CN115920904A - Mesoporous microsphere alumina carrier and preparation method thereof, desulfurization and denitrification catalyst and preparation method thereof - Google Patents
Mesoporous microsphere alumina carrier and preparation method thereof, desulfurization and denitrification catalyst and preparation method thereof Download PDFInfo
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- CN115920904A CN115920904A CN202111107211.1A CN202111107211A CN115920904A CN 115920904 A CN115920904 A CN 115920904A CN 202111107211 A CN202111107211 A CN 202111107211A CN 115920904 A CN115920904 A CN 115920904A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 68
- 230000023556 desulfurization Effects 0.000 title claims abstract description 68
- 239000004005 microsphere Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 36
- 239000002245 particle Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 239000011344 liquid material Substances 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000008367 deionised water Substances 0.000 claims description 49
- 229910021641 deionized water Inorganic materials 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 10
- -1 salt compound Chemical class 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 44
- 239000000463 material Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 21
- 239000003546 flue gas Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 15
- 239000000084 colloidal system Substances 0.000 description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 238000010008 shearing Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 230000009471 action Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 8
- 229910052815 sulfur oxide Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 101100327537 Caenorhabditis elegans cgp-1 gene Proteins 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002156 adsorbate Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- 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
- Catalysts (AREA)
Abstract
The mesoporous microsphere alumina carrier is microspherical alpha-type alumina, the particle size range of the mesoporous microsphere alumina carrier is 2-180um, and the pore volume of the alpha-type alumina is 0.6-1.2 cm 3 G, the average pore diameter is 15-50 nm. Based on the total weight of the catalyst and calculated by metal oxide, the desulfurization and denitrification microspherical catalyst contains 6 to 15 weight percent of metal active component and 8 to 20 weight percent of metal oxideGamma-type active alumina and 65-86 wt% of the mesoporous microsphere alumina carrier, wherein the metal active component is selected from one or more of Ca, mg and Fe, and contains or does not contain one or more of Co, zn and Cu. The desulfurization and denitrification catalyst provided by the invention has good desulfurization and denitrification performance, high strength and higher wear resistance.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a desulfurization and denitrification microsphere catalyst and a preparation method thereof.
Background
Sulfur Oxides (SO) in industrial exhaust fumes 3 And SO 2 Abbreviated as SOx) and nitrogen oxides (mainly NO and NO) 2 NOx for short) is the main cause of acid rain caused by air pollution and also the main 'genuine' which destroys the ecological environment of the atmosphere. With the increasing awareness of environmental protection and the increasing strictness of environmental regulations, strict control of the discharge of air pollutants from industrial plants is required. Therefore, the development of high-efficiency industrial flue gas desulfurization and denitrification technology is needed.
The techniques for removing SOx from flue gas can be divided into wet method, dry method and semi-dry method. Wherein, the dry desulphurization process is relatively simple, the water-saving effect is obvious, and secondary pollutants such as alkaline residue and the like are not generated in the treatment process. However, the popularization and application of the dry desulfurization and denitration technology are limited by some problems, for example, the desorption and regeneration process of the adsorbent needs high temperature and has the problem of energy consumption, and in addition, the waste adsorbent is discarded. Therefore, the wear-resisting strength of the catalyst is improved, the running loss of the catalyst in the using process is reduced, the service life of the catalyst is prolonged, the pressure for treating the waste catalyst is reduced, the reaction activity and the regeneration performance of the catalyst are improved, the energy consumption of dry-method flue gas desulfurization and denitration is reduced, and the competitiveness of the dry-method desulfurization and denitration technology is improved. The catalyst with high wear resistance and high activity for desulfurization and denitrification, which meets the technical requirements, needs to be further developed.
CN105921181A discloses a high-quality desulfurization and denitrification catalyst, and a preparation method and an application method of the high-quality desulfurization and denitrification catalyst. The high-quality desulfurization and denitrification catalyst comprises bauxite, honeycomb activated carbon, neutral clay, starch, samarium oxide, platinum, sodium lauryl sulfate, polypropylene glycol, dicumyl peroxide and carbon fiber.
CN107626292A discloses a flue gas desulfurization and denitration catalyst, a preparation method and application thereof. The flue gas desulfurization and denitration catalyst is prepared from the following raw materials: 5-15 parts of magnesium oxide, 2-5 parts of cocatalyst, 70-80 parts of alumina, 5-15 parts of diatomite and 1-5 parts of wood chips; wherein the cocatalyst is selected from one or more of Na2O, niO and ZnO.
CN107519890A discloses a high-efficiency flue gas desulfurization and denitration catalyst and a preparation method thereof, wherein the high-efficiency flue gas desulfurization and denitration catalyst comprises 8-12 wt% of active components, 5-8 wt% of cocatalyst and 80-87 wt% of carriers; the active components comprise yttrium oxide, cobaltosic oxide, manganese dioxide and aluminum chloride; the cocatalyst is ferric oxide or nickel oxide; the carrier is modified active carbon; the specific surface area of the molecular sieve is 350-500 m 2 The pore diameter is 0.8-1.2 mL/g.
CN105032403B discloses a catalyst for low-temperature desulfurization and denitration of flue gas and a preparation method thereof, wherein the catalyst comprises active carbon modified by nitric acid as a carrier, transition metal Mn and/or rare earth element Ce as active components, and the active components are loaded on the carrier through impregnation and high-temperature roasting, wherein the load of Mn is 0-7wt% of the weight of the catalyst, the load of Ce is 0-9wt% of the weight of the catalyst, and the total load of the active components is not less than 3wt% of the weight of the catalyst. The preparation method of the catalyst comprises the steps of immersing activated carbon into nitric acid for modification, immersing the nitric acid-modified activated carbon into a manganese nitrate solution or/and a cerium nitrate solution, and immersing Mn and/or Ce on the modified activated carbon by evaporating a liquid phase; and (3) placing the modified activated carbon impregnated with Mn and/or Ce in roasting equipment for full roasting to obtain the catalyst loaded with active components and used for flue gas desulfurization and denitration.
