officially proposed on schedule, the convention requires that mercury emission lists of various industries in the signed country are implemented within 5 years, a specific action scheme is required to be proposed by the signing country within 4 years, new pollution source mercury emission is regulated by adopting an optimal technology within 5 years, and the existing pollution source mercury emission is controlled to be feasible by adopting effective measures within 10 years. At present, hg and SO in the flue gas are controlled 3 The method is generally realized by the prior flue gas purification devices (SCR, ESP/FF, FGD and the like) and the conventional pollutants in a synergic manner or the prior flue gas purification devices are added with special activated carbon injection devices, and the technologies have certain effects on the aspects of desulfurization, denitration, dust removal, mercury removal and the like,however, the method has the problems of secondary pollution, unstable pollutant removal efficiency, continuous regeneration of the absorbent (adsorbent), high material consumption and energy consumption and the like.
In order to overcome the problems, the honeycomb-shaped composite adsorption catalyst is prepared from materials such as activated carbon, organic polymers, a modifier and the like, the composite adsorbent can keep high cooperative demercuration and desulfurization efficiency for a long time, and the cooperative removal of multiple pollutants is realized with low cost, so that the honeycomb-shaped composite adsorption catalyst has great significance for the energy conservation and environmental protection industry of China.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas, and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
a preparation method of a composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas comprises the following steps:
1) Modifying the powdered activated carbon with dilute nitric acid to carry out pretreatment, thereby obtaining clean activated carbon;
2) Uniformly mixing active carbon, an organic high-molecular hydrophobic agent, carboxymethyl cellulose and glass fiber yarns according to the mass ratio of (60-90) to (10-30) to (1-5), adding a mercury adsorption modifier and a mixed solution of water and isopropanol, stirring until a large amount of blocky wet pug materials appear, putting the wet pug materials into a vacuum pug mill, and repeatedly kneading under a vacuum condition to obtain a plastic pug material, wherein the mass ratio of a catalyst to the mixture of the mercury adsorption modifier and the water to the isopropanol is 100 to (1-8) to (80-150);
3) And aging the plastic pug, extruding a blank body on an extruder provided with a honeycomb die, drying the blank body to constant weight, and calcining under the protection of inert gas to obtain the honeycomb composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in the flue gas.
In the above technical scheme:
the activated carbon can effectively oxidize sulfur dioxide in the flue gas into sulfur trioxide, and the sulfur trioxide is combined with moisture in the flue gas to form tiny sulfuric acid droplets;
the mercury adsorption modifier can increase the adsorption capacity of the composite adsorption catalyst on mercury in flue gas;
the organic polymer hydrophobing agent has hydrophobic property, can reduce the surface wettability of the composite adsorption catalyst, and can remove SO from flue gas 2 Sulfuric acid droplets generated by oxidation are discharged to the surface of the composite adsorption catalyst, so that self-cleaning and regeneration in the composite adsorption catalyst are improved, the high cooperative demercuration and desulfurization efficiency of the composite adsorption catalyst is kept for a long time, and the service life of the composite adsorption catalyst is prolonged.
The mass percentage concentration of the dilute nitric acid is 1-10%.
Specifically, the step 1) is as follows: weighing powdered activated carbon, adding into diluted HNO 3 And (3) carrying out rotary evaporation on the solution, cooling, filtering, washing with deionized water until the pH is 6-7, drying at 105-115 ℃ until the balance weight is reached, and cooling to obtain the activated carbon.
Specifically, in the step 1): the specific surface area of the powdered activated carbon is more than 700m 2 The iodine value is more than 500mg/g, and the granularity of 325 meshes is more than 80 percent.
Specifically, in the step 2): the organic polymer hydrophobic agent is selected from one or more of Polytetrafluoroethylene (PTFE), perfluoroethylene propylene copolymer (FEP) and perfluoroalkoxy resin (PFA).
Specifically, in the step 2): the mercury adsorption modifier is selected from KI, KBr, KCl, naI, naBr, naCl and NH 4 I、NH 4 Br、NH 4 Cl、CaI 2 、CaBr 2 、CaCl 2 、MgI 2 、MgBr 2 Or MgCl 2 Any one or more of them mixed.
Specifically, in the step 3): the calcining temperature is 250-350 ℃, and the calcining time is 2-4 h.
