CN113209983A - 一种廉价高效烟气脱硫脱硝催化剂及其制备方法 - Google Patents
一种廉价高效烟气脱硫脱硝催化剂及其制备方法 Download PDFInfo
- Publication number
- CN113209983A CN113209983A CN202110547681.3A CN202110547681A CN113209983A CN 113209983 A CN113209983 A CN 113209983A CN 202110547681 A CN202110547681 A CN 202110547681A CN 113209983 A CN113209983 A CN 113209983A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- desulfurization
- flue gas
- denitrification
- powder
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 52
- 230000023556 desulfurization Effects 0.000 title claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003546 flue gas Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 claims abstract description 36
- 230000004913 activation Effects 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 35
- 238000003763 carbonization Methods 0.000 claims description 29
- 238000001994 activation Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 239000003245 coal Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011280 coal tar Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000004939 coking Methods 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 239000010426 asphalt Substances 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002802 bituminous coal Substances 0.000 claims description 3
- 239000005539 carbonized material Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000003223 protective agent Substances 0.000 claims description 2
- 239000010920 waste tyre Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000001099 ammonium carbonate Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 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 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010926 purge 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
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000005406 washing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- B01J35/615—
-
- B01J35/635—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
本发明属于脱硫脱硝领域,涉及一种廉价高效烟气脱硫脱硝催化剂及其制备方法,该催化剂由活性炭及废弃的渣油加氢催化剂组成,在催化剂载体制备过程中加入铵盐,铵盐分解的气体在逃逸过程中形成丰富的孔道,活化气体通过孔道进入载体内部进行反应,在缩短活化时间的同时,可获得大孔容、大比表面、吸附能力强的载体;废弃的渣油加氢催化剂采用饱和浸渍方式负载在载体外层,轻质油汽化冲破堵塞在孔口的焦煤粉和废弃的渣油加氢催化剂层,使得外层具有丰富的孔道,焦煤粉的碳化和收缩,能使废弃的渣油加氢催化剂牢固与载体结合一起并裸露在外表面,使得制备的催化剂具有较高的强度;该方法制备的催化剂活性高,成本低,工艺简单、易操作。
Description
技术领域
本发明属于脱硫脱硝领域,尤其涉及一种廉价高效烟气脱硫脱硝催化剂及其制备方法。
背景技术
我国的能源结构以煤炭为主,煤炭作为燃料被广泛应用于发电、锅炉供暖、冶金等技术领域,煤燃烧时烟气排放量一直居高不下,烟气中含有大量的SO2、NOX等污染物,对环境造成严重的污染,国家已将大气污染治理列入重点防控目标,尤其是硫和氮氧化物指标更是大气污染控制中的重中之重。因此,控制SO2、NOX等污染物的排放,积极研究开发烟气脱硫脱硝技术,是治理环境污染的重要途径。
目前,应用最广泛的是氨选择性催化还原(NH3-SCR)脱硝技术,而催化剂则是NH3-SCR技术中的重要部分。
活性炭具有特殊的表面化学性质,丰富的官能团和大的比表面积以及发达的孔结构和较好的吸附活性;过渡金属Mn、V等作为催化剂活性金属具有较高的脱硫脱硝性能。
中国专利CN106345453A公开了一种炭基材料低温脱硝催化剂及其制备方法,催化剂主要特征是以炭基材料为载体,以钒、钨和铈为活性组分;制备过程中,先用硝酸溶液对炭基材料进行表面处理,在炭基材料上负载钒、钨活性组分,烘干后再负载铈活性组分,然后在氮气氛围下煅烧。该催化剂的缺点是用硝酸处理活性炭和两次负载,制备过程比较复杂。
中国专利CN110961114A公开了一种脱硫脱硝催化剂及其制备方法,该催化剂活性成分为V2O5或V2O5和Fe2O3的混合物、助剂Co、Ce、Mn中的至少一种和经硝酸溶液或氢氧化钠溶液改性处理的活性焦,该催化剂的缺点是载体活性焦需改性,处理过程比较复杂,活性组分前驱物采用偏钒酸铵、硝酸铁,助催化剂前驱物为硝酸钴、硝酸铈、硝酸锰,在焙烧过程中产生NH3、NOX等废气且成本较高。
中国专利CN104056658A公开了一种低温抗硫脱硝催化剂及其制备方法,该催化剂由碳基载体、第一种活性位和第二种活性位组成。其中,第一种活性位由分散入3A分子筛的Mn0.1-0.8Ce0.2-0.9OX或Mn0.1-0.8Mg0.2-0.9OX的活性组分组成,第二种活性位由表面涂敷有TiO2或SiO2保护层的Mn0.1-0.8Mg0.2-0.9OX或Mn0.1-0.8Ce0.2-0.9OX的活性组分组成。第一种活性位的制备方法是将锰、镁或铈的可溶性前驱物盐配成溶液,加入3A分子筛,在一定温度下浸泡一定时间,之后过滤,滤饼再加入上述溶液中浸泡、过滤,如此几次后,经干燥、焙烧得到第一种活性位;第二种活性位的制备方法是将锰、镁或铈的可溶性前驱物盐配成溶液A,将柠檬酸固体颗粒溶于水中配成溶液B,将B溶液倒入A溶液中充分搅拌,确保柠檬酸与金属离子充分反应,之后将混合溶液放入干燥箱中干燥至形成泡沫状固体凝结物,再研磨成粉状,焙烧后得到固体粉末状锰镁氧化混合物,将固体粉末状锰镁或锰铈氧化混合物加入到钛酸四丁酯或硅酸四乙酯溶入无水乙醇配制的溶液中,超声振荡得到悬浮液,再滴加乙醇和水的混合溶液得到固体悬浮物,经过滤、乙醇冲洗、干燥、研磨和焙烧,得到第二种活性位;催化剂制备过程是将活性炭柱状颗粒在H2和N2混合气体氛围和一定温度下进行活化,再在盐酸和硝酸溶液中进行酸化,经干燥后加入至含有第一种活性位和第二种活性位的悬浮液中,超声振荡分散一段时间后过滤、干燥,在惰性气氛焙烧,再放入含有三甲基氯硅烷的溶液中振荡条件下反应,最后经过滤、干燥和惰性气氛下焙烧得到低温抗硫脱硝催化剂。该专利不足之处在于制备过程步骤繁多、复杂,而且制备过程中加入的有机化合物也会对环境造成严重污染。
