CN115301217B - Adsorbent for deeply removing hydrogen sulfide and carbonyl sulfide in blast furnace gas as well as preparation method and application thereof - Google Patents

Adsorbent for deeply removing hydrogen sulfide and carbonyl sulfide in blast furnace gas as well as preparation method and application thereof Download PDF

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CN115301217B
CN115301217B CN202210969984.9A CN202210969984A CN115301217B CN 115301217 B CN115301217 B CN 115301217B CN 202210969984 A CN202210969984 A CN 202210969984A CN 115301217 B CN115301217 B CN 115301217B
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adsorbent
tio
blast furnace
furnace gas
aluminum titanate
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CN115301217A (en
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范兰
万加兵
许琦
李阳
侍大海
陆中飞
丰来国
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Yancheng Institute of Technology
Yancheng Lanfeng Environmental Engineering Technology Co Ltd
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Yancheng Lanfeng Environmental Engineering Technology Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0248—Compounds of B, Al, Ga, In, Tl
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

The invention discloses an adsorbent for deeply removing hydrogen sulfide and carbonyl sulfide in blast furnace gas, a preparation method and application thereof, wherein the adsorbent is prepared from Fe (NO 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and porous aluminum titanate A1 2 TiO 5 The three materials are compounded according to the mass ratio of 1-2:1-2:2. The invention combines the high-efficiency Fe-Zn binary desulfurizer which is easy to deactivate with the porous aluminum titanate A1 2 TiO 5 The composite avoids the inactivation caused by carbonization of Fe and the volatilization loss caused by reduction to Zn simple substance, and the porous structure of the aluminum titanate solves the high dispersion load of Fe and Zn, so that the sulfur capacity of the Fe-Zn desulfurizing agent is not reduced, and more effective sulfur adsorption sites are provided. In addition, the aluminum titanate, the zinc titanate and the Fe-Al composite oxide have extremely high mechanical strength, thermal stability and wear resistance, and the service life of the desulfurizing agent is prolonged.

Description

Adsorbent for deeply removing hydrogen sulfide and carbonyl sulfide in blast furnace gas as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to an adsorbent for deeply removing hydrogen sulfide and carbonyl sulfide in blast furnace gas, and a preparation method and application thereof.
Background
Blast furnace gas is a main byproduct of blast furnace ironmaking production, belongs to combustible gas, and comprises main components of nitrogen, carbon monoxide, carbon dioxide, hydrogen, hydrocarbons, a small amount of sulfur-containing pollutants and particulate matters. Because of the combustible gas such as carbon monoxide, hydrogen and the like, the blast furnace gas has a certain heat value and is often used as self-used gas or civil gas for metallurgical enterprises.
In order to reduce the atmospheric pollution caused by the sulfur emission of downstream users, the blast furnace gas needs to be deeply desulfurized before being utilized. Sulfur-containing pollutants in blast furnace gas are divided into organic sulfur and inorganic sulfur, wherein the organic sulfur mainly comprises carbonyl sulfide, carbon disulfide, thioether mercaptan, thiophene and the like; the inorganic sulfur mainly comprises hydrogen sulfide, sulfur dioxide and the like, and three components of carbonyl sulfide, hydrogen sulfide and carbon disulfide account for more than 90% of the total sulfur content. According to the characteristics of blast furnace gas, a blast furnace alkali spraying device is generally arranged for desulfurization, and the device has a certain effect on removing hydrogen sulfide in the blast furnace gas, but is almost ineffective on organic sulfur mainly comprising carbonyl sulfide. Carbonyl sulfide removal is a key to deep desulfurization of blast furnace gas due to the relatively high content of carbonyl sulfide in sulfur-containing contaminants of blast furnace gas.
