CN106732631B - 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 silicon-containing alumina carrier, active metal and carbon；On the basis of catalyst weight, active metal weight is calculated as 5wt%-20wt% with oxide, and carbon is 1wt%-15wt% based on the element, and silicon-containing alumina carrier is 70wt% ~ 93wt%；On the basis of silicon-containing alumina vehicle weight, dioxide-containing silica is 1wt% ~ 10wt%；Specific surface is 160-300m2/ g, Kong Rongwei 0.4-1.2ml/g.The preparation method is as follows: preparing the polyalcohol and/or monosaccharide aqueous solution of at least two various concentrations, it is sprayed on silicon-containing alumina carrier according to the sequence of concentration from high to low, hydro-thermal charing process is carried out in sealing container, it is 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, active component are easy complete cure, significantly improve the desulphurizing activated of catalyst, and catalyst strength is high, can stablize long-term operating.
Description
Technical field
The present invention relates to a kind of high activity desulfurization catalyst of flue gas and preparation method thereof.
Background technique
SO2The main reason for being Air Pollutants, being acid rain formation, environment seriously being polluted, harm to the human body is serious,
Coal-fired flue-gas discharge is SO2Main source.Traditional flue gas desulfurization is wet desulphurization, this method complex process, investment cost is big,
And secondary pollution is generated, dry desulfurizing process is simple, but desulfurization degree is lower, 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 has many advantages, such as that operating cost is low, by-product (sulphur) using.By SO2It is directly urged from flue gas
Change is reduced to sulphur, compared with traditional sulfur removal technology, shortens process, simplifies technique, and also improve desulfurization effect,
Desulfurization can be combined with the sulphur utilization of resources.
Reducing agent used in catalysis reduction and desulfurization mainly has CH4, CO and H2Equal gases.Presently the most common catalyst one
As be with aluminium 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
It loads on carrier, catalyst then is made by dry, roasting.In roasting process, active metal component is easy and oxidation
Alumina supporter has an effect to form very strong M-O-Al key, and active component is caused to form Spinel and lose activity, or activity
Component can not complete cure to reducing catalyst activity.
CN1298755A discloses a kind of for handling the catalyst and its application method of 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/SO2Molar ratio is 2:1-4:1, can get 85%
Sulphur yield.But interaction forms new compound between the catalyst different activities component of this method preparation, is unfavorable for activity
Component on carrier it is evenly dispersed and it is active further increase, in addition, sulphur yield also up for improve.
CN102962064A discloses a kind of γ type alumina load metal oxide catalyst, preparation method and its answers
With.The γ type aluminium oxide catalyst has good adjustable pore structure, large specific surface area, absorption property, high mechanical strength, surface tool
Have the advantages that acid and thermal stability 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 gas, power station pot
In the fume treatment field of furnace.But it is strong there is also interacting between active component and carrier, it is unfavorable for active component in carrier
Upper evenly dispersed, vulcanization and activity further increase.
Summary of the invention
In view of the deficiencies 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 and carrier function are relatively strong, internal activity
Component is relatively weak with carrier function, and active component is easy complete cure, significantly improves catalyst desulfurizing activity, is catalyzed simultaneously
Agent intensity is high, is suitble to operating steady in a long-term.
High activity desulfurization catalyst of flue gas of the invention, including silicon-containing alumina carrier, active metal and carbon；With catalyst
On the basis of weight, active metal weight is calculated as 5wt%-20wt%, preferably 10wt% ~ 15wt% with oxide, and carbon is based on the element
1wt%-15wt%, preferably 5wt%-10wt%, silicon-containing alumina carrier are 70wt% ~ 93wt%, preferably surplus；It is carried with silicon-containing alumina
On the basis of body weight, dioxide-containing silica is 1wt% ~ 10wt%；Wherein active metal be selected from Co, Ni, Mo, W, Fe, Cu, Mn, Zn,
One or more of La, Ce, preferably one or more of Co, Ni, Mo, W, one of more preferable Ni and W, Co and Mo group
It closes；Specific surface is 160-300m2/ g, Kong Rongwei 0.4-1.2ml/g；Carbon content meets the following conditions: apart from catalyst granules cross
The carbon content ratio of carbon content and catalyst granules cross-section center at kernel of section (hereinafter referred to as center) 1/4R is 60%-
Carbon content and center carbon content ratio are 40%-60%, preferably 45%-55%, distance at 80%, preferably 65% ~ 75%, distance center 1/2R
Carbon content and center carbon content ratio are 20%-40% at the 3/4R of center, preferably 25% ~ 35%, any point in the outer most edge of cross section
Carbon content and center carbon content ratio 5%-20%, preferably 10% ~ 15%, R are outermost for the cross-section center of catalyst granules and cross section
On edge between any point line segment distance.
