CN106732537A - It is a kind of to add attapulgite modified low-temperature SCR catalyst and preparation method thereof - Google Patents
It is a kind of to add attapulgite modified low-temperature SCR catalyst and preparation method thereof Download PDFInfo
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- CN106732537A CN106732537A CN201611045169.4A CN201611045169A CN106732537A CN 106732537 A CN106732537 A CN 106732537A CN 201611045169 A CN201611045169 A CN 201611045169A CN 106732537 A CN106732537 A CN 106732537A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 62
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- 238000007493 shaping process Methods 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 235000003301 Ceiba pentandra Nutrition 0.000 claims description 3
- 244000146553 Ceiba pentandra Species 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 40
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- 239000002002 slurry Substances 0.000 description 15
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 230000001413 cellular effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- -1 metavanadic acid Ammonium salt Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—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
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/56—
-
- 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
Abstract
Attapulgite modified low-temperature SCR catalyst and preparation method thereof is added the invention discloses a kind of, catalyst includes attapulgite, tungstenic titanium dioxide, catalytic active substance V2O5, MOx(Metal oxide), shaping assistant, the low-temperature SCR catalyst preparation process includes:Prepare attapulgite modified;Muddy carrier is prepared with attapulgite modified and tungstenic titanium dioxide;Catalytic active substance V2O5 and MOx are prepared, catalyst fines is obtained;Catalyst fines and shaping assistant are mixed with finished catalyst.High, the long service life it is an object of the invention to provide a kind of denitration efficiency, the out of stock catalyst of low-temperature SCR with low cost and preparation method.
Description
Technical field
The invention belongs to SCR denitration technical field, more particularly to a kind of attapulgite modified low-temperature SCR catalyst of addition
Preparation method.
Background technology
Nitrogen oxides(NOX)It is typically to store the fuel combustion of stove and the exhaust emissions of motor vehicles in thermal power plant, industry
During produce, nitrogen oxides is the one of the main reasons for producing acid rain and acid mist, thus nitrogen oxides emission reduction work always
It is the emphasis of various countries' concern.
In nitrogen oxides(NOX)In emission control technique, SCR denitration technology is, with ammonia as reducing agent, optionally will
Nitrogen oxides is reduced into the denitration technology of nitrogen and water, due to its excellent denitration efficiency and selectivity and technology maturation, steady
It is fixed, the mainstream technology as current denitration market.The core cell of SCR denitration technique is SCR catalyst, and the performance of catalyst is straight
The denitration efficiency of decision systems is connect, it is main at present to use V2O5/TiO2 catalyst series, but the catalyst in actual applications
There is titanium dioxide(TiO2)Catalyst is relatively costly caused by expensive and catalysis activity temperature(More than 300 DEG C)It is required that high
Limitation.And in China, some industry cellar for storing things stove such as flue-gas temperatures such as coking furnace, glass furnace, cement kiln, ceramic production line are relatively low,
Exhaust temperature is often far below 300 DEG C, station boiler atmospheric temperature is relatively low and during underrun, flue-gas temperature can be relatively low,
Therefore the out of stock catalyst of SCR does not reach greater activity, and smoke emissioning concentration can not meet national requirements for environmental protection.Current low temperature
The out of stock technologies of SCR are ripe not enough, and the out of stock catalyst of low-temperature SCR also faces SO2Poisoning and the problem for blocking.
The content of the invention
A kind of high, the long service life it is an object of the invention to provide denitration efficiency, the low-temperature SCR of relative inexpensiveness is out of stock
Catalyst and preparation method.
