CN101306303B - Sulfur compound waste gas catalytic incineration method - Google Patents
Sulfur compound waste gas catalytic incineration method Download PDFInfo
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- CN101306303B CN101306303B CN2007100114159A CN200710011415A CN101306303B CN 101306303 B CN101306303 B CN 101306303B CN 2007100114159 A CN2007100114159 A CN 2007100114159A CN 200710011415 A CN200710011415 A CN 200710011415A CN 101306303 B CN101306303 B CN 101306303B
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Abstract
The invention provides a sulfur-containing compound waste gas catalytic incineration method. The method comprises the following steps: sulfur-containing compound waste gas is mixed with air, the mixture enters a catalytic incineration reactor after being preheated and is emitted after the catalytic incineration or emitted after the further desulphurization; wherein, the mixing ratio of the air is controlled to allow the peroxidation coefficient to be not less than 1.0, the preheating temperature is 200 to 300 DEG C, the reaction temperature is 200 to 400 DEG C, and the air speed is 1500 to 15000h<minus 1>. A catalytic incineration catalyst takes silicon dioxide as a carrier, and the active components are vanadium, iron oxide and silver. The method of the invention is applicable to the various sulfur recovery processes and the catalytic incineration treatment of tail gas of a geothermal power plant. The method of the invention with simple flow can effectively process the sulfur-containing compound waste gas with complicated components.
Description
Technical field
The present invention relates to a kind of sulfur compound waste gas catalytic incineration method, sulfur recovery tail gas catalytic burning technique method particularly, be applicable to that all kinds of sulphur return technology [as Crouse, super Crouse, reduction absorption process (SCOT, SSR), reduction-absorption-recirculation method (RAR) etc.] and the catalytic burning of geothermal power plant's tail gas is handled, hydrogen sulfide, carbon disulfide and cos sulfides in the tail gas can be converted into stink and all lower sulfur dioxide or the sulphur of toxicity.
Background technology
Sulphur in the oil plant processing crude oil is most of to be reclaimed by the form of its sulfur recovery unit with elemental sulfur, sulfur recovery technology comprises claus process and Crouse+tail-gas deep process for purifying two classes, at present in the domestic 77 cover sulfur recovery units of China, 51 covers are simple claus process, and 26 are arranged with tail-gas deep process for purifying such as super Crouse, low-temperature Claus or SCOT.The claus process sulfur recovery rate generally is no more than 96%, and Crouse+tail-gas deep process for purifying sulfur recovery rate is generally 98.5%～99.8%, and the sulphur of Hui Shouing does not enter sulfur recovery tail gas with forms such as hydrogen sulfide, sulfur dioxide, carbon disulfide, cos.No matter adopt which kind of sulfur recovery technology,,, could discharge after must burning for satisfying the odorant pollutant discharge standard because of containing a certain amount of hydrogen sulfide and organic sulfur compound in its tail gas.Since the combustible component (as hydrogen sulfide, cos, carbon monoxide, carbon disulfide, hydrogen, elementary sulfur and a small amount of oil gas) in the Claus tail gases often be lower than the tail gas total amount 3% (percentage composition of gas is a volumn concentration, down together), necessary postcombustion, could completing combustion, and be sulfur dioxide with sulfide oxidation.The tail gas burning process has thermal incineration and catalytic burning two classes, and domestic Cross unit tail gas adopts the thermal incineration method to handle substantially.The thermal incineration method is carried out excessive oxygen and 650～850 ℃ usually.Owing to be difficult to accurately control operating conditions such as incineration temperature, the situation that incinerator crumples often appears in the practice, reduced the service life of incinerator.Burn required auxiliary fuel consumption for reducing, and prolong the service life of incinerator, it is necessary adopting the catalytic burning technology.Catalytic burning can make the hydrogen sulfide in the tail gas be oxidized to sulfur dioxide with lower temperature (as 300～400 ℃) under catalyst action.The investment of catalytic burning is a little more than thermal incineration, and energy consumption and operating cost reduce significantly.The actual gain of catalytic burning is relevant with the scale of device, and the sulfur recovery unit of a 100t/d can be saved 1000m
3The combustion gas of/d, the fuel cost of catalyst length of life saving are more than 10 times of institute's spent catalyst expense.When unit scale was bigger, energy-saving effect was more remarkable.Along with riseing of oil gas price, the sulfur recovery tail gas catalytic burning technology of energy-conserving and environment-protective will progressively replace the higher thermal incineration technology of energy consumption.
