CN106732631A - 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 calculated as 1wt%-15wt% with 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, pore volume is 0.4-1.2ml/g.Preparation method is as follows：The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed on silicon-containing alumina carrier according to concentration order 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, and catalyst strength is high, can stablize and operate for a long time.
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 cause that acid rain is formed, severe contamination environment is serious to harm, coal-fired flue-gas discharge is SO2Main source.Traditional flue gas desulfurization is wet desulphurization, this method complex process, and investment cost is big, and produces secondary pollution, and 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 the desulfurization of coal-fired or smoke of oil-fuel boiler, low with operating cost, accessory substance (sulphur) using the advantages of.By SO2Directly catalysis is reduced to sulphur from flue gas, 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 by catalysis reduction and desulfurization mainly has CH4, CO and H2Deng gas.Presently the most common catalyst is usually the loaded catalyst with the transition metal such as Co, Ni, Mo, W, Fe, Cu, Zn, rare earth oxide and its sulfide as active component as carrier with aluminum oxide, ceria, silica, titanium dioxide etc..Active component is loaded on carrier using the method for dipping or kneading, and catalyst then is obtained by drying, being calcined.In roasting process, active metal component easily has an effect to form very strong M-O-Al keys with alumina support, cause active component formed Spinel and lose activity, or active component cannot complete cure so as to reduce catalyst activity.
CN1298755A discloses a kind of catalyst and its application process for processing SO 2 in waste gas, and each component weight ratio of catalyst is activated coke 80-98%, Co1-10%, Mo1-10%.After catalyst is through vulcanizing treatment, for hydrogen selective catalytic reduction SO2It is elemental sulfur, reaction temperature is 250-400 DEG C, H2/SO2Mol ratio is 2：1-4：1,85% sulphur yield can be obtained.But catalyst different activities component interphase interaction prepared by the method forms new compound, is unfavorable for active component dispersed and active further raising on carrier, in addition, sulphur yield also awaits improving.
CN102962064A discloses a kind of γ types alumina load metal oxide catalyst, preparation method and applications.The γ type aluminium oxide catalysts have the advantages that adjustable pore structure, specific surface area are big, absorption property is good, high mechanical strength, surface have acid and heat endurance good.The catalyst is used for flue gas and desulfurizing and denitrifying, and using CO as reducing agent, nitric oxide and sulfur dioxide to containing in flue gas carry out catalysis reduction, specifically in fluid catalytic cracking FCC flue gases, the fume treatment field of station boiler.But it is strong to there is also active component and carrier interphase interaction, is unfavorable for that active component is dispersed on carrier, vulcanization and activity are further improved.
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, carbon content distribution gradient in catalyst of the present invention, catalyst exterior active component is relatively strong with carrier function, internal active component and carrier acts on relatively weak, the easy complete cure of active component, significantly improves catalyst desulfurizing activity, catalyst strength is high simultaneously, is adapted 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；On the basis of catalyst weight, active metal weight is calculated as 5wt%-20wt%, preferably 10wt% ~ 15wt% with oxide, and carbon is calculated as 1wt%-15wt%, preferably 5wt%-10wt% with element, and silicon-containing alumina carrier is 70wt% ~ 93wt%, preferably surplus；On the basis of silicon-containing alumina vehicle weight, dioxide-containing silica is 1wt% ~ 10wt%；Wherein active metal is selected from one or more in Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce, preferably one or more in Co, Ni, Mo, W, a kind of combination more preferably in Ni and W, Co and Mo；Specific surface is 160-300m2/ g, pore volume is 0.4-1.2ml/g；Carbon content meets following condition：Apart from catalyst granules cross-section center（Hereinafter referred to as center）Carbon content and the carbon content ratio of catalyst granules cross-section center at 1/4R are 60%-80%, it is preferred that 65% ~ 75%, carbon content and center carbon content ratio are 40%-60% at distance center 1/2R, it is preferred that 45%-55%, carbon content and center carbon content ratio are 20%-40% at distance center 3/4R, it is preferred that 25% ~ 35%, the carbon content at any point compares 5%-20% with center carbon content in the outer most edge of cross section, it is preferred that the distance of 10% ~ 15%, R for line segment between any point in the cross-section center and cross section outer most edge of catalyst granules.
