CN107185588B - A kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof - Google Patents
A kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001868 water Inorganic materials 0.000 title claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 21
- 239000011593 sulfur Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 26
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052676 chabazite Inorganic materials 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 43
- 238000007598 dipping method Methods 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 34
- 238000012216 screening Methods 0.000 claims description 17
- 238000003760 magnetic stirring Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 238000001802 infusion Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 29
- 239000007788 liquid Substances 0.000 description 14
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 231100000572 poisoning Toxicity 0.000 description 13
- 230000000607 poisoning effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 12
- 239000010431 corundum Substances 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 239000013049 sediment Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000001846 repelling effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to low-temperature denitration composite molecular sieve catalysts of a kind of sulfur resistive water resistant and preparation method thereof, the catalyst is prepared using infusion process, using chabazite molecular sieve H-SAPO-34 as carrier, active component is the composite oxides of transition metal Cu and Mn, auxiliary agent is one of Ce, Fe, Co, Mo, Cr, load capacity is by mass percentage: the quality of copper and manganese element is respectively 2%~10% in active component, and auxiliary agent is 1~10%.The denitration composite molecular sieve catalyst of the invention is compared with Cu the or Mn base catalyst of one-component, denitration efficiency and thermal stability that more metal synergistic effects significantly improve catalyst is utilized, its active temperature windows effectively has been widened, and has had preferable resistance to SO_2.
Description
Technical field
The present invention relates to low-temperature denitration composite molecular sieve catalysts of a kind of sulfur resistive water resistant and preparation method thereof, belong to atmosphere
Pollutant abatement technology and environment protection catalytic Material Field.
Background technique
The energy resource structure in China decides that China is a coal-fired big country, as the national economy in China develops rapidly, often
A large amount of nitrogen oxides that year discharges into atmosphere cause many areas acid rain, haze, molecule pollution etc. occur, to people
Body, environment, the harm of ecology and all very huge to the destruction of social economy.In recent years, China's discharged nitrous oxides are quick
Increasing, is shown according to the data that environmental protection administration announces, the discharged nitrous oxides total amount in China in 2000 is 12,100,000 tons, and 2012
23,380,000 tons are then reached, have almost been doubled.It was predicted that if not taking further control measure, the year two thousand thirty China's nitrogen oxygen
Compound discharge will be more than 35,000,000 tons.Therefore it is imperative to greatly develop Emission Controlling Technology of Nitric Oxides.
At present in denitrating flue gas field, generally use with NH3For selective catalytic reduction (SCR) technique of reducing agent,
The catalyst of business is mainly V2O5-WO3/TiO2Series, the operation temperature of the catalyst is 300 DEG C~420 DEG C, and price
It is expensive.In order to meet the needs of temperature, generally by catalytic bed arrangement with deduster before, but this method for arranging is on the one hand
It can cause the SO of catalyst2Poisoning and dust blocking, on the other hand need space after biggish furnace；Second is that the vanadium in active component
It is toxic, it is all unfavorable to ecological environment and health；In addition, as the flue gas temperature of the equipment exhaustings such as steel works sintering machine and pelletizing
Therefore degree is at 200 DEG C hereinafter, greatly develop high sulfur resistive not in the active temperature windows range of such high temperature SCR catalyst
The low-temperature SCR technical meaning of performance is great.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and its
Preparation method, the catalyst pass through the synergistic effect of the metals such as active component Cu, Mn and auxiliary agent Ce, Fe, Co, significantly widen
Catalyst denitration reaction temperature, and the denitration efficiency and sulfur resistive water repelling property of catalyst are improved, while the preparation side
Method high, preparation catalyst performance stabilised at low cost, repeated easy to operate.