The invention also provides the composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in the flue gas, which is prepared by the preparation method.
The composite adsorption catalyst provided by the invention can keep more than 90% of stable demercuration effect and more than 70% of desulfurization efficiency within the service time of 120 h. The catalyst has good demercuration and desulfurization performance and stable service life.
Specifically, the aperture of the composite adsorption catalyst is 6-8 mm, and the aperture ratio is 70-80%.
The invention also provides application of the composite adsorption catalyst to removal of mercury and/or sulfur dioxide in flue gas.
The composite adsorption catalyst provided by the invention has good demercuration and desulfurization performance, has stable service life, and is suitable for removing mercury and/or sulfur dioxide in flue gas.
The invention has the following beneficial effects:
when the honeycomb composite adsorption catalyst is prepared, the modifier is used for increasing the adsorption capacity of the composite adsorption catalyst on mercury in flue gas, and simultaneously the hydrophobic property of the organic polymer is used for reducing the surface wettability of the composite adsorption catalyst and treating SO in the flue gas 2 Sulfuric acid droplets generated by oxidation are discharged to the surface of the composite adsorption catalyst, so that self-cleaning and regeneration in the composite adsorption catalyst are improved, the high synergistic demercuration and desulfurization efficiency is kept for a long time, and the service life of the composite adsorption catalyst is prolonged.
Drawings
Fig. 1 is a graph showing the demercuration efficiency and stability of honeycomb composite adsorption catalysts of examples and comparative examples of the present invention.
FIG. 2 is a graph showing desulfurization efficiency and stability of honeycomb composite adsorption catalysts according to examples of the present invention and comparative examples.
Detailed Description
The principles and features of the present invention are described below, and the examples are provided for illustration only and are not intended to limit the scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
A composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and a preparation method thereof comprise the following steps:
(1) Weighing a certain amount of the powder with the specific surface area more than 700m 2 (ii)/g, powdered activated carbon having an iodine value of more than 500mg/g and a particle size of 325 mesh sieve fraction of more than 80%, adding an appropriate amount of 5% HNO 3 And (3) performing rotary evaporation on the solution, cooling, filtering, washing with deionized water until the pH value is approximately equal to 7, then placing at 110 ℃ for drying until the balance weight is reached, and cooling to obtain the pretreated activated carbon.
(2) According to the mass ratio of 70: KBr: the mass ratio of the water/isopropanol (50. And then putting the wet pug into a vacuum pug mill, and repeatedly kneading the wet pug under a vacuum condition for multiple times to obtain the plastic pug.
(3) And aging the plastic pug, extruding a blank with the aperture of 7mm and the aperture ratio of 76% on an extruder provided with a honeycomb die, drying the blank to constant weight, calcining under the protection of inert gas, controlling the calcining temperature to be 260 ℃ and the calcining time to be 3 hours, and thus obtaining the honeycomb composite adsorption catalyst.
Example 2
A composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and a preparation method thereof comprise the following steps:
(1) Weighing a certain amount of the powder with the specific surface area more than 700m 2 (ii)/g, powdered activated carbon having an iodine value of more than 500mg/g and a particle size of 325 mesh sieve fraction of more than 80%, adding an appropriate amount of 5% HNO 3 And (3) performing rotary evaporation on the solution, cooling, filtering, washing with deionized water until the pH value is approximately equal to 7, then placing at 110 ℃ for drying until the balance weight is reached, and cooling to obtain the pretreated activated carbon.
(2) The preparation method comprises the following steps of (1) putting pretreated activated carbon, PTFE, carboxymethyl cellulose and glass fiber filaments into a mixer according to a mass ratio of 80: caCl 2 : the mass ratio of the water/isopropanol (50And water/isopropanol solution, stirred until a large amount of wet mass appeared. And then putting the wet pug into a vacuum pug mill, and repeatedly kneading the wet pug under the vacuum condition to obtain the plastic pug.
(3) And aging the plastic pug, extruding a blank with the aperture of 8mm and the aperture ratio of 79% on an extruder provided with a honeycomb die, drying the blank to constant weight, calcining under the protection of inert gas, controlling the calcining temperature to be 290 ℃, and calcining for 2 hours to obtain the honeycomb composite adsorption catalyst.