The carbon content of carbon content and catalyst granules cross-section center of the present invention at any point in catalyst granules cross-section center 1/4R, 1/2R, 3/4R, cross section outer most edge is measured by electron probe.
Catalyst of the present invention is（It is solid）It is granular, rather than amorphous states such as powder.Used as the shape of the particle, it is conventional use of variously-shaped to enumerate this area desulfurization catalyst of flue gas, such as can further enumerate spherical and column.As described spherical, such as can enumerate spheroidal and elliposoidal etc.；As the column, such as 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 a minimum dimension direction for catalyst granules by exposed whole surface after the geometric center cutting of its shape.Such as, when the catalyst granules is spherical, the cross section refers to radius or short-axis direction along the ball by exposed whole surface after the cutting of its centre of sphere.Or, when the catalyst granules is column, the cross section is referred to perpendicular to the length dimension direction of the post by exposed whole surface after the central point cutting of the length dimension（Referring to Fig. 1）.
In the present invention, the periphery of the exposed surface is referred to as the outer most edge of the cross section, by the geometric center（Than the centre of sphere as the aforementioned or the central point of length dimension）Central point referred to as on the cross section.
The preparation method of high activity desulfurization catalyst of flue gas of the invention, including following content：
（1）Carbon powder is added in the ethanol solution containing silicon source, is well mixed under the conditions of ultrasonic disperse, separation of solid and liquid, solid phase is dried treatment, obtain the modified carbon powder of silicon source；
（2）By step（1）Carbon powder, boehmite dry glue powder, extrusion aid, peptizing agent and the water kneading extrusion molding for obtaining, then high-temperature process in an oxygen-free atmosphere, is calcined in oxygen-containing atmosphere, obtains silicon-containing alumina carrier；
（3）Prepare the polyalcohol and/or the monose aqueous solution of at least two various concentrations, sprayed on silicon-containing alumina carrier according to concentration order from high to low so that the concentration of polyalcohol and/or monose forms ecto-entad in gradient distribution from low to high on silicon-containing alumina carrier；
（4）Carrier after dipping is carried out into hydro-thermal charing process, dried process in sealing container；
（5）With active metal maceration extract impregnation steps（4）The carrier for obtaining, dries, and then anaerobic high-temperature process, obtains desulfurization catalyst of flue gas.
In the inventive method, step（1）Described carbon powder can be selected from commercial goods, such as acetylene carbon black, N330 carbon blacks, FW200 carbon blacks.
In the inventive method, step（1）Described carbon powder is 1 with the solid-liquid mass ratio of the ethanol solution containing silicon source：5~1：30.
In the inventive method, step（1）It is 5 that described silicon source is counted with the mass ratio of carbon powder with silica：1~1：1.
In the inventive method, step（1）Described ultrasonic disperse condition is：The energy density of ultrasonic disperse is 0.2 ~ 4kW/L, and ultrasonic disperse temperature is 15 ~ 80 DEG C, and the ultrasonic disperse time is 0.5 ~ 10 hour.
In the inventive method, step（1）Described separation of solid and liquid can be using usual manners such as filtering, centrifugations.
In the inventive method, step（1）Described drying condition is：30 ~ 100 DEG C of drying temperature, drying time is 0.1 ~ 10 hour.
In the inventive method, step（2）The addition of the modified carbon powder of described silicon source is calculated as 5% ~ 20%, preferably 8% ~ 15% with carbon powder weight, on the basis of boehmite dry glue powder weight.
In the inventive method, step（2）Described extrusion aid, peptizing agent prepare the material commonly used in alumina process for kneading method, one or more in the medium peptizing agent of such as sesbania powder, starch, methylcellulose extrusion aid, and formic acid, acetic acid, citric acid, phosphoric acid, nitric acid.Extrusion aid addition is generally 3% ~ 5%, and the addition of peptizing agent is generally 3% ~ 10%, on the basis of boehmite dry glue powder weight；Wherein the addition of extrusion aid, peptizing agent and water with can kneading formed depending on plastic carries out extrusion molding.
