CN111849562B - Device and method for desulfurizing synthesis gas prepared by coal gasification - Google Patents
Device and method for desulfurizing synthesis gas prepared by coal gasification Download PDFInfo
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- CN111849562B CN111849562B CN202010748811.5A CN202010748811A CN111849562B CN 111849562 B CN111849562 B CN 111849562B CN 202010748811 A CN202010748811 A CN 202010748811A CN 111849562 B CN111849562 B CN 111849562B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
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Abstract
The embodiment of the invention provides a device and a method for desulfurizing synthesis gas prepared by coal gasification, and relates to the technical field of gas desulfurization. The desulfurization method for the synthesis gas prepared by coal gasification comprises the following steps: reacting the synthesis gas prepared by coal gasification with a desulfurizing agent to remove sulfide in the synthesis gas to obtain desulfurized synthesis gas and an inactivated desulfurizing agent, wherein the desulfurizing agent is a desulfurizing agent modified by phosphorus or boron, and the effective components of the desulfurizing agent comprise zinc oxide and hydrogenation active components; reacting the deactivated desulfurizer with oxygen to generate zinc oxide, and oxidizing the hydrogenation active component to obtain an oxidation desulfurizer; the oxidation desulfurizer is contacted with the desulfurization synthesis gas, so that hydrogen in the desulfurization synthesis gas reduces the oxidized hydrogenation active component to obtain the desulfurizer with recovered activity. The coal gasification system synthetic gas desulphurization unit includes: a fluidized bed desulfurization reactor, a fluidized bed reduction reactor, and a fluidized bed oxidation reactor. The device and the method can ensure full desulfurization, the desulfurizer can be recycled in the desulfurization process, and the desulfurization precision and the sulfur capacity can be basically unchanged.
Description
Technical Field
The invention relates to the technical field of gas desulfurization, in particular to a device and a method for desulfurizing synthesis gas prepared by coal gasification.
Background
The synthesis gas (containing fuel gas) prepared by coal gasification is the basis of novel coal chemical industry, is mainly used for synthesizing ammonia in the prior art, is mainly used for producing methanol, glycol, natural gas, special oil products and the like at present, and is also used for synthesizing fine chemicals.
The sulfur-containing compounds in the synthesis gas not only can cause corrosion of production equipment and pipelines and influence production safety, but also can cause poisoning and inactivation on the catalyst of subsequent chemical reaction and directly influence the yield and quality of the final product. The sulfur-containing compounds in the synthesis gas are removed, so that the safety production can be improved, the subsequent reaction efficiency can be guaranteed, and important sulfur resources can be recovered from the sulfur-containing compounds.
The synthesis gas desulfurization mainly comprises two modes of wet desulfurization and dry desulfurization. The wet desulfurization has three processes of chemical absorption, physical absorption and physical and chemical absorption, and has the advantages that the desulfurizer can be continuously circulated for desulfurization and regeneration, is suitable for large-scale production and can recover sulfur. The wet desulphurization has the defects that the wet desulphurization is generally used in the normal-temperature and low-temperature desulphurization process, the operation energy consumption is overhigh for medium-temperature or high-temperature synthesis gas, and the desulphurization precision is low. The dry desulfurization includes adsorption reaction methods such as zinc oxide, iron oxide, manganese oxide, activated carbon method and the like, and particularly, the zinc oxide desulfurization is the most extensive. Dry desulfurization has many advantages of both inorganic sulfur removal and organic sulfur removal, both high temperature desulfurization and low temperature desulfurization, and high desulfurization accuracy, but dry desulfurization is not a desulfurizer regeneration, only periodic operation, not suitable for the removal of a large amount of sulfides.
The sulfur-containing compounds in the coal synthesis gas contain a small amount of organic sulfur compounds such as carbonyl sulfide and carbon disulfide besides hydrogen sulfide with high concentration. The zinc oxide-based desulfurizer has high removal rate for removing hydrogen sulfide and can meet the requirements of downstream processes, but the zinc oxide-based desulfurizer has low removal rate for removing organic sulfur and can not meet the requirements of downstream processes. In order to solve the problem of low organic sulfur removal rate in the dry desulfurization of the synthesis gas, the synthesis gas hydrogenation process is commonly adopted to convert organic sulfur into hydrogen sulfide before the zinc oxide desulfurization, so that the aim of fine desulfurization of the synthesis gas is achieved by fine desulfurization of the zinc oxide. However, the addition of the hydrogenation step of the synthesis gas increases the investment cost and the operation cost correspondingly, and also increases the difficulty of production control.
Therefore, the development of a dry desulfurization method and a dry desulfurization device which can not only carry out reaction regeneration continuously, but also remove hydrogen sulfide and organic sulfur simultaneously is an urgent problem to be solved for the desulfurization of synthesis gas.
Disclosure of Invention
The invention aims to provide a device and a method for desulfurizing synthesis gas produced by coal gasification, which aim to improve at least one problem mentioned in the background technology.
Embodiments of the invention may be implemented as follows:
in a first aspect, an embodiment of the present invention provides a method for desulfurizing a synthesis gas produced by coal gasification, including:
and (3) desulfurizing the synthesis gas: reacting the synthesis gas prepared by coal gasification with a desulfurizing agent to remove sulfur in the synthesis gas to obtain desulfurized synthesis gas and an inactivated desulfurizing agent, wherein the desulfurizing agent is a desulfurizing agent modified by phosphorus or boron, and the effective components of the desulfurizing agent comprise zinc oxide and hydrogenation active components;
and (3) oxidizing a desulfurizing agent: reacting the deactivated desulfurizer with oxidizing gas to generate zinc oxide, and oxidizing the hydrogenation active component to obtain an oxidation desulfurizer;
and (3) reduction of a desulfurizing agent: and (3) contacting the oxidation desulfurizing agent with the desulfurization synthesis gas to ensure that the reducing gas in the desulfurization synthesis gas reduces the oxidized hydrogenation active component to obtain the desulfurizing agent with recovered activity.
In an optional embodiment, in the step of desulfurizing the synthesis gas, the reaction temperature is 200--1The content of sulfur-containing gas in the synthesis gas is 50-10000mg/m3；
In an optional embodiment, the reaction temperature is 350--1The content of sulfur-containing gas in the synthesis gas is 1000-3。
In an optional embodiment, in the oxidation process of the desulfurizing agent, the reaction temperature is 400--1(ii) a More preferably, the reaction temperature is 500-600 ℃, the reaction pressure is 0-4MPa, and the space velocity of the oxidizing gas is 1000-2000h-1。
In an optional embodiment, in the reduction process of the desulfurizing agent, the reaction temperature is 200--1(ii) a More preferably, the reaction temperature is 350-450 ℃, the reaction pressure is 0-4MPa, and the space velocity of the desulfurization synthesis gas is 2000-5000h-1。
In an alternative embodiment, the hydrogenation active component comprises at least one of the metals elemental nickel, molybdenum and cobalt;
in an alternative embodiment, the desulphurating agent comprises zinc oxide, a hydrogenation active component, phosphorus pentoxide and/or boron trioxide and aluminium oxide and/or titanium dioxide.
In a second aspect, an embodiment of the present invention provides a gasification syngas desulfurization apparatus, including: a fluidized bed desulfurization reactor for desulfurizing the synthesis gas, a fluidized bed reduction reactor for reducing the oxidized desulfurizing agent, and a fluidized bed oxidation reactor for oxidizing the inactivated desulfurizing agent;
the lower part of the fluidized bed desulfurization reactor is provided with a synthesis gas inlet, and the position of the fluidized bed desulfurization reactor below the synthesis gas inlet is communicated with the oxidation reactor;
the lower part of the fluidized bed oxidation reactor is provided with an oxidizing gas inlet, and the fluidized bed oxidation reactor is positioned below the oxidizing gas inlet and communicated with the fluidized bed reduction reactor;
the upper end of the fluidized bed desulfurization reactor is communicated with the fluidized bed reduction reactor;
in an alternative embodiment, the fluidized bed desulfurization reactor and the fluidized bed reduction reactor are integrated into a whole, and the fluidized bed reduction reactor is positioned above the fluidized bed desulfurization reactor to form a desulfurization and reduction integrated reactor;
in an alternative embodiment, the desulfurization and reduction integrated reactor further includes a desulfurization gas separation part, the desulfurization gas separation part communicating with an upper portion of the fluidized-bed reduction reactor;
in an alternative embodiment, the fluidized bed oxidation reactor comprises an oxidation reaction part and a flue gas separation part which are communicated in sequence from bottom to top, and the oxidation gas inlet is arranged at the bottom of the oxidation reaction part.
In an optional embodiment, a first stripper communicated with the fluidized bed desulfurization reactor is arranged below the synthesis gas inlet, the first stripper is provided with a first stripping gas inlet, a first conveying gas inlet is further arranged below the first stripping gas inlet, the first conveying gas inlet is communicated with the oxidation reaction part, a second stripper is further arranged below the oxidation reaction part, the second stripper is provided with a second stripping gas inlet, the second stripping gas inlet is provided with a second conveying gas inlet, and the second conveying gas inlet is communicated with the fluidized bed reduction reactor;
in an alternative embodiment, a synthesis gas feeding distributor is further arranged in the fluidized bed desulfurization reactor, and the synthesis gas feeding distributor is communicated with the synthesis gas inlet;
in an alternative embodiment, an oxidizing gas feeding distributor is also arranged in the oxidation reaction part, and the oxidizing gas feeding distributor is communicated with the oxidizing gas inlet;
in an optional embodiment, a first stripping gas distributor is arranged in the first stripper, and the first stripping gas distributor is communicated with the first stripping gas inlet;
in an optional embodiment, a second stripping gas distributor is arranged in the second stripper, and the second stripping gas distributor is communicated with the second stripping gas inlet;
in an alternative embodiment, the oxidation reaction part is further provided with a heat collector for collecting heat;
in an optional embodiment, the wall of the desulfurization and reduction integrated reactor is provided with a desulfurization gas outlet, the desulfurization gas separation part is provided with a first cyclone separator, and an exhaust port of the first cyclone separator is communicated with the desulfurization gas outlet;
in an optional embodiment, the wall of the fluidized bed oxidation reactor is provided with a sulfur-containing gas outlet, the flue gas separation part is provided with a second cyclone separator, and an exhaust port of the second cyclone separator is communicated with the sulfur-containing gas outlet;
in an alternative embodiment, baffles, grids or packing are provided within the fluidized-bed reduction reactor.
In a third aspect, an embodiment of the present invention provides a method for desulfurizing a synthesis gas produced by coal gasification, where the apparatus is used for desulfurizing a synthesis gas.
In an optional embodiment, the reaction temperature in the fluidized bed desulfurization reactor is 200--1The content of sulfur-containing gas in the synthesis gas is 50-10000mg/m3。
In an optional embodiment, the reaction temperature is 350--1The content of sulfur-containing gas in the introduced synthesis gas is 1000-3；
In alternative embodiments, in the oxidation reaction sectionThe reaction temperature is 400--1。
In an optional embodiment, the reaction temperature is 500--1；
In an alternative embodiment, the oxidizing gas introduced into the oxidation reaction part is a gas containing oxygen, and more preferably, the oxidizing gas is air or oxygen.
In an optional embodiment, the reaction temperature in the fluidized bed reduction reactor is 200--1。
In an optional embodiment, the reaction temperature is 350--1。
In an alternative embodiment, a first stripping gas is introduced below the synthesis gas inlet to separate the deactivated desulfurizer from the synthesis gas and strip the synthesis gas carried by the deactivated desulfurizer to the desulfurization reactor, wherein the first stripping gas is at least one of nitrogen and water vapor; the first stripping gas is preferably steam.
In an optional embodiment, a second stripping gas is introduced below the oxidizing gas inlet to separate the oxidizing desulfurizer from the oxidizing gas and strip the oxidizing gas carried by the oxidizing desulfurizer to the fluidized bed oxidation reactor part, wherein the second stripping gas is at least one of nitrogen and water vapor; the second stripping gas is preferably steam.
In an alternative embodiment, a first conveying gas is introduced into the first conveying gas inlet to convey the deactivated desulfurizer to the oxidation reaction part, and the first conveying gas comprises at least one of nitrogen or water vapor; preferably, the first conveying gas is nitrogen.
In an alternative embodiment, a second transport gas is introduced into the second transport gas inlet to transport the oxidative desulfurization agent to the fluidized-bed reduction reactor, the second transport gas comprising at least one of nitrogen or steam; preferably, the second conveying gas is nitrogen.
In an alternative embodiment, the desulfurizing agent is a phosphorus or boron modified desulfurizing agent, and the active ingredients of the desulfurizing agent comprise zinc oxide and hydrogenation active components.
In an alternative embodiment, the desulphurating agent comprises zinc oxide, a hydrogenation active component comprising at least one of the metallic elements nickel, molybdenum and cobalt, phosphorus pentoxide and/or boron trioxide, manganese oxide and/or gallium oxide and aluminium oxide and/or titanium dioxide.
In an alternative embodiment, the desulfurizing agent is added into the desulfurization device for the synthesis gas produced by coal gasification in the form of a desulfurizing agent precursor, and the hydrogenation active component in the desulfurizing agent precursor exists in the form of metal oxide.
In an alternative embodiment, the precursor of the desulphurizing agent comprises, in mass percent, 40-71% of zinc oxide, 3-10% of manganese oxide and/or gallium oxide, 10-15% of nickel oxide and/or cobalt oxide and/or molybdenum oxide, 1-3% of phosphorus pentoxide and/or boron trioxide, and 15-40% of aluminium oxide and/or titanium dioxide and/or silicon dioxide.
The beneficial effects of the embodiment of the invention include, for example:
the desulfurization method for the synthesis gas prepared by coal gasification adopts the desulfurizer with the active ingredients comprising zinc oxide and hydrogenation active components and modified by phosphorus or boron for desulfurization, thereby ensuring that the desulfurizer can effectively remove H2S, and can effectively remove organic sulfur (COS and the like). And then the inactivated desulfurizer is sequentially oxidized and reduced, so that the desulfurizer can be regenerated and recycled for the desulfurization of the synthesis gas prepared by coal gasification. The method can ensure full desulfurization, can ensure continuous regeneration and recycling of the desulfurizer, and basically keeps the desulfurization precision and the sulfur capacity unchanged after repeated cyclic regeneration.
The coal gasification system synthesis gas desulfurization device comprises a desulfurization and reduction integrated reactor and a fluidized bed oxidation reactor, wherein the fluidized bed desulfurization reactor and the fluidized bed reduction reactor are integrated into a whole, so that the device is simpler, and the desulfurization reaction and the desulfurizer regeneration cycle process are quicker. The main working part areas of the device are a fluidized bed desulfurization reactor, an oxidation reaction part and a fluidized bed reduction reactor to desulfurize the synthesis gas produced by coal gasification, and the desulfurizing agent is regenerated by using the oxidizing gas containing oxygen components and the reducing gas containing hydrogen components respectively.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic structural diagram of a gasification-syngas desulfurization apparatus according to an embodiment of the present invention.
Icon: 100-a synthetic gas desulfurization device prepared by coal gasification; 200-desulfurization and reduction integrated reactor; 300-a fluidized bed oxidation reactor; 1-a first stripping gas inlet; 2-a first stripping gas distributor; 3-a first stripper; 4-a syngas inlet; 5-syngas feed distributor; 6-fluidized bed desulfurization reactor; 7-fluidized bed reduction reactor; 8-a sweet gas separation section; 9-a first cyclone separator; 10-a desulfurized gas outlet; 11-a first delivery duct; 12-a second stripping gas inlet; 13-a second stripping gas distributor; 14-a second stripper; 15-an oxidizing gas inlet; 16-an oxidizing gas feed distributor; 17-an oxidation reaction part; 18-a heat collector; 19-a flue gas separation section; 20-a second cyclone separator; 21-a sulfur-containing gas outlet; 22-a second delivery pipe; 23-a first transport gas inlet; 24-second conveying gas inlet.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the 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.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that if the terms "upper", "lower", "inside", "outside", etc. indicate an orientation or a positional relationship based on that shown in the drawings or that the product of the present invention is used as it is, this is only for convenience of description and simplification of the description, and it does not indicate or imply that the device or the element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention.
Furthermore, the appearances of the terms "first," "second," and the like, if any, are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
It should be noted that the features of the embodiments of the present invention may be combined with each other without conflict.
Referring to fig. 1, the present embodiment provides a gasification syngas desulfurization apparatus 100, which includes: a desulfurization and reduction integrated reactor 200, and a fluidized-bed oxidation reactor 300.
The desulfurization and reduction integrated reactor 200 comprises a fluidized bed desulfurization reactor 6, a fluidized bed reduction reactor 7 and a desulfurization gas separation part 8 which are sequentially communicated from bottom to top, and the bottom of the fluidized bed desulfurization reactor 6 is provided with a synthesis gas inlet 4.
The fluidized bed oxidation reactor 300 comprises an oxidation reaction part 17 and a flue gas separation part 19 which are sequentially communicated from bottom to top, and an oxidation gas inlet 15 is arranged at the bottom of the oxidation reaction part 17.
The desulfurization and reduction integrated reactor 200 is communicated with the oxidation reaction part 17 at a position below the syngas inlet 4, and the fluidized-bed oxidation reactor 300 is communicated with the fluidized-bed reduction reactor 7 or the desulfurization gas separation part 8 at a position below the oxidant gas inlet 15.
The coal gasification synthesis gas desulfurization device 100 provided by the embodiment of the invention is used for desulfurizing the coal gasification synthesis gas, and the effective components of the desulfurizing agent used in the desulfurization process comprise zinc oxide and hydrogenation active components. The synthesis gas produced by coal gasification enters a fluidized bed desulfurization reactor 6 from a synthesis gas inlet 4 and contacts with a desulfurizing agent, so that hydrogen in the synthesis gas reacts with organic sulfide to be converted into hydrogen sulfide, and the generated hydrogen sulfide reacts with zinc oxide in the desulfurizing agent to react with the zinc oxide in the desulfurizing agent to generate zinc sulfide and water to complete the desulfurization of the synthesis gas. The desulfurized desulfurizer is inactivated and then is conveyed to the oxidation reaction part 17, the temperature of the oxidation reaction part 17 is raised, so that the inactivated desulfurizer is contacted with oxidizing gas in the oxidation reaction part 17 for combustion, zinc sulfide is oxidized into zinc oxide and sulfur dioxide, the hydrogenation active components in the zinc oxide and sulfur dioxide are oxidized, and the generated sulfur dioxide is separated from the flue gas separation part 19 and enters a subsequent working section for recycling; the oxidized desulfurizing agent is delivered to the fluidized bed reduction reactor 7. The desulfurized synthesis gas moves upwards, the hydrogen and carbon monoxide contained in the synthesis gas react with the oxidized desulfurizer passing through the oxidation reaction part 17 when passing through the fluidized bed reduction reactor 7, the hydrogenation active components in the oxidized desulfurizer are reduced to ensure that the desulfurizer completely recovers activity and continues to move downwards to participate in the desulfurization reaction, and the synthesis gas passing through the fluidized bed reduction reactor continues to move upwards and is separated from the desulfurization gas separation part 8.
The desulfurization and reduction integrated reactor 200 is located below the synthesis gas inlet 4 and is communicated with the oxidation reaction part 17 through a first conveying pipe 11, the fluidized bed oxidation reactor 300 is located below the oxidation gas inlet 15 and is communicated with the fluidized bed reduction reactor 7 through a second conveying pipe 22, specifically, the second conveying pipe 22 is directly communicated with the desulfurization gas separation part 8, the lower part of the desulfurization gas separation part 8 is communicated with the fluidized bed reduction reactor 7, the second conveying pipe 22 is indirectly communicated with the fluidized bed reduction reactor 7, and the second conveying pipe 22 finally conveys the oxidative desulfurization agent to the fluidized bed reduction reactor 7, so that the oxidative desulfurization agent is reduced by the reducing gas in the synthesis gas in the fluidized bed reduction reactor 7.
Preferably, the fluidized bed desulfurization reactor 6 is a fluidized bed adsorption reactor in order to ensure normal, stable and efficient operation of the device. The desulfurized gas separation section 8 and the flue gas separation section 19 are settlers.
Specifically, the wall of the desulfurization and reduction integrated reactor 200 is provided with a desulfurization gas outlet 10, the desulfurization gas separation part 8 is provided with a first cyclone 9, and an exhaust port of the first cyclone 9 is communicated with the desulfurization gas outlet 10. The desulfurized synthesis gas is completely separated from the desulfurizing agent under the action of the first cyclone separator 9 and is discharged from the desulfurized gas outlet 10.
The wall of the fluidized bed oxidation reactor 300 is provided with a sulfur-containing gas outlet 21, the flue gas separation part 19 is provided with a second cyclone separator 20, and the exhaust port of the second cyclone separator 20 is communicated with the sulfur-containing gas outlet 21. The sulfur dioxide generated after the zinc sulfide is oxidized is separated from the solid matters in the device under the action of the second cyclone separator 20 and is discharged from the sulfur-containing gas outlet 21.
Baffles, grids or packings are provided in the fluidized-bed reduction reactor 7. After entering the fluidized bed reduction reactor 7, the oxidized desulfurizing agent moves downwards at a slow speed under the blocking action of a baffle, a grid or a filler, and is reduced by hydrogen contained in the synthesis gas at the slow speed, so that the desulfurizing agent completely recovers activity.
A first stripper 3 communicated with a fluidized bed desulfurization reactor 6 is arranged below the synthesis gas inlet 4, the first stripper 3 is provided with a first stripping gas inlet 1, a first conveying gas inlet 23 is further arranged below the first stripper 3, the first conveying gas inlet 23 is communicated with an oxidation reaction part 17, a second stripper 14 is further arranged below the oxidation reaction part 17, the second stripper 14 is provided with a second stripping gas inlet 12, a second conveying gas inlet 24 is arranged below the second stripping gas inlet 12, and the second conveying gas inlet 24 is communicated with a fluidized bed reduction reactor 7.
The inactivated desulfurizer moves downwards into the first stripper 3, synthesis gas components carried in the inactivated desulfurizer are stripped into the fluidized bed desulfurization reactor under the action of the first stripping gas, combustible synthesis gas is prevented from entering the oxidation reaction part, and the inactivated desulfurizer is separated from the synthesis gas components and then is conveyed into the oxidation reaction part 17 through the first conveying pipe 11 under the action of first conveying gas conveyed by the first conveying gas inlet 23 to perform oxidation reaction with the oxidation gas. The oxidized desulfurizer enters the second stripper 14 under the action of gravity, the oxidized gas component carried in the oxidized desulfurizer is stripped to the oxidation reaction part under the action of second stripping gas, the oxidized gas is prevented from entering the fluidized bed reduction reactor, the oxidized desulfurizer is conveyed to the desulfurization gas separation part 8 through the second conveying pipe 22 under the action of second conveying gas conveyed by the second conveying gas inlet 24, is deposited in the desulfurization gas separation part 8 and enters the fluidized bed reduction reactor 7 under the action of gravity, and is reduced by hydrogen and carbon monoxide in the synthesis gas in the fluidized bed reduction reactor 7.
Furthermore, a synthesis gas feeding distributor 5 is also arranged in the fluidized bed desulfurization reactor 6, and the synthesis gas feeding distributor 5 is communicated with the synthesis gas inlet 4. The synthesis gas entering the apparatus from the synthesis gas inlet 4 is distributed evenly under the action of the synthesis gas feed distributor 5.
Preferably, an oxidizing gas feed distributor 16 is also provided in the oxidation reaction section 17, and the oxidizing gas feed distributor 16 is in communication with the oxidizing gas inlet 15. The oxidation gas is evenly distributed after entering the apparatus from the oxidation gas inlet 15 under the influence of the oxidation gas feed distributor 16.
Preferably, a first stripping gas distributor 2 is arranged in the first stripper 3, and the first stripping gas distributor 2 is communicated with the first stripping gas inlet 1. The stripping gas enters the first stripper 3 from the first stripping gas inlet 1 and is uniformly distributed under the action of the first stripping gas distributor 2.
Preferably, a second stripping gas distributor 13 is arranged in the second stripper 14, and the second stripping gas distributor 13 is communicated with the second stripping gas inlet 12. The stripping gas enters the second stripper 14 from the second stripping gas inlet 12 and is uniformly distributed under the action of the second stripping gas distributor 13.
Preferably, the oxidation reaction portion 17 is further provided with a heat collector 18 for collecting heat. The process of burning and oxidizing the deactivated desulfurizing agent in the oxidation reaction part is a heat releasing process, the heat released in the process can be recycled by arranging the heat collector 18, the heat collector 18 can be internally provided with the oxidation reaction part 17 or externally provided with the oxidation reaction part 17, the heat collecting medium is usually water, nitrogen, heat conducting oil and the like, and the water is preferably used as the heat collecting medium.
The method for desulfurizing the synthesis gas by coal gasification provided by the embodiment of the invention is preferably implemented by adopting the device provided by the invention, and comprises the following specific steps:
s1, desulfurizing the synthesis gas: the synthesis gas prepared by coal gasification reacts with a desulfurizer to remove sulfur in the synthesis gas to obtain desulfurized synthesis gas and an inactivated desulfurizer, wherein the desulfurizer is modified by phosphorus or boron, and the active ingredients of the desulfurizer comprise zinc oxide and hydrogenation active components.
The device and the method provided by the invention are suitable for desulfurizing the synthesis gas prepared by coal gasification, wherein the synthesis gas contains water vapor, and the desulfurizing agent contains phosphorus or boron, so that the structure of the desulfurizing agent can be protected from being damaged by high-temperature water vapor during the desulfurization reaction, and the reaction is efficiently and quickly carried out.
When the method provided by the embodiment of the present invention is implemented by using the apparatus provided by the embodiment of the present invention, the step of desulfurizing the synthesis gas is performed in the fluidized-bed desulfurization reactor 6 of the integrated desulfurization and reduction reactor 200.
The reaction principle is as follows:
in the fluidized bed desulfurization reactor 6, the organic sulfide in the synthesis gas can be converted into hydrogen sulfide through a desulfurizing agent with hydrogenation active components at a certain temperature and pressure, and the formulas (1) and (2) are shown as follows:
COS+H2→CO+H2S (1)
CS2+H2→C+H2S (2)
the hydrogen sulfide generated by the conversion of the hydrogen sulfide and organic sulfide in the synthesis gas reacts with a zinc oxide desulfurizer to generate zinc sulfide, so that the purpose of desulfurizing the synthesis gas is achieved, and the formula (3) is as follows:
H2S+ZnO→ZnS+H2O (3)
the inactivated desulfurizer moves downwards into the first stripper 3, synthesis gas components carried in the inactivated desulfurizer are stripped into the fluidized bed desulfurization reactor under the action of the first stripping gas, combustible synthesis gas is prevented from entering the oxidation reaction part, first conveying gas is introduced into the first conveying gas inlet 23, and the inactivated desulfurizer is separated from the synthesis gas components and then conveyed into the oxidation reaction part 17 through the first conveying pipe 11 under the action of the first conveying gas to perform oxidation reaction with the oxidation gas. Preferably, the first stripping gas is at least one of nitrogen and water vapor; the first stripping gas is preferably steam. Preferably, the first conveying gas comprises at least one of water vapor and nitrogen, more preferably nitrogen.
Preferably, the reaction temperature in the fluidized bed desulfurization reactor 6 is 200--1The content of sulfur-containing gas in the introduced synthetic gas is 50-10000mg/m3。
More preferably, the reaction temperature is 350-550 ℃, the reaction pressure is 0-4MPa (gauge pressure), and the volume space velocity of the synthesis gas is 2000-5000h-1The content of sulfur-containing gas in the introduced synthesis gas is 1000-3。
The desulfurizer used in the method provided by the invention is modified by phosphorus or boron, namely the desulfurizer contains phosphorus or boron. Specifically, the desulfurizing agent used in the embodiment of the present invention mainly comprises zinc oxide, and specifically further comprises a hydrogenation active component, phosphorus pentoxide and/or boron trioxide, manganese oxide and/or gallium oxide, and aluminum oxide and/or titanium dioxide, wherein the hydrogenation active component comprises at least one of metal simple substances nickel, molybdenum and cobalt.
Preferably, because the storage stability of the hydrogenation active component in the form of oxide is better, in actual industrial production, the desulfurizing agent is added into a synthesis gas desulfurization device prepared by coal gasification in the form of a desulfurizing agent precursor, and the hydrogenation active component in the desulfurizing agent precursor exists in the form of metal oxide.
More preferably, the precursor of the desulfurizing agent comprises, by mass percent, 40-71% of zinc oxide, 3-10% of manganese oxide and/or gallium oxide, 10-15% of nickel oxide and/or cobalt oxide and/or molybdenum oxide, 1-3% of phosphorus pentoxide and/or boron trioxide, and 15-40% of aluminum oxide and/or titanium dioxide and/or silicon dioxide. For example: the desulfurizer precursor can be a mixture containing 40% of zinc oxide, 10% of manganese oxide, 15% of nickel oxide, 3% of phosphorus pentoxide and 20% of aluminum oxide; can be zinc oxide 71%, manganese oxide 1%, gallium oxide 2%, cobalt oxide 10%, diboron trioxide 1%, titanium dioxide 15%; can be zinc oxide 42%, gallium oxide 5%, cobalt oxide 10%, molybdenum oxide 1%, phosphorus pentoxide 2%, boron trioxide 1%, titanium dioxide 15%, silicon dioxide 25%; can be zinc oxide 50%, manganese oxide 7%, cobalt oxide 12%, diboron trioxide 3%, titanium dioxide 28%; it may contain zinc oxide 60%, gallium oxide 6%, nickel oxide 2%, cobalt oxide 10%, molybdenum oxide 1%, diboron trioxide 1%, silicon dioxide 20%, etc.
After the deoxidizer precursor is put into the device, the deoxidizer precursor is reduced by the fluidized bed reduction reactor 7 to reduce the metal oxide into the hydrogenation active component, thereby obtaining the desulfurizer.
S2, oxidizing a desulfurizing agent: and (3) reacting the deactivated desulfurizer with oxygen to generate zinc oxide, and oxidizing the hydrogenation active component to obtain the oxidation desulfurizer.
When the method provided by the embodiment of the present invention is implemented using the apparatus provided by the embodiment of the present invention, the syngas desulfurization step is performed in the oxidation reaction part 17 of the fluidized-bed oxidation reactor 300.
The reaction principle is as follows:
in the oxidation reaction part 17, air or oxygen is used as an oxidizing gas, zinc sulfide is converted into zinc oxide by combustion and then returns to the fluidized bed desulfurization reactor 7 for desulfurization, and the reaction in the oxidation reaction part 17 is as shown in formula (4):
ZnS+O2→ZnO+SO2 (4)
meanwhile, the hydrogenation active component (denoted by M) in the desulfurizing agent in the oxidation reaction portion 17 is oxidized into a metal oxide, as shown in the following formula (5):
M+O2→MO (5)
the oxidized desulfurizer enters the second stripper 14 under the action of gravity, the oxidized gas component carried in the oxidized desulfurizer is stripped to the oxidation reaction part 17 under the action of second stripping gas, the oxidized gas is prevented from entering the fluidized bed reduction reactor, second conveying gas is introduced into the second conveying gas inlet 24, the oxidized desulfurizer is conveyed to the desulfurization gas separation part 8 through the second conveying pipe 22 under the action of the second conveying gas, and then enters the fluidized bed reduction reactor 7, and is reduced by hydrogen and carbon monoxide in the fluidized bed reduction reactor 7. The second stripping gas is at least one of nitrogen and water vapor; water vapor is preferred. Preferably, the second conveying gas comprises at least one of water vapor and nitrogen, more preferably nitrogen.
Preferably, the reaction temperature in the oxidation reaction part is 400-800 ℃, the reaction pressure is 0-8MPa, and the volume space velocity of the oxidation gas is 500-5000h-1。
More preferably, the reaction temperature is 500-600 ℃, the reaction pressure is 0-4MPa, and the volume space velocity of the oxidizing gas is 1000-2000h-1。
S3, reduction of a desulfurizing agent: and (3) contacting the oxidized desulfurizer with the desulfurization synthesis gas, and reducing the oxidized hydrogenation active component by using reducing gas in the desulfurization synthesis gas to obtain the desulfurizer with recovered activity.
When the method provided by the embodiment of the present invention is implemented using the apparatus provided by the embodiment of the present invention, the syngas desulfurization step is performed in the fluidized-bed reduction reactor 7 of the integrated desulfurization and reduction reactor 200.
The reaction principle is as follows:
in the fluidized bed reduction reactor 7, the hydrogenation active components in the desulfurizing agent are converted from an oxidation state to a reduction state with hydrogenation activity, and the reaction is as shown in formula (6), so that organic sulfur is converted into hydrogen sulfide in the fluidized bed desulfurization reactor 6.
MO+H2→M+H2O (6)
The reaction temperature in the fluidized bed reduction reactor is 200-700 ℃, the reaction pressure is 0-8Mpa, and the space velocity of the introduced desulfurization synthesis gas is 500-20000h-1(ii) a More preferably, the reaction temperature is 350-450 ℃, the reaction pressure is 0-4MPa, andthe space velocity of the entering desulfurization synthesis gas is 2000--1。
Examples of the experiments
(1) A fixed bed fluidized bed test device is used for simulating the desulfurization, oxidation and reduction tests of the desulfurizer by the method provided by the invention;
(2) the diameter of a dense-phase region of a reactor of the fluidized bed test device is 0.042m, the height of the dense-phase region is 0.4m, and the loading amount of a desulfurizing agent is 200 g;
(3) gas composition for reduction reaction prepared experimentally: h225v％、CO 25v％、CO225v％、H2O25 v%, gas flow 140ml/s (under standard state), reduction temperature 400 ℃, reduction time 60 minutes;
(4) the gas composition of the synthesis gas prepared by simulating coal gasification and prepared by experiment for desulfurization reaction is as follows: h225v％、CO 25v％、CO225v％、H2O 25v％，H2S1800mg/m3，COS200mg/m3The gas flow is 140ml/s (under the standard state), and the desulfurization reaction temperature is 400 ℃;
(5) the desulfurizer is regenerated by air at 550 ℃, the gas flow is 140ml/s (under a standard state), and the regeneration time is 60 minutes;
(6) measuring H of gas outlet with trace sulfur analyzer2S and COS;
(7) four desulfurizing agents are adopted as experimental objects, namely C1, C2, D1 and D2, and the preparation method of each desulfurizing agent comprises the following steps:
c1 preparation of alumina Sol 950g (Al)2O3Content 21%), water and 156g of titanium dioxide powder were slowly added with stirring, and after stirring for 2.0 hours, 32g of ammonium dihydrogen phosphate, 236g of copper nitrate and 1800g of basic zinc carbonate were slowly added with stirring, followed by further stirring for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed adsorbent at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the desulfurizer C1.
C2 preparation of alumina Sol 950g (Al)2O3Content 21%), silica sol 813g (SiO2 content 16%) was slowly added with stirring, and after stirring for 2.0 hours, boric acid 3 was slowly added with stirring6g, 297g of gallium nitrate and 1800g of basic zinc carbonate, and then stirred for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed adsorbent at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the desulfurizer C2.
D1 preparation of alumina sol 807g (Al)2O3Content 21%), water and 82g of titanium dioxide powder were slowly added with stirring, and after stirring for 2.0 hours, 27g of ammonium dihydrogen phosphate, 100g of copper nitrate and 1700g of basic zinc carbonate were slowly added with stirring, followed by further stirring for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed adsorbent at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the desulfurizer D01.
196g of nickel nitrate and 86g of ammonium paramolybdate are dissolved in 600ml of water, the desulfurizer D016 is soaked in the solution at the temperature of 50 ℃ for hours, then the desulfurizer D001 is dried at the temperature of 110 ℃ for 4 hours, and finally the desulfurizer D001 is roasted at the temperature of 500 ℃ for 5 hours.
The desulfurizer D001 is at normal pressure, temperature of 400 ℃ and space velocity of 2000h-1Under the conditions of (1), with H2+CO(H250v percent and CO 50v percent) for 60 minutes to obtain the finished product of the desulfurizer D1.
D2 preparation of alumina sol 726g (Al)2O3Content 21%), water and 82g of titanium dioxide powder were slowly added with stirring, and after stirring for 2.0 hours, 27g of ammonium dihydrogen phosphate, 100g of copper nitrate and 1700g of basic zinc carbonate were slowly added with stirring, followed by further stirring for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed adsorbent at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the desulfurizer D02.
196g of nickel nitrate, 86g of ammonium paramolybdate and 20g of cobalt nitrate are dissolved in 600ml of water, the desulfurizer D026 is soaked in the solution at the temperature of 50 ℃ for hours, then the solution is dried at the temperature of 110 ℃ for 4 hours, and finally the solution is roasted at the temperature of 500 ℃ for 5 hours to obtain the desulfurizer D002.
The desulfurizer D002 is at normal pressure, temperature 400 deg.C and space velocity 2000h-1Under the conditions of (1), with H2+CO(H250v percent and CO 50v percent) for 60 minutes to obtain the finished product of the desulfurizer D2.
The differences between D1 and D2 relative to C1 and C2 are primarily that they contain a hydrogenation-active component. Examples evaluation of physical properties of desulfurizing agents is shown in Table 1.
(8) The evaluation results of the precision of the desulfurizing agent are recorded in table 2, the evaluation results of the sulfur capacity of the desulfurizing agent are recorded in table 3, and the precision and the change of the sulfur capacity of the desulfurizing agent after the desulfurizing agent is subjected to multiple times of desulfurization, oxidation and reduction are recorded in tables 4 and 5.
TABLE 1 physical Properties of desulfurizing agent
TABLE 2 evaluation results of desulfurization accuracy
TABLE 3 evaluation results of sulfur capacity of desulfurizing agent
| Desulfurizing agent | C1 | C2 | D1 | D2 |
| Sulfur capacity, g sulfur/100 |
18 | 17 | 17 | 16 |
As can be seen from Table 2, the desulfurizing agent containing no hydrogenation active component and the desulfurizing agent containing hydrogenation active component remove H2S is very accurate and the purified gas H2S＜1mg/m3However, the removal rate of COS of desulfurizing agents C1 and C2 which do not contain hydrogenation active components is lower, and the COS is more than 20mg/m3Far from meeting the requirements of subsequent processes, contains hydrogenation active components and passes through H2The COS removing precision of the desulfurizing agents D1 and D2 after CO reduction is very high and is less than 1mg/m3And the requirements of subsequent processes can be met. Shows that the desulfurizer containing the hydrogenation component can efficiently remove H after hydrogenation reduction2S and COS can be efficiently removed, and the device and the method provided by the invention can be used for carrying out desulfurization reaction to thoroughly and efficiently remove sulfur-containing gas in the synthesis gas prepared by coal gasification.
As can be seen from Table 3, the desulfurizing agent contained a hydrogenation-active component and used H2The sulfur capacity of the desulfurizer is not influenced after the CO is reduced.
TABLE 4 evaluation results of desulfurization accuracy
TABLE 5 evaluation results of sulfur capacity of desulfurizing agent
As can be seen from tables 4 and 5, the desulfurization precision and sulfur capacity of the desulfurizing agent are basically unchanged after a plurality of cycles of desulfurization, oxidation and reduction, and the device and the method provided by the invention are very suitable for removing sulfide in synthesis gas.
The synthesis gas desulfurization device and the synthesis gas desulfurization method provided by the invention have the following advantages:
(1) the zinc oxide-based desulfurizer has high desulfurization precision and large sulfur capacity; the zinc oxide-based desulfurizer is subjected to modification treatment by metal oxides such as nickel oxide and/or cobalt oxide and/or molybdenum oxide, and organic sulfides in the synthesis gas are completely converted into hydrogen sulfide, so that the desulfurization efficiency of the desulfurizer is improved; the zinc oxide-based desulfurizer is subjected to modification treatment by metal oxides such as copper oxide and/or gallium oxide, and the activity attenuation of the desulfurizer is not obvious after the desulfurizer is regenerated for many times; the zinc oxide-based desulfurizer is particularly suitable for the desulfurization process and the oxidation regeneration process of synthesis gas with high water vapor content through phosphorus or boron modification treatment so as to keep the desulfurization activity and the desulfurization stability of the desulfurizer; the desulfurizer which takes the alumina and/or the silicon oxide and/or the titanium dioxide as the carrier has strong wear resistance, large specific surface area and pore volume, and is particularly suitable for the working conditions of fluidized bed adsorption desulfurization and regeneration; the zinc oxide based microsphere desulfurizer prepared by utilizing the spray drying and forming technology is particularly suitable for the working conditions of fluidized bed adsorption desulfurization and regeneration.
(2) The technological process comprising fluidized bed desulfurizing reaction, fluidized bed desulfurizing agent oxidation and fluidized bed desulfurizing agent reduction can realize the continuous process of simultaneously removing hydrogen sulfide and organic sulfur in the synthesis gas dry process, thereby overcoming the defects of periodic operation of fixed bed dry process desulfurization and combined hydrogenation and desulfurization processes.
(3) The synthesis gas desulfurization device composed of the fluidized bed desulfurization reactor, the fluidized bed desulfurizer oxidizer and the fluidized bed desulfurizer reducer ingeniously combines the fluidized bed desulfurization reactor and the fluidized bed desulfurizer reducer to form a series-connected fluidized bed reactor, and the desulfurizer reducer is not required to be arranged independently, so that the investment is saved, and the purified synthesis gas can be used as a reducing agent to reduce the regenerated desulfurizer into the desulfurizer with hydrogenation activity, but the high-concentration hydrogen is not required to be arranged independently as the reducing agent.
(4) The contact time and the fluidization state of the desulfurizer and the purified synthesis gas are controlled by adding internal members (grids, baffles or fillers) in the fluidized bed reduction reactor, so that the full reduction of the desulfurizer is ensured. The fluidized-bed reduction reactor internals may be either various baffles and grids, or other effective packing.
(5) The device consisting of the fluidized bed desulfurization reactor, the fluidized bed oxidation reactor of the fluidized bed desulfurizer and the fluidized bed reduction reactor of the fluidized bed desulfurizer can realize dry desulfurization of synthesis gas in a wide temperature range, overcomes the defect that the wet desulfurization can only operate at low temperature and normal temperature, and can remove inorganic sulfur and organic sulfur.
(6) The device consisting of the fluidized bed desulfurization reactor, the fluidized bed oxidation reactor of the fluidized bed desulfurizer and the fluidized bed reduction reactor of the fluidized bed desulfurizer can realize dry desulfurization of the synthesis gas within a wide pressure range, and particularly overcomes the defect that the reduction reaction of the desulfurizer must operate at high pressure, so that the pressure of the whole desulfurization process can be set according to the pressure of a synthesis gas system, the feeding pressure of the synthesis gas does not need to be adjusted, and energy conservation and consumption reduction are realized.
By utilizing the device and the method provided by the invention, the concentration of sulfur-containing gas (hydrogen sulfide agent contains organic matters) in the synthesis gas prepared by coal gasification can be reduced to 1.0mg/m3The requirements of the subsequent process are met below.
In summary, according to the desulfurization method for the synthesis gas produced by coal gasification provided by the invention, the desulfurization is performed by using the desulfurizer with the active ingredients including zinc oxide and hydrogenation active components and modified by phosphorus or boron, so that the sufficient desulfurization can be ensured. And then the inactivated desulfurizer is sequentially oxidized and reduced, so that the desulfurizer can be regenerated and recycled for the desulfurization of the synthesis gas prepared by coal gasification. The method can ensure full desulfurization, can ensure continuous regeneration and recycling of the desulfurizer, and basically keeps the desulfurization precision and the sulfur capacity unchanged after repeated cycle regeneration.
The coal gasification synthesis gas desulfurization device provided by the invention is composed of a desulfurization and reduction integrated reactor and a fluidized bed oxidation reactor, and integrates the fluidized bed desulfurization reactor and the fluidized bed reduction reactor into a whole, so that the device is simpler, and the desulfurization reaction and desulfurizer regeneration cycle process are quicker. The main working part areas of the device are a fluidized bed desulfurization reactor, an oxidation reaction part and a fluidized bed reduction reactor to desulfurize the synthesis gas prepared by coal gasification, and the desulfurizing agent is regenerated by respectively using the oxidizing gas containing oxygen components and the reducing gas containing hydrogen components of the synthesis gas.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (30)
1. A coal gasification system synthetic gas desulphurization device is characterized by comprising: a fluidized bed desulfurization reactor for desulfurizing the synthesis gas, a fluidized bed reduction reactor for reducing the oxidized desulfurizing agent, and a fluidized bed oxidation reactor for oxidizing the inactivated desulfurizing agent;
the lower part of the fluidized bed desulfurization reactor is provided with a synthesis gas inlet, and the fluidized bed desulfurization reactor is positioned below the synthesis gas inlet and communicated with the oxidation reactor;
an oxidizing gas inlet is formed in the lower part of the fluidized bed oxidation reactor, and the fluidized bed oxidation reactor is positioned below the oxidizing gas inlet and communicated with the fluidized bed reduction reactor;
the upper end of the fluidized bed desulfurization reactor is communicated with the fluidized bed reduction reactor;
the fluidized bed desulfurization reactor and the fluidized bed reduction reactor are integrated into a whole, and the fluidized bed reduction reactor is positioned above the fluidized bed desulfurization reactor to form a desulfurization and reduction integrated reactor; a baffle, a grid or a filler is arranged in the fluidized bed reduction reactor;
the desulfurization and reduction integrated reactor also comprises a desulfurization gas separation part which is communicated with the upper part of the fluidized bed reduction reactor; the fluidized bed oxidation reactor comprises an oxidation reaction part and a flue gas separation part which are sequentially communicated from bottom to top, and the oxidation gas inlet is arranged at the bottom of the oxidation reaction part;
the desulfurization and reduction integrated reactor is positioned below the synthesis gas inlet and communicated with the oxidation reaction part through a first conveying pipe, and the fluidized bed oxidation reactor is positioned below the oxidation gas inlet and communicated with the fluidized bed reduction reactor through a second conveying pipe; the second conveying pipe is directly communicated with the desulfurization gas separation part, the lower part of the desulfurization gas separation part is communicated with the fluidized bed reduction reactor, the second conveying pipe is indirectly communicated with the fluidized bed reduction reactor, and the oxidizing desulfurizer is finally conveyed to the fluidized bed reduction reactor through the second conveying pipe so as to be reduced by the reducing gas in the synthesis gas in the fluidized bed reduction reactor.
2. The coal gasification syngas desulfurization apparatus of claim 1, wherein a first stripping device is disposed below the syngas inlet and communicates with the fluidized bed desulfurization reactor, the first stripping device is provided with a first stripping gas inlet, a first conveying gas inlet is further disposed below the first stripping gas inlet, the first conveying gas inlet communicates with the oxidation reaction section, a second stripping device is further disposed below the oxidation reaction section, the second stripping device is provided with a second stripping gas inlet, the second stripping gas inlet is provided with a second conveying gas inlet, and the second conveying gas inlet communicates with the fluidized bed reduction reactor.
3. The coal gasification syngas desulfurization apparatus of claim 2, wherein a syngas feed distributor is further disposed within the fluidized bed desulfurization reactor, the syngas feed distributor being in communication with the syngas inlet.
4. The coal gasification syngas desulfurization apparatus of claim 2, wherein an oxidizing gas feed distributor is further disposed within the oxidation reaction section, said oxidizing gas feed distributor being in communication with the oxidizing gas inlet.
5. The coal gasification syngas desulfurization apparatus of claim 2, wherein a first stripping gas distributor is disposed within the first stripper, the first stripping gas distributor being in communication with the first stripping gas inlet.
6. The coal gasification syngas desulfurization apparatus of claim 2, wherein a second stripping gas distributor is disposed within the second stripper, the second stripping gas distributor being in communication with the second stripping gas inlet.
7. The coal gasification syngas desulfurization apparatus according to claim 2, wherein the oxidation reaction section is further provided with a heat collector for collecting heat.
8. The coal gasification syngas desulfurization device of claim 2, wherein the wall of the desulfurization and reduction integrated reactor is provided with a desulfurization gas outlet, the desulfurization gas separation part is provided with a first cyclone, and the exhaust port of the first cyclone is communicated with the desulfurization gas outlet.
9. The coal gasification syngas desulfurization apparatus of claim 2, wherein the wall of the fluidized bed oxidation reactor is provided with a sulfur-containing gas outlet, the flue gas separation part is provided with a second cyclone separator, and the exhaust port of the second cyclone separator is communicated with the sulfur-containing gas outlet.
10. A method for desulphurizing synthesis gas produced by coal gasification, characterized in that the device according to claim 2 is used for desulphurizing synthesis gas.
11. The desulfurization method for synthesis gas through coal gasification according to claim 10, wherein the reaction temperature in the fluidized bed desulfurization reactor is 200--1Synthesis ofThe sulfur-containing gas content in the gas is 50-10000mg/m3。
12. The desulfurization method for synthesis gas through coal gasification according to claim 10, characterized in that the reaction temperature is 350--1The content of sulfur-containing gas in the introduced synthesis gas is 1000-3。
13. The desulfurization method for synthesis gas through coal gasification according to claim 10, wherein the reaction temperature in the oxidation reaction part is 400--1。
14. The desulfurization method for synthesis gas through coal gasification according to claim 13, characterized in that the reaction temperature is 500--1。
15. The method for desulfurizing coal gasification syngas according to claim 10, wherein the oxidizing gas introduced into the oxidation reaction section is a gas containing oxygen.
16. The method for desulfurizing coal gasification syngas according to claim 15, wherein the oxidizing gas is air or oxygen.
17. The desulfurization method for synthesis gas through coal gasification according to claim 10, wherein the reaction temperature in the fluidized bed reduction reactor is 200--1。
18. The desulfurization method for synthesis gas through coal gasification according to claim 17, characterized in that the reaction temperature is 350--1。
19. The method for desulfurizing coal gasification synthesis gas according to claim 10, wherein a first stripping gas is introduced below the synthesis gas inlet to separate the deactivated desulfurization agent from the synthesis gas and strip the synthesis gas carried by the deactivated desulfurization agent to the desulfurization reactor, and the first stripping gas is at least one of nitrogen and steam.
20. The method for desulfurizing coal gasification syngas according to claim 19, wherein the first stripping gas is steam.
21. The method for desulfurizing coal gasification syngas according to claim 19 or 20, wherein a second stripping gas is introduced below the oxidizing gas inlet to separate the oxidizing desulfurization agent from the oxidizing gas and strip the oxidizing gas carried by the oxidizing desulfurization agent to the fluidized bed oxidation reactor, and the second stripping gas is at least one of nitrogen and steam.
22. The method for desulfurizing coal gasification syngas according to claim 21, wherein the second stripping gas is steam.
23. The coal gasification syngas desulfurization method of claim 19 or 20, wherein a first transport gas comprising at least one of nitrogen or steam is introduced into the first transport gas inlet to transport the deactivated desulfurization agent to the oxidation reaction section.
24. The method for desulfurizing coal gasification syngas according to claim 23, wherein the first transport gas is nitrogen.
25. The method for desulfurizing coal gasification syngas according to claim 23, wherein passing a second transport gas into the second transport gas inlet delivers the oxidizing desulfurization agent to the fluidized-bed reduction reactor, and the second transport gas comprises at least one of nitrogen or steam.
26. The method for desulfurizing coal gasification syngas according to claim 25, wherein the second transport gas is nitrogen.
27. The method for desulfurizing synthesis gas through coal gasification according to claim 23, wherein the desulfurizing agent is a phosphorus or boron modified desulfurizing agent, and the effective components of the desulfurizing agent comprise zinc oxide and hydrogenation active components.
28. The coal gasification syngas desulfurization method of claim 27, wherein the desulfurization agent comprises zinc oxide, the hydrogenation active component, phosphorus pentoxide and/or boron trioxide, manganese oxide and/or gallium oxide, and aluminum oxide and/or titanium dioxide, and the hydrogenation active component comprises at least one of metallic elementary nickel, molybdenum, and cobalt.
29. The method for desulfurizing coal gasification syngas according to claim 27, wherein the desulfurizing agent is added to the coal gasification syngas desulfurization unit as a desulfurizing agent precursor, and the hydrogenation-active component in the desulfurizing agent precursor is present in the form of metal oxide.
30. The coal gasification syngas desulfurization method of claim 27, wherein the desulfurizing agent precursor comprises, by mass, 40-71% of zinc oxide, 3-10% of manganese oxide and/or gallium oxide, 10-15% of nickel oxide and/or cobalt oxide and/or molybdenum oxide, 1-3% of phosphorus pentoxide and/or boron trioxide, and 15-40% of aluminum oxide and/or titanium dioxide and/or silicon dioxide.
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| CN104437032A (en) * | 2014-11-11 | 2015-03-25 | 浙江三龙催化剂有限公司 | Synthetic raw material gas deep fine desulfurization process and fine desulfurization device |
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| CN110589767A (en) * | 2019-10-08 | 2019-12-20 | 中国石油化工股份有限公司 | Device and method for desulfurizing synthesis gas prepared by coal gasification |
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| CN103272610A (en) * | 2013-06-08 | 2013-09-04 | 沈炳龙 | Ti-based fine desulfurization catalyst, as well as preparation method and use method thereof |
| CN104437032A (en) * | 2014-11-11 | 2015-03-25 | 浙江三龙催化剂有限公司 | Synthetic raw material gas deep fine desulfurization process and fine desulfurization device |
| CN107335445A (en) * | 2017-08-17 | 2017-11-10 | 江苏天东新材料科技有限公司 | A kind of preparation method and application of double-function fine desulfurizing agent |
| CN110589767A (en) * | 2019-10-08 | 2019-12-20 | 中国石油化工股份有限公司 | Device and method for desulfurizing synthesis gas prepared by coal gasification |
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