Example 3
A composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and a preparation method thereof comprise the following steps:
(1) Weighing a certain amount of the powder with the specific surface area more than 700m 2 (ii)/g, powdered activated carbon having an iodine value of more than 500mg/g and a particle size of 325 mesh sieve fraction of more than 80%, adding an appropriate amount of 5% HNO 3 And (3) performing rotary evaporation on the solution, cooling, filtering, washing with deionized water until the pH value is approximately equal to 7, then placing at 110 ℃ for drying until the balance weight is reached, and cooling to obtain the pretreated activated carbon.
(2) The preparation method comprises the following steps of (1) putting pretreated activated carbon, PTFE, carboxymethyl cellulose and glass fiber filaments into a mixer according to a mass ratio of 65: KCl: the mass ratio of the water/isopropanol (50. And then putting the wet pug into a vacuum pug mill, and repeatedly kneading the wet pug under a vacuum condition for multiple times to obtain the plastic pug.
(3) And aging the plastic pug, extruding a blank with the aperture of 6mm and the aperture ratio of 73% on an extruder provided with a honeycomb die, drying the blank to constant weight, calcining under the protection of inert gas, controlling the calcining temperature to be 310 ℃, and calcining for 4 hours to obtain the honeycomb composite adsorption catalyst.
Comparative example
This comparative example differs from example 1 in that: when the honeycomb-shaped composite adsorption catalyst is prepared, organic polymers and modifiers are not added, wherein the corresponding share of the organic polymers is replaced by pretreated powdered activated carbon, and other steps and process parameters are the same as those in the embodiment 1.
In the above examples, the organic polymer, the kind of the modifier and the amount of the raw material added in the honeycomb composite adsorption catalyst were examined, and the pore diameter, the open pore ratio and the calcination temperature of the honeycomb were also examined.
The composite adsorption catalysts prepared in the above examples and comparative examples were subjected to mercury removal and desulfurization performance tests: the demercuration and desulfurization performance test is carried out in a fixed bed, the composite adsorption catalyst is cut into samples with the size of (20-30) mmX (20-30) mm X50 mm along the pore canal direction, and the samples are placed in a bed layer along the axial line of a reactor; the component of the flue gas is that the concentration of Hg is approximately equal to 1.0mg/m 3 、H 2 O concentration is approximately equal to 6 percent and O 2 Concentration is approximately equal to 6 percent, and CO 2 Concentration is approximately equal to 12 percent and SO 2 The concentration is about 1500ppm, the NO concentration is about 300ppm, and N 2 The airspeed of the mixed gas is 3000-5000 h for balancing gas -1 The temperature of the reactor is approximately equal to 60 ℃, and the test results are shown in figure 1 and figure 2.
As can be seen from fig. 1, the composite adsorption catalysts prepared by the same organic polymer, the type of the modifier, and different parameters such as pore size, opening ratio, calcination condition, etc., show different demercuration effects, wherein the composite adsorption catalyst of example 1 has the best demercuration effect, maintains more than 90% of stable demercuration effect at nearly 120h, and has the most outstanding service life effect, while the composite adsorption catalysts of examples 2 and 3 have reduced demercuration efficiency and stability, but have improved demercuration efficiency and stability compared with the comparative examples.
As can be seen from fig. 2, similar to the demercuration rate, the desulfurization effects of the composite adsorption catalysts prepared by the same organic polymer, the same type of modifier, and different parameters such as pore diameter, open pore ratio, calcination condition, etc. are different, wherein the desulfurization effect of the composite adsorption catalyst of example 1 is the best, the desulfurization efficiency is maintained to be more than 70% within 120h, while the desulfurization efficiency of the composite adsorption catalysts of examples 2 and 3 is slightly lower than that of example 1, and the desulfurization effects of the composite adsorption catalysts of examples 1 to 3 are better than that of the comparative example.
The composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and the preparation method thereof have good performance of mercury removal and desulfurization at the same time, and have stable service life.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (9)
1. A preparation method of a composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas is characterized by comprising the following steps:
1) Pretreating the powdered activated carbon with dilute nitric acid to obtain clean activated carbon
2) Uniformly mixing pretreated active carbon, organic polymer hydrophobing agent, carboxymethyl cellulose and glass fiber yarn according to the mass ratio of (60-90) to (10-30) to (1-5), adding a mercury adsorption modifier and a mixed solution of water and isopropanol to obtain wet pug, and then pugging to obtain plastic pug, wherein the mass ratio of the active carbon to the mercury adsorption modifier to the mixed solution of water and isopropanol is 100 (1-8) to (80-150);
3) And aging the plastic pug, extruding a blank body on an extruder provided with a honeycomb die, drying the blank body to constant weight, and calcining under the protection of inert gas to obtain the honeycomb composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in the flue gas.