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 that (solid) is granular, rather than the amorphous states such as powder.As described
The shape of grain, can enumerate the conventional use of various shape of this field desulfurization catalyst of flue gas, for example can further enumerate ball
Shape and column.As the spherical shape, for example spheroidal and elliposoidal can be enumerated etc.；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 " refers to the minimum dimension side along a catalyst granules
The whole surface of exposure after to the geometric center cutting by its shape.For example, when the catalyst granules is spherical, it is described
Cross section refers to the whole surface of exposure after cutting along the radius or short-axis direction of the ball by its centre of sphere.Alternatively, institute
When to state catalyst granules be column, the cross section refers to that the length dimension direction perpendicular to the column passes through the length dimension
The whole surface of exposure after central point cutting (referring to Fig. 1).
In the present invention, the periphery of the exposed surface is known as to the outer most edge of the cross section, by the geometric center (such as
The central point of the centre of sphere or length dimension above-mentioned) it is known as the central point on the cross section.
The preparation method of high activity desulfurization catalyst of flue gas of the invention, including following content:
(1) carbon black powder is added in the ethanol solution containing silicon source, is uniformly mixed under the conditions of ultrasonic disperse, solid-liquid point
From solid phase is dried, and obtains the modified carbon black powder of silicon source；
(2) carbon black powder, boehmite dry glue powder, extrusion aid, peptizing agent and water kneading that step (1) obtains are extruded into
Type, then high-temperature process in an oxygen-free atmosphere roast in oxygen-containing atmosphere, obtain silicon-containing alumina carrier；
(3) polyalcohol and/or monosaccharide aqueous solution for preparing at least two various concentrations, according to the sequence of concentration from high to low
It sprays on silicon-containing alumina carrier, so that the concentration of polyalcohol and/or monosaccharide is formed on silicon-containing alumina carrier by extroversion
Interior is in gradient distribution from low to high；
(4) carrier after dipping is carried out to hydro-thermal charing process in sealing container, is dried；
(5) carrier obtained with active metal maceration extract impregnation steps (4), dry, then anaerobic high-temperature process, obtains cigarette
Qi exhaustion sulfur catalyst.
In the method for the present invention, carbon black powder described in step (1) can be selected from commercial goods, as acetylene carbon black, N330 carbon black,
FW200 carbon black etc..
In the method for the present invention, the solid-liquid mass ratio of carbon black powder described in step (1) and the ethanol solution containing silicon source be 1:5 ~
1:30.
In the method for the present invention, silicon source described in step (1) is 5:1~1:1 with the mass ratio of carbon black powder in terms of silica.
In the method for the present invention, ultrasonic disperse condition described in step (1) are as follows: the energy density of ultrasonic disperse is 0.2 ~ 4kW/
L, ultrasonic disperse temperature are 15 ~ 80 DEG C, and the ultrasonic disperse time is 0.5 ~ 10 hour.
In the method for the present invention, separation of solid and liquid described in step (1) can be using usual manners such as filtering, centrifugations.
In the method for the present invention, drying condition described in step (1) are as follows: 30 ~ 100 DEG C of drying temperature, drying time be 0.1 ~
10 hours.
In the method for the present invention, the additional amount of the modified carbon black powder of silicon source described in step (2) is calculated as 5% with carbon black powder weight ~
20%, preferably 8% ~ 15%, on the basis of boehmite dry glue powder weight.