CN102989466A discloses a flue gas desulfurization and denitrification catalyst by a reduction method and application thereof, and belongs to the technical field of industrial catalysis and flue gas treatment. The catalyst is prepared by adopting a known isometric impregnation method, and comprises the following components in percentage by mass: 80 to 99.9 percent of carrier active carbon, 0.1 to 10 percent of active component yttrium oxide and 0 to 10 percent of cocatalyst nickel monoxide or cobalt monoxide.
The desulfurization and denitrification catalyst disclosed above is mostly used in a fixed bed reactor, and the preparation method of the catalyst is limited to a small-dose laboratory scale, and does not relate to a preparation method of a microspherical catalyst suitable for a fluidized bed reactor, and cannot meet the requirements of the fluidized bed reactor for both high reactivity and high abrasion strength of the catalyst.
Disclosure of Invention
The invention provides a mesoporous microsphere alumina carrier and a preparation method thereof on the basis of the prior art.
The second technical problem to be solved by the invention is to provide a desulfurization and denitrification microspherical catalyst with high activity and high wear resistance suitable for a fluidized bed reactor and a preparation method thereof.
A mesoporous microsphere alumina carrier is microspherical alpha-type alumina with the particle size ranging from 2 to 180um, and the pore volume of the alpha-type alumina is 0.6 to 1.2cm 3 (ii)/g, the average pore diameter is 15-50 nm.
The preparation method of the mesoporous microsphere alumina carrier comprises the following steps:
(1) Mixing an aluminum source, inorganic acid, a water-soluble high-molecular polymer, absolute ethyl alcohol, propylene oxide and deionized water in a ratio of 1:0.1-0.3:0.01-0.05:0.2-0.5:0.2-0.8:5-15 to obtain a liquid material L3;
(2) And (2) spray-drying the liquid material L3 obtained in the step (1) to obtain microspheres, and drying and roasting to obtain the mesoporous microsphere alumina carrier.
A desulfurization and denitrification microspherical catalyst comprises, by taking the total weight of the catalyst as a reference and taking metal oxides as the basis, 6-15 wt% of metal active components, 8-20 wt% of gamma-type active alumina and 65-86 wt% of the mesoporous microspherical alumina carrier, wherein the metal active components are selected from one or more of Ca, mg and Fe, and contain or do not contain one or more of Co, zn and Cu.
A preparation method of a desulfurization and denitrification microspherical catalyst comprises the following steps:
s1: dissolving a water-soluble salt compound of a metal active component in water according to a proportion, adding a water-soluble high molecular polymer, mixing to obtain a liquid material L4, and carrying out flash evaporation, drying and roasting on the liquid material L4 to obtain powder M1 containing the metal active component; mixing powder M1, a water-soluble high-molecular polymer, an aluminum source and deionized water according to a mass ratio of 1-0.01-0.1;
s2: and (2) soaking the mesoporous microsphere alumina carrier obtained by the preparation method by using the liquid material L5 obtained in the step (S1), and filtering, drying and roasting to obtain the desulfurization and denitrification microspherical catalyst.
The mesoporous microsphere alumina carrier and the preparation method thereof provided by the invention have the beneficial effects that:
the mesoporous microsphere alumina carrier prepared by the method has higher porosity, communicated pore channel structures, high strength and wear resistance.
The desulfurization and denitrification microspherical catalyst and the preparation method thereof provided by the invention have the beneficial effects that:
the catalyst prepared by the method provided by the invention has good desulfurization and denitrification performances and excellent high-wear-resistance characteristics, and is particularly suitable for desulfurization and denitrification processes under the fluidized bed operation condition.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In a first aspect, the invention provides a mesoporous microsphere alumina carrier which is microspherical alpha-type alumina, the particle size range is 2-180um, the average particle size is 50-90um, and the pore volume of the alpha-type alumina is 0.6-1.2 cm 3 G, the average pore diameter is 15-50 nm.
In a second aspect, the invention provides a preparation method of a mesoporous microsphere alumina carrier, which comprises the following steps:
(1) Mixing an aluminum source, inorganic acid, a water-soluble high-molecular polymer, absolute ethyl alcohol, propylene oxide and deionized water in a ratio of 1:0.1-0.3:0.01-0.05:0.2-0.5:0.2-0.8:5-15 to obtain a liquid material L3;
(2) And (2) spray-drying the liquid material L3 obtained in the step (1) to obtain microspheres, and drying and roasting to obtain the mesoporous microsphere alumina carrier.
Preferably, step (1) is: uniformly mixing a water-soluble high molecular polymer with water, and simultaneously adding absolute ethyl alcohol and propylene oxide to obtain a liquid material L1, wherein the mass ratio of the water-soluble high molecular polymer to the water to the absolute ethyl alcohol to the propylene oxide is as follows: 1:50-80:10-15:15-25; mixing an aluminum source, acid and deionized water in a ratio of 1:0.1-0.25:3-8 to obtain a liquid material L2; mixing the L1 and the L2 to obtain a liquid material L3, wherein the ratio of L2: the mass ratio of L1 is 1:0.1-0.5, preferably L2: the mass ratio of L1 is 0.2-0.4.
Preferably, the aluminum source in the step (1) is selected from one or more of pseudo-boehmite, aluminum trichloride, aluminum hydroxide and aluminum sol; the acid is hydrochloric acid, phosphoric acid or nitric acid; the water-soluble high molecular polymer is selected from one or more of polyethylene oxide, polyethylene glycol, methyl starch, starch acetate and hydroxymethyl cellulose.