To achieve the above objectives, the following scheme that the present invention is provided:
It is a kind of to add attapulgite modified low-temperature SCR catalyst, it is characterised in that:The low-temperature SCR catalyst is with concavo-convex
Rod soil and tungstenic titanium dioxide are made carrier, and supported on carriers catalytic active substance V2O5, formula are formed for the metal oxide of MOx
Catalyst, its preparation method comprises the following steps:
(1)Prepare attapulgite modified;
(2)Take above-mentioned attapulgite modified and tungstenic titanium dioxide and prepare muddy carrier;
(3)Catalytic active substance V2O5 and MOx are prepared, catalyst fines is obtained;
(4)Above-mentioned catalyst fines is prepared into finished catalyst.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
State step(1)Middle preparation attapulgite modified be
During attapulgite is placed in into 4-8mol/L, 80 DEG C of acid solution, 8 hours of mechanical agitation;With deionized water by concave convex rod
Soil is washed to neutrality, and 12 hours are dried at a temperature of 80-105 DEG C, that is, obtain attapulgite modified.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
State step(2)In prepare muddy carrier be will attapulgite modified and tungstenic titanium dioxide it is dry-mixed, well mixed, modified attapulgite
Native components by weight percent is 5~10 parts, tungstenic titanium dioxide composition by weight is 70~80 parts, is subsequently adding deionized water, according to liquid-solid ratio
1.5-2:1 is configured to muddy carrier.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
State step(3)Catalytic active substance V2O5 and MOx are prepared, it is the ammonium metavanadate composition by weight in terms of dry to obtain catalyst fines
For 3~5 parts, nitrate composition by weight be 3~10 parts, will prepare ammonium metavanadate solution, with nitrate configure nitrate it is molten
Liquid adds the muddy carrier, stirs, and recycles Rotary Evaporators vacuum distillation, and it is complete that evaporation removes moisture drying
Afterwards, then calcined under 300-500 DEG C of high temperature, ammonium metavanadate decomposes generation V2O5, nitrate decomposes generation MOx, is catalyzed
Active material;Material after drying and calcining is ground to 400 mesh, that is, obtain catalyst powder.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
State step(4)The preparation of middle finished catalyst is placed in agitator by by catalyst powder, shaping assistant, shaping assistant weight
Component is 3~10 parts, is added water and a small amount of 5% ammoniacal liquor, stirs a period of time, plasticity pug is prepared into, according to catalyst shape
It is required that, pug is made catalyst blank, dried with a temperature of in certain humidity, when being calcined one section under 500-650 DEG C of high temperature
Between i.e. obtain finished catalyst.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
It is 2-4 that acid solution is stated with the liquid-solid ratio of attapulgite:1, acid solution is the one kind in nitric acid, sulfuric acid, hydrochloric acid solution.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
It is during ammonium metavanadate added into hot water dissolved with a small amount of monoethanolamine, 2 hours to be stirred at a temperature of 100 DEG C to state ammonium metavanadate solution
Obtain.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
It is one or more in manganese, iron, copper, cobalt, cerium to state the metal in nitrate solution, and wherein manganese nitrate is using technical grade 50%
Manganese nitrate solution.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
Shaping assistant is stated for stearic acid, sodium carboxymethylcellulose, glass fibre, kapok and PEO, glycerine, stearic acid, carboxylic first
The combination of one or more in base sodium cellulosate, glass fibre, wherein stearic acid, sodium carboxymethylcellulose, glass fibre, wood
Cotton and PEO, glycerine, stearic acid, sodium carboxymethylcellulose components by weight percent are 1~3 part, and glass fiber weight component is 2
~5 parts.
As described above it is a kind of add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is characterized in that:Institute
Vacuum distillation negative pressure is stated 600 between 1000Pa.
Beneficial effects of the present invention:
1st, attapulgite is a kind of clay pit for having fiber pattern layer chain transition structure, with adsorptivity and certain plastic
Property and cohesive force, to the selective suction-operated of ammonia, contribute to catalyst to mould and be molded, increase catalyst strength, be conducive to
The absorption of out of stock reactant and the carrying out of reduction reaction;Attapulgite also has water absorbing and retaining properties, can improve the elasticity of catalyst
With thermal stress resistance performance, dust impacts the abrasion and corrosion for bringing in reducing flue gas, extends the service life of catalyst;It is recessed
Convex rod soil resource is enriched, cheap, and part tungstenic titanium dioxide is replaced with attapulgite, and effective utilization has been carried out to resource,
Reduce Catalyst Production cost.
2nd, in the present invention in treatment is modified to attapulgite with sulfuric acid or hydrochloric acid or nitric acid, in eliminating attapulgite
Containing to the unfavorable impurity of SCR denitration, and there is uneven, discontinuous dissolving and local four due to octahedra in attapulgite
The factors such as the corrosion of face body silicon, attapulgite duct open and enlarged-diameter, specific surface area increase, to catalysis activity heavy metal from
The adsorption capacity of son increases, and improves catalysis activity, increases catalyst denitration efficiency.