Technology contents: the present invention provides a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant, the catalyst
Comprising carrier, active component and auxiliary agent, the carrier is chabazite molecular sieve, and the active component is the oxidation of copper manganese composition metal
Object, the auxiliary agent are one of Ce, Fe, Co, Mo or Cr；On the basis of the quality of carrier, in active component copper and
The quality of manganese element is respectively 2%~10%, and the quality of auxiliary agent is 1~10%.
Wherein:
The chabazite molecular sieve is chabazite molecular sieve H-SAPO-34.
The present invention also provides a kind of low-temperature denitration composite molecular sieve catalysts of sulfur resistive water resistant as described in claim 1
Preparation method, method includes the following steps:
It 1) will be spare after the drying of carrier chabazite molecular sieve original powder end；
2) the soluble-salt dissolution for weighing copper in the active component in proportion in deionized water, stirs
Afterwards, it is proportionally added into the soluble-salt of the soluble-salt of manganese and the auxiliary agent in active component, is sufficiently stirred and mixed solution is made；
3) the chabazite molecular sieve original powder end in step 1) after drying is taken to be dissolved in mixed solution made from step 2), sufficiently
After stirring dipping, solution is heated up and continues stirring dipping, after moisture is evaporated, successively after drying, grinding, screening, calcining
Obtain the sulfur resistive water resistant low-temperature denitration complex type molecular sieve catalysis (Cu-Mn-X/SAPO-34, wherein X be Ce, Fe,
One of Co, Mo, Cr).
Wherein:
The temperature of drying described in step 1) is 100~105 DEG C, and the time is 25~30min.
The soluble-salt of copper described in step 2) is Cu (NO3)2·3H2O or Cu (CH3COO)2·H2O, the soluble-salt of manganese
For manganese nitrate or Mn (CH3COO)2·4H2O), the soluble-salt of Ce is Ce (NO3)3·6H2O or Ce (CH3COO)3·5H2O, Co
Soluble-salt be Co (NO3)2·6H2O or Co (CH3COO)2·4H2O), the soluble-salt of Fe is Fe (NO3)3·9H2O, Mo's
Soluble-salt is Mo (NO3)3·5H2The soluble-salt of O, Cr are Cr (NO3)3·9H2O。
After dipping is sufficiently stirred described in step 3), solution, which is heated up, and continues stirring dipping is specifically referred in bath temperature
Under the conditions of 20~30 DEG C, using magnetic stirring apparatus 6~8h of continual stirring, bath temperature is risen to 75~85 DEG C simultaneously later
Continue 2~4h of stirring dipping.
The speed of agitator of the magnetic stirring apparatus is 40~50r/s.
Drying described in step 3) refers to dries 8~12h in the baking oven that temperature is 80~100 DEG C；Described in step 3)
Calcining temperature be 450~550 DEG C, the time be 4~6h；The grit number of crossing of screening described in step 3) is 40~80 mesh.
The utility model has the advantages that compared with prior art, the low-temperature denitration complex type molecular sieve catalysis of sulfur resistive water resistant of the invention
It is effective to drop due to the synergy of two kinds of active components and auxiliary agent relative to existing single copper-based or manganese-based catalyst
The low denitration reaction temperature of catalyst, improves the thermal stability of catalyst, sulfur resistive water-resistance, while it is de- to have widened catalyst
The temperature window of nitre reaction.Prepared catalyst carries out denitration performance test in miniature fixed bed under the conditions of simulated flue gas,
It was found that the catalyst has lower light-off temperature, higher denitration efficiency and wider temperature window.
Detailed description of the invention
Fig. 1 is the denitration performance test chart of the complex type molecular sieve catalysis prepared in present example；
Fig. 2 is the water repelling property test chart of the complex type molecular sieve catalysis prepared in present example；
Fig. 3 is the anti-SO of the complex type molecular sieve catalysis prepared in present example2Performance test figure；
Fig. 4 is the SEM figure of the complex type molecular sieve catalysis poisoning front and back prepared in present example；Wherein: a is not change
Property fresh catalyst SEM figure, b be unmodified catalyst SO2SEM figure, c after poisoning are 2%Ce modified catalyst SO2
SEM figure, d after poisoning are 2%Co modified catalyst SO2SEM figure, e after poisoning are 2%Fe modified catalyst SO2After poisoning
SEM figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.
