CN101306367B - Sulfurated hydrogen gas containing catalytic incineration catalyst and preparation method thereof - Google Patents
Sulfurated hydrogen gas containing catalytic incineration catalyst and preparation method thereof Download PDFInfo
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- CN101306367B CN101306367B CN200710011416A CN200710011416A CN101306367B CN 101306367 B CN101306367 B CN 101306367B CN 200710011416 A CN200710011416 A CN 200710011416A CN 200710011416 A CN200710011416 A CN 200710011416A CN 101306367 B CN101306367 B CN 101306367B
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Abstract
The invention provides a catalyst which is used for catalytically combusting gas containing sulfureted hydrogen as well as the preparation method thereof. The catalyst carrier is silicon dioxide, the first active constituent is the oxide of bismuth, and the content of the bismuth is 0.5 percent to 10 percent calculated by weight of the catalyst. The second active constituent is the oxide of cerium, copper or lanthanum, and the mol ratio of the cerium, the copper or lanthanum and the bismuth is 0.5:1-5:1. The catalyst of the invention with high activity and vitriolization resistance is applicable to the catalytic combustion treatment of the gas containing the sulfureted hydrogen, and oxidizes the gas containing the sulfureted hydrogen into sulfur, sulfur dioxide and water. The catalyst of the invention can be applied to the catalytic combustion treatment of various waste gases containing the sulfureted hydrogen, and the oxidation rate of the sulfureted hydrogen is higher than 99.9 percent and the generation rate of the sulfur dioxide is higher than 90 percent under suitable conditions.
Description
Technical field
The present invention relates to H 2 S-containing gas catalyst to burned and preparation method thereof, be applicable to all kinds of hydrogen sulfide containing exhaust-gas treatments, hydrogen sulfide can be converted into all lower sulfur dioxide of stink and toxicity or sulphur, the catalytic burning that is specially adapted to sulfur recovery claus process tail gas, geothermal power plant's waste gas is handled.
Background technology
Hydrogen sulfide is the stronger odorant pollutant of a kind of toxicity, and mainly from industrial tail gas such as oil refining, natural gas, chemical industry, sewage disposal, geothermal power generations, China has issued its discharging of the strict qualification of odorant pollutant discharge standard (GB 14554-93).With oil plant or gas plant is example, contains a certain amount of hydrogen sulfide in its sulfur recovery tail gas, for satisfying the odorant pollutant discharge standard, could discharge after must burning.Because the combustible component (as hydrogen sulfide, cos, carbon monoxide, carbon disulfide, hydrogen, elementary sulfur and a small amount of oil gas) in the tail gas often is lower than 3% (the gas percentage composition is the volume percentage composition) of tail gas total amount, necessary postcombustion, could completing combustion, and the hydrogen sulfide sulfides is oxidized to sulfur dioxide or sulphur.The tail gas burning process has thermal incineration and catalytic burning two classes.The thermal incineration method is carried out excessive oxygen and 700～850 ℃ usually.Owing to be difficult to accurately control operating conditions such as incineration temperature, the situation that incinerator crumples often appears, reduced the service life of incinerator.Catalytic burning can make the hydrogen sulfide sulfides in the tail gas be oxidized to sulfur dioxide or sulphur with lower temperature (as 300～400 ℃) under catalyst action.The output investment ratio thermal incineration of catalytic burning is slightly high, and energy consumption and operating cost are significantly less than thermal incineration.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.Along with riseing of crude oil and Gas Prices, the catalytic burning power savings advantages is more remarkable.By the control process conditions, can regulate the sulfur dioxide of catalytic burning technique process generation and the ratio of sulphur, reduce the discharging of catalytic burning tail gas sulphur dioxide.Therefore, catalytic burning can satisfy environmental protection and energy-conservation needs simultaneously.
