CN116059956B - EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration, and preparation method and application thereof - Google Patents
EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration, and preparation method and application thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 65
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 58
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003546 flue gas Substances 0.000 title claims abstract description 30
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 33
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000009434 installation Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- -1 Al 2O3 Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- ISIHFYYBOXJLTM-UHFFFAOYSA-N vanadium;pentasilicate Chemical compound [V].[V].[V].[V].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] ISIHFYYBOXJLTM-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J20/06—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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present disclosure relates to an EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration, and a preparation method and an application thereof. The catalytic adsorbent comprises a carrier and an active component loaded on the carrier; wherein the carrier comprises an EVS-10 molecular sieve, and the active component comprises CeO 2. The active component containing CeO 2 is successfully loaded on the EVS-10 molecular sieve, the CeO 2 loaded by the catalytic adsorbent has high dispersity, can simultaneously have excellent mercury removal efficiency and higher denitration efficiency, has good application effect in the aspect of cooperatively removing elemental mercury and nitrogen oxides in coal-fired flue gas, and reduces equipment installation and use cost; the catalyst adsorbent is relatively simple to synthesize, can be recycled, greatly reduces the comprehensive cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of environmental protection and air pollution control, in particular to an EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration, and a preparation method and application thereof.
Background
The flue gas discharged by the coal-fired power plant contains mercury, the mercury is a toxic heavy metal, serious harm is caused to human health and ecological environment, and the coal-fired power plant is considered as the largest global artificial mercury discharge source and also considered as one of the most important artificial mercury discharge sources. The mercury contained in the flue gas of the coal-fired power plant mainly comprises three forms of Hg 2+、Hgp and Hg 0. Wherein Hg 2+ is dissolved in water, so that the Hg 2+ can be efficiently removed by adopting a wet desulphurization device of pollutant control equipment; hg p in the flue gas is easy to combine with fly ash, so that the Hg p can be removed by particulate matter control equipment, such as a cloth bag dust remover or an electrostatic dust remover; hg 0 is insoluble in water and has strong volatility, is quite stable at low temperature, and is difficult to remove by the existing pollutant control equipment, so that the Hg 0 is directly discharged into the atmosphere in the flue gas discharge process to cause environmental pollution and harm to human health. Therefore, the key to removing mercury from flue gas of coal-fired power plants is to control the emission of Hg 0.
The two main research directions of mercury removal at present are mercury removal by an adsorbent method and mercury removal by a catalytic oxidation method respectively. The mercury removal by the adsorbent method is to remove Hg 0 by physical or chemical adsorption on the surface of the adsorbent and then by a particulate matter control device; the catalyst is used for catalytic oxidation and demercuration, and Hg 0 is efficiently oxidized into Hg 2+ and then removed by a wet desulphurization device. The EVS-10 molecular sieve is a molecular sieve which is formed by completely replacing titanium in the titanosilicate molecular sieve ETS-10 and mainly comprises vanadium-oxygen octahedra and silicon-oxygen tetrahedra, and is linked through common angle oxygen atoms, and finally a three-dimensional network structure is formed, and the molecular sieve is similar to an industrial vanadium-carrying catalyst, and can catalyze and oxidize elemental mercury. However, experimental test results show that the material has low mercury catalytic oxidation efficiency of about 48%.
In addition to elemental mercury, nitrogen oxides are also a common air pollutant from coal burning, which can cause acid rain and the greenhouse effect. The proportion of NO in the nitrogen oxide (NO x) is higher, and the proportion is more than 95 percent. Therefore, the efficient removal of NO is a key to the realization of removal of nitrogen oxides. The most effective and widely used technology for removing NO from coal-fired flue gas is NH 3 Selective Catalytic Reduction (SCR) technology. The SCR catalyst studied at present is mainly prepared by loading metal oxides such as V2O5、CuO、Cr2O3、CeO2、Fe2O3、MnOx、Co2O3 and the like on carriers such as Al 2O3、SiO2、TiO2、ZrO2, carbon materials, molecular sieves and the like. However, the existing EVS-10 molecular sieve has certain mercury removal capability, but has poor catalytic denitration performance, and only has 14 percent of removal efficiency, so that the effects of high-efficiency mercury removal and denitration cannot be achieved at the same time; and the particles are easy to agglomerate into larger particles in the repeated recycling process, which is not beneficial to the repeated recycling of the molecular sieve.