Be lower than 99.5% common claus process for sulfur recovery rate, sulfur dioxide is difficult to qualified discharge in the tail gas.The many genus of these sulfur recovery units are middle-size and small-size, and production capacity is generally less than 10kt/a, substantially all is secondary or three grades of Crouses (Claus) technology, and the total sulfur conversion ratio is no more than 96%.If want qualified discharge, the total sulfur recovery of sulfur recovery unit must be higher than 99.5%.In the industrialized tail gas treatment process, have SCOT technology and similar technology (SSR, RAR etc.) only and can satisfy discharge standard.Along with the increase of sour crude processing capacity and the execution of discharge standard of air pollutants (GB16297-1996), sulfur recovery unit will be tending towards maximizing, and progressively adopt Crouse+tail-gas deep process for purifying (as SCOT, SSR, RAR etc.).Its key reaction is as follows:
Claus reaction:
3H
2S+3/2O
2→3S+2H
2O
H
2S+3/2O
2→SO
2+2H
2O
2H
2S+SO
2→3/2S+2H
2O
Crouse's side reaction:
CO
2+H
2S→COS+H
2O
COS+H
2S→CS
2+H
2O
2COS→CO
2+CS
2
The SCOT reaction:
S
2+2H
2→2H
2S
SO
2+3H
2→H
2S+2H
2O
CO+H
2O→CO
2+H
2
COS+H
2O→CO
2+H
2S
CS
2+2H
2O→CO
2+2H
2S
The SCOT side reaction:
SO
2+3CO→COS+2CO
2
S
2+2CO→2COS
H
2S+CO→COS+H
2
The concentration of hydrogen sulfide is about 500～1000ppm in the SCOT tail gas, cos is about 10～150ppm, nitrogen+argon gas accounts for 50%～60%, and (the gas percentage composition is a volumn concentration, down together), steam accounts for 20%～30%, hydrogen accounts for 0.5%～1.0%, and carbon monoxide accounts for 0.2%, and carbon dioxide accounts for 5%～15%.Hydrogen sulfide and organic sulfur compound (as carbon disulfide, cos) are that a class has the odorant pollutant of toxicity in various degree to human body, and for satisfying GB 14554-93 odorant pollutant discharge standard, SCOT tail gas must burn the back discharging.Sulfur recovery tail gas catalytic burning and thermal incineration contrast see Table 1, and from energy-conservation and environmental angle, catalytic burning obviously is better than thermal incineration.Claus tail gases and SCOT tail gas butt are formed contrast and are seen Table 2.The SCOT process tail gas is than Claus tail gases " cleaning ", wherein the concentration of carbon monoxide, sulfur dioxide, cos, carbon disulfide etc. is lower, and concentration of hydrogen sulfide is higher, and this class tail gas is difficult for polluting catalyst, be more suitable for handling in catalytic burning, the treatment effect of its sulfide is better.
