CN106984300A - A kind of vanadium titanium oxide catalyst and its production and use - Google Patents
A kind of vanadium titanium oxide catalyst and its production and use Download PDFInfo
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- CN106984300A CN106984300A CN201710384707.0A CN201710384707A CN106984300A CN 106984300 A CN106984300 A CN 106984300A CN 201710384707 A CN201710384707 A CN 201710384707A CN 106984300 A CN106984300 A CN 106984300A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
The invention provides a kind of vanadium titanium oxide catalyst and its production and use.The catalyst is in vanadium titanium tungsten oxide catalyst doped with elements Si.The catalyst has the performance of excellent high high-temp stability, and the silicon components especially adulterated are improving V2O5/WO3‑TiO2While catalyst high high-temp stability, on the active without influence of SCR catalyst；The preparation method of vanadium titanium oxide catalyst of the present invention is simple and easy to apply, with very excellent N2Generation selectivity；Meanwhile, Si is nontoxic component, and health and ecological environment will not be caused harm.
Description
Technical field
The present invention relates to environmental catalysis technical field, and in particular to a kind of vanadium titanium oxide catalyst and preparation method thereof and
Purposes, more particularly to a kind of vanadium titanium oxide catalyst of silicon doping and its production and use.
Background technology
Nitrogen oxides (NOx) it is one of major pollutants now in air, its photochemical fog triggered, acid rain, temperature
The environmental problem such as room effect and depletion of the ozone layer and its biology breathing toxicity cause huge to ecological environment and human health
Harm.Therefore, how NO is effectively removedxEmphasis problem as current environmental protection.
With NH under excess oxygen3For reducing agent in the presence of catalyst selective reduction NOxThe nontoxic N of generation2
And H2O, i.e. NH3/ Urea-SCR technologies, are to remove stationary source NOxWith moving source NOxOne of maximally efficient technology.By NH3-SCR
Technology is applied to stationary source NOxCatalytic elimination to be 1970s grow up first in Japan, and in the U.S. and
The countries and regions such as Europe are widely used.Moving source NOxDuring catalytic elimination, due to being equipped with NH3There is certain danger in storage tank
Dangerous, the denitration technology of large-scale practical application is Urea-SCR technologies, i.e., by reducing agent NH3It is replaced with the higher urine of security
Plain solution, its NOxRemove principle and NH3- SCR technology is essentially identical, only increases the hydrolytic process of urea.
In order to meet increasingly strict NOxAbgasgesetz, external numerous automobile and engine manufacturing enterprises are energetically
Carry out Urea-SCR systematic differenceizations to study and started commercialization.At present, nearly all European Truck manufacturer
Urea-SCR technologies are employed to reduce the NO in cargo vehicle tail gasxDischarge.For in the current diesel vehicle recoverable amount of China
Reality based on heavy-duty diesel vehicle, it is contemplated that current fuel qualities and post-processing technology level, the combination skill based on SCR
Art meets the national conditions that emission control standard is especially suitable for China, and numerous domestic enterprise also begins to carry out using Urea-SCR technologies
Tail gas denitration.It can be seen that, NH3/ Urea-SCR technologies are widely used in the NO of exhaust gas from diesel vehiclexRemoval has been trend of the times.
Catalyst system is whole NH3The core and key of-SCR technology.Traditional vanadium-based catalyst systems are in stationary source
Coal-fired flue gas denitration field industrial applications more than 40 years, is the classical formalism in NH3-SCR catalyst, and conduct
European first generation diesel vehicle is applied with SCR catalyst.At home, in view of diesel vehicle state IV stage emission standards
Implement in full, exploitation meets NOxThe Urea-SCR systems and its corollary equipment of purification efficiency are imperative, and research and application are all most
It is that the catalytic component based on vanadium of maturation turns into first choice at this stage.In addition, for the numerous inland river marine diesel of China, its institute
Be generally heavy oil with fuel, complicated component, especially sulfur content are high, can under the conditions of high sulfur content tail gas high-efficient purification NOx's
SCR catalyst system nor catalytic component based on vanadium do not belong to.Therefore, for vanadia-based SCR catalysts produced problem in actual applications
Improved, exploitation is adapted to the efficient stable of China's national situation and is suitable for the SCR catalyst system of complex work condition with weight
The realistic meaning wanted.