Optionally, the operating conditions of the spray drying in step (2) are: the air inlet temperature is 350-600 ℃, preferably 450-550 ℃, the air outlet temperature is 110-160 ℃, preferably 120-150 ℃; the roasting temperature in the roasting step is 1000-1400 ℃, preferably 1150-1300 ℃, and the roasting time is 1.5-5.0 h. Preferably, the roasting process is to heat the mixture from room temperature to 450-650 ℃ for 0.5-4.5 hours, and then heat the mixture to 1000-1400 ℃ for 0.5-4.5 hours.
In a third aspect, the mesoporous microsphere alumina carrier prepared by the preparation method of the mesoporous microsphere alumina carrier provided by the invention.
In a fourth aspect, the invention provides a desulfurization and denitrification microspherical catalyst, which comprises, by taking the total weight of the catalyst as a reference and taking metal oxides as the basis, 6-15 wt% of metal active components, 8-20 wt% of gamma-type active alumina and 65-86 wt% of the mesoporous microspherical alumina carrier, wherein the metal active components are selected from one or more of Ca, mg and Fe, and may or may not contain one or more of Co, zn and Cu.
Preferably, the content of the metal active component is as follows based on the total weight of the catalyst: 0.5 to 5 weight percent of calcium oxide, 0.5 to 5 weight percent of magnesium oxide, 5 to 12 weight percent of ferric oxide, 0 to 2 weight percent of cobalt oxide, 0 to 1.5 weight percent of zinc oxide and 0 to 1 weight percent of copper oxide.
In a fifth aspect, the invention provides a preparation method of a desulfurization and denitrification microspherical catalyst, which comprises the following steps:
s1: dissolving a water-soluble salt compound of a metal active component in water according to a proportion, adding a water-soluble high-molecular polymer, mixing to obtain a liquid material L4, and carrying out flash evaporation drying and roasting on the liquid material L4 to obtain powder M1 containing the metal active component; mixing powder M1, a water-soluble high-molecular polymer, an aluminum source and deionized water according to a mass ratio of 1-0.01-0.1;
s2: and (2) impregnating the mesoporous microsphere catalyst carrier with the liquid material L5 obtained in the step (S1), and filtering, drying and roasting to obtain the desulfurization and denitrification catalyst.
Preferably, in step S1, iron oxide powder is also added;
preferably, the powder M1 obtained is crushed to a powder M2 having an average particle size of less than 1 μ M; mixing the powder M2, the water-soluble high molecular polymer, an aluminum source and deionized water to obtain a liquid material, and grinding and crushing the liquid material until the particle size of solid particles is less than 0.5 mu M to obtain a liquid material L5.
Preferably, in the step (4), the mesoporous microsphere alumina carrier is impregnated with the liquid material L5 obtained in the step S1, the surface of a filter cake is rinsed with deionized water after filtration, and the desulfurization and denitrification catalyst is obtained after drying and roasting.
Optionally, the metal active component in step S1 is selected from one or more of Ca, mg and Fe, with or without one or more of Co, zn and Cu; the water-soluble high molecular polymer is selected from one or more of polyethylene oxide, polyethylene glycol, methyl starch, starch acetate and hydroxymethyl cellulose; the aluminum source is selected from one or more of pseudo-boehmite, aluminum trichloride, aluminum hydroxide and aluminum sol.
Optionally, in S2, the roasting temperature is 350-650 ℃, preferably 450-550 ℃, and the roasting time is 1.5-5.0 h, preferably 2.0-4.0 h.
In a sixth aspect, the catalyst prepared by the preparation method of the microspherical catalyst for desulfurization and denitrification provided by the invention.
The preparation method of the desulfurization and denitrification microspherical catalyst provided by the invention comprises the steps of firstly carrying out spray drying and forming on a high molecular polymer solution containing an aluminum source, and roasting at a high temperature of more than 1000 ℃ to prepare a mesoporous microspherical alumina carrier with high wear resistance and high porosity; preparing slurry containing active metal components and active gamma-alumina components; then, impregnating the active metal component and the active alumina on the mesoporous microsphere catalyst carrier to obtain the desulfurization and denitrification microsphere catalyst.
Specifically, a preferred embodiment of the present invention comprises the following steps:
(1) Adding absolute ethyl alcohol into deionized water in a stirring tank (ethyl alcohol: deionized water = 0.05-0.3); adding polyoxyethylene (polyoxyethylene: deionized water = 0.01-0.2) until completely dissolved; then adding propylene oxide (propylene oxide: deionized water = 0.05-0.3) and continuing stirring for 0.5-2.5 hours to obtain a transparent liquid material L1.
(2) Mixing and stirring 5-25 wt% of alumina powder, deionized water and hydrochloric acid in a stirring kettle for 0.5-2 hours according to the proportion, and then standing the colloid for 0.5-2.5 hours to obtain a colloidal liquid material L2.
(3) Slowly adding the liquid material L1 obtained in the step (1) into the liquid material L2 obtained in the step (2) (the charging time is 20-50 minutes) and stirring for 0.5-2.5 hours to obtain a liquid material L3.
(4) And (4) carrying out spray drying and molding on the liquid material L3 obtained in the step (3), and then carrying out temperature programming roasting on the molded microsphere particles, wherein the roasting process is to raise the temperature from room temperature to 450-650 ℃ at the heating rate of 3-20 ℃/s and keep the temperature for 0.5-4.5 hours, and then raise the temperature to 1000-1400 ℃ at the heating rate of 3-20 ℃/s and keep the temperature for 0.5-4.5 hours to obtain the mesoporous microsphere alumina carrier, the particle size of the obtained mesoporous microsphere alumina carrier is 2-180 mu m, and the average particle size is 50-90 mu m.
(5) Dissolving one or more of magnesium nitrate, calcium nitrate, cobalt nitrate and copper nitrate in deionized water to prepare a clarified solution, controlling the water content of the solution to be 70-98%, adding polyoxyethylene (polyoxyethylene: deionized water = 0.001-0.05) until the solution is completely dissolved, then adding iron oxide powder into the solution, controlling the water content of the solution to be 15-35 wt%, forming a uniform liquid material L4 under the action of a shearing machine, shearing and stirring for 0.5-2.5 hours, then introducing the slurry into a flash evaporation drier for drying, and roasting for 0.5-2.5 hours at the temperature of 450-650 ℃ to obtain powder M2.
