CN108977234B - Decarburization method for coke oven gas and converter and/or blast furnace gas - Google Patents
Decarburization method for coke oven gas and converter and/or blast furnace gas Download PDFInfo
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- CN108977234B CN108977234B CN201810829336.7A CN201810829336A CN108977234B CN 108977234 B CN108977234 B CN 108977234B CN 201810829336 A CN201810829336 A CN 201810829336A CN 108977234 B CN108977234 B CN 108977234B
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000005261 decarburization Methods 0.000 title claims description 38
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 118
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 63
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/024—Dust removal by filtration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
- C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
Abstract
A method for decarbonizing coke oven gas and converter and/or blast furnace gas comprises the following steps: s1), filtering and removing impurities from the coke oven gas and the converter and/or blast furnace gas, and pressurizing an MDEA barren solution; s2), CO2Separating; s3), purifying the coke oven gas and the converter and/or blast furnace gas; s4), and recycling the MDEA lean solution. The decarbonization method of the coke oven gas and the converter and/or blast furnace gas has the advantages of high absorption rate, large absorption capacity, high purification degree and the like, can be used for removing carbon dioxide and sulfide, has wide application and development prospects, and simultaneously creatively completes the decarbonization of the converter and/or blast furnace gas through two steps of pressure swing adsorption coarse decarbonization and MDEA solution fine decarbonization, realizes the breakthrough of the decarbonization of the converter and/or blast furnace gas, and has very important significance for promoting the technical progress and economic development of the refining industry in China.
Description
Technical Field
The invention relates to the field of gas purification, in particular to a decarburization method of coke oven gas and converter and/or blast furnace gas.
Background
Energy and environmental problems are becoming the focus of concern in the world and various regions, and the steel industry is a traditional industry with high logistics, high energy consumption and high pollution and is an industry with important energy conservation and emission reduction. From the industry of carbon dioxide generation, about 50% of carbon dioxide emission comes from industrial production, the carbon dioxide emission of the domestic steel industry accounts for about 14% of the whole country, the iron-making process is the main source of the carbon dioxide emission of the steel industry and accounts for more than 90% of the carbon dioxide emission of the whole steel production process, and the carbon dioxide emission of the domestic steel industry accounts for about 50% of the world steel industry, so that the reduction of the carbon dioxide emission of the steel plant is significant for improving the environment, and has great strategic significance for the sustainable development of the economy and the environment of China.
Coke oven gas, which is a combustible gas produced during the production of coke and tar products by high-temperature dry distillation of several kinds of bituminous coal in a coke oven, is a byproduct of the coking industry, and is mainly composed of 56% and 27% of hydrogen and a small amount of carbon monoxide, carbon dioxide, nitrogen, oxygen and other hydrocarbons, and is used for synthesizing ammonia, ethylene glycol, methanol and the like after separation, and other components such as methane and ethylene can be used as organic synthesis raw materials2Is removed to the level of PPM. The converter gas is a mixed gas of carbon monoxide and a small amount of carbon dioxide generated by carbon in molten iron at high temperature and oxygen blown in during converter steelmaking, the blast furnace gas is a combustible gas byproduct during blast furnace ironmaking production, the effective components of the blast furnace gas comprise carbon dioxide, carbon monoxide, hydrogen, nitrogen, hydrocarbons and a small amount of sulfur dioxide, the converter gas and the blast furnace gas have the characteristics of being rich in carbon and hydrogen, the effective components such as CO in the gas are often combusted for power generation, and the excessive carbon dioxide is directly discharged to the airIn particular, it has a serious influence on the environment. In order to avoid the influence of steel production on the environment and realize green production, the secondary utilization of converter gas and blast furnace gas is of great importance, which is beneficial to energy conservation and emission reduction of steel enterprises, green production and brings good economic benefit to the steel enterprises, however, the secondary utilization of converter gas and/or blast furnace gas and the removal of carbon dioxide are necessary conditions, and CO also needs to be removed2The content of the phosphorus is removed to the PPM level, and simultaneously, impurities such as phosphine, hydrogen fluoride and the like in converter gas and blast furnace gas are also removed. The removal of carbon dioxide in the chemical industry is partly industrialized, and the removal methods are different based on the difference in the concentration of carbon dioxide in the treated gas, and mainly include absorption methods, adsorption methods, condensation methods, membrane separation methods and the like. However, at present, no specific process technology aiming at separating and recovering the coke oven gas and the carbon dioxide gas in the converter and the blast furnace gas simultaneously exists in China.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides a method for decarbonizing coke oven gas and converter and/or blast furnace gas.