In the inventive method, step（2）The graininess silicon-containing alumina carrier for obtaining can be that spherical or cylindricality is wherein spherical can be for spheroidal or elliposoidal, and cylindricality can be with cylinder, square column type or abnormity（Clover, bunge bedstraw herb or five tooth balls）.
In the inventive method, step（2）Described oxygen-free atmosphere is inert atmosphere, N2, CO or CO2Etc. one or more in atmosphere, oxygen-free atmosphere high-temperature process temperature is 350 ~ 450 DEG C, and process time is 2 ~ 8 hours.
In the inventive method, step（2）Described oxygen-containing atmosphere is generally the one kind in the mixture of the mixture of air, oxygen and nitrogen or oxygen and inert gas, and oxygen volume fraction in the gas phase is 20% ~ 40%.Described sintering temperature is 350~800 DEG C, and preferably 500~700 DEG C, roasting time is 2~8 hours, preferably 3~5 hours.
In the inventive method, step（3）Described polyalcohol including xylitol, sorbierite, mannitol or arabite etc. in one or more；Described monose including glucose, ribose or fructose etc. in one or more.
In the inventive method, step（3）Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5% ~ 50%.
In the inventive method, step（3）It is described according to concentration from high to low spray order, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5% ~ 30%, preferably 10% ~ 20%；It is preferred that preparing 2 ~ 4 kinds of polyalcohols and/or the monose aqueous solution of various concentrations.
In the inventive method, step（3）The described maceration extract consumption for spraying every time is 10%-60%, the preferably 20%-30% of silicon-containing alumina carrier saturated water adsorptive value, and the total consumption of maceration extract for repeatedly spraying is the saturated water adsorptive value of silicon-containing alumina carrier, to ensure that carrier saturation impregnates.
In the inventive method, step（3）It is preferred that the polyalcohol and/or the monose aqueous solution of preparing 3 kinds of various concentrations are sprayed, detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, the consumption of polyalcohol and/or the monose aqueous solution is the 20%-30% of silicon-containing alumina carrier water absorption；Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10%-30%, the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of silicon-containing alumina carrier water absorption；Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, and the consumption of polyalcohol and/or the monose aqueous solution is the 10%-40% of silicon-containing alumina carrier water absorption.
In the inventive method, step（4）Described hydro-thermal charing process temperature is 180-250 DEG C, and preferably 200-230 DEG C, hydrothermal conditions are 6-12 hours, and preferably 8-10 hours, hydro-thermal process pressure was self-generated pressure, ensure that polyalcohol and/or monose are carbonized completely under this hydro-thermal carbonization condition.Wherein, self-generated pressure is relevant with treatment temperature, when temperature is 100 DEG C, pressure 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（4）Described silicon-containing alumina carrier carries out sealing heat treatment preferably before charing process, and heat treatment condition is：80 ~ 130 DEG C are processed 0.5 ~ 2 hour.
In the inventive method, step（5）Described load active component used volume impregnation, incipient impregnation or spray impregnating method, and dip time is 1-5 hours, preferably crosses volume impregnation.Wherein, the soluble compound of active component is chosen in the preparation of maceration extract, and the specific concentration of maceration extract can be according to depending on the active metallic content on final catalyst.
In the inventive method, described drying condition is and is dried at 80-120 DEG C 6-10 hours.
In the inventive method, step（5）Described anaerobic high-temperature process condition is：Treatment temperature is 400-600 DEG C, and process time is 3-6 hours；Wherein the atmosphere of anaerobic high-temperature process can be nitrogen or inert atmosphere, and wherein inert atmosphere is one or more in helium, neon or argon gas.