Disclosure of Invention
The invention aims to provide an EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration, a preparation method and application thereof, and the catalytic adsorbent can realize the synergistic removal of mercury and nitrogen oxides.
In order to achieve the above object, a first aspect of the present disclosure provides an EVS-10-based cerium-supported catalytic adsorbent for flue gas mercury removal and denitration, the catalytic adsorbent comprising a support and an active component supported on the support; wherein the carrier comprises an EVS-10 molecular sieve, and the active component comprises CeO 2.
Optionally, the mass fraction of the carrier is 85-99 wt% and the mass fraction of the active component is 1-15 wt% based on the total weight of the catalytic adsorbent.
A second aspect of the present disclosure provides a method of preparing the catalytic adsorbent for mercury removal and denitration according to the first aspect of the present disclosure, comprising the steps of: (1) Mixing an EVS-10 molecular sieve, a cerium source and water to obtain a raw material mixture; (2) adding an alkaline solution to the raw material mixture; then adding alcohol to obtain a colloid precursor; (3) calcining the colloid precursor.
Optionally, in the step (1), the weight ratio of the EVS-10 molecular sieve to the cerium source to the water is (90-95): (13-18);
optionally, the cerium source is a soluble cerium salt, preferably one or more selected from cerium acetate, cerium chloride and cerium nitrate.
Optionally, step (1) further comprises: carrying out ultrasonic treatment on the EVS-10 molecular sieve in water for 5-30 minutes, and then adding the cerium source and an optional dispersing auxiliary for mixing to obtain the raw material mixture; preferably, the dispersing aid is selected from one or more of polymethacrylic acid, polyacrylic acid and hydrolyzed polymaleic anhydride, and more preferably polymethacrylic acid.
Optionally, the weight ratio of the dispersing aid to the cerium source is (34-68): (13-18).
Optionally, in step (2), the alkaline solution comprises aqueous ammonia; the alcohol comprises ethanol; further preferably, the addition volume ratio (4 to 8) of the aqueous ammonia to the alcohol is: (60-70).
Optionally, step (2) further comprises:
Adding the alkaline solution into the raw material mixture obtained in the step (1), and performing ultrasonic treatment for 5-30 minutes; and
Before the roasting treatment, the colloid precursor is subjected to ultrasonic treatment for 5-30 minutes, and then is evaporated at 70-100 ℃.
Optionally, in step (3), the conditions of the baking treatment include: the roasting temperature is 350-600 ℃ and the roasting time is 1-4 hours;
Optionally, step (3) further comprises: and cooling the roasting treatment product, sieving, and taking the undersize product to obtain the catalytic adsorbent.
A third aspect of the disclosure provides an application of the catalytic adsorbent for mercury removal and denitration in the field of mercury removal and denitration in flue gas of coal-fired power plants.
Through the technical scheme, the EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration as well as the preparation method and application thereof are provided, and the EVS-10 molecular sieve is loaded with the active component containing CeO 2 with high dispersity, so that the catalytic adsorbent has good mercury removal efficiency and high denitration efficiency, and has good application effect in the aspect of cooperatively removing elemental mercury and nitrogen oxides in coal-fired flue gas; the catalytic adsorbent is relatively simple to synthesize and can be recycled, so that the comprehensive cost is greatly reduced, and the catalytic adsorbent is suitable for industrial production; the sulfur poisoning resistance of the catalyst adsorbent is improved, the process adaptability and compatibility are good, the catalyst adsorbent is suitable for being used in series with dust removal and desulfurization equipment, is particularly suitable for upgrading and reconstruction of mercury removal by expanding enterprises with the desulfurization and dust removal equipment, reduces equipment installation and use cost, and has industrial application prospect.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The inventor of the present disclosure found in the study that, loading the active component containing CeO 2 on the EVS-10 molecular sieve can not only greatly improve the mercury removal efficiency of the EVS-10 molecular sieve (about 48% to 97%), but also make the molecular sieve loaded with CeO 2 give consideration to better performance of removing nitrogen oxides (about 86%); the inventor further tests the CeO 2 -loaded active component molecular sieve for a long time in the complex flue gas environment of SO 2, the performance is not obviously attenuated, and the sulfur poisoning resistance and the service life of the CeO 2 -loaded active component molecular sieve are improved.
