CN113968572B - System and process for deoxidizing and producing hydrogen by using mixed gas of blast furnace gas and converter gas - Google Patents
System and process for deoxidizing and producing hydrogen by using mixed gas of blast furnace gas and converter gas Download PDFInfo
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- CN113968572B CN113968572B CN202111229677.9A CN202111229677A CN113968572B CN 113968572 B CN113968572 B CN 113968572B CN 202111229677 A CN202111229677 A CN 202111229677A CN 113968572 B CN113968572 B CN 113968572B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
Abstract
The invention discloses a system and a process for preparing hydrogen by deoxidizing mixed gas of blast furnace and converter gas, wherein the process comprises the following steps: 1) Blast furnace gas and converterMixing the coal gas in a coal gas cabinet; 2) Compressing the mixed coal gas into a surge tank through a compressor; 3) The pressurized mixed gas enters an oxygen content adjusting tower for oxygen content adjustment after being heated; 4) Carrying out organic sulfur hydrolysis conversion on the mixed gas with the adjusted oxygen content; 5) The mixed gas after the organic sulfur hydrolysis passes through a gas-gas blending device, and the ratio between water gas and gas is regulated; 6) The mixed gas with the water vapor content regulated enters a CO conversion device for reaction to generate CO 2 And H 2 . According to the invention, the mixed gas is subjected to oxygen content adjustment, organic sulfur conversion and gas-steam adjustment, so that the service lives of an organic sulfur conversion catalyst and a conversion catalyst are greatly prolonged, a multi-stage reaction device required by CO conversion is simplified, and CO in the mixed gas can be effectively converted into hydrogen through one-time reaction under the action of the conversion catalyst.
Description
Technical Field
The invention relates to the technical field of gas recycling, in particular to a system and a process for preparing hydrogen by deoxidizing mixed gas of blast furnace and converter gas.
Background
The product of hydrogen combustion is water, and therefore, it is considered as the most environmentally friendly fuel. However, the main raw materials of hydrogen production at present mainly use fossil resources such as petroleum, natural gas, coal and the like, and the consumption of the resources is acknowledged to pollute the environment. On the other hand, in the production of steel, a certain amount of fossil resources are consumed, and a large amount of blast furnace gas, a small portion of converter gas, and the like are produced. Blast furnace gas has considerable combustion value, with a carbon monoxide volume content of about 28%, a hydrogen volume content of about 1%, and a methane volume content of about 0.5%. Blast furnace gas is usually sent to hot blast stoves, heating furnaces, coke ovens, boilers and gas units in a fuel mode for combustion. This simple combustion is of low value.
Research shows that if hydrogen is produced by CO conversion, the utilization value of the furnace gas is improved. The prior art CN 112374458A discloses a method and a device for producing hydrogen by using iron-making blast furnace gas, which comprise the following steps: after desulfurization treatment is carried out on blast furnace gas, nitrogen is removed by a pressure swing adsorption technology, and then hydrogen production is carried out by four-stage CO conversion through a high-temperature conversion, two medium-temperature conversion and a low-temperature conversion device in sequence. However, the method has complex process, high bed resistance and high energy consumption.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a system and a process for preparing hydrogen by deoxidizing mixed gas of blast furnace gas and converter gas, which directly converts CO in the blast furnace gas into hydrogen at one time by utilizing a high-efficiency low-temperature CO conversion catalyst through improving the process, thereby simplifying the existing blast furnace gas hydrogen preparation technology and greatly improving the hydrogen preparation efficiency.
The invention adopts the following technical scheme:
the system comprises a gas cabinet, a compressor, a pressure stabilizing gas tank, an oxygen content regulating tower, an organic sulfur conversion device, a gas-gas allocation device and a CO conversion device which are sequentially connected in series, wherein one side of the gas cabinet is provided with a first gas inlet and a second gas inlet, the other side of the gas cabinet is provided with a mixed gas outlet, the mixed gas outlet is communicated with the gas inlet of the compressor, the gas outlet of the compressor is communicated with the gas inlet arranged below the side wall of the pressure stabilizing gas tank, the gas outlet above the side wall of the pressure stabilizing gas tank is communicated with the gas inlet arranged at the top of the oxygen content regulating tower, the gas outlet at the bottom of the oxygen content regulating tower is communicated with the gas inlet arranged at the top of the organic sulfur conversion device, the gas outlet at the bottom of the organic sulfur conversion device is communicated with the gas inlet arranged below the side wall of the gas allocation device, the gas outlet above the side wall of the gas-gas allocation device is communicated with the gas inlet arranged at the top of the CO conversion device, and the gas outlet at the bottom of the CO conversion device is communicated with an external hydrogen separation device; the CO conversion device is a radial controllable heat-transfer conversion reactor, a conversion catalyst is filled in the radial controllable heat-transfer conversion reactor, and the conversion catalyst is filled in two layers and more in the CO conversion device.