In the method for the present invention, extrusion aid described in step (2), peptizing agent are that kneading method is prepared in alumina process commonly
Substance, such as sesbania powder, starch, methylcellulose extrusion aid and the medium peptization of formic acid, acetic acid, citric acid, phosphoric acid, nitric acid
One or more of agent.Extrusion aid additional amount is generally 3% ~ 5%, and the additional amount of peptizing agent is generally 3% ~ 10%, to intend thin water
On the basis of aluminium stone dry glue powder weight；Wherein the additional amount of extrusion aid, peptizing agent and water with can kneading formed plastic carry out
Depending on extrusion molding.
In the method for the present invention, the graininess silicon-containing alumina carrier that step (2) obtains can be spherical or cylindricality wherein ball
Shape can be spheroidal or elliposoidal, and cylindricality can cylindrical, square column type or abnormity (clover, bunge bedstraw herb or five tooth balls).
In the method for the present invention, oxygen-free atmosphere described in step (2) is inert atmosphere, N2, CO or CO2Etc. one of atmosphere
Or it is several, oxygen-free atmosphere high-temperature process temperature is 350 ~ 450 DEG C, and the processing time is 2 ~ 8 hours.
In the method for the present invention, oxygen-containing atmosphere described in step (2) is generally the mixture or oxygen of air, oxygen and nitrogen
One of with the mixture of inert gas, the volume fraction of oxygen in the gas phase is 20% ~ 40%.The maturing temperature is
350~800 DEG C, preferably 500~700 DEG C, calcining time are 2~8 hours, preferably 3~5 hours.
In the method for the present invention, polyalcohol described in step (3) includes xylitol, sorbierite, mannitol or arabite etc.
One or more of；The monosaccharide includes one or more of glucose, ribose or fructose etc..
In the method for the present invention, the mass concentration of polyalcohol described in step (3) and/or monosaccharide aqueous solution is 5% ~ 50%.
In the method for the present invention, described in step (3) according to concentration from high to low spray sequence, adjacent polyalcohol twice
And/or the concentration difference of monosaccharide aqueous solution is 5% ~ 30%, preferably 10% ~ 20%；It is preferred that prepare 2 ~ 4 kinds of various concentrations polyalcohol and/
Or monosaccharide aqueous solution.
In the method for the present invention, the maceration extract dosage sprayed every time described in step (3) is that silicon-containing alumina carrier saturation is inhaled
The 10%-60% of water, preferably 20%-30%, the total dosage of the maceration extract repeatedly sprayed are the saturated water adsorptive value of silicon-containing alumina carrier,
To ensure carrier saturation dipping.
In the method for the present invention, the preferred polyalcohol for preparing 3 kinds of various concentrations of step (3) and/or monosaccharide aqueous solution are sprayed
Leaching, detailed process is as follows: spray for the first time, the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 30%-50%, polyalcohol and/
Or the dosage of monosaccharide aqueous solution is the 20%-30% of silicon-containing alumina carrier water absorption；It sprays for the second time, polyalcohol and/or monosaccharide
The mass concentration of aqueous solution is 10%-30%, and the dosage of polyalcohol and/or monosaccharide aqueous solution is silicon-containing alumina carrier water absorption
40%-60%；Third time sprays, and the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 5%-10%, polyalcohol and/or monosaccharide water
The dosage of solution is the 10%-40% of silicon-containing alumina carrier water absorption.
In the method for the present invention, hydro-thermal charing process temperature described in step (4) be 180-250 DEG C, preferably 200-230 DEG C,
Hydrothermal conditions are 6-12 hours, and preferably 8-10 hours, hydro-thermal process pressure was self-generated pressure, under this hydro-thermal carbonization condition
It can guarantee that polyalcohol and/or monosaccharide carbonize completely.Wherein, self-generated pressure is related 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 method for the present invention, silicon-containing alumina carrier described in step (4) is sealed hot place preferably before charing process
Reason, heat treatment condition are as follows: 80 ~ 130 DEG C are handled 0.5 ~ 2 hour.
In the method for the present invention, load active component described in step (5) 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
The specific concentration of soluble compound, maceration extract can be depending on the active metallic content on final catalyst.