The first aspect of the present disclosure provides an EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration, the catalytic adsorbent comprising a carrier and an active component loaded on the carrier; wherein the carrier comprises an EVS-10 molecular sieve, and the active component comprises CeO 2.
The active components containing CeO 2 with high dispersity are loaded on the EVS-10 molecular sieve, so that the catalytic adsorbent has good mercury removal efficiency and high denitration efficiency, and has good application effect in the aspect of cooperatively removing elemental mercury and nitrogen oxides in coal-fired flue gas; the catalytic adsorbent is relatively simple to synthesize and can be recycled, so that the comprehensive cost is greatly reduced, and the catalytic adsorbent is suitable for industrial production; the sulfur poisoning resistance of the catalyst adsorbent is improved, the process adaptability and compatibility are good, the catalyst adsorbent is suitable for being used in series with dust removal and desulfurization equipment, is particularly suitable for upgrading and reconstruction of mercury removal by expanding enterprises with the desulfurization and dust removal equipment, reduces equipment installation and use cost, and has industrial application prospect.
In the present disclosure, the EVS-10 molecular sieve has high hydrothermal stability, large specific surface area and fast heat and mass transfer, and is an excellent catalyst and carrier. The method is characterized in that CeO 2 is loaded on an EVS-10 molecular sieve to obtain a catalytic adsorbent, wherein the molecular sieve framework contains vanadium, so that part of elemental mercury can be catalytically oxidized; and CeO 2 has good denitration performance, and can also catalyze and oxidize elemental mercury, and the vanadium in the framework and the loaded CeO 2 can realize synergistic mercury denitration.
In one embodiment, the mass fraction of the support is 85 to 99 wt% and the mass fraction of the active component is 1 to 15 wt%, based on the total weight of the catalytic adsorbent. When the content of each component in the catalytic adsorbent is within the range of the embodiment, the catalytic adsorbent can achieve a better synergistic effect of removing elemental mercury and nitrogen oxides.
In one embodiment, the support is an EVS-10 molecular sieve; in terms of element mole, si in the EVS-10 molecular sieve: na: k: the molar ratio of V is 3.92:1.39:0.48:1. specifically, XRF spectroscopy can be used to determine the chemical composition of the EVS-10 molecular sieve.
A second aspect of the present disclosure provides a method of preparing the catalytic adsorbent for mercury removal and denitration according to the first aspect of the present disclosure, comprising the steps of:
(1) Mixing an EVS-10 molecular sieve, a cerium source and water to obtain a raw material mixture;
(2) Adding an alkaline solution into the raw material mixture, and then adding alcohol to obtain a colloid precursor;
(3) And roasting the colloid precursor.
The synthesis method provided by the disclosure is stable and reliable, the comprehensive use cost of the catalytic adsorbent is low, and the method has good industrial application prospect.
Specifically, the addition amount of the raw materials or the weight ratio between different raw materials, such as the addition amount or the weight ratio of the EVS-10 molecular sieve and the cerium source, in the present disclosure is adjusted to obtain the mass fraction of each component in the catalytic adsorbent provided according to the first aspect of the present disclosure. The EVS-10 molecular sieves can be prepared according to existing methods, for example, as disclosed in document Zijian Zhou,Tiantian Cao,et al."Vanadium silicate(EVS)-supported silver nanoparticles:A novel catalytic sorbent for elemental mercury removal from flue gas".Journal of Hazardous Materials,375(2019)1-8.