Table 1 sulfur recovery tail gas catalytic burning and thermal incineration contrast
Table 2 Claus tail gases and SCOT tail gas are formed contrast
Sulfur recovery tail gas catalytic burning technology is commercial Application at home not as yet, the sulfur recovery tail gas catalytic burning technique extensive use abroad of the Shell Oil Company and IFP, Shell Oil Company's catalytic burning technique is mainly used in SCOT tail gas, and the sulfur recovery catalytic burning technique of IFP is mainly used in Claus tail gases.Two kinds of technological processes are similar, and air and sulfur recovery tail gas are mixed at preheater, through fuel gas burning preheating, enter reactor catalysis and burn, and tail gas effluxes atmosphere through chimney.The tail gas catalyzed burning process main operating parameters of the SCOT of the Shell Oil Company is: catalyst based S-099 of ball-aluminium oxide or CRITERION099,370 ℃ of reaction temperatures, air speed 7500h
-1, hydrogen sulfide exit concentration＜10ppm.IFP's sulfur recovery tail gas catalytic burning technique main operating parameters is: catalyst based RS 103 of ball-aluminium oxide or RS 105,300～400 ℃ of operating temperatures, catalyst air speed 2500～5000h
-1, peroxide amount 0.5%～1.5% (v/v), outlet hydrogen sulfide≤5ppm, carbon disulfide+cos≤150ppm.Above-mentioned two kinds of direct-fired preheatings of process using naked light, temperature and explosion-proof control are comparatively complicated, and the anti-sulfation ability of alumina base catalyst is relatively poor, and service life is shorter.
CN 1410149A discloses catalyst to burned and the preparation and the using method of hydrogen sulfide in a kind of gas, and the carrier of this catalyst is a silica, and active component is the oxide of iron and vanadium, 250～350 ℃ of operating temperatures, air speed 1000～10000h
-1, this technology and catalyst are relatively poor to the oxidation activity of organic sulfurs such as cos.CN1163785A discloses the catalytic burning technique of hydrogen sulfide in a kind of gas, is suitable for handling Claus tail gases, and with the active carbon catalyst, be under 200～400 ℃ in temperature, be sulfur dioxide with the hydrogen sulfide catalytic oxidation; Hydrogen sulfide content is 0.5%～4% (v/v), moisture content 4%～30% (v/v), air speed 3000～10000h
-1, the conversion ratio of hydrogen sulfide is 100%, sulfur dioxide production rate 90%～99%; This technology and catalyst are relatively poor to the oxidation activity of organic sulfurs such as cos.USP4576184, USP4444908, USP4528277, USP4444741, USP4444742, USP4314983 discloses a class hydrogen sulfide catalytic burning technique and a catalyst, the activity of such catalysts component comprises vanadium and bismuth, also can constitute by vanadium and tin or antimony, carrier is the porous refractory oxide, by aluminium oxide, silica-alumina, silica, titanium dioxide, zirconia, silica-titania, silica-zirconia, one or more formations in silica-zirconia-titanium dioxide, hydrogen sulfide can be oxidized to sulphur or sulfur dioxide, characteristics are when steam exists, and still have high activity and stability; For example active component is 11.6%Bi
2O
3+ 8.6%V
2O
5The catalyst of (it is the quality percentage composition that catalyst is formed percentage composition) is at 240 ℃ of reaction temperatures, air speed 2000h
-1, the hydrogen sulfide of 2717ppm is converted into sulfur dioxide fully, and hydrogen and methane are not oxidized; This technology and catalyst are relatively poor to the oxidation activity of organic sulfurs such as cos.USP4012486 discloses a kind of Claus tail gases catalytic burning technique, and catalyst carrier is an aluminium oxide, and active component is a bismuth, 150～450 ℃ of reaction temperatures.USP6019953 discloses a kind of gas burning process, is applicable to the catalytic burning of sulphide-rich gas.First metal component of catalyst is bismuth, molybdenum or chromium, and second metal component is one or more of Group IIA metal, and carrier is a refractory oxide, can not contain aluminium and phosphorus simultaneously in the carrier, and the hydrogen sulfide complete oxidation temperature that example provides is 500 ℃.USP4169136, USP4092404, USP4171347, USP4088743 disclose the catalytic burning technique of hydrogen sulfide in the class gas, this technology can be oxidized to sulfur dioxide with hydrogen sulfide, operating temperature is 150～480 ℃, the activity of such catalysts component is the oxide of vanadium and/or the sulfide of vanadium, and carrier is non-alkaline porous refractory oxide.A kind of well behaved catalyst is 5%～15% V
2O
5/ hydrogenation mordenite or aluminium oxide.Hydrogen in the feeding gas, carbon monoxide, lighter hydrocarbons and ammonia are not oxidized, and patent has been used for geothermal power plant's treatment of waste gas.USP 4399112 discloses a kind of sulphur-containing exhaust gas catalytic burning technique, can be used for the processing of Claus tail gases, this technology has two stages to constitute, be hydrogen sulfide at first with carbon disulfide, cos, mercaptan sulfides hydrogenating reduction, and then be sulfur dioxide with the hydrogen sulfide catalytic oxidation, the catalyst of its oxidation panel is ferric sulfate/titanium dioxide.