Catalyst is the pith of hydrogen sulfide gas catalytic burning technology, and the key of this class catalyst performance is how to overcome the sulfation of catalyst active center, the stability of the long-time running of maintenance catalyst and active.CN1049299A discloses a kind of sulfur-bearing organic catalyst to burned waste gas and preparation method thereof, and this catalyst is a carrier with the natural mordenite zeolite of sulfuric acid treatment modification, V
2O
5Be main active component, noble metals such as a spot of platinum, palladium are the auxiliary activity component, V
2O
5Content is 0.4%～0.7%, and (it is the quality percentage composition that catalyst is formed percentage composition, down together), platinum content is 0.01%～0.02%, and palladium content is 0.02%～0.03%, also can contain one or more of 0.01%～0.07% cobalt, manganese, molybdenum, nickel, potassium, na oxide.At 320～380 ℃ of reaction temperatures, air speed 4800～10000h
-1, during organic sulfur concentration 800～10000mg/L, conversion ratio 〉=99%.This catalyst loading noble metal, cost is higher, sulfur poisoning-resistant is limited in one's ability.CN1163785A discloses the catalytic burning technique of hydrogen sulfide in a kind of gas, is suitable for handling Claus tail gases, and with the activated 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 sulphur hydrogen is 100%, sulfur dioxide production rate 90%～99%.CN1410149A 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.USP4576184, USP4444908, USP4528277, USP4444741, USP4444742, USP4314983 discloses a class hydrogen sulfide oxidation catalyst and a technology, this 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
5Catalyst, at 240 ℃ of reaction temperatures, air speed 2000h
-1, the hydrogen sulfide of 0.27% (v/v) is converted into sulfur dioxide fully, and hydrogen and methane are not oxidized.USP4427576, USP4937058 discloses a kind of catalyst and preparation technology thereof who hydrogen sulfide or organic sulfur is oxidized to sulfur dioxide, the carrier of this catalyst is a titanium dioxide, or the mixture of titanium dioxide and zirconia or silica, active component is made of at least a of a kind of alkali earth metal sulfate and following metal: copper, silver, zinc, cadmium, yttrium, lanthanum, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, rhodium, iridium, nickel, palladium, platinum, tin and bismuth, the content of carrier is 60%～99%, the content of alkali earth metal sulfate is 1%～40%, and the specific surface of catalyst is 20～500m
2/ g.380 ℃ of reaction temperatures, air speed 1800h
-1Feeding gas sulfide hydrogen 0.08% (v/v), cos 0.01% (v/v), carbon disulfide 0.05% (v/v), sulfur dioxide 0.04% (v/v), oxygen 2%, steam 30%, nitrogen 67.82%, the catalytic conversion of hydrogen sulfide＞99%, the catalytic conversion 61%～98% of carbon disulfide, the catalytic conversion 52%～94% of cos.It can be the catalyst of sulfur dioxide with selective oxidation of sulfur containing compounds in particular that USP5278123 discloses a kind of, and carrier is a titanium dioxide, and active component is iron and platinum.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 the kind of Group IIA metal or multiple, and carrier is a refractory oxide, can not contain aluminium and phosphorus simultaneously in the carrier.The hydrogen sulfide complete oxidation temperature that example provides is 500 ℃.USP4169136,4092404,4171347,4088743 discloses 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.USP4399112 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 catalytic incineration catalyst for sulfur-containing compound exhaust air generally has the component complexity, sulfur tolerance is poor, cost is high and need to adopt one or more deficiencies in the complex techniques process etc.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of sulfide hydrogen waste gas catalytic incineration Catalysts and its preparation method, catalyst of the present invention has advantages such as cost is low, catalytic activity is high, the applicable craft flow process is simple.
Sulfide hydrogen waste gas catalytic incineration catalyst of the present invention is carrier with silica, and first kind of active component is the oxide of bismuth, and in catalyst weight, the content of bismuth is 0.5%～10%, is preferably 2%～8%.In the oxide that second kind of active component is cerium, copper and lanthanum one or more, the mol ratio of second activity component metal and first activity component metal is 5: 1～0.5: 1.The specific area of catalyst is 180～350m
2/ g, pore volume are 0.2～0.8ml/g.