In the conventional blast furnace gas desulfurization technology, in consideration of the fact that organic sulfur is difficult to remove, hydrolysis, catalytic hydrogenation and other methods are generally adopted to convert the organic sulfur into inorganic hydrogen sulfide which is easy to remove, and then the hydrogen sulfide is removed, so that the process is complex and the cost is high. In the air pollution treatment technology, the adsorption method is widely applied due to the advantages of simple operation, high efficiency and the like, and iron oxide, zinc oxide and the most widely applied desulfurizing agent are easily carbonized to deactivate, and zinc oxide is easily reduced to be volatilized and lost as Zn simple substance. In addition, desulfurizing agents have extremely high requirements for mechanical strength, thermal temperature and wear resistance. If the iron oxide and the zinc oxide can be supported on a certain carrier and the problems are solved through the interaction between the iron oxide and the carrier, a new simple, efficient and low-cost idea is provided for deep removal of the hydrogen sulfide and the carbonyl sulfide of the blast furnace gas.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a blast furnace gas hydrogen sulfide and carbonyl sulfide deep removal adsorbent, and a preparation method and application thereof, so as to solve the problems that iron oxide and zinc oxide adsorbents are easy to carbonize and deactivate and are easy to reduce into simple substances and volatilize and lose in the desulfurization process in the prior art. The invention adopts the technical scheme that:
a deep removing adsorbent for hydrogen sulfide and carbonyl sulfide of blast furnace gas is prepared from Fe (NO 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and porous aluminum titanate A1 2 TiO 5 Is compounded into Fe (NO) 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and A1 2 TiO 5 The mass ratio of (2) is 1-2:1-2:2.
Further, the porous aluminum titanate A1 2 TiO 5 The pore diameter of (C) is 10-13nm.
The preparation method of the deep removal adsorbent for the hydrogen sulfide and carbonyl sulfide of the blast furnace gas comprises the following steps:
step 1: preparation of porous aluminum titanate A1 2 TiO 5 Will A1 2 O 3 、TiO 2 And dispersing the activated carbon nano powder in deionized water, adding ammonium polyacrylate solution to prepare mixed slurry, wherein the ball-to-material ratio is 1:2 ball milling for 4 hours under the condition of 2, drying, and roasting in a silicon-molybdenum furnace at 1450 ℃ for 2 hours;
step 2: fe (NO) 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 Mixing O and the porous aluminum titanate prepared in the step 1 uniformly, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then carrying out low-temperature plasma treatment to prepare a precursor of the adsorbent;
and 3, placing the adsorbent precursor prepared in the step 2 into a tube furnace, and heating to 500 ℃ at a speed of 5 ℃/min under an inert atmosphere to bake for 4 hours to obtain the target product.
Further, in the step 1, A1 2 O 3 、TiO 2 And the molar ratio of the active carbon nano powder is 1:1:0.2; solid phase volume of the mixed slurryThe content was 45V%.
Fe (NO) in said step 2 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 The mass ratio of O to the porous aluminum titanate is 1-2:1-2:2; the power of the low-temperature plasma treatment is 100W, and the treatment time is 20min.
Preferably, the inert atmosphere in step 3 is 99.99% helium.
The specific method steps in the application are that a double-tower parallel fixed bed adsorber is adopted to remove H in the blast furnace gas 2 S or/and COS, adding an adsorbent into an adhesive, preparing and molding, filling the adhesive into two adsorption towers, introducing 500-700 ℃ blast furnace gas to be treated into a tower I, indicating adsorption saturation when the total concentration of sulfide detected in the outlet gas is close to the emission standard value, transferring the blast furnace gas to a tower II at the moment for continuous desulfurization, and introducing 2%O into the tower I 2 +98%N 2 And (3) the mixed gas is heated to 700 ℃ to purge and regenerate the adsorbent, when sulfide components are hardly detected in the outlet gas, the adsorbent is completely regenerated, air inlet and heating are stopped for standby, when the adsorption of the tower II is saturated, the blast furnace gas is switched to the tower I again, and the tower II is purged and regenerated, so that the continuous operation of circulating adsorption-desorption of sulfide in the blast furnace gas can be realized.
Furthermore, the adhesive is sesbania gum powder.