3rd, the carrier formed with attapulgite modified substitution part tungstenic titanium dioxide, increases the specific surface area of catalyst, carries
Catalytic efficiency high;Assign catalyst abundant multi-stage artery structure, be conducive to the carrying out of mass transfer, prevent harmful substances from flue gases from existing
Catalyst surface is deposited.
4th, excessive transition metal manganese, iron, copper, cobalt, the oxide M Ox of cerium are added, contributes to the reduction reaction of nitrogen oxides
Carry out, increased the SCR denitration activity under low temperature;And can be reacted with SO2 in low temperature environment, anti-SO2 poisonings can be used for coking
Removal of nitrogen oxide under the relatively low working condition of the flue-gas temperatures such as stove, glass furnace, cement kiln, ceramic production line.
Brief description of the drawings
It is catalyst denitration efficiency at different temperatures such as Fig. 1.
Specific embodiment
Embodiment 1:
Attapulgite is placed in the HCl solution of 8mol/L, 8 hours are stirred at 80 DEG C, after washing, drying process, grinding
To 400 mesh.By the attapulgite being modified and tungstenic titanium dioxide according to 1:5 ratio is dry-mixed uniform, adds deionized water to prepare
Into slurry, the ammonium metavanadate solution that will be prepared, manganese nitrate solution are added in above-mentioned slurry, and ammonium metavanadate solution is according to five oxygen
Change two vanadium and account for vehicle weight percentage for 1.5% adds, manganese nitrate solution is 5% according to the percentage by weight that Mn oxide accounts for carrier
Add.Above-mentioned slurry is evaporated under reduced pressure using Rotary Evaporators and removes moisture.The complete material of drying is forged under 500 DEG C of high temperature
Burn, Activation Activity is ground to 400 mesh, obtains catalyst powder.It is by a certain percentage that catalyst powder, shaping assistant methyl is fine
Dimension element, polyethylene glycol oxide, stearic acid, MEA, lactic acid, wood pulp cotton, glycerine and glass fibre, are placed in agitator, add water
With a small amount of 5% ammoniacal liquor, stir a period of time, be prepared into plasticity pug.Pug is extruded into size for 150 × 150 × 1000mm
The cellular blank in 20 holes.Above-mentioned blank is uniformly dried at a slow speed according to certain drying system, in the highest temperature after the completion of drying
It is 480 DEG C of temperature lower calcinations to spend, and obtains finished catalyst.
Denitration experiment is carried out to simulated flue gas using above-mentioned catalyst, NO concentration 500ppm in air inlet controls NH3Rubbed with NO
You are than being 1:1, SO2Concentration is 500ppm, O2Concentration 5%, N2It is Balance Air, air speed is controlled in 32000h-1, catalyst is in 200-
In the range of 450 DEG C, with 94% denitration efficiency.
Embodiment 2:
Attapulgite is placed in the HCl solution of 8mol/L, 8 hours are stirred at 80 DEG C, after washing, drying process, grinding
To 400 mesh.By the attapulgite being modified and tungstenic titanium dioxide according to 1:3 ratio is dry-mixed uniform, adds deionized water to prepare
Into slurry, the ammonium metavanadate solution that will be prepared, manganese nitrate solution, cerous nitrate solution are added in above-mentioned slurry, ammonium metavanadate
Solution accounts for vehicle weight percentage for 1.5% adds according to vanadic anhydride, and manganese nitrate solution accounts for vehicle weight according to Mn oxide
Percentage is 5% addition, and cerous nitrate solution accounts for vehicle weight percentage for 2% adds according to ceria.Above-mentioned slurry is utilized
Rotary Evaporators are evaporated under reduced pressure and remove moisture.The complete material of drying is calcined under 500 DEG C of high temperature, Activation Activity is ground to
400 mesh, obtain catalyst powder.By a certain percentage by catalyst powder, shaping assistant methylcellulose, polyethylene glycol oxide, hard
Resin acid, MEA, lactic acid, wood pulp cotton, glycerine and glass fibre, are placed in agitator, add water and a small amount of 5% ammoniacal liquor, stirring one
Section the time, be prepared into plasticity pug.Pug is extruded into the cellular blank in 20 holes that size is 150 × 150 × 1000mm.Press
Above-mentioned blank is uniformly dried at a slow speed according to certain drying system, dry after the completion of maximum temperature be 500 DEG C of temperature lower calcinations,
Obtain finished catalyst.