In the method for the present invention, the drying condition is 6-10 hours dry at 80-120 DEG C.
In the method for the present invention, anaerobic high-temperature process condition described in step (5) are as follows: treatment temperature is 400-600 DEG C, processing
Time is 3-6 hours；Wherein the atmosphere of anaerobic high-temperature process can be nitrogen or inert atmosphere, wherein inert atmosphere be helium,
One or more of neon or argon gas.
High activity desulfurization catalyst of flue gas of the invention is used for catalytic reducing smoke desulphurization reaction, general technology condition are as follows:
With H2It (can also be CH as going back for Primordial Qi4, the reducibility gas such as CO), H2/SO2Molar 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。
Catalyst of the present invention has the advantages that with prior art ratio
(1) in the prior art by the property of Si modification alumina carrier surface, can not generally have target to aluminium oxide
The specific duct of carrier is modified, and in modifying process, silica solution micelle is easily penetrated into aluminium oxide major part duct (macropore, mesoporous)
In, cause the Kong Rong of carrier to be greatly lowered.The present invention prepares carrying alumina in kneading by wrapping up silicon source on carbon black powder surface
It during body, is heat-treated by anaerobic, so that silicon source comes into full contact with aluminium oxide, and is converted into silica, is further passed through
Calcination process removes carbon powder particle, while reaming, SiO2The big hole surface for remaining stuck to carbon powder particle formation, plays branch
Support effect, enhances the intensity of alumina support, while SiO2Modifying function, reduce active component and carrying alumina body surface
The interaction in face and the acidity for improving macroporous aluminium oxide surface, improve the activity of catalyst, additionally, due to SiO2's
Supporting role ensure that the intensity of aluminium oxide macropore, so that alumina support is not easy to collapse, in preparation process, can be added and compare
The more carbon black powders of the prior art, so that more macropores are formed, to improve the mass-transfer efficiency of flue gas desulfurization, catalyst pores
Road is not easy to plug, and extends the service life of catalyst.
(2) polyalcohol of the method for the present invention various concentration and/or monosaccharide aqueous solution spray dip forming silicon-containing alumina
Carrier (carrier) forms carbon-coating on carrier surface and duct inner wall then by hydro-thermal charing process；Spray dipping process
In, maceration extract is gradually permeated to center under the effect of carrier duct capillary force from surface, when spraying dipping due to multistep, maceration extract
The concentration of middle polyalcohol and/or monosaccharide gradually decreases, and ensure that the concentration of polyalcohol and/or monosaccharide is in by carrier surface to center
It is incremented by distribution.After charing the thickness of carbon-coating from a surface to center in being incremented by distribution, i.e., outside carrier the relatively thin internal carbon-coating of carbon-coating compared with
It is thick.Heat treatment is sealed to the carrier after dipping before carbon precursor charing, promotes absorption and carbon of the carbon precursor on carrier
The formation of layer；For material after impregnating active component in anaerobic high-temperature process, the presence of carbon-coating effectively prevents metal group
Divide the strong interaction between carrier, due to the gradient distribution of carbon layers having thicknesses, the effect between active metal and carrier is by outer
Gradually weaken to interior, i.e., catalyst activity is gradually increased from outside to inside, in flue gas desulfurization course, promotes in catalyst duct
The reaction in portion effectively prevents that Dry FGD is made acutely to cause catalyst pores since outer surface active component activity is higher
The phenomenon that road blocks and makes catalyst inactivation, extends the service life of catalyst while improving catalyst activity.
Detailed description of the invention
Fig. 1 catalyst granules is cylindrical cross-sectional view.
Specific embodiment
The effect and effect of the method for the present invention are further illustrated below with reference to embodiment, but are not limited to following implementation
Example.
Carbon and active metallic content are measured by Japan Electronics JXA-8230 electron probe in catalyst of the present invention, are surveyed
The acceleration voltage that timing selects is 15KV, and probe current is 8 × 10-8A, beam spot size are 3 μm.
Measurement method: 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 obtains the ratio between each content then by division calculation between point.