(6) And adding the powder M2 into an airflow crusher until the average particle size of the material is less than 1um to obtain powder M3.
(7) Adding polyoxyethylene to deionized water (polyoxyethylene: deionized water = 0.01-0.1) in a stirring tank until completely dissolved; adding the M3 obtained in the step (6) into the materials (M3: deionized water = 0.1-0.4), adding aluminum sol (aluminum oxide: deionized water = 0.05-0.3), and continuously stirring for 0.5-2.5 hours; and finally, enabling the obtained liquid material to pass through a wet sand mill to enable the average particle size of the liquid material to be smaller than 0.5um, and obtaining the liquid material L5.
(8) And (3) adding a certain amount of the mesoporous alumina carrier obtained in the step (4) into the liquid material L5 obtained in the step (7), soaking for 0.5-2.5 hours under the action of ultrasonic waves, then pouring the material into a 300-mesh screen for filtering, and washing a filter cake with deionized water.
(9) And (3) drying the material obtained after filtering and cleaning in the step (8) at 90-180 ℃ for 0.5-4 hours, and roasting at 350-650 ℃ for 0.5-4 hours to obtain the final desulfurization and denitrification catalyst.
The technical solutions and effects of the present invention are further illustrated by the following examples, but the present invention is not limited thereto.
Example 1
(1) Adding 450 g of absolute ethanol (analytically pure) to 3000 g of deionized water and stirring for 10 minutes; then 35 g of polyethylene oxide (FW: 1000000) were added until complete dissolution; 680 g of propylene oxide (analytically pure) were added and stirring was continued for 1.5 hours to obtain a liquid L1.
(2) 9000 g of deionized water was charged into a 20L stirred tank, and after stirring was started, 1800 g of alumina (alumina content 64% by weight, produced by Shandong aluminum works) and 160 g of hydrochloric acid (HCl content 30% by weight) were mixed and stirred in a stirred tank for 0.5 hour, and then the colloid was allowed to stand for 1.5 hours to obtain a liquid material L2.
(3) And (3) slowly adding 3500 g of the liquid L1 obtained in the step (1) into the colloid L2 prepared in the step (2) (the adding time is 20-50 minutes), wherein the adding time is 30 minutes, and continuously stirring for 1.5 hours to obtain a colloid which is a liquid material L3.
(4) And (4) carrying out spray drying and molding on the liquid material L3 obtained in the step (3), then carrying out temperature programming roasting on the molded microsphere particles, wherein the roasting process is to raise the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/s and keep the temperature for 2 hours, and then raise the temperature to 1250 ℃ at the heating rate of 10 ℃/s and keep the temperature for 2 hours, so as to obtain the mesoporous microsphere alumina carrier. The particle size ranges from 2 to 180 μm, and the average particle size is 75 μm.
(5) 530 g of anhydrous magnesium nitrate (analytically pure, the content of which is more than 99 percent) and 780 g of anhydrous calcium nitrate (analytically pure, the content of which is more than 99 percent) are dissolved in 10000 g of deionized water to prepare a clear solution, 50g of polyethylene oxide (analytically pure, FW: 1000000) is added under the stirring condition until the calcium nitrate is completely dissolved, 1800 g of ferric oxide (analytically pure, the content of which is more than 98 percent) is added into the solution to prepare uniform material slurry L4 under the action of a shearing machine, the shearing and stirring time is 1.5 hours, and finally the slurry L4 is introduced into a flash dryer (the inlet temperature is 180 ℃ and the outlet temperature is 105 ℃) to be dried to obtain powder M1.
(6) And roasting the powder M1 for 2 hours at the temperature of 550 ℃, adding the material into an airflow crusher after the material is cooled until the average particle size of the material is less than 1um, and obtaining the powder M2.
(7) 25 grams of polyethylene oxide was weighed into 2000 grams of deionized water in a stirred vessel until completely dissolved; then weighing 300 g of M2 obtained in the step (6), adding into the material, adding 1050 g of alumina sol (the content of alumina is 21%), and continuing stirring for 2 hours; and finally, enabling the obtained liquid material to pass through a wet sand mill to enable the average particle size of the liquid material to be smaller than 0.5um, and obtaining the liquid material L5.
(8) And (3) adding 500 g of the mesoporous microsphere alumina carrier obtained in the step (4) into 2000 g of the liquid material L5 obtained in the step (7), soaking for 0.5 hour under the action of ultrasonic waves, then pouring the material into a 300-mesh screen for filtering, and washing with deionized water.
(9) And (3) drying the material obtained after filtering and cleaning in the step (8) at 110 ℃ for 2 hours, and roasting at 450 ℃ for 2.5 hours to obtain the desulfurization and denitrification catalyst A.
Example 2
(1) To 3000 grams of deionized water, 350 grams of absolute ethanol (analytical grade) was added and stirred for 10 minutes; then 28 g of polyethylene oxide (FW: 1000000) were added until complete dissolution; an additional 750 grams of propylene oxide (analytically pure) was added and stirring continued for 1.5 hours to give a liquid mass L1.
(2) 9000 g of deionized water was charged into a 20L stirred tank, and after stirring was started, 1800 g of alumina (alumina content 64% by weight, produced by Shandong aluminum works) and 160 g of hydrochloric acid (HCl content 30% by weight) were mixed and stirred in a stirred tank for 0.5 hour, and then the colloid was allowed to stand for 1.5 hours to obtain a liquid material L2.
(3) And (3) slowly adding 3900 g of the liquid material L1 obtained in the step (1) (the adding time is 20-50 minutes) into the liquid material L2 obtained in the step (2), wherein the adding time is 30 minutes, and continuously stirring for 1.5 hours to obtain a colloid, namely a liquid material L3.