The content of the invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a kind of vanadium titanium oxide catalyst, described
Doped with elements Si in vanadium titanium oxide catalyst, with excellent high high-temp stability.
For up to this purpose, the present invention uses following technical scheme：
Doped with elements Si in a kind of vanadium titanium oxide catalyst, the vanadium titanium oxide catalyst.
In the vanadium titanium oxide catalyst of the present invention, elements Si and element V mol ratio are 0.57~28.67, excellent
Elect 0.57~16, more preferably 0.7~27, more preferably 6~25 as, be still more preferably 1~14, such as 0.7,
0.9th, 1.6,8.9,14.3,15.0,26.7,27.1 etc..
Vanadium titanium oxide catalyst of the present invention is urging including but not limited to elemental vanadium and element titanyl compound
Agent, the oxide of transition metal, described vanadium titanium oxide catalyst such as can also include element W and/or elements Mo
It is a kind of catalyst well-known to those skilled in the art, the selection of its various elements and the ratio of each element can be by this areas
The professional knowledge that technical staff grasps according to oneself is selected, and those skilled in the art are simultaneously it will be clearly understood that described is various
In transition metal oxide, the valence state of metallic element is alternatively, such as WOp, it is mixed for different valence state W oxide
Body, such as W5+And W6+Mixture；MoOq, it is different valence state Mo oxide mixture, such as Mo5+And Mo6+Mixing
Thing；FeOr, it is different valence state Fe oxide mixture, such as Fe2+And Fe3+Mixture, etc..
Preferably, the vanadium titanium oxide catalyst is V2O5/SiO2-(MoO3)x-(WO3)1-x-TiO2, wherein, x is selected from 0
~1, preferably x are selected from 0 or 1.
Preferably, counted using the quality of metal oxide as 100%, in the vanadium titanium oxide catalyst of Si doping, V2O5Contain
Measure as 0.5~5wt%, more preferably preferably 0.5~3wt%, more preferably 0.9~5wt%, 1~4wt%, for example
0.7wt%, 1.2wt%, 1.8wt%, 2.4wt%, 3.6wt%, 4.7wt%, 4.9wt% etc.；SiO2Content for 1~
5wt%, preferably 2~4wt%, more preferably 1~3wt%, more preferably 3~5wt%, such as 1.7wt%,
2.5wt%, 3.7wt%, 4.1wt%, 4.9wt% etc.；WO3Content be 9.5~9.9wt%, preferably 9.5~9.7wt%,
More preferably 9.6~9.9wt%, such as 9.6wt%, 9.7wt%, 9.8wt%；Surplus is TiO2。
" comprising " of the present invention, it is intended that it can also include other components, these other components in addition to the component
Assign the catalyst different characteristics.The element such as can add scandium (Sc), titanium (Ti), chromium (Cr), in addition, this hair
Bright described " comprising ", may be replaced by enclosed " being " or " by ... constitute ".
Wherein, vanadium titanium oxide catalyst of the present invention is prepared by vanadium precursor solution by infusion process.
Infusion process, is one of the method for manufacturing solid catalyst, will one or more of active components pass through impregnated carrier
It is supported on the method on carrier.Infusion process is typically to be contacted with carrier with the aqueous solution of metallic salt, inhales metal salt solution
Attached or storage in the carrier, removes superfluous solution, then through the obtained catalyst of drying, calcining and activation.
Preferably, V presomas are water-soluble V, the element V valence states in the preparation process of catalyst of the present invention
The present invention is not limited, can be+trivalent ,+4 valencys ,+5 valencys etc., described water-soluble V is that prior art or new technology are disclosed
Any water-soluble V salt.
Preferably, the one kind or at least two of the vanadium presoma in sodium metavanadate, ammonium metavanadate and potassium metavanadate
Mixture, typical but unrestricted is combined as sodium metavanadate；Ammonium metavanadate；Potassium metavanadate；Sodium metavanadate and ammonium metavanadate
Mixture；The mixture of potassium metavanadate and sodium metavanadate；The mixture of ammonium metavanadate and potassium metavanadate；Sodium metavanadate and metavanadic acid
The mixture of ammonium, potassium metavanadate.