The EVS-10 molecular sieve adopted in the disclosure can be prepared by a hydrothermal method, and in a specific embodiment, the method comprises the following steps: dissolving sodium silicate in deionized water; then NaOH, KCl, naF and NaCl were added to the solution to give solution A. Then VOSO 4 was dissolved in deionized water to give solution B. Solution a and solution B were mixed and stirred and aged at room temperature. The aged mixture was transferred to an autoclave for continued aging. And washing the synthesized product with deionized water and drying to obtain the EVS-10 molecular sieve. The amount of each reactant and the reaction conditions in the preparation process can be adjusted according to actual requirements.
In one embodiment, in the step (1), the weight ratio of the EVS-10 molecular sieve, the cerium source and the water is (90-95): (13-18); optionally, the cerium source is a soluble cerium salt, preferably one or more of cerium acetate, cerium chloride and cerium nitrate.
In a preferred embodiment, step (1) further comprises: carrying out ultrasonic treatment on the EVS-10 molecular sieve in water for 5-30 minutes, and then adding the cerium source and an optional dispersing auxiliary for mixing to obtain the raw material mixture; preferably, the weight ratio of the dispersing aid to the cerium source is (34 to 68): (13-18).
In a preferred embodiment, the dispersing aid is selected from one or more of polymethacrylic acid, polyacrylic acid and hydrolyzed polymaleic anhydride, and more preferably polymethacrylic acid. The inventors of the present disclosure have found in the study that, when cerium is introduced into an EVS-10 molecular sieve, one or more of polymethacrylic acid, polyacrylic acid and hydrolyzed polymaleic anhydride are added to the raw material mixture, the dispersity of cerium ions can be improved and the mercury removal and denitration performance of the finally prepared catalyst adsorbent can be further improved.
The present disclosure employs a dispersing aid to form a complex with Ce ions in solution, such that Ce ions are uniformly dispersed in the system in the form of a complex. When alkaline solution (such as ammonia water) is added in the subsequent process, a Ce (OH) 4 complex which is uniformly dispersed can be obtained, so that the agglomeration phenomenon is further avoided; after the alcohol is added, the complex in the system forms dispersion auxiliary agent-Ce polymer particles (such as PMAA-Ce polymer particles) on the surface of the EVS-10 molecular sieve, the electrostatic repulsive interaction among the particles enables the system to be stable, and the dispersity of Ce ions in the preparation system is ensured, so that the particle size of CeO 2 loaded in the finally synthesized catalytic adsorbent is smaller and evenly distributed.
In one embodiment, in step (2), the alkaline solution comprises aqueous ammonia; the alcohol comprises ethanol; further preferably, the addition volume ratio (4 to 8) of the aqueous ammonia to the alcohol is: (60-70).
In one embodiment, step (2) further comprises: adding the alkaline solution into the raw material mixture obtained in the step (1), and performing ultrasonic treatment for 5-30 minutes; and
Before the roasting treatment, the colloid precursor is subjected to ultrasonic treatment for 5-30 minutes and then evaporated at 70-100 ℃. Sonication in the present disclosure means sonication using conventional ultrasonic equipment to more uniformly mix or disperse materials.
In one embodiment, in step (3), the conditions of the firing treatment include: the roasting temperature is 350-600 ℃ and the roasting time is 1-4 hours;
Optionally, step (3) further comprises: and cooling the roasting treatment product, sieving, and taking the undersize product to obtain the catalytic adsorbent. For example, after cooling to room temperature, sieving with a 100 mesh sieve, and taking the undersize as the final catalytic adsorbent.
A third aspect of the disclosure provides an application of the catalytic adsorbent according to the first aspect of the disclosure in the field of flue gas mercury removal and denitration; optionally, the flue gas is flue gas of a coal-fired power plant.
The invention is further illustrated below in connection with specific embodiments, but the scope of the invention as claimed is not limited to the examples described.
The chemicals used in each example were commercially available from public sources.
The EVS-10 molecular sieves used in the examples and comparative examples below were prepared according to the methods disclosed in document Zijian Zhou,Tiantian Cao,et al."Vanadium silicate(EVS)-supported silver nanoparticles:A novel catalytic sorbent for elemental mercury removal from flue gas".Journal of Hazardous Materials,375(2019)1-8.