The invention combines the high-efficiency Fe-Zn binary desulfurizer which is easy to deactivate with the porous aluminum titanate A1 2 TiO 5 Compounding, wherein Fe and A1 2 TiO 5 The Fe-Al composite oxide is formed, so that the inactivation caused by carbonization of Fe is avoided; zn and A1 2 TiO 5 The zinc titanate ZnxTiyOz is formed, and the volatilization loss caused by reduction to Zn simple substance is avoided. Aluminum titanate itself has no desulfurization ability, however, the porous structure of aluminum titanate solves the high dispersion load of Fe and Zn, not only does not reduce the sulfur capacity of Fe-Zn desulfurizing agent, but also provides more effective sulfur adsorption sites. In addition, the aluminum titanate, the zinc titanate and the Fe-Al composite oxide have extremely high mechanical strength, thermal stability and wear resistance, and improve the mechanical strengthThe service life of the desulfurizing agent is prolonged.
Drawings
FIG. 1 shows Fe prepared in comparative example 2 1 Zn 1 And Fe prepared in example 2 1 Zn 1 @A1 2 TiO 5 H of adsorbent 2 S, cyclic adsorption-desorption performance test;
FIG. 2 is a diagram showing Fe produced in comparative example 2 1 Zn 1 And Fe prepared in example 2 1 Zn 1 @A1 2 TiO 5 COS cycle adsorption-desorption performance test of the adsorbent.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Will A1 2 O 3 、TiO 2 And the molar ratio of the active carbon nano powder is 1:1:0.2 dispersing in deionized water, adding ammonium polyacrylate solution as a dispersing agent, preparing mixed slurry with the solid phase volume content of 45V percent, and mixing the slurry with the spherical material ratio of 1:2, ball milling for 4 hours under the condition of 2, drying, then placing in a silicon-molybdenum furnace, roasting for 2 hours at 1450 ℃, and preparing the porous aluminum titanate A1 2 TiO 5 。
(2) Fe (NO) 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and porous aluminum titanate according to a mole ratio of 1:2:2, uniformly mixing, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then adopting low-temperature plasma treatment for 20 minutes under the power of 100W to prepare a precursor of the adsorbent;
(3) Placing the adsorbent precursor into a tube furnace, heating to 500 ℃ at a speed of 5 ℃/min under helium atmosphere, and roasting for 4 hours to obtain a desulfurization adsorbent, which is marked as Fe 1 Zn 2 @A1 2 TiO 5 。
H in blast furnace gas is removed by adopting fixed bed adsorbers connected in parallel with double towers 2 S and/or COS, fe 1 Zn 2 @A1 2 TiO 5 Adding cross-linking agent into adsorbent, preparing, filling into two adsorption towers, introducing 500-700 deg.C blast furnace gas to be treated into tower I, when the total concentration of sulfide detected in outlet gas is close to discharge standard value, indicating that adsorption is saturated, transferring blast furnace gas into tower II at this time to continuously desulfurizing, introducing '2%O' into tower I 2 +98%N 2 And (3) the mixed gas is heated to 700 ℃ to purge and regenerate the adsorbent, when sulfide components are hardly detected in the outlet gas, the adsorbent is completely regenerated, air inlet and heating are stopped for standby, when the adsorption of the tower II is saturated, the blast furnace gas is switched to the tower I again, and the tower II is purged and regenerated, so that the continuous operation of circulating adsorption-desorption of sulfide in the blast furnace gas is realized.