Embodiment 1:
(1) 8g chabazite molecular sieve (H-SAPO-34) original powder end is weighed, is put it into the Noah's ark of corundum material, together
It is spare to be placed in 100 DEG C of dry 25min in blowing-type drying box；
(2) 0.3775gCu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 30ml, is sufficiently stirred
After uniformly, the manganese nitrate solution that 2.7412g concentration is 50% is added, two kinds of active components being made containing different proportion are sufficiently stirred
Mixed solution.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 8h on 30 DEG C of water-baths, magnetic stirring apparatus are warming up to 75 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 100 DEG C dry 8h, is subsequently placed in pipe by stirring dipping 2h after moisture is evaporated
In formula furnace, 6h is calcined in 450 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (2)-Mn (6)/SAPO- by calcined sediment grinding screening to partial size
34 (450) catalyst, the formula indicate that the quality that the quality of Cu is 2%, Mn of carrier is carrier using SAPO-34 as carrier
6%, calcination temperature is 450 DEG C.
Embodiment 2:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
103 DEG C of dry 30min are spare in blowing-type drying box；
(2) 0.3775g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 35ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 0.1549g Ce (NO that 0.9091g concentration is 50% is added3)3·6H2O powder, is sufficiently stirred
Mixing is at two kinds of active components containing different proportion and containing the mixed solution of cerium promoter.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 20 DEG C of water-baths, magnetic stirring apparatus are warming up to 85 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 80 DEG C dry 12h, is subsequently placed in pipe by stirring dipping 4h after moisture is evaporated
In formula furnace, 6h is calcined in 500 DEG C of high temperature aerobic environment；
(1) calcined sediment grinding screening to partial size is 40~80 mesh to get having arrived Cu (2)-Mn (2)-Ce by (4)
(1)/SAPO-34 (500) catalyst, the formula indicate that using SAPO-34 as carrier, the quality that the quality of Cu is 2%, Mn of carrier is
The quality of 2%, Ce of carrier is the 1% of carrier, and calcination temperature is 450 DEG C.
Embodiment 3:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
105 DEG C of dry 30min are spare in blowing-type drying box；
(2) 0.3775g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 40ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 0.3099g Ce (NO that 2.7412g concentration is 50% is added3)3·6H2O powder, is sufficiently stirred
Mixing is at two kinds of active components containing different proportion and containing the mixed solution of cerium promoter.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 20 DEG C of water-baths, magnetic stirring apparatus are warming up to 85 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 80 DEG C dry 12h, is subsequently placed in pipe by stirring dipping 4h after moisture is evaporated
In formula furnace, 6h is calcined in 550 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (2)-Mn (6)-Ce by calcined sediment grinding screening to partial size
(2)/SAPO-34 (550) catalyst.
Embodiment 4:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
105 DEG C of dry 30min are spare in blowing-type drying box；
(2) 1.8875g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 50ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 1.5504g Ce (NO that 4.5455g concentration is 50% is added3)3·6H2O powder, is sufficiently stirred
Mixing is at two kinds of active components containing different proportion and containing the mixed solution of cerium promoter.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 20 DEG C of water-baths, magnetic stirring apparatus are warming up to 85 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 80 DEG C dry 12h, is subsequently placed in pipe by stirring dipping 4h after moisture is evaporated
In formula furnace, 6h is calcined in 450 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (10)-Mn (10)-Ce by calcined sediment grinding screening to partial size
(10)/SAPO-34 (450) catalyst.