发明内容
针对现有技术的不足,本发明提供一种廉价高效烟气脱硫脱硝催化剂及其制备方法。本发明催化剂以活性炭为载体,以废弃的渣油加氢催化剂中钼、镍、钒等金属为活性组分,催化剂制备工艺简单,成本低廉,所制备的脱硝催化剂适应的活性温度范围宽,脱硫脱硝活性高。本发明的上述目的是通过以下技术方案实现的:
一种廉价高效烟气脱硫脱硝催化剂的制备方法,包括如下步骤:
(1)将焦煤与含碳物质混合均匀,并磨成粉体;
(2)将步骤(1)所得的粉体与助挤剂、铵盐及水投入碾压机中碾压、混合;
(3)步骤(2)所得混合均匀物料进入压条机,挤条成型,并进行干燥;
(4)步骤(3)所得成型物进入碳化炉进行碳化,控制碳化温度和碳化时间;
(5)步骤(4)碳化后的物料进入活化炉进行活化,控制活化温度和活化时间,活化后即为本发明烟气脱硫脱催化剂载体。
(6)将焦煤粉、废弃的渣油加氢催化剂、轻质油配制成悬浊液,浸渍在步骤(5)载体上,经干燥、焙烧制得本发明烟气脱硫脱催化剂。
进一步的,步骤(1)所述含碳物质包括原煤、沥青粉、烟煤、果壳、木屑、石油焦、废旧塑料及废旧轮胎中的一种以上;所述焦煤与含碳物质混合的质量比为1:0.5~1:4.5;所述粉体研磨目数>300目,优选350目。
进一步的,步骤(2)所述助挤剂为煤焦油、重柴油、蜡油和渣油中的一种以上,优选煤焦油;所述铵盐为无机铵或有机铵,如碳酸铵、碳酸氢铵、尿素、六次甲基四胺等中的一种以上;所述加入粉体、助挤剂、铵盐和水的质量比为粉体:助挤剂:铵盐:水=1:(0.1~0.45):(0.01~0.06):(0.1~1.5)。
进一步的,步骤(3)所述压条机的挤条压力≥15MPa;挤条形状为圆柱形、拉西环、异型条等中的一种,直径为2~8mm;所述干燥温度为150~200℃,干燥时间为4~10小时。
进一步的,步骤(4)所述碳化氛围是在惰性气体条件下进行,所述惰性气氛为氮气、氦气、氖气、氩气中的一种,优选为氮气;所述碳化温度为500~650℃;所述碳化时间为5~30min。
进一步的,步骤(5)所述活化氛围为活化时通入水蒸汽或CO2;所述活化温度为800~1000℃;所述活化时间为20~100min。
进一步的,步骤(6)所述焦煤粉粒度>300目,优选>350目;所述废弃的渣油加氢催化剂为沉积大量镍、钒的渣油加氢保护剂、脱金属剂、脱硫剂和脱残炭废催化剂中的一种以上,优选渣油加氢脱金属废催化剂,所述废催化剂粒度>300目,优选>350目;所述轻质油为低温煤焦油、中温煤焦油、轻柴油及重柴油中的一种以上;所述悬浊液中焦煤粉含量为50~200g/L,废弃的渣油加氢催化剂为100~500g/L;所述浸渍采用饱和浸渍或过饱和浸渍;所述干燥温度为150~180℃,干燥时间4~8h;所述焙烧在惰性气氛下进行,所述惰性气氛为氮气、氦气、氖气、氩气中的一种,优选为氮气;所述焙烧温度为450~650℃,焙烧时间为2~8h。
一种廉价高效烟气脱硫脱硝催化剂,如所述的步骤(1)-步骤(6)的制备方法制备。
进一步的,催化剂孔容≥0.55mL/g,比表面≥450m2/g,废弃的渣油加氢催化剂含量8%~30%。
本发明与现有技术相比的有益效果是:
本发明在烟气脱硫脱催化剂载体制备过程中加入铵盐,在载体干燥及碳化过程中,铵盐分解的气体在逃逸过程中形成丰富的孔道,在活化过程中,活化气体通过孔道进入载体内部进行反应,缩短活化时间的同时,可获得大孔容、大比表面、吸附能力强的载体;
本发明采用饱和浸渍方式负载焦煤粉和废弃的渣油加氢催化剂,焦煤粉和废弃的渣油加氢催化剂在载体外层,轻质油进入载体孔道内,在干燥、焙烧过程中,轻质油汽化冲破堵塞在孔口的焦煤粉和废弃的渣油加氢催化剂,使得外层具有丰富的孔道,便于反应物的扩散,同时,焙烧过程中焦煤粉的碳化和收缩,能使废弃的渣油加氢催化剂牢固与载体结合一起并裸露在外表面,使得制备的催化剂具有较高的强度,且能充分发挥废弃的渣油加氢催化剂中活性金属的性能;