High activity desulfurization catalyst of flue gas of the invention is used for catalytic reducing smoke desulphurization reaction, and general technology condition is：With H2As a example 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。
Catalyst of the present invention has the following advantages that with prior art ratio：
（1）In the prior art by the property of Si modification alumina carrier surface, the specific duct to alumina support that cannot typically have target is modified, and in modifying process, Ludox micelle is easily penetrated into aluminum oxide major part duct（It is macropore, mesoporous）In, cause the pore volume of carrier to be greatly lowered.The present invention wraps up silicon source by carbon black powder surface, during kneading prepares alumina support, is heat-treated by anaerobic, so that silicon source is fully contacted with aluminum oxide, and is converted into silica, further by calcination process, remove carbon powder particle, while reaming, SiO2The big hole surface of carbon powder particle formation is remained stuck to, is played a supporting role, the intensity of alumina support is enhanced, while SiO2Modifying function, the interaction for reducing active component and alumina carrier surface and the acidity for improving macroporous aluminium oxide surface improve the activity of catalyst, additionally, due to SiO2Supporting role ensure that the intensity of aluminum oxide macropore, so that alumina support is difficult to cave in, in preparation process, more carbon powders compared to existing technology can be added, so as to form more macropores, so as to improve the mass-transfer efficiency of flue gas desulfurization, catalyst duct is not easily blocked, and extends the life-span of catalyst.
（2）Polyalcohol and/or the monose aqueous solution spray dip forming silicon-containing alumina carrier of the inventive method various concentrations（Carrier）, then by hydro-thermal charing process, carbon-coating is formed on carrier surface and duct inwall；In spray dipping process, maceration extract is gradually permeated from surface under the effect of carrier duct capillary force to center, because when multistep is sprayed to be impregnated, the concentration of polyalcohol and/or monose is gradually reduced in maceration extract, it is ensured that the concentration of polyalcohol and/or monose is by carrier surface to center in incremental distribution.The thickness of carbon-coating is thicker in the relatively thin internal carbon-coating of distribution, i.e. carrier outside carbon-coating is incremented by from a surface to center after charing.Carrier after before carbon precursor is carbonized to dipping carries out sealing heat treatment, promotes the formation of absorption and carbon-coating of the carbon precursor on carrier；Material after dipping active component is in anaerobic high-temperature process, the presence of carbon-coating effectively prevents the strong interaction between metal component and carrier, because the gradient of carbon layers having thicknesses is distributed, effect between active metal and carrier gradually weakens from outside to inside, i.e. catalyst activity is gradually stepped up from outside to inside, in flue gas desulfurization course, promote the reaction inside catalyst duct, effectively prevent due to the outer surface active component activity phenomenon for making Dry FGD acutely cause catalyst duct to block and inactivating catalyst higher, the service life of catalyst is extended while catalyst activity is improved.
Brief description of the drawings
Fig. 1 catalyst granules is the cross-sectional view of cylinder.
Specific embodiment
The effect and effect of the inventive method are further illustrated with reference to embodiment, but is not limited to following examples.
Carbon and active metallic content are measured by JEOL's JXA-8230 electron probes in catalyst of the present invention, and the accelerating potential selected during measure is 15KV, and probe current is 8 × 10-8A, beam spot size is 3 μm.
Metering system：Respectively at measurement catalyst cross-section center and with catalyst cross-section center at distance be the carbon content and active metallic content at 1/4R, 1/2R, 3/4R and R, wherein R is the distance of line segment between any point in cross-section center and cross section outer most edge, then by division calculation, the ratio between each content is obtained.
Embodiment 1
（1）Carbon powder is added in the ethanol solution containing tetraethyl orthosilicate（Wherein solid-liquid mass ratio is 1：8, tetraethyl orthosilicate is with SiO2Meter is 2 with the mass ratio of carbon powder：1）, under the conditions of ultrasonic disperse（The energy density of ultrasonic disperse is 0.6kW/L, and ultrasonic disperse temperature is 40 DEG C, and the ultrasonic disperse time is 1 hour）Well mixed, filtering is dried 2 hours, dried process at 50 DEG C of solid phase, obtains the modified carbon powder of silicon source；
（2）By step（1）The carbon powder 54g for obtaining（In terms of carbon powder weight）, boehmite dry glue powder 600g（Aluminum oxide butt 65wt%）Add 6g nitric acid, 3g citric acids, 3g sesbania powders and 360g pure water kneading extrusion moldings, then in nitrogen 400 DEG C process 3 hours, 500 DEG C are calcined 5 hours in air atmosphere, obtain silicon-containing alumina carrier；
（3）By step（2）100 grams of the silicon-containing alumina carrier for obtaining is put into spray rolling pot, under rotary state, with atomizing type to the xylose alcohol solution 25ml that the carrier spray impregnating effect concentration in rolling pot is 40%；Then continued to spray oxide impregnation alumina supporter with the xylose alcohol solution 40ml that mass concentration is 20%；Finally continued to spray oxide impregnation alumina supporter with the xylose alcohol solution 40ml that mass concentration is 10%.Dipping terminates to be transferred to alumina support in autoclave, in 80 DEG C of sealing heat treatment 120 minutes, then heats to 180 DEG C, charing process 9 hours under self-generated pressure, naturally cools to room temperature.Then dried 3 hours at the alumina support after hydro-thermal process being placed in into 120 DEG C.