Above-mentioned existing sulfur compound waste gas catalytic incineration technology generally has the process complexity, can not handle complex component waste gas, the high deficiency of the complicated cost of catalytic component.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of sulfur compound waste gas catalytic incineration technology, it is simple that technology of the present invention has flow process, sulfur-containing compound conversion ratio advantages of higher.
Sulfur-containing compound catalytic incineration method of the present invention comprises following content, and sulfur-containing compound exhaust air mixes with air, enters the catalytic burning reactor after preheating, discharges after discharging behind the catalytic burning or the further desulfurization.The Air mixing proportion control is crossed oxygen quotient 〉=1.0, and best 1.5～3.0; Preheat temperature is 200～300 ℃, best 270～290 ℃; Reaction temperature is 200～400 ℃, best 320～350 ℃; Air speed is 1500～15000h
-1, best 6000～7500h
-1Desulfurization behind the catalytic burning adopts water elution to remove sulfur vapor, or adopts calcium, magnesium oxide to remove methods such as sulfur dioxide.
Catalytic incineration catalyst is carrier with silica, and active component is the oxide and the silver of vanadium, iron.In catalyst weight: the content of carrier is 65%～95%, and the oxide content of vanadium is 0.5%～15%, and the best is 4.0%～6.0%; The oxide content of iron is 0.5%～15%, and the best is 3.5%～5.5%; The content of silver is 0.05%～5%, and the best is 1.0%.Catalyst adopts conventional immersion process for preparing.
Catalytic burning technique of the present invention is applicable to that the catalytic burning that all kinds of sulphur return technology and geothermal power plant's tail gas handles, and the catalytic burning of absorption process and similar technology (SCOT, SSR, RAR) tail gas of being specially adapted to reduce is handled.Contain the tail gas of hydrogen sulfide, carbon disulfide and cos sulfides and stoichiometric air in blender mixed evenly after, enter preheater and be heated to assigned temperature, enter the catalyst based reactor of filling preparing spherical SiO 2 then, specifying under catalyst and the temperature, above-mentioned sulfide is converted into stink and all lower sulfur dioxide or the sulphur of toxicity, incineration tail gas removes sulfur vapor or sulfur dioxide in devulcanizer after, directly enter atmosphere by chimney.Preheater uses electric heater.
Possible catalytic reaction is as follows:
H
2S+1/2O
2→S+H
2O
S+O
2→SO
2
H
2S+3/2O
2→SO
2+H
2O
COS+3/2O
2→SO
2+CO
2
COS+1/2O
2→S+CO
2
COS+H
2O→H
2S+CO
2
CS
2+3O
2→2SO
2+CO
2
CS
2+2H
2O→2H
2S+CO
2
Under representative condition, as 350 ℃ of reaction temperatures, air speed 6000h
-1, when crossing oxygen quotient 2.0, concentration of hydrogen sulfide 0.2% (v/v), cos concentration 0.05% (v/v), the clearance of hydrogen sulfide is higher than 99.9%, the clearance of cos is higher than 90%.
Cross the ratio of oxygen quotient for the amount of the required oxygen of combustible complete oxidation in the amount of using oxygen and the waste gas.