Embodiment 1
(1) carbon black powder is added in the ethanol solution containing ethyl orthosilicate to (wherein solid-liquid mass ratio is 1:8, positive silicon
Acetoacetic ester is with SiO2Meter is 2:1 with the mass ratio of carbon black powder), (energy density of ultrasonic disperse is under the conditions of ultrasonic disperse
0.6kW/L, ultrasonic disperse temperature are 40 DEG C, and the ultrasonic disperse time is 1 hour) it is uniformly mixed, filtering, dry 2 at 50 DEG C of solid phase
Hour, it is dried, obtains the modified carbon black powder of silicon source；
(2) the carbon black powder 54g(for obtaining step (1) is in terms of carbon black powder weight), boehmite dry glue powder 600g(oxidation
Aluminium butt 65wt%) 6g nitric acid, 3g citric acid, 3g sesbania powder and 360g pure water kneading extrusion molding is added, then in nitrogen
400 DEG C are handled 3 hours, are roasted 5 hours for 500 DEG C in air atmosphere, are obtained silicon-containing alumina carrier；
(3) by step (2) obtains 100 grams of silicon-containing alumina carrier be put into spray rolling pot, under rotary state, with mist
The xylose alcohol solution 25ml that carrier spray impregnating effect concentration of the change mode into rolling pot is 40%；Then it is with mass concentration
20% xylose alcohol solution 40ml continues to spray oxide impregnation alumina supporter；The xylose alcohol solution for being finally 10% with mass concentration
40ml continues to spray oxide impregnation alumina supporter.Dipping terminates for alumina support to be transferred in autoclave, is heat-treated in 80 DEG C of sealings
120 minutes, then heat to 180 DEG C, charing process 9 hours under self-generated pressure, cooled to room temperature.Then by hydro-thermal process
Alumina support afterwards is placed at 120 DEG C 3 hours dry.
(4) carrier after drying uses the maceration extract containing cobalt and molybdenum (cobalt nitrate and ammonium molybdate) to impregnate above-mentioned carrier 3 hours, filter
Fall redundant solution, 8 hours dry at 110 DEG C, the material after drying roasts 5 hours at 550 DEG C in a nitrogen atmosphere, is made
Desulfurization catalyst of flue gas C1, catalyst property are shown in Table 1.
Embodiment 2
(1) carbon black powder is added in the ethanol solution containing ethyl orthosilicate to (wherein solid-liquid mass ratio is 1:15, positive silicon
Acetoacetic ester is with SiO2Meter is 3:1 with the mass ratio of carbon black powder), (energy density of ultrasonic disperse is under the conditions of ultrasonic disperse
1kW/L, ultrasonic disperse temperature are 50 DEG C, and the ultrasonic disperse time is 0.5 hour) it is uniformly mixed, filtering, dry 2 at 50 DEG C of solid phase
Hour, it is dried, obtains the modified carbon black powder of silicon source；
(2) the carbon black powder 160g(for obtaining step (1) is in terms of carbon black powder weight), boehmite dry glue powder 1000g(oxygen
Change aluminium butt 65wt%), 10g nitric acid, 4g citric acid, 4g sesbania powder and 350g pure water kneading extrusion molding is added, then in nitrogen
It is handled 3 hours for 450 DEG C in gas, is roasted 5 hours for 500 DEG C in air atmosphere, obtain silicon-containing alumina carrier；
(3) with 1 step of embodiment (3), the sorbierite for being 30% with 30ml mass concentration when only spray impregnates for the first time
Aqueous solution, the aqueous solution for the sorbierite that second of spray is 10% with 50ml mass concentration when impregnating are used when spray dipping for the third time
The aqueous solution for the sorbierite that 20ml mass concentration is 5%, heat treatment temperature are 130 DEG C, and heat treatment time is 60 minutes.At charing
Temperature is 200 DEG C when reason, and carbonization time is 8 hours；
(4) carrier after drying uses the maceration extract containing cobalt and molybdenum (cobalt nitrate and ammonium molybdate) to impregnate above-mentioned carrier 3 hours, filter
Fall redundant solution, 6 hours dry at 120 DEG C, the material after drying roasts 4 hours at 550 DEG C in a nitrogen atmosphere, is made
Desulfurization catalyst of flue gas C2, catalyst property are shown in Table 1.
