CN108435220A - A kind of combined type SCR denitration that anti-poisoning capability is strong and its application - Google Patents
A kind of combined type SCR denitration that anti-poisoning capability is strong and its application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
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- 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
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- 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
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Abstract
The present invention relates to a kind of combined type SCR denitration that anti-poisoning capability is strong and its applications, belong to technical field of atmospheric pollution control.The strong combined type SCR denitration of anti-poisoning capability of the invention is two-part combination catalyst；By CePO/TiO2And V2O5‑WO3/TiO2It constitutes, wherein CePO and V2O5‑WO3For active component, TiO2For carrier, its be anatase crystal；The CePO/TiO2And V2O5‑WO3/TiO2Mass ratio be 3：1~1：3.Relatively traditional vanadium tungsten titanium catalyst, combination catalyst after optimization provided by the invention can under broader temperature range efficient elimination nitrogen oxides, there is stronger alkali resistant, anti-arsenic poisoning ability simultaneously, and the manufacturing cost of denitrating catalyst can be reduced, there is preferable industrial application value.Two-part combination catalyst provided by the invention can be applicable to monoblock type SCR denitration, include the purification of the tail gas nitrogen oxides such as various coal-burning power plants, boiler for fixed combustion device, have preferable industrial application value.
Description
Technical field
The invention belongs to technical field of atmospheric pollution control, and in particular to a kind of combined type SCR that anti-poisoning capability is strong is de-
Denox catalyst and its application.
Background technology
Nitrogen oxides (NOx) it is one of major pollutants of atmosphere pollution, a large amount of discharges can not only form acid rain but also can be with
Hydrocarbon combines and forms photochemical fog, and serious harm is brought to natural environment and human production activity.China's nitrogen oxidation
Object pollution is extremely serious.2012, China's discharged nitrous oxides total amount reached 2337.8 ten thousand tons.Wherein, there are about nearly 70% to come from
In the direct burning of coal, coal-fired power plant discharge capacity accounts for 50% or so of coal-fired total release.If not taking effective control
Measure processed, China NOxDischarge capacity is up to 30,000,000 tons in the year two thousand twenty.Therefore, eliminating the work of nitrogen oxides becomes very tight
It forces to make peace necessity.There are many method of NO_x elimination, wherein with NH3For reducing agent Selective Catalytic Reduction of NOx, i.e. NH3-SCR
(4NH3+4NO+O2→4N2+6H2O) technology is current most effective stationary source NOxTechnology for eliminating, this mainly has benefited from its height
Efficiency and highly selective.Commercialized NH3SCR catalyst is V2O5-WO3/TiO2, optimum activity temperature is 350 DEG C or so, is belonged to
Middle-temperature section catalyst.Although V2O5-WO3/TiO2Catalyst has denitration efficiency height, anti-SO2The advantages that poisoning capability is strong, and exist
It is used widely in flue gas denitration, but the catalyst system still has many deficiencies：Contain noxious material V2O5If using
V occurs in the process2O5It falls off, entering has bio-toxicity in environment；Operation temperature window is relatively narrow, high temperature when generate a large amount of temperature
Room gas N2O；High temperature easy-sintering thermal stability is poor；Alkali resistant and anti-arsenic ability are weaker；(ammonium paratungstate is vanadium tungsten higher price
110000 yuan/ton, 80000 yuan/ton of ammonium metavanadate) the shortcomings of.Therefore, many researchers are dedicated to developing novel with height
NH3SCR activity, wide operation temperature window, high-temperature stability are good, anti-poisoning capability is strong without vanadium or the cheap denitration catalyst of low vanadium
Agent.
Publication No. CN106215931A Chinese patent applications disclose a kind of low vanadium wide active temperature (denitrating catalyst height
Active temperature windows extend to 250-420 DEG C) window denitrating catalyst and preparation method thereof.By the vanadium (＜ for controlling low content
1%), to which in the cost for reducing catalyst to a certain degree, the low content of vanadium within the scope of this is not easy to cause secondary pollution, but should
Catalyst still has high temperature easy-sintering, the problem of thermostabilization difference.The Chinese patent of Publication No. CN103638939A provides
A kind of composition metal sulfate system catalyst for denitrating flue gas and preparation method thereof, the invention is using titanium dioxide as carrier, cerous sulfate
For active component, transition metal sulfate shows preferable denitration activity at 300-500 DEG C, widens as co-catalyst
High temperature denitration activity temperature window.The Chinese patent of Publication No. CN101642715A is provided restores nitrogen for selective catalysis
The cerium pyrophosphate catalyst of oxide.The catalyst can have higher selection also in 200-600 DEG C wider of temperature range
Former nitrogen oxides activity, stability, especially have higher generation N at high temperature2Selectivity.Document (chemcatchem,
2010,2 (11)：1416-1419) report a kind of novel Ce-P-O catalysis that can be used for ammonia selective catalysis nitrogen oxides reduction
Agent, shows higher NO conversion ratios, which has certain resistance to vapor and SO2In ability and preferable alkali resistant
Toxicity energy.But this kind of non-vanadium system SCR denitration mostly only not sulfur-bearing, it is anhydrous under the conditions of just show higher denitration
Water resistant is used for a long time in ability, sulfur resistance is deteriorated.In addition in SCR denitration system actual moving process, the As in flue gas cigarette ash
And alkalosis is to cause business V2O5-WO3/TiO2One of common cause of catalyst inactivation.Therefore, novel tool is researched and developed
There is high NH3It is cheap de- that SCR activity, wide operation temperature window, high-temperature stability are good, anti-poisoning (As, alkali) ability is strong
Denox catalyst is very necessary.