It can be various suitable shape that the present invention uses catalyst, and as sphere, sheet shape, bar shaped etc., optimum shape is 4～6mm sphere, adopts saturated dipping or spraying-saturated immersion process for preparing, and preparation procedure is as follows:
(1) earlier the water soluble compound of vanadium is dissolved in oxalic acid solution, adds the water soluble compound of the silver of the water soluble compound of iron and dilute nitric acid dissolution then successively, be prepared into maceration extract.Silica supports is after 650 ℃～750 ℃ high-temperature process 2～4h and cooling, with the spraying earlier of above-mentioned maceration extract, saturated then dipping.Gained sample drying, roasting, the water soluble compound of vanadium is decomposed into V through roasting
2O
5, the water soluble compound of iron is decomposed into Fe through roasting
2O
3, the water soluble compound of silver is decomposed into simple substance silver through roasting.Baking temperature is 110～150 ℃, and be 2～12h drying time, and sintering temperature is 450～550 ℃, and roasting time is 2～5h.The water soluble compound of vanadium is preferably ammonium metavanadate, and ammonium metavanadate need be by oxalic acid: the ammonium metavanadate mol ratio was dissolved in the oxalic acid solution in 2: 1～4: 1.The water soluble compound of iron is preferably ferric nitrate, and the water soluble compound of silver is preferably silver nitrate.
(2) elder generation is dissolved in oxalic acid solution with the water soluble compound of vanadium, and the water soluble compound that adds iron then is prepared into maceration extract 1.The water soluble compound of silver is dissolved in dilute nitric acid solution, is prepared into maceration extract 2.Silica supports is after 650 ℃～750 ℃ high-temperature process 2～4h and cooling, with maceration extract 1 spraying earlier, saturated then dipping.After gained sample drying, the roasting, use maceration extract 2 saturated dippings again.Gained sample drying, roasting, the water soluble compound of vanadium is decomposed into V through roasting
2O
5, the water soluble compound of iron is decomposed into Fe through roasting
2O
3, the water soluble compound of silver is decomposed into simple substance silver through roasting.Baking temperature is 110～150 ℃, and be 2～12h drying time, and sintering temperature is 450～550 ℃, and roasting time is 2～5h.The water soluble compound of vanadium is preferably ammonium metavanadate, and ammonium metavanadate need be by oxalic acid: the ammonium metavanadate mol ratio was dissolved in the oxalic acid solution in 2: 1～4: 1.The water soluble compound of iron is preferably ferric nitrate, and the water soluble compound of silver is preferably silver nitrate.
(3) elder generation is dissolved in oxalic acid solution with the water soluble compound of vanadium, and the dilute nitric acid solution that adds the water soluble compound of silver then is prepared into maceration extract 1.The water soluble compound of iron is dissolved in pure water, is prepared into maceration extract 2.Silica supports is after 650 ℃～750 ℃ high-temperature process 2～4h and cooling, with maceration extract 1 spraying earlier, saturated then dipping.After gained sample drying, the roasting, use maceration extract 2 saturated dippings again.Gained sample drying, roasting, the water soluble compound of vanadium is decomposed into V through roasting
2O
5, the water soluble compound of iron is decomposed into Fe through roasting
2O
3, the water soluble compound of silver is decomposed into simple substance silver through roasting.Baking temperature is 110～150 ℃, and be 2～12h drying time, and sintering temperature is 450～550 ℃, and roasting time is 2～5h.The water soluble compound of vanadium is preferably ammonium metavanadate, and ammonium metavanadate need be by oxalic acid: the ammonium metavanadate mol ratio was dissolved in the oxalic acid solution in 2: 1～4: 1.The water soluble compound of iron is preferably ferric nitrate, and the water soluble compound of silver is preferably silver nitrate.