The second object of the present invention is to provide a kind of preparation method of vanadium titanium oxide catalyst, comprised the following steps：
1) vanadium precursor solution is prepared；
2) to step 1) add titanium tungsten powder and titanium tungsten silica flour mixed carrier in obtained vanadium precursor solution, stirring load,
Dry, be calcined, the vanadium titanium oxide catalyst of Si doping is made.
Step 1) in, the one kind or at least two of the vanadium presoma in sodium metavanadate, ammonium metavanadate and potassium metavanadate
The mixture planted.
Step 2) in, in the titanium tungsten powder and titanium tungsten silica flour mixed carrier the weight ratio of titanium tungsten powder and titanium tungsten silica flour for 9~
1, preferably 8~2, more preferably 7~3, more preferably 9~4, be still more preferably 6~1, such as 8.7,6.3,
4.2nd, 3,2.8,1.1 etc.；
Carrier of the present invention is titanium dioxide, and the titanium dioxide is with titanium tungsten powder and titanium tungsten silica flour mixed carrier
What form was added.
Preferably, the quality of the titanium tungsten powder and titanium tungsten silica flour mixed carrier is molten for (0.5~6) g/10mL vanadium presomas
Liquid, i.e., per 10mL vanadium precursor solutions in the titanium tungsten powder that adds and titanium tungsten silica flour mixed carrier quality be 0.5~6g, 0.7~
4.2g, 1~3g, 2~3g, 0.6g, 2.1g, 3.3g, 4.1g, 5.8g etc.；It is highly preferred that the titanium tungsten powder is mixed with titanium tungsten silica flour
The quality of carrier is (0.8~5) g/10mL vanadium precursor solutions；It is further preferred that the titanium tungsten powder is mixed with titanium tungsten silica flour
The quality of carrier is 4g/10mL vanadium precursor solutions.
Step 2) in, it is described stirring load temperature be 20~30 DEG C, such as 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25
DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C, 30 DEG C etc., further preferred 25 DEG C；The time of the stirring load is 1~2h, for example
1h、1.1h、1.2h、1.3h、1.4h、1.5h、1.6h、1.7h、1.8h、1.9h、2h。
Drying is operation well-known to those skilled in the art, and drying means disclosed in any prior art or new technology is equal
Available for the present invention, typical but non-limiting example has forced air drying, infra-red drying, microwave drying, natural drying etc..
Preferably, step 2 of the present invention) drying is selected from heat drying or natural drying, preferred heat drying, further
It is preferred that any one in convection oven drying, infra-red drying or microwave drying.
Preferably, the temperature of the drying be 100~120 DEG C, such as 100 DEG C, 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C,
105℃、106℃、107℃、108℃、109℃、110℃、111℃、112℃、113℃、114℃、115℃、116℃、117
DEG C, 118 DEG C, most preferably 119 DEG C, 120 DEG C, 110 DEG C；Drying temperature is too low, and drying is not thorough, and the time cost spent is high；
Drying temperature is too high, easily causes the change of the property of filter cake to be dried；The time of the drying be 9~12h, such as 9h,
10h, 11h, 12h, most preferably 10h.
It is calcined (Roasting), is the course of reaction that solid material is carried out under conditions of high temperature is not melted, can be with
There are oxidation, pyrolysis, reduction, halogenation etc., be technology well-known to those skilled in the art.Preferably, the temperature of the roasting is
400~500 DEG C, such as 400 DEG C, 410 DEG C, 420 DEG C, 430 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C,
500 DEG C, the time of the roasting is 3~8h, such as 3h, 4h, 5h, 6h, 7h, 8h.
Those skilled in the art can be selected from roasting apparatus according to actual conditions, it is preferable that step 2) in, the roasting exists
Carried out in Muffle furnace.
The third object of the present invention, which is also resided in, provides a kind of purposes of vanadium titanium oxide catalyst, and vanadium titanium oxide is catalyzed
The method that agent is applied to selective catalyst reduction of nitrogen oxides.