Invention content
The object of the present invention is to provide a kind of combined type SCR denitration that anti-poisoning capability is strong and its application, this hairs
Bright combined type SCR denitration can under broader temperature range efficient elimination nitrogen oxides, while having more
Strong alkali resistant, anti-arsenic poisoning ability, and the manufacturing cost of denitrating catalyst can be reduced, there is preferable commercial Application valence
Value.
To achieve the goals above, technical scheme of the present invention is specific as follows：
A kind of combined type SCR denitration that anti-poisoning capability is strong is two-part combination catalyst；
By CePO/TiO2And V2O5-WO3/TiO2It constitutes, wherein CePO and V2O5-WO3For active component, TiO2For carrier,
It is anatase crystal.
In the above-mentioned technical solutions, the CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 3：1~1：3.
In the above-mentioned technical solutions, the CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 1：1.
In the above-mentioned technical solutions, the CePO/TiO2In：
The presoma of Ce is cerous nitrate, cerous sulfate or cerium chloride；
The presoma of P is the mixture of phosphoric acid or pyrophosphoric acid or the two；
The mass percent of each component is with carrier TiO2Quality on the basis of：
Wherein, the content of Ce is 5%~20%, Ce：The molar ratio of P is 0.8~1.2.
In the above-mentioned technical solutions, the V2O5-WO3/TiO2In：
V2O5Presoma be ammonium metavanadate；
WO3Presoma be ammonium paratungstate；
The mass percent of each component is with carrier TiO2Quality on the basis of：
Wherein, V2O5Content be 0.5%~2%, WO3Content be 3~8%.
The present invention also provides a kind of application for the combined type SCR denitration that anti-poisoning capability is strong, the combined type SCR
Denitrating catalyst is suitable for monoblock type SCR denitration, and type of feed is：The CePO/TiO2It is seated in air inlet, institute
State V2O5-WO3/TiO2It is seated in gas outlet.
In the above-mentioned technical solutions, the CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 3：1~1：3.
In the above-mentioned technical solutions, the CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 1：1.
In the above-mentioned technical solutions, the CePO/TiO2And V2O5-WO3/TiO2It is by the way that shaping assistant is added through mixed respectively
The cellular monolithic catalyst that refining, aging, extrusion molding, drying and roasting obtain.
In the above-mentioned technical solutions, the shaping assistant include inorganic binder, organic binder, plasticizer, releasing agent,
Moisturizer and reinforcing agent.
The beneficial effects of the invention are as follows：
Combined type SCR denitration provided by the invention, outstanding feature are：It is a kind of two-part combination catalysis
Agent, comprehensive utilization of C ePO/TiO2The stronger alkali resistant of catalyst, anti-arsenic ability, high-temperature stability is good, the relatively low (cerium oxide of cost
12500 yuan/ton) and V2O5-WO3/TiO2Active high, the stronger feature of resistance to SO_2, improves full vanadium denitration catalyst (V2O5-
WO3/TiO2) temperature window is narrow, poor high temperature stability, alkali resistant, anti-arsenic poisoning ability are weak, and cost is higher and non-vanadium base denitration is urged
The sulfur resistance of agent is bad, the not high disadvantage of activity.
Relatively traditional vanadium tungsten titanium catalyst, the combined type SCR denitration after optimization provided by the invention can be more
Efficient elimination nitrogen oxides under wide temperature range, while there is stronger alkali resistant, anti-arsenic poisoning ability, and can drop
The manufacturing cost of low denitrating catalyst has preferable industrial application value.
In addition, combined type SCR denitration provided by the invention can be applicable to monoblock type SCR denitration,
Include the purification of the tail gas nitrogen oxides such as various coal-burning power plants, boiler for fixed combustion device, there is preferable commercial Application
Value.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is CePO/TiO2The XRD spectra of catalyst.
Fig. 2 is V2O5-WO3/TiO2The XRD spectra of catalyst.
Fig. 3 is CePO/TiO2, V2O5-WO3/TiO2And the NH of combination S CR denitrating catalysts3SCR activity figure.
Fig. 4 is the alkali resistant poisoning performance schematic diagram of the combination S CR denitrating catalysts of the present invention.