2. The preparation method of the composite adsorption catalyst for synergistically removing mercury and sulfur dioxide from flue gas according to claim 1, wherein the step 1) is as follows: weighing powdered activated carbon, adding into diluted HNO 3 And (3) performing rotary evaporation on the solution, cooling, filtering, washing with deionized water until the pH is = 6-7, drying at 105-115 ℃ until the weight is balanced, and cooling to obtain the pretreated activated carbon.
3. Synergy according to claim 2The preparation method of the composite adsorption catalyst for removing mercury and sulfur dioxide in flue gas is characterized in that in the step 1): the specific surface area of the powdered activated carbon is more than 700m 2 The iodine value is more than 500mg/g, and the sieve rate of the particle size of 325 meshes is more than 80 percent.
4. The method for preparing the composite adsorption catalyst for synergistically removing mercury and sulfur dioxide from flue gas according to claim 1, wherein in the step 2): the organic polymer hydrophobic agent is selected from one or more of polytetrafluoroethylene, perfluoroethylene propylene copolymer and perfluoroalkoxy resin.
5. The method for preparing the composite adsorption catalyst for synergistically removing mercury and sulfur dioxide from flue gas according to claim 1, wherein in the step 2): the mercury adsorption modifier is selected from KI, KBr, KCl, naI, naBr, naCl and NH 4 I、NH 4 Br、NH 4 Cl、CaI 2 、CaBr 2 、CaCl 2 、MgI 2 、MgBr 2 Or MgCl 2 Any one or more of them.
6. The method for preparing the composite adsorption catalyst for synergistically removing mercury and sulfur dioxide from flue gas according to any one of claims 1 to 5, wherein in the step 3): the calcining temperature is 250-350 ℃, and the calcining time is 2-4 h.
7. A composite adsorption catalyst for synergistically removing mercury and sulfur dioxide from flue gas, prepared by the preparation method according to any one of claims 1 to 6.
8. The composite adsorption catalyst for synergistically removing mercury and sulfur dioxide from flue gas according to claim 7, wherein: the aperture is 6-8 mm, and the aperture ratio is 70-80%.
9. The application of the composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas according to claim 7 or 8 is characterized in that: used for removing mercury and/or sulfur dioxide in flue gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210871195.1A CN115155523A (en) | 2022-07-22 | 2022-07-22 | Composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210871195.1A CN115155523A (en) | 2022-07-22 | 2022-07-22 | Composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115155523A true CN115155523A (en) | 2022-10-11 |
Family
ID=83496491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210871195.1A Pending CN115155523A (en) | 2022-07-22 | 2022-07-22 | Composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115155523A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311714A (en) * | 1998-04-07 | 2001-09-05 | 千代田化工建设株式会社 | Desulphurization of exhaust gases using activated carbon catalyst |
| CN1772340A (en) * | 2004-11-09 | 2006-05-17 | 戈尔企业控股股份有限公司 | Flue-gas processing technique based on adsorbent-polymer composite material |
| CN104475122A (en) * | 2014-12-02 | 2015-04-01 | 浙江大学 | Forming SCR catalyst with both water resistance and sulphur resistance and preparation method thereof |
| CN106345482A (en) * | 2016-08-31 | 2017-01-25 | 无锡华光新动力环保科技股份有限公司 | Mixing technology of synergic denitration and demercuration catalyst for flue gas of coal-fired power plant |
| CN107530620A (en) * | 2015-02-27 | 2018-01-02 | W.L.戈尔及同仁股份有限公司 | Use the flue gas cleaning system and method for absorbent polymer composite |
| CN110227560A (en) * | 2019-07-19 | 2019-09-13 | 西安热工研究院有限公司 | A kind of preparation method of honeycomb copper chloride/SCR demercuration catalyst |
| CN110339701A (en) * | 2019-07-08 | 2019-10-18 | 北京清新环境技术股份有限公司 | A kind of System and method for of cooperation-removal mercury in flue gas and sulfur dioxide |
| CN113351155A (en) * | 2021-06-11 | 2021-09-07 | 清华大学 | Adsorbing material and preparation method and application thereof |