The technical solution of the invention is as follows: a method for decarbonizing coke oven gas and converter and/or blast furnace gas comprises the following steps:
s1), filtering and removing impurities from the coke oven gas and the converter and/or blast furnace gas, and pressurizing MDEA barren solution
Respectively filtering the coke oven gas and the converter and/or blast furnace gas, and removing impurities; simultaneously, pressurizing the MDEA solution;
S2)、CO2separation of
Respectively carrying out reverse flow and mass transfer heat exchange on the coke oven gas and the converter and/or the blast furnace gas which are processed by the step S1 and the pressurized MDEA barren solution, and absorbing CO in the coke oven gas and the converter and/or the blast furnace gas by the MDEA barren solution2Forming an MDEA rich solution;
s3), purifying coke oven gas and converter and/or blast furnace gas
S31), separating CO in the step S22Cooling the coke oven gas and the converter and/or blast furnace gas;
s32), respectively carrying out gas-liquid separation on the coke oven gas cooled in the step S31 and converter and/or blast furnace gas;
s33), respectively filtering the coke oven gas and the converter and/or blast furnace gas after gas-liquid separation in the step S32, separating mechanical impurities and free liquid, and finishing decarburization of the coke oven gas and the converter and/or blast furnace gas;
s4), MDEA barren liquor circulation regeneration
S41), respectively mixing the liquid obtained after gas-liquid separation in the step S32 with the mechanical impurities and free liquid obtained in the step S33, and reducing the pressure of the MDEA rich liquid in the step S2;
s42), the mixture of the liquid, the mechanical impurities and the free liquid in the step S41 and the MDEA rich solution after pressure reduction are flashed;
s43), conveying the flashed gas to a diffusing system for diffusing, filtering the flashed liquid to remove mechanical impurities to form MDEA rich liquid, and exchanging heat with MDEA barren liquid formed in the subsequent process to raise the temperature;
s44), carrying out reverse flow and mass transfer heat exchange on the MDEA rich solution subjected to heat exchange in the step S43 and stripping steam, resolving acid gas in the MDEA rich solution through the stripping steam, and completing primary resolution of the acid gas of the MDEA rich solution;
s45), heating the MDEA rich solution subjected to the primary analysis of the acid gas in the step S44, analyzing the acid gas in the MDEA rich solution through steam, and performing secondary analysis on the acid gas of the MDEA rich solution to form an MDEA barren solution; cooling the stripped steam, performing gas-liquid separation, discharging gas after gas-liquid separation into the atmosphere, boosting the pressure of liquid after gas-liquid separation, and flashing together with the liquid, the mechanical impurities, the free liquid mixture and the decompressed MDEA rich solution in the step S41;
s46), cooling the MDEA lean solution formed in step S45 after exchanging heat with the MDEA rich solution in step S43, and forming the MDEA lean solution in step S1.
Further, before step S1, converter and/or blast furnace gas is subjected to coarse decarburization and phosphine removal by pressure swing adsorption; the volume fraction of carbon dioxide of converter and/or blast furnace gas after pressure swing adsorption is 5.8-6.2%, and the content of phosphine is 1-5 PPM.
Further, the method for the coarse decarburization and the removal of phosphine of the gas of the converter and/or the blast furnace by adopting a pressure swing adsorption mode comprises the following steps: the converter and/or blast furnace gas is subjected to gas-liquid separation to remove liquid, and then enters an adsorption tower group, the adsorption tower group comprises 8 adsorption towers which are connected in parallel, when the adsorption tower group is used for adsorption, a pumping-out process of two-tower adsorption and five-time pressure equalization is adopted, each adsorption tower sequentially undergoes the steps of adsorption, one-tower uniform reduction, two-tower uniform reduction, three-tower uniform reduction, four-tower uniform reduction, five-tower uniform reduction, reverse release, pumping-out, five-tower uniform rise, four-tower uniform rise, three-tower uniform rise, two-tower uniform rise, one-tower uniform rise and final rise, purified gas is obtained from the tower top, and decarbonized and decomposed gas is.
