CN102000585B - A kind of denitrating catalyst and preparation method thereof - Google Patents
A kind of denitrating catalyst and preparation method thereof Download PDFInfo
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- CN102000585B CN102000585B CN201010254249.7A CN201010254249A CN102000585B CN 102000585 B CN102000585 B CN 102000585B CN 201010254249 A CN201010254249 A CN 201010254249A CN 102000585 B CN102000585 B CN 102000585B
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Abstract
The present invention relates to a kind of denitrating catalyst and preparation method thereof, belong to the environment protection catalytic Material Field used in atmosphere pollution, specifically a kind of flue gas selective catalytic reduction denitrating catalyst utilizing stone coal ash to prepare and preparation method thereof.This denitrating catalyst, it consists of: carrier and active component composition, described carrier is anatase-type nanometer titanium dioxide, and described active component is the mixed-metal oxides of vanadium, aluminium, iron.The present invention has that component is reasonable in design, level of activity is high, not easily lost efficacy, cheap, reliable and stable, technological design rationally, the advantage of low, the constant product quality of energy-conserving and environment-protective, cost.
Description
Technical field
The present invention relates to a kind of denitrating catalyst and preparation method thereof, belong to the environment protection catalytic Material Field used in atmosphere pollution, specifically a kind of flue gas selective catalytic reduction denitrating catalyst utilizing stone coal ash to prepare and preparation method thereof.
Background technology
Nitrogen oxide (NO
x) be one of the Air Pollutants that countries in the world are generally acknowledged.It damages the ozone layer, and forms acid rain and photochemical fog, influence ecological environment, and harm humans is healthy, and current nitrogen oxide reduction of discharging has been subject to people and has paid close attention to greatly.Selective catalytic reduction (SCR) gas denitrifying technology has the advantage such as catalytic activity, selective and heat endurance and be widely used in Flue Gas Denitrification Engineering both domestic and external preferably because of it, also becomes the mainstream technology of coal-fired flue gas denitration.Activity due to catalyst determines the denitration efficiency of SCR flue gas denitrification system largely, therefore the catalyst of good activity becomes the key of SCR gas denitrifying technology.Meanwhile, because catalyst active component addition is large and expensive, therefore how to develop the hot issue that efficient, cheap SCR catalyst for denitrating flue gas has become domestic and international denitrating flue gas field.
The patent of the relevant SCR catalyst for denitrating flue gas applied at present has multiple, and as can be seen from disclosed patent, carrier and the active component of all kinds of SCR catalyst for denitrating flue gas use are different.Vanadium class catalyst and the large class of non-vanadium class catalyst two can be divided into according to catalyst main active.Vanadium class catalyst as patent (CN101284229) be titanium-base ceramics is flooded titanium zirconium vanadium complex sol after, then drying, roasting are prepared from.Patent (CN101352679) adopts step impregnation method, and with ceramic honey comb, metallic plate, glass corrugated plating for carrier, active component is V
2o
5, WO
3and ZrO
2, one or more of simultaneously adding the rare earth metals such as appropriate Pr, Nd are co-catalyst component.
Non-vanadium class catalyst is for main active with other transition metal or rare-earth oxide, if patent (CN101507920) adopts chromium and cerium to be key component, realize active constituent loading by coprecipitation or infusion process, then obtain low-temperature denitration catalyst through calcination.Patent (CN101234345) is flooded by Al-base ceramic after Alumina gel drying and roasting prepares aluminum oxide coating layer, then flood cerium salt and doped metal salt composite solution prepares active catalytic components coating.
Although SCR catalyst for denitrating flue gas prepared by existing catalyst preparation technology can obtain higher denitration activity, but owing to being all the technique of the finished product raw material Kaolinite Preparation of Catalyst precursor liquid and then the generation catalyst after suitable proportioning that adopt active component corresponding, the cost of catalyst is remained high; Meanwhile, existing SCR catalyst for denitrating flue gas to the moisture in flue gas and sulfur dioxide more responsive, when moisture and content of sulfur dioxide higher time, denitration activity decline.Therefore, while guarantee catalyst denitration activity, how to reduce the preparation cost of catalyst and improve its stability, becoming the significant problem that solution is needed in China's denitrating flue gas field badly.
Summary of the invention
Technical problem to be solved by this invention is to provide that a kind of component is reasonable in design, level of activity is high, not easily lost efficacy, cheap, reliable and stable denitrating catalyst.
Another technical problem to be solved by this invention be to provide a kind of technological design rationally, the preparation method of the denitrating catalyst of low, the constant product quality of energy-conserving and environment-protective, cost.
It is this denitrating catalyst that the present invention solves the problems of the technologies described above adopted technical scheme, and it consists of: carrier and active component composition, described carrier is anatase-type nanometer titanium dioxide, and described active component is the mixed-metal oxides of vanadium, aluminium, iron.
As preferably, the mass percent of anatase-type nanometer titanium dioxide of the present invention is 80 ~ 97.5% of gross weight, and the mass percent of the mixed-metal oxides of described vanadium, aluminium, iron is 2.5 ~ 20% of gross weight.
As preferably, the mixed-metal oxides of vanadium of the present invention, aluminium, iron, wherein V
2o
5mass percent be 0.5 ~ 6%, Al of gross weight
2o
3mass percent be 1 ~ 8%, Fe of gross weight
2o
3mass percent be 1 ~ 6% of gross weight.
The present invention solves the problems of the technologies described above the preparation method of adopted technical scheme or a kind of denitrating catalyst, and preparation process is:
A, stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μm, obtain powdery stone coal ash.
B, to be joined in sulfuric acid solution by powdery stone coal ash and carry out stirring acidleach, leaching time is 2 ~ 4 hours, and solid-liquid weight ratio is 1:2 ~ 4, after filtration pickle liquor.
C, in pickle liquor, add excessive (NH
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:5 ~ 8, at the uniform velocity stir in adition process, pickle liquor is cooled to room temperature, cool time is 2 ~ 4 hours, ammonia-alum crystalline deposit, filtration obtains thick ammonia-alum and containing vanadium mother liquid, obtains smart ammonia-alum after thick ammonia-alum being adopted the impurity such as reduction-recrystallization method secondary crystallization removing iron ion wherein.
D, heating are containing vanadium mother liquid to separating out intermediate salt crystal, more after filtration, obtain intermediate salt after washing, filtrate reclaim sulfuric acid is reused.
E, preparation mass concentration are the oxalic acid solution of 5 ~ 10%, and then add intermediate salt, solid-liquid weight ratio is 1:5 ~ 20, stirs until intermediate salt is dissolved completely under temperature is 50 ~ 60 DEG C of conditions, forms grass green solution.
F, grass green solutions overnight is left standstill after, add Powdered dried anatase-type nanometer titanium dioxide, under at the uniform velocity stirring condition, dipping is after 3 ~ 6 hours, and the white slurry obtained puts into ultrasonic cleaner ultrasonic immersing 2 ~ 4 hours, obtains impregnation product.
G, by after dry for impregnation product, roasting, obtained denitrating catalyst.
As preferably, the sulfuric acid volumetric concentration in step b of the present invention is 40 ~ 50%, and acidleach temperature is 100 ~ 120 DEG C.
As preferably, heat in steps d of the present invention containing vanadium mother liquid to 120 ~ 150 DEG C, 2 ~ 4 hours retention times.The intermediate salt main component separated out in solution is the sulfate of vanadium, aluminium, iron.
As preferably, the dipping in step f of the present invention, the solid-liquid volume ratio of dipping is 1:1 ~ 2.
As preferably, the drying in step g of the present invention carries out in air dry oven, and baking temperature is 110 DEG C, and drying time is 4 ~ 8 hours.
As preferably, the roasting in step g of the present invention carries out under temperature is 350 ~ 450 DEG C of conditions, and roasting time is 3 ~ 6 hours.
The present invention compares with existing technology, has the following advantages and feature:
1, combined with SCR catalyst for denitrating flue gas preparation technology by stone coal ash process for extracting vanadium, technique is simple, workable, is applicable to scale application.
2, can carry out comprehensive reutilization to the metal in stone coal ash, consumption of raw materials is low, has good environmental benefit.
3, while the catalyst prepared by ensureing has NO_x Reduction by Effective activity, the cost of catalyst is significantly reduced.
4, in use procedure, denitration activity declines few, and steady quality, the life-span is long.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 40%, and acidleach temperature is 110 DEG C, leaching time 3 hours, and solid-liquid weight ratio is 1:3, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:5, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 2 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 120 DEG C, and the time is 4 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 10%, and then add intermediate salt, solid-liquid weight ratio is 1:15, under 60 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1.2, and the time is 4 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 2 hours.
7, dry, roasting
Dry 5 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 4 hours under 400 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 2: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid of 50%, and acidleach temperature is 120 DEG C, leaching time 4 hours, and solid-liquid weight ratio is 1:4, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:7.At the uniform velocity stir in adition process, use running water solution to be cooled to room temperature, 3 hours cool times.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 150 DEG C, and the time is 3 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 10%, and then add intermediate salt, solid-liquid weight ratio is 1:20, under 50 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1.5, and the time is 4 hours.Then obtained white slurry is put into supersonic wave cleaning machine ultrasonic immersing 2 hours.
7, dry, roasting
Dry 6 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 3 hours under 450 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 3: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 42%, and acidleach temperature is 100 DEG C, leaching time 3 hours, and solid-liquid weight ratio is 1:3, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:6, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 2 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 150 DEG C, and the time is 2 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 8%, and then add intermediate salt, solid-liquid weight ratio is 1:16, under 60 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1.3, and the time is 4 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 2 hours.
7, dry, roasting
Dry 4 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 3 hours under 380 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 4: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 46%, and acidleach temperature is 115 DEG C, leaching time 4 hours, and solid-liquid weight ratio is 1:2, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:7, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 3 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 140 DEG C, and the time is 2 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 7%, and then add intermediate salt, solid-liquid weight ratio is 1:12, under 50 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1.4, and the time is 5 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 3 hours.
7, dry, roasting
Dry 5 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 4 hours under 450 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 5: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 50%, and acidleach temperature is 120 DEG C, leaching time 3 hours, and solid-liquid weight ratio is 1:3, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:5, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 3 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 130 DEG C, and the time is 3 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 6%, and then add intermediate salt, solid-liquid weight ratio is 1:7, under 55 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1.8, and the time is 6 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 3 hours.
7, dry, roasting
Dry 7 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 5 hours under 350 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 6: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 48%, and acidleach temperature is 118 DEG C, leaching time 3 hours, and solid-liquid weight ratio is 1:4, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:6, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 4 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 135 DEG C, and the time is 3 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 7%, and then add intermediate salt, solid-liquid weight ratio is 1:11, under 58 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1.5, and the time is 3 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 4 hours.
7, dry, roasting
Dry 6 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 4 hours under 370 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 7: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 44%, and acidleach temperature is 116 DEG C, leaching time 3 hours, and solid-liquid weight ratio is 1:4, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:8, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 3 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 145 DEG C, and the time is 3 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 9%, and then add intermediate salt, solid-liquid weight ratio is 1:18, under 60 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1, and the time is 3 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 2 hours.
7, dry, roasting
Dry 6 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 6 hours under 420 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 8: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 45%, and acidleach temperature is 105 DEG C, leaching time 2 hours, and solid-liquid weight ratio is 1:2, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:7, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 4 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 125 DEG C, and the time is 4 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 5%, and then add intermediate salt, solid-liquid weight ratio is 1:5, under 52 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:2, and the time is 4 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 3 hours.
7, dry, roasting
Dry 8 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 3 hours under 430 DEG C of conditions, namely obtained final denitrating catalyst.
Embodiment 9: the preparation method that following section describes denitrating catalyst of the present embodiment:
1, slag fine grinding is expected
Stone coal ash is dropped into coal pulverizer and is finely ground to granularity≤200 μm.
2, slag acidleach is expected
Stone coal ash after fine grinding being joined volumetric concentration is carry out stirring acidleach in the sulfuric acid solution of 47%, and acidleach temperature is 110 DEG C, leaching time 4 hours, and solid-liquid weight ratio is 1:3, obtains pickle liquor after filtration.
3, ammonia-alum crystallization
Excessive (NH is added in pickle liquor
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:6, at the uniform velocity stir in adition process.Use running water that solution is cooled to room temperature, cool time is 3 hours.Ammonia-alum crystalline deposit, can obtain thick ammonia-alum after filtration, filtrate is containing vanadium mother liquid.Adopt reduction-recrystallization method to remove the impurity such as the iron ion in thick ammonia-alum again, smart ammonia-alum can be obtained through secondary crystallization.
4, intermediate salt crystallization
What obtain after heating ammonia-alum filters contains vanadium mother liquid to 130 DEG C, and the time is 3 hours, separates out intermediate salt crystal in solution, then obtains intermediate salt after washing after filtration.
5, the preparation of activity component impregnation liquid
Preparation mass concentration is the oxalic acid solution of 8%, and then add intermediate salt, solid-liquid weight ratio is 1:12, under 55 DEG C of conditions, add thermal agitation until intermediate salt is dissolved completely, forms grass green solution.
6, the load of active component
After maceration extract overnight stand, toward wherein adding anatase type nano TiO
2powder floods, and solid-liquid volume ratio is 1:1.3, and the time is 5 hours.Then obtained white slurry is put into Ultrasonic Cleaning and think highly of ultrasonic immersing 4 hours.
7, dry, roasting
Dry 4 hours of drying case again.Muffle furnace put into by dried catalyst, high-temperature roasting 4 hours under 360 DEG C of conditions, namely obtained final denitrating catalyst.
Following table to describe in embodiment 1-9 obtain the composition of denitrating catalyst: (unit is weight percentage)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Anatase-type nanometer titanium dioxide | 95 | 86 | 92 | 90 | 80 | 87 | 97.5 | 82 | 92 |
| V 2O 5 | 0.8 | 4 | 2 | 5 | 6 | 4 | 0.5 | 5.5 | 1.5 |
| Al 2O 3 | 1.5 | 5 | 4.5 | 3 | 8 | 3.5 | 1 | 7 | 2 |
| Fe 2O 3 | 2.7 | 5 | 1.5 | 2 | 6 | 5.5 | 1 | 5.5 | 4.5 |
Catalyst denitration activity test case:
Pulverized and sieved by catalyst prepared in embodiment 2, obtaining granularity is catalyst granules between 30 ~ 60 orders, and get this catalyst granules 3 ml and put into catalyst activity evaluating apparatus, activity rating is carry out in the quartz tube reactor of 10 mm at internal diameter; Simulated flue gas consists of 500 ppm NO, 5% O
2, NH
3/ NO
xbe 1, N
2for Balance Air, air speed is 24000 h
-1.400 DEG C time, NO
xremoval efficiency be 95%.
Moisture and sulfur dioxide are to catalyst denitration activity test case
Pulverized and sieved by catalyst prepared in embodiment 2, obtaining granularity is catalyst granules between 30 ~ 60 orders, and get this catalyst granules 3 ml and put into catalyst activity evaluating apparatus, activity rating is carry out in the quartz tube reactor of 10 mm at internal diameter; Simulated flue gas consists of 500 ppm NO, 5% O before adding moisture and sulfur dioxide
2, N
2for Balance Air, air speed is 24000 h
-1.Reaction temperature 400 DEG C, NH
3/ NO
xbe 1.The catalyst of preparation has good water resistant and divides and anti-sulfur poisonous performance.
In addition, it should be noted that, the specific embodiment described in this description, its formula, title that technique is named etc. can be different.All equivalences of doing according to structure, feature and the principle described in inventional idea of the present invention or simple change, be included in the protection domain of patent of the present invention.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment; only otherwise depart from structure of the present invention or surmount this scope as defined in the claims, protection scope of the present invention all should be belonged to.
Although the present invention with embodiment openly as above; but it is also not used to limit protection scope of the present invention; any technical staff being familiar with this technology, not departing from the change and retouching done in the spirit and scope of the present invention, all should belong to protection scope of the present invention.
Claims (3)
1. a denitrating catalyst, is characterized in that: it consists of: carrier and active component composition, and described carrier is anatase-type nanometer titanium dioxide, and described active component is the mixed-metal oxides of vanadium, aluminium, iron; The mass percent of described anatase-type nanometer titanium dioxide is 82 ~ 87% of gross weight, and the mass percent of the mixed-metal oxides of described vanadium, aluminium, iron is 13 ~ 18% of gross weight; The mixed-metal oxides of described vanadium, aluminium, iron, wherein V
2o
5mass percent be 0.5 ~ 6%, Al of gross weight
2o
3mass percent be 1 ~ 8%, Fe of gross weight
2o
3mass percent be 1 ~ 6% of gross weight.
2. denitrating catalyst according to claim 1, its preparation method is:
A, stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μm, obtain powdery stone coal ash;
B, to be joined in sulfuric acid solution by powdery stone coal ash and carry out stirring acidleach, leaching time is 2 ~ 4 hours, and solid-liquid weight ratio is 1:2 ~ 4, after filtration pickle liquor;
C, in pickle liquor, add excessive (NH
4)
2sO
4, its consumption is control Al
3+and NH
4 +mol ratio be 1:5 ~ 8, at the uniform velocity stir in adition process, pickle liquor is cooled to room temperature, cool time is 2 ~ 4 hours, ammonia-alum crystalline deposit, filtration obtains thick ammonia-alum and containing vanadium mother liquid, obtains smart ammonia-alum after thick ammonia-alum being adopted the impurity such as reduction-recrystallization method secondary crystallization removing iron ion wherein;
D, heating are containing vanadium mother liquid to separating out intermediate salt crystal, more after filtration, obtain intermediate salt after washing, filtrate reclaim sulfuric acid is reused;
E, preparation mass concentration are the oxalic acid solution of 5 ~ 10%, and then add intermediate salt, solid-liquid weight ratio is 1:5 ~ 20, stirs until intermediate salt is dissolved completely under temperature is 50 ~ 60 DEG C of conditions, forms grass green solution;
F, grass green solutions overnight is left standstill after, add Powdered dried anatase-type nanometer titanium dioxide, under at the uniform velocity stirring condition, dipping is after 3 ~ 6 hours, and the white slurry obtained puts into ultrasonic cleaner ultrasonic immersing 2 ~ 4 hours, obtains impregnation product;
G, by after dry for impregnation product, roasting, obtained denitrating catalyst;
Sulfuric acid volumetric concentration in described step b is 40 ~ 50%, and acidleach temperature is 100 ~ 120 DEG C;
In described steps d, heating is containing vanadium mother liquid to 120 ~ 150 DEG C, 2 ~ 4 hours retention times;
Drying in described step g carries out in air dry oven, and baking temperature is 110 DEG C, and drying time is 4 ~ 8 hours;
Roasting in described step g carries out under temperature is 350 ~ 450 DEG C of conditions, and roasting time is 3 ~ 6 hours.
3. denitrating catalyst according to claim 2, is characterized in that: the dipping in described step f, and the solid-liquid volume ratio of dipping is 1:1 ~ 2.
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| CN102836716A (en) * | 2011-06-24 | 2012-12-26 | 北京石油化工学院 | Nanometer titanium dioxide loaded metal oxide catalyst, preparation method and applications thereof |
| CN102716753B (en) * | 2012-06-08 | 2015-06-17 | 华电电力科学研究院 | Catalyst for low-temperature selective catalytic reduction of nitric oxide and preparation method of catalyst |
| CN102921404B (en) * | 2012-09-11 | 2014-06-04 | 河南佰利联化学股份有限公司 | Preparation method of titanium-tungsten composite powder for denitrification catalyst |
| CN103506121A (en) * | 2013-07-22 | 2014-01-15 | 大连理工大学 | Low-temperature denitration catalyst with iron loaded on carbon nanotube and preparation method thereof |
| CN104959145A (en) * | 2015-06-24 | 2015-10-07 | 方耀 | Solid catalyst used for denitration of coal-fired flue gas |
| CN106513008A (en) * | 2016-10-18 | 2017-03-22 | 佛山慧创正元新材料科技有限公司 | Catalyst for removing NOx and preparation method therefor |
| CN107519862B (en) * | 2017-08-23 | 2020-02-04 | 北京工业大学 | Method for preparing medium-temperature denitration catalytic material from ferrosilicon slag |
| CN109351358A (en) * | 2018-10-18 | 2019-02-19 | 中国科学院城市环境研究所 | A kind of transition metal oxide composite catalyst and its preparation method and application |
| CN113929199B (en) * | 2021-10-26 | 2022-11-08 | 伊犁新天煤化工有限责任公司 | Method for reducing chemical oxygen demand of coal gasification wastewater by utilizing coal gasification ash |
| CN115814783A (en) * | 2022-12-29 | 2023-03-21 | 华电电力科学研究院有限公司 | Anti-potassium poisoning SCR denitration catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4314913A (en) * | 1979-03-05 | 1982-02-09 | Rhone-Poulenc Industries | Catalyst for removing NOx from gas streams |
| CN101381818A (en) * | 2008-09-29 | 2009-03-11 | 浙江大学 | Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash |
-
2010
- 2010-08-16 CN CN201010254249.7A patent/CN102000585B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4314913A (en) * | 1979-03-05 | 1982-02-09 | Rhone-Poulenc Industries | Catalyst for removing NOx from gas streams |
| CN101381818A (en) * | 2008-09-29 | 2009-03-11 | 浙江大学 | Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash |
Non-Patent Citations (2)
| Title |
|---|
| 朱崇兵,等.V2O5-WO3/TiO2烟气脱硝催化剂的载体选择.《中国电机工程学报》.2008,第28卷(第11期),第41页摘要、引言、第2栏第2-3段,第42页第1.2节. * |
| 田永淑,等.石煤灰渣中提取五氧化二钒的新工艺.《矿产综合利用》.2006,第6卷(第3期),第22-23页第1-3节,图1,表6、7. * |
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