-
2022
- 2022-07-22 CN CN202210871195.1A patent/CN115155523A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311714A (en) * | 1998-04-07 | 2001-09-05 | 千代田化工建设株式会社 | Desulphurization of exhaust gases using activated carbon catalyst |
| CN1772340A (en) * | 2004-11-09 | 2006-05-17 | 戈尔企业控股股份有限公司 | Flue-gas processing technique based on adsorbent-polymer composite material |
| CN104475122A (en) * | 2014-12-02 | 2015-04-01 | 浙江大学 | Forming SCR catalyst with both water resistance and sulphur resistance and preparation method thereof |
| CN107530620A (en) * | 2015-02-27 | 2018-01-02 | W.L.戈尔及同仁股份有限公司 | Use the flue gas cleaning system and method for absorbent polymer composite |
| CN106345482A (en) * | 2016-08-31 | 2017-01-25 | 无锡华光新动力环保科技股份有限公司 | Mixing technology of synergic denitration and demercuration catalyst for flue gas of coal-fired power plant |
| CN110339701A (en) * | 2019-07-08 | 2019-10-18 | 北京清新环境技术股份有限公司 | A kind of System and method for of cooperation-removal mercury in flue gas and sulfur dioxide |
| CN110227560A (en) * | 2019-07-19 | 2019-09-13 | 西安热工研究院有限公司 | A kind of preparation method of honeycomb copper chloride/SCR demercuration catalyst |
| CN113351155A (en) * | 2021-06-11 | 2021-09-07 | 清华大学 | Adsorbing material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4860076B2 (en) | Process for producing a catalyst for selective catalytic reduction of nitrogen oxides | |
| WO2015149499A1 (en) | Low-temperature and highly efficient denitration catalyst and preparation method therefor | |
| CN109225248B (en) | Honeycomb type low-temperature denitration catalyst and preparation process thereof | |
| CN101428212B (en) | Selective catalysis reduction denitrate catalyst for composite carrier flue gas and preparation method thereof | |
| CN106582606B (en) | Non-vanadium low-temperature denitration catalyst and preparation method thereof | |
| CN106824168B (en) | Catalyst for exhaust gas treatment and method for producing same | |
| CN102974368A (en) | Deactivated SCR denitration catalyst regeneration method | |
| CN1843575A (en) | Method and apparatus for optic catalytic oxidizing, desulfurizing and denitrifying flue gas simultaneously | |
| CN109224874A (en) | A kind of catalytic membrane and preparation method thereof for air cleaning | |
| CN107126949B (en) | A kind of SCR denitration and preparation method thereof of anti-arsenic poisoning | |
| CN104001371A (en) | Method for recycling waste dust removal filter material | |
| CN106268786A (en) | A kind of low-temperature denitration catalyst and preparation method thereof | |
| CN112938969A (en) | Method for preparing nitrogen-sulfur co-doped activated carbon by pore-forming/doping integrated activating agent and application of method | |
| CN108993504B (en) | Modified activated coke for demercuration of sulfur-containing flue gas and preparation method thereof | |
| TW562697B (en) | A method for preparing a catalyst for selective catalytic reduction of nitrogen oxides at high temperature window | |
| WO1994021373A1 (en) | Nitrogen oxide decomposing catalyst and denitration method using the same | |
| KR100668926B1 (en) | Method of regenerating scr catalyst | |
| CN108607542A (en) | A kind of denitration demercuration catalyst and preparation method thereof | |
| CN115155523A (en) | Composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and preparation method and application thereof | |
| CN112121816A (en) | Low-temperature catalyst special for waste incineration | |
| CA2427081C (en) | Catalyst compound for purifying exhaust gas, catalyst comprising the compound, and processes for producing them | |
| JP4873211B2 (en) | Catalyst for selective catalytic reduction of nitrogen oxides and method for producing the same. | |
| CN108654311A (en) | A kind of high-efficiency desulfurization denitration absorbent and preparation method thereof | |
| CN115364868A (en) | Catalyst for catalytic decomposition of ozone and preparation method thereof | |
| CN105582910A (en) | Preparation method of cooperating catalyst for demercuration and denitration |
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 |