The characteristics of technology of the present invention are to adopt simple process flow just can handle the sulfur-containing compound exhaust air of complex component.Employed catalyst is a main active component with vanadium and ferriferous oxide, use low level of active ingredients silver simultaneously, under the condition that keeps the hydrogen sulfide higher conversion, improve the conversion rate of oxidation of carbon disulfide and cos greatly, can adopt simple one section catalytic burning technique simultaneous oxidation to handle multiple sulfur compound.Under optimum conditions, the oxygenation efficiency of hydrogen sulfide is higher than 99.9%, and the oxygenation efficiency of carbon disulfide and cos is higher than 90%, and the sulfur dioxide production rate is higher than 90%; Catalyst life is longer, all anti-sulfation of carrier and active component; 200～400 ℃ of operating temperatures, empty scooter 15000h
-1Can control the selectivity that generates sulfur dioxide and sulphur, can not only effectively transform poisonous, malodor components-hydrogen sulfide, carbon disulfide and cos in the tail gas, also can effectively reduce the discharging of sulfur dioxide; Adopt electrical heating, temperature and explosion-proof control are comparatively simple and reliable; Further desulfurization of incineration tail gas reduces the discharging of sulfur dioxide.
The specific embodiment
Embodiment 1
Take by weighing 55.5g oxalic acid (C
2H
2O
42H
2O) be dissolved in 80ml distilled water (heating is short molten in water-bath), add 19.8g ammonium metavanadate (NH then
4VO
3), after fully reacting and leaving standstill 2h, add 70.0g ferric nitrate (Fe (NO
3)
39H
2O), fully after the dissolving, add silver nitrate (AgNO
3) solution [4.8g AgNO
3Be dissolved in rare nitric acid (5ml nitric acid+25ml distilled water)], leave standstill 2h after, be settled to 220ml, be prepared into maceration extract.With the even external diameter 4～6mm preparing spherical SiO 2 carrier 100g of 700 ℃ of high-temperature process 2h of spraying and cooling of this maceration extract, treat that carrier when saturated, is dipped in it in maceration extract, stir and place 8h.The gained sample is 120 ℃ of dry 6h, 500 ℃ of roasting 4h in air atmosphere.Make the V that consists of of catalyst
2O
55.0%, Fe
2O
34.5%, Ag 1.0%, SiO
289.5%, specific area is 218m
2/ g, pore volume are 0.64ml/g, and average pore size is 11.8nm.
On small-sized catalytic burning experimental rig, this catalyst is estimated.Evaluation index is as follows:
Feeding gas consists of hydrogen sulfide 0.24% (v/v), cos 0.06% (v/v), steam 3.0% (v/v), oxygen 0.90% (v/v), all the other are high pure nitrogen, 350 ℃ of reaction temperatures, air speed 6000h
-1The conversion ratio of hydrogen sulfide and cos is respectively 100% and 76%, and the sulfur dioxide production rate is 80%, and the sulphur production rate is 20%.
Embodiment 2
Take by weighing 60.5g oxalic acid (C
2H
2O
42H
2O) be dissolved in 100ml distilled water (heating is short molten in water-bath), add 21.3g ammonium metavanadate (NH then
4VO
3), after fully reacting and leaving standstill 2h, add 75.5g ferric nitrate (Fe (NO
3)
39H
2O), fully after the dissolving, leave standstill 2h after, be settled to 240ml, be prepared into maceration extract.With the even external diameter 4～6mm preparing spherical SiO 2 carrier 100g of 700 ℃ of high-temperature process 2h of spraying and cooling of this maceration extract, treat that carrier when saturated, is dipped in it in maceration extract, stir and place 8h.The gained sample is 120 ℃ of dry 6h, 500 ℃ of roasting 4h in air atmosphere, are dipped in silver nitrate (AgNO after the cooling again
3) solution (4.0g AgNO
3Be dissolved in distilled water and constant volume in 200ml) in, stir and place 8h.Obtain sample 120 ℃ of dry 4h, 500 ℃ of roasting 4h in air atmosphere.Make the V that consists of of catalyst
2O
55.0%, Fe
2O
34.5%, Ag 1.0%, SiO
289.5%, specific area is 200m
2/ g, pore volume are 0.64ml/g, and average pore size is 12.7nm.