Denitration experiment is carried out to simulated flue gas using above-mentioned catalyst, NO concentration 500ppm in air inlet controls NH3Rubbed with NO
You are than being 1:1, SO2Concentration is 500ppm, O2Concentration 5%, N2It is Balance Air, air speed is controlled in 32000h-1, catalyst is in 200-
In the range of 500 DEG C, with 92% denitration efficiency.
Embodiment 3:
Attapulgite is placed in the HCl solution of 8mol/L, 8 hours are stirred at 80 DEG C, after washing, drying process, grinding
To 400 mesh.By the attapulgite being modified and tungstenic titanium dioxide according to 1:3 ratio is dry-mixed uniform, adds deionized water to prepare
Into slurry, the ammonium metavanadate solution that will be prepared, manganese nitrate solution, iron nitrate solution are added in above-mentioned slurry, ammonium metavanadate
Solution accounts for vehicle weight percentage for 1.5% adds according to vanadic anhydride, and manganese nitrate solution accounts for vehicle weight according to Mn oxide
Percentage is 5% addition, and iron nitrate solution accounts for vehicle weight percentage for 2% adds according to iron oxide.By above-mentioned slurry using rotation
Turn evaporation under reduced pressure evaporation and remove moisture.The complete material of drying is calcined under 500 DEG C of high temperature, Activation Activity is ground to 400
Mesh, obtains catalyst powder.By a certain percentage by catalyst powder, shaping assistant methylcellulose, polyethylene glycol oxide, tristearin
Acid, MEA, lactic acid, wood pulp cotton, glycerine and glass fibre, are placed in agitator, add water and a small amount of 5% ammoniacal liquor, stir one section
Time, it is prepared into plasticity pug.Pug is extruded into the cellular blank in 20 holes that size is 150 × 150 × 1000mm.According to
Certain drying system is uniformly dried at a slow speed to above-mentioned blank, dry after the completion of maximum temperature be 450 DEG C of temperature lower calcinations, obtain
To finished catalyst.
Denitration experiment is carried out to simulated flue gas using above-mentioned catalyst, NO concentration 500ppm in air inlet controls NH3Rubbed with NO
You are than being 1:1, SO2Concentration is 500ppm, O2Concentration 5%, N2It is Balance Air, air speed is controlled in 32000h-1, catalyst is in 200-
In the range of 500 DEG C, with 87% denitration efficiency.
Embodiment 4:
Attapulgite is placed in the H of 4mol/L2SO4In solution, 8 hours are stirred at 80 DEG C, through washing, after drying process, ground
It is milled to 400 mesh.By the attapulgite being modified and tungstenic titanium dioxide according to 1:4 ratio is dry-mixed uniform, adds deionized water system
For into slurry, the ammonium metavanadate solution that will be prepared, manganese nitrate solution, copper nitrate solution are added in above-mentioned slurry, metavanadic acid
Ammonium salt solution accounts for vehicle weight percentage for 1.3% adds according to vanadic anhydride, and manganese nitrate solution accounts for carrier weight according to Mn oxide
Amount percentage is 5% addition, and copper nitrate solution accounts for vehicle weight percentage for 3% adds according to cupric oxide.Above-mentioned slurry is utilized
Rotary Evaporators are evaporated under reduced pressure and remove moisture.The complete material of drying is calcined under 500 DEG C of high temperature, Activation Activity is ground to
400 mesh, obtain catalyst powder.By a certain percentage by catalyst powder, shaping assistant methylcellulose, polyethylene glycol oxide, hard
Resin acid, MEA, lactic acid, wood pulp cotton, glycerine and glass fibre, are placed in agitator, add water and a small amount of 5% ammoniacal liquor, stirring one
Section the time, be prepared into plasticity pug.Pug is extruded into the cellular blank in 20 holes that size is 150 × 150 × 1000mm.Press
Above-mentioned blank is uniformly dried at a slow speed according to certain drying system, dry after the completion of maximum temperature be 430 DEG C of temperature lower calcinations,
Obtain finished catalyst.