(4) And (3) carrying out spray drying and molding on the liquid material L3 obtained in the step (3), and then carrying out temperature programming roasting on the molded microsphere particles, wherein the roasting process is to raise the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/second and keep the temperature for 2 hours, and then raise the temperature to 1150 ℃ at the heating rate of 10 ℃/second and keep the temperature for 2 hours, so as to obtain the mesoporous alumina microsphere carrier. The particle size range is 2-180 μm, and the average particle size is 82 μm.
(5) 530 g of anhydrous magnesium nitrate (analytically pure, the content of which is more than 99 percent) and 780 g of anhydrous calcium nitrate (analytically pure, the content of which is more than 99 percent) are dissolved in 10000 g of deionized water to prepare a clear solution, 50g of polyoxyethylene (analytically pure, FW: 1000000) is added under the stirring condition until the anhydrous magnesium nitrate is completely dissolved, 1800 g of ferric oxide (analytically pure, the content of which is more than 98 percent) is added into the solution to prepare uniform material slurry under the action of a shearing machine, the shearing and stirring time is 1.5 hours, and finally the slurry is introduced into a flash dryer (the inlet temperature is 180 ℃, the outlet temperature is 105 ℃) to be dried and is roasted for 2 hours at 550 ℃ to obtain the powder material M1.
(6) And adding the powder M2 into an airflow crusher until the average particle size of the material is less than 1um, and obtaining the powder M2.
(7) 25 grams of polyethylene oxide was weighed into 2000 grams of deionized water in a stirred vessel until completely dissolved; then weighing 300 g of M2 obtained in the step (6), adding into the material, adding 1350 g of aluminum sol (the content of alumina is 21%), and continuing stirring for 2 hours; and finally, enabling the obtained liquid material to pass through a wet sand mill to enable the average particle size of the liquid material to be smaller than 0.5um, and obtaining the liquid material L5.
(8) And (5) adding 500 g of the mesoporous microsphere alumina carrier obtained in the step (4) into 2000 g of the liquid material L5 obtained in the step (7), soaking for 0.5 hour under the action of ultrasonic waves, then pouring the material into a 300-mesh screen for filtering, and washing with deionized water.
(9) And (4) drying the material obtained after filtering and cleaning in the step (8) at 110 ℃ for 2 hours, and roasting at 450 ℃ for 2.5 hours to obtain the desulfurization and denitrification catalyst B.
Example 3
(1) Adding 450 g of absolute ethanol (analytically pure) to 3000 g of deionized water and stirring for 10 minutes; then 35 g of polyethylene oxide (FW: 1000000) were added until complete dissolution; an additional 680 g of propylene oxide (analytically pure) was added and stirring continued for 1.5 hours to give a liquid mass L1.
(2) 9000 g of deionized water was charged into a 20L stirring tank, and after stirring was started, 1800 g of alumina (alumina content 64% by weight, available from Shandong aluminum works) and 160 g of hydrochloric acid (HCl content 30% by weight) were mixed and stirred in a stirring tank for 0.5 hour, and then the colloid was allowed to stand for 1.5 hours to obtain a liquid material L2.
(3) 3500 g of the liquid material L1 obtained in the step (1) is slowly added (the adding time is 20-50 minutes) into the colloid L2 prepared in the step (2), the adding time is 30 minutes, and the stirring is continued for 1.5 hours, so that a liquid material L3 is obtained.
(4) And (3) carrying out spray drying and forming on the liquid material L3 obtained in the step (3), then carrying out temperature programming roasting on the formed microsphere particles, wherein the roasting process is to raise the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/second and keep the temperature for 2 hours, and then raise the temperature to 1250 ℃ at the heating rate of 10 ℃/second and keep the temperature for 2 hours, so as to obtain the mesoporous microsphere alumina carrier. The particle size range is 2-180 μm, and the average particle size is 68 μm.
(5) 690 g of anhydrous magnesium nitrate (analytically pure, the content of which is more than 99 percent) and 820 g of anhydrous calcium nitrate (analytically pure, the content of which is more than 99 percent) are dissolved in 10000 g of deionized water to prepare a clear solution, 35 g of polyethylene oxide (analytically pure, FW: 1000000) is added under the stirring condition until the calcium nitrate is completely dissolved, 1200 g of ferric oxide (analytically pure, the content of which is more than 98 percent) is added into the solution to prepare uniform material slurry under the action of a shearing machine, the shearing and stirring time is 1.5 hours, and finally the slurry is introduced into a flash evaporation dryer (the inlet temperature is 180 ℃, the outlet temperature is 105 ℃) to be dried and roasted for 2 hours under the 550 ℃ condition to obtain powder M1.
(6) And adding the powder M1 into an airflow crusher until the average particle size of the material is less than 1um, thus obtaining the powder M2.
(7) 25 grams of polyethylene oxide was weighed into 2000 grams of deionized water in a stirred vessel until completely dissolved; then weighing 300 g of the powder M2 obtained in the step (6), adding the powder into the material, adding 1350 g of alumina sol (the content of alumina is 21%), and continuing stirring for 2 hours; and finally, enabling the obtained liquid material to pass through a wet sand mill to enable the average particle size of the liquid material to be smaller than 0.5um, and obtaining the liquid material L5.
(8) And (3) adding 500 g of the mesoporous microsphere alumina carrier obtained in the step (4) into 2000 g of the liquid material L5 obtained in the step (7), soaking for 0.5 hour under the action of ultrasonic waves, then pouring the material into a 300-mesh screen for filtering, and washing with deionized water.
(9) And (4) drying the material obtained after filtering and cleaning in the step (8) at 110 ℃ for 2 hours, and roasting at 450 ℃ for 2.5 hours to obtain the desulfurization and denitrification catalyst C.