该方法利用废弃的渣油加氢催化剂中沉积的金属作为脱硫脱硝催化剂的活性金属,降低了脱硫脱硝催化剂的成本,也解决了废弃的渣油加氢催化剂处理困难、污染环境的问题,本发明工艺简单、易操作。
附图说明
图1为催化剂在不同反应时间脱硫率、脱硝率的变化情况。
具体实施方式
下面通过具体实施例详述本发明,但不限制本发明的保护范围。如无特殊说明,本发明所采用的实验方法均为常规方法,所用实验器材、材料、试剂等均可从商业途径获得。
本发明中,所述的比表面积、孔容是采用低温液氮吸附法测得的。
某炼油厂废弃渣油加氢脱金属催化剂分析结果(单位,ppm)
废催化剂 | Mo | Mg | Mn | Co | Ni | V | Fe |
A | 16920 | 153 | 120.1 | 389.6 | 62970 | 167300 | 12210 |
B | 16800 | 146.7 | 69.41 | 326.3 | 60270 | 157000 | 7686 |
实施例1
(1)将100g焦煤与150g沥青粉混合均匀,并研磨成350目的粉体;
(2)将步骤(1)所得粉体、50g煤焦油、12g碳酸铵加入碾压机中,混合均匀后加入205g水,继续碾压、混合至块状结束;
(3)将步骤(2)所得块状物料在挤条机上挤出Φ6mm圆柱形条,保持压条机的挤条压力为20MPa,挤出物料在170℃下干燥时间8小时;
(4)步骤(3)所得圆柱形条物料进入碳化炉,在氮气气氛下进行碳化,控制碳化温度550℃,碳化时间25min;
(5)步骤(4)碳化后的物料进入活化炉,在水蒸汽氛围下进行活化,控制活化温度830℃,活化时间45min,活化后即为本发明烟气脱硫脱催化剂载体。
(6)将12g粒度为400目的焦煤粉、45g废弃渣油加氢脱金属催化剂A、120g低温煤焦油配制成焦煤粉含量为93g/L、废弃渣油加氢脱金属催化剂A含量为349g/L的悬浊液,采用浸渍方式浸渍催化剂载体,在130℃下干燥6小时,再经氮气气氛下550℃焙烧3h,制得本发明烟气脱硫脱催化剂C-1,其分析结果见表1,催化剂脱硫、的脱硝性能见表2。
实施例2
制备过程如实施例1,只是将步骤(1)的沥青粉改为烟煤,步骤(2)的碳酸铵改为碳酸氢铵,所得催化剂C-2性质见表1,不同反应时间脱硫率、脱硝率变化情况见图1。
实施例3
制备过程如实施例1,只是将步骤(1)的沥青粉加入量改为200g,步骤(2)的煤焦油加入量改为65g,所得催化剂C-3性质见表1,催化剂的脱硫、脱硝性能见表2。
实施例4
制备过程如实施例1,只是将步骤(4)的碳化温度改为630℃,碳化时间改为15min,所得催化剂C-4性质见表1,催化剂的脱硫、脱硝性能见表2。
实施例5
制备过程如实施例1,只是将活化温度改为950℃,活化时间改为35min,所得催化剂C-5性质见表1,不同反应时间脱硫率、脱硝率变化情况见图1。
实施例6
制备过程如实施例1,只是将步骤(6)的焦煤粉改为8g,废弃渣油加氢脱金属催化剂改为B,加入量改为30g,悬浊液的焦煤粉含量改为63.5g/L、废弃渣油加氢脱金属催化剂改为B含量为238.5g/L的,所得催化剂C-6,其分析结果见表1,催化剂的脱硫、脱硝性能见表2,不同时间反应脱硫率、脱硝率变化情况见图1。
比较例1
(1)将100g焦煤与150g沥青粉混合均匀,并研磨成350目的粉体;
(2)将步骤(1)所得粉体、50g煤焦油加入碾压机中,混合均匀后加入205g水,继续碾压、混合至块状结束;
(3)步骤(2)所得块状物料在挤条机上挤出Φ6mm圆柱形条,保持压条机的挤条压力为20MPa,挤出物料在170℃下干燥时间8小时;
(4)步骤(3)所得圆柱形条物料进入碳化炉,在氮气气氛下进行碳化,控制碳化温度550℃,碳化时间25min;
(5)步骤(4)后物料进入活化炉,在水蒸汽氛围下进行活化,控制活化温度830℃,活化时间45min,活化后即为本发明烟气脱硫脱催化剂载体。
(6)将12g粒度为400目的焦煤粉、45g废弃渣油加氢脱金属催化剂A、120g低温煤焦油配制成焦煤粉含量为93g/L、废弃渣油加氢脱金属催化剂A含量为349g/L的悬浊液,采用浸渍方式浸渍催化剂载体,在130℃下干燥6小时,再经氮气气氛下550℃焙烧3h制得烟气脱硫脱催化剂B-1,其分析结果见表1,催化剂脱硫、脱硝性能见表2。