Further, the MDEA solution is pressurized and divided into 2 paths, one path is mixed with the other path after impurity removal, and the step S2 is carried out.
Furthermore, before step S1, the effective components of the coke oven gas comprise 20-25% of methane by volume, 55-60% of hydrogen by volume, 8-12% of carbon monoxide by volume, 0.0005-0.0007% of oxygen by volume, 2-4% of carbon dioxide by volume, and tar and dust content not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3(ii) a In the effective components of the converter and/or blast furnace gas, the volume fraction of carbon monoxide is 55-65%, the volume fraction of carbon dioxide is 5.8-6.2%, the volume fraction of nitrogen is 28-32%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%; the content of phosphine is 1-5PPM, and the content of tar and dust is not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3；
After step S33, the effective components of the coke oven gas comprise 20-25% of methane by volume, 57-62% of hydrogen by volume, 8-12% of carbon monoxide by volume, 0.0005-0.0007% of oxygen by volume, 0.0015-0.0019% of carbon dioxide by volume, and tar and dust content not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3(ii) a Effective components of converter and/or blast furnace gas include carbon monoxide 60-70 vol%, carbon dioxide 0.0015-0.0019 vol%, nitrogen 31-33 vol%, and hydrogenThe volume fraction of (A) is 1-4%, and the volume fraction of oxygen is 0.001-0.005%; the content of phosphine is 1-5PPM, and the content of tar and dust is not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3。
Further, nitrogen is introduced for nitrogen sealing in the flash evaporation process and the gas-liquid separation process after cooling of the stripping steam.
Further, before step S1, the coke oven gas is primarily purified by the coke oven gas, and the primarily purifying of the coke oven gas includes the following steps:
s01), dedusting and detarring
Dust removal and tar removal are carried out on coke oven gas, so that the total amount of dust and tar in the coke oven gas is not higher than 3mg/Nm3；
S02), compression
Compressing the coke oven gas obtained in the step S01 to 0.58-0.62 Mpa;
s03), crude desulfurization
The coke oven gas after the step S02 is roughly desulfurized to make H in the coke oven gas2S content not higher than 1mg/Nm3。
S04), removing impurities
Removing impurities from the coke oven gas in the step S03 to ensure that the content of the impurities in the coke oven gas is not higher than 0.1mg/Nm3；
S05), secondary compression
Compressing the coke oven gas obtained in the step S04 to 4-4.2 Mpa;
s06), oxygen-removing fine desulfurization
The coke oven gas after the step S05 is deoxidized and refined desulfurized to ensure that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of not more than 1mg/Nm3。
Further, before coarse decarburization and phosphine removal of converter and/or blast furnace gas by adopting a pressure swing adsorption mode, the converter and/or blast furnace gas is primarily purified by the converter and/or blast furnace gas, and the primary purification of the converter and/or blast furnace gas comprises the following steps:
s01), dedusting and detarring
Dedusting and detarring converter and/or blast furnace gas to make converter and/or blast furnace coalThe total amount of dust and tar in the gas is not higher than 3mg/Nm3；
S02), compression
Compressing the converter and/or blast furnace gas from step S01 to 0.95-1 MPa;
s03), removing impurities
Removing impurities from the converter and/or blast furnace gas in the step S02 to ensure that the impurity content in the converter and/or blast furnace gas is not higher than 1mg/Nm3；
S04), oxygen-removing fine desulfurization
The converter gas and/or the blast furnace gas after the step S03 are deoxidized and refined desulfurized to ensure that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of less than 30mg/Nm3。
Further, in step S06, the coke oven gas after the step S05 is deoxidized and refined desulfurized to ensure that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of not more than 1mg/Nm3The method comprises the following steps:
s061), heat exchange and temperature rise
Heating the compressed coke oven gas to 180-300 ℃ through heat exchange;
s062), pre-hydroconversion and first hydroconversion
Performing pre-hydrogenation conversion and primary hydrogenation conversion on the coke oven gas subjected to the step S061 in sequence to convert organic sulfur in the coke oven gas subjected to the step S061 into hydrogen sulfide, removing oxygen by hydrogenation, saturating unsaturated hydrocarbon by hydrogenation, and removing impurities;
s063), primary desulfurization
Performing primary desulfurization on the coke oven gas obtained in the step S062 to remove inorganic sulfur and hydrogen chloride;
s064), secondary heat exchange and temperature rise
Heating the coke oven gas subjected to S063 to 280-340 ℃ through heat exchange;
s065), two-stage hydroconversion
Carrying out secondary hydrogenation reaction on the coke oven gas subjected to S064, and deeply hydrogenating and converting organic sulfur, unsaturated hydrocarbon and oxygen remained in the coke oven gas subjected to S064;
s066), secondary fine desulfurization
And performing secondary fine desulfurization on the coke oven gas subjected to secondary hydroconversion.
Further, in step S04, the converter gas and/or the blast furnace gas after the step S03 is deoxidized and refined desulfurized so that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of less than 30mg/Nm3The method comprises the following steps:
s041), desulfurization
Desulfurizing converter and/or blast furnace gas to remove organic sulfur and inorganic sulfur;
s042) mixing
Mixing the converter and/or blast furnace gas desulfurized in the step S041 with deoxygenated gas with the volume fraction of oxygen of 0.001-0.005%, and controlling the volume fraction of oxygen in the mixed gas to be not more than 0.7%;
s043), deoxidation
Deoxidizing the mixed gas mixed in the step S2 to ensure that the volume fraction of oxygen in the deoxidized coal gas is 0.001-0.005%;
s044), blending and fine desulfurization
Shunting the deoxidized coal gas deoxidized in the step S043, mixing a part of deoxidized coal gas with the converter and/or blast furnace gas desulfurized in the step S041 in the step S042, and controlling the volume fraction of oxygen in the mixed coal gas to be not more than 0.7%; and carrying out fine desulfurization on the rest deoxidized coal gas to form purified gas.
Compared with the prior art, the invention has the advantages that:
1. compared with other decarburization technologies, the decarburization method of the coke oven gas and the converter and/or the blast furnace gas improves the reaction rate and the absorption capacity of the solution cost, reduces the regeneration energy consumption of the solution, has the advantages of high absorption rate, large absorption capacity, high purification degree and the like, can be used for removing carbon dioxide and removing sulfides, has wide application and development prospects, and has very important significance for promoting the technical progress and the economic development of the refining industry in China.
2. In the decarbonization method of the coke oven gas and the converter and/or blast furnace gas, the decarbonization of the converter and/or blast furnace gas is creatively completed through two steps of pressure swing adsorption rough decarbonization and MDEA solution fine decarbonization, so that the breakthrough of the decarbonization of the converter and/or blast furnace gas is realized, and the decarbonization method has very important significance for promoting the technical progress and the economic development of the steel-making industry in China.
3. According to the method for decarbonizing the coke oven gas and the converter and/or the blast furnace gas, the content of carbon dioxide in the converter and/or the blast furnace gas is reduced to 5.8-6.2%, particularly 6% through pressure swing adsorption rough decarbonization, if the content of carbon dioxide in the converter and/or the blast furnace gas after rough decarbonization exceeds the range, the load of subsequently using the MDEA solution for decarbonizing the converter and/or the blast furnace gas is greatly increased, the decarbonization cost is greatly increased, industrialization cannot be achieved, if the content of carbon dioxide in the converter and/or the blast furnace gas after rough decarbonization is lower than the range, effective circulation of the MDEA solution cannot be achieved, and the subsequent using of the MDEA solution for decarbonizing the converter and/or the blast furnace gas cannot be started or the converter and/or the blast furnace gas can be operated at low efficiency.
Drawings
FIG. 1 is a flowchart of a method for decarbonizing coke oven gas and converter and/or blast furnace gas according to the present invention.
FIG. 2 is a schematic view of a decarburization apparatus for carrying out a method of decarburizing coke oven gas and converter and/or blast furnace gas according to the present invention.
FIG. 3 is a schematic view of a converter and/or blast furnace gas rough decarburization device in the method for decarburizing coke oven gas and converter and/or blast furnace gas according to the present invention.
FIG. 4 is a flow chart of a coke oven gas oxygen removal and fine desulfurization method in the decarburization method of a coke oven gas and a converter and/or a blast furnace gas according to the present invention.
FIG. 5 is a schematic view of a coke oven gas oxygen removal and fine desulfurization apparatus for carrying out the coke oven gas oxygen removal and fine desulfurization method in the decarburization method of the coke oven gas and the converter and/or the blast furnace gas of the present invention.