Embodiment 3
(1) carbon black powder is added in the ethanol solution containing ethyl orthosilicate to (it is 1:25, positive silicon that wherein liquid, which consolidates mass ratio,
Acetoacetic ester is with SiO2Meter is 4:1 with the mass ratio of carbon black powder), (energy density of ultrasonic disperse is under the conditions of ultrasonic disperse
2kW/L, ultrasonic disperse temperature are 30 DEG C, and the ultrasonic disperse time is 0.5 hour) it is uniformly mixed, filtering, dry 2 at 50 DEG C of solid phase
Hour, it is dried, obtains the modified carbon black powder of silicon source；
(2) the carbon black powder 160g(for obtaining step (1) is in terms of carbon black powder weight), boehmite dry glue powder 800g(oxygen
Change aluminium butt 65wt%), 7g nitric acid, 3g citric acid, 3g sesbania powder and 350g pure water kneading extrusion molding is added, then in nitrogen
It is handled 3 hours for 400 DEG C in gas, is roasted 5 hours for 500 DEG C in air atmosphere, obtain silicon-containing alumina carrier；
(3) dense with 20ml mass when spray dipping for the first time only using four spray dippings with 1 step of embodiment (3)
The aqueous solution for the mannitol that degree is 50%, the aqueous solution for the sorbierite that second of spray is 30% with 40ml mass concentration when impregnating,
The aqueous solution for the sorbierite for being 20% with 20ml mass concentration when third time spray dipping, with 20ml matter when the 4th spray impregnates
The aqueous solution for the sorbierite that concentration is 10% is measured, heat treatment temperature is 100 DEG C, and heat treatment time is 90 minutes.Temperature when charing process
Degree is 240 DEG C, and carbonization time is 12 hours；
(4) carrier after drying is impregnated above-mentioned carrier 3 hours with nickeliferous and tungsten (nickel nitrate and ammonium metatungstate) maceration extract,
Redundant solution is filtered, 8 hours dry at 110 DEG C, the material after drying roasts 5 hours at 550 DEG C in a nitrogen atmosphere, makes
Desulfurization catalyst of flue gas C3 is obtained, catalyst property is shown in Table 1.
Comparative example 1
With embodiment 1, the carbon black modified process of the process of step (1) is only omitted, step (2) is not obtained without silicon
The modified alumina support in source, the xylitol of step (3) changes the sorbierite that mass ratio is 1:1 into and the mixed alcohol of mannitol is water-soluble
Liquid dipping, temperature is 220 DEG C when charing process, and the processing time is 10 hours.Desulfurization catalyst of flue gas C4 of the present invention, catalysis is made
Agent property is shown in Table 1.
Comparative example 2
With embodiment 1, only before alumina support dipping active component without alcohol and/or sugar juice dipping and hydro-thermal at
Reason, is made comparative catalyst C5, and catalyst property is shown in Table 1.
Comparative example 3
With embodiment 1, only impregnates, 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 C6 is made, and catalyst property is shown in Table 1.
Comparative example 4
With embodiment 1, the xylose alcohol solution of same volume and mass concentration is mixed into primary spray leaching when only impregnating
Comparative catalyst C7 is made in stain, and catalyst property is shown in Table 1.
1 catalyst property of table.
Embodiment 9
The following examples illustrate desulfurization catalyst of flue gas provided by the invention and the catalytic performance of comparative catalyst.Catalysis
The benchmark test selection of agent C1-C7 carries out in atmospheric fixed bed reactor, and reactor material is quartz glass, internal diameter 10
Mm, the dosage of catalyst are 0.5g.Before catalyst is for reacting, at 600 DEG C, 0.5% SO of 35ml/min2/ 2.5% H2/
N2Presulfurization 2.5h in gaseous mixture.
The reaction temperature of evaluation test is 400 DEG C, reaction velocity 10000h-1, SO2And H2It is mixed after being diluted respectively with nitrogen
It closes and enters reactor, n (H2)/n(SO2) ratio be 3, inlet SO2Volume fraction is 0.3%, react generation elemental sulfur and
Vapor is collected by the condenser for being placed in reactor outlet, with flue gas analyzer to the SO in exit2On-line analysis is carried out, is calculated
SO2Conversion ratio and simple substance Recovery ratio, evaluation result are shown in Table 2.
2 desulfurization catalyst of flue gas performance comparison of table.
| C1 | C2 | C3 | C4 | C5 | C6 | C7 | |
| SO2Conversion ratio, % | 96.2 | 97.6 | 99.4 | 95.6 | 73.7 | 75.4 | 86.6 |
| S yield, % | 88.6 | 85.7 | 86.5 | 81.7 | 56.2 | 60.7 | 63.9 |
It can be seen from 2 data of table compared with comparative catalyst, catalyst flue gas with higher provided by the invention is de-
Sulphur activity and simple substance Recovery ratio.
Claims (15)
1. a kind of high activity desulfurization catalyst of flue gas, including silicon-containing alumina carrier, active metal and carbon；It is with catalyst weight
Benchmark, active metal weight are calculated as 5wt%-20wt% with oxide, and carbon is 1wt%-15wt%, silicon-containing alumina carrier based on the element
For 70wt% ~ 93wt%；On the basis of silicon-containing alumina vehicle weight, dioxide-containing silica is 1wt% ~ 10wt%；Wherein activity gold
Belong to selected from one or more of Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce；Specific surface is 160-300m2/ g, Kong Rongwei
0.4-1.2mL/g；The preparation method of the high activity desulfurization catalyst of flue gas, including following content: (1) carbon black powder is added
It into the ethanol solution containing silicon source, is uniformly mixed, is separated by solid-liquid separation under the conditions of ultrasonic disperse, solid phase is dried, obtains
The carbon black powder modified to silicon source；(2) carbon black powder that obtains step (1), boehmite dry glue powder, extrusion aid, peptizing agent and
Water kneading extrusion molding, then high-temperature process in an oxygen-free atmosphere roast in oxygen-containing atmosphere, obtain silicon-containing alumina carrier；(3)
The polyalcohol and/or monosaccharide aqueous solution for preparing at least two various concentrations, spray according to the sequence of concentration from high to low siliceous
On alumina support so that the concentration of polyalcohol and/or monosaccharide formed on silicon-containing alumina carrier ecto-entad be in by as low as
High gradient distribution；(4) carrier after dipping is carried out to hydro-thermal charing process in sealing container, is dried；(5) with activity
The carrier that metal impregnation liquid impregnation steps (4) obtain, dry, then anaerobic high-temperature process, obtains desulfurization catalyst of flue gas.
2. catalyst described in accordance with the claim 1, it is characterised in that: carbon content meets the following conditions: apart from catalyst granules
The carbon content ratio of carbon content and catalyst granules cross-section center at cross-section center 1/4R is 60%-80%, apart from catalyst
Carbon content and catalyst granules cross-section center carbon content ratio are 40%-60% at the 1/2R of particle cross section center, apart from catalyst
Carbon content and catalyst granules cross-section center carbon content ratio are 20%-40% at the 3/4R of particle cross section center, and cross section is outermost
The carbon content at any point and catalyst granules cross-section center carbon content ratio 5%-20% on edge, R are catalyst granules cross section
Center is between any point in the outer most edge of cross section at a distance from line segment.
3. a kind of preparation method of high activity desulfurization catalyst of flue gas of any of claims 1 or 2, it is characterised in that including as follows
Carbon black powder: (1) being added in the ethanol solution containing silicon source by content, is uniformly mixed under the conditions of ultrasonic disperse, is separated by solid-liquid separation,
Solid phase is dried, and obtains the modified carbon black powder of silicon source；(2) carbon black powder, the boehmite dry glue obtained step (1)
Powder, extrusion aid, peptizing agent and water kneading extrusion molding, then high-temperature process in an oxygen-free atmosphere are roasted in oxygen-containing atmosphere, are obtained
Silicon-containing alumina carrier；(3) prepare at least two various concentrations polyalcohol and/or monosaccharide aqueous solution, according to concentration by height to
Low sequence sprays on silicon-containing alumina carrier, so that the concentration of polyalcohol and/or monosaccharide shape on silicon-containing alumina carrier
At ecto-entad in gradient distribution from low to high；(4) carrier after dipping is carried out to hydro-thermal charing process in sealing container,
It is dried；(5) carrier obtained with active metal maceration extract impregnation steps (4), dry, then anaerobic high-temperature process, obtains
Desulfurization catalyst of flue gas.