Fig. 5 is the anti-arsenic poisoning performance schematic diagram of the combination S CR denitrating catalysts of the present invention.
Specific implementation mode
The present invention invention thought be：The present invention is bad for existing vanadium based denitration catalyst high-temperature stability, and alkali resistant resists
The not strong disadvantage of the weak and non-vanadium based denitration catalyst sulfur poisoning resistance of arsenic poisoning ability, it is each using Ce-P systems and V-W systems
It is combined, optimizes from advantage, develop two-part combination catalyst, it can the efficient elimination under wider temperature range
Nitrogen oxides has preferable anti-poisoning capability, and can reduce the cost of denitrating catalyst, has preferable commercial Application
Value.
The present invention is described in detail below in conjunction with the accompanying drawings.
The present invention provides a kind of combined type SCR denitration that anti-poisoning capability is strong, is two-part combination catalyst；
By CePO/TiO2And V2O5-WO3/TiO2It constitutes, which uses anatase crystal TiO2For carrier, respectively with the phosphoric acid of Ce
Salt CePO and V2O5-WO3For active component.It is preferred that two-part combination catalyst type of feed is CePO/TiO2In air inlet,
V2O5-WO3/TiO2In gas outlet.Concrete operations can be based on smoke characteristic to CePO/TiO2And V2O5-WO3/TiO2Group composition and division in a proportion
Example (mass ratio) is 3：1~1：It is adjusted in 3 ranges, preferred mass ratio is 1:1.
In the combined type SCR denitration of the present invention, the CePO/TiO2The presoma of Ce is nitric acid in catalyst
The presoma of cerium, cerous sulfate or cerium chloride, phosphorus is phosphoric acid, pyrophosphoric acid or the two mixture.The mass percent of each component with
Carrier TiO2Quality on the basis of：Wherein, the content of Ce is 5%~20%, Ce：P (molar ratio) is 0.8~1.2.
The first patent of the Publication No. CN101642715A of applicant in this case, provides for nitrogen oxides selective catalysis
The cerium pyrophosphate catalyst and preparation method of reduction, wherein describing the preparation method and property in relation to cerium composite phosphorus oxide in detail
Matter, so, about the phosphatic preparation method of Ce, which is incorporated herein by reference by the present invention.
In the combined type SCR denitration of the present invention, the V2O5-WO3/TiO2Catalyst, wherein V2O5Presoma
For ammonium metavanadate, WO3Presoma be ammonium paratungstate, the mass percent of each component is with carrier TiO2Quality on the basis of：
V2O5Content be 0.5%~2%, WO3Content be 3~8%, the preparation method of catalyst using generally acknowledged infusion process side
Method, in anatase crystal TiO2Carrier surface introduces active component (V2O5And WO3), it can improve activearm by stirring dipping
The dispersibility divided.
The combined type SCR denitration of the present invention can also amplify that (present invention is with cellular whole applied to monoblock type
Illustrated for catalyst) SCR denitration, the CePO/TiO2And V2O5-WO3/TiO2It is to be molded by being added respectively
The cellular monolithic catalyst that auxiliary agent is obtained through mixing, aging, extrusion molding, drying and roasting.Two are loaded in Benitration reactor
A catalyst bed CePO/TiO2And V2O5-WO3/TiO2, two layers of catalyst loading pattern is CePO/TiO2In air inlet, V2O5-
WO3/TiO2It, can be according to smoke characteristic CePO/TiO in gas outlet2And V2O5-WO3/TiO2Portfolio ratio (mass ratio) 3：
1~1：It is adjusted in 3 ranges, preferred mass ratio is 1:1.
It is prepared by combination S CR denitrating catalysts
CePO/TiO2It prepares：
With reference to the first patent of Publication No. CN101642715A, cerium precursor (cerous nitrate, cerous sulfate or cerium chloride) is taken
It is soluble in water, cerium precursor aqueous solution is poured into the container containing phosphoric acid or pyrophosphoric acid, after stirring is completely dissolved, urine is added
TiO is added after urea is entirely molten in element2, 95-100 DEG C is then begun to warm up, solution is evaporated, then is placed in 110 DEG C of baking ovens and does
Dry 12h is finally roasted 5 hours at 500 DEG C, broken and sieve as CePO/TiO that grain size is 40~60 mesh after product cooling2It urges
Agent；The CePO/TiO2Catalyst, Ce contents are 5%~20%, Ce：P (molar ratio) is 0.8~1.2.
