CN1879963A - Adjuvant-adding desulfurization catalyst regeneration and method for preparing sulfur simultaneously - Google Patents
Adjuvant-adding desulfurization catalyst regeneration and method for preparing sulfur simultaneously Download PDFInfo
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- CN1879963A CN1879963A CNA2006100127084A CN200610012708A CN1879963A CN 1879963 A CN1879963 A CN 1879963A CN A2006100127084 A CNA2006100127084 A CN A2006100127084A CN 200610012708 A CN200610012708 A CN 200610012708A CN 1879963 A CN1879963 A CN 1879963A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for regenerating desulfurizer and a method for producing sulfur, wherein when the catalyst carrying alkali metal agent absorbs sulfur to be saturated, control the regenerate temperature of desulfurizer at 330-450Deg. C; then input hydrogen gas or the mixture between hydrogen gas and inert gas, at the speed as 400-1000ml/min, and the pressure as 0.05-0.2MPa; when the mol ratio between H2 and Cu is 8, stop feeding H2; the temperature between the outlet of reactor and the cold well is kept between 250Deg. C and the regenerate temperature; when the airflow passes the cold well, the sulfur will be condensed, and the left gas via gas cycle pump is pumped into reactor to be cycled. The inventive catalyst has high efficiency in the desulfurizing process, as well as producing sulfur, while two processes are complete in one reactor via one catalyst.
Description
Technical field
The invention belongs to a kind of renovation process of flue gas dry desulfurizing agent and the technology of resource, concrete is exactly about the CuO (M) behind the interpolation auxiliary agent/Al
2O
3Hydrogen regeneration and prepare simultaneously the technology of sulphur.
Background technology
With CuO/Al
2O
3Be used for removing the SO of flue gas
2Research start from the seventies in last century, AirPollut.Control.Assoc., 20 (1970) 819-824 are first to CuO/Al
2O
3Independent desulphurizing activated the evaluation, find have more than 300 ℃ higher desulphurizing activated.Afterwards, people to catalyst again desulphurization denitration behavior simultaneously study, find 300 ℃ of-400 ℃ of temperature windows have higher in the desulphurization denitration activity.But its one of problem as dry-desulphurizer is that Sulfur capacity is on the low side, causes the frequent catalyst of changing in the use, has increased desulphurization cost.According to the literature, at the Cu loading be 8% CuO/Al
2O
3Behind the upper interpolation appropriate bases metal promoter, the saturated Sulfur capacity of catalyst be by can being increased dramatically, thereby effectively solves the problem of catalyst Sulfur capacity deficiency.
Need it is regenerated after catalyst suction sulphur is saturated, regeneration gas has H
2, NH
3, CO, CH
4Deng reducibility gas, product is high concentration SO
2Gas carries out different sulfur recovery processing to it and can make different sulfur-bearing product such as sulfate or simple substance sulphur etc.Wherein, use H
2For reducing agent can be with SO
2Catalytic reduction makes the method for simple substance sulphur, is convenient to store transportation owing to product sulphur has, is easy to advantage such as deep processing and is considered to one of best sulfur recovery method.But this technological requirement desulfurization and regenerated resourcesization two cover systems, resource process need just can obtain finished product sulphur, the process complexity behind the catalyst action in addition.Therefore, be necessary to develop a kind of desulfurization and regeneration recovery integrated technique, in desulfurization reactor, realize sulphur production, simplify processing procedure, reduce the sulfur recovery cost.The author finds in the research in early stage, is not adding the CuO/Al of auxiliary agent
2O
3In the catalyst hydrogen regenerative process, by with reactor outlet gas by in the process of a cold-trap circulation Returning reactor, can be at CuO/Al
2O
3Use H under the autocatalysis
2With the SO that bears again
2Be reduced to simple substance sulphur, under certain reaction condition, the sulphur productive rate can reach about more than 80%.
At Catalysts Cu O/Al
2O
3Behind the upper interpolation alkali metal promoter, greatly improved saturated Sulfur capacity, how it will have important impact to the industrial applications in this series catalysts future in the catalytic activity that hydrogen regeneration prepares in the sulphur process simultaneously.
Summary of the invention
The invention relates to the CuO/Al that has added alkali metal promoter
2O
3Base desulfurizer (is denoted as CuO (M)/Al
2O
3) renovation process and the sulphur resource technology for preparing sulphur, be characterized in same reactor, realizing desulfurization, regeneration and sulphur preparation process.And whole process only relates to a kind of CuO (M)/Al
2O
3Base desulfurizer.Need not to be specifically designed to the catalyst of catalytic preparation sulphur.