Embodiment 5:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
100 DEG C of dry 25min are spare in blowing-type drying box；
(2) 0.3775g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 30ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 0.3607g Fe (NO that 0.9091g concentration is 50% is added3)3·9H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Fe containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 8h on 30 DEG C of water-baths, magnetic stirring apparatus are warming up to 75 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 100 DEG C dry 8h, is subsequently placed in pipe by stirring dipping 2h after moisture is evaporated
In formula furnace, 6h is calcined in 450 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (2)-Mn (2)-Fe by calcined sediment grinding screening to partial size
(1)/SAPO-34 (450) catalyst.
Embodiment 6:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
105 DEG C of dry 25min are spare in blowing-type drying box；
(2) 1.8875g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 50ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 3.6071g Fe (NO that 4.5455g concentration is 50% is added3)3·9H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Fe containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 8h on 30 DEG C of water-baths, magnetic stirring apparatus are warming up to 75 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 100 DEG C dry 8h, is subsequently placed in pipe by stirring dipping 2h after moisture is evaporated
In formula furnace, 6h is calcined in 550 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (10)-Mn (10)-Fe by calcined sediment grinding screening to partial size
(10)/SAPO-34 (550) catalyst.
Embodiment 7:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
100 DEG C of dry 27min are spare in blowing-type drying box；
(2) 0.3775g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 30ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 0.2469g Co (NO that 0.9091g concentration is 50% is added3)2·6H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Co containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 25 DEG C of water-baths, magnetic stirring apparatus are warming up to 80 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 90 DEG C dry 10h, is subsequently placed in pipe by stirring dipping 3h after moisture is evaporated
In formula furnace, 6h is calcined in 450 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (2)-Mn (2)-Co by calcined sediment grinding screening to partial size
(1)/SAPO-34 (450) catalyst.
Embodiment 8:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
105 DEG C of dry 27min are spare in blowing-type drying box；
(2) 1.8875g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 50ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 2.4661g Co (NO that 4.5455g concentration is 50% is added3)2·6H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Co containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 25 DEG C of water-baths, magnetic stirring apparatus are warming up to 80 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 90 DEG C dry 10h, is subsequently placed in pipe by stirring dipping 3h after moisture is evaporated
In formula furnace, 6h is calcined in 550 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (10)-Mn (10)-Co by calcined sediment grinding screening to partial size
(10)/SAPO-34 (550) catalyst.
Embodiment 9:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
100 DEG C of dry 29min are spare in blowing-type drying box；
(2) 0.3775g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 30ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 0.2287g Mo (NO that 0.9091g concentration is 50% is added3)2·5H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Mo containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 28 DEG C of water-baths, magnetic stirring apparatus are warming up to 85 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 80 DEG C dry 12h, is subsequently placed in pipe by stirring dipping 4h after moisture is evaporated
In formula furnace, 6h is calcined in 450 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (2)-Mn (2)-Mo by calcined sediment grinding screening to partial size
(1)/SAPO-34 (450) catalyst.
Embodiment 10:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
105 DEG C of dry 29min are spare in blowing-type drying box；
(2) 1.8875g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 50ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 2.2865g Mo (NO that 4.5455g concentration is 50% is added3)2·5H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Mo containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 28 DEG C of water-baths, magnetic stirring apparatus are warming up to 85 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 80 DEG C dry 12h, is subsequently placed in pipe by stirring dipping 4h after moisture is evaporated
In formula furnace, 6h is calcined in 550 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (10)-Mn (10)-Mo by calcined sediment grinding screening to partial size
(10)/SAPO-34 (550) catalyst.
Embodiment 11:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
100 DEG C of dry 30min are spare in blowing-type drying box；
(2) 0.3775g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 30ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 0.3847g Cr (NO that 0.9091g concentration is 50% is added3)3·9H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Cr containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 20 DEG C of water-baths, magnetic stirring apparatus are warming up to 85 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 80 DEG C dry 12h, is subsequently placed in pipe by stirring dipping 4h after moisture is evaporated
In formula furnace, 6h is calcined in 450 DEG C of high temperature aerobic environment；
It (4) is 40~80 mesh to get having arrived Cu (2)-Mn (2)-Cr by calcined sediment grinding screening to partial size
(1)/SAPO-34 (450) catalyst.
