CN111579708A - Device and method for evaluating activity of desulfurization catalyst - Google Patents
Device and method for evaluating activity of desulfurization catalyst Download PDFInfo
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Abstract
The invention belongs to the field of desulfurization catalyst activity evaluation, and particularly relates to a desulfurization catalyst activity evaluation device and method. The activity evaluation device of the desulfurization catalyst comprises an air supply unit and a reaction unit, wherein the reaction unit comprises a deoxidation unit, a hydrolysis unit and an adsorption unit which are sequentially communicated; the detecting element, including oxygen detecting element, organic sulfur detecting element and hydrogen sulfide detecting element, oxygen detecting element set up in between deoxidation unit and the unit of hydrolysising, organic sulfur detecting element set up in hydrolysising between unit and the adsorption unit, hydrogen sulfide detecting element with the gas outlet of adsorption unit is connected, the air feed unit with the air inlet of deoxidation unit is connected. The activity evaluation device of the desulfurization catalyst provided by the invention can simultaneously test several groups of different catalyst performances suitable for a blast furnace gas desulfurization series by one-time gas distribution, and is closer to the actual use condition of the catalyst.
Description
Technical Field
The invention belongs to the field of desulfurization catalyst activity evaluation, and particularly relates to a desulfurization catalyst activity evaluation device and method.
Background
The blast furnace gas contains combustible gases such as carbon monoxide, hydrogen and methane, wherein the combustible gases comprise about 23-30% of carbon monoxide, about 12-16% of carbon dioxide, about 0.8-1.9% of hydrogen, about 0.6-1.8% of oxygen, about 0.4-0.8% of methane and 200mg/Nm3COS at about 50mg/Nm3Left and right H2S and about 50% nitrogen. The blast furnace gas without desulfurization can emit more than 200mg/Nm after being combusted and used3SO2And the acid rain is formed and seriously pollutes the environment when the acid rain is directly discharged into the atmosphere. With the increasing awareness of environmental protection, the emission limit of sulfur is becoming more and more strict, and each terminal using blast furnace gas builds up a huge flue gas desulfurization device. The dispersed desulfurization device not only greatly wastes the limited steel mill space, but also increasingly highlights the cost and secondary pollution of flue gas desulfurization.
Currently, many different catalysts are needed for the technology of desulphurization and purification of blast furnace gas, for example, the prior art CN110218590A discloses a method and a system for desulphurization of blast furnace gas, wherein the method for desulphurization of blast furnace gas involves converting organic sulfur in blast furnace gas into hydrogen sulfide by using a COS hydrolyzing agent, and then adsorbing the hydrogen sulfide in blast furnace gas by using a hydrogen sulfide adsorbent to complete the desulphurization process. Among them, the used adsorbents and the like also need to be periodically regenerated by using sulfur-free clean blast furnace gas. However, how to quickly screen different desulfurization catalysts which can be matched and act synergistically in blast furnace gas is still an important technical problem to be solved urgently.
Disclosure of Invention
Therefore, the invention aims to overcome the defect that different desulfurization catalysts which can be matched and act synergistically cannot be quickly screened in the conventional blast furnace gas desulfurization process, and further provides a device and a method for evaluating the activity of the desulfurization catalysts.
Therefore, the invention adopts the technical proposal that,
an activity evaluation device of a desulfurization catalyst comprises an air supply unit and also comprises a desulfurization unit,
the reaction unit comprises a deoxidation unit, a hydrolysis unit and an adsorption unit which are sequentially communicated;
the detecting element, including oxygen detecting element, organic sulfur detecting element and hydrogen sulfide detecting element, oxygen detecting element set up in between deoxidation unit and the unit of hydrolysising, organic sulfur detecting element set up in hydrolysising between unit and the adsorption unit, hydrogen sulfide detecting element with the gas outlet of adsorption unit is connected, the air feed unit with the air inlet of deoxidation unit is connected.
Optionally, the deoxidation unit comprises a first deoxidation device and a second deoxidation device arranged in parallel;
the adsorption unit comprises a first adsorption device and a second adsorption device which are arranged in parallel.
Optionally, the gas outlet of the adsorption unit is connected with the gas inlet of the deoxidation unit, and the gas outlet of the deoxidation unit is connected with the gas inlet of the adsorption unit.
Optionally, the gas supply unit comprises a gas inlet pipeline, a gas mixing device and a saturated water vapor generation device which are connected in sequence, and a gas outlet of the saturated water vapor generation device is connected with a gas inlet of the deoxidation unit.
Optionally, the air inlet pipeline includes a carbon monoxide air inlet pipeline, a carbon dioxide air inlet pipeline, a hydrogen air inlet pipeline, a methane air inlet pipeline, a COS air inlet pipeline, a hydrogen sulfide air inlet pipeline, an oxygen air inlet pipeline, and a nitrogen air inlet pipeline.
Optionally, the hydrogen sulfide detection device further comprises a tail gas treatment device, and the tail gas treatment device is connected with the gas outlet of the hydrogen sulfide detection unit.
Optionally, the hydrolysis unit includes a hydrolysis device, and the first deoxidation device, the second deoxidation device, the first adsorption device, the second adsorption device, and the hydrolysis device each include a reactor and a heating device for heating the reactor.
The invention also provides an activity evaluation method of the desulfurization catalyst, which comprises the following steps:
1) contacting the simulated blast furnace gas with a deoxidizing agent or a regenerative deoxidizing agent to deoxidize the simulated blast furnace gas to obtain the deoxidized simulated blast furnace gas, and measuring the oxygen content of the deoxidized simulated blast furnace gas;
2) contacting the deoxidized simulated blast furnace gas with an organic sulfur hydrolyzing agent to convert organic sulfur in the simulated blast furnace gas into hydrogen sulfide to obtain hydrolyzed simulated blast furnace gas, and measuring the content of organic sulfur in the hydrolyzed simulated blast furnace gas;
3) and contacting the hydrolyzed simulated blast furnace gas with a hydrogen sulfide adsorbent or a regenerated hydrogen sulfide adsorbent to adsorb hydrogen sulfide in the simulated blast furnace gas to obtain the desulfurized simulated blast furnace gas, and measuring the content of the hydrogen sulfide in the desulfurized simulated blast furnace gas.
Preferably, in step 3), the desulfurized simulated blast furnace gas is sequentially contacted with the deactivated deoxidizer and the deactivated hydrogen sulfide adsorbent to regenerate the deactivated deoxidizer and the deactivated hydrogen sulfide adsorbent, so as to obtain a regenerated simulated blast furnace gas, and the hydrogen sulfide content of the regenerated simulated blast furnace gas is measured.
The space velocity of the simulated blast furnace gas in contact with the deoxidizer or the regenerative deoxidizer is 500-600h-1(ii) a The space velocity of the deoxidized simulated blast furnace gas when contacting with the organic sulfur hydrolytic agent is 500--1(ii) a The space velocity of the hydrolyzed simulated blast furnace gas when the simulated blast furnace gas contacts with the hydrogen sulfide adsorbent or the regenerated hydrogen sulfide adsorbent is 500--1(ii) a The space velocity of the desulfurized simulated blast furnace gas when the simulated blast furnace gas is sequentially contacted with the deactivated deoxidizer and the deactivated hydrogen sulfide adsorbent is 500--1。
The preparation method of the simulated blast furnace gas comprises the steps of mixing carbon monoxide, carbon dioxide, hydrogen, methane, carbonyl sulfide, hydrogen sulfide, oxygen and nitrogen, and then mixing the mixture with saturated steam to obtain the simulated blast furnace gas.