比较例2
(1)将100g焦煤与150g沥青粉混合均匀,并研磨成350目的粉体;
(2)将步骤(1)所得粉体、50g煤焦油、12g碳酸铵加入碾压机中,混合均匀后加入205g水,继续碾压、混合至块状结束;
(3)步骤(2)所得块状物料在挤条机上挤出Φ6mm圆柱形条,保持压条机的挤条压力为20MPa,挤出物料在170℃下干燥时间8小时;
(4)步骤(3)所得圆柱形条物料进入碳化炉,在氮气气氛下进行碳化,控制碳化温度550℃,碳化时间25min;
(5)步骤(4)后物料进入活化炉,在水蒸汽氛围下进行活化,控制活化温度830℃,活化时间45min,活化后即为烟气脱硫脱催化剂B-2,其分析结果见表1,催化剂脱硫、的脱硝性能见表2。
比较例3
(1)将100g焦煤与150g沥青粉混合均匀,并研磨成350目的粉体;
(2)将步骤(1)所得粉体、50g煤焦油、12g碳酸铵加入碾压机中,混合均匀后加入205g水,继续碾压、混合至块状结束;
(3)将步骤(2)所得块状物料在挤条机上挤出Φ6mm圆柱形条,保持压条机的挤条压力为20MPa,挤出物料在170℃下干燥时间8小时;
(4)步骤(3)所得圆柱形条物料进入碳化炉,在氮气气氛下进行碳化,控制碳化温度550℃,碳化时间25min;
(5)步骤(4)后物料进入活化炉,在水蒸汽氛围下进行活化,控制活化温度830℃,活化时间45min,活化后即为本发明烟气脱硫脱催化剂载体。
(6)将45g废弃渣油加氢脱金属催化剂A、120g低温煤焦油配制成废弃渣油加氢脱金属催化剂A含量为355g/L的悬浊液,采用浸渍方式浸渍催化剂载体,在130℃下干燥6小时,再经氮气气氛下550℃焙烧3h制得烟气脱硫脱催化剂B-3,其分析结果见表1,不同反应时间脱硫率、脱硝率变化情况见图1。
表1本发明制备活性炭的性质
编号 | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | B-1 | B-2 | B-3 |
孔容,mL/g | 0.583 | 0.581 | 0.593 | 0.577 | 0.604 | 0.592 | 0.501 | 0.596 | 0.580 |
比表面积,m<sup>2</sup>/g | 530 | 532 | 520 | 551 | 521 | 537 | 435 | 527 | 535 |
A/B含量,% | 21.5 | 21.9 | 18.79 | 23.7 | 22.2 | 12.3 | 21.8 | - | 22.2 |
分别将制备的催化剂C-1、C-3、C-4、C-6和B-1、B-2放置在微型石英反应器中,模拟烟气组成:NO浓度为1300ppm,SO2浓度为580ppm,H2O蒸汽体积比为11%,O2体积比5.5%,NH3浓度为1050ppm,N2作为平衡气体,空速为29000h-1,控制反应温度为120~260℃,催化剂在不同温度下的脱硫率、脱硝率如表2所示。
表2催化剂在不同温度下的脱硫率和脱硝率
注:SO2、NO的脱硫、脱硝活性由下式计算:活性=[(C0-C)/C0]×100%。式中,C0为SO2、NO初始浓度,C为
处理后气体中SO2、NO浓度。
由表2看出,所本发明制备的脱硫、脱硝催化剂具有很好的低温活性。
分别将制备的催化剂C-2、C-5、C-6和B-3放置在微型石英反应器中,模拟烟气组成:NO浓度为1300ppm,SO2浓度为580ppm,H2O蒸汽体积比11%,O2体积比5.5%,NH3浓度为1050ppm,N2作为平衡气体,空速为29000h-1,反应温度为120℃时,催化剂在不同反应时间脱硫率、脱硝率的变化情况图1。
由图1看出,本发明制备的催化剂具有稳定的脱硫活性,催化剂C-2、C-5和C-6具有稳定的脱硝活性,而催化剂B-3的脱硝活性衰减较快,这是因为催化剂在浸渍过程中没有加入焦煤粉,使得负载的废弃渣油加氢脱金属催化剂A与载体结合牢固,在大空速烟气吹扫下废弃渣油加氢脱金属催化剂A流失所至。
以上所述实施方式仅为本发明的优选实施例,而并非本发明可行实施的全部实施例。对于本领域一般技术人员而言,在不背离本发明原理和精神的前提下对其所作出的任何显而易见的改动,都应当被认为包含在本发明的权利要求保护范围之内。