Preferably, vanadium titanium oxide catalyst of the invention includes applied to the method for selective catalyst reduction of nitrogen oxides
Following steps：
A) vanadium titanium oxide catalyst is carried on exhaust gas channel；
B) tail gas is passed through in exhaust pipe and carries out SCR；
Preferably, step a) process is：Vanadium titanium oxide catalyst is coated in tail gas stream all in the form of coating
On the wall surface in road, the wall surface of the tail gas circulation passage preferably can for example have with fixed catalyst in the material on its surface
There is cavernous material, typical but non-limiting example has porous resin, many hollow fibers, ceramics or the gold with honeycomb
Metal products etc., the honeycomb being preferably made with ceramics or metal.In actual conditions, if catalyst is fixed on tail gas circulation
There is installation difficulty on the wall surface of passage, the wall surface of such as passage does not have cellular material, then, it is provided by the present invention
Catalyst spherical or tabular can be made be placed in exhaust gas channel, when tail gas flows through the catalyst being placed in exhaust gas channel,
It can be reacted with the reducibility gas of presence.
SCR denitration reaction is to depend on ammonia (NH3) it is used as reducing agent and NOxChemically react, to reach the purpose of denitration,
Therefore, ammonia is exactly the direct reducer of denitration reaction.The acquisition of ammonia should be those skilled in the art according to prior art
Or new technology can be obtained, the acquisition methods of current existing ammonia mainly have two kinds：Urea method prepares ammonia and liquid ammonia process for caustic soda purification
Prepare ammonia.Described urea method, which prepares ammonia, can include hydrolyzing urea or being pyrolyzed urea obtaining ammonia；Described liquid ammonia process for caustic soda purification
Prepare ammonia liquefied ammonia is evaporated into ammonia.Those skilled in the art are it will be clearly understood that the acquisition methods of ammonia of the present invention
Above two method is not limited to, the disclosed method for obtaining ammonia of any prior art and new technology is used equally for this hair
It is bright.
Preferably, step b) process is：Reducing agent is sprayed into the upstream of vanadium titanium oxide catalyst, tail gas is passed through,
Reduction reaction is carried out after reducing agent and the tail gas mixing；
Preferably, the reducing agent uses ammonia or urea；
Preferably, the tail gas is moving source gas containing nitrogen oxide or stationary source gas containing nitrogen oxide；
Preferably, the tail gas is exhaust gas from diesel vehicle, coal-fired plant flue gas or industrial furnace smoke.
Catalyst of the present invention is a kind of vanadium titanium oxide catalyst of Si doping, for improving ammonia selective catalyst
The high high-temp stability of the vanadium titanium catalyst of nitrogen oxides reduction.The vanadium titanium oxide catalyst of the silicon doping of the present invention is to vanadium
The high high-temp stability of titanium catalyst is improved, and specifically used titanium tungsten powder prepares the catalysis of vanadium titanium with titanium tungsten silica flour mixed carrier
Agent, so as to improve its high high-temp stability, and does not influence the denitration activity and selectivity of vanadium titanium catalyst.The vanadium titanium of the present invention
The preparation method of oxide catalyst adds Si in vanadium titanium oxide catalyst, simple and easy to apply, improves the high temperature that vanadium titanium is urged
Heat endurance, extends service life when it is used for exhaust gas from diesel vehicle catalytic purification of nitroxide.
Compared with prior art, beneficial effects of the present invention are：
(1) the vanadium titanium oxide catalyst of silicon of the invention doping has excellent high high-temp stability, especially adulterates
Silicon components improving V2O5/SiO2-WO3-TiO2While the high high-temp stability of catalyst, to its SCR catalyst activity
Without influence；
(2) preparation method is simple and easy to apply, does not change the production technology of catalytic component based on vanadium；
(3) there is very excellent N2Generation selectivity；
(4) Si newly added is nontoxic component, and health and ecological environment will not be caused harm.