The 25% aqueous ammonia used in the following examples, comparative examples and comparative examples was aqueous ammonia having an NH 3·H2 O content of 25% by weight.
The ultrasonic treatment uses conventional ultrasonic equipment to more uniformly mix or disperse the materials.
Example 1
(1) 9.0G of EVS-10 molecular sieve was dispersed in 50mL of deionized water, and after 15 minutes of ultrasonic treatment, 1.8g (CH 3CO2)3 Ce hydrate and 6.8g of polymethacrylic acid were added;
(2) Adding 8mL of 25% ammonia water, performing ultrasonic treatment for 15 minutes, adding 70mL of ethanol to form a colloid precursor, continuing ultrasonic treatment for 30 minutes, evaporating a sample at 80 ℃, finally roasting the sample in a muffle furnace at 500 ℃ for 2 hours, cooling to room temperature, sieving with a 100-mesh sieve, taking out the sieved particles, and obtaining the catalyst adsorbent loaded with CeO 2, which is marked as sample 1.
Comparative example 1
A catalytic adsorbent was prepared by a procedure similar to example 1, except that in example 1: the EVS-10 molecular sieve was replaced with a commercially available ETS-10 molecular sieve. The other preparation steps were the same as in example 1, to obtain a CeO 2 -supported catalyst adsorbent, which was designated as sample D-1.
Example 2
(1) 9.5G of EVS-10 molecular sieve was dispersed in 60mL of deionized water, and after 15 minutes of ultrasonic treatment, 1.3g of Ce (NO 3)3·6H2 O and 3.4g of polymethacrylic acid were added;
(2) Adding 4mL of 25% ammonia water, performing ultrasonic treatment for 15 minutes, adding 60mL of ethanol to form a colloid precursor, continuing ultrasonic treatment for 30 minutes, evaporating a sample at 80 ℃, finally roasting the sample in a muffle furnace at 600 ℃ for 2 hours, cooling to room temperature, sieving with a 100-mesh sieve, taking out the sieved particles, and obtaining the catalyst adsorbent loaded with CeO 2, which is marked as sample 2.
Example 3
A catalytic adsorbent was prepared by a procedure similar to example 1, except that in example 1: in the step (1), the polymethacrylic acid dispersing aid was not added, and the other preparation process and reaction conditions were the same as in example 1. The CeO 2 -loaded catalytic adsorbent was obtained and was designated as sample 3.
Comparative example 2
4.3G of AgNO 3 is weighed and dissolved in 100ml of deionized water, then 10g of EVS-10 molecular sieve is added, magnetic stirring is carried out for 6 hours in a light-proof environment, suction filtration is carried out, and the solution is repeatedly washed by the deionized water, dried at 80 ℃, and then placed in a tubular furnace for roasting for 1 hour under the nitrogen atmosphere at 250 ℃. The catalyst adsorbent carrying only silver nanoparticles was obtained and was designated as sample D-2.
The mass fractions of the carrier molecular sieve and CeO 2 in the samples obtained in the above examples and comparative examples are shown in Table 1.
TABLE 1
Simulated smoke test case
The samples synthesized in the examples and the comparative examples are placed on an experimental system for simulating flue gas to perform mercury removal and denitration performance test. The simulated flue gas conditions were as follows: the concentration of 5% O 2,12％CO2,400ppm NO,400ppm NH3,600ppm SO2,30ppm HCl,Hg0 was 110 μg/m 3, the balance gas was N 2, the flow rate was 500mL/min, and the test temperature was 250 ℃. The results of the mercury removal and denitration test are shown in table 2 below.
TABLE 2
| Sample of | Hg 0 removal efficiency (%) | NO x removal efficiency (%) |
| 1 | 97 | 86 |
| D-1 | 74 | 67 |
| 2 | 93 | 84 |
| 3 | 83 | 67 |
| D-2 | 100 | 21 |
As can be seen from table 2 above, the catalyst prepared using the EVS-10 molecular sieve in example 1 of the present disclosure has better Hg 0 removal efficiency and NO x removal efficiency than the commercial ETS-10 molecular sieve in comparative example 1.