Claims (9)
1.一种廉价高效烟气脱硫脱硝催化剂的制备方法,其特征是,包括如下步骤:
(1)将焦煤与含碳物质混合均匀,并磨成粉体;
(2)将步骤(1)所得的粉体与助挤剂、铵盐及水投入碾压机中碾压、混合;
(3)步骤(2)所得混合均匀物料进入压条机,挤条成型,并进行干燥;
(4)步骤(3)所得成型物进入碳化炉进行碳化,控制碳化温度和碳化时间;
(5)步骤(4)碳化后的物料进入活化炉进行活化,控制活化温度和活化时间,活化后即为烟气脱硫脱催化剂载体;
(6)将焦煤粉、废弃的渣油加氢催化剂、轻质油配制成悬浊液,浸渍在步骤(5)载体上,经干燥、焙烧制得烟气脱硫脱催化剂。
2.如权利要求1所述的一种廉价高效烟气脱硫脱硝催化剂的制备方法,其特征是,步骤(1)所述含碳物质包括原煤、沥青粉、烟煤、果壳、木屑、石油焦、废旧塑料及废旧轮胎中的一种以上;所述焦煤与含碳物质混合的质量比为1:0.5~1:4.5;所述粉体研磨目数>300目。
3.如权利要求1所述的一种廉价高效烟气脱硫脱硝催化剂的制备方法,其特征是,步骤(2)所述助挤剂为煤焦油、重柴油、蜡油和渣油中的一种以上;所述铵盐为无机铵或有机铵;所述加入粉体、助挤剂、铵盐和水的质量比为粉体:助挤剂:铵盐:水=1:(0.1~0.45):(0.01~0.06):(0.1~1.5)。
4.如权利要求1所述的一种廉价高效烟气脱硫脱硝催化剂的制备方法,其特征是,步骤(3)所述压条机的挤条压力≥15MPa;挤条形状为圆柱形、拉西环、异型条中的一种,直径为2~8mm;所述干燥温度为150~200℃,干燥时间为4~10小时。
5.如权利要求1所述的一种廉价高效烟气脱硫脱硝催化剂的制备方法,其特征是,步骤(4)所述碳化氛围是在惰性气体条件下进行,所述惰性气氛为氮气、氦气、氖气、氩气中的一种;所述碳化温度为500~650℃;所述碳化时间为5~30min。
6.如权利要求1所述的一种廉价高效烟气脱硫脱硝催化剂的制备方法,其特征是,步骤(5)所述活化氛围为活化时通入水蒸汽或CO2;所述活化温度为800~1000℃;所述活化时间为20~100min。
7.如权利要求1所述的一种廉价高效烟气脱硫脱硝催化剂的制备方法,其特征是,步骤(6)所述焦煤粉粒度>300目;所述废弃的渣油加氢催化剂为沉积大量镍、钒的渣油加氢保护剂、脱金属剂、脱硫剂和脱残炭废催化剂中的一种以上,所述废催化剂粒度>300目;所述轻质油为低温煤焦油、中温煤焦油、轻柴油及重柴油中的一种以上;所述悬浊液中焦煤粉含量为50~200g/L,废弃的渣油加氢催化剂为100~500g/L;所述浸渍采用饱和浸渍或过饱和浸渍;所述干燥温度为150~180℃,干燥时间4~8h;所述焙烧在惰性气氛下进行,所述惰性气氛为氮气、氦气、氖气、氩气中的一种;所述焙烧温度为450~650℃,焙烧时间为2~8h。
8.一种廉价高效烟气脱硫脱硝催化剂,其特征是,如权利要求1所述的步骤(1)-步骤(6)的制备方法制备。
9.如权利要求8所述的一种廉价高效烟气脱硫脱硝催化剂,其特征是,催化剂孔容≥0.55mL/g,比表面≥450m2/g,废弃的渣油加氢催化剂含量8%~30%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110547681.3A CN113209983B (zh) | 2021-05-19 | 2021-05-19 | 一种廉价高效烟气脱硫脱硝催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110547681.3A CN113209983B (zh) | 2021-05-19 | 2021-05-19 | 一种廉价高效烟气脱硫脱硝催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113209983A true CN113209983A (zh) | 2021-08-06 |
CN113209983B CN113209983B (zh) | 2023-08-29 |
Family