V2O5-WO3/TiO2It prepares：
The preparation of catalyst uses step impregnation method, i.e., in TiO2Area load WO3Supported V again afterwards2O5, prepare V2O5-
WO3/TiO2Catalyst, maceration extract are ammonium metavanadate, ammonium paratungstate aqueous solution, and preparation process, which adds a certain amount of oxalic acid, to be contributed to
Dissolving.By TiO2Powder is heated to 60-70 DEG C of stirring 4h, then in an oven in 105 DEG C of dryings in secondary tungsten acid ammonium solution
500 DEG C of 12h, Muffle furnace roasting 5h, calcining matter are heated to 60-70 DEG C of stirring after cooling, crushing in ammonium metavanadate aqueous solution
4h, it is broken and to sieve as grain size be 40~60 after product cooling in 105 DEG C of dry 12h, 500 DEG C of roasting 5h of Muffle furnace in baking oven
Purpose V2O5-WO3/TiO2Catalyst.The V2O5-WO3/TiO2Catalyst, V2O5Content is 0.5%~2%, WO3Content is 3
~8%.
The combination of combination S CR denitrating catalysts and activity rating
Two-part combination catalyst type of feed is CePO/TiO2In air inlet, V2O5-WO3/TiO2It, can be according in gas outlet
According to smoke characteristic CePO/TiO2And V2O5-WO3/TiO2Portfolio ratio (mass ratio) 3：1~1：It is adjusted in 3 ranges.
Catalyst, which is positioned in tubular fixed-bed reactor, to react, and tests the SCR activity of catalyst, the following institute of experiment condition
Show：
NO：500ppm, NH3：500ppm, O2：5%, Ar are Balance Air, total gas flow rate 100mL/min, reaction velocity
(GHSV) it is 20000h-1.Reaction temperature section is from 200 DEG C to 550 DEG C.NO and NH3Use Mass Spectrometer Method.
The combination of monoblock type SCR denitration and activity rating
CePO/TiO2And V2O5-WO3/TiO2Powder be separately added into various shaping assistants (inorganic binder, organic binder,
Plasticizer, releasing agent, moisturizer and reinforcing agent etc.) obtained through mixing, aging, extrusion molding, drying and roasting it is cellular whole
Body catalyst.By CePO/TiO2、V2O5-WO3/TiO2Honeycomb monolith catalyst is placed in reactor according to certain combination
In, it is passed through typical boiler smoke, specific composition is 500mL/m3NO, 400mL/m3SO2, 15% CO2, 7% H2O,
Remaining is N2, air speed 20000h-1, NOx/NH3It is 1.1, carries out SCR activity evaluation.
The technical solution further illustrated the present invention below by embodiment, but the present invention is not limited to following examples.
Embodiment 1：
It is poured into containing in 1.40g phosphoric acid after weighing the dissolving of 6.20g cerous nitrates, then 8.57g is added in stirring into solution
10.0gTiO is added after urea is entirely molten in urea2Then carrier is begun to warm up to 95 DEG C, solution stirring is evaporated, then is placed in
110 DEG C of oven drying 12h are finally roasted 5 hours at 500 DEG C, and after product cooling, it is 40~60 purposes to be crushed and sieve as grain size
CePO/TiO2Catalyst, wherein Ce contents are carrier TiO220%, Ce of quality：P (molar ratio) is 1：1.
It weighs 1.0g oxalic acid to be added in the aqueous solution of the ammonium paratungstate containing 0.55g, stirring and dissolving, by 10.0gTiO2Powder exists
It is heated to 60-70 DEG C in secondary tungsten acid ammonium solution and stirs 4h, then in an oven in 500 DEG C of 105 DEG C of dry 12h, Muffle furnace roastings
5h is burnt, calcining matter is after cooling, crushing in the heated in water solution of the ammonium metavanadate containing 0.13g to 60-70 DEG C of stirring 4h, baking oven
In 105 DEG C of dry 12h, 500 DEG C of roasting 5h of Muffle furnace are broken and sieve as V that grain size is 40~60 mesh after product cooling2O5-
WO3/TiO2Catalyst.Wherein V2O5Content is carrier TiO21%, WO of quality3Content is carrier TiO2The 5% of quality.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is CePO/TiO2In upper (air inlet), V2O5-WO3/TiO2(gas outlet), CePO/TiO under2And V2O5-WO3/
TiO2Mass ratio is 1: 1.Then simulated flue gas situation carries out active appraisal experiment under normal pressure, and the flue gas of simulation is by NOx, NH3,
O2, Ar composition gaseous mixture be passed through tubular type reactor catalysis reaction.Wherein, NO：500ppm, NH3：500ppm, O2：5%, Ar are flat
Weigh gas, total gas flow rate 100mL/min, and reaction velocity (GHSV) is 20000h-1.Reaction temperature section is from 200 DEG C to 550
℃.On-line gas analysis is carried out using mass spectrograph, to obtain NOxConversion ratio.NOxConversion ratio refer to table 1.
Embodiment 2：
The preparation method is the same as that of Example 1 for graded catalyst.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is CePO/TiO2In upper (air inlet), V2O5-WO3/TiO2(gas outlet), CePO/TiO under2And V2O5-WO3/
TiO2Mass ratio is 1: 2.Catalyst activity evaluation means are the same as embodiment 1, NOxConversion ratio refer to table 1.