The bottom of the pressure stabilizing gas tank is provided with a first water outlet, a plurality of baffle plates I inclining downwards are staggered from top to bottom in the pressure stabilizing gas tank, and condensed water in the pressure stabilizing gas tank is collected to the bottom of the pressure stabilizing gas tank through the baffle plates I and is discharged through the first water outlet.
Preferably, the downward inclination angle of the baffle I is 20 degrees.
The oxygen content regulating tower is filled with deoxidization catalyst, and the deoxidization catalyst is filled with three layers and more in the oxygen content regulating tower.
The organic sulfur conversion device is internally filled with an organic sulfur conversion catalyst, the organic sulfur conversion catalyst is divided into two layers and more in the organic sulfur conversion device, and the lower part of the organic sulfur conversion device is provided with an oxygen inlet.
The first heat exchanger is also provided with a first hot gas inlet and a first hot gas outlet, the second heat exchanger is also provided with a second hot gas inlet and a second hot gas outlet, the first hot gas inlet and the first hot gas outlet are used as a pair of communicated, and the second hot gas inlet and the second hot gas outlet are used as a pair of communicated and are respectively used for heating coal gas passing through the first heat exchanger and the second heat exchanger.
The bottom of the gas-steam mixing device is provided with a second water outlet and a steam inlet, a baffle II, a baffle III and a baffle IV are sequentially arranged in the gas-steam mixing device from top to bottom, the baffle II is horizontally arranged in the middle of the gas-steam mixing device, the baffle III is obliquely arranged on the upper edge of the air inlet of the gas-steam mixing device, the baffle IV is obliquely arranged between the second water outlet and the steam inlet, and the plane where the baffle III is parallel to the plane where the baffle IV is.
Preferably, the downward inclination angle of the baffle III is 20 degrees, and the upward inclination angle of the baffle IV is 20 degrees.
The gas outlet of the CO conversion device is respectively communicated with the first hot gas inlet and the second hot gas inlet through pipelines, and the first hot gas outlet and the second hot gas outlet are respectively communicated with an external hydrogen separation device through pipelines.
And a third heat exchanger is further arranged on a pipeline between the air outlet of the CO conversion device and the first hot gas inlet, a third heat exchange air inlet and a third heat exchange air outlet are arranged on the third heat exchanger, the third heat exchange air inlet is communicated with the air outlet of the CO conversion device, and the third heat exchange air outlet is communicated with the first hot gas inlet.
A process for preparing hydrogen by deoxidizing mixed gas of blast furnace and converter gas comprises the following steps:
s1, adding blast furnace gas and converter gas into a gas holder through a first gas inlet and a second gas inlet respectively for mixing to obtain mixed gas, wherein the volume content of CO in the mixed gas is between 20 and 50 percent;
s2, compressing the mixed gas into a pressure stabilizing gas tank through a compressor, and pressurizing the mixed gas;
s3, the pressurized mixed gas enters an oxygen content adjusting tower, and the oxygen content in the mixed gas is adjusted to enable the oxygen volume content to be between 0.2 and 0.3 percent;
s4, the mixed gas with the oxygen content adjusted enters an organic sulfur conversion device from the top to react, so that organic sulfur in the mixed gas is converted into hydrogen sulfide;
s5, heating the mixed gas containing the hydrogen sulfide, and then entering a gas-gas mixing device to adjust the ratio between water gas and gas in the mixed gas;
s6, the mixed gas regulated in the step S5 enters a CO conversion device from the top for reaction, and CO in the mixed gas reacts with water to generate CO through conversion catalysis 2 And H 2 Forming a hydrogen-rich mixed gas;
s7, separating the hydrogen-rich mixed gas generated by the shift reaction by an external hydrogen separation device to prepare hydrogen, and preparing the hydrogen-rich mixed gas into raw material gas of synthetic ammonia by hydrogen and nitrogen.
The pressure of the mixed gas in the pressure stabilizing gas tank in the step S2 is controlled to be 0.4-0.8 MPa;
the volume ratio of water vapor and gas in the mixed gas in the step S5 is 0.4-1.0.
Preferably, in the step S3, the pressurized mixed gas is heated by the first heat exchanger and then enters the oxygen content adjusting tower, the temperature of the first heat exchanger is 220-250 ℃ when the first heat exchanger works, and the temperature of the first heat exchanger is 150-180 ℃ when the first heat exchanger works.
Preferably, in the step S5, the mixed gas containing hydrogen sulfide is heated by a second heat exchanger and then enters a gas-gas blending device, and the heat exchange working temperature of the second heat exchanger is 230-270 ℃.
In the step S3, when the oxygen content in the mixed gas is more than 0.3%, the temperature of the first heat exchanger is increased to 220-250 ℃, and the oxygen content is reduced by reacting with a deoxidizing catalyst; when the oxygen content is less than 0.3%, the temperature of the first heat exchanger can be properly reduced to 150-180 ℃ to enable the deoxidization catalyst to be in a waiting working state.
The catalyst used in the shift catalysis in the step S6 is a potassium auxiliary modified cobalt-molybdenum sulfur-tolerant shift catalyst.
The temperature of the air inlet of the CO conversion device in the step S6 is 190-230 ℃, and the temperature of the air outlet of the CO conversion device is 280-320 ℃.
Preferably, in step S7, after the heat of the hydrogen-rich mixed gas generated by the shift reaction is subjected to heat exchange and utilization by the first heat exchanger and the second heat exchanger, the hydrogen-rich mixed gas is separated by an external hydrogen separation device to produce hydrogen. When the temperature of the first heat exchanger is 150-180 ℃, the third heat exchanger is started to carry out supplementary heating on the gas discharged by the CO conversion device and then discharged to the inlet of the first hot gas inlet of the first heat exchanger.
The technical scheme of the invention has the following advantages:
according to the invention, the oxygen content adjustment, the organic sulfur conversion treatment and the gas-gas adjustment are carried out on the mixed gas of the blast furnace and the converter gas, so that the service lives of the organic sulfur conversion catalyst and the conversion catalyst are greatly prolonged; the CO conversion device selects a radial controllable heat-transfer conversion reactor, and the conversion catalyst is filled in a plurality of layers in the CO conversion device, so that not only is a multistage reaction device required by CO conversion simplified, but also the bed resistance can be greatly reduced, and CO in the mixed gas can be effectively converted into hydrogen with higher economic value by one-time reaction under the action of the efficient low-temperature CO conversion catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are required for the embodiments will be briefly described, and it will be apparent that the drawings in the following description are some embodiments of the present invention and that other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the overall structure of a system for deoxidizing and producing hydrogen by using mixed gas of blast furnace and converter gas;
FIG. 2 is a flow chart of the process for preparing hydrogen by deoxidizing the gas mixture of the blast furnace and the converter.
The figures are identified as follows:
1-a gas cabinet, 11-a first gas inlet, 12-a second gas inlet and 13-a mixed gas outlet; a 2-compressor; 3-a pressure stabilizing gas tank, 31-a first water outlet and 32-a baffle I; 4-a first heat exchanger, 41-a first heat exchange air inlet, 42-a first heat exchange air outlet, 43-a first hot gas inlet, 44-a first hot gas outlet; a 5-oxygen content adjusting column; 6-organic sulfur conversion device, 61-oxygen inlet; 7-a second heat exchanger, 71-a second heat exchange air inlet, 72-a second heat exchange air outlet, 73-a second hot gas inlet, 74-a second hot gas outlet; 8-a gas-steam allocating device, 81-a second water outlet, 82-a steam inlet, 83-a baffle II, 84-a baffle III and 85-a baffle IV; a 9-CO conversion device; 10-third heat exchanger, 101-third heat exchange air inlet, 102-third heat exchange air outlet.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. 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.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific 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 explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
As shown in figure 1, the invention provides a mixed gas deoxidation hydrogen production system for blast furnace and converter gas, which comprises a gas tank 1, a compressor 2, a pressure stabilizing gas tank 3, a first heat exchanger 4, an oxygen content regulating tower 5, an organic sulfur conversion device 6, a second heat exchanger 7, a gas-gas allocating device 8 and a CO conversion device 9 which are sequentially arranged in series, wherein one side of the gas tank 1 is provided with a first gas inlet 11 and a second gas inlet 12, the other side of the gas tank 1 is provided with a mixed gas outlet 13, the first heat exchanger 4 is provided with a first heat exchange gas inlet 41 and a first heat exchange gas outlet 42, the second heat exchanger 7 is provided with a second heat exchange gas inlet 71 and a second heat exchange gas outlet 72, and the mixed gas outlet 3 is communicated with a gas inlet of the compressor 2, the gas outlet of the compressor 2 is communicated with a gas inlet arranged below the side wall of the pressure stabilizing gas tank 3, the gas outlet above the side wall of the pressure stabilizing gas tank 3 is communicated with a first heat exchange gas inlet 41, a first heat exchange gas outlet 42 is communicated with a gas inlet arranged at the top of the oxygen content adjusting tower 5, the gas outlet at the bottom of the oxygen content adjusting tower 5 is communicated with a gas inlet arranged at the top of the organic sulfur conversion device 6, the gas outlet at the bottom of the organic sulfur conversion device 6 is communicated with a second heat exchange gas inlet 71, a second heat exchange gas outlet 72 is communicated with a gas inlet arranged below the side wall of the gas-gas mixing device 8, the gas outlet above the side wall of the gas-gas mixing device 8 is communicated with a gas inlet arranged at the top of the CO conversion device 9, and the gas outlet at the bottom of the CO conversion device 9 is communicated with an external hydrogen separation device. The CO conversion device 9 is a radial controllable heat-transfer conversion reactor, the conversion catalyst is filled in the reactor, and the conversion catalyst is filled in two or more layers in the CO conversion device 9, namely, at least two catalyst beds are arranged in the CO conversion device 9. According to the invention, through the arrangement of the oxygen content adjusting tower 5, the organic sulfur conversion device 6 and the gas-gas mixing device 8, the oxygen content adjustment, the organic sulfur conversion treatment and the gas-gas adjustment are respectively carried out on the mixed gas of the blast furnace and the converter gas, so that the service lives of the organic sulfur conversion catalyst in the organic sulfur conversion device 6 and the conversion catalyst in the CO conversion device 9 are greatly prolonged; the CO conversion device selects a radial controllable heat-transfer conversion reactor, and the conversion catalyst is filled in a plurality of layers in the CO conversion device, so that the multi-stage reaction device required by CO conversion is simplified, the layered filling is beneficial to the uniform distribution of reaction air flow, the bed resistance can be greatly reduced, the reaction efficiency is improved, and CO in the mixed gas can be effectively converted into hydrogen with higher economic value by one-time reaction under the action of the high-efficiency low-temperature CO conversion catalyst.
Further, a first water outlet 31 is formed in the bottom of the pressure stabilizing gas tank 3, a plurality of baffles I32 inclining downwards are arranged in the pressure stabilizing gas tank 3 in a staggered mode from top to bottom, the downward inclination angle of the baffles I32 is 20 degrees, condensed water in the pressure stabilizing gas tank 3 is collected to the bottom of the pressure stabilizing gas tank 3 through the baffles I32, and the condensed water is discharged through the first water outlet 31.
The oxygen content adjusting tower 5 is filled with a deoxidizing catalyst for adjusting the oxygen content in the mixed gas so that the oxygen volume content in the mixed gas is controlled between 0.2 and 0.3 percent, and when the oxygen content in the mixed gas is more than 0.3 percent, the temperature of the first heat exchanger 4 is increased, and the oxygen content is reduced by the deoxidizing catalyst for reaction; when the oxygen content is less than 0.3%, the temperature of the first heat exchanger 4 can be appropriately lowered to bring the deoxidation catalyst into a standby state. The deoxidizing catalyst is packed in three layers or more in the oxygen content adjusting tower 5, namely, at least three catalyst beds are arranged in the oxygen content adjusting tower 5, which is beneficial to the full reaction. The deoxidizing catalyst is a supported noble metal deoxidizing agent.
The organic sulfur conversion device 6 is filled with organic sulfur conversion catalyst, the organic sulfur in the mixed gas is converted into hydrogen sulfide through hydrolysis reaction under the action of the organic sulfur conversion catalyst, and the organic sulfur conversion catalyst is filled in the organic sulfur conversion device 6 in two or more layers, namely at least two catalyst beds are arranged in the organic sulfur conversion device 6. The organic sulfur conversion catalyst is alkaline metal modified alumina or magnesia-alumina spinel material. An oxygen inlet 61 is arranged at the lower part of the organic sulfur conversion device 6, and when the oxygen content in the hydrolyzed mixed gas is lower than 0.2 percent, oxygen is added through the oxygen inlet 61 to ensure that the oxygen content is 0.2 percent.
The bottom of the gas-steam mixing device 8 is provided with a second water outlet 81 and a steam inlet 82, a baffle II 83, a baffle III 84 and a baffle IV 85 are sequentially arranged in the gas-steam mixing device 8 from top to bottom, the baffle II 83 is horizontally arranged at the middle of the gas-steam mixing device 8, the baffle III 84 is obliquely arranged at the upper edge of the air inlet of the gas-steam mixing device 8 by 20 degrees, the baffle IV 85 is obliquely arranged between the second water outlet 81 and the steam inlet 82 by 20 degrees, and the plane where the baffle III 84 is arranged is parallel to the plane where the baffle IV 85 is arranged. The ratio between the water vapor and the gas in the mixed gas discharged from the gas outlet of the gas-vapor allocating device 8 is adjusted through the steam inlet 82 and the second water outlet 81. The three baffles are arranged on the gas-steam blending device 8 to fully mix the water vapor and the dry gas, which is beneficial to the subsequent transformation reaction. Without these baffles, the reaction outlet had a lower hydrogen content.
The CO conversion device 9 is a radial controllable heat-transfer conversion reactor, a conversion catalyst is filled in the reactor, and CO in the mixed gas and H are reacted under the action of the conversion catalyst 2 O reacts to generate CO 2 And H 2 The shift catalyst is packed in two or more layers in the CO shift device 9.
The gas outlet of the CO shift device 9 is respectively communicated with the first hot gas inlet 43 and the second hot gas inlet 73 through pipelines, and the first hot gas outlet 44 and the second hot gas outlet 74 are respectively communicated with an external hydrogen separation device through pipelines.
The first heat exchanger 4 is further provided with a first hot gas inlet 43 and a first hot gas outlet 44, the second heat exchanger 7 is further provided with a second hot gas inlet 73 and a second hot gas outlet 74, the first hot gas inlet 43 and the first hot gas outlet 44 are used as a communicated pair, and the second hot gas inlet 73 and the second hot gas outlet 74 are used as a communicated pair for heating the gas passing through the first heat exchanger 4 and the second heat exchanger 7 respectively.