The technical scheme of the invention has the following advantages:
1. the activity evaluation device of the desulfurization catalyst provided by the invention removes oxygen in the simulated blast furnace gas by the gas supply unit through the deoxidation unit to obtain the deoxidized simulated blast furnace gas, then the oxygen content in the simulated blast furnace gas after the deoxidation treatment is detected by an oxygen detection unit, evaluating the deoxidizing performance of the deoxidizer or the regenerated deoxidizer in the deoxidizing unit according to the measured oxygen content, then, the simulation blast furnace gas after the deoxidation treatment passes through a hydrolysis unit to Convert Organic Sulfur (COS) in the simulation blast furnace gas into hydrogen sulfide to obtain the simulation blast furnace gas after the hydrolysis, the simulation blast furnace gas after the hydrolysis passes through an organic sulfur detection unit to detect the content of organic sulfur in the simulation blast furnace gas, and the hydrolysis performance of a hydrolysis agent in the hydrolysis unit is evaluated according to the detected content of organic sulfur; and then the hydrolyzed simulated blast furnace gas passes through an adsorption unit to adsorb hydrogen sulfide in the simulated blast furnace gas to obtain the desulfurized simulated blast furnace gas, the content of hydrogen sulfide in the desulfurized simulated blast furnace gas is detected by a hydrogen sulfide detection unit, and the adsorption performance of a hydrogen sulfide adsorbent or a regenerated hydrogen sulfide adsorbent in the adsorption unit is evaluated according to the content of hydrogen sulfide. The simulated blast furnace gas sequentially passes through the deoxidation unit, the oxygen detection unit, the hydrolysis unit, the organic sulfur detection unit, the adsorption unit and the hydrogen sulfide detection unit, so that a plurality of groups of blast furnace gas desulfurization catalysts can be connected in series and in parallel organically, and a plurality of groups of different catalysts suitable for a blast furnace gas desulfurization series can be tested simultaneously by one-time gas distribution, so that the evaluation time of the catalysts is greatly shortened, and meanwhile, the synergistic effect of the series of desulfurization catalysts and the reliability of mutual matching can be evaluated directly, and the actual use condition of the catalysts is closer.
2. In the activity evaluation device of the desulfurization catalyst provided by the present invention, the gas outlet of the adsorption unit is connected to the gas inlet of the deoxidation unit, and the gas outlet of the deoxidation unit is connected to the gas inlet of the adsorption unit. According to the invention, the gas outlet of the adsorption unit is connected with the gas inlet of the deoxidation unit, and the gas outlet of the deoxidation unit is connected with the gas inlet of the adsorption unit, so that the inactivated deoxidizer in the deoxidation unit and the inactivated hydrogen sulfide adsorbent in the adsorption unit can be effectively regenerated by utilizing the desulfurized simulated blast furnace gas, then the gas flow direction of the simulated blast furnace gas is controlled by the valve, and the simulated blast furnace gas sequentially passes through the regenerated deoxidizer, the organic sulfur hydrolytic agent and the regenerated hydrogen sulfide adsorbent, so that the regeneration performances of the regenerated deoxidizer and the regenerated hydrogen sulfide adsorbent are evaluated according to the detection results of the corresponding detection units, the gas utilization rate is greatly improved, and the evaluation time of the catalyst is effectively shortened. Meanwhile, the initial activity, the regeneration performance and the stability of the desulfurization catalyst can be tested and evaluated by one-time gas distribution through the connection arrangement.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of an activity evaluation apparatus for a desulfurization catalyst of the present invention;
FIG. 2 is a schematic view of the activity evaluation method of the desulfurization catalyst in example 2 of the present invention;
FIG. 3 is a schematic view of the activity evaluation method of the desulfurization catalyst in example 3 of the present invention;
wherein the reference numerals are represented as:
1. a first deoxidation device; 2. a second deoxidation device; 3. an oxygen detection device; 4. a hydrolysis device; 5. an organic sulfur detection device; 6. a first adsorption device; 7. a second adsorption device; 8. an air supply unit; 9. a deoxygenation unit;
10. an adsorption unit; 11. a hydrogen sulfide detection device; 12. a tail gas treatment device; 13. an air intake line; 14. a mass flow controller; 15. a gas mixing device; 16. a water vapor generating device; 17. a first valve; 18. a second valve; 19. a third valve; 20. a fourth valve; 21. a fifth valve; 22. a sixth valve; 23. and a seventh valve.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
As shown in fig. 1, the present invention provides an activity evaluation device for a desulfurization catalyst, comprising an air supply unit 8, further comprising,
the reaction unit comprises a deoxidation unit 9, a hydrolysis unit and an adsorption unit 10 which are sequentially communicated;
the detecting element, including oxygen detecting element, organic sulfur detecting element and hydrogen sulfide detecting element, oxygen detecting element set up in between deoxidation unit 9 and the unit of hydrolysising, organic sulfur detecting element set up in hydrolysising between unit and the adsorption unit 10, hydrogen sulfide detecting element with the gas outlet of adsorption unit 10 is connected, air feed unit 8 with the air inlet of deoxidation unit 9 is connected.
The method comprises the steps of enabling simulated blast furnace gas to pass through a deoxidation unit 9 through a gas supply unit 8 to remove oxygen in the simulated blast furnace gas to obtain the simulated blast furnace gas after deoxidation treatment, enabling the simulated blast furnace gas after the deoxidation treatment to pass through an oxygen detection unit to detect the oxygen content in the simulated blast furnace gas after the deoxidation treatment, evaluating the deoxidation performance of a deoxidizer or a regenerative deoxidizer in the deoxidation unit 9 according to the detected oxygen content, enabling the simulated blast furnace gas after the deoxidation treatment to pass through a hydrolysis unit to Convert Organic Sulfur (COS) in the simulated blast furnace gas into hydrogen sulfide to obtain the hydrolyzed simulated blast furnace gas, enabling the hydrolyzed simulated blast furnace gas to pass through an organic sulfur detection unit to detect the organic sulfur content in the simulated blast furnace gas, and evaluating the hydrolysis performance of a hydrolysis agent in the hydrolysis unit according to the detected organic sulfur content; and then, passing the hydrolyzed simulated blast furnace gas through an adsorption unit 10 to adsorb hydrogen sulfide in the simulated blast furnace gas to obtain the desulfurized simulated blast furnace gas, detecting the content of hydrogen sulfide in the desulfurized simulated blast furnace gas through a hydrogen sulfide detection unit, and evaluating the adsorption performance of a hydrogen sulfide adsorbent or a regenerated hydrogen sulfide adsorbent in the adsorption unit 10 according to the content of hydrogen sulfide. The simulated blast furnace gas sequentially passes through the deoxidation unit 9, the oxygen detection unit, the hydrolysis unit, the organic sulfur detection unit, the adsorption unit 10 and the hydrogen sulfide detection unit, so that a plurality of groups of blast furnace gas desulfurization catalysts can be organically connected in series and in parallel, a plurality of groups of different catalysts suitable for a blast furnace gas desulfurization series can be simultaneously tested by one-time gas distribution, and meanwhile, the synergistic effect of the series desulfurization catalysts can be directly realized, and the reliability of mutual matching is evaluated, so that the real use condition of the catalysts is more approximate.