Fixed bed or moving bed reaction technology are adopted in technological process of the present invention, and catalyst is used H after suction sulphur is saturated
2For reducing agent carries out reducing/regenerating, and in the circulating resources process, prepare sulphur for catalytic reduction.Concrete operations step of the present invention is as follows:
The catalyst that supports alkali metal promoter inhale sulphur saturated after, the regeneration temperature of inhaling sulfur catalyst is controlled between 330-450 ℃, the gaseous mixture of input hydrogen or hydrogen and inert gas, flow velocity is 400-1000ml/min, pressure is 0.05-0.2MPa, works as H
2With the mol ratio of Cu is to stop into H at 8 o'clock
2, reactor outlet to temperature maintenance between the cold-trap 250 ℃-regeneration temperature, the gas that flows out from reactor during through cold-trap sulphur be condensed, residual gas continues circular response by gas circulator suction reactor again.
Aforesaid alkali metal promoter is Na or K.
H
2Input mode adopt batch sampling or continuous sample introduction; The gaseous mixture of property gas.
The present invention has following advantage
1. Catalysts Cu O (M)/Al
2O
3Have efficient desulfurization performance, prepare the sulphur process in catalysis simultaneously and have again high catalytic activity, two processes only can be finished at a reactor with a kind of catalyst, have simplified flow process.
2. desulfurization and regeneration temperature Window match can equality of temperature be regenerated.
3. regeneration and preparation sulphur process are the gas phase cyclic process, regeneration gas H
2Can make full use of.
4. the product that obtains of sulphur resource is important chemical products sulphur.
The specific embodiment
Embodiment 1:
Desulfurizing agent CuO8 (Na0.5)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the Na loading is 0.5% CuO8 (Na0.5) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (Na0.5) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (Na0.5) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 1.65mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst was inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 400 ℃, and systemic circulation speed was 400ml/min, and after systemic circulation operated steadily, beginning is input reducing gases H continuously
2The cyclic process system pressure is 0.1MPa.Reactor outlet to temperature maintenance between the cold-trap at 250 ℃; 400 ℃ of down renewable total sulfur S that go out
t=0.66mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=70mg.The solid sulfur productive rate is Y
s=S
p/ S
t=83%.
Embodiment 2:
Desulfurizing agent CuO8 (Na2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the Na loading is 2% CuO8 (Na2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (Na2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (Na2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 1.8mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst is inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 370 ℃; Systemic circulation speed is 600ml/min; After systemic circulation operates steadily, import continuously reducing gases H
2, system pressure is 0.07MPa.Reactor outlet to temperature maintenance between the cold-trap at 300 ℃; The renewable total sulfur S that goes out
t=0.72mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=78mg.The solid sulfur productive rate is Y
s=S
p/ S
t=85%.
Embodiment 3:
Desulfurizing agent CuO8 (Na3)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the Na loading is 2% CuO8 (Na3) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (Na3) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (Na3) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 2mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst was inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 400 ℃, and systemic circulation speed was 1000ml/min; After systemic circulation operated steadily, beginning is input reducing gases H continuously
2System pressure is 0.12MPa.Reactor outlet to temperature maintenance between the cold-trap at 320 ℃; The renewable total sulfur S that goes out
t=0.8mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=92mg.The solid sulfur productive rate is Y
s=S
p/ S
t=90%.
Embodiment 4:
Desulfurizing agent CuO8 (K2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and KNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the K loading is 2% CuO8 (K2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (K2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (K2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 1.6mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst is inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 400 ℃; Systemic circulation speed is 700ml/min; After systemic circulation operates steadily, import continuously reducing gases H
2System pressure is 0.05MPa.Reactor outlet to temperature maintenance between the cold-trap at 370 ℃; The renewable total sulfur S that goes out
t=0.62mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=65mg.The solid sulfur productive rate is Y
s=S
p/ S
t=82%.
Embodiment 5:
Desulfurizing agent CuO2 (Na2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 2wt%, the Na loading is 2% CuO2 (Na2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO2 (Na2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO2 (Na2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 0.5mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst is inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 400 ℃; Systemic circulation speed is 500ml/min; After systemic circulation operates steadily, import continuously reducing gases H
2System pressure is 0.12MPa.Reactor outlet to temperature maintenance between the cold-trap at 280 ℃, the renewable total sulfur S that goes out
t=0.32mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=30mg.The solid sulfur productive rate is Y
s=S
p/ S
t=75%.
Embodiment 6:
Desulfurizing agent CuO10 (Na2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 10wt%, the Na loading is 2% CuO10 (Na2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO10 (Na2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO10 (Na2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 2.07mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst was inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 380 ℃, and systemic circulation speed was 1000ml/min; After systemic circulation operates steadily, import continuously reducing gases H
2System pressure is 0.15MPa.Reactor outlet to temperature maintenance between the cold-trap at 250 ℃; The renewable total sulfur S that goes out
t=0.82mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=86mg.The solid sulfur productive rate is Y
s=S
p/ S
t=82%.
Embodiment 7:
Desulfurizing agent CuO8 (Na2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the Na loading is 2% CuO8 (Na2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (Na2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (Na2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 1.8mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst was inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 400 ℃, and systemic circulation speed was 400ml/min; After systemic circulation operates steadily, intermittent input reducing gases H
2Circulatory system pressure is 0.12MPa.Reactor outlet to temperature maintenance between the cold-trap at 370 ℃; The renewable total sulfur S that goes out
t=0.72mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=87mg.The solid sulfur productive rate is Y
s=S
p/ S
t=95%.
Embodiment 8:
Desulfurizing agent CuO8 (Na2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the Na loading is 2% CuO8 (Na2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (Na2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (Na2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 1.8mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst was inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 350 ℃, and systemic circulation speed was 500ml/min; After systemic circulation operates steadily, import continuously reducing gases H
2Circulatory system pressure is 0.08MPa.Reactor outlet to temperature maintenance between the cold-trap at 300 ℃; The renewable total sulfur S that goes out
t=0.60mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=57mg.The solid sulfur productive rate is Y
s=S
p/ S
t=75%.
Embodiment 9:
Desulfurizing agent CuO8 (Na2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the Na loading is 2% CuO8 (Na2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (Na2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (Na2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 1.8mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst was inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 420 ℃, and systemic circulation speed was 400ml/min; After systemic circulation operates steadily, import continuously reducing gases H
2Circulatory system pressure process scope is 0.15MPa.Reactor outlet to temperature maintenance between the cold-trap at 380 ℃; The renewable total sulfur S that goes out
t=0.96mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=100mg.The solid sulfur productive rate is Y
s=S
p/ S
t=82%.
Embodiment 10:
Desulfurizing agent CuO8 (Na2)/Al
2O
3Preparation: adopt the equal-volume co-impregnation.Under the room temperature, with certain density Cu (NO
3)
2Solution and NaNO
3Mixed solution incipient impregnation γ-Al
2O
3Particle (30-60 order, BET surface area 185m
2/ g) behind the 2h, respectively at 50 ℃ and 100 ℃ of dry 12h and 5h, then with air in 400 ℃ of calcining 8h, making the Cu loading is 8wt%, the Na loading is 2% CuO8 (Na2) Al
2O
3Desulfurizing agent.
Inhale the sulphur process: get 4g CuO8 (Na2) Al
2O
3Place fixed bed reactors, reactor is warming up to 400 ℃, passes into the normal pressure simulated flue gas, and gas flow rate is 400ml/min.CuO8 (Na2) Al when suction sulphur is saturated
2O
3The saturated Sulfur capacity of desulfurizing agent is 1.8mmolSO
2/ gcat..
Hydrogen regeneration and preparation sulphur process:
After catalyst was inhaled sulphur, reactor is switched to regeneration and preparation sulphur process: system temperature is controlled at 450 ℃, and systemic circulation speed was 800ml/min, after systemic circulation operates steadily, imports continuously H
2Gaseous mixture (H with inert gas (Ar)
2Account for 50%); Its sample introduction ratio reaches H
2/ Cu=8 stops into H when (mol/mol)
2Circulatory system pressure process scope is 0.20MPa.Reactor outlet to temperature maintenance between the cold-trap at 400 ℃; The renewable total sulfur S that goes out
t=0.70mmolS/gcat. (in sulphur).The solid sulfur that obtains in the cold-trap under the room temperature is weighed after drying and is obtained product sulphur S
p=73mg.The solid sulfur productive rate is Y
s=S
p/ S
t=81%.
Claims (4)
1, a kind of method of adding the regeneration of auxiliary agent desulphurization catalyst and preparing simultaneously sulphur is characterized in that comprising the steps:
The catalyst that supports alkali metal promoter inhale sulphur saturated after, the regeneration temperature of inhaling sulfur catalyst is controlled between 330-450 ℃, the gaseous mixture of input hydrogen or hydrogen and inert gas, flow velocity is 400-1000ml/min, pressure is 0.05-0.2MPa, works as H
2With the mol ratio of Cu is to stop into H at 8 o'clock
2, reactor outlet to temperature maintenance between the cold-trap 250 ℃-regeneration temperature, the gas that flows out from reactor during through cold-trap sulphur be condensed, residual gas continues circular response by gas circulator suction reactor again.
2, a kind of method of adding the regeneration of auxiliary agent desulphurization catalyst and preparing simultaneously sulphur as claimed in claim 1 is characterized in that fixed bed or moving bed are adopted in the regeneration of described suction sulfur catalyst.
3, a kind of method of adding the regeneration of auxiliary agent desulphurization catalyst and preparing sulphur simultaneously as claimed in claim 1 is characterized in that described alkali metal promoter is Na or K.
4, a kind of again Renhe of adding the auxiliary agent desulphurization catalyst as claimed in claim 1 prepares the method for sulphur simultaneously, it is characterized in that described H
2Input mode adopt batch sampling or continuous sample introduction.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107175108A (en) * | 2017-07-10 | 2017-09-19 | 中国科学院过程工程研究所 | A kind of cobalt series catalyst that sulphur processed is reduced for sulfur dioxide in flue gas and its production and use |
-
2006
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CN107175108A (en) * | 2017-07-10 | 2017-09-19 | 中国科学院过程工程研究所 | A kind of cobalt series catalyst that sulphur processed is reduced for sulfur dioxide in flue gas and its production and use |
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