Embodiment 3：
The preparation method is the same as that of Example 1 for graded catalyst.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is CePO/TiO2In upper (air inlet), V2O5-WO3/TiO2(gas outlet), CePO/TiO under2And V2O5-WO3/
TiO2Mass ratio is 1: 3.Catalyst activity evaluation means are the same as embodiment 1, NOxConversion ratio refer to table 1.
Embodiment 4：
The preparation method is the same as that of Example 1 for graded catalyst.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is V2O5-WO3/TiO2In upper (air inlet), CePO/TiO2(gas outlet), CePO/TiO under2And V2O5-WO3/
TiO2Mass ratio is 1: 1.Catalyst activity evaluation means are the same as embodiment 1, NOxConversion ratio refer to table 1.
Table 1：NH of the catalyst under various combination mode3SCR activity
| Sample | 200℃ | 250℃ | 300℃ | 350℃ | 400℃ | 450℃ | 500℃ | 550℃ |
| CePO/TiO2 | 10.2% | 50.3% | 90.9% | 96.3% | 96.5% | 97.5% | 96.8% | 95.2% |
| V2O5-WO3/TiO2 | 35.6% | 78.2% | 96.1% | 96.4% | 96.7% | 94.5% | 88.2% | 70.8% |
| Embodiment 1 | 15.4% | 65.8% | 95.3% | 96.1% | 96.6% | 97.4% | 95.4% | 90.2% |
| Embodiment 2 | 25.2% | 68.7% | 94.2% | 96.5% | 96.7% | 95.3% | 93.3% | 85.2% |
| Embodiment 3 | 30.3% | 75.3% | 95.5% | 96.2% | 96.8% | 94.3% | 88.7% | 75.3% |
| Embodiment 4 | 34.5% | 80.4% | 96.2% | 97.7% | 93.1% | 85.0% | 70.2% | 50.6% |
As it can be seen from table 1 two-part combination catalyst type of feed is CePO/TiO2In upper (air inlet), V2O5-
WO3/TiO2Gained catalyst activity is best when (gas outlet) under, and temperature window is wider.
Embodiment 5：
It is poured into containing in 0.79g pyrophosphate solutions after weighing the dissolving of 2.66g cerium chlorides, then stirring is added into solution
10.0gTiO is added after urea is entirely molten in 4.28g urea2Then carrier is begun to warm up to 95 DEG C, solution stirring is evaporated, then
110 DEG C of oven drying 12h are placed in, are finally roasted 5 hours at 500 DEG C, after product cooling, it is 40~60 to be crushed and sieve as grain size
Purpose CePO/TiO2Catalyst, wherein Ce are carrier TiO210%, Ce of quality：P (molar ratio) is 0.8：1.
It weighs 1.0g oxalic acid to be added in the aqueous solution of the ammonium paratungstate containing 0.55g, stirring and dissolving, by 10.0gTiO2Powder exists
It is heated to 60-70 DEG C in secondary tungsten acid ammonium solution and stirs 4h, then in an oven in 500 DEG C of 105 DEG C of dry 12h, Muffle furnace roastings
5h is burnt, calcining matter is after cooling, crushing in the heated in water solution of the ammonium metavanadate containing 0.25g to 60-70 DEG C of stirring 4h, baking oven
In 105 DEG C of dry 12h, 500 DEG C of roasting 5h of Muffle furnace are broken and sieve as V that grain size is 40~60 mesh after product cooling2O5-
WO3/TiO2Catalyst.Wherein V2O5Content is carrier TiO22%, WO of quality3Content is carrier TiO2The 5% of quality.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is CePO/TiO2In upper (air inlet), V2O5-WO3/TiO2(gas outlet), CePO/TiO under2And V2O5-WO3/
TiO2Mass ratio is 1: 1.Then simulated flue gas situation carries out active appraisal experiment under normal pressure, and the flue gas of simulation is by NOx, NH3,
O2, Ar composition gaseous mixture be passed through tubular type reactor catalysis reaction.Wherein, NO：500ppm, NH3：500ppm, O2：5%, Ar are flat
Weigh gas, total gas flow rate 100mL/min, and reaction velocity (GHSV) is 20000h-1.Reaction temperature section is from 200 DEG C to 550
℃.On-line gas analysis is carried out using mass spectrograph, to obtain NOxConversion ratio.NOxConversion ratio refer to table 2.
Embodiment 6：
Graded catalyst preparation method is the same as embodiment 4.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is V2O5-WO3/TiO2In upper (air inlet), CePO/TiO2(gas outlet), V under2O5-WO3/TiO2And CePO/
TiO2Mass ratio is 1: 1.Catalyst activity evaluation means are the same as embodiment 1, NOxConversion ratio refer to table 2.