In an alternative embodiment, the deoxidation unit 9 comprises a first deoxidation apparatus 1 and a second deoxidation apparatus 2 arranged in parallel; the air inlets of the first deoxidation device 1 and the second deoxidation device 2 are connected with the air inlet of the deoxidation unit, and the air outlet is connected with the air outlet of the deoxidation unit; the adsorption unit 10 comprises a first adsorption device 6 and a second adsorption device 7 which are arranged in parallel; the air inlets of the first adsorption device 6 and the second adsorption device 7 are connected with the air inlet of the adsorption unit, and the air outlet is connected with the air outlet of the adsorption unit. The first deoxidation device 1 and the second deoxidation device 2 can be selected to be filled with a deoxidizer or a regenerated deoxidizer or an inactivated deoxidizer, wherein the inactivated deoxidizer refers to the deoxidizer with the catalytic deoxidation of the simulated blast furnace gas, the deoxidation activity of the deoxidizer is reduced or the deoxidation activity is completely lost, namely the inactivated deoxidizer; the regenerated deoxidizer is used for regenerating the inactivated deoxidizer to improve the deoxidizing activity of the inactivated deoxidizer or recover the deoxidizing activity of the inactivated deoxidizer, and the obtained deoxidizer is the regenerated deoxidizer; one of the first adsorption device 6 and the second adsorption device 7 can be filled with a hydrogen sulfide adsorbent or a regenerated hydrogen sulfide adsorbent or an inactivated hydrogen sulfide adsorbent, where the inactivated hydrogen sulfide adsorbent refers to an adsorbent which is decreased in adsorption activity or completely loses adsorption activity along with adsorption of hydrogen sulfide in the hydrolyzed simulated blast furnace gas by the hydrogen sulfide adsorbent, and is the inactivated hydrogen sulfide adsorbent; the regeneration of the hydrogen sulfide adsorbent refers to regenerating the deactivated hydrogen sulfide adsorbent to improve the adsorption activity of the deactivated hydrogen sulfide adsorbent or recover the adsorption activity of the deactivated hydrogen sulfide adsorbent, and the obtained adsorbent is the regeneration hydrogen sulfide adsorbent; the present invention can simultaneously evaluate the deoxidizing activity of the deoxidizing agent or the regenerated deoxidizing agent, and the adsorption activity of the hydrogen sulfide adsorbent or the regenerated hydrogen sulfide adsorbent by alternatively filling the deoxidizing agent or the regenerated deoxidizing agent or the inactivated deoxidizing agent in the first deoxidizing device 1 and the second deoxidizing device 2, and alternatively filling the hydrogen sulfide adsorbent or the regenerated hydrogen sulfide adsorbent or the inactivated hydrogen sulfide adsorbent in the first adsorption device 6 and the second adsorption device 7.
In an alternative embodiment, the air outlet of the adsorption unit 10 is connected with the air inlet of the deoxidation unit 9, and the air outlet of the deoxidation unit 9 is connected with the air inlet of the adsorption unit 10. According to the invention, the gas outlet of the adsorption unit 10 is connected with the gas inlet of the deoxidation unit 9, the gas outlet of the deoxidation unit 9 is connected with the gas inlet of the adsorption unit 10, the desulfurized simulated blast furnace gas can be effectively utilized to regenerate the inactivated deoxidizer in the deoxidation unit 9 and the inactivated hydrogen sulfide adsorbent in the adsorption unit 10, then the gas flow direction of the simulated blast furnace gas is controlled through the valve, and the simulated blast furnace gas sequentially passes through the regenerated deoxidizer, the organic sulfur hydrolytic agent and the regenerated hydrogen sulfide adsorbent, so that the regeneration performances of the regenerated deoxidizer and the regenerated hydrogen sulfide adsorbent are evaluated according to the detection results of the corresponding detection units, the gas utilization rate is greatly improved, and the evaluation time of the catalyst is effectively shortened. Meanwhile, the initial activity, the regeneration performance and the stability of the desulfurization catalyst can be tested and evaluated by one-time gas distribution through the connection arrangement. The evaluation indexes of the invention on the initial activity and the regeneration performance of the desulfurization catalyst (comprising a deoxidizer, an organic sulfur hydrolytic agent and a hydrogen sulfide adsorbent) are conventional evaluation indexes in the field. The evaluation indexes adopted by the invention are specifically as follows: the oxygen content in the simulated blast furnace gas after the deoxidation treatment is detected by the oxygen detection unit to be lower than 0.2 percent (volume content), which shows that the deoxidation performance of the deoxidizer or the regenerative deoxidizer is good; the organic sulfur detection unit detects that the content of organic sulfur in the simulated blast furnace gas is less than 2mg/m3So that the organic sulfur hydrolytic agent has good hydrolytic property; the hydrogen sulfide detection unit detects that the content of the hydrogen sulfide in the desulfurized simulated blast furnace gas is lower than 1mg/m3It is indicated that the adsorption performance of the hydrogen sulfide adsorbent or the regenerated hydrogen sulfide adsorbent is good, or the regeneration of the deactivated hydrogen sulfide adsorbent is completed.
In an alternative embodiment, the air supply unit 8 comprises an air inlet pipeline 13, a gas inlet pipeline and a gas outlet pipeline which are connected in sequence,A gas mixing device 15 and a saturated water vapor generating device 16, wherein the gas outlet of the saturated water vapor generating device 16 is connected with the gas inlet of the deoxidizing unit 9. The invention obtains the simulated blast furnace gas by introducing each component gas contained in the blast furnace gas into a gas mixing device 15 through an air inlet pipeline 13 for mixing, and then introducing the mixed gas into a saturated steam generating device 16 for mixing with saturated steam. According to the invention, the air inlet pipeline 13, the gas mixing device 15 and the saturated steam generating device 16 are connected in sequence, so that the preparation of the simulated blast furnace gas is realized, and the simulated blast furnace gas is applied to the evaluation of the activity of the blast furnace gas desulfurization catalyst, so that the activity of the desulfurization catalyst is closer to the actual use condition of the catalyst. Optionally, a mass flow controller 14 is arranged on the air inlet line 13 for controlling the flow of the gas in the air inlet line 13. Optionally, the saturated steam generating device 16 may control the water content in the simulated blast furnace gas to be 0-50% (volume content), preferably 2-30%. Optionally, the air intake pipeline 13 includes a carbon monoxide air intake pipeline, a carbon dioxide air intake pipeline, a hydrogen air intake pipeline, a methane air intake pipeline, a COS air intake pipeline, a hydrogen sulfide air intake pipeline, an oxygen air intake pipeline, and a nitrogen air intake pipeline. Preferably, the simulated blast furnace gas comprises carbon monoxide, carbon dioxide, hydrogen, methane, carbonyl sulfide, hydrogen sulfide, oxygen, nitrogen and saturated steam. Preferably, the simulated blast furnace gas comprises 180-210mg/Nm3COS of (A), 0.6-1.8% (volume content) oxygen, 23-30% (volume content) carbon monoxide, 0.8-1.9% (volume content) hydrogen, 12-16% (volume content) carbon dioxide, 0.4-0.8% (volume content) methane, 45-55mg/Nm340-60% (volume content) of nitrogen and 2-30% (volume content) of saturated water vapor.
