CN105618069B - A kind of high activity desulfurization catalyst of flue gas and preparation method thereof - Google Patents
A kind of high activity desulfurization catalyst of flue gas and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of high activity desulfurization catalyst of flue gas and preparation method thereof, including alumina support, active metal and carbon, on the basis of catalyst weight, active metal is in terms of oxide, Mo and/or W weight content is 6.0wt% 15wt%, Co and/or Ni weight contents are 1.0wt% 4.0wt%, and carbon is calculated as 1wt% 15wt%, preferably 5wt% 10wt% with element；Carbon content gradually reduces from catalyst granules center to outer surface.Preparation method is as follows：The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed on the alumina support according to the order of concentration from high to low, hydro-thermal charing process is carried out in sealing container, dry, impregnate active component, dry, anaerobic high-temperature process, obtains desulfurization catalyst of flue gas.Carbon content distribution gradient in catalyst of the present invention, the easy complete cure of active component, significantly improves the desulphurizing activated of catalyst.
Description
Technical field
The present invention relates to a kind of high activity desulfurization catalyst of flue gas and preparation method thereof.
Background technology
SO2It is Air Pollutants, is the main reason for acid rain is formed, seriously pollutes environment, harm to the human body is serious,
Coal-fired flue-gas discharge is SO2Main source.Traditional flue gas desulfurization is wet desulphurization, and this method complex process, investment cost is big,
And secondary pollution is produced, dry desulfurizing process is simple, but desulfurization degree is relatively low, and catalytic desulfurization greatly improves dry desulfurization efficiency.
SO in flue gas2Catalytic reduction technique is current flue gas desulfurization technique advanced in the world, can be applied to coal-fired or combustion
The desulfurization of oil cauldron kiln gas, have operating cost it is low, accessory substance (sulphur) using the advantages that.By SO2Directly urged from flue gas
Change is reduced to sulphur, compared with traditional sulfur removal technology, shortens flow, simplifies technique, and also improves desulfurized effect,
Desulfurization can be combined with the sulphur utilization of resources.
Reducing agent used in catalysis reduction and desulfurization mainly has CH4, CO and H2Deng gas.Presently the most common catalyst one
As be with aluminum oxide, ceria, silica, titanium dioxide etc. for carrier, with the transition such as Co, Ni, Mo, W, Fe, Cu, Zn gold
Category, rare earth oxide and its sulfide are the loaded catalyst of active component.Active component is using dipping or the method for kneading
Load on carrier, catalyst then is made by drying, being calcined.In roasting process, active metal component easily with oxidation
Alumina supporter has an effect to form very strong M-O-Al keys, causes active component to form Spinel and lose activity, or activity
Component can not complete cure so as to reducing catalyst activity.
CN1298755A discloses a kind of catalyst and its application process for being used to handle SO 2 in waste gas, catalysis
The each component weight ratio of agent is activated coke 80-98%, Co1-10%, Mo1-10%.Catalyst selects after vulcanizing treatment for hydrogen
Selecting property catalysis reduction SO2For elemental sulfur, reaction temperature is 250-400 DEG C, H2/SO2Mol ratio is 2：1-4：1,85% can be obtained
Sulphur yield.But catalyst different activities component interphase interaction prepared by this method forms new compound, is unfavorable for activity
Component dispersed and active further raising on carrier, in addition, sulphur yield is also up for improving.
CN102962064A discloses a kind of γ types alumina load metal oxide catalyst, preparation method and its answered
With.The γ type aluminium oxide catalysts have adjustable pore structure, specific surface area are big, absorption property is good, high mechanical strength, surface tool
Have the advantages that acid and heat endurance is good.The catalyst is used for flue gas and desulfurizing and denitrifying, using CO as reducing agent, to flue gas
In the nitric oxide that contains and sulfur dioxide carry out catalysis reduction, specifically in fluid catalytic cracking FCC flue gases, power station pot
In the fume treatment field of stove.But there is also active component and carrier interphase interaction is strong, it is unfavorable for active component in carrier
Upper dispersed, vulcanization and activity further improve.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of high activity desulfurization catalyst of flue gas and preparation method thereof, this
Carbon content distribution gradient in invention catalyst, catalyst exterior active component is relatively strong with carrier function, internal activity
Component is relatively weak with carrier function, the easy complete cure of active component, significantly improves catalyst desulfurizing activity.