Fig. 6 is a schematic structural diagram of a pre-hydrogenation reactor I in the coke oven gas oxygen removal fine desulfurization device in fig. 5.
FIG. 7 is a schematic structural diagram of a primary desulfurization reactor I in the coke oven gas oxygen removal fine desulfurization device in FIG. 5.
FIG. 8 is a flowchart of a converter and/or blast furnace gas oxygen removal and fine desulfurization method in the method for decarbonizing a coke oven gas and a converter and/or a blast furnace gas according to the present invention.
Fig. 9 is a schematic view of a converter and/or a blast furnace gas oxygen removal and fine desulfurization apparatus for carrying out the converter and/or blast furnace gas oxygen removal and fine desulfurization method in the decarburization method of a coke oven gas and a converter and/or a blast furnace gas of the present invention.
FIG. 10 is a schematic structural diagram of a deoxygenation reactor in the converter and/or the blast furnace gas oxygen-removing fine desulfurization unit in FIG. 9.
Detailed Description
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention. Furthermore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
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.
As shown in FIGS. 1 to 10, a method for decarbonizing coke oven gas and converter and/or blast furnace gas, wherein the flow rate of the coke oven gas is 78000 and 80000Nm3H, the pressure is 3.5-4Mpa, and the temperature is 38-42 ℃; the effective components comprise methane 20-25%, hydrogen 55-60%, carbon monoxide 8-12%, oxygen 0.0005-0.0007%, carbon dioxide 2-4%, and tar and dust content not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3(ii) a The flow rate of the converter and/or blast furnace gas is 28000 and 30000Nm3H, the pressure is 0.75-0.85Mpa, and the temperature is 38-42 ℃; in the effective components, the volume fraction of carbon monoxide is 55-65%, the volume fraction of carbon dioxide is 5.8-6.2%, the volume fraction of nitrogen is 28-32%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%; the content of phosphine is 1-5PPM, and the total sulfur content is not higher than 0.1mg/Nm3。
The decarbonization device for the coke oven gas and the converter and/or the blast furnace gas decarbonizes the coke oven gas and the converter and/or the blast furnace gas, so that the flow rate of the decarbonized coke oven gas is 78000-3H, the pressure is 3.5-4Mpa, and the temperature is 38-42 ℃; the effective components comprise methane 20-25%, hydrogen 57-62%, carbon monoxide 8-12%, oxygen 0.0005-0.0007%, carbon dioxide 0.0015-0.0019%, and tar and dust not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3(ii) a The flow rate of the converter and/or blast furnace gas after decarburization is 27000-28500Nm3H, the pressure is 0.7-0.8Mpa, and the temperature is 38-42 ℃; in the effective components, the volume fraction of carbon monoxide is 60-70%, the volume fraction of carbon dioxide is 0.0015-0.0019%, the volume fraction of nitrogen is 31-33%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%; the content of phosphine is 1-5PPM, and the total sulfur content is not higher than 0.1mg/Nm3。
The decarbonization device of the coke oven gas and the converter and/or the blast furnace gas comprises a coke oven gas filter 101, a coke oven gas tower top filter 102, a rich liquor filter 104, a coke oven gas absorption tower 111, a regeneration tower 112, a coke oven gas cooler 121, a lean and rich liquor heat exchanger 122, a regeneration tower top cooler 123, a reboiler 124, a lean liquor cooler 125, a coke oven gas separator 131, a flash tank 132, a lean liquor buffer tank 133, a regeneration tower top gas-liquid separator 134, a coke oven gas lean liquor pump 141, a recovery pump 142, a converter and/or blast furnace gas filter 151, a converter and/or blast furnace gas tower top filter 152, a converter and/or blast furnace gas absorption tower 161, a converter and/or blast furnace gas cooler 171, a converter and/or blast furnace gas separator 181 and a converter and/or blast furnace gas lean liquor pump 191; the lean solution buffer tank 133 is provided with a first MDEA lean solution outlet and a second MDEA lean solution outlet; the first MDEA barren solution outlet is communicated with the coke oven gas barren solution pump 141 and the top inlet of the coke oven gas absorption tower 111 in sequence; an outlet of the coke oven gas filter 101 is communicated with a bottom inlet of the coke oven gas absorption tower 111; the gas outlet at the top of the coke oven gas absorption tower 111 is sequentially communicated with a gas inlet of a coke oven gas cooler 121 and a gas inlet of a coke oven gas separator 131, the liquid outlet at the bottom of