In an optional embodiment, the system further comprises a tail gas treatment device 12, and the tail gas treatment device 12 is connected with the gas outlet of the hydrogen sulfide detection unit. The tail gas treatment device 12 can be internally provided with alkali liquor for absorbing hydrogen sulfide in the tail gas, and then the tail gas is discharged into the air.
In an alternative embodiment, the hydrolysis unit comprises a hydrolysis device 4, and the first deoxygenating device 1, the second deoxygenating device 2, the first adsorbing device 6, the second adsorbing device 7 and the hydrolysis device 4 each comprise a reactor and a heating device for heating the reactor. The reactor can be a U-shaped quartz tube, and a desulfurization catalyst can be arranged in the U-shaped quartz tube; the heating device can be a heating furnace for heating the U-shaped quartz tube, and optionally, the heating temperature can be 50-500 ℃.
In an alternative embodiment, the first deoxidation apparatus 1 further comprises a first valve 17 for allowing or preventing gas to pass into the first deoxidation apparatus 1; the second deoxidation apparatus 2 further comprises a second valve 18 for passing gas into the second deoxidation apparatus 2 or preventing gas from passing into the second deoxidation apparatus 2; the oxygen detection unit comprises an oxygen detection device 3, and the oxygen detection device 3 comprises a third valve 19 for allowing gas to enter the oxygen detection device 3 or preventing gas from entering the oxygen detection device 3; the hydrolysis unit comprises a hydrolysis device 4, and the hydrolysis device 4 comprises a fourth valve 20 for allowing gas to pass into the hydrolysis device 4 or preventing gas from passing into the hydrolysis device 4; the organic sulfur detection unit comprises an organic sulfur detection device 5, and the organic sulfur detection device 5 comprises a fifth valve 21 for allowing gas to pass into the organic sulfur detection device 5 or preventing gas from passing into the organic sulfur detection device 5; the first adsorption means 6 further comprises a sixth valve 22 for letting gas into the first adsorption means 6 or for preventing gas from letting into the first adsorption means 6; the second adsorption device 7 further comprises a seventh valve 23 for allowing gas to pass into the second adsorption device 7 or preventing gas from passing into the second adsorption device 7. Optionally, the first valve 17, the second valve 18, the third valve 19, the fourth valve 20, the fifth valve 21, the sixth valve 22, and the seventh valve 23 may be six-way valves. Optionally, the third valve 19 is further communicated with the dosing ring, and the fifth valve 21 is further communicated with the dosing ring.
The reactors in the first deoxidation device 1 and the second deoxidation device 2 can be internally provided with a deoxidizer or a regeneration deoxidizer or an inactivated deoxidizer or an oxygen adsorbent; the reactor in the hydrolysis device 4 is internally provided with an organic sulfur hydrolysis agent, and the reactors in the first adsorption device 6 and the second adsorption device 7 can be internally provided with a hydrogen sulfide adsorbent or a regenerated hydrogen sulfide adsorbent or an inactivated hydrogen sulfide adsorbent. The desulfurization catalyst of the invention is a desulfurization catalyst commonly used in the field, and the specific type of the desulfurization catalyst is not particularly limited. Optionally, the deoxidizer is at least one selected from a noble metal deoxidizer and a non-noble metal cobalt molybdenum sulfur type deoxidizer; preferably, the noble metal deoxidizer is a supported noble metal deoxidizer, the active component in the supported noble metal deoxidizer is selected from one or more of gold, platinum, palladium and ruthenium, and the carrier is an oxide carrier or a ceramic carrier. Preferably, the oxide carrier is selected from one or more of alumina, silica, magnesia, titania, zirconia and ceria. The hydrolytic agent is a supported hydrolytic agent, the active component of the supported hydrolytic agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium oxalate, potassium oxalate, sodium sulfate and potassium sulfate, and the carrier is selected from one or more of carbon nitride, alumina, silica, magnesia, titania, zirconia and ceria; the adsorbent is a supported adsorbent, the active component of the supported adsorbent is selected from one or more of iron oxide, cobalt oxide, nickel oxide and copper oxide, and the carrier is selected from one or more of modified bauxite, carbon nitride, alumina, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide and cerium oxide.
In an optional embodiment, the present invention uses a carbon monoxide gas inlet pipeline, a carbon dioxide gas inlet pipeline, a hydrogen gas inlet pipeline, a methane gas inlet pipeline, a COS gas inlet pipeline, a hydrogen sulfide gas inlet pipeline, an oxygen gas inlet pipeline, and a nitrogen gas inlet pipeline to introduce the respective component gases into a gas mixing device 15 according to a certain ratio, the gas mixing device 15 may be a gas mixer, the flow rate of the respective component gases may be controlled by a mass flow controller 14 on the gas inlet pipeline, and the mixed respective component gases are introduced into a saturated steam generation device 16 to be mixed with saturated steam, so as to obtain the simulated blast furnace gas. The saturated steam generating device 16 may be a saturated steam generator. The first valve 17 in the first deoxidation device 1 is communicated with a built-in U-shaped quartz tube reactor, the second valve 18 in the second deoxidation device 2 is communicated with the built-in U-shaped quartz tube reactor, the fourth valve 20 in the hydrolysis device 4 is communicated with the built-in U-shaped quartz tube reactor, the sixth valve 22 in the first adsorption device 6 is communicated with the built-in U-shaped quartz tube reactor, the seventh valve 23 in the second adsorption device 7 is communicated with the built-in U-shaped quartz tube reactor, and the third valve 19 in the oxygen detection device 3 is communicated with an oxygen detector; the fifth valve 21 in the organic sulfur detecting device 5 is communicated with the organic sulfur detector. In the invention, whether the simulated blast furnace gas is introduced into the corresponding device is controlled by the seven valves.
In an alternative embodiment, according to the requirement of desulfurization process, deactivated deoxidizer is placed in the first deoxidation device 1, deoxidizer is placed in the second deoxidation device 2, organic sulfur hydrolytic agent is placed in the hydrolysis device 4, deactivated hydrogen sulfide adsorbent is placed in the first adsorption device 6, and hydrogen sulfide adsorbent is placed in the second adsorption device 7. As shown in fig. 2, the configured simulated blast furnace gas passes through the A, B gas ports of the first to seventh valves 23 in sequence; the C, D air ports of the first valve 17, the second valve 18, the fourth valve 20, the sixth valve 22 and the seventh valve 23 are respectively communicated with the air inlet and the air outlet of the U-shaped quartz tube reactor in the corresponding device; the A gas port of the seventh valve 23 is communicated with the E gas port of the first valve 17, the F gas port of the first valve 17 is communicated with the E gas port of the second valve 18, the F gas port of the second valve 18 is communicated with the F gas port of the sixth valve 22, the E gas port of the sixth valve 22 is communicated with the F gas port of the seventh valve 23, the E gas port of the seventh valve 23 is communicated with the hydrogen sulfide detection device 11, the hydrogen sulfide detection device 11 is communicated with the tail gas treatment device 12, the E gas port of the fourth valve 20 is communicated with the inert gas, the F gas port is exhausted, and the inert gas can be introduced into the hydrolysis device 4 in a balance gas mode. The C, D air port of the third valve 19 is communicated with the quantitative ring and can be used for detecting the oxygen content, and the E, F air port of the third valve 19 is communicated with the oxygen detector; the port C, D of the fifth valve 21 is in communication with a dosing ring for detecting the level of organic sulfur, and the port E, F of the fifth valve 21 is in communication with an organic sulfur detector.
In an optional embodiment, the prepared simulated blast furnace gas is controlled by the first valve 17 and the second valve 18 to be introduced into the first deoxidation device 1 or the second deoxidation device 2, the first deoxidation device 1 or the second deoxidation device 2 is used for the performance test of the deoxidizer, and the material flow after the catalytic reaction is the deoxidized simulated blast furnace gas; introducing the deoxidized simulated blast furnace gas into a hydrolysis device 4 under the control of a fourth valve 20, wherein the hydrolysis device 4 is used for performance test of a base sulfur hydrolysis catalyst, and the material flow after catalytic reaction is the hydrolyzed simulated blast furnace gas; the hydrolyzed simulated blast furnace gas is introduced into the first adsorption device 6 or the second adsorption device 7 under the control of the sixth valve 22 and the seventh valve 23, the first adsorption device 6 and the second adsorption device 7 are used for performance test of a hydrogen sulfide adsorbent or a regenerated hydrogen sulfide adsorbent, the material flow after catalytic reaction is the desulfurized simulated blast furnace gas, the desulfurized simulated blast furnace gas is introduced into the first deoxidation device 1 or the second deoxidation device 2 again under the control of the first valve 17 and the second valve 18 and is used for regeneration performance evaluation of a deoxidizer in the first deoxidation device 1 or the first deoxidation device 1, and the evaluated material flow is the regenerated simulated blast furnace gas; the simulated blast furnace gas after the regeneration treatment passes through the first adsorption device 6 or the second adsorption device 7 under the control of the sixth valve 22 and the seventh valve 23, and the first adsorption device 6 and the second adsorption device 7 are used for the regeneration performance test of the hydrogen sulfide adsorbent.
In an alternative embodiment, when the deoxidizer in the first deoxidizing device 1 is subjected to deoxidization initial activity evaluation, the inactivated deoxidizer in the second deoxidizing device 2 can be regenerated, the first valve 17 is controlled to enable the simulated blast furnace gas to be introduced into the first deoxidizing device 1, and the second valve 18 is controlled to prevent the simulated blast furnace gas from being introduced into the second deoxidizing device 2; when the deoxidizer in the first deoxidizing device 1 is regenerated, the deoxidizer in the second deoxidizing device 2 can be subjected to a deoxidizing initial activity evaluation test, the first valve 17 is controlled to prevent the simulated blast furnace gas from flowing into the first deoxidizing device 1, and the second valve 18 is controlled to simulate the blast furnace gas from flowing into the second deoxidizing device 2. When the organic sulfur hydrolytic agent in the hydrolytic device 4 is subjected to the initial activity evaluation of hydrolysis, the fourth valve 20 is controlled to make the deoxidized simulated blast furnace gas flow into the hydrolytic device 4. When the hydrogen sulfide adsorbent in the first adsorption device 6 is subjected to the adsorption initial activity evaluation, the deactivated hydrogen sulfide adsorbent in the second adsorption device 7 can be regenerated, the sixth valve 22 is controlled to enable the simulated blast furnace gas to be introduced into the first adsorption device 6, and the seventh valve 23 is controlled to prevent the simulated blast furnace gas from being introduced into the second adsorption device 7; when the hydrogen sulfide adsorbent in the first adsorption device 6 is regenerated, the adsorbent in the second adsorption device 7 can be subjected to an adsorption initial activity evaluation test, the sixth valve 22 is controlled to prevent the simulated blast furnace gas from flowing into the first adsorption device 6, and the seventh valve 23 is controlled to simulate the blast furnace gas from flowing into the second adsorption device 7.
The deoxidizer of the invention is a conventional deoxidizer in the field, the organic sulfur hydrolytic agent is a conventional hydrolytic agent in the field, and the hydrogen sulfide adsorbent is a conventional adsorbent in the field. The deoxidizer, the hydrolyzing agent and the adsorbent in the field can be obtained commercially or prepared by the conventional method in the field. Optionally, the preparation method of the deoxidizer comprises the following steps: and (3) soaking the carrier in an active component aqueous solution, and then sequentially drying and roasting to obtain the deoxidizer. And when the carrier is a composite carrier, mixing the components of the carrier, ball-milling and roasting to prepare the composite carrier. Optionally, the mass ratio of the active component to the carrier in the deoxidizer is (2-40): 100. the bulk density of the deoxidizer is 0.5-1.5kg/m3The grain size of the deoxidizer is 0.1-2 mm. Optionally, the preparation method of the organic sulfur hydrolyzing agent comprises the following steps: and (3) soaking the carrier in an active component aqueous solution, and then drying to obtain the hydrolytic agent. And when the carrier is a composite carrier, mixing the components of the carrier, ball-milling and roasting to prepare the composite carrier. Optionally, the mass ratio of the active component to the carrier in the hydrolytic agent is (2-40): 100. the bulk density of the hydrolytic agent is 0.5-0.9kg/m3The grain size of the hydrolytic agent is 0.1-5 mm. Optionally, the preparation method of the hydrogen sulfide adsorbent comprises the following steps: soaking the carrier in an active component soaking solution, and then sequentially drying and roasting to obtain the adsorbent. And when the carrier is a composite carrier, mixing the components of the carrier, ball-milling and roasting to prepare the composite carrier. Optionally, the active component impregnation solution is one or more aqueous solutions selected from iron nitrate, cobalt nitrate, nickel nitrate, ferric sulfate, cobalt sulfate, nickel sulfate, ferric chloride, cobalt chloride, nickel chloride, ferric oxalate, cobalt oxalate, nickel oxalate, copper nitrate, copper acetate, copper chloride and copper sulfate. The mass ratio of the active component to the carrier in the adsorbent is (2-40): 100. the bulk density of the adsorbent is 0.5-1.5kg/m3The particle size of the adsorbent is 0.1-5 mm.
The deoxidizer, the organic sulfur hydrolyzing agent and the hydrogen sulfide absorbent used in the following examples 2 to 4 of the present invention were prepared as follows.
The preparation method of the ceramic carrier loaded ruthenium metal deoxidizer comprises the following steps: preparing a ruthenium chloride aqueous solution with the mass fraction of 5%, placing a ceramic carrier in the ruthenium chloride aqueous solution, soaking for 1 hour, drying for 2 hours at 100 ℃, roasting for 10 minutes at 450 ℃ to obtain the ceramic carrier loaded ruthenium metal deoxidizer, wherein the mass ratio of metal ruthenium to the ceramic carrier in the ceramic carrier loaded ruthenium metal deoxidizer is 9: 50; the bulk density of the ruthenium metal deoxidizer loaded on the ceramic carrier is 0.8kg/m3The grain diameter is 0.3-0.5 mm.
The Na is2CO3/Al2O3The preparation method comprises the following steps: preparing 10 percent of Na by mass fraction2CO3Aqueous solution, placing alumina carrier in Na2CO3Soaking in water solution for 3 hr, and drying at 90 deg.C for 0.8 hr to obtain Na2CO3/Al2O3A hydrolyzing agent of said Na2CO3/Al2O3Na in the hydrolytic agent2CO3The mass ratio of the alumina carrier to the alumina carrier is 6: 58; the Na is2CO3/Al2O3The bulk density of the hydrolytic agent is 0.6kg/m3The grain diameter is 2-3 mm.
Said Fe2O3/Al2O3-C3N4In the adsorbent, active groupIs divided into Fe2O3The carrier is a mixed carrier of carbon nitride and aluminum oxide, and the Fe2O3/Al2O3-C3N4The preparation method of the adsorbent comprises the following steps:
1) preparing a carrier: mixing carbon nitride powder and alumina powder in equal mass, ball milling for 15 hours, and roasting at 900 ℃ for 5 hours to prepare a carrier for later use;
2) preparing 8 mass percent ferric nitrate aqueous solution, soaking the carrier in the ferric nitrate aqueous solution for 3 hours, then drying at 100 ℃ for 1.2 hours, and roasting at 800 ℃ for 30 minutes to obtain the Fe2O3/Al2O3-C3N4Adsorbent of said Fe2O3/Al2O3-C3N4Fe in adsorbent2O3The mass ratio of the carrier to the carrier is 1: 7, said Fe2O3/Al2O3-C3N4The bulk density of the adsorbent was 0.9kg/m3The particle size is 1-2 mm.
Example 2
As shown in fig. 2, the present embodiment provides a method for evaluating the activity of a desulfurization catalyst, comprising the steps of:
1) loading a catalyst: the first deoxidizing device 1 is filled with an inactivated deoxidizing agent (the inactivated deoxidizing agent is an inactivated ruthenium metal deoxidizer loaded on a honeycomb ceramic carrier), the second deoxidizing device 2 is filled with a deoxidizing agent (the deoxidizing agent is a ruthenium metal deoxidizer loaded on a honeycomb ceramic carrier), and the hydrolysis device 4 is filled with an organic sulfur hydrolyzing agent (the organic sulfur hydrolyzing agent is Na)2CO3/Al2O3A hydrolytic agent), the first adsorption device 6 is filled with deactivated hydrogen sulfide adsorbent (the deactivated hydrogen sulfide adsorbent is deactivated Fe)2O3/Al2O3-C3N4Adsorbent), the second adsorption device 7 is filled with hydrogen sulfide adsorbent (the hydrogen sulfide adsorbent is Fe)2O3/Al2O3-C3N4An adsorbent);
2) preparation simulation blast furnaceCoal gas: introducing corresponding gas groups into a gas mixer through a carbon monoxide gas inlet pipeline, a carbon dioxide gas inlet pipeline, a hydrogen gas inlet pipeline, a methane gas inlet pipeline, a COS gas inlet pipeline, a hydrogen sulfide gas inlet pipeline, an oxygen gas inlet pipeline and a nitrogen gas inlet pipeline for mixing (controlling the flow of the corresponding gas through a mass flow controller 14 arranged on the gas inlet pipeline), introducing the mixed gas into a saturated steam generator for mixing with saturated steam again to obtain simulated blast furnace gas (the blast furnace gas contains 200 mg/Nm)3COS of (1.0% by volume of oxygen, 28% by volume of carbon monoxide, 1.2% by volume of hydrogen, 15% by volume of carbon dioxide, 0.6% by volume of methane, 50mg/Nm3Hydrogen sulfide of (a), 40% (volume content) of nitrogen, and the balance of saturated water vapor);
3) the simulated blast furnace gas (the temperature of the simulated blast furnace gas is 70 ℃) is used for 500h-1The volume space velocity of the oxygen-containing gas is introduced into the second deoxidation device 2 to be contacted with the deoxidizer to deoxidize the simulated blast furnace gas to obtain the deoxidized simulated blast furnace gas, the deoxidized simulated blast furnace gas can detect the oxygen content in the deoxidized simulated blast furnace gas through the oxygen detection device 3, and the deoxidation performance of the deoxidizer is evaluated according to the oxygen content; the deoxidized simulated blast furnace gas takes 500h-1The volume space velocity is introduced into a hydrolysis device 4 to be contacted with an organic sulfur hydrolytic agent so as to convert organic sulfur in the simulated blast furnace gas into hydrogen sulfide to obtain hydrolyzed simulated blast furnace gas, the hydrolyzed simulated blast furnace gas can detect the Content of Organic Sulfur (COS) in the simulated blast furnace gas through an organic sulfur detection device 5, the organic sulfur conversion rate is calculated according to the content of the organic sulfur, and the hydrolysis performance of the organic sulfur hydrolytic agent on the organic sulfur is evaluated according to the organic sulfur conversion rate; the hydrolyzed simulated blast furnace gas is used for 500h-1The volume space velocity of the gas is introduced into the second adsorption device 7 and is contacted with a hydrogen sulfide adsorbent in the second adsorption device 7 to adsorb the hydrogen sulfide in the simulated blast furnace gas, so as to obtain the desulfurized simulated blast furnace gas;
4) the desulfurized simulated blast furnace gas is used for 500 hours-1Is introduced into the first deoxidizing device 1 to contact with the inactivated deoxidizing agent, and utilizes the reducibility in the simulated blast furnace gas after desulfurizationRegenerating the deactivated deoxidizer in the atmosphere, and then regenerating the deoxidizer for 500h-1The volume space velocity of the gas is introduced into the first adsorption device 6 to contact with the inactivated hydrogen sulfide adsorbent, the inactivated hydrogen sulfide adsorbent is regenerated by utilizing the reducing atmosphere in the desulfurized simulated blast furnace gas to obtain the regenerated simulated blast furnace gas, the regenerated simulated blast furnace gas can detect the hydrogen sulfide content in the regenerated simulated blast furnace gas through the hydrogen sulfide detection device 11, the regeneration condition of the hydrogen sulfide adsorbent is evaluated according to the hydrogen sulfide content, the simulated blast furnace gas detected by the hydrogen sulfide detection device 11 can perform tail gas absorption treatment on the simulated blast furnace gas through the tail gas treatment device 12, and the tail gas is evacuated after the tail gas absorption treatment. Through tests, compared with the method for evaluating the initial activity and the regeneration performance of the deoxidizer, the organic sulfur hydrolytic agent and the hydrogen sulfide adsorbent by each gas distribution, the method for evaluating the initial activity and the regeneration performance of the deoxidizer, the organic sulfur hydrolytic agent and the hydrogen sulfide adsorbent is completed by the method in the embodiment, and the time is shortened by 4-5 times.