The thing of the silica supports that catalytic incineration catalyst of the present invention uses is amorphous phase mutually, can select the gross porosity spherical silica gel for use, and its specific area is 200～400m
2/ g, pore volume are 0.4～0.9mL/g.The oxide of bismuth is Bi
2O
3, the oxide of cerium is CeO
2, the oxide of copper is CuO, the oxide of lanthanum is La
2O
3
Catalyst activity height of the present invention, anti-sulfation, the catalytic burning that can be used for H 2 S-containing gas is handled, and it is oxidized to sulphur, sulfur dioxide and water.The operating temperature of catalyst is 200～400 ℃, and air speed is 1500～15000h
-1, cross oxygen quotient and be not less than 1.0.As 350 ℃ of catalyst operating temperatures, air speed 6000h
-1, when crossing oxygen quotient 2.0, concentration of hydrogen sulfide 0.21% (v/v), the oxygenation efficiency of hydrogen sulfide is higher than 99.9%, the sulfur dioxide production rate is higher than 90%.
The optimum shape of catalyst of the present invention is 4～6mm sphere, also can adopt other suitable shape, and as bar shaped, sheet shape, cylindricality etc., active component adopts spraying-saturated infusion process load, and preparation procedure is as follows:
(1) elder generation is dissolved in dilute nitric acid solution with the water soluble compound of bismuth, adds the water soluble compound of cerium then, or the copper water soluble compound, or the water soluble compound of lanthanum is prepared into maceration extract.Silica supports is at 650 ℃～750 ℃ high-temperature process 2～4h and cool off the back loading active component.With the spraying earlier of above-mentioned maceration extract, saturated then dipping.Gained sample drying, roasting, the water soluble compound of bismuth is decomposed into Bi through roasting
2O
3, the water soluble compound of cerium is decomposed into CeO through roasting
2, the water soluble compound of copper is decomposed into CuO through roasting, and the water soluble compound of lanthanum is decomposed into La through roasting
2O
3Baking temperature is 110～150 ℃, and be 2～12h drying time, and sintering temperature is 450～550 ℃, and roasting time is 2～5h.The most handy bismuth nitrate of the water soluble compound [Bi (NO of bismuth
3)
35H
2O], the most handy cerous nitrate of the water soluble compound [Ce (NO of cerium
3)
36H
2O], the most handy copper nitrate of the water soluble compound [Cu (NO of copper
3)
23H
2O], the most handy lanthanum nitrate of the water soluble compound [La (NO of lanthanum
3)
36H
2O].
(2) respectively the water soluble compound of bismuth and the water soluble compound of copper are dissolved in ammoniacal liquor, mix two kinds of solution then, and be prepared into maceration extract with the distilled water constant volume, 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 bismuth is decomposed into Bi through roasting
2O
3, the water soluble compound of copper is decomposed into CuO 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 most handy bismuth citrate of the water soluble compound [Bi (NO of bismuth
3)
35H
2O], the most handy copper nitrate of copper water soluble compound [Cu (NO
3)
23H
2O].
Second active component can be one or more in the catalyst.In general, when the catalyst activity constituent content was higher, its activity was higher, but cost increases.Concrete constituent content can be determined according to concrete instructions for use.
Catalyst of the present invention is used for the catalytic burning of H 2 S-containing gas, is specially adapted to the catalytic burning of oil plant Sulfur Recovery Unit process tail gas.Its technical process is: H 2 S-containing gas is mixed with excess air, after the preheating, with 1500～15000h
-1Air speed by the catalytic burning stove, under 200～400 ℃ of reaction temperatures, hydrogen sulfide is sulfur dioxide, sulphur and water by catalytic oxidation.
Catalytic incineration catalyst of the present invention makes catalyst have good serviceability by the type and the consumption of preferred two kinds of active components.Catalyst specifically of the present invention has following characteristics: the catalytic activity height, and under optimum conditions, the oxygenation efficiency of hydrogen sulfide is higher than 99.9%, 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
-1
The specific embodiment
Embodiment 1
Take by weighing 37.8g bismuth nitrate [Bi (NO
3)
35H
2O] be dissolved in the rare nitric acid of 100ml10%, add 37.2g copper nitrate [Cu (NO then
3)
23H
2O], after fully dissolving and leaving standstill 2h, 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.Making the catalyst activity constituent content is Bi5%, Cu 3%, and the Cu/Bi mol ratio is about 2: 1, and specific area is 210m
2/ g, pore volume are 0.60mL/g, and average pore size is 11.0nm.