Comparing examples 1-3 of the present disclosure with comparative example 2, comparative example 2 can achieve better elemental mercury removal efficiency, but the nitrogen oxide removal efficiency is extremely low, only 21%. The catalytic adsorbent samples prepared by the method provided by the disclosure in examples 1-3 have high elemental mercury removal efficiency and nitrogen oxide removal efficiency, and realize synergistic removal of Hg 0 and NO x.
Further comparing examples 1 to 3, it is evident that the catalyst adsorbent obtained in examples 1 to 2 has higher Hg 0 removal efficiency and NO x removal efficiency when the dispersing aid is added.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (12)
1. The EVS-10-based cerium-loaded catalytic adsorbent for flue gas mercury removal and denitration is characterized by comprising a carrier and an active component loaded on the carrier; wherein the carrier comprises an EVS-10 molecular sieve, and the active component comprises CeO 2; based on the total weight of the catalytic adsorbent, the mass fraction of the carrier is 85-99 wt%, and the mass fraction of the active component is 1-15 wt%;
The catalytic adsorbent is prepared by a method comprising the following steps:
(1) Mixing an EVS-10 molecular sieve, a cerium source and water to obtain a raw material mixture;
(2) Adding an alkaline solution to the raw material mixture; then adding alcohol to obtain a colloid precursor;
(3) For the colloid precursor roasting the body;
Step (1) further comprises: carrying out ultrasonic treatment on the EVS-10 molecular sieve in water for 5-30 minutes, and then adding the cerium source and a dispersing auxiliary for mixing to obtain the raw material mixture; the dispersing aid is selected from one or more of polymethacrylic acid, polyacrylic acid and hydrolyzed polymaleic anhydride.
2. The catalytic adsorbent of claim 1, wherein in step (1), the weight ratio of EVS-10 molecular sieve, cerium source, and water is (90-95): (13-18);
The cerium source is a soluble cerium salt.
3. The catalytic sorbent of claim 2, wherein the source of cerium is selected from one or more of cerium acetate, cerium chloride, and cerium nitrate.
4. The catalytic adsorbent of claim 1 wherein the dispersing aid is polymethacrylic acid.
5. The catalytic adsorbent of claim 1, wherein the weight ratio of the dispersing aid to the cerium source is (34-68): (13-18).
6. The catalytic adsorbent of claim 1 wherein in step (2), the alkaline solution comprises aqueous ammonia; the alcohol comprises ethanol.
7. The catalytic adsorbent of claim 6, wherein in step (2), the addition volume ratio of the ammonia water to the alcohol is (4-8): (60-70).
8. The catalytic adsorbent of claim 1, wherein step (2) further comprises:
Adding the alkaline solution into the raw material mixture obtained in the step (1), and performing ultrasonic treatment for 5-30 minutes; and
And before the roasting treatment, carrying out ultrasonic treatment on the colloid precursor for 5-30 minutes, and then evaporating at 70-100 ℃.
9. The catalytic adsorbent of claim 1 wherein in step (3), the conditions of the calcination treatment comprise: the roasting temperature is 350-600 ℃, and the roasting time is 1-4 hours.
10. The catalytic adsorbent of claim 9, wherein step (3) further comprises: and cooling the roasting treatment product, sieving, and taking the undersize product to obtain the catalytic adsorbent.
11. The use of the catalytic adsorbent according to any one of claims 1-10 in the field of flue gas mercury removal and denitration.
12. The use according to claim 11, wherein the flue gas is coal fired power plant flue gas.
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| CN107597139A (en) * | 2017-11-02 | 2018-01-19 | 山东大学 | A kind of demercuration collaboration denitrating catalyst and preparation method thereof |
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| CN105833894B (en) * | 2016-04-20 | 2019-05-31 | 复旦大学 | Have both the denitrating catalyst and its preparation method and application of alkali resistant (soil) metal and sulfur resistive water resistant function |
| KR102429131B1 (en) * | 2016-06-10 | 2022-08-05 | 존슨 맛쎄이 퍼블릭 리미티드 컴파니 | NOx adsorbent catalyst |
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