Example 3
As shown in fig. 3, the present embodiment provides a method for evaluating the activity of a desulfurization catalyst, comprising the steps of:
1) loading a catalyst: a deoxidizer (the deoxidizer is a ruthenium metal deoxidizer loaded on a honeycomb ceramic carrier) is filled in the first deoxidizing device 1, an inactivated deoxidizer (the inactivated deoxidizer is a ruthenium metal deoxidizer loaded on a honeycomb ceramic carrier) is filled in the second deoxidizing device 2, and an organic sulfur hydrolytic agent (the organic sulfur hydrolytic agent is Na) is filled in the hydrolytic device 42CO3/Al2O3A hydrolytic agent), the first adsorption device 6 is filled with a hydrogen sulfide adsorbent (the hydrogen sulfide adsorbent is Fe)2O3/Al2O3-C3N4Adsorbent), the second adsorption device 7 is filled with deactivated hydrogen sulfide adsorbent (the deactivated hydrogen sulfide adsorbent is deactivated Fe2O3/Al2O3-C3N4An adsorbent);
2) preparing simulated blast furnace gas: introducing corresponding gas groups into a gas mixer through a carbon monoxide gas inlet pipeline, a carbon dioxide gas inlet pipeline, a hydrogen gas inlet pipeline, a methane gas inlet pipeline, a COS gas inlet pipeline, a hydrogen sulfide gas inlet pipeline, an oxygen gas inlet pipeline and a nitrogen gas inlet pipeline for mixing (controlling the flow of the corresponding gas through a mass flow controller 14 arranged on the gas inlet pipeline), introducing the mixed gas into a saturated steam generator for mixing with saturated steam again to obtain simulated blast furnace gas (the blast furnace gas contains 200 mg/Nm)3COS of (1.0% by volume of oxygen, 28% by volume of carbon monoxide, 1.2% by volume of hydrogen, 15% by volume of carbon dioxide, 0.6% by volume of methane, 50mg/Nm3Hydrogen sulfide of (a), 40% (volume content) of nitrogen, and the balance of saturated water vapor);
3) the simulated blast furnace gas (the temperature of the simulated blast furnace gas is 90 ℃) is used for 500h-1The volume space velocity of the oxygen-containing gas is introduced into the first deoxidation device 1 to be contacted with the deoxidizer to deoxidize the simulated blast furnace gas to obtain the deoxidized simulated blast furnace gas, the deoxidized simulated blast furnace gas can detect the oxygen content in the deoxidized simulated blast furnace gas through the oxygen detection device 3, and the deoxidation performance of the deoxidizer is evaluated according to the oxygen content; the deoxidized simulated blast furnace gas takes 500h-1The volume space velocity is introduced into a hydrolysis device 4 to be contacted with an organic sulfur hydrolytic agent so as to convert organic sulfur in the simulated blast furnace gas into hydrogen sulfide to obtain hydrolyzed simulated blast furnace gas, the hydrolyzed simulated blast furnace gas can detect the Content of Organic Sulfur (COS) in the simulated blast furnace gas through an organic sulfur detection device 5, the organic sulfur conversion rate is calculated according to the content of the organic sulfur, and the hydrolysis performance of the organic sulfur hydrolytic agent on the organic sulfur is evaluated according to the organic sulfur conversion rate; the hydrolyzed simulated blast furnace gas is used for 500h-1The volume space velocity of the gas is introduced into the first adsorption device 6 to contact with a hydrogen sulfide adsorbent in the first adsorption device 6 so as to adsorb hydrogen sulfide in the simulated blast furnace gas, and the desulfurized simulated blast furnace gas is obtained;
4) the desulfurized simulated blast furnace gas is used for 500 hours-1Is introduced into the second deoxidizing device 2 to contact with the inactivated deoxidizing agent, and the desulfurized deoxidizing agent is utilizedThe deactivated deoxidizer is regenerated in the reducing atmosphere in the simulated blast furnace gas, and then the regenerated deoxidizer is used for 500 hours-1The volume space velocity of the gas is introduced into the second adsorption device 7 to contact with the inactivated hydrogen sulfide adsorbent, the inactivated hydrogen sulfide adsorbent is regenerated by utilizing the reducing atmosphere in the desulfurized simulated blast furnace gas to obtain the regenerated simulated blast furnace gas, the regenerated simulated blast furnace gas can detect the hydrogen sulfide content in the regenerated simulated blast furnace gas through the hydrogen sulfide detection device 11, the regeneration condition of the hydrogen sulfide adsorbent is evaluated according to the hydrogen sulfide content, the simulated blast furnace gas detected by the hydrogen sulfide detection device 11 can perform tail gas absorption treatment on the simulated blast furnace gas through the tail gas treatment device 12, and the tail gas is evacuated after the tail gas absorption treatment. Through tests, compared with the method for evaluating the initial activity and the regeneration performance of the deoxidizer, the organic sulfur hydrolytic agent and the hydrogen sulfide adsorbent by each gas distribution, the method for evaluating the initial activity and the regeneration performance of the deoxidizer, the organic sulfur hydrolytic agent and the hydrogen sulfide adsorbent is completed by the method in the embodiment, and the time is shortened by 4-5 times.
