CN107185588A - 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
- Publication number
- CN107185588A CN107185588A CN201710333319.XA CN201710333319A CN107185588A CN 107185588 A CN107185588 A CN 107185588A CN 201710333319 A CN201710333319 A CN 201710333319A CN 107185588 A CN107185588 A CN 107185588A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- low
- water resistant
- soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 51
- 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 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001868 water Inorganic materials 0.000 title claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 239000011593 sulfur Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 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 25
- 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 9
- 238000000034 method Methods 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 46
- 239000000843 powder Substances 0.000 claims description 43
- 238000007598 dipping method Methods 0.000 claims description 34
- 238000001354 calcination Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical group [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 2
- 238000007873 sieving Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical group 0.000 abstract description 2
- 241000269350 Anura Species 0.000 abstract 1
- 238000001802 infusion Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 29
- 239000000463 material Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 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
- 239000002245 particle Substances 0.000 description 12
- 239000013049 sediment Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 229910052684 Cerium Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 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
- 239000011148 porous material Substances 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
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000001846 repelling effect Effects 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 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
- 235000011130 ammonium sulphate Nutrition 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
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 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
- 239000000126 substance 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
Landscapes
- 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)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof, the catalyst is prepared using infusion process, it is carrier with chabazite molecular sieve H SAPO 34, active component is transition metal Cu and Mn composite oxides, auxiliary agent is one kind in Ce, Fe, Co, Mo, Cr, and 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, it make use of many significant denitration efficiencies and heat endurance for improving catalyst of metal synergy, effectively its active temperature windows has been widened, and have preferable resistance to SO_2.
Description
Technical field
The present invention relates to a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof, belong to air
Pollutant abatement technology and environment protection catalytic Material Field.
Background technology
The energy resource structure of China decides that China is a coal-fired big country, is developed rapidly with the national economy of China, often
A large amount of nitrogen oxides that year discharges into air, cause many areas to occur in that acid rain, haze, molecule pollution etc., to people
Body, environment, ecological harm and all very huge to the destruction of social economy.In recent years, China's discharged nitrous oxides are quick
Increase, the data display announced according to environmental administration, the discharged nitrous oxides total amount of China in 2000 is 12,100,000 tons, and 2012
23,380,000 tons have then been reached, some has almost been turned over.If it was predicted that do not took further control measure, the year two thousand thirty China's nitrogen oxygen
Compound discharge will be more than 35,000,000 tons.Therefore Emission Controlling Technology of Nitric Oxides is greatly developed imperative.
At present in denitrating flue gas field, generally use with NH3For SCR (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.The need for meeting temperature, typically by catalytic bed arrangement with deduster before, but this method for arranging on the one hand
The SO of catalyst can be caused2Poisoning and dust are blocked, and on the other hand need space after larger stove；Two be the vanadium in active component
It is toxic, to ecological environment and healthy all unfavorable；In addition, as the flue gas temperature of the equipment exhaustings such as steel works sintering machine and pelletizing
Degree, not in the active temperature windows scope of such high temperature SCR catalyst, therefore, greatly develops high sulfur resistive below 200 DEG C
The low-temperature SCR technical meaning of performance is great.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and its
Preparation method, the catalyst is significantly widened by the cooperative effect of the metal such as active component Cu, Mn and auxiliary agent Ce, Fe, Co
Catalyst denitration reaction temperature, and the denitration efficiency and sulfur resistive water repelling property of catalyst are improved, while the preparation side
Method cost simple to operate is low, repeated high, preparation catalyst performance stabilised.
Technology contents：The 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 aoxidizes for copper manganese composition metal
Thing, the auxiliary agent is one kind in 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：
Described chabazite molecular sieve is chabazite molecular sieve H-SAPO-34.
Present invention also offers a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 1
Preparation method, this method comprises the following steps：
1) it is standby after the former powder of carrier chabazite molecular sieve is dried；
2) the soluble-salt dissolving for weighing copper in the active component in proportion in deionized water, is stirred
Afterwards, the soluble-salt of the soluble-salt of manganese and the auxiliary agent in active component is proportionally added into, is sufficiently stirred for that mixed solution is made；
3) take step 1) in the former powder of dried chabazite molecular sieve be dissolved in step 2) made from mixed solution, fully
After stirring dipping, solution is heated up and continues stirring dipping, after moisture is evaporated, successively after drying, grinding, screening, calcining
Obtain described sulfur resistive water resistant low-temperature denitration complex type molecular sieve catalysis (Cu-Mn-X/SAPO-34, wherein X be Ce, Fe,
One kind in Co, Mo, Cr).
Wherein：
Step 1) described in drying temperature be 100~105 DEG C, the time be 25~30min.
Step 2) described in copper soluble-salt be Cu (NO3)2·3H2O or Cu (CH3COO)2·H2O, the soluble-salt of manganese
For manganese nitrate or Mn (CH3COO)2·4H2O), Ce soluble-salt is Ce (NO3)3·6H2O or Ce (CH3COO)3·5H2O, Co
Soluble-salt be Co (NO3)2·6H2O or Co (CH3COO)2·4H2O), Fe soluble-salt is Fe (NO3)3·9H2O, Mo's
Soluble-salt is Mo (NO3)3·5H2O, Cr soluble-salt are Cr (NO3)3·9H2O。
Step 3) described in be sufficiently stirred for after dipping, by solution heat up and continue stirring dipping specifically refer 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 afterwards
Continue to stir 2~4h of dipping.
The speed of agitator of described magnetic stirring apparatus is 40~50r/s.
Step 3) described in drying refer to dry 8~12h in temperature is 80~100 DEG C of baking oven；Step 3) described in
Calcining temperature be 450~550 DEG C, the time be 4~6h；Step 3) described in screening cross grit number be 40~80 mesh.
Beneficial effect：Compared with prior art, the low-temperature denitration complex type molecular sieve catalysis of sulfur resistive water resistant of the invention
Relative to existing single copper-based or manganese-based catalyst, due to two kinds of active components and the synergy of auxiliary agent, effective drop
The low denitration reaction temperature of catalyst, improves the heat endurance of catalyst, sulfur resistive water-resistance, is taken off while having 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 relatively low light-off temperature, higher denitration efficiency and wider temperature window.
Brief description of the drawings
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；
SEM before and after Fig. 4 is poisoned for the complex type molecular sieve catalysis prepared in present example schemes；Wherein：A is not change
Property fresh catalyst SEM figures, b be unmodified catalyst SO2SEM figures, c after poisoning are 2%Ce modified catalysts SO2
SEM figures, d after poisoning are 2%Co modified catalysts SO2SEM figures, e after poisoning are 2%Fe modified catalysts SO2After poisoning
SEM schemes.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.
Embodiment 1：
(1) weigh in the former powder of 8g chabazite molecular sieves (H-SAPO-34), the Noah's ark for putting it into corundum material, together
It is placed in 100 DEG C of dry 25min in blowing-type drying box standby；
(2) 0.3775gCu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 30ml deionized water, is sufficiently stirred for
After uniform, the manganese nitrate solution that 2.7412g concentration is 50% is added, is sufficiently stirred for being made two kinds of active components containing different proportion
Mixed solution.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 8h in liquid, the water-bath, magnetic stirring apparatus at 30 DEG C, sufficiently after dipping, is warming up to 75 DEG C and is continued
Stirring dipping 2h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 100 DEG C and dries 8h, pipe is subsequently placed in
In formula stove, 6h is calcined in 450 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (2)-Mn (6)/SAPO-
34 (450) catalyst, the formula represents that using SAPO-34 as carrier the quality that Cu quality is 2%, Mn of carrier is carrier
6%, calcining heat is 450 DEG C.
Embodiment 2：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
103 DEG C of dry 30min are standby in blowing-type drying box；
(2) 0.3775g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 35ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 0.1549g Ce (NO that 0.9091g concentration is 50% are added3)3·6H2O powder, is fully stirred
Mixing is into two kinds of active components containing different proportion and the mixed solution containing cerium promoter.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 20 DEG C, sufficiently after dipping, is warming up to 85 DEG C and is continued
Stirring dipping 4h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 80 DEG C and dries 12h, pipe is subsequently placed in
In formula stove, 6h is calcined in 500 DEG C of high temperature aerobic environment；
(1) sediment grinding screening to the particle diameter after calcining is 40~80 mesh by (4), that is, has obtained Cu (2)-Mn (2)-Ce
(1)/SAPO-34 (500) catalyst, the formula represents that using SAPO-34 as carrier Cu quality is for 2%, Mn of carrier quality
2%, Ce of carrier quality is the 1% of carrier, and calcining heat is 450 DEG C.
Embodiment 3：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
105 DEG C of dry 30min are standby in blowing-type drying box；
(2) 0.3775g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 40ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 0.3099g Ce (NO that 2.7412g concentration is 50% are added3)3·6H2O powder, is fully stirred
Mixing is into two kinds of active components containing different proportion and the mixed solution containing cerium promoter.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 20 DEG C, sufficiently after dipping, is warming up to 85 DEG C and is continued
Stirring dipping 4h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 80 DEG C and dries 12h, pipe is subsequently placed in
In formula stove, 6h is calcined in 550 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (2)-Mn (6)-Ce
(2)/SAPO-34 (550) catalyst.
Embodiment 4：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
105 DEG C of dry 30min are standby in blowing-type drying box；
(2) 1.8875g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 50ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 1.5504g Ce (NO that 4.5455g concentration is 50% are added3)3·6H2O powder, is fully stirred
Mixing is into two kinds of active components containing different proportion and the mixed solution containing cerium promoter.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 20 DEG C, sufficiently after dipping, is warming up to 85 DEG C and is continued
Stirring dipping 4h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 80 DEG C and dries 12h, pipe is subsequently placed in
In formula stove, 6h is calcined in 450 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (10)-Mn (10)-Ce
(10)/SAPO-34 (450) catalyst.
Embodiment 5：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
100 DEG C of dry 25min are standby in blowing-type drying box；
(2) 0.3775g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 30ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 0.3607g Fe (NO that 0.9091g concentration is 50% are added3)3·9H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Fe containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 8h in liquid, the water-bath, magnetic stirring apparatus at 30 DEG C, sufficiently after dipping, is warming up to 75 DEG C and is continued
Stirring dipping 2h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 100 DEG C and dries 8h, pipe is subsequently placed in
In formula stove, 6h is calcined in 450 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (2)-Mn (2)-Fe
(1)/SAPO-34 (450) catalyst.
Embodiment 6：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
105 DEG C of dry 25min are standby in blowing-type drying box；
(2) 1.8875g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 50ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 3.6071g Fe (NO that 4.5455g concentration is 50% are added3)3·9H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Fe containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 8h in liquid, the water-bath, magnetic stirring apparatus at 30 DEG C, sufficiently after dipping, is warming up to 75 DEG C and is continued
Stirring dipping 2h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 100 DEG C and dries 8h, pipe is subsequently placed in
In formula stove, 6h is calcined in 550 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (10)-Mn (10)-Fe
(10)/SAPO-34 (550) catalyst.
Embodiment 7：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
100 DEG C of dry 27min are standby in blowing-type drying box；
(2) 0.3775g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 30ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 0.2469g Co (NO that 0.9091g concentration is 50% are added3)2·6H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Co containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 25 DEG C, sufficiently after dipping, is warming up to 80 DEG C and is continued
Stirring dipping 3h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 90 DEG C and dries 10h, pipe is subsequently placed in
In formula stove, 6h is calcined in 450 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (2)-Mn (2)-Co
(1)/SAPO-34 (450) catalyst.
Embodiment 8：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
105 DEG C of dry 27min are standby in blowing-type drying box；
(2) 1.8875g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 50ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 2.4661g Co (NO that 4.5455g concentration is 50% are added3)2·6H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Co containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 25 DEG C, sufficiently after dipping, is warming up to 80 DEG C and is continued
Stirring dipping 3h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 90 DEG C and dries 10h, pipe is subsequently placed in
In formula stove, 6h is calcined in 550 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (10)-Mn (10)-Co
(10)/SAPO-34 (550) catalyst.
Embodiment 9：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
100 DEG C of dry 29min are standby in blowing-type drying box；
(2) 0.3775g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 30ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 0.2287g Mo (NO that 0.9091g concentration is 50% are added3)2·5H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Mo containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 28 DEG C, sufficiently after dipping, is warming up to 85 DEG C and is continued
Stirring dipping 4h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 80 DEG C and dries 12h, pipe is subsequently placed in
In formula stove, 6h is calcined in 450 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (2)-Mn (2)-Mo
(1)/SAPO-34 (450) catalyst.
Embodiment 10：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
105 DEG C of dry 29min are standby in blowing-type drying box；
(2) 1.8875g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 50ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 2.2865g Mo (NO that 4.5455g concentration is 50% are added3)2·5H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Mo containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 28 DEG C, sufficiently after dipping, is warming up to 85 DEG C and is continued
Stirring dipping 4h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 80 DEG C and dries 12h, pipe is subsequently placed in
In formula stove, 6h is calcined in 550 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (10)-Mn (10)-Mo
(10)/SAPO-34 (550) catalyst.
Embodiment 11：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
100 DEG C of dry 30min are standby in blowing-type drying box；
(2) 0.3775g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 30ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 0.3847g Cr (NO that 0.9091g concentration is 50% are added3)3·9H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Cr containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 20 DEG C, sufficiently after dipping, is warming up to 85 DEG C and is continued
Stirring dipping 4h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 80 DEG C and dries 12h, pipe is subsequently placed in
In formula stove, 6h is calcined in 450 DEG C of high temperature aerobic environment；
(4) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (2)-Mn (2)-Cr
(1)/SAPO-34 (450) catalyst.
Embodiment 12：
(1) weigh in the former powder of 8g chabazite molecular sieves H-SAPO-34, the Noah's ark for putting it into corundum material, put together
105 DEG C of dry 30min are standby in blowing-type drying box；
(2) 1.8875g Cu (NO are weighed in proportion3)2·3H2O powder, is dissolved in 50ml deionized water, fully stirs
After mixing uniformly, manganese nitrate solution and 3.8465g Cr (NO that 4.5455g concentration is 50% are added3)3·9H2O, is sufficiently stirred for system
Into two kinds of active components containing different proportion and the mixed solution of the Cr containing auxiliary agent.
(3) dried H-SAPO-34 molecular screen primaries powder 5g is taken in step (1) to be dissolved in the obtained mixing of step (2) molten
Continual stirring 6h in liquid, the water-bath, magnetic stirring apparatus at 20 DEG C, sufficiently after dipping, is warming up to 85 DEG C and is continued
Stirring dipping 4h, after moisture is evaporated, the product of evaporative crystallization is put into baking oven at 80 DEG C and dries 12h, pipe is subsequently placed in
In formula stove, 6h is calcined in 550 DEG C of high temperature aerobic environment；
(5) it is 40~80 mesh by sediment grinding screening to the particle diameter after calcining, that is, has obtained Cu (10)-Mn (10)-Cr
(10)/SAPO-34 (550) catalyst.
Embodiment 13：Catalyst activity is determined and the test of sulfur resistive water repelling property
Catalyst tabletting screening obtained by above-described embodiment is taken respectively, takes the catalyst granules loading fixed bed of 40~60 mesh 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 is 15000h-1, feed gas volume content：NO：350×10-6, NH3：350×10-6, O2：3%, carrier gas：
N2, total gas flow rate is 500ml/min, and progressively mixing finally enters air pre-mixing device and filled each road gas after mass flowmenter
Divide mixing；Reactor is internal diameter 10mm stainless steel tube, and three sections of heating vertical tubular furnaces with temperature control system provide reaction temperature
Condition；Analyzed with airbag after thief hatch collection flue gas by the flue gas analyzers of Testo 350.
The activity of catalyst is evaluated with NO conversion ratio：
Wherein, NOin、NOoutFixed bed reactors entrance and exit NO concentration is represented respectively, and all data are de-
Read after nitre stable reaction.Active testing result is shown in accompanying drawing 1, it can be seen that the addition of auxiliary agent can improve compound point
The addition performance of the denitration activity of sub- sieve catalyst, wherein Ce is the most obvious, Cu-Mn-Ce/SAPO-34 many metal composites point
Sub- sieve catalyst is in 120 DEG C of temperature, and NO conversion ratios can just reach more than 82%, temperature equal energy between 180 DEG C~300 DEG C
Up to more than 90%, activity reaches as high as 99.6%.
Catalyst water resistant sulfur resistance test result is shown in accompanying drawing 2 and accompanying drawing 3, prepares fresh catalyst and carries out active testing
After the stable 1h of question response, the vapor or SO of various concentrations are passed through2Concentration, progress poisons to be stopped being passed through water and SO after experiment 8h2。
Accompanying drawing 2 is the situation of change of catalyst denitration activity under the water vapor atmosphere of various concentrations, it can be seen that being passed through water
The denitration activity of steam rear catalyst has declined with the increase of water concentration, but when stopping is passed through vapor rear catalyst
Activity substantially can return to initial level, show that catalyst water repelling property is preferable；Accompanying drawing 3 is added Ce, Co, Fe etc.
The composite molecular sieve catalyst sulfur resistance test result of several different auxiliary agents, it can be seen that being not added with the Cu- of auxiliary agent
SO of the Mn/SAPO-34 molecular sieves in 500ppm2In poison after 8h, the activity of catalyst is down to 65% by 95%, adds auxiliary agent
The sulfur resistance of Ce, Fe, Co rear catalyst has substantially been lifted, and wherein Ce addition is the most obvious, Cu-Mn-Ce/SAPO-34
The activity for poisoning 8h rear catalysts is only down to 82% or so by 95%, and stopping is passed through SO2Activity can be recovered and stably exist afterwards
85% or so.
Embodiment 14：BET specific surface area and pore structure study
Surveyed using the full-automatic specific surface areas of Micromeritics companies of U.S. ASAP 2020M and micropore analyzer
It is fixed.The specific surface area of catalyst is measured the absorption of nitrogen and desorption by catalyst, is manufactured in adsorption process using liquid nitrogen
Low temperature environment, makes nitrogen be full of each micropore, then makes catalyst at a temperature of close to zero degree to the full extent
It is desorbed, the nitrogen in hole is discharged.Using hydrogen as carrier gas, nitrogen makees N under adsorbed gas, liquid nitrogen temperature (77K)2Inhaled
It is attached, with A12O3Reference is done, specific surface area is calculated using Brunauer-Emmett-Teller (BET) method, and pore volume and aperture make
Calculated with Barrett-Joyner-Halenda (BJH) method.
The BET specific surface area and pore structure study of the complex type molecular sieve catalysis of table 1
Table 1 is the catalyst SO to tri- kinds of different transition metal promoter additions of Ce, Co, Fe2BET tables are carried out before and after poisoning
Levy.As can be seen from the table, the specific surface area of addition auxiliary agent rear catalyst, pore volume have been reduced, and aperture increased.May
It is due to that these auxiliary agents are covered in catalyst surface or entered caused by molecular sieve pore passage.Before and after the modified catalyst poisoning of contrast
The change of physicochemical property parameter, it can be seen that modified catalyst SO2The size of specific surface area decrement is Fe successively before and after poisoning>
Co>Ce.By the minimum of specific surface area of catalyst reduction modified 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
Rear catalyst BET specific surface area reduces the ammonium sulfate that main cause is generation and is attached to catalyst surface.Show that addition is appropriate
Ce and Co can be good at improving catalyst anti-SO2Poisoning performance.
Embodiment 15：ESEM (SEM) combination X-ray energy spectrum (EDS) analysis
Catalyst surface active component crystal pattern, pore size, reunion degree etc. can all directly influence catalyst
Performance, ESEM (SEM) can clearly reflect these microscopic characteristics, and X-ray energy spectrum (EDS) can be to surface crystal element
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 SEM, its resolution ratio is 150eV.
EDS is analyzed after the complex type molecular sieve catalysis poisoning parent prepared in the present example of table 2
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 analyses, this it appears that unmodified catalyst SO from figure2In
Malicious rear catalyst surface occurs to reunite seriously, there is the material of many brilliant whites, is analyzed with reference to EDS and above XRD, TG-DTG points
Analysis understands that the material is ammonium sulfate salts substances.Modified catalyst SO2Rear catalyst surface be poisoned substantially than unmodified
Catalyst SO2, there is not substantial amounts of agglomeration yet in the smooth many in surface after poisoning.Catalyst SO modified Ce2Poisoning
The mass content of surface S elements is significantly lower than other several catalyst afterwards, illustrates that through catalyst modified Ce sulphur can be reduced
Acid ammonium salt class material is deposited in catalyst surface, it may be possible to because Ce can reduce NH4 +And SO4 -2Between bond energy, make
(NH4)2SO4Heat endurance is reduced, it is easier to decomposed, so as to reduce accumulation of the ammonium sulfate in catalyst surface.
Claims (8)
1. a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant, it is characterised in that：The catalyst includes carrier, activity
Component and auxiliary agent, the carrier are chabazite molecular sieve, and the active component is copper manganese metal composite oxide, and the auxiliary agent is
One kind in Ce, Fe, Co, Mo or Cr；On the basis of the quality of carrier, the quality of copper and manganese element point in active component
Not Wei 2%~10%, the quality of auxiliary agent is 1~10%.
2. a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 1, it is characterised in that：It is described
Chabazite molecular sieve be chabazite molecular sieve H-SAPO-34.
3. a kind of preparation method of the low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 1, it is special
Levy and be：This method comprises the following steps：
1) it is standby after the former powder of carrier chabazite molecular sieve is dried；
2) the soluble-salt dissolving for weighing copper in the active component in proportion in deionized water, after stirring, is pressed
Ratio adds the soluble-salt and the soluble-salt of the auxiliary agent of manganese in active component, is sufficiently stirred for that mixed solution is made；
3) take step 1) in the former powder of dried chabazite molecular sieve be dissolved in step 2) made from mixed solution, stirring dipping
Afterwards, solution is heated up and continues stirring dipping, after moisture is evaporated, obtain described after drying, grinding, screening, calcining successively
Sulfur resistive water resistant low-temperature denitration composite molecular sieve catalyst.
4. a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 3, it is characterised in that：Step
1) temperature of the drying described in is 100~105 DEG C, and the time is 25~30min.
5. a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 3, it is characterised in that：Step
2) soluble-salt of the copper described in is Cu (NO3)2·3H2O or Cu (CH3COO)2·H2O, the soluble-salt of manganese is manganese nitrate or Mn
(CH3COO)2·4H2O), Ce soluble-salt is Ce (NO3)3·6H2O or Ce (CH3COO)3·5H2O, Co soluble-salt is
Co(NO3)2·6H2O or Co (CH3COO)2·4H2O), Fe soluble-salt is Fe (NO3)3·9H2O, Mo soluble-salt are Mo
(NO3)3·5H2O, Cr soluble-salt are Cr (NO3)3·9H2O。
6. a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 3, it is characterised in that：Step
3) being sufficiently stirred for after dipping described in, heating up and continue stirring dipping solution specifically refers in bath temperature be 20~30 DEG C of bars
Under part, using magnetic stirring apparatus 6~8h of continual stirring, bath temperature is risen to 75~85 DEG C afterwards and continues stirring dipping
2~4h.
7. a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 6, it is characterised in that：It is described
Magnetic stirring apparatus speed of agitator be 40~50r/s.
8. a kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant as claimed in claim 3, it is characterised in that：Step
3) drying described in refers to dry 8~12h in temperature is 80~100 DEG C of baking oven；Step 3) described in screening sieving
Mesh number is 40~80 mesh；Step 3) described in calcining temperature be 450~550 DEG C, the time be 4~6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710333319.XA CN107185588B (en) | 2017-05-12 | 2017-05-12 | A kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710333319.XA CN107185588B (en) | 2017-05-12 | 2017-05-12 | A kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107185588A true CN107185588A (en) | 2017-09-22 |
| CN107185588B CN107185588B (en) | 2019-11-12 |
Family
ID=59873945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710333319.XA Active CN107185588B (en) | 2017-05-12 | 2017-05-12 | A kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107185588B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620123A (en) * | 2018-05-17 | 2018-10-09 | 东南大学 | It is a kind of using Mn as active metal, using Nd as middle low-temperature denitration catalyst of auxiliary agent and preparation method thereof |
| CN108913518A (en) * | 2018-06-12 | 2018-11-30 | 安徽省金裕皖酒业有限公司 | A kind of liquor aging method for using for reference the new vinegar after-ripening technique of mature vinegar |
| CN109433254A (en) * | 2018-11-09 | 2019-03-08 | 大连交通大学 | A kind of confinement molecular sieve denitrating catalyst and preparation method thereof |
| CN110026182A (en) * | 2019-05-20 | 2019-07-19 | 中国人民大学 | Low-temperature denitration catalyst and its preparation and application in high sulfur resistive |
| CN110292944A (en) * | 2019-07-31 | 2019-10-01 | 北京工业大学 | A kind of ultra-wide temperature window SCR denitration and preparation method thereof |
| CN112844424A (en) * | 2020-12-30 | 2021-05-28 | 山东天璨环保科技有限公司 | Low-temperature denitration catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903477A (en) * | 2016-04-22 | 2016-08-31 | 中国矿业大学(北京) | Low temperature wide-active temperature window SCR denitration catalyst and preparation method thereof |
-
2017
- 2017-05-12 CN CN201710333319.XA patent/CN107185588B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903477A (en) * | 2016-04-22 | 2016-08-31 | 中国矿业大学(北京) | Low temperature wide-active temperature window SCR denitration catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIMING HUANG等: ""Cu–Mn bimetal ion-exchanged SAPO-34 as an active SCR catalyst for removal of NOx from diesel engine exhausts"", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620123A (en) * | 2018-05-17 | 2018-10-09 | 东南大学 | It is a kind of using Mn as active metal, using Nd as middle low-temperature denitration catalyst of auxiliary agent and preparation method thereof |
| CN108913518A (en) * | 2018-06-12 | 2018-11-30 | 安徽省金裕皖酒业有限公司 | A kind of liquor aging method for using for reference the new vinegar after-ripening technique of mature vinegar |
| CN109433254A (en) * | 2018-11-09 | 2019-03-08 | 大连交通大学 | A kind of confinement molecular sieve denitrating catalyst and preparation method thereof |
| CN109433254B (en) * | 2018-11-09 | 2021-11-09 | 大连交通大学 | Confined molecular sieve denitration catalyst and preparation method thereof |
| CN110026182A (en) * | 2019-05-20 | 2019-07-19 | 中国人民大学 | Low-temperature denitration catalyst and its preparation and application in high sulfur resistive |
| CN110292944A (en) * | 2019-07-31 | 2019-10-01 | 北京工业大学 | A kind of ultra-wide temperature window SCR denitration and preparation method thereof |
| CN110292944B (en) * | 2019-07-31 | 2022-11-08 | 北京工业大学 | SCR denitration catalyst with ultra-wide temperature window and preparation method thereof |
| CN112844424A (en) * | 2020-12-30 | 2021-05-28 | 山东天璨环保科技有限公司 | Low-temperature denitration catalyst and preparation method thereof |
| CN112844424B (en) * | 2020-12-30 | 2022-05-17 | 山东天璨环保科技有限公司 | Low-temperature denitration catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107185588B (en) | 2019-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107185588B (en) | A kind of low-temperature denitration composite molecular sieve catalyst of sulfur resistive water resistant and preparation method thereof | |
| Ri et al. | Manganese-cerium composite oxide pyrolyzed from metal organic framework supporting palladium nanoparticles for efficient toluene oxidation | |
| Khan et al. | SO2-tolerant NOx reduction over ceria-based catalysts: Shielding effects of hollandite Mn-Ti oxides | |
| Li et al. | Effects of impregnation sequence for Mo-modified V-based SCR catalyst on simultaneous Hg (0) oxidation and NO reduction | |
| CN106345527A (en) | Mn base metal organic skeletal catalyst, and preparation method and application thereof in air pollution prevention | |
| Yang et al. | Significant promoting effect of La doping on the wide temperature NH3-SCR performance of Ce and Cu modified ZSM-5 catalysts | |
| CN106268787A (en) | A kind of samarium doping MnOxlow-temperature SCR catalyst and its preparation method and application | |
| Chen et al. | Poisoning mechanism of KCl, K2O and SO2 on Mn-Ce/CuX catalyst for low-temperature SCR of NO with NH3 | |
| CN105854932A (en) | Cu-Mn bimetallic composite type low-temperature denitration catalyst and preparation method thereof | |
| YAN et al. | Poisoning effect of SO2 on Mn-Ce/TiO2 catalysts for NO reduction by NH3 at low temperature | |
| CN106268935A (en) | Cu/SAPO 34 molecular sieve catalyst and its preparation method and application | |
| CN112316946A (en) | Low-temperature CO-SCR denitration Cu-Ni/AC catalyst and preparation method thereof | |
| US11596933B2 (en) | Catalyst capable of simultaneously removing COS and H2S in garbage gasification and preparation method thereof | |
| CN104785099A (en) | Method for purifying acrylonitrile device absorption tower tail gas by using CeMn/Me-beta molecular sieve | |
| Hao et al. | Constructing and synthesizing optimal Cu-BTC and its application in low-temperature denitration | |
| CN112264027B (en) | Copper-cobalt-cerium composite oxide catalytic combustion catalyst and preparation method and application thereof | |
| CN110479245A (en) | A kind of molybdenum cerium support type catalyst for denitrating flue gas and its preparation method and application | |
| Ren et al. | Enhancement effect of RuO2 doping on the reduction process of NOx by NH3 via V2O5-WO3/TiO2 particle catalyst under low-temperature: Structure-activity relationship and reaction mechanism | |
| HAO et al. | Experimental study of Fe modified Mn/CeO2 catalyst for simultaneous removal of NO and toluene at low temperature | |
| Zhang et al. | Mn (CeZr) Ox chelation-induced synthesis and its hydrothermal aging characteristics for catalytic abatement of toluene | |
| CN106466607B (en) | A kind of environmental-friendly sections antimony composite oxides denitrating catalyst and preparation method thereof | |
| CN110302830A (en) | VOCs purification molecular sieve based catalyst under high humidity environment and the preparation method and application thereof | |
| CN109529808A (en) | A kind of preparation method improving charcoal base SCR catalyst low temperature active | |
| CN107321343A (en) | Vanadium-free denitration catalyst and preparation method thereof | |
| Jiang et al. | Investigation of La-doped MnOx in PTFE filter bag for low-temperature selective catalytic reduction of NOx in cement industry flue gas with NH3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |