阅读说明：本技术 一种高炉煤气部分脱氧脱硫方法及系统 (Blast furnace gas partial deoxidation and desulfurization method and system ) 是由 江莉龙 郑勇 曹彦宁 肖益鸿 刘福建 刘时球 于 2020-05-19 设计创作，主要内容包括：本发明属于大气净化环境保护领域,具体涉及一种高炉煤气部分脱氧脱硫方法及系统。本发明提供的高炉煤气部分脱氧脱硫方法,包括以下步骤：将高炉煤气进行脱氧处理,脱氧处理后的原料气中氧气的体积含量为0.1-0.3％；将脱氧处理后的原料气在水解剂的作用下进行水解处理,水解处理后的原料气经过吸附剂的吸附处理,得到脱硫后的高炉煤气。本发明提供的高炉煤气部分脱氧脱硫方法,通过在高炉煤气水解前对高炉煤气进行脱氧处理,有效解决了现有高炉煤气脱硫工艺对高炉煤气直接进行水解易造成水解剂中毒,进而影响脱硫工艺进程和脱硫效果的缺陷,大大延长了水解剂的使用寿命。(The invention belongs to the field of atmosphere purification and environmental protection, and particularly relates to a method and a system for partial deoxidation and desulfurization of blast furnace gas. The invention provides a blast furnace gas partial deoxidation and desulfurization method, which comprises the following steps: deoxidizing blast furnace gas, wherein the volume content of oxygen in the raw gas after the deoxidation treatment is 0.1-0.3%; and (3) carrying out hydrolysis treatment on the deoxidized raw gas under the action of a hydrolytic agent, and carrying out adsorption treatment on the hydrolyzed raw gas by using an adsorbent to obtain the desulfurized blast furnace gas. The blast furnace gas partial deoxidation and desulfurization method provided by the invention effectively overcomes the defect that the existing blast furnace gas desulfurization process directly hydrolyzes blast furnace gas and easily causes the poisoning of a hydrolytic agent, thereby influencing the process and desulfurization effect of the desulfurization process, and greatly prolongs the service life of the hydrolytic agent by deoxidizing the blast furnace gas before hydrolyzing the blast furnace gas.)

1. The blast furnace gas partial deoxidation and desulfurization method is characterized by comprising the following steps of:

1) deoxidizing blast furnace gas to obtain a raw gas subjected to deoxidation treatment, wherein the volume content of oxygen in the raw gas subjected to deoxidation treatment is 0.1-0.3%;

2) hydrolyzing the deoxidized feed gas under the action of a hydrolyzing agent to obtain a hydrolyzed feed gas;

3) and (4) carrying out adsorption treatment on the hydrolyzed raw material gas by using an adsorbent to obtain desulfurized blast furnace gas.

2. The blast furnace gas partial deoxidation and desulphurization method according to claim 1, characterized in that the deoxidation treatment in step 1) comprises the following steps: the blast furnace gas is divided into two parts, the first part of the blast furnace gas sequentially passes through the first heat exchange area and the second heat exchange area, and then the first part of the blast furnace gas and the second part of the blast furnace gas are mixed and sequentially pass through the first deoxidation area and the second deoxidation area so as to perform deoxidation treatment on the blast furnace gas.

3. The blast furnace gas partial deoxidation and desulfurization method according to claim 1 or 2, characterized in that the first and second deoxidation zones are filled with a deoxidizer selected from at least one of noble metal deoxidizers and non-noble metal cobalt molybdenum sulfur type deoxidizers;

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.

4. The blast furnace gas partial deoxidation and desulfurization method according to any one of claims 1 to 3, characterized in that the first deoxidation zone is filled with a non-noble metal cobalt molybdenum sulfur type deoxidizer and the second deoxidation zone is filled with a supported noble metal deoxidizer.

5. The blast furnace gas partial deoxidation and desulfurization method according to any one of claims 1 to 4, further comprising the step of regenerating the adsorbent with at least partially desulfurized blast furnace gas to obtain sulfur;

cooling the deoxidized raw material gas in step 1), preferably, cooling the deoxidized raw material gas to 60-100 ℃ in step 1).

6. The partial deoxidation and desulfurization method for blast furnace gas according to any one of claims 1 to 5, characterized in that,

in the step 1), the temperature of the blast furnace gas is 50-80 ℃, so that the first part of the blast furnace gas passes through the first heat exchange region and the second heat exchange region in sequence, and then the temperature after mixing with the second part of the blast furnace gas is 120-;

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 ferric oxide, cobalt oxide and nickel oxide, and the carrier is selected from one or more of carbon nitride, alumina, silica, magnesia, titania, zirconia and ceria.

7. A blast furnace gas partial deoxidation and desulfurization system is characterized by comprising,

the deoxidation device is provided with a first deoxidation air inlet, a second deoxidation air inlet and a deoxidation air outlet,

the hydrolysis device is provided with a hydrolysis air inlet and a hydrolysis air outlet, the deoxidation air outlet of the deoxidation device is connected with the hydrolysis air inlet of the hydrolysis device,

and the adsorption device is provided with an adsorption air inlet and an adsorption air outlet, and the adsorption air inlet of the adsorption device is connected with the hydrolysis air outlet of the hydrolysis device.

8. The blast furnace gas partial deoxidation and desulfurization system according to claim 7, wherein the deoxidation device comprises a first heat exchange unit, a second heat exchange unit, a first deoxidation unit and a second deoxidation unit which are sequentially communicated, wherein a gas inlet of the first heat exchange unit is connected with a first deoxidation gas inlet of the deoxidation device, and a gas outlet of the second deoxidation unit is connected with a deoxidation gas outlet of the deoxidation device.

9. The blast furnace gas partial deoxygenation and desulfurization system according to any one of claims 7 to 8, further comprising,

the flow dividing device is provided with a flow dividing air inlet, a first flow dividing air outlet and a second flow dividing air outlet, the first flow dividing air outlet of the flow dividing device is connected with the first deoxidation air inlet of the deoxidation device,

and a confluence device having a first confluence air inlet, a second confluence air inlet, and a confluence air outlet, wherein the first confluence air inlet of the confluence device is connected to the second split air outlet of the split device, the second confluence air inlet of the confluence device is connected to the air outlet of the second heat exchange unit, and the confluence air outlet of the confluence device is connected to the second deoxygenation air inlet of the deoxygenation device.

10. The blast furnace gas partial deoxygenation and desulfurization system according to any one of claims 7 to 9, characterized by comprising at least 2 adsorption devices arranged in parallel;

also comprises the following steps of (1) preparing,

the heat exchange device is provided with a heat exchange air inlet and a heat exchange air outlet,

the adsorption device is also provided with an adsorption regeneration air inlet and an adsorption regeneration air outlet, the heat exchange air inlet of the heat exchange device is connected with the adsorption air outlet of the adsorption device, and the heat exchange air outlet of the heat exchange device is connected with the adsorption regeneration air inlet of the adsorption device;

and the sulfur storage device is provided with a sulfur storage air inlet and a sulfur storage air outlet, and the sulfur storage air inlet of the sulfur storage device is connected with the adsorption regeneration air outlet of the adsorption device.

Technical Field

The invention belongs to the field of atmosphere purification and environmental protection, and particularly relates to a method and a system for partial deoxidation and desulfurization of blast furnace gas.

Background

The blast furnace gas contains combustible gases such as carbon monoxide, hydrogen, methane and the like, wherein the volume content of the carbon monoxide is about 28%, the volume content of the hydrogen is about 1%, and the volume content of the methane is about 0.5%. In addition, blast furnace gas also contains about 1% oxygen. In the actual production and application process, the blast furnace gas generally utilizes a residual pressure turbine power generation unit (TRT) to recover the pressure energy and heat energy of the blast furnace gas, and the obtained low-temperature and low-pressure blast furnace gas is generally sent to a hot blast stove, a heating furnace, a coke oven, a boiler and a gas turbine unit in a fuel mode for combustion and use. However, in addition to the above-mentioned gases, the blast furnace gas contains COS (carbonyl sulfide) and CS₂、H₂S, wherein the main component of the sulfide is COS, and the total sulfur concentration generally reaches 200mgS/Nm³The above. These sulfides may be SO, if not limited₂Is discharged into the air, thereby causing a large amount of acid rain to form. 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. Therefore, the adoption of source desulphurization to blast furnace gas is an ideal method for treating sulfur species.

Disclosure of Invention

Therefore, the invention aims to solve the technical problem that the direct hydrolysis of blast furnace gas by the existing blast furnace gas desulfurization process easily causes the poisoning of a hydrolytic agent, thereby influencing the desulfurization process and desulfurization effect, and provides a blast furnace gas desulfurization method and a blast furnace gas desulfurization system.

Therefore, the invention adopts the technical proposal that,

a blast furnace gas partial deoxidation and desulfurization method comprises the following steps:

1) deoxidizing blast furnace gas to obtain a raw gas subjected to deoxidation treatment, wherein the volume content of oxygen in the raw gas subjected to deoxidation treatment is 0.1-0.3%;

2) hydrolyzing the deoxidized feed gas under the action of a hydrolyzing agent to obtain a hydrolyzed feed gas;

3) and (4) carrying out adsorption treatment on the hydrolyzed raw material gas by using an adsorbent to obtain desulfurized blast furnace gas.

Preferably, the deoxidation treatment in the step 1) comprises the following steps: the blast furnace gas is divided into two parts, the first part of the blast furnace gas sequentially passes through the first heat exchange area and the second heat exchange area, and then the first part of the blast furnace gas and the second part of the blast furnace gas are mixed and sequentially pass through the first deoxidation area and the second deoxidation area so as to perform deoxidation treatment on the blast furnace gas.

Preferably, the first deoxidation area and the second deoxidation area are filled with a deoxidizer, and the deoxidizer is selected from at least one of a noble metal deoxidizer and a non-noble metal cobalt-molybdenum-sulfur 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.

Preferably, the first deoxidizing zone is filled with a non-noble metal cobalt molybdenum sulfur type deoxidizing agent, and the second deoxidizing zone is filled with a load type noble metal deoxidizing agent.

The active component in the non-noble metal cobalt molybdenum sulfur type deoxidizer is selected from CoMo₂S、CoMo₃S、CoMo₄S, CoMoS; the carrier is alumina and/or titania.

Preferably, the method also comprises the step of regenerating the adsorbent by using at least part of the desulfurized blast furnace gas to obtain sulfur; the regeneration step is to subject the desulfurized blast furnace gas to 500-600h^-1Is contacted with the adsorbent to be regenerated.

Cooling the deoxidized raw material gas in step 1), preferably, cooling the deoxidized raw material gas to 60-100 ℃ in step 1).

Preferably, the temperature at which the adsorbent is regenerated is 150-200 ℃.

Preferably, the first and second liquid crystal materials are,

in the step 1), the temperature of the blast furnace gas is 50-80 ℃, so that the first part of the blast furnace gas passes through the first heat exchange area and the second heat exchange area in sequence, and then the temperature after mixing with the second part of the blast furnace gas is 120-200 ℃.

The deoxidation treatment of the invention is realized when the blast furnace gas is contacted with the deoxidizer,the space velocity of the blast furnace gas when contacting with the deoxidizer is 500-600h^-1(ii) a The hydrolysis treatment is realized when the deoxidized feed gas is contacted with a hydrolytic agent, and the space velocity when the deoxidized feed gas is contacted with the hydrolytic agent is 500-600h^-1(ii) a The adsorption treatment is realized when the hydrolyzed raw material gas is contacted with an adsorbent, and the space velocity when the hydrolyzed raw material gas is contacted with the adsorbent is 500-600h^-1。

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 ferric oxide, cobalt oxide and nickel oxide, and the carrier is selected from one or more of carbon nitride, alumina, silica, magnesia, titania, zirconia and ceria. Preferably, the deoxidizer, the adsorbent and the hydrolyzer can be granular or honeycomb.

The invention provides a blast furnace gas partial deoxidation and desulfurization system, which comprises,

the deoxidation device is provided with a first deoxidation air inlet, a second deoxidation air inlet and a deoxidation air outlet,

the hydrolysis device is provided with a hydrolysis air inlet and a hydrolysis air outlet, the deoxidation air outlet of the deoxidation device is connected with the hydrolysis air inlet of the hydrolysis device,

and the adsorption device is provided with an adsorption air inlet and an adsorption air outlet, and the adsorption air inlet of the adsorption device is connected with the hydrolysis air outlet of the hydrolysis device.

Optionally, the deoxidation device comprises a first heat exchange unit, a second heat exchange unit, a first deoxidation unit and a second deoxidation unit which are sequentially communicated, wherein an air inlet of the first heat exchange unit is connected with a first deoxidation air inlet of the deoxidation device, and an air outlet of the second deoxidation unit is connected with a deoxidation air outlet of the deoxidation device.

Optionally, the method further comprises the step of,

the flow dividing device is provided with a flow dividing air inlet, a first flow dividing air outlet and a second flow dividing air outlet, the first flow dividing air outlet of the flow dividing device is connected with the first deoxidation air inlet of the deoxidation device,

and a confluence device having a first confluence air inlet, a second confluence air inlet, and a confluence air outlet, wherein the first confluence air inlet of the confluence device is connected to the second split air outlet of the split device, the second confluence air inlet of the confluence device is connected to the air outlet of the second heat exchange unit, and the confluence air outlet of the confluence device is connected to the second deoxygenation air inlet of the deoxygenation device.

Optionally, at least 2 adsorption devices arranged in parallel are included;

also comprises the following steps of (1) preparing,

the heat exchange device is provided with a heat exchange air inlet and a heat exchange air outlet,

the adsorption device is also provided with an adsorption regeneration air inlet and an adsorption regeneration air outlet, the heat exchange air inlet of the heat exchange device is connected with the adsorption air outlet of the adsorption device, and the heat exchange air outlet of the heat exchange device is connected with the adsorption regeneration air inlet of the adsorption device;

and the sulfur storage device is provided with a sulfur storage air inlet and a sulfur storage air outlet, and the sulfur storage air inlet of the sulfur storage device is connected with the adsorption regeneration air outlet of the adsorption device.

The technical scheme of the invention has the following advantages:

1. according to the blast furnace gas partial deoxidation and desulfurization method provided by the invention, the blast furnace gas is subjected to deoxidation treatment before the blast furnace gas is hydrolyzed, so that the defects that the hydrolysis agent poisoning is easily caused when the blast furnace gas is directly hydrolyzed by the conventional blast furnace gas desulfurization process, and the desulfurization process progress and the desulfurization effect are influenced are effectively overcome, and the service life of the hydrolysis agent is greatly prolonged; meanwhile, the volume content of oxygen in the raw material gas after the deoxidation treatment is controlled to be 0.1-0.3%, so that the blast furnace gas is partially deoxidized, the partially deoxidized blast furnace gas is matched with the hydrolysis step and the adsorption step to carry out source desulphurization on the blast furnace gas, so that a blast furnace gas user does not need to use desulphurization equipment, the sulfur emission is intensively treated, the aim of directly discharging the blast furnace gas after combustion up to the standard is fulfilled, and meanwhile, the completely desulfurized blast furnace gas contains 0.1-0.3% of oxygen, and if the adsorbent is regenerated, the hydrogen sulfide adsorbed on the adsorbent can be oxidized into elemental sulfur, so that the sulfur resource can be effectively utilized. The desulfurization method provided by the invention has the advantages of stable operation, wide operation window, low cost and small influence on oxygen-containing environment.

2. The blast furnace gas partial deoxidation and desulfurization method provided by the invention further comprises the following steps in the step 1): the blast furnace gas is divided into two parts, the first part of the blast furnace gas sequentially passes through the first heat exchange area and the second heat exchange area, and then the first part of the blast furnace gas and the second part of the blast furnace gas are mixed and sequentially pass through the first deoxidation area and the second deoxidation area so as to perform deoxidation treatment on the blast furnace gas. The method heats the first part of the blast furnace gas through two-stage heat exchange, and the heated blast furnace gas is mixed with the second part of the blast furnace gas, so that the temperature of the blast furnace gas is increased, the deoxidant can exert deoxidization performance, then the heated blast furnace gas sequentially passes through the first deoxidization area and the second deoxidization area, and the treatment of the specific step is mutually matched with the subsequent hydrolysis step and the adsorption step, so that the desulfuration effect of the blast furnace gas is greatly improved.

3. The blast furnace gas partial deoxidation and desulfurization method provided by the invention further comprises the step of filling a non-noble metal cobalt molybdenum sulfur type deoxidizer in the first deoxidation area, and filling a supported noble metal deoxidizer in the second deoxidation area. According to the invention, the non-noble metal cobalt molybdenum sulfur type deoxidizer is filled in the first deoxidizing area, the supported noble metal deoxidizer is filled in the second deoxidizing area, and the blast furnace gas sequentially passes through the two deoxidizing areas loaded with the specific deoxidizers.

4. The blast furnace gas partial deoxidation and desulfurization method further comprises the step of regenerating the adsorbent by using at least part of desulfurized blast furnace gas to obtain sulfur; the invention regenerates the adsorbent by utilizing the specific oxygen content in the desulfurized blast furnace gas, can oxidize the hydrogen sulfide adsorbed on the adsorbent into elemental sulfur, changes the sulfur species from harmful waste into available elemental sulfur, and can greatly reduce the use of the adsorbent.

5. The invention provides a blast furnace gas partial deoxidation and desulfurization system which comprises a deoxidation device, a hydrolysis device and an adsorption device, wherein the deoxidation device is provided with a first deoxidation gas inlet, a second deoxidation gas inlet and a deoxidation gas outlet, the deoxidation gas outlet of the deoxidation device is connected with the hydrolysis gas inlet of the hydrolysis device, the adsorption device is provided with an adsorption gas inlet and an adsorption gas outlet, and the adsorption gas inlet of the adsorption device is connected with the hydrolysis gas outlet of the hydrolysis device. The blast furnace gas passes through the deoxidizing device, the hydrolyzing device and the adsorption device which are connected in sequence, so that the desulfurizing efficiency of the blast furnace gas can be effectively improved, meanwhile, the deoxidizing device is arranged in front, and oxygen is removed before the blast furnace gas is hydrolyzed, so that the defects that the direct hydrolysis of the blast furnace gas by the conventional blast furnace gas desulfurizing process easily causes the poisoning of a hydrolyzing agent, the desulfurizing process and the desulfurizing effect are influenced, and the service life of the hydrolyzing agent is greatly prolonged.

6. The blast furnace gas partial deoxidation and desulfurization system provided by the invention further comprises a first heat exchange unit, a second heat exchange unit, a first deoxidation unit and a second deoxidation unit which are sequentially communicated, wherein a gas inlet of the first heat exchange unit is connected with a first deoxidation gas inlet of the deoxidation device, and a gas outlet of the second deoxidation unit is connected with a deoxidation gas outlet of the deoxidation device. The blast furnace gas passes through the heat exchange unit and the deoxidation unit which are specially arranged in sequence, so that the oxygen in the blast furnace gas can be removed, and the desulfurization effect of the blast furnace gas can be effectively improved by matching with the hydrolysis device and the adsorption device.

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 a partial deoxidation and desulfurization system for blast furnace gas according to the present invention.

Wherein the reference numerals are represented as:

1. a deoxidation device; 2. a hydrolysis device; 3. a third adsorption device; 4. a heat exchange device; 5. a first sulfur storage device; 6. a first deoxygenating gas inlet; 7. a second deoxygenating gas inlet; 8. a deoxidation gas outlet; 9. a hydrolysis air inlet; 10. a hydrolysis air outlet; 11. an adsorption air inlet; 12. an adsorption gas outlet; 13. a heat exchange air inlet; 14. a heat exchange air outlet; 15. an adsorption regeneration air inlet; 16. an adsorption regeneration gas outlet; 17. a sulfur storage air inlet; 18. a sulfur storage air outlet; 19. a sulfur outlet; 20. a first heat exchange unit; 21. a second heat exchange unit; 22. a first deoxidizing unit; 23. a second deoxidizing unit; 24. a flow divider; 25. a flow-splitting air inlet; 26. a first split air outlet; 27. a second split air outlet; 28. a confluence device; 29. a second converging air inlet; 30. a first converging air inlet; 31. a confluence air outlet; 32. a first adsorption device; 33. a second adsorption device; 34. and a second sulfur storage device.

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.