Denitration experiment is carried out to simulated flue gas using above-mentioned catalyst, NO concentration 500ppm in air inlet controls NH3Rubbed with NO
You are than being 1:1, SO2Concentration is 500ppm, O2Concentration 5%, N2It is Balance Air, air speed is controlled in 32000h-1, catalyst is in 200-
In the range of 500 DEG C, with 88% denitration efficiency.
Embodiment 5:
Attapulgite is placed in the HNO of 6mol/L3In solution, 8 hours are stirred at 80 DEG C, after washing, drying process, grinding
To 400 mesh.By the attapulgite being modified and tungstenic titanium dioxide according to 1:4 ratio is dry-mixed uniform, adds deionized water to prepare
Into slurry, the ammonium metavanadate solution that will be prepared, manganese nitrate solution, cobalt nitrate solution are added in above-mentioned slurry, ammonium metavanadate
Solution accounts for vehicle weight percentage for 1.3% adds according to vanadic anhydride, and manganese nitrate solution accounts for vehicle weight according to Mn oxide
Percentage is 5% addition, and cobalt nitrate solution accounts for vehicle weight percentage for 3% adds according to cobalt oxide.By above-mentioned slurry using rotation
Turn evaporation under reduced pressure evaporation and remove moisture.The complete material of drying is calcined under 500 DEG C of high temperature, Activation Activity is ground to 400
Mesh, obtains catalyst powder.By a certain percentage by catalyst powder, shaping assistant methylcellulose, polyethylene glycol oxide, tristearin
Acid, MEA, lactic acid, wood pulp cotton, glycerine and glass fibre, are placed in agitator, add water and a small amount of 5% ammoniacal liquor, stir one section
Time, it is prepared into plasticity pug.Pug is extruded into the cellular blank in 20 holes that size is 150 × 150 × 1000mm.According to
Certain drying system is uniformly dried at a slow speed to above-mentioned blank, dry after the completion of maximum temperature be 430 DEG C of temperature lower calcinations, obtain
To finished catalyst.
Denitration experiment is carried out to simulated flue gas using above-mentioned catalyst, NO concentration 500ppm in air inlet controls NH3Rubbed with NO
You are than being 1:1, O2Concentration 5%, N2It is Balance Air, air speed is controlled in 32000h-1, catalyst has in the range of 200-500 DEG C
93% denitration efficiency.
Claims (10)
- It is 1. a kind of to add attapulgite modified low-temperature SCR catalyst, it is characterised in that:Including attapulgite, tungstenic titanium dioxide, Catalytic active substance V2O5, formula are the metal oxide of MOx, and shaping assistant, the low-temperature SCR catalyst preparation method includes Following steps:(1)Prepare attapulgite modified;(2)Take above-mentioned attapulgite modified and tungstenic titanium dioxide and prepare muddy carrier;(3)Catalytic active substance V2O5 and MOx are prepared, catalyst fines is obtained;(4)Above-mentioned catalyst fines and shaping assistant are prepared by mixing into finished catalyst.
- 2. it is a kind of according to claim 1 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The metal oxide is the metal oxide that nitrate is thermally decomposed to generate, the metal in the nitrate be manganese, One or more in iron, copper, cobalt, cerium.
- 3. it is a kind of according to claim 1 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The step(1)Middle preparation attapulgite modified beDuring attapulgite is placed in into 4-8mol/L, 80 DEG C of acid solution, 8 hours of mechanical agitation;With deionized water by concave convex rod Soil is washed to neutrality, and 12 hours are dried at a temperature of 80-105 DEG C, that is, obtain attapulgite modified.
- 4. it is a kind of according to claim 1 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The step(2)In prepare muddy carrier be will attapulgite modified and tungstenic titanium dioxide it is dry-mixed, well mixed, change Property attapulgite components by weight percent be 5~10 parts, tungstenic titanium dioxide composition by weight be 70~80 parts, be subsequently adding deionized water, by According to liquid-solid ratio 1.5-2:1 is configured to muddy carrier.