Embodiment 12:
(1) 8g chabazite molecular sieve H-SAPO-34 original powder end is weighed, puts it into the Noah's ark of corundum material, sets together
105 DEG C of dry 30min are spare in blowing-type drying box；
(2) 1.8875g Cu (NO is weighed in proportion3)2·3H2O powder, is dissolved in the deionized water of 50ml, sufficiently stirs
After mixing uniformly, manganese nitrate solution and 3.8465g Cr (NO that 4.5455g concentration is 50% is added3)3·9H2System is sufficiently stirred in O
At the mixed solution of two kinds of active components containing different proportion and the Cr containing auxiliary agent.
(3) the H-SAPO-34 molecular screen primary powder 5g in step (1) after drying is taken to be dissolved in step (2) mixing obtained molten
Liquid, the continual stirring 6h on 20 DEG C of water-baths, magnetic stirring apparatus are warming up to 85 DEG C and are continued adequately after dipping
The product of evaporative crystallization is put into baking oven at 80 DEG C dry 12h, is subsequently placed in pipe by stirring dipping 4h after moisture is evaporated
In formula furnace, 6h is calcined in 550 DEG C of high temperature aerobic environment；
It (5) is 40~80 mesh to get having arrived Cu (10)-Mn (10)-Cr by calcined sediment grinding screening to partial size
(10)/SAPO-34 (550) catalyst.
Embodiment 13: catalyst activity measurement and the test of sulfur resistive water repelling property
The screening of catalyst tabletting obtained by above-described embodiment is taken respectively, takes the catalyst granules of 40~60 mesh to be packed into fixed bed anti-
Device is answered to carry out catalyst activity test.Activity determination condition is as follows: reaction system temperature is 90 DEG C~350 DEG C, and reaction pressure is
Normal pressure, unstripped gas air speed are 15000h-1, feed gas volume content: NO:350 × 10-6, NH3: 350 × 10-6, O2: 3%, carrier gas:
N2, total gas flow rate 500ml/min, gradually mixing finally enters air pre-mixing device and fills each road gas after mass flowmenter
Divide mixing；Reactor is the stainless steel tube of internal diameter 10mm, and three sections of heating vertical tubular furnaces with temperature control system provide reaction temperature
Condition；It is analyzed after thief hatch acquires flue gas by 350 flue gas analyzer of Testo with airbag.
The activity of catalyst is evaluated with the conversion ratio of NO:
Wherein, NOin、NOoutThe concentration of fixed bed reactors entrance and exit NO is respectively indicated, all data are de-
It is read after nitre stable reaction.The results are shown in attached figure 1 for active testing, it can be seen from the figure that the addition of auxiliary agent can improve compound point
The denitration activity of sub- sieve catalyst, wherein the addition performance of Ce is the most obvious, the more metal composites of Cu-Mn-Ce/SAPO-34 point
For sub- sieve catalyst at 120 DEG C of temperature, NO conversion ratio can reach 82% or more, temperature equal energy between 180 DEG C~300 DEG C
Up to 90% or more, activity reaches as high as 99.6%.
Catalyst water resistant sulfur resistance test result is shown in attached drawing 2 and attached drawing 3, prepares fresh catalyst and carries out active testing
After stable reaction 1h, it is passed through the vapor or SO of various concentration2Concentration carries out stopping being passed through water and SO after poisoning experiment 8h2。
Attached drawing 2 is the situation of change of catalyst denitration activity under the water vapor atmosphere of various concentration, it can be seen from the figure that being passed through water
The denitration activity of steam rear catalyst is declined with the increase of water concentration, but when stopping is passed through vapor rear catalyst
Activity substantially can be restored to initial level, show that catalyst water repelling property is preferable；Attached drawing 3 is added Ce, Co, Fe etc.