On small-sized catalytic burning experimental rig, this catalyst to be estimated, feeding gas consists of hydrogen sulfide 0.20% (v/v), steam 3.0% (v/v), oxygen 0.60% (v/v), all the other are high pure nitrogen, 350 ℃ of reaction temperatures, air speed 6000h
-1, the conversion ratio of hydrogen sulfide is 100%, and the sulfur dioxide production rate is 90%, and the sulphur production rate is 10%.
Embodiment 2
Take by weighing 38.0g bismuth nitrate [Bi (NO
3)
35H
2O] be dissolved in the rare nitric acid of 100ml10%, add 35.6g cerous nitrate [Ce (NO then
3)
36H
2O], after fully dissolving and leaving standstill 2h, 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.Making the catalyst activity constituent content is Bi 5%, Ce 3.5%, and the Ce/Bi mol ratio is about 1: 1, and specific area is 225m
2/ g, pore volume are 0.65ml/g, and average pore size is 11.5nm.
On small-sized catalytic burning experimental rig, this catalyst is estimated, feeding gas consists of hydrogen sulfide 0.19% (v/v), cos 0.07% (v/v), steam 3.0% (v/v), oxygen 0.80% (v/v), all the other are high pure nitrogen, 350 ℃ of reaction temperatures, air speed 6000h
-1, the conversion ratio of hydrogen sulfide and cos is respectively 100% and 52%, and the sulfur dioxide production rate is 85%, and the sulphur production rate is 15%.
Embodiment 3
Take by weighing 17.9g bismuth citrate (C
6H
5BiO
7), add 50ml distilled water and stir evenly, add 40ml ammoniacal liquor then, heating is until molten entirely in water-bath.Take by weighing 11.9g copper nitrate [Cu (NO
3)
23H
2O], add 50ml ammoniacal liquor, stir the four ammonium network copper that all are dissolved as avy blue until the Kocide SD precipitation of white.Above-mentioned solution is mixed, filtration, constant volume is made maceration extract in 240ml.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 4h.The gained sample is 120 ℃ of dry 6h, 550 ℃ of roasting 4h in air atmosphere.Making the catalyst activity constituent content is Bi3%, Cu 1%, and the Cu/Bi mol ratio is about 1.1: 1, and specific area is 218m
2/ g, pore volume are 0.63mL/g, and average pore size is 12.2nm.
On small-sized catalytic burning experimental rig, this catalyst is estimated, feeding gas consists of hydrogen sulfide 0.19% (v/v), cos 0.07% (v/v), steam 3.0% (v/v), oxygen 0.80% (v/v), all the other are high pure nitrogen, 350 ℃ of reaction temperatures, air speed 6000h
-1, the conversion ratio of hydrogen sulfide and cos is respectively 100% and 61%, and the sulfur dioxide production rate is 90%, and the sulphur production rate is 10%.
Embodiment 4
Take by weighing 37.9g bismuth nitrate [Bi (NO
3)
35H
2O] be dissolved in the rare nitric acid of 100ml10%, add 33.6g lanthanum nitrate [La (NO then
3)
36H
2O], after fully dissolving and leaving standstill 2h, 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.Making the catalyst activity constituent content is Bi 5%, La 3.3%, and the La/Bi mol ratio is about 1: 1, and specific area is 228m
2/ g, pore volume are 0.66ml/g, and average pore size is 11.8nm.
On small-sized catalytic burning experimental rig, this catalyst is estimated, feeding gas consists of hydrogen sulfide 0.20% (v/v), cos 0.05% (v/v), steam 3.0% (v/v), oxygen 0.75% (v/v), all the other are high pure nitrogen, 350 ℃ 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 88%, and the sulphur production rate is 12%.
Embodiment 5
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 3%, Ce 2.0%, and the Ce/Bi mol ratio is about 1: 1.
Embodiment 6
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 1.5%, Ce 1.0%, and the Ce/Bi mol ratio is about 1: 1.
Embodiment 7
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi1.0%, Ce 0.7%, and the Ce/Bi mol ratio is about 1: 1.
Embodiment 8
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 1.5%, Cu 0.5%, and the Ce/Bi mol ratio is about 1: 1.
Embodiment 9
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi7.5%, Cu 2.3%, and the Ce/Bi mol ratio is about 1: 1.
Embodiment 10
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi3.0%, Cu 0.5%, and the Cu/Bi mol ratio is about 0.5: 1.
Embodiment 11
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 3.0%, Cu 1.4%, and the Cu/Bi mol ratio is about 1.5: 1.
Embodiment 12
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 3.0%, Cu 3.0%, and the Cu/Bi mol ratio is about 3.3: 1.
Embodiment 13
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 3.0%, Cu 4.5%, and the Cu/Bi mol ratio is about 4.9: 1.
Embodiment 14
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi3.0%, Ce 1.0%, and the Ce/Bi mol ratio is about 0.5: 1.
Embodiment 15
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 3.0%, Ce 3.0%, and the Ce/Bi mol ratio is about 1.5: 1.
Embodiment 16
Press the preparation method of embodiment 1, catalyst carrier is a silica, and active component content is Bi 3.0%, Cu 6.0%, and the Cu/Bi mol ratio is about 3.0: 1.
Embodiment 17
According to evaluation method and the condition of implementing 1 catalyst, embodiment 5～16 described catalyst are estimated, the result is as follows.
| Catalyst | The hydrogen sulfide conversion ratio, % | The sulfur dioxide production rate, % | The sulphur production rate, % |
| Embodiment 5 | 100 | 82 | 18 |
| Embodiment 6 | 98 | 80 | 20 |
| Embodiment 7 | 96 | 80 | 20 |
| Embodiment 8 | 99 | 88 | 12 |
| Embodiment 9 | 100 | 90 | 10 |
| Embodiment 10 | 96 | 85 | 15 |
| Embodiment 11 | 100 | 89 | 11 |
| Embodiment 12 | 100 | 88 | 12 |
| Embodiment 13 | 100 | 89 | 11 |
| Embodiment 14 | 95 | 75 | 25 |
| Embodiment 15 | 100 | 83 | 17 |
| Embodiment 16 | 100 | 87 | 13 |
Claims (10)
1. sulfide hydrogen waste gas catalytic incineration catalyst, with silica is carrier, first kind of active component is the oxide of bismuth, in catalyst weight, the content of bismuth is 0.5%～10%, second kind of active component is one or more in cerium and the lanthanum-oxides, and the mol ratio of second activity component metal and first activity component metal is 5: 1～0.5: 1.
2. according to the described catalyst of claim 1, the specific area that it is characterized in that described catalyst is 180～350m
2/ g, pore volume are 0.2～0.8ml/g.
3. according to the described catalyst of claim 1, it is characterized in that the thing of described carrier silica supports is amorphous phase mutually.
4. according to the described catalyst of claim 1, it is characterized in that described carrier silica is selected from the gross porosity spherical silica gel.
5. according to claim 1 or 4 described catalyst, the specific area that it is characterized in that described carrier silica is 200～400m
2/ g, pore volume are 0.4～0.9mL/g.
6. according to the described catalyst of claim 1, the oxide that it is characterized in that described bismuth is Bi
2O
3, the oxide of cerium is CeO
2, the oxide of lanthanum is La
2O
3
7. the described Preparation of catalysts method of claim 1 is a carrier with silica, adopts spraying-saturated infusion process load active component.
8. it is preceding at 650 ℃～750 ℃ high-temperature process 2～4h in accordance with the method for claim 7, to it is characterized in that silica supports uses.
9. in accordance with the method for claim 7, it is characterized in that carrier loaded active component after, carry out drying and roasting, sintering temperature is 450～550 ℃, roasting time is 2～5h.
10. in accordance with the method for claim 7, it is characterized in that bismuth from bismuth nitrate or bismuth citrate, cerium is from cerous nitrate, and lanthanum is from lanthanum nitrate.
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| CN102309919B (en) * | 2010-07-07 | 2014-04-16 | 中国石油化工股份有限公司 | Combined treatment method for waste gas containing sulfur compounds |
| CN102649690A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester |
| CN110763801B (en) * | 2019-11-12 | 2022-04-12 | 北京联合大学 | Low-temperature catalytic luminous sensitive material of hydrogen sulfide in air |
| CN112892569B (en) * | 2021-01-26 | 2023-09-12 | 中国科学院大学 | Silicon carbide loaded cerium oxide catalyst and method for preparing sulfur by hydrogen sulfide selective oxidation under medium-high temperature condition by adopting same |
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