（4）Dried carrier is with containing 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 in being calcined 5 hours at 550 DEG C, is obtained desulfurization catalyst of flue gas C1 in a nitrogen atmosphere, and catalyst property is shown in Table 1.
Embodiment 2
（1）Carbon powder is added in the ethanol solution containing tetraethyl orthosilicate（Wherein solid-liquid mass ratio is 1：15, tetraethyl orthosilicate is with SiO2Meter is 3 with the mass ratio of carbon powder：1）, under the conditions of ultrasonic disperse（The energy density of ultrasonic disperse is 1kW/L, and ultrasonic disperse temperature is 50 DEG C, and the ultrasonic disperse time is 0.5 hour）Well mixed, filtering is dried 2 hours, dried process at 50 DEG C of solid phase, obtains the modified carbon powder of silicon source；
（2）By step（1）The carbon powder 160g for obtaining（In terms of carbon powder weight）, boehmite dry glue powder 1000g（Aluminum oxide butt 65wt%）, add 10g nitric acid, 4g citric acids, 4g sesbania powders and 350g pure water kneading extrusion moldings, then in nitrogen 450 DEG C process 3 hours, 500 DEG C are calcined 5 hours in air atmosphere, obtain silicon-containing alumina carrier；
（3）With the step of embodiment 1（3）With the aqueous solution of the sorbierite that 30ml mass concentrations are 30% when simply spray impregnates for the first time, with the aqueous solution of the sorbierite that 50ml mass concentrations are 10% during second spray dipping, with the aqueous solution of the sorbierite that 20ml mass concentrations are 5% during third time spray dipping, heat treatment temperature is 130 DEG C, and heat treatment time is 60 minutes.Temperature is 200 DEG C during charing process, and carbonization time is 8 hours；
（4）Dried carrier is with containing 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 in being calcined 4 hours at 550 DEG C, is obtained desulfurization catalyst of flue gas C2 in a nitrogen atmosphere, and catalyst property is shown in Table 1.
Embodiment 3
（1）Carbon powder is added in the ethanol solution containing tetraethyl orthosilicate（The wherein solid mass ratio of liquid is 1：25, tetraethyl orthosilicate is with SiO2Meter is 4 with the mass ratio of carbon powder：1）, under the conditions of ultrasonic disperse（The energy density of ultrasonic disperse is 2kW/L, and ultrasonic disperse temperature is 30 DEG C, and the ultrasonic disperse time is 0.5 hour）Well mixed, filtering is dried 2 hours, dried process at 50 DEG C of solid phase, obtains the modified carbon powder of silicon source；
（2）By step（1）The carbon powder 160g for obtaining（In terms of carbon powder weight）, boehmite dry glue powder 800g（Aluminum oxide butt 65wt%）, add 7g nitric acid, 3g citric acids, 3g sesbania powders and 350g pure water kneading extrusion moldings, then in nitrogen 400 DEG C process 3 hours, 500 DEG C are calcined 5 hours in air atmosphere, obtain silicon-containing alumina carrier；
（3）With the step of embodiment 1（3）Simply using four spray dippings, for the first time with the aqueous solution of the mannitol that 20ml mass concentrations are 50% during spray dipping, with the aqueous solution of the sorbierite that 40ml mass concentrations are 30% during second spray dipping, with the aqueous solution of the sorbierite that 20ml mass concentrations are 20% during third time spray dipping, with the aqueous solution of the sorbierite that 20ml mass concentrations are 10% during the 4th spray dipping, heat treatment temperature is 100 DEG C, and heat treatment time is 90 minutes.Temperature is 240 DEG C during charing process, and carbonization time is 12 hours；
（4）Dried carrier is with nickeliferous and tungsten（Nickel nitrate and ammonium metatungstate）Maceration extract impregnate above-mentioned carrier 3 hours, filter redundant solution, dried 8 hours at 110 DEG C, dried material in being calcined 5 hours at 550 DEG C, is obtained desulfurization catalyst of flue gas C3 in a nitrogen atmosphere, and catalyst property is shown in Table 1.