Example 4
(1) To 3000 g of deionized water was added 450 g of absolute ethanol (analytical grade) and stirred for 10 minutes; then 35 g of polyethylene oxide (FW: 1000000) were added until complete dissolution; 680 g of propylene oxide (analytically pure) were added and stirring was continued for 1.5 hours to obtain a liquid L1.
(2) 9000 g of deionized water was charged into a 20L stirred tank, and after stirring was started, 1800 g of alumina (alumina content 64% by weight, produced by Shandong aluminum works) and 160 g of hydrochloric acid (HCl content 30% by weight) were mixed and stirred in a stirred tank for 0.5 hour, and then the colloid was allowed to stand for 1.5 hours to obtain a liquid material L2.
(3) And (3) slowly adding 3500 g of the liquid material L1 obtained in the step (1) (the adding time is 20-50 minutes) into the liquid material L2 obtained in the step (2), wherein the adding time is 30 minutes, and continuously stirring for 1.5 hours to obtain a liquid material L3.
(4) And (3) carrying out spray drying and forming on the liquid material L3 obtained in the step (3), and then carrying out temperature programming roasting on the formed microsphere particles, wherein the roasting process is to raise the temperature from room temperature to 650 ℃ at the heating rate of 10 ℃/second and keep the temperature for 3 hours, and then raise the temperature to 1350 ℃ at the heating rate of 10 ℃/second and keep the temperature for 2.5 hours, so as to obtain the mesoporous microsphere alumina carrier. The particle size range is 2-180 μm, and the average particle size is 88 μm.
(5) 530 g of anhydrous magnesium nitrate (analytically pure, the content of which is more than 99 percent) and 780 g of anhydrous calcium nitrate (analytically pure, the content of which is more than 99 percent) are dissolved in 10000 g of deionized water to prepare a clear solution, 50g of polyethylene oxide (analytically pure, FW: 1000000) is added under the stirring condition until the calcium nitrate is completely dissolved, 1800 g of ferric oxide (analytically pure, the content of which is more than 98 percent) is added into the solution to prepare uniform material slurry under the action of a shearing machine, the shearing and stirring time is 1.5 hours, and finally the slurry is introduced into a flash evaporation dryer (the inlet temperature is 180 ℃, the outlet temperature is 105 ℃) to be dried and roasted for 2 hours under the 550 ℃ condition to obtain powder M1.
(6) And adding the powder material M1 into an airflow crusher until the average particle size of the material is less than 1um, and obtaining the powder material M2.
(7) 25 grams of polyethylene oxide was weighed into 2000 grams of deionized water in a stirred vessel until completely dissolved; then 300 g of the powder M2 obtained in the step (6) is weighed and added into the materials, 1550 g of aluminum sol (with the content of alumina being 21%) is added, and stirring is continued for 2 hours; and finally, enabling the obtained liquid material to pass through a wet sand mill to enable the average particle size of the liquid material to be smaller than 0.5um, and obtaining the liquid material L5.
(8) And (5) adding 500 g of the mesoporous microsphere alumina carrier obtained in the step (4) into 2000 g of the liquid material L5 obtained in the step (7), soaking for 0.5 hour under the action of ultrasonic waves, then pouring the material into a 300-mesh screen for filtering, and washing a filter cake with deionized water.
(9) And (4) drying the material obtained after filtering and cleaning in the step (8) at 110 ℃ for 2 hours, and roasting at 450 ℃ for 2.5 hours to obtain the desulfurization and denitrification catalyst D.
Comparative example 1
The method disclosed in CN107519890A is used for preparing a desulfurization and denitrification catalyst, which comprises 2.62wt% of yttrium oxide, 1.79wt% of cobaltosic oxide, 2.69wt% of manganese dioxide, 0.90wt% of aluminum chloride, 5wt% of ferric oxide and 87wt% of activated carbon. The preparation method comprises the steps of calculating the amounts of yttrium oxide, cobaltosic oxide, manganese dioxide, aluminum chloride and ferric oxide, weighing corresponding precursor materials of yttrium nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and ferric nitrate, dissolving the yttrium nitrate, the cobalt nitrate, the manganese nitrate, the aluminum nitrate and the ferric nitrate in deionized water, uniformly stirring, adding graphitized activated carbon, placing in a muffle furnace after ultrasonic dispersion for 40min, roasting at 600 ℃, and cooling to room temperature to obtain the desulfurization and denitrification catalyst E.
Comparative example 2
The method disclosed in CN107626292A is used to prepare a catalyst for desulfurization and denitrification, which comprises 10.0wt% of magnesium oxide, 75.0wt% of aluminum oxide, 3.0wt% of Na2O, 10.0wt% of diatomite and 2.0wt% of wood chips. The preparation method comprises mixing magnesium oxide and Na 2 And (3) fully grinding the mixture, adding alumina, diatomite and wood chips, mixing, adding water, and fully stirring to obtain a pasty mixture. Putting the pasty mixture into a forming machine to form a sphere; drying at 105 ℃ for 3 hours, and roasting at 600 ℃ for 5 hours to obtain the desulfurization and denitrification catalyst F.
Comparative example 3
The method disclosed by CN102989466A is used for preparing the desulfurization and denitrification catalyst, and the desulfurization and denitrification catalyst comprises the following components in percentage by mass: 91wt% of carrier active carbon, 6wt% of yttrium oxide and 3wt% of nickel protoxide. Weighing 11.2G of Y (NO 3) 3.6H 2O and 6.4G of Ni (NO 3) 2.6H 2O, dissolving in 80ml of deionized water to obtain a yttrium nitrate and nickel nitrate mixed solution, putting 50G of activated carbon particles into the yttrium nitrate and cobalt nitrate mixed solution by adopting an isometric immersion method, uniformly stirring and standing for 10H, drying at the temperature of 100 ℃, and roasting in nitrogen at the temperature of 800 ℃ for 3H to obtain the desulfurization and denitrification catalyst G.