Example 4
The embodiment provides an activity evaluation method of a desulfurization catalyst, which comprises the following steps:
1) loading a catalyst: a deoxidizer (the deoxidizer is a ruthenium metal deoxidizer loaded on a honeycomb ceramic carrier) is filled in the first deoxidizing device 1, an inactivated deoxidizer (the inactivated deoxidizer is a ruthenium metal deoxidizer loaded on a honeycomb ceramic carrier) is filled in the second deoxidizing device 2, and an organic sulfur hydrolytic agent (the organic sulfur hydrolytic agent is Na) is filled in the hydrolytic device 42CO3/Al2O3A hydrolytic agent), the first adsorption device 6 is filled with a hydrogen sulfide adsorbent (the hydrogen sulfide adsorbent is Fe)2O3/Al2O3-C3N4Adsorbent), the second adsorption device 7 is filled with deactivated hydrogen sulfide adsorbent (the deactivated hydrogen sulfide adsorbent is deactivated Fe2O3/Al2O3-C3N4An adsorbent);
2) preparing simulated blast furnace gas: introducing corresponding gas groups into a gas mixer through a carbon monoxide gas inlet pipeline, a carbon dioxide gas inlet pipeline, a hydrogen gas inlet pipeline, a methane gas inlet pipeline, a COS gas inlet pipeline, a hydrogen sulfide gas inlet pipeline, an oxygen gas inlet pipeline and a nitrogen gas inlet pipeline for mixing (controlling the flow of the corresponding gas through a mass flow controller 14 arranged on the gas inlet pipeline), introducing the mixed gas into a saturated steam generator for mixing with saturated steam again to obtain simulated blast furnace gas (the blast furnace gas contains 210 mg/Nm)3COS of (1.0% by volume of oxygen, 30% by volume of carbon monoxide, 1.4% by volume of hydrogen, 18% by volume of carbon dioxide, 0.7% by volume of methane, 53mg/Nm343% by volume of nitrogen and the balance saturated steam);
3) the simulated blast furnace gas (the temperature of the simulated blast furnace gas is 90 ℃) is used for 700h-1The volume space velocity of the oxygen-containing gas is introduced into the first deoxidation device 1 to be contacted with the deoxidizer to deoxidize the simulated blast furnace gas to obtain the deoxidized simulated blast furnace gas, the deoxidized simulated blast furnace gas can detect the oxygen content in the deoxidized simulated blast furnace gas through the oxygen detection device 3, and the deoxidation performance of the deoxidizer is evaluated according to the oxygen content; the deoxidized simulated blast furnace gas takes 600h-1The volume space velocity is introduced into a hydrolysis device 4 to be contacted with an organic sulfur hydrolytic agent so as to convert organic sulfur in the simulated blast furnace gas into hydrogen sulfide to obtain hydrolyzed simulated blast furnace gas, the hydrolyzed simulated blast furnace gas can detect the Content of Organic Sulfur (COS) in the simulated blast furnace gas through an organic sulfur detection device 5, the organic sulfur conversion rate is calculated according to the content of the organic sulfur, and the hydrolysis performance of the organic sulfur hydrolytic agent on the organic sulfur is evaluated according to the organic sulfur conversion rate; the hydrolyzed simulated blast furnace gas is used for 600 hours-1The volume space velocity of the gas is introduced into the first adsorption device 6 to contact with a hydrogen sulfide adsorbent in the first adsorption device 6 so as to adsorb hydrogen sulfide in the simulated blast furnace gas, and the desulfurized simulated blast furnace gas is obtained; the desulfurized simulated blast furnace gas can detect the content of hydrogen sulfide in the simulated blast furnace gas through the hydrogen sulfide detection device 11, evaluate the adsorption performance of the hydrogen sulfide adsorbent according to the content of the hydrogen sulfide,the simulated blast furnace gas detected by the hydrogen sulfide detection device 11 can be subjected to tail gas absorption treatment by the tail gas treatment device 12, and the tail gas is exhausted after the tail gas absorption treatment. Through tests, compared with the method for evaluating the initial activities of the deoxidizer, the organic sulfur hydrolytic agent and the hydrogen sulfide adsorbent independently for each gas distribution, the method for evaluating the initial activities of the deoxidizer, the organic sulfur hydrolytic agent and the hydrogen sulfide adsorbent in the embodiment shortens the time by 4-5 times, and therefore, the method in the embodiment achieves the purpose of rapidly screening different desulfurization catalysts which can be matched with each other and have synergistic effect.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An activity evaluation device of a desulfurization catalyst comprises an air supply unit and is characterized by also comprising a desulfurization unit,
the reaction unit comprises a deoxidation unit, a hydrolysis unit and an adsorption unit which are sequentially communicated;
the detecting element, including oxygen detecting element, organic sulfur detecting element and hydrogen sulfide detecting element, oxygen detecting element set up in between deoxidation unit and the unit of hydrolysising, organic sulfur detecting element set up in hydrolysising between unit and the adsorption unit, hydrogen sulfide detecting element with the gas outlet of adsorption unit is connected, the air feed unit with the air inlet of deoxidation unit is connected.
2. The apparatus for evaluating the activity of a desulfurization catalyst according to claim 1, characterized in that the deoxidation unit comprises a first deoxidation apparatus and a second deoxidation apparatus arranged in parallel;
the adsorption unit comprises a first adsorption device and a second adsorption device which are arranged in parallel.
3. The apparatus for evaluating the activity of a desulfurization catalyst according to claim 1 or 2, characterized in that a gas outlet of the adsorption unit is connected to a gas inlet of the deoxidation unit, and a gas outlet of the deoxidation unit is connected to a gas inlet of the adsorption unit.
4. The apparatus for evaluating the activity of a desulfurization catalyst according to any one of claims 1 to 3, wherein the gas supply unit comprises a gas inlet line, a gas mixing device and a saturated water vapor generation device connected in this order, and a gas outlet of the saturated water vapor generation device is connected to a gas inlet of the deoxidation unit.
5. The apparatus for evaluating the activity of a desulfurization catalyst according to any one of claims 1 to 4, wherein said intake line comprises a carbon monoxide intake line, a carbon dioxide intake line, a hydrogen intake line, a methane intake line, a COS intake line, a hydrogen sulfide intake line, an oxygen intake line, and a nitrogen intake line.
6. The apparatus for evaluating the activity of a desulfurization catalyst according to any one of claims 1 to 5, characterized by further comprising an exhaust gas treatment device connected to the outlet of the hydrogen sulfide detection unit.
7. The apparatus for evaluating the activity of a desulfurization catalyst according to any one of claims 1 to 6, wherein the hydrolysis unit comprises a hydrolysis device, and each of the first deoxidation device, the second deoxidation device, the first adsorption device, the second adsorption device and the hydrolysis device comprises a reactor and a heating device for heating the reactor.
8. A method for evaluating the activity of a desulfurization catalyst, comprising the steps of:
1) contacting the simulated blast furnace gas with a deoxidizing agent or a regenerative deoxidizing agent to deoxidize the simulated blast furnace gas to obtain the deoxidized simulated blast furnace gas, and measuring the oxygen content of the deoxidized simulated blast furnace gas;
2) contacting the deoxidized simulated blast furnace gas with an organic sulfur hydrolyzing agent to convert organic sulfur in the simulated blast furnace gas into hydrogen sulfide to obtain hydrolyzed simulated blast furnace gas, and measuring the content of organic sulfur in the hydrolyzed simulated blast furnace gas;
3) and contacting the hydrolyzed simulated blast furnace gas with a hydrogen sulfide adsorbent or a regenerated hydrogen sulfide adsorbent to adsorb hydrogen sulfide in the simulated blast furnace gas to obtain the desulfurized simulated blast furnace gas, and measuring the content of the hydrogen sulfide in the desulfurized simulated blast furnace gas.
9. The method for evaluating the activity of a desulfurization catalyst according to claim 8, characterized in that in step 3), the desulfurized simulated blast furnace gas is contacted with the deactivated deoxidizer and the deactivated hydrogen sulfide adsorbent in this order to regenerate the deactivated deoxidizer and the deactivated hydrogen sulfide adsorbent, thereby obtaining a regenerated simulated blast furnace gas, and the hydrogen sulfide content of the regenerated simulated blast furnace gas is measured.
10. The method for evaluating the activity of a desulfurization catalyst according to claim 8 or 9, characterized in that the method for producing a simulated blast furnace gas comprises mixing carbon monoxide, carbon dioxide, hydrogen, methane, carbonyl sulfide, hydrogen sulfide, oxygen, and nitrogen, and then mixing the mixture with saturated steam to obtain the simulated blast furnace gas.
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| CN117030920A (en) * | 2023-08-03 | 2023-11-10 | 北京铝能清新环境技术有限公司 | Performance test device and method for integral skid-mounted blast furnace gas fine desulfurization agent |
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| CN117030920B (en) * | 2023-08-03 | 2024-04-12 | 北京铝能清新环境技术有限公司 | Performance test device and method for integral skid-mounted blast furnace gas fine desulfurization agent |
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