Brief description of the drawings
Fig. 1 is the catalyst activity evaluation result schematic diagram of embodiments of the invention 2；
Fig. 2 is the catalyst activity evaluation result schematic diagram of embodiments of the invention 4；
Fig. 3 is the catalyst XRD spectrum of embodiments of the invention 5；
Fig. 4 is the catalyst activity evaluation result schematic diagram after heat ageing of embodiments of the invention 7；
Fig. 5 is the catalyst XRD spectrum after heat ageing of embodiments of the invention 8.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
Different V are prepared using infusion process2O5The catalytic component based on vanadium of content, uses business titanium tungsten powder powder DT52 (WO3Content
10wt%) with business silicon titanium tungsten powder DT58 (SiO2Content 10wt%, WO3Content 9wt%), using ammonium metavanadate as vanadic salts, V2O5It is negative
Carrying capacity is 3.5%, by presoma salt be dissolved as the aqueous solution and it is well mixed after, then press into the solution default part by weight
Addition DT58 and DT52 mixed carriers, DT58 and DT52 part by weight are respectively 1:9、1:4、1:1 and 4:1, liquor capacity with
Titanium tungsten powder mass ratio is 2.5:1 (mL/g), is continuously stirred at 30 DEG C after 2h, rotary evaporation, and the catalyst of acquisition is put into
Stayed overnight in baking oven in 100 DEG C of drying, being most calcined 3h in 500 DEG C of air through Muffle furnace afterwards is made powder catalyst.It will be made
Catalyst grind, sieving, take 40-60 mesh standby, referred to as mixed carrier catalytic component based on vanadium 3.5V/DT58-DT52 (1:9)、
3.5V/DT58-DT52(1:4)、3.5V/DT58-DT52(1:1) with 3.5V/DT58-DT52 (1:4).
Comparative example 1
It is identical with the experiment condition of embodiment 1, but without using mixed carrier, and respectively using titanium tungsten powder DT52 and titanium tungsten silicon
Powder DT58 prepares catalytic component based on vanadium, referred to as 3.5V/DT52 and 3.5V/DT58.
Embodiment 2
With 3.5V/DT58-DT52,3.5V/DT52 and 3.5V/DT58 catalyst made from embodiment 1 and comparative example 1 certainly
NH is carried out on the micro fixed-bed reactor of system3Selective Catalytic Reduction of NOxThe investigation of reactivity.The usage amount of catalyst is
300mg, the composition of reaction mixture gas is：[NO]=[NH3]=500ppm, [O2]=5%, N2Make Balance Air, total gas flow rate is
500mL/min, air speed is 50000h-1, 150-450 DEG C of reaction temperature.NO and NH3And accessory substance N2O、NO2Utilize infrared-gas
Pond is determined, and catalyst activity evaluation result is as shown in Figure 1.
Fig. 1 data display, catalytic component based on vanadium contrast prepared by pure carrier, 3.5V/DT52 low temperature active is better than 3.5V/
DT58；Catalytic component based on vanadium contrast prepared by mixed carrier, DT58:DT52 is 1:4、1:1 and 4:1 mixed carrier catalyst it is low
Warm activity is close to 3.5V/DT52, better than 3.5V/DT58, illustrates that the mixed carrier of appropriate Si doping has substantially no effect on VWTi catalysis
The activity of agent.
Embodiment 3
First prepare DT58 and DT52 mixed carrier DT58-DT52：By 1:DT58 is dissolved in by 1 part by weight with DT52
Ionized water, liquor capacity is 2.5 with titanium tungsten powder mass ratio:1 (mL/g), is continuously stirred at 30 DEG C after 2h, rotary evaporation, will
The sample of acquisition is put into baking oven to be stayed overnight in 100 DEG C of drying, and being most calcined 3h in 500 DEG C of air through Muffle furnace afterwards is made powdered
Mixed carrier, referred to as DT58-DT52.
It is identical with the experiment condition of embodiment 1, using above-mentioned DT58-DT82 mixed carriers, prepare, V2O5Load capacity is
3.5% mixed carrier catalytic component based on vanadium, referred to as 3.5V/DT58-DT52.
Embodiment 4
With 3.5V/DT58-DT52,3.5V/DT52 and 3.5V/DT58 catalyst made from embodiment 3 and comparative example 1 certainly
NH is carried out on the micro fixed-bed reactor of system3Selective Catalytic Reduction of NOxThe investigation of reactivity.The usage amount of catalyst is
300mg, the composition of reaction mixture gas is：[NO]=[NH3]=500ppm, [O2]=5%, N2Make Balance Air, total gas flow rate is
500mL/min, air speed is 50000h-1, 150-450 DEG C of reaction temperature.NO and NH3And accessory substance N2O、NO2Utilize infrared-gas
Pond is determined.Catalyst activity evaluation result is as shown in Figure 2.
Fig. 2 data display NH of fresh catalyst3- SCR catalytic activity：The catalytic component based on vanadium pair prepared with pure carrier
Than 3.5V/DT58-DT52 low temperature active is closer to 3.5V/DT58, less than 3.5V/DT52.