ID=77093194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110547681.3A Active CN113209983B (zh) | 2021-05-19 | 2021-05-19 | 一种廉价高效烟气脱硫脱硝催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113209983B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114452811A (zh) * | 2021-12-27 | 2022-05-10 | 深圳华明环保科技有限公司 | 一种脱硫脱硝剂及其制备方法 |
CN116060033A (zh) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | 一种石蜡加氢精制催化剂及其制备方法和应用 |
CN116102013A (zh) * | 2023-04-13 | 2023-05-12 | 成都华域环保有限公司 | 一种利用废催化剂制备蜂窝活性炭的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR950031233A (ko) * | 1994-05-30 | 1995-12-18 | 조규향 | 디젤차량 입자상물질 제거용 촉매 조성물 |
EP1214971A2 (en) * | 2000-12-16 | 2002-06-19 | SK Corporation | Catalyst for removing dioxin and preparation method thereof |
CN101590357A (zh) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | 一种利用废分子筛催化剂制备脱硫剂的方法 |
CN103495434A (zh) * | 2013-09-13 | 2014-01-08 | 北京矿迪科技有限公司 | 一种基于生物质废料的脱硫脱硝剂及其制备方法 |
CN111014249A (zh) * | 2019-12-24 | 2020-04-17 | 青岛大学 | 一种二维过渡金属硫族化合物-碳复合材料的制备方法 |
CN111924841A (zh) * | 2020-07-17 | 2020-11-13 | 中冶南方都市环保工程技术股份有限公司 | 一种活性焦脱硫脱硝废焦回用方法 |
-
2021
- 2021-05-19 CN CN202110547681.3A patent/CN113209983B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR950031233A (ko) * | 1994-05-30 | 1995-12-18 | 조규향 | 디젤차량 입자상물질 제거용 촉매 조성물 |
EP1214971A2 (en) * | 2000-12-16 | 2002-06-19 | SK Corporation | Catalyst for removing dioxin and preparation method thereof |
CN101590357A (zh) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | 一种利用废分子筛催化剂制备脱硫剂的方法 |
CN103495434A (zh) * | 2013-09-13 | 2014-01-08 | 北京矿迪科技有限公司 | 一种基于生物质废料的脱硫脱硝剂及其制备方法 |
CN111014249A (zh) * | 2019-12-24 | 2020-04-17 | 青岛大学 | 一种二维过渡金属硫族化合物-碳复合材料的制备方法 |
CN111924841A (zh) * | 2020-07-17 | 2020-11-13 | 中冶南方都市环保工程技术股份有限公司 | 一种活性焦脱硫脱硝废焦回用方法 |
Non-Patent Citations (1)
Title |
---|
(法)勒巴日(J.F.LEPAGE)著, 石油工业出版社 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116060033A (zh) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | 一种石蜡加氢精制催化剂及其制备方法和应用 |
CN114452811A (zh) * | 2021-12-27 | 2022-05-10 | 深圳华明环保科技有限公司 | 一种脱硫脱硝剂及其制备方法 |
CN116102013A (zh) * | 2023-04-13 | 2023-05-12 | 成都华域环保有限公司 | 一种利用废催化剂制备蜂窝活性炭的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN113209983B (zh) | 2023-08-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113209983B (zh) | 一种廉价高效烟气脱硫脱硝催化剂及其制备方法 | |
EP0348204B1 (en) | Porous, metal-containing carbonaceous material | |
CN109225179B (zh) | 一种吸附饱和含氯代烃类有机化合物废弃活性炭再生及其废气处理工艺 | |
CN109433236B (zh) | 多孔炭材料负载零价Fe-Fe3C的脱硝催化剂及其制备、使用方法 | |
CN103706368A (zh) | 一种用于处理有机混合废气的铁碳催化填料及其制备方法 | |
CN113198523A (zh) | 一种高效烟气脱硫脱硝催化剂制备方法 | |
CN111229209A (zh) | 一种荷叶源生物炭负载锰氧化物的低温scr烟气脱硝催化剂及其制备方法与应用 | |
CN108654633B (zh) | 一种低温脱硝催化剂及其制备方法和使用方法 | |
CN111569864A (zh) | 一种催化净化甲醛的活性炭复合材料及制备方法 | |
KR101527028B1 (ko) | 활성화된 탄소 촉매 | |
CN106744952A (zh) | 污水污泥制备改性活性焦的方法 | |
CN103769219A (zh) | 水分稳定性得到提高的用于去除毒性气体的低温氧化催化剂 | |
CN112934229A (zh) | 一种添加含钒矿石制备活性炭的方法 | |
CN116216717A (zh) | 活性炭和低温scr脱硝催化剂的制备方法以及烟气脱硝方法 | |
CN104707618B (zh) | 一种NOx吸附还原双功能催化剂的分步分区制备方法 | |
CN110152659A (zh) | 脱硝脱voc催化剂、制备方法、再生方法 | |
CN109248688B (zh) | 一种原位制备煤-生物质制碳基NOx吸附还原催化剂的方法 | |
Chen et al. | Comparative study of carbon-deNOx process by different sewage sludge chars | |
CN1240467C (zh) | 用于催化转化物质的方法和装置 | |
CN113304770A (zh) | 一种氮改性含铬革屑制备富氮金属催化剂的方法及应用 | |
KR20110034400A (ko) | 질소산화물 제거용 담지 촉매, 그 제조 방법 및 이를 이용한 질소산화물의 제거 방법 | |
CN108283920B (zh) | 一种脱NOx催化剂及其制备方法 | |
CN115093885B (zh) | 一种适用于移动床工艺过程的合成气脱硫剂及其制备方法 | |
CN114700036B (zh) | 一种改性烟杆基生物质多级孔炭及其制备方法和应用 | |
CN115093886B (zh) | 一种气化合成气脱硫除尘的循环移动床工艺方法及装置 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |