CN109794300A - A kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst and preparation method thereof - Google Patents
A kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalysts and preparation method thereof, belong to technical field of atmospheric pollution control.A kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, the catalyst use Detitanium-ore-type TiO2As carrier, active component is formed by phosphomolybdic acid, copper nitrate, polyethylene glycol (PEG) and cetyl trimethylammonium bromide (CTAB)；The preparation process of the catalyst are as follows: phosphomolybdic acid, copper nitrate, Surfactant CTAB and PEG are placed in after dissolution in crucible, dry, drying, calcining after obtaining active component, then by active component and TiO2It is put into togerther stirring in the crucible equipped with distilled water, dry, drying, calcining, obtains Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst.Using Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, it can enhance catalyst on the basis of guaranteeing low-temperature denitration efficiency and resist SO2With the ability of vapor.
Description
Technical field
The present invention relates to technical field of atmospheric pollution control, de- more specifically to a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low temperature
Denox catalyst and preparation method thereof.
Background technique
Industrial smoke (coke oven flue gas, sintering flue gas, glass furnace fume etc.) is currently the nitrogen oxides in addition to coal-fired flue-gas
(NOx) main source.NOxIt is toxic gas, the eyes of people can be stimulated and respiratory system and form photochemical fog and acid rain
Equal environmental pollutions.China NOxDischarge amount radix is big, shows according to the data that " China Environmental State Bulletin " is announced, NO in 2015xRow
It is high-volume 1851.9 ten thousand tons, wherein industrial discharge amount is 1180.9 ten thousand tons, sixty percent or more total amount is accounted for, wherein every year with coke oven flue gas
The NO generated with sintering flue gasxThe sum of close to 2,000,000 tons, discharge amount should not be underestimated.National relevant ministries and commissions are from since the " 12th Five-Year Plan "
Also it puts into effect and has revised a series of environmental regulations and standard to reinforce for NOxControl.
NO in current control industrial smokexThere are many ways to, wherein technology is most mature, efficiency highest, business application
It is most widely selective catalytic reduction (Selective Catalytic Reduction, SCR) denitration technology.Denitration catalyst
Agent is the core of entire SCR technology.The current most common SCR catalyst is vanadium tungsten titanium catalyst series (V2O5-WO3/TiO2),
The catalyst optimum activity temperature is at 300-400 DEG C or so.However exist for gas temperatures such as steel sintering flue gas, coke oven flue gas
Between 120-300 DEG C and contain a large amount of SO2Under the operating condition of water vapour, vanadium tungsten titanium catalyst is difficult to play its excellent denitration
Efficiency, furthermore SO2Catalyst can be also poisoned with water vapour causes the decline of its efficiency even to inactivate.Therefore it develops a kind of efficient, steady
Fixed, applicability is wide, sulfur resistive water repelling property is good SCR low temperature catalyst is the hot spot of current research, it may have very strong theory is ground
Study carefully and practical application value.
Some researchs are pointed out in recent years, because of SO2It is sour gas, it can if catalyst has stronger surface acidity
To inhibit SO2In the absorption and reaction of catalyst surface, so that catalyst be made to resist SO2Murder by poisoning ability enhances (Applied
Catalysis B:Environmental, 2013,142-143:705~717；Applied Catalysis B:
Environmental, 2008,78 (3-4): 301~308).QiuL etc. (Catalysis Communications, 2016,78:
22~25) Mn-Co-Ce/TiO is prepared for sulfuric acid treatment2/SiO2Catalyst, 50ppm SO2NO at lower 250 DEG CxConversion ratio is
99.5%, NOx conversion efficiency does not reduce within the temperature range of 190~280 DEG C, and catalyst is by sulfuric acid treatment rear surface acid
The main reason for raising of degree and specific surface area is catalytic activity and sulfur resistance rising.
Heteropoly acid, because there is stronger electron transport ability, has as a kind of high-performance solid that Bronsted acidity is strong acidAcidic site and active high " Lattice Oxygen " structure, become the hot spot of current research.Such as, Chinese patent CN
103990496 A disclose a kind of middle low temperature SCR denitration catalyst that Ce doping phosphotungstic acid is prepared by dry-mixed grinding, this application
Case has excellent middle low-temperature denitration performance and to SO2Excellent anti-poisoning capability is suffered from alkali metal.Chinese patent
CN104801349A discloses a kind of V for adulterating Dawson type molybdovanaphosphoric acid2O5-WO3/TiO2Middle low-temperature SCR low-temperature denitration catalysis
Agent, active component V2O5With molybdovanaphosphoric acid H8P2Mo16V2O62Mixture, the catalyst have stronger catalysis oxidation also
Proper energy power and acidic site can achieve higher catalytic reaction activity under lower reaction temperature, effectively raise low temperature
The denitration efficiency of SCR.Chinese patent CN 106984349A discloses a kind of coke oven flue gas denitrating catalyst and preparation method thereof,
It prepares VPO heteropoly acid active component by way of phosphoric acid is added in catalytic component based on vanadium and adjusts surface acidity, is loaded
To nanoscale TiO2VPO/TiO is made on carrier2Solid acid catalysts, active testing show to reach in 150 DEG C of NO conversion ratios
93% or more, 200~350 DEG C can achieve 99%, in 8vol.% water vapour, 1000ppm high concentration SO2In the presence of in the case of,
The activity of catalyst does not decline in 20h.
To sum up, domestic and foreign scholars achieve some significant achievements in terms of studying low-temperature denitration catalyst, but will be miscellaneous
Polyacid theory, which is applied to develop to have, to be still in and visits compared with high/low temperature activity and certain sulfur resistive water repelling property SCR denitration aspect
Rope stage, the low-temperature catalytic activity of gained catalyst and anti-SO2Still need to be further increased with water vapour ability.
Summary of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome existing SCR low temperature catalyst to resist SO2The poor deficiency with the ability of water vapour,
A kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst and preparation method thereof is provided, using Copper-cladding Aluminum Bar phosphomolybdic acid low temperature of the invention
Denitrating catalyst can make catalyst resist SO on the basis of guaranteeing low-temperature denitration efficiency2Enhance with the ability of vapor.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, it is characterised in that: the catalyst uses anatase
Type TiO2As carrier, active component is formed by phosphomolybdic acid, copper nitrate, polyethylene glycol and cetyl trimethylammonium bromide.
Further, the molar ratio of Cu and Mo is (0~4) in the active component: 1, cetyl in active component
The quality of trimethylammonium bromide accounts for the 10~60% of phosphomolybdic acid quality, and the quality of active component accounts for catalyst gross mass in catalyst
5~15%.
Further, the Detitanium-ore-type TiO2Specific surface area be 300-350m2/g。
Further, the preparation process of the active component are as follows: by phosphomolybdic acid, copper nitrate, cetyl trimethyl bromine
Change ammonium and polyethylene glycol is dissolved in distilled water and is uniformly mixed, then through drying, drying and calcination processing up to active component.
The preparation method of a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, which is characterized in that including as follows
Step:
Step 1: the preparation of active component
(1) it is dissolved after mixing phosphomolybdic acid, copper nitrate, cetyl trimethylammonium bromide and polyethylene glycol, and constant speed is stirred
Mix 1~1.5h；
(2) mixture in step (1) is subjected to constant rate of drying, and moisture is evaporated；
(3) the mixture constant temperature drying that will be prepared in step (2)；
(4) mixture after drying in step (3) is calcined into 3~3.5h, obtains active component after cooling；
Step 2: the preparation of Copper-cladding Aluminum Bar phosphomolybdic acid catalyst
(1) by the active component prepared in step 1 and TiO2Merging is weighed in proportion to be equipped in the crucible of distilled water, and
Constant speed stirs 1~1.5h on magnetic stirring apparatus；
(2) mixture in step (1) is subjected to constant rate of drying, and moisture is evaporated；
(3) the mixture constant temperature drying that will be prepared in step (2)；
(4) mixture after drying in step (3) is calcined into 3~3.5h, obtains Copper-cladding Aluminum Bar phosphomolybdic acid low temperature after cooling
Denitrating catalyst.
Further, in the step 1 PEG quality be molybdenum phosphate quality 0.5~1%, Cu and Mo molar ratio
For (0~4): 1, CTAB and the mass ratio of phosphomolybdic acid be (0~0.6): 1, it is total to account for catalyst for the quality of active component in step 2
The 5~15% of quality.
Further, in the step 1 and step 2, magnetic stirring apparatus constant speed whipping temp is 25~30 DEG C, magnetic force
Drying temperature is 85~90 DEG C on blender, and the heating temperature of drying box is 100~110 DEG C, and the calcination temperature of Muffle furnace is 350
~450 DEG C.
Further, the magnetic stirring apparatus constant speed whipping temp is 25 DEG C, and drying temperature is 85 on magnetic stirring apparatus
DEG C, the heating temperature of drying box is 105 DEG C, and the calcination temperature of Muffle furnace is 350 DEG C.
Further, the mass percent that active component accounts for catalyst in step 2 (1) is 10%.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, the catalyst use Detitanium-ore-type TiO2Make
For carrier, with phosphomolybdic acid, copper nitrate, polyethylene glycol (PEG) and surfactant cetyl trimethylammonium bromide (CTAB) group
Viability component regulates and controls the surface acidity and architectural characteristic of catalyst by the coordination and collective effect of each component, from
And the surface acidity of catalyst and the exposed amount of active site are increased, the low-temperature denitration activity of catalyst is improved, is made simultaneously
Obtaining catalyst has certain anti-SO2The performance poisoned with water vapour is beneficial to expand low-temperature denitration of flue gas technology in practical work
Application in industry production.
(2) a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, using phosphomolybdic acid and copper nitrate as active group
Point, since phosphomolybdic acid is a kind of heteropoly acid with structure with Keggin, with more acidic site and active oxide structure, and
Its surface acidity and redox property are strong, meanwhile, it is former that the doping of transition metal Cu atom can increase active oxygen in phosphomolybdic acid
The amount of son generates Cu+/Cu2+Redox reaction promotes the progress of denitration reaction, is conducive to NO Molecular Adsorption in catalyst table
Face enhances redox and the electronic storage capacities of catalyst.
(3) a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, the Surfactant CTAB in active component
Cation CTA is generated in water+, substitute the H in Cu metallic atom surface hydroxyl+, surfactant aoxidizes when active component is calcined
Decomposition becomes gas discharge, leaves more L acidic sites, can reach the purpose of the ratio of regulation catalyst B acid and L acid；
CTAB can also reduce the combination energy of Lattice Oxygen, improve surface adsorbed oxygen OβRatio, promote NO to NO2Conversion, promote " fast
The progress of fast SCR reaction ", and then promote the low-temperature denitration activity of catalyst；Meanwhile the addition of polyethylene glycol increases effectively work
The empty degree of property component, enhances its adsorption capacity, is carried on active component preferably on carrier.
(4) a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention passes through Cu and Mo in control active component
Molar ratio, the quality of surfactant, the quality of active component and TiO2Specific surface area, further improve catalyst and exist
Catalytic activity and anti-SO under cryogenic conditions2The ability being poisoned with water vapour, and with TiO2For carrier, further increase
The exposed amount in surface-active site.
(5) preparation method of a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention, by each reaction raw materials
Proportion, each reaction process parameter, such as whipping temp, drying temperature, heating temperature, calcination temperature, mixing time carry out be tight
Lattice control, so as to so that the catalytic activity and sulfur resistive and steam-resistant ability of catalyst obtain optimal cooperation, and its preparation
Technical process is simple, and raw material sources are extensive, price is lower and nontoxic, and low temperature active with higher and certain sulfur resistive are anti-
Aqueous energy；Wherein, when the mass percent that active component accounts for catalyst is 10%, magnetic stirring apparatus constant speed whipping temp is 25
DEG C, drying temperature is 85 DEG C on magnetic stirring apparatus, and the heating temperature of drying box is 105 DEG C, and the calcination temperature of Muffle furnace is 350 DEG C
When, the catalytic activity of catalyst and denitration efficiency can be made to reach most preferably, and make the anti-SO of catalyst2It is poisoned with water vapour
Ability is improved to the greatest extent.
Detailed description of the invention
Fig. 1 is the denitration activity figure of catalyst in the Catalyst Preparation Example 1-10 of the present embodiment；
Fig. 2 is the SO of the present embodiment2With water vapour to the influence diagram of catalyst denitration activity.
Specific embodiment
To further appreciate that the contents of the present invention, the present invention will be further described with reference to the examples below.
A kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the present embodiment, the catalyst use Detitanium-ore-type TiO2As
Carrier is formed with phosphomolybdic acid, copper nitrate, polyethylene glycol (PEG) and surfactant cetyl trimethylammonium bromide (CTAB)
Active component, the molar ratio of Cu and Mo is (0~4) in active component: 1, the quality of surfactant accounts for phosphorus in active component
The 0~60% of molybdic acid quality, the quality of active component accounts for the 5~15% of catalyst gross mass, and Detitanium-ore-type in catalyst
TiO2Specific surface area be 300-350m2/g。
Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the invention is prepared using infusion process: first with phosphato-molybdic heteropolyacid
For active predecessor, the auxiliary agents such as CTAB, copper nitrate, PEG are added, constant speed is stirred to react under 25 DEG C of water bath conditions, and reaction is mixed
Active component is obtained after closing dry object, drying and calcining；Finally by active component and TiO2Carrier is proportionally added into distilled water and stirs
Mixing is mixed, obtains catalyst after drying, drying and calcining.Preparation method is as follows:
Step 1: the preparation of active component
(1) a certain amount of phosphomolybdic acid, copper nitrate, Surfactant CTAB and PEG are placed in crucible, add distillation water-soluble
Solution, constant speed stirs 1~1.5h on magnetic stirring apparatus, and whipping temp is 25~30 DEG C；
(2) by mixture constant rate of drying on magnetic stirring apparatus in step (1), moisture is evaporated, drying temperature be 85~
90℃；
(3) by constant temperature drying in the mixture merging drying box prepared in step (2), the heating temperature of drying box is 100
~110 DEG C；
(4) by the mixture merging Muffle furnace in step (3) after drying 350~450 DEG C of temperature lower calcinations 3~
3.5h obtains active component after cooling.
Step 2: the preparation of Copper-cladding Aluminum Bar phosphomolybdic acid catalyst
(1) by the active component prepared in step 1 and TiO2Merging is weighed in proportion to be equipped in the crucible of distilled water, and
Constant speed stirs 1~1.5h on magnetic stirring apparatus, and whipping temp is 25~30 DEG C；
(2) by mixture constant rate of drying on magnetic stirring apparatus in step (1), moisture is evaporated, drying temperature be 85~
90℃；
(3) by constant temperature drying in the mixture merging drying box prepared in step (2), the heating temperature of drying box is 100
~110 DEG C；
(4) by the mixture merging Muffle furnace in step (3) after drying 350~450 DEG C of temperature lower calcinations 3~
3.5h obtains Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst after cooling.
The active component phosphomolybdic acid of low-temperature denitration catalyst of the present invention is a kind of heteropoly acid with structure with Keggin,
With more acidic site and active oxide structure, surface acidity and redox property are strong, while catalyst is with larger
(specific surface area is not less than 300m to specific surface area2/ g) TiO2For carrier, the exposed amount in surface-active site is further increased.
Specifically, analysis principle of the invention is as follows:
NH during SCR denitration reaction, in gas phase3Be adsorbed on first catalyst surface active acidic site (
Acid or Lewis acid) on, form the Dissociative species-NH of transition state2,-NH2It is further reacted with the NO in gas phase and generates N2With
H2O.NH at 300-400 DEG C3In-SCR reaction,The NH adsorbed on sour position3It plays a major role；And in low temperature
NH3In-SCR reaction, the NH that is adsorbed on Lewis acid position3It plays a major role.