In addition, a third heat exchanger 10 is further arranged on a pipeline between the air outlet of the CO conversion device 9 and the first hot gas inlet 43, a third heat exchange air inlet 101 and a third heat exchange air outlet 102 are arranged on the third heat exchanger 10, the third heat exchange air inlet 101 is communicated with the air outlet of the CO conversion device 9, and the third heat exchange air outlet 102 is communicated with the first hot gas inlet 43.
The invention also provides a process for preparing hydrogen by deoxidizing the mixed gas of the blast furnace and the converter gas, which is shown in figure 2 and comprises the following steps:
s1, adding blast furnace gas and converter gas into a gas tank 1 through a first gas inlet 11 and a second gas inlet 12 respectively for mixing to obtain mixed gas, wherein the volume content of CO in the mixed gas is between 20 and 50 percent.
S2, compressing the mixed gas into a pressure stabilizing gas tank 3 through a compressor 2, and pressurizing the mixed gas to control the pressure of the mixed gas in the pressure stabilizing gas tank 3 to be between 0.4 and 0.8 MPa.
S3, heating the pressurized mixed gas by a first heat exchanger 4, and then, feeding the heated mixed gas into an oxygen content adjusting tower 5, and adjusting the oxygen content in the mixed gas to enable the oxygen volume content to be between 0.2 and 0.3 percent, wherein experiments show that the mixed gas is beneficial to subsequent conversion reaction when the oxygen content is between 0.2 and 0.3 percent; when the oxygen content in the mixed gas is more than 0.3%, the temperature of the first heat exchanger 4 is increased to 220-250 ℃, and the oxygen content is reduced by reacting with a deoxidizing catalyst; when the oxygen content is less than 0.3%, the temperature of the first heat exchanger 4 can be properly reduced to 150-180 ℃ to enable the deoxidization catalyst to be in a waiting working state; the temperature of the first heat exchanger 4 is 220-250 ℃ when in heat exchange operation, the temperature is 150-180 ℃ when in operation, namely when the oxygen content is less than 0.3%, deoxidation is not needed, the reaction temperature can be reduced to 150-180, and when deoxidation is needed, the temperature is increased to 220-250, so that the energy consumption is saved.
S4, the mixed gas with the oxygen content adjusted enters an organic sulfur conversion device 6 from the top for reaction, so that organic sulfur in the mixed gas is converted into hydrogen sulfide.
S5, heating the mixed gas containing hydrogen sulfide by a second heat exchanger 7, and then entering a gas-gas mixing device 8, and adjusting the volume ratio of water gas and gas in the mixed gas to be 0.4-1.0; the heat exchange working temperature of the second heat exchanger 7 is 230-270 ℃.
S6, the mixed gas regulated in the step S5 enters a CO conversion device 9 from the top for reaction, and CO of the mixed gas reacts with water to generate CO through conversion catalysis 2 And H 2 Forming a hydrogen-rich mixed gas; the temperature of the air inlet of the CO conversion device 9 is 190-230 ℃, the temperature of the air outlet is 280-320 ℃, and the catalyst used for conversion catalysis is a potassium auxiliary agent modified cobalt-molybdenum sulfur-resistant conversion catalyst with high low-temperature activity.
S7, after heat of the hydrogen-rich mixed gas generated by the shift reaction is subjected to heat exchange utilization through the first heat exchanger 4 and the second heat exchanger 7, the hydrogen-rich mixed gas is separated through an external hydrogen separation device to prepare hydrogen, and the hydrogen-rich mixed gas can be prepared into raw material gas for synthesizing ammonia through hydrogen and nitrogen; when the heat required by the first heat exchanger 4 is insufficient, for example, the temperature is 150-180 ℃, the third heat exchanger 10 is started to carry out supplementary heating on the gas discharged by the CO conversion device 9, and then the gas is discharged to the inlet of the first hot gas inlet 43 of the first heat exchanger 4.
According to the invention, the oxygen content adjustment, the organic sulfur conversion treatment and the gas-gas adjustment are carried out on the mixed gas of the blast furnace and the converter gas, so that the service lives of the organic sulfur conversion catalyst and the conversion catalyst are greatly prolonged; the CO conversion device selects a radial controllable heat-transfer conversion reactor, and the conversion catalyst is filled in a plurality of layers in the CO conversion device, so that not only is a multistage reaction device required by CO conversion simplified, but also the bed resistance can be greatly reduced, and CO in the mixed gas can be effectively converted into hydrogen with higher economic value by one-time reaction under the action of the efficient low-temperature CO conversion catalyst.
Application example 1:
introducing blast furnace gas and converter gas into a gas tank 1 for mixing, wherein the volume content of CO in the obtained mixed gas is 32%, the oxygen content is 0.6%, and the COS concentration is 100mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Then the mixed gas is passed throughThe compressor 2 compresses to a pressure of 0.4MPa, and when the water level of the surge tank 3 reaches the set water level, automatic drainage is performed through the first drain port 31 at the lower portion of the surge tank 3. The pressurized mixed gas is heated to 200 ℃ by a first heat exchanger 4 and enters an oxygen content adjusting tower 5 for deoxidization treatment, so that the oxygen content is controlled between 0.2 and 0.3 percent. The deoxidized mixed gas enters an organic sulfur conversion device 6 again to carry out organic sulfur conversion, so that the organic sulfur in the mixed gas is reduced to 2mg/m 3 The following are set forth; then, the mixed gas is subjected to secondary temperature rise to 240 ℃ through a second heat exchanger 7, then is introduced into a gas-gas mixing device 8, high-temperature steam of 240 ℃ is added from a steam inlet 82 on the gas-gas mixing device 8, and the water-gas/dry-gas ratio of the mixed gas is adjusted to be 0.6:1; then the mixture enters a CO conversion device 9 for reaction, the inlet temperature is 210 ℃, the outlet temperature is 300 ℃, the content of CO in the dry gas at the outlet is measured to be 3.0%, and H is measured 2 The content was 22%.
Application example 2:
introducing blast furnace gas and converter gas into a gas tank 1 for mixing, wherein the volume content of CO in the obtained mixed gas is 20%, the oxygen content is 0.5%, and the COS concentration is 90mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Then the mixture is compressed to a pressure of 0.6MPa by the compressor 2, and when the water level of the surge tank 3 reaches the set water level, the mixture is automatically drained through the first drain outlet 31 at the lower part of the surge tank 3. The pressurized mixed gas is heated to 220 ℃ by a first heat exchanger 4 and enters an oxygen content adjusting tower 5 for deoxidization treatment, so that the oxygen content is controlled between 0.2 and 0.3 percent. The deoxidized mixed gas enters an organic sulfur conversion device 6 again to carry out organic sulfur conversion, so that the organic sulfur in the mixed gas is reduced to 2mg/m 3 The following are set forth; then, the mixed gas is subjected to secondary temperature rising to 230 ℃ through a second heat exchanger 7, then is introduced into a gas-gas mixing device 8, high-temperature steam at 230 ℃ is added from a steam inlet 82 on the gas-gas mixing device 8, and the water-gas/dry-gas ratio of the mixed gas is adjusted to be 0.4:1; then the mixture enters a CO conversion device 9 for reaction, the inlet temperature is 190 ℃, the outlet temperature is 280 ℃, the content of CO in the dry gas at the outlet is measured to be 2.8 percent, and H is measured 2 The content was 14%.
Application example 3:
introducing blast furnace gas and converter gas into a gas tank 1 for mixing, and obtaining a mixed gasThe volume content of CO in the catalyst is 50%, the oxygen content is 0.7%, and the COS concentration is 100mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Then the mixture is compressed to a pressure of 0.8MPa by the compressor 2, and when the water level of the surge tank 3 reaches the set water level, the mixture is automatically drained through the first drain outlet 31 at the lower part of the surge tank 3. The pressurized mixed gas is heated to 250 ℃ by a first heat exchanger 4 and enters an oxygen content adjusting tower 5 for deoxidization treatment, so that the oxygen content is controlled between 0.2 and 0.3 percent. The deoxidized mixed gas enters an organic sulfur conversion device 6 again to carry out organic sulfur conversion, so that the organic sulfur in the mixed gas is reduced to 2mg/m 3 The following are set forth; then, the mixed gas is subjected to secondary temperature rising to 270 ℃ through a second heat exchanger 7, then is introduced into a gas-gas mixing device 8, high-temperature steam at 270 ℃ is added from a steam inlet 82 on the gas-gas mixing device 8, and the water-gas/dry-gas ratio of the mixed gas is adjusted to be 1:1; then the mixture enters a CO conversion device 9 for reaction, the inlet temperature is 230 ℃, the outlet temperature is 320 ℃, the content of CO in the dry gas at the outlet is measured to be 3.1 percent, and H is measured 2 The content was 32%.
The invention is applicable to the prior art where it is not described.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.
Claims (14)
1. The system is characterized by comprising a gas tank (1), a compressor (2), a pressure stabilizing gas tank (3), an oxygen content regulating tower (5), an organic sulfur conversion device (6), a gas-gas mixing device (8) and a CO conversion device (9) which are sequentially connected in series, wherein a first gas inlet (11) and a second gas inlet (12) are arranged on one side of the gas tank (1), a mixed gas outlet (13) is arranged on the other side of the gas tank, the mixed gas outlet (13) is communicated with the gas inlet of the compressor (2), the gas outlet of the compressor (2) is communicated with the gas inlet arranged below the side wall of the pressure stabilizing gas tank (3), the gas outlet above the side wall of the pressure stabilizing gas tank (3) is communicated with the gas inlet arranged at the top of the oxygen content regulating tower (5), the gas outlet at the bottom of the oxygen content regulating tower (5) is communicated with the gas inlet arranged at the top of the organic sulfur conversion device (6), the gas outlet at the bottom of the organic sulfur conversion device (6) is communicated with the gas inlet arranged below the gas device (8), and the gas mixing device is communicated with the gas inlet (9) arranged at the top of the CO conversion device (9) at the top of the gas inlet;
the CO conversion device (9) is a radial controllable heat-transfer conversion reactor, a conversion catalyst is filled in the reactor, and the conversion catalyst is filled in two layers and more in the CO conversion device (9);
a first heat exchanger (4) is arranged between the pressure stabilizing air tank (3) and the oxygen content adjusting tower (5), a first heat exchange air inlet (41) and a first heat exchange air outlet (42) are arranged on the first heat exchanger (4), an air outlet above the side wall of the pressure stabilizing air tank (3) is communicated with the first heat exchange air inlet (41), and the first heat exchange air outlet (42) is communicated with an air inlet arranged at the top of the oxygen content adjusting tower (5); the bottom of the pressure stabilizing air tank (3) is provided with a first water outlet (31), a plurality of baffle plates I (32) inclining downwards are staggered from top to bottom in the pressure stabilizing air tank (3), condensed water in the pressure stabilizing air tank (3) is collected to the bottom of the pressure stabilizing air tank (3) through the baffle plates I (32), and is discharged through the first water outlet (31);
the oxygen content regulating tower (5) is filled with a deoxidizing catalyst, and the deoxidizing catalyst is filled with three layers and more in the oxygen content regulating tower (5);
the organic sulfur conversion device (6) is filled with an organic sulfur conversion catalyst, the organic sulfur conversion catalyst is filled in two layers and more in the organic sulfur conversion device (6), and an oxygen inlet (61) is arranged at the lower part of the organic sulfur conversion device (6);
the bottom of the gas-steam mixing device (8) is provided with a second water outlet (81) and a steam inlet (82), a baffle II (83), a baffle III (84) and a baffle IV (85) are sequentially arranged in the gas-steam mixing device (8) from top to bottom, the baffle II (83) is horizontally arranged at the middle of the gas-steam mixing device (8), the baffle III (84) is obliquely arranged at the upper edge of the air inlet of the gas-steam mixing device (8), the baffle IV (85) is obliquely arranged between the second water outlet (81) and the steam inlet (82), and the plane where the baffle III (84) is parallel to the plane where the baffle IV (85) is arranged.
2. The system for deoxidizing and producing hydrogen by using mixed gas of blast furnace and converter gas according to claim 1, wherein a second heat exchanger (7) is arranged between the organic sulfur conversion device (6) and the gas-gas mixing device (8), a second heat exchange air inlet (71) and a second heat exchange air outlet (72) are arranged on the second heat exchanger (7), the air outlet at the bottom of the organic sulfur conversion device (6) is communicated with the second heat exchange air inlet (71), and the second heat exchange air outlet (72) is communicated with an air inlet arranged below the side wall of the gas-gas mixing device (8).
3. The system for deoxidizing and producing hydrogen by using mixed gas of blast furnace and converter gas according to claim 2, wherein a first hot gas inlet (43) and a first hot gas outlet (44) are further arranged on the first heat exchanger (4), a second hot gas inlet (73) and a second hot gas outlet (74) are further arranged on the second heat exchanger (7), the first hot gas inlet (43) and the first hot gas outlet (44) are used as a communicated pair, and the second hot gas inlet (73) and the second hot gas outlet (74) are used as a communicated pair for heating the gas passing through the first heat exchanger (4) and the second heat exchanger (7) respectively;
the gas outlet of the CO conversion device (9) is respectively communicated with the first hot gas inlet (43) and the second hot gas inlet (73) through pipelines, and the first hot gas outlet (44) and the second hot gas outlet (74) are respectively communicated with an external hydrogen separation device through pipelines.
4. A system for deoxygenation of mixed gas of blast furnace and converter gas according to claim 3, wherein a third heat exchanger (10) is further arranged on a pipeline between the gas outlet of the CO conversion device (9) and the first hot gas inlet (43), a third heat exchange gas inlet (101) and a third heat exchange gas outlet (102) are arranged on the third heat exchanger (10), the third heat exchange gas inlet (101) is communicated with the gas outlet of the CO conversion device (9), and the third heat exchange gas outlet (102) is communicated with the first hot gas inlet (43).
5. The process for preparing the hydrogen by deoxidizing the mixed gas of the blast furnace and the converter gas is characterized by comprising the following steps of:
s1, adding blast furnace gas and converter gas into a gas tank (1) through a first gas inlet (11) and a second gas inlet (12) respectively to mix to obtain mixed gas, wherein the volume content of CO in the mixed gas is 20-50%;
s2, compressing the mixed gas into a pressure stabilizing gas tank (3) through a compressor (2), and pressurizing the mixed gas;
s3, the pressurized mixed gas enters an oxygen content adjusting tower (5) to adjust the oxygen content in the mixed gas so that the oxygen volume content is between 0.2 and 0.3 percent;
s4, the mixed gas with the oxygen content adjusted enters an organic sulfur conversion device (6) from the top for reaction, so that organic sulfur in the mixed gas is converted into hydrogen sulfide;
s5, heating the mixed gas containing the hydrogen sulfide, and then entering a gas-gas mixing device (8) to adjust the ratio between water gas and gas in the mixed gas;
s6, enabling the mixed gas regulated in the step S5 to enter a CO conversion device (9) from the top for reaction, and enabling CO in the mixed gas to react with water to generate CO through conversion catalysis 2 And H 2 Forming a hydrogen-rich mixed gas;
s7, separating the hydrogen-rich mixed gas generated by the shift reaction through an external hydrogen separation device to prepare hydrogen.
6. The process for deoxidizing and producing hydrogen by using the mixed gas of the blast furnace and the converter gas according to claim 5, wherein the pressure of the mixed gas in the pressure stabilizing gas tank (3) in the step S2 is controlled to be 0.4-0.8 MPa;
and in the step S5, the volume ratio of water vapor to gas in the mixed gas is 0.4-1.0.
7. The process for deoxidizing and producing hydrogen by using the mixed gas of the blast furnace and the converter according to claim 5, wherein in the step S3, the pressurized mixed gas enters an oxygen content adjusting tower (5) after being heated by a first heat exchanger (4), the temperature of the first heat exchanger (4) is 220-250 ℃ when the first heat exchanger works, and the temperature of the first heat exchanger is 150-180 ℃ when the first heat exchanger works;
in the step S5, the mixed gas containing the hydrogen sulfide is heated by a second heat exchanger (7) and then enters a gas-gas mixing device (8), and the heat exchange working temperature of the second heat exchanger (7) is 230-270 ℃.
8. The process for deoxidizing and producing hydrogen by using the mixed gas of blast furnace and converter gas according to claim 5, wherein in the step S3, when the oxygen content in the mixed gas is greater than 0.3%, the temperature of the first heat exchanger (4) is increased to 220-250 ℃, and the oxygen content is reduced by reacting with a deoxidizing catalyst.
9. The process for producing hydrogen by deoxidizing a mixed gas of blast furnace and converter gas according to claim 5, wherein in the step S3, when the oxygen content is less than 0.3%, the temperature of the first heat exchanger (4) can be properly reduced to 150-180 ℃ to make the deoxidizing catalyst in a waiting state.
10. The process for producing hydrogen by deoxidizing a mixed gas of blast furnace and converter gas according to claim 5, wherein the catalyst used in the shift catalysis in the step S6 is a potassium auxiliary modified cobalt-molybdenum sulfur-tolerant shift catalyst.
11. The process for deoxidizing and producing hydrogen by using a mixed gas of blast furnace gas and converter gas according to claim 5, wherein the temperature of the gas inlet of the CO conversion device (9) in the step S6 is 190-230 ℃ and the temperature of the gas outlet thereof is 280-320 ℃.
12. The process for producing hydrogen by deoxidizing the mixed gas of blast furnace and converter gas according to claim 5, wherein in the step S7, the heat of the hydrogen-rich mixed gas generated by the shift reaction is utilized by heat exchange through the first heat exchanger (4) and the second heat exchanger (7), and then the hydrogen-rich mixed gas is separated by an external hydrogen separation device to produce hydrogen.
13. The process for producing hydrogen by deoxidizing a mixed gas of blast furnace and converter gas according to claim 5, wherein in step S7, the hydrogen-rich mixed gas produced by the shift reaction is prepared into a raw gas for synthesizing ammonia by hydrogen and nitrogen.
14. The process for deoxidizing and producing hydrogen by using the mixed gas of the blast furnace and the converter gas according to claim 5, wherein when the temperature of the first heat exchanger (4) is 150-180 ℃, the third heat exchanger (10) is started to heat the gas discharged from the CO conversion device (9) in a supplementary manner and then the gas is discharged to the inlet of the first hot gas inlet (43) of the first heat exchanger (4).
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| US6821501B2 (en) * | 2001-03-05 | 2004-11-23 | Shell Oil Company | Integrated flameless distributed combustion/steam reforming membrane reactor for hydrogen production and use thereof in zero emissions hybrid power system |
| JP2003243018A (en) * | 2002-02-15 | 2003-08-29 | Babcock Hitachi Kk | Hydrogen manufacturing equipment and its operation method |
| AT508250B1 (en) * | 2009-09-11 | 2010-12-15 | Siemens Vai Metals Tech Gmbh | METHOD FOR REMOVING CO2 FROM EXHAUST GASES SUCH AS EXHAUST GASES FROM PLANTS FOR THE PRODUCTION OF REFRIGERATED STEEL OR EXTRACTIONS FROM SYNTHESEGAS PLANTS |
| CN102431967A (en) * | 2011-07-18 | 2012-05-02 | 何巨堂 | Method for preparing hydrogen and nitrogen gas with specific composition from multi-ingredient gas containing H2 and N2 |
| CN103407963A (en) * | 2013-06-21 | 2013-11-27 | 内蒙古庆华集团庆华煤化有限责任公司 | Coke oven gas hydrogen generation process |
| CN108977237B (en) * | 2018-07-25 | 2020-06-09 | 戴乐亭 | Converter and/or blast furnace gas oxygen-removing fine desulfurization method |
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