Embodiment 7：
Graded catalyst preparation method is the same as embodiment 4.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is V2O5-WO3/TiO2In upper (air inlet), CePO/TiO2(gas outlet), V under2O5-WO3/TiO2And CePO/
TiO2Mass ratio is 1: 3.Catalyst activity evaluation means are the same as embodiment 1, NOxConversion ratio refer to table 2.
Table 2：NH of the catalyst under various combination mode3SCR activity
| Sample | 200℃ | 250℃ | 300℃ | 350℃ | 400℃ | 450℃ | 500℃ | 550℃ |
| CePO/TiO2 | 6.2% | 30.7% | 70.2% | 95.3% | 96.5% | 97.2% | 96.7% | 97.0% |
| V2O5-WO3/TiO2 | 50.4% | 87.1% | 94.5% | 95.1% | 96.6% | 97.1% | 85.4% | 65.6% |
| Embodiment 5 | 25.5% | 50.2% | 88.5% | 95.4% | 95.1% | 97.0% | 90.8% | 80.6% |
| Embodiment 6 | 45.7% | 85.3% | 90.7% | 96.9% | 97.2% | 80.1% | 65.6% | 40.4% |
| Embodiment 7 | 15.2% | 35.8% | 75.2% | 90.0% | 95.1% | 97.8% | 90.0% | 85.2% |
From table 2 it can be seen that two-part combination catalyst activity is affected by type of feed and mass ratio, CePO/
TiO2In upper (air inlet), V2O5-WO3/TiO2Under (gas outlet), and mass ratio is 1：Gained catalyst activity is best when 1.
Embodiment 8：
It is poured into containing in 0.42g phosphoric acid solutions after weighing the dissolving of 1.44g cerous sulfates, then stirring is added into solution
10.0gTiO is added after urea is entirely molten in 2.14g urea2Then carrier is begun to warm up to 95 DEG C, solution stirring is evaporated, then
110 DEG C of oven drying 12h are placed in, are finally roasted 5 hours at 500 DEG C, after product cooling, it is 40~60 to be crushed and sieve as grain size
Purpose CePO/TiO2Catalyst, wherein Ce contents are carrier TiO25%, Ce of quality：P (molar ratio) is 1：1.2.
It weighs 1.0g oxalic acid to be added in the aqueous solution of the ammonium paratungstate containing 0.55g, stirring and dissolving, by 10.0gTiO2Powder exists
It is heated to 60-70 DEG C in secondary tungsten acid ammonium solution and stirs 4h, then in an oven in 500 DEG C of 105 DEG C of dry 12h, Muffle furnace roastings
5h is burnt, calcining matter is after cooling, crushing in the heated in water solution of the ammonium metavanadate containing 0.07g to 60-70 DEG C of stirring 4h, baking oven
In 105 DEG C of dry 12h, 500 DEG C of roasting 5h of Muffle furnace are broken and sieve as V that grain size is 40~60 mesh after product cooling2O5-
WO3/TiO2Catalyst.Wherein V2O5Content is carrier TiO20.5%, WO of quality3Content is carrier TiO2The 5% of quality.
It is divided to prepare two kinds of catalyst to the constant temperature zone that upper and lower two catalyst beds are loaded on reactor, two layers of catalysis
Agent type of feed is CePO/TiO2In upper (air inlet), V2O5-WO3/TiO2(gas outlet), CePO/TiO under2And V2O5-WO3/
TiO2Mass ratio is 1: 1.Then simulated flue gas situation carries out active appraisal experiment under normal pressure, and the flue gas of simulation is by NOx, NH3,
O2, Ar composition gaseous mixture be passed through tubular type reactor catalysis reaction.Wherein, NO：500ppm, NH3：500ppm, O2：5%, Ar are flat
Weigh gas, total gas flow rate 100mL/min, and reaction velocity (GHSV) is 20000h-1.Reaction temperature section is from 200 DEG C to 550
℃.On-line gas analysis is carried out using mass spectrograph, to obtain NOxConversion ratio.NOxConversion ratio refer to table 3.
Table 3：NH of the catalyst under various combination mode3SCR activity
| Sample | 200℃ | 250℃ | 300℃ | 350℃ | 400℃ | 450℃ | 500℃ | 550℃ |
| CePO/TiO2 | 2.6% | 20.2% | 50.8% | 80.6% | 95.1% | 96.0% | 95.2% | 96.3% |
| V2O5-WO3/TiO2 | 15.2% | 40.5% | 80.1% | 96.4% | 96.4% | 90.6% | 78.8% | 55.2% |
| Embodiment 8 | 10.9% | 35.2% | 70.4% | 90.8% | 95.0% | 93.2% | 89.5% | 80.1% |
From table 3 it can be seen that the combined rear activity of catalyst prepared by different formulations is better than the catalyst of one-component.