Embodiment 5
3.5V/DT58-DT52,3.5V/DT52 and 3.5V/ made from embodiment 3 and comparative example 1 are determined by XRD
The phase structure of DT58 catalyst.Using Dutch PANalytical X ' Pert Pro type X-ray diffractometers come determination sample
Diffracting spectrum.Under the conditions of tube voltage 40kV and tube current 40mA, using Cu K alpha rays, λ=0.15406nm, in 5-90 ° of model
It is scanned in enclosing, sweep speed is 8 °/min, scanning step is 0.07 °, and catalyst XRD spectrum is as shown in Figure 3.
From Fig. 3 from the point of view of the XRD results of fresh catalyst, mixed carrier catalyst is similar to pure carried catalyst, only goes out
Detitanium-ore-type TiO is showed2(101) characteristic peak of crystal face.
Embodiment 6
By 3.5V/DT58-DT52,3.5V/DT52 and 3.5V/DT58 catalyst made from embodiment 3 and comparative example 1 through horse
Not stove is calcined 36h in 650 DEG C of air, obtains the catalyst after high Hygrothermal Aging, referred to as 3.5V/DT58-DT52A, 3.5V/
DT52A and 3.5V/DT58A.
Embodiment 7
With 3.5V/DT58-DT52A, 3.5V/DT52A and 3.5V/DT58A catalyst made from embodiment 6 homemade micro-
NH is carried out on type fixed bed reactors3Selective Catalytic Reduction of NOxThe investigation of reactivity.The usage amount of catalyst is 300mg,
The composition of reaction mixture gas is：[NO]=[NH3]=500ppm, [O2]=5%, N2Make Balance Air, total gas flow rate is 500mL/
Min, air speed is 50000h-1, 150-450 DEG C of reaction temperature.NO and NH3And accessory substance N2O、NO2Surveyed using infrared-gas pond
Fixed, the catalyst activity evaluation result after heat ageing is as shown in Figure 4.
The activity of 3.5V/DT58-DT52A after Fig. 4 data display, heat ageing is closer to 3.5V/DT58A, hence it is evident that high
In 3.5V/DT52A, preferable heat endurance is shown, illustrates that Si doping can significantly improve the heat endurance of VWTi catalyst.
Embodiment 8
3.5V/DT58-DT52A, 3.5V/DT52A and 3.5V/ made from embodiment 3 and comparative example 1 are determined by XRD
The phase structure of DT58A catalyst.Using Dutch PANalytical X ' Pert Pro type X-ray diffractometers come determination sample
Diffracting spectrum.Under the conditions of tube voltage 40kV and tube current 40mA, using Cu K alpha rays, λ=0.15406nm, in 5-90 ° of model
It is scanned in enclosing, sweep speed is 8 °/min, scanning step is 0.07 °, catalyst XRD spectrum such as Fig. 5 institutes after heat ageing
Show.
XRD results in Fig. 5 show that the catalyst after heat ageing all occurs in that Detitanium-ore-type TiO to some extent2
(101) crystal face, rutile TiO2(110) crystal face and WO3The characteristic peak of crystalline phase, illustrates Detitanium-ore-type TiO under high temperature2Carrier
Sinter and TiO2From Detitanium-ore-type to rutile-type phase transformation, surface WOxSpecies are reunited.3.5V/DT58-DT52 XRD results connect
Nearly 3.5V/DT58, and 3.5V/DT52 rutile TiOs2(110) characteristic peak of crystal face be significantly stronger than 3.5V/DT58-DT52 with
3.5V/DT58, illustrates that Si doping can suppress the TiO in VWTi catalyst2Carrier is at high temperature from anatase to the phase of rutile
Become, so as to improve its heat endurance.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of vanadium titanium oxide catalyst, it is characterised in that doped with elements Si in the vanadium titanium oxide catalyst.
2. vanadium titanium oxide catalyst according to claim 1, it is characterised in that in the vanadium titanium oxide catalyst,
Elements Si and element V mol ratio are 0.57~28.67；
Preferably, the vanadium titanium oxide catalyst is V2O5/SiO2-(MoO3)x-(WO3)1-x-TiO2, wherein, x is selected from 0~1,
It is preferred that x is selected from 0 or 1；
Preferably, counted using the quality of metal oxide as 100%, in the vanadium titanium oxide catalyst of Si doping, V2O5Content be
0.5~5wt%, SiO2Content be 1~5wt%, WO3Content be 9.5~9.9wt%.