On small-sized catalytic burning experimental rig, this catalyst is estimated, feeding gas consists of hydrogen sulfide 0.21% (v/v), cos 0.07% (v/v), steam 3.0% (v/v), oxygen 0.84% (v/v), all the other are high pure nitrogen, 320 ℃ of reaction temperatures, air speed 6000h
-1, the conversion ratio of hydrogen sulfide and cos is respectively 100% and 55%, and the sulfur dioxide production rate is 70%, and the sulphur production rate is 30%.350 ℃ of reaction temperatures, other condition is the same, and the conversion ratio of hydrogen sulfide and cos is respectively 100% and 74%, and the sulfur dioxide production rate is 82%, and the sulphur production rate is 18%.
Embodiment 3
Catalyst A
Take by weighing 90.8g oxalic acid (C
2H
2O
42H
2O) be dissolved in 80ml distilled water (heating is short molten in water-bath), add 32.0g ammonium metavanadate (NH then
4VO
3), after fully reacting and leaving standstill 2h, add 111.8g ferric nitrate (Fe (NO
3)
39H
2O), fully after the dissolving, add silver nitrate (AgNO
3) solution [5.5g AgNO
3Be dissolved in rare nitric acid (2ml nitric acid+14ml distilled water)], leave standstill 2h after, be settled to 240ml, be prepared into maceration extract.The spherical active aluminum oxide carrier of the anti-sulphur 150g of external diameter 4～6mm of 150 ℃ of oven dry and cooling are dipped in the maceration extract, stir and place 8h.The gained sample is 150 ℃ of dry 4h, 500 ℃ of roasting 4h in air atmosphere.Make the V that consists of of catalyst
2O
54.5%, Fe
2O
34.0%, Ag 1.0%, Al
2O
390.5%, specific area is 195m
2/ g, pore volume are 0.41ml/g, and average pore size is 8.9nm.
Catalyst B
Take by weighing 55.5g oxalic acid (C
2H
2O
42H
2O) be dissolved in 80ml distilled water (heating is short molten in water-bath), add 19.8g ammonium metavanadate (NH then
4VO
3), after fully reacting and leaving standstill 2h, add 70.0g ferric nitrate (Fe (NO
3)
39H
2O), fully after the dissolving, add silver nitrate (AgNO
3) solution [4.8g AgNO
3Be dissolved in rare nitric acid (5ml nitric acid+25ml distilled water)], leave standstill 2h after, be settled to 220ml, be prepared into maceration extract.With the even external diameter 4～6mm preparing spherical SiO 2 carrier 100g of 700 ℃ of high-temperature process 2h of spraying and cooling of this maceration extract, treat that carrier when saturated, is dipped in it in maceration extract, stir and place 8h.The gained sample is 120 ℃ of dry 6h, 500 ℃ of roasting 4h in air atmosphere.Make the V that consists of of catalyst
2O
55.0%, Fe
2O
34.5%, Ag 1.0%, SiO
289.5%, specific area is 218m
2/ g, pore volume are 0.64ml/g, and average pore size is 11.8nm.
Catalyst C
Take by weighing 60.5g oxalic acid (C
2H
2O
42H
2O) be dissolved in 100ml distilled water (heating is short molten in water-bath), add 21.3g ammonium metavanadate (NH then
4VO
3), after fully reacting and leaving standstill 2h, add 75.5g ferric nitrate (Fe (NO
3)
39H
2O), fully after the dissolving, leave standstill 2h after, be settled to 240ml, be prepared into maceration extract.With the even external diameter 4～6mm preparing spherical SiO 2 carrier 100g of 700 ℃ of high-temperature process 2h of spraying and cooling of this maceration extract, treat that carrier when saturated, is dipped in it in maceration extract, stir and place 8h.The gained sample is 120 ℃ of dry 6h, 500 ℃ of roasting 4h in air atmosphere, are dipped in silver nitrate (AgNO after the cooling again
3) solution (4.0g AgNO
3Be dissolved in distilled water and constant volume in 200ml) in, stir and place 8h.Obtain sample 120 ℃ of dry 4h, 500 ℃ of roasting 4h in air atmosphere.Make the V that consists of of catalyst
2O
55.0%, Fe
2O
34.5%, Ag 1.0%, SiO
289.5%, specific area is 200m
2/ g, pore volume are 0.64ml/g, and average pore size is 12.7nm.