Example 2
(1) Will A1 2 O 3 、TiO 2 And the molar ratio of the active carbon nano powder is 1:1:0.2 dispersing in deionized water, adding ammonium polyacrylate solution as a dispersing agent, preparing mixed slurry with the solid phase volume content of 45V percent, and mixing the slurry with the spherical material ratio of 1:2, ball milling for 4 hours under the condition of 2, drying, then placing in a silicon-molybdenum furnace, roasting for 2 hours at 1450 ℃, and preparing the porous aluminum titanate A1 2 TiO 5 。
(2) Fe (NO) 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and porous aluminum titanate according to a mole ratio of 1:1:2, uniformly mixing, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then adopting low-temperature plasma treatment for 20 minutes under the power of 100W to prepare a precursor of the adsorbent;
(3) Placing the adsorbent precursor into a tube furnace, heating to 500 ℃ at a speed of 5 ℃/min under helium atmosphere, and roasting for 4 hours to obtain a desulfurization adsorbent, which is marked as Fe 1 Zn 1 @A1 2 TiO 5 。
Example 3
(1) Will A1 2 O 3 、TiO 2 And the molar ratio of the active carbon nano powder is 1:1:0.2 dispersing in deionized water, adding ammonium polyacrylate solution as a dispersing agent, preparing mixed slurry with the solid phase volume content of 45V percent, and mixing the slurry with the spherical material ratio of 1:2, ball milling for 4 hours under the condition of 2, drying, then placing in a silicon-molybdenum furnace, roasting for 2 hours at 1450 ℃, and preparing the porous aluminum titanate A1 2 TiO 5 。
(2) Fe (NO) 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and porous aluminum titanate in a molar ratio of 2:1:2, uniformly mixing, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then adopting low-temperature plasma treatment for 20 minutes under the power of 100W to prepare a precursor of the adsorbent;
(3) Placing the adsorbent precursor into a tube furnace, heating to 500 ℃ at a speed of 5 ℃/min under helium atmosphere, and roasting for 4 hours to obtain a desulfurization adsorbent, which is marked as Fe 2 Zn 1 @A1 2 TiO 5 。
Comparative example 1
(2) Fe (NO) 3 ) 2 ·9H 2 O and Zn (NO) 3 ) 2 ·6H 2 O is in a molar ratio of 1:2, uniformly mixing, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then adopting low-temperature plasma treatment for 20 minutes under the power of 100W to prepare a precursor of the adsorbent;
(3) Placing the adsorbent precursor into a tube furnace, heating to 500 ℃ at a speed of 5 ℃/min under helium atmosphere, and roasting for 4 hours to obtain a desulfurization adsorbent, which is marked as Fe 1 Zn 2 。
Comparative example 2
(2) Fe (NO) 3 ) 2 ·9H 2 O and Zn (NO) 3 ) 2 ·6H 2 O is in a molar ratio of 1:1, uniformly mixing, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then adopting low-temperature plasma treatment for 20 minutes under the power of 100W to prepare a precursor of the adsorbent;
(3) Placing the above adsorbent precursor into a tube furnace, and heating to 500 deg.C/min under helium atmosphereRoasting for 4 hours at the temperature to obtain the desulfurization adsorbent, which is marked as Fe 1 Zn 1 。
Comparative example 3
(2) Fe (NO) 3 ) 2 ·9H 2 O and Zn (NO) 3 ) 2 ·6H 2 O is calculated according to the mole ratio of 2:1, uniformly mixing, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then adopting low-temperature plasma treatment for 20 minutes under the power of 100W to prepare a precursor of the adsorbent;
(3) Placing the adsorbent precursor into a tube furnace, heating to 500 ℃ at a speed of 5 ℃/min under helium atmosphere, and roasting for 4 hours to obtain a desulfurization adsorbent, which is marked as Fe 2 Zn 1 。
And testing the low-temperature nitrogen physical adsorption desorption isotherm of the desulfurizing agent by adopting a specific surface area and pore diameter analyzer, carrying out degassing pretreatment by adopting a heating and vacuumizing mode before testing, and calculating the specific surface area, pore volume and pore diameter distribution according to BET, HK and BJK theory.
The fixed bed adsorbers are adopted to respectively test the adsorbent to H at 600 DEG C 2 Adsorption amount of S and COS, sieving and weighing the powder adsorbent, loading the powder adsorbent into an adsorber, and charging H in the air 2 S content of 40 mg/m 3 The COS content was 60mg/m 3 And detecting the concentration of the outlet gas on line by adopting gas chromatography, stopping the experiment when the concentration of the outlet gas is stable and is close to the inlet gas concentration, taking out the adsorbent after cooling, weighing again, and obtaining the weight difference of the adsorbent before and after the test as the sulfur adsorption amount.
Specific surface area, pore volume, H of adsorbents produced in comparative examples 1 to 3 and examples 1 to 3 2 The S and COS adsorption amount test results are shown in Table 1.