The present invention high activity desulfurization catalyst of flue gas, including porous inorganic refractory oxide carrier, active metal and
Carbon；On the basis of catalyst weight, active metal weight is calculated as 5wt%-20wt%, preferably 10wt% ~ 15wt% with oxide, carbon with
Element is calculated as 1wt%-15wt%, preferably 5wt%-10wt%, and porous inorganic refractory oxide is 70wt% ~ 93wt%, preferably surplus；
Wherein one or more of the active metal in Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce, preferably in Co, Ni, Mo, W
A kind of combination in one or more, more preferably Ni and W, Co and Mo；It is 160-300m than surface2/ g, pore volume 0.4-
1.2ml/g；Carbon content meets following condition：Apart from catalyst granules cross-section center（Hereinafter referred to as center）Carbon at 1/4R contains
Amount and the carbon content ratio of catalyst granules cross-section center are 60%-80%, preferably 65% ~ 75%, carbon content at distance center 1/2R
It is 40%-60%, preferably 45%-55% with center carbon content ratio, carbon content and center carbon content ratio are 20%- at distance center 3/4R
40%, preferably 25% ~ 35%, in the outer most edge of cross section the carbon content at any point and center carbon content than 5%-20%, preferably 10% ~
15%, R are the distance of line segment between any point in the cross-section center and cross section outer most edge of catalyst granules.
In catalyst of the present invention, described porous inorganic refractory oxide group ii, III in the periodic table of elements
One or more in the oxide of race and Group IV element, are more preferably selected from silica, aluminum oxide, magnesia, silica
One or more in aluminium, silica magnesium and magnesium aluminium oxide, further preferred aluminum oxide.
The present invention is at any point in catalyst granules cross-section center 1/4R, 1/2R, 3/4R, cross section outer most edge
Carbon content and the carbon content of catalyst granules cross-section center be measured by electron probe.
Catalyst of the present invention is（It is solid）It is granular, rather than the amorphous state such as powder.As described
The shape of grain, it is conventional use of variously-shaped to enumerate this area desulfurization catalyst of flue gas, for example can further enumerate ball
Shape and column.As described spherical, for example spheroidal and elliposoidal etc. can be enumerated；As the column, for example can enumerate
Cylindric, flat column and profiled-cross-section（Such as clover, bunge bedstraw herb etc.）Column etc..
In the present invention, so-called " cross section of catalyst granules " is referred to along the minimum dimension side of a catalyst granules
The whole surface of exposure after to the geometric center cutting by its shape.Such as when the catalyst granules is spherical, it is described
Cross section refers to the whole surface of exposure after being cut along the radius or short-axis direction of the ball by its centre of sphere.Or in institute
When to state catalyst granules be column, the cross section refers to passing through the length dimension perpendicular to the length dimension direction of the post
The whole surface of exposure after central point cutting（Referring to Fig. 1）.
In the present invention, the periphery of the exposed surface is referred to as to the outer most edge of the cross section, by the geometric center（Such as
The foregoing centre of sphere or the central point of length dimension）Central point referred to as on the cross section.
The preparation method of the high activity desulfurization catalyst of flue gas of the present invention, including following content：
（1）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, according to the order of concentration from high to low
Spray on porous inorganic refractory oxide carrier so that the concentration of polyalcohol and/or monose is in porous inorganic refractory oxygen
Ecto-entad is formed in compound in gradient distribution from low to high；
（2）Carrier after dipping is subjected to hydro-thermal charing process, drying process in sealing container；
（3）With active metal maceration extract impregnation steps（2）Obtained carrier, dry, then anaerobic high-temperature process, obtains cigarette
Qi exhaustion sulfur catalyst.