Comparative example 1
With embodiment 1, step is simply omitted（1）Process carbon black modified process, step（2）The alumina support being modified without silicon source, step are not obtained（3）Xylitol change mass ratio into for 1:1 sorbierite and the mixed alcohol aqueous impregnation of mannitol, temperature is 220 DEG C during charing process, and process time is 10 hours.Desulfurization catalyst of flue gas C4 of the present invention is obtained, catalyst property is shown in Table 1.
Comparative example 2
With embodiment 1, comparative catalyst C5 simply is obtained without alcohol and/or sugar juice dipping and hydro-thermal process before alumina support dipping active component, catalyst property is shown in Table 1.
Comparative example 3
With embodiment 1, simply impregnated without polyalcohol and/or monosaccharide solutions before alumina support dipping active component, hydro-thermal process is carried out with deionized water dipping and in autoclave, comparative catalyst C6 is obtained, catalyst property is shown in Table 1.
Comparative example 4
The xylose alcohol solution of same volume and mass concentration is mixed into once spray dipping with embodiment 1, when simply impregnating comparative catalyst C7 is obtained, catalyst property is shown in Table 1.
The catalyst property of table 1.
Embodiment 9
Desulfurization catalyst of flue gas and the catalytic performance of comparative catalyst that the following examples explanation present invention is provided.The benchmark test selection of catalyst C1-C7 is carried out in atmospheric fixed bed reactor, and reactor material is quartz glass, the mm of internal diameter 10, and the consumption of catalyst is 0.5g.Before catalyst is used to react, 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, and reaction velocity is 10000h-1, SO2And H2Reactor, n (H are mixed into after being diluted with nitrogen respectively2)/n(SO2) ratio be 3, porch SO2Volume fraction is 0.3%, and the elemental sulfur and vapor for reacting generation are collected by the condenser for being placed in reactor outlet, with flue gas analyzer to the SO in exit2On-line analysis is carried out, SO is calculated2Conversion 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 | |
| SO2Conversion ratio, % | 96.2 | 97.6 | 99.4 | 95.6 | 73.7 | 75.4 | 86.6 |
| S yields, % | 88.6 | 85.7 | 86.5 | 81.7 | 56.2 | 60.7 | 63.9 |
Be can be seen that compared with comparative catalyst by the data of table 2, the catalyst that the present invention is provided has flue gas desulfurization activity and simple substance Recovery ratio higher.
Claims (15)
1. a kind of high activity desulfurization catalyst of flue gas, 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 calculated as 1wt%-15wt% with element, and silicon-containing alumina carrier is 70wt% ~ 93wt%；On the basis of silicon-containing alumina vehicle weight, dioxide-containing silica is 1wt% ~ 10wt%；Wherein active metal is selected from one or more in Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce；Specific surface is 160-300m2/ g, pore volume is 0.4-1.2ml/g.
2. according to the catalyst described in claim 1, it is characterised in that：Carbon content meets following condition：Apart from catalyst granules cross-section center（Hereinafter referred to as center）Carbon content and the carbon content ratio of catalyst granules cross-section center at 1/4R are 60%-80%, carbon content and center carbon content ratio are 40%-60% at distance center 1/2R, carbon content and center carbon content ratio are 20%-40% at distance center 3/4R, with center carbon content than 5%-20%, R is the distance of line segment between any point in the cross-section center and cross section outer most edge of catalyst granules to the carbon content at any point in the outer most edge of cross section.