- 5. it is a kind of according to claim 1 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The step(3)In with dry count ammonium metavanadate composition by weight be 3~5 parts, nitrate composition by weight be 3~10 parts, Ammonium metavanadate solution, the nitrate solution addition muddy carrier that will be prepared, stir, and recycle Rotary Evaporators to subtract Pressure distillation, after evaporation removing moisture drying is complete, then calcines under 300-500 DEG C of high temperature, and ammonium metavanadate decomposes generation V2O5, Nitrate decomposes generation correspondence MOx, obtains catalytic active substance;Material after drying and calcining is ground to 400 mesh, that is, be catalyzed Agent powder.
- 6. it is a kind of according to claim 1 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The step(4)The preparation of middle finished catalyst is placed in agitator by by catalyst powder, shaping assistant, shaping Auxiliary agent composition by weight is 3~10 parts, is added water and a small amount of 5% ammoniacal liquor, stirring a period of time, plasticity pug is prepared into, according to urging Agent shape need, catalyst blank is made by pug, is dried with a temperature of in certain humidity, is roasted under 500-650 DEG C of high temperature Burn and obtain finished catalyst for a period of time.
- 7. it is a kind of according to claim 1 and 6 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof it is special Levy and be:The shaping assistant is stearic acid, sodium carboxymethylcellulose, glass fibre, kapok and PEO, glycerine, hard The combination of one or more in resin acid, sodium carboxymethylcellulose, glass fibre, wherein stearic acid, sodium carboxymethylcellulose, glass Glass fiber, kapok and PEO, glycerine, stearic acid, sodium carboxymethylcellulose components by weight percent are 1~3 part, glass fibre weight Amount component is 2~5 parts.
- 8. it is a kind of according to claim 3 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The acid solution is 2-4 with the liquid-solid ratio of attapulgite:1, acid solution is the one kind in nitric acid, sulfuric acid, hydrochloric acid solution.
- 9. it is a kind of according to claim 5 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The ammonium metavanadate solution is during ammonium metavanadate added into hot water dissolved with a small amount of monoethanolamine, to be stirred at a temperature of 100 DEG C What 2 hours obtained.
- 10. it is a kind of according to claim 5 to add attapulgite modified low-temperature SCR catalyst and preparation method thereof its feature It is:The vacuum distillation negative pressure is 600 between 1000Pa.
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CN107694575A (en) * | 2017-09-15 | 2018-02-16 | 大唐南京环保科技有限责任公司 | A kind of complex carrier SCR denitration and preparation method |
CN107952449A (en) * | 2017-12-15 | 2018-04-24 | 江苏龙净科杰催化剂再生有限公司 | Low temperature collaboration denitration Tuo bioxin demercuration honeycombed catalysts and preparation method thereof |
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CN114433071A (en) * | 2021-12-29 | 2022-05-06 | 江苏世清环保科技有限公司 | Denitration catalyst prepared by taking attapulgite as carrier and preparation method thereof |
CN115739072A (en) * | 2022-11-18 | 2023-03-07 | 山西普丽环境工程股份有限公司 | Wear-resistant plate type low-temperature denitration catalyst and preparation method thereof |
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2016
- 2016-11-24 CN CN201611045169.4A patent/CN106732537A/en not_active Withdrawn
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107694575A (en) * | 2017-09-15 | 2018-02-16 | 大唐南京环保科技有限责任公司 | A kind of complex carrier SCR denitration and preparation method |
CN107952449A (en) * | 2017-12-15 | 2018-04-24 | 江苏龙净科杰催化剂再生有限公司 | Low temperature collaboration denitration Tuo bioxin demercuration honeycombed catalysts and preparation method thereof |
CN107970948A (en) * | 2017-12-15 | 2018-05-01 | 江苏龙净科杰催化剂再生有限公司 | Flue gas denitration at the same time takes off VOCs honeycombed catalysts and preparation method thereof |
CN114433071A (en) * | 2021-12-29 | 2022-05-06 | 江苏世清环保科技有限公司 | Denitration catalyst prepared by taking attapulgite as carrier and preparation method thereof |
CN115739072A (en) * | 2022-11-18 | 2023-03-07 | 山西普丽环境工程股份有限公司 | Wear-resistant plate type low-temperature denitration catalyst and preparation method thereof |
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