Embodiment 9：
Weigh 10KgCePO/TiO2(Ce 5%, Ce：P=1：1) powder, 0.5Kg Nano-meter SiO_2s2(1-10nm), mixing are equal
It is even, add 0.20Kg stearic acid, 0.15Kg hypromellose, 0.10Kg polyethylene glycol oxides, 0.60Kg glass fibres, side
Add waterside to stir, and ammonium hydroxide is added to adjust pug pH=7.5, by aging one day of obtained pug, aging good mud after stirring evenly
Material is put into vacuum-extruder, by grinding tool integral extrusion at cellular green body.Green body is in 30 DEG C, the condition that relative humidity is 90%
Lower drying 4 days, then 40 DEG C, relative humidity be 70% under conditions of it is 3 days dry, 50 DEG C, under conditions of relative humidity 40%
Dry 2 days, 65 DEG C, relative humidity it is 2 days dry under conditions of being 20%.By 580 DEG C of calcining 12h of dried green body to get to
CePO/TiO2Integral honeycombed catalyst finished product.
V2O5-WO3/TiO2(V2O5For 1%, WO3It is same as above for 5%) integral honeycombed catalyst preparation method.
By comparative sample V2O5-WO3/TiO2Full vanadium base honeycomb monolith catalyst and CePO/TiO2+V2O5-WO3/TiO2Two sections
Formula honeycomb integral catalyst is according to CePO/TiO2In upper (air inlet), V2O5-WO3/TiO2The combination of (gas outlet) under
(CePO/TiO2And V2O5-WO3/TiO2Mass ratio is 1: 1) being placed in reactor, be passed through typical boiler smoke, specific composition is
500mL/m3NO, 400mL/m3SO2, 15% CO2, 7% H2O, remaining is N2, air speed 20000h-1, NOx/NH3For
1.1, carry out SCR activity evaluation, NOxConversion ratio refer to table 4.
Table 4：The NH of combined type monolithic catalyst3SCR activity
From table 4, it can be seen that the NH of combined type monolithic catalyst3SCR activity is substantially better than V2O5-WO3/TiO2。
Embodiment 10：
CePO/TiO prepared by embodiment 82+V2O5-WO3/TiO2Two-part honeycomb integral catalyst and V2O5-WO3/
TiO2Two sections of full vanadium honeycomb integral catalysts are handled respectively in 400 DEG C of KCl steam, until XRF detections K contents account for the total matter of catalyst
After the 1% of amount, then active testing is carried out, for active testing with described in embodiment 8, Activity Results are as shown in table 5 below, the results showed that
CePO/TiO2+V2O5-WO3/TiO2Two-part combination catalyst has stronger alkali resistant poisoning capability than full vanadium catalyst.
Table 5：Alkali is to combined type SCR denitration NH3The influence of SCR activity
Embodiment 11：
CePO/TiO prepared by embodiment 82+V2O5-WO3/TiO2Two-part honeycomb integral catalyst and V2O5-WO3/
TiO2Two sections of full vanadium honeycomb integral catalysts are respectively at 400 DEG C of As2O3It is handled in steam, until to account for catalyst total for XRF detections As contents
After the 1% of quality, then active testing is carried out, for active testing with described in embodiment 8, Activity Results are as shown in table 6 below, the results showed that
CePO/TiO2+V2O5-WO3/TiO2Two-part combination catalyst has stronger anti-arsenic poisoning ability than full vanadium catalyst.
Table 6：Arsenic is to combined type SCR denitration NH3The influence of SCR activity
Fig. 1 and Fig. 2 is respectively CePO/TiO2And V2O5-WO3/TiO2The XRD spectra of catalyst.As can be seen from the figure：
CePO/TiO2And V2O5-WO3/TiO2Only has carrier anatase TiO in the XRD spectra of catalyst2Diffraction maximum, illustrate cerium phosphorus
Hydrochlorate and vanadium, the tungsten high degree of dispersion on carrier.
Fig. 3 is CePO/TiO2, V2O5-WO3/TiO2And the NH of combination S CR denitrating catalysts3SCR activity figure.From figure
As can be seen that the two-part combination catalyst of the present invention has broader temperature window.
Fig. 4 is the alkali resistant poisoning performance of combination S CR denitrating catalysts.It can be seen from the figure that being urged relative to full vanadium base SCR
Agent, two-part combination catalyst of the invention have stronger alkali resistant poisoning capability.
Fig. 5 is the anti-arsenic poisoning performance of combination S CR denitrating catalysts.It can be seen from the figure that being urged relative to full vanadium base SCR
Agent, two-part combination catalyst of the invention have stronger anti-arsenic poisoning ability.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of combined type SCR denitration that anti-poisoning capability is strong, which is characterized in that it is two-part combination catalyst；
By CePO/TiO2And V2O5-WO3/TiO2It constitutes, wherein CePO and V2O5-WO3For active component, TiO2For carrier, its be
Anatase crystal.
2. the strong combined type SCR denitration of anti-poisoning capability according to claim 1, which is characterized in that described
CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 3：1~1：3.