3. vanadium titanium oxide catalyst according to claim 1 or 2, it is characterised in that the vanadium titanium oxide catalyst
Prepared by vanadium precursor solution by infusion process；
Preferably, the one kind or at least two of the vanadium presoma in sodium metavanadate, ammonium metavanadate and potassium metavanadate is mixed
Compound.
4. the preparation method of a kind of vanadium titanium oxide catalyst as described in one of claim 1-3, it is characterised in that including such as
Lower step：
1) vanadium precursor solution is prepared；
2) to step 1) add titanium tungsten powder and titanium tungsten silica flour mixed carrier in obtained vanadium precursor solution, stirring load, dry,
Roasting, is made the vanadium titanium oxide catalyst of Si doping.
5. preparation method according to claim 4, it is characterised in that step 1) in, the vanadium presoma is selected from metavanadic acid
Sodium or potassium metavanadate.
6. the preparation method according to claim 4 or 5, it is characterised in that step 2) in, the titanium tungsten powder and titanium tungsten silica flour
The weight ratio of titanium tungsten powder and titanium tungsten silica flour is 9~1 in mixed carrier；
Preferably, the quality of the titanium tungsten powder and titanium tungsten silica flour mixed carrier is (0.5~6) g/10mL vanadium precursor solutions；
Preferably, the quality of the titanium tungsten powder and titanium tungsten silica flour mixed carrier is (0.8~5) g/10mL vanadium precursor solutions；
Preferably, the quality of the titanium tungsten powder and titanium tungsten silica flour mixed carrier is 4g/10mL vanadium precursor solutions.
7. the preparation method according to one of claim 4-6, it is characterised in that step 2) in, the temperature of the stirring load
Spend for 20~30 DEG C, the time of the stirring load is 1~2h；
Preferably, the temperature of the drying is 100~120 DEG C, and the time of the drying is 9~12h；
Preferably, the temperature of the roasting is 400~500 DEG C, and the time of the roasting is 3~8h.
8. the preparation method according to one of claim 4-7, it is characterised in that step 2) in, the roasting is in Muffle furnace
It is middle to carry out.
9. a kind of purposes of vanadium titanium oxide catalyst, it is characterised in that by the vanadium titanium oxide described in one of claim 1-3
The method that catalyst is applied to selective catalyst reduction of nitrogen oxides.
10. purposes according to claim 9, it is characterised in that the vanadium titanium oxide catalyst is applied to selectivity and urged
The method for changing nitrogen oxides reduction comprises the following steps：
A) vanadium titanium oxide catalyst is carried on exhaust gas channel；
B) tail gas is passed through in exhaust pipe and carries out SCR；
Preferably, step a) process is：Vanadium titanium oxide catalyst is coated in tail gas circulation passage in the form of coating
On wall surface, the wall surface of the tail gas circulation passage preferably has the honeycomb that ceramics or metal are made；
Preferably, step a) process is：Vanadium titanium oxide catalyst is made into spherical or tabular to be placed in exhaust gas channel；
Preferably, step b) process is：Reducing agent is sprayed into the upstream of vanadium titanium oxide catalyst, tail gas is passed through, it is described
Reduction reaction is carried out after reducing agent and tail gas mixing；
Preferably, the reducing agent uses ammonia or urea；
Preferably, the tail gas is moving source gas containing nitrogen oxide or stationary source gas containing nitrogen oxide；
Preferably, the tail gas is exhaust gas from diesel vehicle, coal-fired plant flue gas or industrial furnace smoke.
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| CN107774242A (en) * | 2017-10-25 | 2018-03-09 | 宝鸡市渭滨区怡鑫金属加工厂 | A kind of catalyst carrier prepared using titanium oxide as raw material |
| CN108031466A (en) * | 2017-11-14 | 2018-05-15 | 浙江浙能催化剂技术有限公司 | Have the low SO of anti-arsenic poisoning and wide active temperature windows concurrently2Oxygenation efficiency SCR denitration and preparation method thereof |
| CN108863849A (en) * | 2018-08-22 | 2018-11-23 | 泰州百力化学股份有限公司 | A kind of technique of one-step synthesis method 2- hydroxy-phenylformonitrile |
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