Comparative example 4
(1) 530 g of anhydrous magnesium nitrate (analytically pure, the content of which is more than 99 percent) and 780 g of anhydrous calcium nitrate (analytically pure, the content of which is more than 99 percent) are dissolved in 10000 g of deionized water to prepare a clear solution, 50g of polyethylene oxide (analytically pure, FW: 1000000) is added under the stirring condition until the calcium nitrate is completely dissolved, 1800 g of ferric oxide (analytically pure, the content of which is more than 98 percent) is added into the solution to prepare uniform material slurry under the action of a shearing machine, the shearing and stirring time is 1.5 hours, and finally the slurry is introduced into a flash dryer (the inlet temperature is 180 ℃, the outlet temperature is 105 ℃) to be dried.
(2) Roasting the dried material at 550 ℃ for 1.5 hours, cooling the material, adding the material into an airflow crusher until the average particle size of the material is less than 5um (the particle size of the material is determined by a laser particle size method), and obtaining the active metal oxide composite material, wherein the M is recorded as M 1 。
(3) Adding 450 g of absolute ethanol (analytically pure) to 3000 g of deionized water and stirring for 10 minutes; then 35 g of polyethylene oxide (FW: 1000000) were added until complete dissolution; 680 g of propylene oxide (analytically pure) are added and the mixture is stirred for 1.5 hours to obtain a transparent liquid material L 1 。
(4) 9000 g of deionized water was placed in a 20L stirred tank, and after stirring was started, 1800 g of alumina (alumina content: 64% by weight, obtained from Shandong aluminum works) and 160 g of hydrochloric acid (HCl content: 30% by weight) were mixed and stirred in a stirred tank for 0.5 hour, and then the colloid was allowed to stand for 1.5 hours to obtain a colloidal liquid L 2 。
(5) Weighing 320 g of M1 obtained in the step (2), adding into the colloid prepared in the step (4), stirring for 0.5 hour, and then adding the liquid material L obtained in the step (3) 1 3500 g of the catalyst colloid was weighed and added to the above colloid and stirred for 0.5 hour to obtain a catalyst colloid.
(6) And (3) carrying out spray drying molding on the catalyst colloid obtained in the step (5), wherein the spray drying air inlet temperature is 550 ℃ and the air outlet temperature is 160 ℃, and then roasting the molded microsphere particles at 550 ℃ for 2 hours to obtain the final desulfurization and denitrification catalyst H.
Method for analyzing pore volume and average pore diameter of alumina carrier
The specific surface area is measured by an AUTOSORB-1-C type full-automatic specific surface analyzer manufactured by Congta instruments of America. The sample before measurement was subjected to an evacuation treatment under conditions of 1.33X 10-2Pa and 573K for 4 hours, and then to a high purity N 2 As an adsorbate, it was adsorbed and desorbed at 77K at an isothermal temperature, and the isotherm was determined. The pore volume of the sample, calculated from the BET (Brunauer-Emmett-Teller) equation, and the pore size distribution, the average pore size, were calculated by the BJH method of desorption isotherm.
In examples 1 to 4, the pore volume, the average pore diameter, the particle size range and the average particle size of the prepared mesoporous microspherical alumina carrier are shown in table 1, and the composition of the prepared desulfurization and denitrification catalyst is shown in table 1.
TABLE 1
Examples 5 to 8
Evaluation example of desulfurization and denitrification catalyst:
the desulfurization and denitrification catalysts prepared in the examples 1 to 4 were respectively loaded in a fixed bed reactor, the loading amount was 5 g, the simulated flue gas was introduced into the fixed bed reactor after being depressurized, the space velocity of the flue gas was 3000/hr, and the flue gas components were: 2500ppmNO,1000ppmSO 2 And the balance of nitrogen. The reaction pressure is 0.2bar, the desulfurization and denitrification reactions are carried out at the reaction temperatures of 120 ℃ and 400 ℃ respectively, sulfur oxides and nitrogen oxides in the flue gas after the reactions are analyzed, and the desulfurization and denitrification efficiencies are calculated. The desulfurization and denitrification efficiencies of the desulfurization and denitrification catalysts prepared in the examples and comparative examples are shown in Table 2.
Wherein: the NO removal rate = (content of NO in simulated smoke-NO content in smoke after reaction)/content of NO in simulated smoke;
SO 2 removal rate = (SO in simulated flue gas) 2 content-SO in flue gas after reaction 2 content)/SO in simulated flue gas 2 And (4) content.
The method for analyzing sulfur oxides and nitrogen oxides in flue gas comprises the following steps:
raw materials and tail gas in the flue gas desulfurization and denitrification process are analyzed on line by adopting an MGS300 multi-component continuous gas measurement system. The MGS300 multi-component continuous gas measurement system integrates a flue gas heat preservation sampling unit, a pretreatment unit, a Fourier transform infrared (FT-IR) quasi-in-situ gas analyzer, an oxygen analyzer, a hydrogen analyzer and a post-treatment unit.
Comparative examples 5 to 8
Evaluation example of desulfurization and denitrification catalyst:
the catalyst evaluation method of example 5 was adopted, and the desulfurization and denitrification catalysts prepared in comparative examples 1 to 4 were respectively loaded in a fixed bed reactor for evaluation, unlike example 5, and the evaluation results are shown in table 2.
TABLE 2
Catalyst attrition index analysis examples
Abrasion index analysis the abrasion index was calculated as the mass percent of fines collected per unit time of the spray treatment to the total charge sample using an abrasion index determinator model 8920, MAXTROL corporation, usa, according to ASTM 5757-00. The attrition indexes of the desulfurization and denitrification catalysts obtained in examples 1 to 4 and comparative examples 1 to 4, respectively, and a commercial cracking catalyst (No. CGP-1) were measured, and the results are shown in Table 3. Wherein, the comparative example catalysts E, F and G are ground and sieved to obtain the same particle size as the microsphere catalyst in the example, and then the abrasion strength analysis is carried out.
TABLE 3 attrition index of the catalyst
The abrasion index is the loss rate of the sample after abrasion test, and the larger the value is, the worse the abrasion resistance of the sample is; a smaller wear index indicates a better wear resistance of the sample. As can be seen from table 3, the desulfurization and denitrification catalyst prepared by the method provided by the invention has significantly improved wear resistance, and is suitable for use in a fluidized bed reactor.
Claims (11)
1. The mesoporous microsphere alumina carrier is characterized by being microspherical alpha-type alumina with the particle size range of 2-180um, and the pore volume of the alpha-type alumina is 0.6-1.2 cm 3 G, the average pore diameter is 15-50 nm.
2. A desulfurization and denitrification microspherical catalyst is characterized by comprising 6-15 wt% of metal active components, 8-20 wt% of gamma-type active alumina and 65-86 wt% of the mesoporous microspherical alumina carrier according to claim 1, wherein the metal active components are one or more selected from Ca, mg and Fe, and contain or do not contain one or more selected from Co, zn and Cu, calculated by metal oxides based on the total weight of the catalyst.
3. The microspherical catalyst for desulfurization and denitrification according to claim 2, wherein the contents of the metal active components based on the total weight of the catalyst are as follows: 0.5 to 5 weight percent of calcium oxide, 0.5 to 5 weight percent of magnesium oxide, 5 to 12 weight percent of ferric oxide, 0 to 2 weight percent of cobalt oxide, 0 to 1.5 weight percent of zinc oxide and 0 to 1 weight percent of copper oxide.
4. The preparation method of the mesoporous microsphere alumina carrier of claim 1 is characterized by comprising the following steps:
(1) Mixing an aluminum source, inorganic acid, a water-soluble high-molecular polymer, absolute ethyl alcohol, propylene oxide and deionized water in a ratio of 1:0.1-0.3:0.01-0.05:0.2-0.5:0.2-0.8:5-15 to obtain a liquid material L3;
(2) Spray-drying the liquid material L3 obtained in the step (1) into microspheres, and drying and roasting to obtain a mesoporous microsphere alumina carrier;
preferably, step (1) is: uniformly mixing a water-soluble high molecular polymer with water, and simultaneously adding absolute ethyl alcohol and propylene oxide to obtain a liquid material L1, wherein the mass ratio of the water-soluble high molecular polymer to the water to the absolute ethyl alcohol to the propylene oxide is as follows: 1:50-100:10-20:15-30 parts of; mixing an aluminum source, acid and deionized water in a ratio of 1:0.1-0.3:3-10 to obtain a liquid material L2; mixing the liquid material L1 and the liquid material L2 to obtain a liquid material L3, wherein the ratio of L2: the mass ratio of L1 is 1:0.1-0.5.
5. The preparation method of the mesoporous microsphere alumina carrier according to claim 4, characterized in that the aluminum source in the step (1) is one or more selected from pseudo-boehmite, aluminum trichloride, aluminum hydroxide and aluminum sol; the acid is hydrochloric acid, phosphoric acid or nitric acid; the water-soluble high molecular polymer is selected from one or more of polyethylene oxide, polyethylene glycol, methyl starch, starch acetate and hydroxymethyl cellulose.
6. The preparation method of mesoporous microsphere alumina supporter according to claim 4, wherein the spray drying in step (2) is performed under the conditions of 350-600 ℃ of inlet air temperature and 110-160 ℃ of outlet air temperature; the roasting is carried out for 1.5 to 4.5 hours at the temperature of 1000 to 1400 ℃.
7. The mesoporous microsphere catalyst carrier prepared by the preparation method of the mesoporous microsphere catalyst carrier according to any one of claims 3 to 6.
8. A preparation method of a desulfurization and denitrification microspherical catalyst is characterized by comprising the following steps:
s1: dissolving a water-soluble salt compound of a metal active component in water according to a proportion, adding a water-soluble high molecular polymer, mixing to obtain a liquid material L4, and carrying out flash evaporation, drying and roasting on the liquid material L4 to obtain powder M1 containing the metal active component; mixing powder M1, a water-soluble high-molecular polymer, an aluminum source and deionized water according to a mass ratio of 1-0.01-0.1;
s2: dipping the mesoporous microsphere alumina carrier obtained by the preparation method of the mesoporous microsphere alumina carrier in any one of claims 4 to 7 by using the liquid material L5 obtained in the step S1, and filtering, drying and roasting to obtain a desulfurization and denitrification catalyst;
preferably, in step S1, iron oxide powder is also added; crushing the obtained powder M1 into powder M2 with the average particle size of less than 1 mu M; mixing the powder M2, a water-soluble high-molecular polymer, an aluminum source and deionized water to obtain a liquid material, and grinding and crushing the liquid material until the particle size of solid particles is less than 0.5 mu M to obtain a liquid material L5;
preferably, in step S2, the mesoporous microsphere alumina support is impregnated with the liquid material L5 obtained in step S1, and after filtration, the impregnated mesoporous microsphere alumina support is washed, where the washing refers to rinsing the filter cake surface with deionized water.
9. The preparation method of the microspherical catalyst for desulfurization and denitrification according to claim 8, wherein the metal active component in the step S1 is one or more selected from Ca, mg and Fe, with or without one or more selected from Co, zn and Cu; the water-soluble high molecular polymer is selected from one or more of polyethylene oxide, polyethylene glycol, methyl starch, starch acetate and hydroxymethyl cellulose; the aluminum source is selected from one or more of pseudo-boehmite, aluminum trichloride, aluminum hydroxide and aluminum sol.
10. The preparation method of the desulfurization and denitrification microspherical catalyst of claim 8, wherein in step S2, the calcination temperature is 350 to 650 ℃ and the calcination time is 1.5 to 4.5 hours.
11. The catalyst prepared by the preparation method of the desulfurization and denitrification microspherical catalyst of any one of claims 8-10.
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