3. the strong combined type SCR denitration of anti-poisoning capability according to claim 1, which is characterized in that described
CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 1：1.
4. the strong combined type SCR denitration of anti-poisoning capability according to claim 1-3 any one, feature exist
In the CePO/TiO2In：
The presoma of Ce is cerous nitrate, cerous sulfate or cerium chloride；
The presoma of P is the mixture of phosphoric acid or pyrophosphoric acid or the two；
The mass percent of each component is with carrier TiO2Quality on the basis of：
Wherein, the content of Ce is 5%~20%, Ce：The molar ratio of P is 0.8~1.2.
5. the strong combined type SCR denitration of anti-poisoning capability according to claim 1-3 any one, feature exist
In the V2O5-WO3/TiO2In：
V2O5Presoma be ammonium metavanadate；
WO3Presoma be ammonium paratungstate；
The mass percent of each component is with carrier TiO2Quality on the basis of：
Wherein, V2O5Content be 0.5%~2%, WO3Content be 3~8%.
6. a kind of application for the combined type SCR denitration that anti-poisoning capability described in claim 1 is strong, which is characterized in that
The combined type SCR denitration is suitable for monoblock type SCR denitration, and type of feed is：The CePO/TiO2Dress
It fills out in air inlet, the V2O5-WO3/TiO2It is seated in gas outlet.
7. the application of the strong combined type SCR denitration of anti-poisoning capability according to claim 6, which is characterized in that
The CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 3：1~1：3.
8. the application of the strong combined type SCR denitration of anti-poisoning capability according to claim 6, which is characterized in that
The CePO/TiO2And V2O5-WO3/TiO2Mass ratio be 1：1.
9. the application of the strong combined type SCR denitration of anti-poisoning capability according to claim 6-8 any one,
It is characterized in that, the CePO/TiO2And V2O5-WO3/TiO2Be respectively by be added shaping assistant through mixing, aging, be extruded into
The cellular monolithic catalyst that type, drying and roasting obtain.
10. the application of the strong combined type SCR denitration of anti-poisoning capability according to claim 9, which is characterized in that
The shaping assistant includes inorganic binder, organic binder, plasticizer, releasing agent, moisturizer and reinforcing agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832807A (en) * | 2022-06-02 | 2022-08-02 | 东方凯特瑞(成都)环保科技有限公司 | SCR denitration catalyst and preparation method thereof |
| CN116673047A (en) * | 2023-04-07 | 2023-09-01 | 浙江大学 | Catalyst capable of cooperatively removing nitrogen oxides and CO, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441406A (en) * | 2011-10-19 | 2012-05-09 | 西北化工研究院 | Catalyst for removing nitric oxides and preparation method of catalyst |
| CN102600832A (en) * | 2012-02-28 | 2012-07-25 | 北京化工大学 | Combined catalyst for improving denitration performance and application thereof |
| CN104998680A (en) * | 2015-07-13 | 2015-10-28 | 煤炭工业济南设计研究院有限公司 | Low temperature denitration catalyst for anti-SO2 and H2O poisoning and preparation method of same |
| CN107233912A (en) * | 2017-06-23 | 2017-10-10 | 中国科学院长春应用化学研究所 | A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof |
| US20170312740A1 (en) * | 2016-04-27 | 2017-11-02 | Ford Global Technologies, Llc | Phosphorus tolerant catalyst washcoat structure |
-
2018
- 2018-04-26 CN CN201810385527.9A patent/CN108435220A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441406A (en) * | 2011-10-19 | 2012-05-09 | 西北化工研究院 | Catalyst for removing nitric oxides and preparation method of catalyst |
| CN102600832A (en) * | 2012-02-28 | 2012-07-25 | 北京化工大学 | Combined catalyst for improving denitration performance and application thereof |
| CN104998680A (en) * | 2015-07-13 | 2015-10-28 | 煤炭工业济南设计研究院有限公司 | Low temperature denitration catalyst for anti-SO2 and H2O poisoning and preparation method of same |
| US20170312740A1 (en) * | 2016-04-27 | 2017-11-02 | Ford Global Technologies, Llc | Phosphorus tolerant catalyst washcoat structure |
| CN107233912A (en) * | 2017-06-23 | 2017-10-10 | 中国科学院长春应用化学研究所 | A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LI FEI,ET AL: "A novel Ce-P-O catalyst for the selective catalytic reduction of NO with NH3", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832807A (en) * | 2022-06-02 | 2022-08-02 | 东方凯特瑞(成都)环保科技有限公司 | SCR denitration catalyst and preparation method thereof |
| CN116673047A (en) * | 2023-04-07 | 2023-09-01 | 浙江大学 | Catalyst capable of cooperatively removing nitrogen oxides and CO, and preparation method and application thereof |
| CN116673047B (en) * | 2023-04-07 | 2024-04-12 | 浙江大学 | Catalyst capable of cooperatively removing nitrogen oxides and CO, and preparation method and application thereof |
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