The composite molecular sieve catalyst sulfur resistance test result of several difference auxiliary agents, it can be seen from the figure that being not added with the Cu- of auxiliary agent
SO of the Mn/SAPO-34 molecular sieve in 500ppm2In poison 8h after, the activity of catalyst is down to 65% by 95%, adds auxiliary agent
The sulfur resistance of Ce, Fe, Co rear catalyst is obviously promoted, and wherein the addition of Ce is the most obvious, Cu-Mn-Ce/SAPO-34
The activity for poisoning 8h rear catalyst is only down to 82% or so by 95%, and stopping is passed through SO2Activity can be restored and stablize afterwards
85% or so.
Embodiment 14:BET specific surface area and pore structure study
It is surveyed using the full-automatic specific surface area of Micromeritics company, U.S. ASAP 2020M and micropore analyzer
It is fixed.By catalyst to the specific surface area of the absorption of nitrogen and desorption measurement catalyst, manufactured in adsorption process using liquid nitrogen
Low temperature environment makes nitrogen full of each micropore to the full extent, then close to zero degree at a temperature of make catalyst
It is desorbed, the nitrogen in hole is discharged.Using hydrogen as carrier gas, nitrogen makees adsorbed gas, N under liquid nitrogen temperature (77K)2It is inhaled
It is attached, with A12O3Reference is done, specific surface area is calculated using Brunauer-Emmett-Teller (BET) method, and Kong Rong and aperture make
It is calculated with Barrett-Joyner-Halenda (BJH) method.
The BET specific surface area and pore structure study of 1 complex type molecular sieve catalysis of table
Table 1 is the catalyst SO to tri- kinds of Ce, Co, Fe different transition metal promoter additions2Poisoning front and back carries out BET table
Sign.As can be seen from the table, the specific surface area of addition auxiliary agent rear catalyst, Kong Rongjun are reduced, and aperture increased.It may
It is to be covered on catalyst surface due to these auxiliary agents or enter caused by molecular sieve pore passage.Compare modified catalyst poisoning front and back
The variation of physicochemical property parameter, it can be seen that modified catalyst SO2Poisoning front and back specific surface area reduction amount size be successively Fe >
Co>Ce.By the minimum of the modified specific surface area of catalyst reduction of Ce, only by 423.14m2/ mg is reduced to 390.30m2/ mg,
And it is not added with the catalyst SO of additive modification2Specific surface area is by 456.58m after poisoning2/ mg is down to 331.47m2/ mg, SO2Poisoning
It is that the ammonium sulfate generated is attached to catalyst surface that rear catalyst BET specific surface area, which reduces main cause,.Show that addition is appropriate
Ce and Co can be good at improve the anti-SO of catalyst2Poisoning performance.
Embodiment 15: scanning electron microscope (SEM) is combined X-ray energy spectrum (EDS) analysis
Catalyst surface active component crystal pattern, pore size, reunion degree etc. can all directly influence catalyst
Performance, scanning electron microscope (SEM) can clearly reflect that these microscopic characteristics, X-ray energy spectrum (EDS) can be to surface crystal elements
Composition carries out qualitative and quantitative analysis.Scanning electron microscope sem combination EDS herein is the SIRION- using Dutch FEI Co.'s production
50 type scanning electron microscope, resolution ratio 150eV.