3. the preparation method of the high activity desulfurization catalyst of flue gas described in a kind of claim 1 or 2, it is characterised in that including following content：（1）Carbon powder is added in the ethanol solution containing silicon source, is well mixed under the conditions of ultrasonic disperse, separation of solid and liquid, solid phase is dried treatment, obtain the modified carbon powder of silicon source；（2）By step（1）Carbon powder, boehmite dry glue powder, extrusion aid, peptizing agent and the water kneading extrusion molding for obtaining, then high-temperature process in an oxygen-free atmosphere, is calcined in oxygen-containing atmosphere, obtains silicon-containing alumina carrier；（3）Prepare the polyalcohol and/or the monose aqueous solution of at least two various concentrations, sprayed on silicon-containing alumina carrier according to concentration order from high to low so that the concentration of polyalcohol and/or monose forms ecto-entad in gradient distribution from low to high on silicon-containing alumina carrier；（4）Carrier after dipping is carried out into hydro-thermal charing process, dried process in sealing container；（5）With active metal maceration extract impregnation steps（4）The carrier for obtaining, dries, and then anaerobic high-temperature process, obtains desulfurization catalyst of flue gas.
4. in accordance with the method for claim 3, it is characterised in that：Step（1）Described carbon powder is 1 with the solid-liquid mass ratio of the ethanol solution containing silicon source：5~1：30.
5. in accordance with the method for claim 3, it is characterised in that：Step（1）It is 5 that described silicon source is counted with the mass ratio of carbon powder with silica：1~1：1.
6. in accordance with the method for claim 3, it is characterised in that：Step（1）Described ultrasonic disperse condition is：The energy density of ultrasonic disperse is 0.2 ~ 4kW/L, and ultrasonic disperse temperature is 15 ~ 80 DEG C, and the ultrasonic disperse time is 0.5 ~ 10 hour.
7. in accordance with the method for claim 3, it is characterised in that：Step（2）The addition of the modified carbon powder of described silicon source is calculated as 5% ~ 20% with carbon powder weight, on the basis of boehmite dry glue powder weight.
8. in accordance with the method for claim 3, it is characterised in that：Step（2）Described oxygen-free atmosphere is inert atmosphere, N2, CO or CO2One or more in atmosphere, oxygen-free atmosphere high-temperature process temperature is 350 ~ 450 DEG C, and process time is 2 ~ 8 hours.
9. in accordance with the method for claim 3, it is characterised in that：Step（2）Described oxygen-containing atmosphere is the one kind in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and oxygen volume fraction in the gas phase is 20% ~ 40%；Described sintering temperature is 350~800 DEG C, and roasting time is 2~8 hours.
10. in accordance with the method for claim 3, it is characterised in that：Step（3）Described polyalcohol includes one or more in xylitol, sorbierite, mannitol or arabite；Described monose includes one or more in glucose, ribose or fructose；Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5% ~ 50%.
11. in accordance with the method for claim 3, it is characterised in that：Step（3）It is described according to concentration from high to low spray order, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5% ~ 30%.
12. in accordance with the method for claim 3, it is characterised in that：Step（3）The polyalcohol and/or the monose aqueous solution for preparing 3 kinds of various concentrations are sprayed, and detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, the consumption of polyalcohol and/or the monose aqueous solution is the 20%-30% of silicon-containing alumina carrier water absorption；Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10%-30%, the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of silicon-containing alumina carrier water absorption；Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, and the consumption of polyalcohol and/or the monose aqueous solution is the 10%-40% of silicon-containing alumina carrier water absorption.
13. in accordance with the method for claim 3, it is characterised in that：Step（4）Described hydro-thermal charing process temperature is 180-250 DEG C, and hydrothermal conditions are 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
14. in accordance with the method for claim 3, it is characterised in that：In the inventive method, step（5）Described anaerobic high-temperature process condition is：Treatment temperature is 400-600 DEG C, and process time is 3-6 hours；Wherein the atmosphere of anaerobic high-temperature process is nitrogen or inert atmosphere, and wherein inert atmosphere is one or more in helium, neon or argon gas.
High activity desulfurization catalyst of flue gas described in a kind of 15. claims 1 or 2 is used for catalytic reducing smoke desulphurization reaction.
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