In the inventive method, step（1）Described polyalcohol includes xylitol, sorbierite, mannitol or arabite etc.
In one or more；Described monose includes the one or more in glucose, ribose or fructose etc..
In the inventive method, step（1）Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5% ~ 50%.
In the inventive method, step（1）It is described according to concentration from high to low spray order, adjacent polyalcohol twice
And/or the concentration difference of the monose aqueous solution is 5% ~ 30%, preferably 10% ~ 20%；It is preferred that prepare 2 ~ 4 kinds of various concentrations polyalcohol and/
Or the monose aqueous solution.
In the inventive method, step（1）The described maceration extract dosage sprayed every time is the 10%- of carrier saturated water adsorptive value
60%, preferably 20%-30%, the total dosage of maceration extract repeatedly sprayed are the saturated water adsorptive value of carrier, to ensure that carrier saturation impregnates.
In the inventive method, step（1）It is preferred that the polyalcohol and/or the monose aqueous solution of 3 kinds of various concentrations of preparation are sprayed
Leaching, detailed process are as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution be 30%-50%, polyalcohol with/
Or the 20%-30% that the dosage of the monose aqueous solution is porous inorganic refractory oxide water absorption；Spray for the second time, polyalcohol and/
Or the mass concentration of the monose aqueous solution is 10%-30%, the dosage of polyalcohol and/or the monose aqueous solution is porous inorganic refractory oxygen
The 40%-60% of compound water absorption；Third time sprays, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, polyalcohol
And/or the 10%-40% that the dosage of the monose aqueous solution is porous inorganic refractory oxide water absorption.
In the inventive method, step（1）Described porous inorganic refractory oxide is graininess, can be spherical or post
It can be spheroidal or elliposoidal that shape is wherein spherical, and cylindricality can cylinder, square column type or abnormity（Clover, bunge bedstraw herb or five
Tooth ball）.Porous inorganic refractory oxide can use it is commercially available, can also use conventional method made from be suitable for flue gas
The porous inorganic refractory oxide of desulphurization catalyst.
In the inventive method, step（2）Described hydro-thermal charing process temperature be 180-250 DEG C, preferably 200-230 DEG C,
Hydrothermal conditions are 6-12 hours, preferably 8-10 hours, and hydro-thermal process pressure is self-generated pressure, under this hydro-thermal carbonization condition
It can ensure that polyalcohol and/or monose carbonize completely.Wherein, self-generated pressure is relevant with treatment temperature, when temperature is 100 DEG C, pressure
Force value（Gauge pressure）General 0.1MPa, at 150 DEG C, pressure value is generally 0.43MPa, and at 250 DEG C, pressure value is generally 1.95MPa.
In the inventive method, step（2）Described porous inorganic refractory oxide is carried out close preferably before charing process
Envelope heat treatment, heat treatment condition are：80 ~ 130 DEG C are handled 0.5 ~ 2 hour.
In the inventive method, step（3）Described load active component used volume impregnation, incipient impregnation or spray
The methods of dipping, dip time are 1-5 hours, preferably cross volume impregnation.Wherein, maceration extract preparation choose active component can
Soluble compound, the specific concentration of maceration extract can be depending on the active metallic content on final catalyst.
In the inventive method, described drying condition is that 6-10 hours are dried at 80-120 DEG C.
In the inventive method, step（3）Described anaerobic high-temperature process condition is：Treatment temperature is 400-600 DEG C, processing
Time is 3-6 hours；The wherein atmosphere of anaerobic high-temperature process can be nitrogen or inert atmosphere, wherein inert atmosphere be helium,
One or more in neon or argon gas.
The high activity desulfurization catalyst of flue gas of the present invention is used for catalytic reducing smoke desulphurization reaction, and general technology condition is：
With H2Exemplified by also Primordial Qi（Can also be CH4, the reducibility gas such as CO）, H2/SO2Mol ratio be 1-5, preferably 1.5-
3.5, entrance SO2Volume fraction is 0.1%-0.5%, preferably 0.2%-0.4%, 350-500 DEG C of reaction temperature, preferably 400-450 DEG C,
Reaction velocity 5000-25000h-1, preferably 8000-15000h-1。
Polyalcohol and/or the monose aqueous solution spray dip forming porous inorganic refractory of the inventive method various concentrations
Oxide（Carrier）, then by hydro-thermal charing process, carbon-coating is formed on carrier surface and duct inwall；Spray dipping process
In, maceration extract is gradually permeated under the effect of carrier duct capillary force from surface to center, when spraying dipping due to multistep, maceration extract
The concentration of middle polyalcohol and/or monose gradually reduces, and the concentration that ensure that polyalcohol and/or monose is in by carrier surface to center
Incremental distribution.After charing the thickness of carbon-coating from a surface to center in incremental distribution, i.e., outside carrier the relatively thin internal carbon-coating of carbon-coating compared with
It is thick.Sealing heat treatment is carried out to the carrier after dipping before the charing of carbon precursor, promotes absorption and carbon of the carbon precursor on carrier
The formation of layer；The material after active component is impregnated in anaerobic high-temperature process, and the presence of carbon-coating effectively prevents metal group
The strong interaction divided between carrier, because the gradient of carbon layers having thicknesses is distributed, the effect between active metal and carrier is by outer
Gradually weaken to interior, i.e., catalyst activity gradually steps up from outside to inside, in flue gas desulfurization course, promotes in catalyst duct
The reaction in portion, effectively prevent makes Dry FGD acutely cause catalyst pores because outer surface active component activity is higher
Road is blocked and makes the phenomenon of catalyst inactivation, and the service life of catalyst is extended while catalyst activity is improved.
Brief description of the drawings
Fig. 1 catalyst granules is cylindrical cross-sectional view.
Embodiment
The effect of the inventive method and effect are further illustrated with reference to embodiment, but is not limited to following implementation
Example.The commercially available shaped alumina alumina supporter used in embodiment, the pore volume of alumina support is 0.8-1.5ml/g, and specific surface area is
160-300m2/ g, bore dia are that 10-20nm hole accounts for the 70%-90% of total pore volume, crushing strength 130-160N/cm, water absorption
1g/g。
Carbon and active metallic content are measured by JEOL's JXA-8230 electron probes in catalyst of the present invention, are surveyed
The accelerating potential of timing selection is 15KV, and probe current is 8 × 10-8A, beam spot size are 3 μm.
Metering system：Be respectively 1/4R at measurement catalyst cross-section center and with distance at catalyst cross-section center,
Carbon content and active metallic content at 1/2R, 3/4R and R, wherein R be cross-section center with it is any one in the outer most edge of cross section
The distance of line segment, then by division calculation, obtains the ratio between each content between point.
Embodiment 1
It is 0.9ml/g, specific surface area 220m to weigh pore volume2/ g 100 grams of γ phase cylinder bar shapeds alumina support is put into
In spray rolling pot, under rotary state, impregnating effect concentration is sprayed as 40% xylitol using carrier of the atomizing type into rolling pot
Aqueous solution 25ml；Then continue to spray oxide impregnation alumina supporter with the xylose alcohol solution 40ml that mass concentration is 20%；Finally use
The xylose alcohol solution 40ml that mass concentration is 10% continues to spray oxide impregnation alumina supporter.Dipping terminates to turn alumina support
Enter in autoclave, in 80 DEG C of sealing heat treatment 120 minutes, then heat to 180 DEG C, charing process 9 hours under self-generated pressure, from
So it is cooled to room temperature.Then the alumina support after hydro-thermal process is placed at 120 DEG C and dried 3 hours.
Dried carrier, which is used, contains cobalt and molybdenum（Cobalt nitrate and ammonium molybdate）Maceration extract impregnate above-mentioned carrier 3 hours, filter
Redundant solution, dried 8 hours at 110 DEG C, dried material is calcined 5 hours at 550 DEG C in a nitrogen atmosphere, and cigarette is made
Qi exhaustion sulfur catalyst C1, catalyst property are shown in Table 1.
Embodiment 2
With embodiment 1, aqueous solution when simply spray impregnates for the first time with 30ml mass concentrations for 30% sorbierite, the
Sprayed when secondary spraying impregnates with the aqueous solution for the sorbierite that 50ml mass concentrations are 10%, third time when impregnating with 20ml mass
Concentration is the aqueous solution of 5% sorbierite, and heat treatment temperature is 130 DEG C, and heat treatment time is 60 minutes.Temperature during charing process
For 200 DEG C, carbonization time is 8 hours.
Dried carrier, which is used, contains cobalt and molybdenum（Cobalt nitrate and ammonium molybdate）Maceration extract impregnate above-mentioned carrier 3 hours, filter
Redundant solution, dried 6 hours at 120 DEG C, dried material is calcined 4 hours at 550 DEG C in a nitrogen atmosphere, and cigarette is made
Qi exhaustion sulfur catalyst C2, catalyst property are shown in Table 1.
Embodiment 3
With embodiment 1, simply impregnated using four sprays, be for the first time 50% with 20ml mass concentrations during spray dipping
The aqueous solution of mannitol, sprayed when second of spray impregnates with the aqueous solution for the sorbierite that 40ml mass concentrations are 30%, third time
During dipping with 20ml mass concentrations be 20% sorbierite the aqueous solution, the 4th time spray dipping when with 20ml mass concentrations be 10%
Sorbierite the aqueous solution, heat treatment temperature be 100 DEG C, heat treatment time be 90 minutes.Temperature is 240 DEG C during charing process,
Carbonization time is 12 hours.
The nickeliferous and tungsten of dried carrier（Nickel nitrate and ammonium metatungstate）Maceration extract impregnate above-mentioned carrier 3 hours, filter
Fall redundant solution, dried 8 hours at 110 DEG C, dried material is calcined 5 hours at 550 DEG C in a nitrogen atmosphere, is made
Desulfurization catalyst of flue gas C3, catalyst property are shown in Table 1.
Embodiment 4
With embodiment 1, it is 1 that simply xylitol, which changes mass ratio into,:The mixing alcohol solution leaching of 1 sorbierite and mannitol
Stain, temperature is 220 DEG C during charing process, and processing time is 10 hours.Desulfurization catalyst of flue gas C4 of the present invention, catalyst performance is made
Matter is shown in Table 1.
Embodiment 5
With embodiment 1, simply xylose alcohol solution changes the aqueous solution dipping of glucose into, and temperature is 230 during charing process
DEG C, processing time is 9 hours.Desulfurization catalyst of flue gas C5 of the present invention is made, catalyst property is shown in Table 1.
Embodiment 6
With embodiment 1, simply xylose alcohol solution changes ribose aqueous solution dipping into, and temperature is 190 DEG C during charing process,
Processing time is 6 hours, and desulfurization catalyst of flue gas C6 is made, and catalyst property is shown in Table 1.
Embodiment 7
With embodiment 1, it is 1 that simply xylitol, which changes mass ratio into,:1 glucose and the fructose aqueous solution dipping, charing process
Shi Wendu is 240 DEG C, and processing time is 9 hours, obtains desulfurization catalyst of flue gas C7 of the present invention.
Comparative example 1
With embodiment 1, simply before alumina support dipping active component without alcohol and/or sugar juice dipping and hydro-thermal at
Reason, is made comparative catalyst C8, and catalyst property is shown in Table 1.
Comparative example 2
With embodiment 1, simply impregnate, use without polyalcohol and/or monosaccharide solutions before alumina support dipping active component
Deionized water dipping simultaneously carries out hydro-thermal process in autoclave, and comparative catalyst C9 is made, and catalyst property is shown in Table 1.
Comparative example 3
With embodiment 1, the xylose alcohol solution of same volume and mass concentration is mixed into once spray when simply impregnating and soaked
Comparative catalyst C10 is made in stain, and catalyst property is shown in Table 1.
The catalyst property of table 1.
Embodiment 9
The following examples illustrate desulfurization catalyst of flue gas provided by the invention and the catalytic performance of comparative catalyst.Implement
Catalyst C8-C10 prepared by catalyst C1-C7 and comparative example 1-3 prepared by example 1-7 benchmark test selection is consolidated in normal pressure
Carried out in fixed bed reactor, reactor material is quartz glass, and the mm of internal diameter 10, the dosage of catalyst is 0.5g.Catalyst is used for
Before reaction, at 600 DEG C, 35ml/min 0.5% SO2/ 2.5% H2/ N2Presulfurization 2.5h in gaseous mixture.
The reaction temperature of evaluation test is 400 DEG C, reaction velocity 10000h-1, SO2And H2Mixed after being diluted respectively with nitrogen
Conjunction enters reactor, n (H2)/n(SO2) ratio be 3, porch SO2Volume fraction is 0.3%, react generation elemental sulfur and
Vapor is collected by the condenser for being placed in reactor outlet, the SO with flue gas analyzer to exit2On-line analysis is carried out, is calculated
SO2Conversion ratio and simple substance Recovery ratio, evaluation result are shown in Table 2.
The desulfurization catalyst of flue gas performance comparison of table 2.
| C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 | |
| SO2Conversion ratio, % | 96.2 | 97.6 | 99.4 | 93.6 | 92.4 | 91.7 | 90.9 | 73.7 | 75.4 | 86.6 |
| S yields, % | 85.8 | 84.7 | 86.5 | 81.7 | 80.2 | 78.1 | 77.4 | 52.2 | 56.7 | 65.9 |
It can be seen from the data of table 2 compared with comparative catalyst, there is catalyst provided by the invention higher flue gas to take off
Sulphur activity and simple substance Recovery ratio.
Claims (16)
- A kind of 1. high activity desulfurization catalyst of flue gas, it is characterised in that：Including porous inorganic refractory oxide carrier, activity gold Category and carbon；On the basis of catalyst weight, active metal weight is calculated as 5wt%-20wt% with oxide, and carbon is calculated as with element 1wt%-15wt%, porous inorganic refractory oxide are 70wt% ~ 93wt%；Wherein active metal is in Ni and W, Co and Mo One kind combination；Carbon content meets following condition：Apart from catalyst granules cross-section center（Hereinafter referred to as center）Carbon at 1/4R The carbon content ratio of content and catalyst granules cross-section center is 60%-80%, and carbon content contains with center carbon at distance center 1/2R It is 40%-60% to measure ratio, and carbon content and center carbon content ratio are 20%-40% at distance center 3/4R, in the outer most edge of cross section arbitrarily For the carbon content of any with center carbon content than 5%-20%, R is that the cross-section center of catalyst granules is taken up an official post with cross section outer most edge The distance of line segment between anticipating a bit.
- 2. according to the catalyst described in claim 1, it is characterised in that：On the basis of catalyst weight, active metal weight with Oxide is calculated as 10wt% ~ 15wt%, and carbon is calculated as 5wt%-10wt% with element, and porous inorganic refractory oxide is surplus；Wherein A kind of combination of the active metal in Ni and W, Co and Mo.
- 3. according to the catalyst described in claim 1, it is characterised in that：It is 160-300m than surface2/ g, pore volume 0.4- 1.2mL/g。
- 4. according to the catalyst described in claim 1, it is characterised in that：Described porous inorganic refractory oxide is selected from element One or more in periodic table in the oxide of group iia, group III A and group IVA element, porous inorganic refractory oxygen Compound is graininess.
- 5. according to the catalyst described in claim 1 or 4, it is characterised in that：Described porous inorganic refractory oxide is selected from One or more in silica, aluminum oxide, magnesia, oxidation sial, silica magnesium and magnesium aluminium oxide.
- 6. the preparation method of the high activity desulfurization catalyst of flue gas described in a kind of claim 1, it is characterised in that in following Hold：（1）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed according to the order of concentration from high to low On porous inorganic refractory oxide carrier so that the concentration of polyalcohol and/or monose is in porous inorganic refractory oxide The upper ecto-entad that formed is in gradient distribution from low to high；（2）Carrier after dipping is subjected to hydro-thermal charing in sealing container Processing, drying process；（3）With active metal maceration extract impregnation steps（2）Obtained carrier, dry, then anaerobic high-temperature process, Obtain desulfurization catalyst of flue gas.
- 7. in accordance with the method for claim 6, it is characterised in that：Step（1）Described polyalcohol includes xylitol, sorb One or more in alcohol, mannitol or arabite；Described monose includes one kind or several in glucose, ribose or fructose Kind.
- 8. in accordance with the method for claim 6, it is characterised in that：Step（1）Described polyalcohol and/or the monose aqueous solution Mass concentration is 5% ~ 50%.
- 9. in accordance with the method for claim 6, it is characterised in that：Step（1）Described the spraying from high to low according to concentration Sequentially, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5% ~ 30%.
- 10. in accordance with the method for claim 6, it is characterised in that：Step（1）The middle polyalcohol for preparing 2 ~ 4 kinds of various concentrations And/or the monose aqueous solution.
- 11. in accordance with the method for claim 6, it is characterised in that：Step（1）The described maceration extract dosage sprayed every time is The 10%-60% of carrier saturated water adsorptive value, the total dosage of maceration extract repeatedly sprayed are the saturated water adsorptive value of carrier.
- 12. in accordance with the method for claim 6, it is characterised in that：Step（1）Prepare 3 kinds of various concentrations polyalcohol and/or The monose aqueous solution is sprayed, and detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is The dosage of 30%-50%, polyalcohol and/or the monose aqueous solution is the 20%-30% of porous inorganic refractory oxide water absorption；Second Secondary to spray, the mass concentration of polyalcohol and/or the monose aqueous solution is 10%-30%, and the dosage of polyalcohol and/or the monose aqueous solution is The 40%-60% of porous inorganic refractory oxide water absorption；Third time sprays, and the quality of polyalcohol and/or the monose aqueous solution is dense Spend for 5%-10%, the dosage of polyalcohol and/or the monose aqueous solution is the 10%-40% of porous inorganic refractory oxide water absorption.
- 13. in accordance with the method for claim 6, it is characterised in that：Step（2）Described hydro-thermal charing process temperature is 180- 250 DEG C, hydrothermal conditions are 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
- 14. in accordance with the method for claim 6, it is characterised in that：Step（2）Described carrier is carried out before charing process Sealing heat treatment, heat treatment condition are：80 ~ 130 DEG C are handled 0.5 ~ 2 hour.
- 15. in accordance with the method for claim 6, it is characterised in that：Step（3）Described anaerobic high-temperature process condition is：Place It is 400-600 DEG C to manage temperature, and processing time is 3-6 hours；The wherein atmosphere of anaerobic high-temperature process is nitrogen or inert atmosphere, its Middle inert atmosphere is the one or more in helium, neon or argon gas.
- 16. the high activity desulfurization catalyst of flue gas described in a kind of claim 1 is used for catalytic reducing smoke desulphurization reaction, technique bar Part is：With H2As also Primordial Qi, H2/SO2Mol ratio be 1-5, entrance SO2Volume fraction is 0.1%-0.5%, reaction temperature 350-500 DEG C, reaction velocity 5000-25000h-1。
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| CN106732631B (en) * | 2015-11-20 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of high activity desulfurization catalyst of flue gas and preparation method thereof |
| CN109420505B (en) * | 2017-08-31 | 2021-06-04 | 中国石油化工股份有限公司 | Flue gas desulfurization catalyst and preparation method thereof |
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