4. according to the method for claim 3, it is characterised in that: carbon black powder described in step (1) and the ethyl alcohol containing silicon source are molten
The solid-liquid mass ratio of liquid is 1:5 ~ 1:30.
5. according to the method for claim 3, it is characterised in that: silicon source described in step (1) is in terms of silica and carbon black
The mass ratio of powder is 5:1~1:1.
6. according to the method for claim 3, it is characterised in that: ultrasonic disperse condition described in step (1) are as follows: ultrasonic disperse
Energy density be 0.2 ~ 4kW/L, ultrasonic disperse temperature be 15 ~ 80 DEG C, the ultrasonic disperse time be 0.5 ~ 10 hour.
7. according to the method for claim 3, it is characterised in that: the addition of the modified carbon black powder of silicon source described in step (2)
Amount is calculated as 5% ~ 20% with carbon black powder weight, on the basis of boehmite dry glue powder weight.
8. according to the method for claim 3, it is characterised in that: oxygen-free atmosphere described in step (2) is inert atmosphere, N2、CO
Or CO2One or more of atmosphere, oxygen-free atmosphere high-temperature process temperature are 350 ~ 450 DEG C, and the processing time is 2 ~ 8 hours.
9. according to the method for claim 3, it is characterised in that: oxygen-containing atmosphere described in step (2) is air, oxygen and nitrogen
One of mixture or oxygen and the mixture of inert gas of gas, the volume fraction of oxygen in the gas phase are 20% ~ 40%；Institute
The maturing temperature stated is 350~800 DEG C, and calcining time is 2~8 hours.
10. according to the method for claim 3, it is characterised in that: polyalcohol described in step (3) includes xylitol, sorb
One or more of alcohol, mannitol or arabite；The monosaccharide includes one of glucose, ribose or fructose or several
Kind；The mass concentration of the polyalcohol and/or monosaccharide aqueous solution is 5% ~ 50%.
11. according to the method for claim 3, it is characterised in that: described in step (3) according to concentration spraying from high to low
Sequentially, the concentration difference of adjacent polyalcohol twice and/or monosaccharide aqueous solution is 5% ~ 30%.
12. according to the method for claim 3, it is characterised in that: step (3) prepare 3 kinds of various concentrations polyalcohol and/or
Monosaccharide aqueous solution is sprayed, and detailed process is as follows: being sprayed for the first time, the mass concentration of polyalcohol and/or monosaccharide aqueous solution is
The dosage of 30%-50%, polyalcohol and/or monosaccharide aqueous solution is the 20%-30% of silicon-containing alumina carrier water absorption；Second of spray
Leaching, the mass concentration of polyalcohol and/or monosaccharide aqueous solution are 10%-30%, and the dosage of polyalcohol and/or monosaccharide aqueous solution is siliceous
The 40%-60% of alumina support water absorption；Third time sprays, and the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 5%-10%,
The dosage of polyalcohol and/or monosaccharide aqueous solution is the 10%-40% of silicon-containing alumina carrier water absorption.
13. according to the method for claim 3, it is characterised in that: hydro-thermal charing process temperature described in step (4) is 180-
250 DEG C, hydrothermal conditions are 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
14. according to the method for claim 3, it is characterised in that: in the method for the present invention, anaerobic high temperature described in step (5)
Treatment conditions are as follows: treatment temperature is 400-600 DEG C, and the processing time is 3-6 hours；Wherein the atmosphere of anaerobic high-temperature process is nitrogen
Or inert atmosphere, wherein inert atmosphere is one or more of helium, neon or argon gas.
15. a kind of high activity desulfurization catalyst of flue gas answering in catalytic reducing smoke desulphurization reaction of any of claims 1 or 2
With.
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