EDS is analyzed after the complex type molecular sieve catalysis poisoning parent prepared in 2 present example of table
Fig. 4 and table 2 are to unmodified fresh catalyst, unmodified SO2Catalyst after poisoning and change through Ce, Co, Fe
Property SO2Catalyst after poisoning has carried out SEM combination EDS analysis, and Cong Tuzhong is this it appears that unmodified catalyst SO2In
Malicious rear catalyst surface occurs to reunite seriously, and there are many substances of brilliant white, and in conjunction with EDS analysis and above XRD, TG-DTG points
The substance known to analysis is ammonium sulfate substance.Modified catalyst SO2Rear catalyst surface be poisoned obviously than unmodified
Catalyst SO2The smooth many in surface after poisoning, also without there is a large amount of agglomeration.The modified catalyst SO of Ce2Poisoning
The mass content of rear surface S element is significantly lower than other several catalyst, illustrates that sulphur can be reduced through the modified catalyst of Ce
Acid ammonium salt substance is deposited in catalyst surface, it may be possible to since Ce can reduce NH4 +And SO4 -2Between bond energy, make
(NH4)2SO4Thermal stability reduces, it is easier to decompose, to reduce ammonium sulfate in the accumulation of catalyst surface.
Claims (4)
1. a kind of preparation method of the low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant, it is characterised in that: the catalyst packet
Containing carrier, active component and auxiliary agent, the carrier is chabazite molecular sieve, and the active component is the oxidation of copper manganese composition metal
Object, the auxiliary agent are one of Ce, Fe, Co, Mo or Cr；On the basis of the quality of carrier, in active component copper and
The quality of manganese element is respectively 2%~10%, and the quality of auxiliary agent is 1~10%；
Wherein the chabazite molecular sieve is chabazite molecular sieve H-SAPO-34；
Method includes the following steps:
It 1) will be spare after the drying of carrier chabazite molecular sieve original powder end；
2) the soluble-salt dissolution for weighing copper in the active component in proportion in deionized water, after stirring, is pressed
The soluble-salt of manganese and the soluble-salt of the auxiliary agent in active component is added in ratio, is sufficiently stirred and mixed solution is made；
3) the chabazite molecular sieve original powder end in step 1) after drying is taken to be dissolved in mixed solution made from step 2), stirring dipping
Afterwards, solution is heated up and continues stirring dipping, after moisture is evaporated, successively obtained after drying, grinding, screening, calcining described
Sulfur resistive water resistant low-temperature denitration composite molecular sieve catalyst；
After wherein dipping is sufficiently stirred in step 3), solution is heated up and continue stirring dipping specifically refer to bath temperature be 20~
Under the conditions of 30 DEG C, using magnetic stirring apparatus 6~8h of continual stirring, bath temperature is risen to 75~85 DEG C later and continues to stir
Mix 2~4h of dipping；
The speed of agitator of the magnetic stirring apparatus is 40~50r/s.
2. the preparation method of the low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as described in claim 1, feature exist
In: the temperature of drying described in step 1) is 100~105 DEG C, and the time is 25~30min.
3. the preparation method of the low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as described in claim 1, feature exist
In: the soluble-salt of copper described in step 2) is Cu (NO3)2·3H2O or Cu (CH3COO)2·H2O, the soluble-salt of manganese are nitre
Sour manganese or Mn (CH3COO)2·4H2The soluble-salt of O, Ce are Ce (NO3)3·6H2O or Ce (CH3COO)3·5H2O, Co's is solvable
Property salt be Co (NO3)2·6H2O or Co (CH3COO)2·4H2The soluble-salt of O, Fe are Fe (NO3)3·9H2The solubility of O, Mo
Salt is Mo (NO3)3·5H2The soluble-salt of O, Cr are Cr (NO3)3·9H2O。
4. the preparation method of the low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as described in claim 1, feature exist
In: drying described in step 3) refers to dries 8~12h in the baking oven that temperature is 80~100 DEG C；
The grit number of crossing of screening described in step 3) is 40~80 mesh；The temperature of calcining described in step 3) is 450~550
DEG C, the time is 4~6h.
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| "Cu–Mn bimetal ion-exchanged SAPO-34 as an active SCR catalyst for removal of NOx from diesel engine exhausts";Liming Huang等;《Catalysis Communications》;20160404;第81卷;摘要，第2.1节 * |
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