Inventor passes through lot of experiments, and discovery transition metal Cu doping can increase active oxygen atom in phosphomolybdic acid
Amount generates Cu+/Cu2+Redox promotes the progress of denitration reaction, is conducive to NO Molecular Adsorption in catalyst surface, Cu ion
The Hydrogen Proton that phosphomolybdic acid surface can be substituted in the reaction is biased to low temperature in regulation catalyst B acid/L acid partial navigation acid centre
" Cu-O-Mo " heterodoxy bridging result catalytic center is formed while section, so that redox and the electronic storage capacities of catalyst
It is improved；Surfactant CTAB generates cation CTA in water+, substitute the H in Cu metallic atom surface hydroxyl+, activity
Surfactant oxygenolysis becomes gas discharge when component is calcined, and leaves more L acidic sites, can reach regulation catalyst
The purpose of the ratio of B acid and L acid；CTAB can also reduce the combination energy of Lattice Oxygen, improve surface adsorbed oxygen OβRatio, promote
NO is to NO2Conversion, promote the progress of " quick SCR reaction ".Thus, catalyst of the present invention has preferable low-temperature denitration
Activity.
Due to being usually mingled with a certain amount of SO in industrial smoke2, SO2It is a kind of sour gas, by catalyst surface
Competitive Adsorption occupies active site and active component sulfation can be caused to catalyst activity reduction, therefore can pass through enhancing
Catalyst surface acidity inhibits SO2Absorption and sulfation to active component.Catalyst preparation process of the present invention
It is living to add surface as one of active component for the middle phosphato-molybdic heteropolyacid using surface acidity relatively strong (being better than general inorganic oxacid)
Property agent CTAB and doping metals Cu regulates and controls surface acidity, and then improves the anti-SO of catalyst2The performance poisoned.
Water vapour in flue gas occupies active site by competitive Adsorption and low-temperature denitration catalyst activity is caused to decline
Another key factor.By research, find at any temperature hydrone in catalyst surface there is absorption and desorption equilibrium,
And it is certain that hydrone, which occupies the percentage in catalyst surface active site,.Catalyst of the invention uses during the preparation process
Specific surface area is larger, and (specific surface area is not less than 300m2/ g) Detitanium-ore-type TiO2As carrier, catalyst surface active is increased
The exposed amount in site can be improved denitration activity site absolute quantity of the catalyst under water vapour existence condition, and then improve
The water repelling property of catalyst.
The present invention will be further described with reference to the examples below.
Embodiment 1
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%) and (control of 2g copper nitrate
Cu and Mo molar ratio is 2: 1) being placed in crucible, 40ml distilled water is added to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control is stirred
Mixing temperature is 25 DEG C；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control is dry
Dry temperature is 85 DEG C；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；
4th step obtains active component after cooling to 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 3.0g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
85℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th step,
To 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 2
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%) and 4.7658g copper nitrate
In (control Cu and Mo molar ratio is 3: 1) merging crucible, 40ml distilled water is added to dissolve, constant speed stirs 1h on magnetic stirring apparatus,
Controlling whipping temp is 25 DEG C；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated,
Controlling drying temperature is 85 DEG C；Third step, by constant temperature drying in the mixture merging drying box of second step, controlling drying temperature is
105℃；4th step obtains active group after cooling to 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying
Point.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 2.7g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
85℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th step,
To 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 3
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%) and a certain amount of copper nitrate
In (control Cu and Mo molar ratio is 4: 1) merging crucible, 40ml distilled water is added to dissolve, constant speed stirs 1h on magnetic stirring apparatus,
Controlling whipping temp is 25 DEG C；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated,
Controlling drying temperature is 85 DEG C；Third step, by constant temperature drying in the mixture merging drying box of second step, controlling drying temperature is
105℃；4th step obtains active group after cooling to 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying
Point.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 2.7g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
85℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th step,
To 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 4
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%), 0.1g surfactant
In CTAB (being weighed by phosphomolybdic acid quality 10%) and 4.7658g copper nitrate (control Cu and Mo molar ratio is 3: 1) merging crucible, add
The dissolution of 40ml distilled water, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 25 DEG C；Second step, to the first step
Mixture constant rate of drying on magnetic stirring apparatus, moisture is evaporated, and control drying temperature is 85 DEG C；Third step, by second step
Mixture is placed in constant temperature drying in drying box, and control drying temperature is 105 DEG C；4th step, to the mixture after third step drying
350 DEG C of calcining 3h in Muffle furnace are placed in, obtain active component after cooling.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 2.7g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
85℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th step,
To 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 5
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%), 0.2g surfactant
In CTAB (being weighed by phosphomolybdic acid quality 20%) and 4.7658g copper nitrate (control Cu and Mo molar ratio is 3: 1) merging crucible, add
The dissolution of 40ml distilled water, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 25 DEG C；Second step, to the first step
Mixture constant rate of drying on magnetic stirring apparatus, moisture is evaporated, and control drying temperature is 85 DEG C；Third step, by second step
Mixture is placed in constant temperature drying in drying box, and control drying temperature is 105 DEG C；4th step, to the mixture after third step drying
350 DEG C of calcining 3h in Muffle furnace are placed in, obtain active component after cooling.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 2.8g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
85℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th step,
To 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 6
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%), 0.4g surfactant
In CTAB (being weighed by phosphomolybdic acid quality 40%) and 4.7658g copper nitrate (control Cu and Mo molar ratio is 3: 1) merging crucible, add
The dissolution of 40ml distilled water, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 25 DEG C；Second step, to the first step
Mixture constant rate of drying on magnetic stirring apparatus, moisture is evaporated, and control drying temperature is 85 DEG C；Third step, by second step
Mixture is placed in constant temperature drying in drying box, and control drying temperature is 105 DEG C；4th step, to the mixture after third step drying
350 DEG C of calcining 3h in Muffle furnace are placed in, obtain active component after cooling.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 2.7g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
85℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th step,
To 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 7
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%), 0.2g surfactant
In CTAB (being weighed by phosphomolybdic acid quality 20%) and 4.7658g copper nitrate (control Cu and Mo molar ratio is 3: 1) merging crucible, add
The dissolution of 40ml distilled water, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 25 DEG C；Second step, to the first step
Mixture constant rate of drying on magnetic stirring apparatus, moisture is evaporated, and control drying temperature is 85 DEG C；Third step, by second step
Mixture is placed in constant temperature drying in drying box, and control drying temperature is 100 DEG C；4th step, to the mixture after third step drying
400 DEG C of calcining 3h in Muffle furnace are placed in, obtain active component after cooling.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 2.7g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
85℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 100 DEG C；4th step,
To 400 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 8
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%), 0.2g surfactant
In CTAB (being weighed by phosphomolybdic acid quality 20%) and 4.7658g copper nitrate (control Cu and Mo molar ratio is 3: 1) merging crucible, add
The dissolution of 40ml distilled water, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 25 DEG C；Second step, to the first step
Mixture constant rate of drying on magnetic stirring apparatus, moisture is evaporated, and control drying temperature is 90 DEG C；Third step, by second step
Mixture is placed in constant temperature drying in drying box, and control drying temperature is 110 DEG C；4th step, to the mixture after third step drying
450 DEG C of calcining 3h in Muffle furnace are placed in, obtain active component after cooling.
Step 2: the preparation of catalyst
The first step weighs 0.32g active component (by load capacity 10%) and 3.2g Detitanium-ore-type TiO2(specific surface area is not low
In 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is
25℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is
90℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 110 DEG C；4th step,
To 450 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying, catalyst is obtained after cooling.
Embodiment 9
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.005g PEG (weighing by phosphomolybdic acid quality 0.5%), 0.2g surfactant
In CTAB (being weighed by phosphomolybdic acid quality 20%) and 4.7658g copper nitrate (control Cu and Mo molar ratio is 3: 1) merging crucible, add
The dissolution of 40ml distilled water, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 30 DEG C；Second step, to the first step
Mixture constant rate of drying on magnetic stirring apparatus, moisture is evaporated, and control drying temperature is 87 DEG C；Third step, by second step
Mixture is placed in constant temperature drying in drying box, and control drying temperature is 105 DEG C；4th step, to the mixture after third step drying
350 DEG C of calcining 3h in Muffle furnace are placed in, obtain active component after cooling.
Step 2: the preparation of catalyst
The first step weighs 0.3g active component (by load capacity 10%) and 3g Detitanium-ore-type TiO2(specific surface area is not less than
300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 30
℃；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and control drying temperature is 87
℃；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th step is right
350 DEG C of calcining 3h in mixture merging Muffle furnace after third step drying, obtain catalyst after cooling.
Embodiment 10
Step 1: the preparation of active component
The first step weighs 1g phosphomolybdic acid, 0.01g PEG (weighing by phosphomolybdic acid quality 1%), 0.6g Surfactant CTAB
In (weighing by phosphomolybdic acid quality 60%) and 4.7658g copper nitrate (control Cu and Mo molar ratio is 3: 1) merging crucible, add 40ml
Distilled water dissolution, constant speed stirs 1h on magnetic stirring apparatus, and control whipping temp is 25 DEG C；Second step, the mixing to the first step
Object constant rate of drying on magnetic stirring apparatus, moisture is evaporated, and control drying temperature is 85 DEG C；Third step, by the mixing of second step
Object is placed in constant temperature drying in drying box, and control drying temperature is 105 DEG C；4th step is placed in the mixture after third step drying
450 DEG C of calcining 3h of Muffle furnace obtain active component after cooling.
Step 2: the preparation of catalyst
The first step weighs 0.38g active component (by load capacity 15%) and 2.55g Detitanium-ore-type TiO2(specific surface area is not
Lower than 300m2/ g) it is placed in crucible, add 40ml distilled water to dissolve, constant speed stirs 1h on magnetic stirring apparatus, controls whipping temp
It is 25 DEG C；Second step, mixture constant rate of drying on magnetic stirring apparatus to the first step, moisture is evaporated, and controls drying temperature
It is 85 DEG C；Third step, by constant temperature drying in the mixture merging drying box of second step, control drying temperature is 105 DEG C；4th
Step obtains catalyst after cooling to 350 DEG C of calcining 3h in the mixture merging Muffle furnace after third step drying.
Two, the performance detection of catalyst
Embodiment 11
The catalyst 0.47g prepared in Catalyst Preparation Example 1-10 is weighed respectively, and being respectively placed in internal diameter is 8mm's
Its denitration activity is tested in fixed bed reactors.In test process, with high-purity N2Make carrier gas, control air speed is 15000h-1, control
NO concentration at the inlet is 500ppm, NH3With the molar ratio 1, O of NO2Volumetric concentration is 8%, and Range of measuring temp is 150-350 DEG C, knot
Fruit is as listed by Fig. 1.
It can be seen that from the active testing data in Fig. 1 when there is no SO in simulated flue gas2With condition existing for water vapour
Under, within the temperature range of 200-350 DEG C, utilize the catalyst n O in embodiment 1-10xConversion ratio be above 93%；Its
The denitrification rate of catalyst reaches 80% or more at 150 DEG C in middle embodiment 5,6,9, can stablize at 200-300 DEG C
100%；Wherein from Fig. 1 it can also be seen that the catalyst denitration activity in embodiment 5 is best, NO at 150 DEG CxConversion ratio
It can stablize for 82%, 200-350 DEG C of denitration efficiency 100%.
Embodiment 12
The catalyst 0.47g prepared in Catalyst Preparation Example 5 is weighed respectively, and being respectively placed in internal diameter is consolidating for 8mm
In fixed bed reactor, with high-purity N2Make carrier gas, control air speed is 15000h-1, control NO concentration at the inlet is 500ppm, NH3And NO
Molar ratio be 1, O2Volumetric concentration is 8%, and test temperature is 200 DEG C, has investigated SO2Concentration and water vapour are to NOxConversion ratio
It influences, as a result as listed by Fig. 2.
It can be seen that from the data in Fig. 2 as SO in simulated flue gas2For concentration within the scope of 100-550ppm, water vapour is dense
When degree is 0, the catalyst NOx conversion rate in embodiment 5 is higher than 92%.As SO in simulated flue gas2Concentration is 0, water vapor concentration
In the range of 4-12%vol., the catalyst NOx conversion rate in embodiment 5 is higher than 95%.As SO in simulated flue gas2Concentration is
400ppm, catalyst n O when water vapor concentration is 8%vol., in embodiment 5xConversion ratio is able to maintain when reaction carries out 1h
95% or more, as reaction continues gradually to drop to 50% or so, stop 3h conversion ratio after logical sulphur water flowing can restore to
99% or so.
In conclusion Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst of the present invention low temperature active with higher and excellent
Different sulfur resistive water repelling property.Simultaneously, it should be noted that using the other embodiment of the present invention scheme matched made from urge
Though agent effect is without the anti-SO of embodiment 52It is good with water vapour effect, but compared to the anti-SO of existing catalyst2With water vapour effect
Still it has a clear superiority.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according in this specification
Hold, can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is to preferably explain this hair
Bright principle and practical application, so that skilled artisan be enable to be well understood by and utilize the present invention.The present invention
It is limited only by the claims and their full scope and equivalents.
Claims (9)
1. a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst, it is characterised in that: the catalyst uses Detitanium-ore-type TiO2As load
Body forms active component by phosphomolybdic acid, copper nitrate, polyethylene glycol and cetyl trimethylammonium bromide.
2. a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst according to claim 1, it is characterised in that: the active group
The molar ratio of Cu and Mo is (0~4) in point: 1, the quality of cetyl trimethylammonium bromide accounts for phosphomolybdic acid quality in active component
10~60%, the quality of active component accounts for the 5~15% of catalyst gross mass in catalyst.
3. a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst according to claim 1, it is characterised in that: the anatase
Type TiO2Specific surface area be 300-350m2/g。
4. a kind of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst according to any one of claim 1-3, it is characterised in that:
The preparation process of the active component are as follows: phosphomolybdic acid, copper nitrate, cetyl trimethylammonium bromide and polyethylene glycol are dissolved in steaming
It in distilled water and is uniformly mixed, then through drying, drying and calcination processing up to active component.
5. a kind of preparation method of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst, which comprises the steps of:
Step 1: the preparation of active component
(1) it is dissolved after mixing phosphomolybdic acid, copper nitrate, cetyl trimethylammonium bromide and polyethylene glycol, and constant speed stirring 1~
1.5h；
(2) mixture in step (1) is subjected to constant rate of drying, and moisture is evaporated；
(3) the mixture constant temperature drying that will be prepared in step (2)；
(4) mixture after drying in step (3) is calcined into 3~3.5h, obtains active component after cooling；
Step 2: the preparation of Copper-cladding Aluminum Bar phosphomolybdic acid catalyst
(1) by the active component prepared in step 1 and TiO2It weighs merging in proportion to be equipped in the crucible of distilled water, and in magnetic force
Constant speed stirs 1~1.5h on blender；
(2) mixture in step (1) is subjected to constant rate of drying, and moisture is evaporated；
(3) the mixture constant temperature drying that will be prepared in step (2)；
(4) mixture after drying in step (3) is calcined into 3~3.5h, obtains Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration after cooling
Catalyst.
6. a kind of preparation method of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst according to claim 5, it is characterised in that:
The molar ratio that the quality of PEG is 0.5~1%, the Cu and Mo of molybdenum phosphate quality in the step 1 is (0~4): 1, CTAB and phosphorus
The mass ratio of molybdic acid is (0~0.6): 1, the quality of active component accounts for the 5~15% of catalyst gross mass in step 2.
7. a kind of preparation method of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst according to claim 5 or 6, feature exist
In: in the step 1 and step 2, constant speed whipping temp is 25~30 DEG C, and drying temperature is 85~90 DEG C, and heating temperature is
100~110 DEG C, calcination temperature is 350~450 DEG C.
8. a kind of preparation method of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst according to claim 7, it is characterised in that:
The magnetic stirring apparatus constant speed whipping temp is 25 DEG C, and drying temperature is 85 DEG C on magnetic stirring apparatus, the heating temperature of drying box
It is 105 DEG C, the calcination temperature of Muffle furnace is 350 DEG C.
9. a kind of preparation method of Copper-cladding Aluminum Bar phosphomolybdic acid low-temperature denitration catalyst according to claim 5 or 6, feature exist
In: it is 10% that active component, which accounts for the mass percent of catalyst, in step 2 (1).
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