Catalyst D (comparison)
By the catalyst A preparation method, just do not use component Ag.
On the small-sized catalytic burning experimental rig, investigated the catalyst of embodiment 1 preparation and catalyst A, B, C, D conversion ratio to the variable concentrations cos.At 280 ℃ of preheat temperatures, 350 ℃ of reaction temperatures, excess oxygen coefficient 1.5～2.0, air speed 6000h
-1, water vapor concentration 3%～5% (v/v), the conversion ratio of cos sees Table 3.
The conversion ratio of table 3 variable concentrations cos
| Cos concentration, ppm | 153 | 395 | 697 | 890 | 395 |
| Catalyst | Embodiment 1 | Catalyst A | Catalyst B | Catalyst C | Catalyst D |
| The cos conversion rate, % | 82.3 | 88.3 | 82.0 | 85.6 | 45.2 |
Embodiment 4
On small-sized catalytic burning experimental rig, investigated the catalytic burning effect of the catalyst vulcanization hydrogen of embodiment 1 preparation.280 ℃ of preheat temperatures, 350 ℃ of reaction temperatures, excess oxygen coefficient 1.5～2.0, air speed 6000h
-1, water vapor concentration 3%～5% (v/v), feeding gas concentration of hydrogen sulfide be about 2000ppm, the 4h that turns round every day, the catalytic burning effect of hydrogen sulfide sees Table 4.
The catalytic burning effect of table 4 hydrogen sulfide
| Days of operation, d | 1 | 2 | 3 | 4 | 5 |
| The hydrogen sulfide conversion ratio, % | 99.97 | 99.99 | 99.99 | 99.99 | 99.97 |
| The sulfur dioxide production rate, % | 81.2 | 80.6 | 78.8 | 80.1 | 80.6 |
Claims (7)
1. a sulfur compound waste gas catalytic incineration method comprises following content, and sulfur-containing compound exhaust air mixes with air, enters the catalytic burning reactor after preheating, discharges after discharging behind the catalytic burning or the further desulfurization; Wherein the Air mixing proportion control is crossed oxygen quotient 〉=1.0, and preheat temperature is 200～300 ℃, and reaction temperature is 200～400 ℃, and air speed is 1500～15000h
-1Catalytic incineration catalyst is carrier with silica, and active component is the oxide and the silver of vanadium, iron, and the oxide content of vanadium is 0.5%～15%, and the oxide content of iron is 3.5%～5.5%, and the content of silver is 0.05%～5%; Contain hydrogen sulfide, carbon disulfide and cos in the waste gas.
2. in accordance with the method for claim 1, it is characterized in that described oxygen quotient excessively is 1.5～3.0, preheat temperature is 270～290 ℃, and reaction temperature is 320～350 ℃, and air speed is 6000～7500h
-1
3. in accordance with the method for claim 1, it is characterized in that the desulfurization behind the described catalytic burning adopts water elution to remove sulfur vapor, or adopt calcium, magnesium oxide to remove sulfur dioxide.
4. in accordance with the method for claim 1, it is characterized in that described catalytic incineration catalyst is in catalyst weight: the content of carrier is 65%～95%.
5. in accordance with the method for claim 4, the oxide content that it is characterized in that vanadium in the described catalytic incineration catalyst is 4.0%～6.0%.
6. in accordance with the method for claim 1, it is characterized in that described sulfur-containing compound exhaust air comes bin cure to return the tail gas of technology or geothermal power plant.
7. in accordance with the method for claim 1, it is characterized in that described preheating use electric heater.
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