TABLE 1 specific surface area, pore volume, H of adsorbents 2 Adsorption amount of S and COS
As can be seen from Table 1, the specific surface areas of the FeZn adsorbents were all lower than 30m 2 Per g, pore volume is less than 0.1. 0.1 cm 3 And/g, both of which slightly increase with increasing Fe and Zn molar ratio. With porous aluminium titanate A1 2 TiO 5 After compounding, the specific surface area of the adsorbent is higher than 150m 2 Per g, pore volume higher than 0.3. 0.3 cm 3 And/g, the molar ratio of Fe to Zn is slightly increased, the specific surface area and the pore volume of the adsorbent can be obviously improved by the porous aluminum titanate, the dispersibility of Fe and Zn species is improved, and the active adsorption sites of sulfur-containing pollutants are increased. Thus, feZn@A1 2 TiO 5 H of series adsorbents 2 The S adsorption amount and COS adsorption amount are obviously higher than FeZn series.
In addition, H of two series adsorbents 2 S adsorption capacity is higher than COS adsorption capacity, H 2 The S adsorption quantity is increased along with the increase of the mole ratio of Fe and Zn, fe 2 Zn 1 @A1 2 TiO 5 With highest H 2 The S adsorption amount was 390mg/g. The adsorption amount of COS is slightly reduced along with the increase of the mole ratio of Fe and Zn, fe 1 Zn 2 @A1 2 TiO 5 Has the highest COS adsorption quantity of 196mg/g.
Selection of Fe 1 Zn 1 And Fe (Fe) 1 Zn 1 @A1 2 TiO 5 The adsorbent is represented by, and the two are tested for H 2 Cyclic adsorption and desorption properties of S and COS. Completion of H at 600 ℃ 2 After adsorption testing of S or COS, the intake air was converted to 2%O 2 +98%N 2 And (3) the mixed gas is subjected to purging regeneration after the temperature is increased to 700 ℃, and then the adsorption experiment can be performed again after the temperature is reduced to 600 ℃. Fe (Fe) 1 Zn 1 And Fe (Fe) 1 Zn 1 @A1 2 TiO 5 H of two adsorbents 2 The S-cycle adsorption-desorption performance test results are shown in fig. 1. After 5 times of cyclic adsorption-desorption, fe 1 Zn 1 H of (2) 2 S adsorption quantity is reduced from 327 mg/g to 254mg/g, and attenuation rate is up to 22.32%; and Fe (Fe) 1 Zn 1 @A1 2 TiO 5 H of (2) 2 The S adsorption amount is reduced from 371 to mg/g to 346mg/g, and the attenuation rate is only 6.7%. Fe (Fe) 1 Zn 1 And Fe (Fe) 1 Zn 1 @A1 2 TiO 5 COS cycle adsorption-desorption performance of two adsorbentsThe test results are shown in fig. 2. After 5 times of cyclic adsorption-desorption, fe 1 Zn 1 The COS adsorption amount of the catalyst is reduced from 172mg/g to 145mg/g, and the attenuation rate is up to 15.7%; and Fe (Fe) 1 Zn 1 @A1 2 TiO 5 The COS adsorption amount of (2) was decreased from 187/mg/g to 172mg/g, and the attenuation was only 8.0%.
FeZn series adsorbent is made of Fe 2 O 3 Is compounded with ZnO, fe 2 O 3 The high-temperature fuel gas is quickly reduced into highly dispersed element Fe, the components with desulfurization activity are element Fe and ZnO, and the element Fe and ZnO adsorb H 2 S or COS followed by FeS and ZnS, wherein Fe 2 O 3 For coarse desulfurization, whereas ZnO is used for fine desulfurization, the sulfide concentration in the outlet gas can be reduced to below 10 ppm. The ZnO desulfurizing agent has quick desulfurization reaction within the range of 600-700 ℃ and high desulfurization rate, but is easy to be reduced into Zn simple substance in reducing atmosphere above 600 ℃ to volatilize and lose, so that the theoretical optimal desulfurization temperature is 600 ℃, the desulfurization effect can be considered, the loss rate of the desulfurizing agent can be reduced to a certain extent, and the Zn loss rate is still higher in a circulating sulfur adsorption and desorption experiment. In addition, the Fe component is also susceptible to carbonization and deactivation during desulfurization.
FeZn binary desulfurizing agent capable of efficiently desulfurizing at 600 ℃ and easy to deactivate and porous aluminum titanate A1 2 TiO 5 Compounding, fe and A1 2 TiO 5 The Fe-Al composite oxide is formed, so that the inactivation caused by carbonization of Fe is avoided; zn and A1 2 TiO 5 Formation of zinc titanate Zn x Ti y O z Avoiding volatilization loss caused by reduction to Zn simple substance, thus FeZn@A1 2 TiO 5 The circulating sulfur adsorption and desorption performance of the series of adsorbents is obviously improved. Aluminum titanate itself has no desulfurization ability, however, the porous structure of aluminum titanate solves the high dispersion load of Fe and Zn, not only does not reduce the sulfur capacity of Fe-Zn desulfurizing agent, but also provides more effective sulfur adsorption sites, thus FeZn@A1 2 TiO 5 H of series adsorbents 2 The S adsorption amount and COS adsorption amount are obviously higher than FeZn series. In addition, aluminum titanate, zinc titanate and Fe-Al composite oxide have extremely high mechanical strength, thermal stability andwear resistance and prolonged service life of the desulfurizing agent. In summary, feZn@A1 of the present invention 2 TiO 5 The series of adsorbents have high sulfur capacity, good circulating sulfur adsorption and desorption performance and extremely high mechanical strength, thermal stability and wear resistance, thereby realizing blast furnace gas H 2 Deep removal of S and COS.

Claims (5)

1. An adsorbent for deeply removing hydrogen sulfide and carbonyl sulfide from blast furnace gas is characterized by that Fe (NO 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and porous aluminum titanate A1 2 TiO 5 Is compounded into Fe (NO) 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 O and A1 2 TiO 5 The mass ratio of (2) is 1-2:1-2:2, and the specific preparation method is as follows:
step 1: preparation of porous aluminum titanate A1 2 TiO 5 Will A1 2 O 3 、TiO 2 And dispersing the activated carbon nano powder in deionized water, adding ammonium polyacrylate solution to prepare mixed slurry, wherein the ball-to-material ratio is 1:2, ball milling for 4 hours under the condition of 2, drying, and roasting in a silicon-molybdenum furnace at 1450 ℃ for 2 hours, wherein A1 2 O 3 、TiO 2 And the molar ratio of the active carbon nano powder is 1:1:0.2; the solid phase volume content of the mixed slurry is 45 VOL;
step 2: fe (NO) 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 Mixing O and the porous aluminum titanate prepared in the step 1 uniformly, adding deionized water with the same volume, stirring for 12 hours, drying at 100 ℃, and then carrying out low-temperature plasma treatment to prepare a precursor of the adsorbent, wherein Fe (NO 3 ) 2 ·9H 2 O、Zn(NO 3 ) 2 ·6H 2 The mass ratio of O to the porous aluminum titanate is 1-2:1-2:2; the power of the low-temperature plasma treatment is 100W, and the treatment time is 20min;
and 3, placing the adsorbent precursor prepared in the step 2 into a tube furnace, and heating to 500 ℃ at a speed of 5 ℃/min under an inert atmosphere to bake for 4 hours to obtain the target product.
2. The adsorbent for deep removal of hydrogen sulfide and carbonyl sulfide from blast furnace gas according to claim 1, characterized in that the porous aluminum titanate A1 2 TiO 5 The pore diameter of (C) is 10-13nm.
3. The method for preparing the adsorbent for deep removal of hydrogen sulfide and carbonyl sulfide from blast furnace gas according to claim 1, wherein the inert atmosphere in the step 3 is 99.99% helium.
4. The use of the adsorbent for deep removal of hydrogen sulfide and carbonyl sulfide from blast furnace gas according to claim 1 or 2, wherein the specific method step in the use is that two fixed bed adsorbers connected in parallel with the adsorption towers are adopted, the adsorbent is added into an adhesive for preparation and molding, and then is filled into the two adsorption towers, and the blast furnace gas to be treated at 500-700 ℃ is introduced for deep removal.
5. The method for deeply removing hydrogen sulfide and carbonyl sulfide from blast furnace gas as claimed in claim 4, wherein after the adsorbent is saturated, the adsorbent is heated to 700 ℃ for purging and regenerating.
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