the coke oven gas absorption tower 111 is communicated with an inlet of a flash tank 132, the gas outlet of the coke oven gas separator 131 is communicated with the inlet of a coke oven gas overhead filter 102, the gas outlet of the coke oven gas overhead filter 102 is communicated with the outside, the impurity discharge port of the coke oven gas overhead filter 102 is communicated with the liquid inlet of the coke oven gas separator 131, and the liquid outlet of the coke oven gas separator 131 is communicated with the inlet of the flash tank 132; the second MDEA lean solution outlet is communicated with a converter and/or blast furnace gas lean solution pump 191 and a top inlet of a converter and/or blast furnace gas absorption tower 161 in sequence; the outlet of the converter and/or blast furnace gas filter 151 is communicated with the bottom inlet of the converter and/or blast furnace gas absorption tower 161; the gas outlet at the top of the converter and/or blast furnace gas absorption tower 161 is communicated with the gas inlets of the converter and/or blast furnace gas cooler 171 and the converter and/or blast furnace gas separator 181 in turn, the liquid outlet at the bottom of the converter and/or blast furnace gas absorption tower 161 is communicated with the inlet of the flash tank 132, the gas outlet of the converter and/or blast furnace gas-coal separator 181 is communicated with the inlet of the converter and/or blast furnace gas overhead filter 152, the gas outlet of the converter and/or blast furnace gas top filter 152 is in communication with the outside, the impurity discharge outlet of the converter and/or blast furnace gas top filter 152 is communicated with the liquid inlet of the converter and/or blast furnace gas-coal separator 181, the liquid outlet of the converter and/or blast furnace gas-coal separator 181 is communicated with the inlet of the flash tank 132; a top gas outlet of the flash tank 132 is communicated with the outside, and a liquid outlet at the bottom of the flash tank 132 is communicated with a liquid inlet at the top of the regeneration tower 112, the lean-rich liquid heat exchanger 122 and the rich liquid filter 104 in sequence; a steam inlet of the reboiler 124 is communicated with an external steam source, a steam outlet of the reboiler 124 is communicated with a steam inlet at the bottom of the regeneration tower 112, a gas outlet at the top of the regeneration tower 112 is sequentially communicated with inlets of a regeneration tower top cooler 123 and a regeneration tower top gas-liquid separator 134, a gas outlet of the regeneration tower top gas-liquid separator 134 is communicated with the outside, and a liquid outlet of the regeneration tower top gas-liquid separator 134 is sequentially communicated with inlets of a recovery pump 142 and a flash tank 132; a liquid outlet at the bottom of the regeneration tower 112 is communicated with a liquid inlet of the reboiler 124, and a solution outlet of the reboiler 124 is sequentially communicated with the lean-rich liquid heat exchanger 122, the lean liquid cooler 125 and the first MDEA lean liquid inlet of the lean liquid buffer tank 133.
Preferably, a coke oven gas barren solution filtering and supplying path is arranged in parallel on a coke oven gas barren solution supplying path which is communicated with the coke oven gas barren solution pump 141 and the top inlets of the coke oven gas absorption tower 111, and a coke oven gas barren solution filter 103 is arranged on the coke oven gas barren solution filtering and supplying path.
Preferably, a converter and/or blast furnace gas lean solution filtering and supplying line is provided in parallel on a converter and/or blast furnace gas lean solution supplying line communicating the converter and/or blast furnace gas lean solution pump 191 and the top inlet of the converter and/or blast furnace gas absorption tower 161, and the converter and/or blast furnace gas lean solution filtering and supplying line is provided with a converter and/or blast furnace gas aerosol filter 153.
Preferably, the coke oven gas cooler 121, the coke oven gas separator 131 and the coke oven gas tower top filter 102 are arranged at the top of the coke oven gas absorption tower 111; the converter and/or blast furnace gas cooler 171, the converter and/or blast furnace gas separator 181 and the converter and/or blast furnace gas top filter 152 are disposed on the top of the converter and/or blast furnace gas absorption tower 161.
Preferably, the regeneration overhead cooler 123 and the regeneration overhead gas-liquid separator 134 are disposed at the top of the regeneration column 112.
Preferably, the MDEA barren solution discharged from the first MDEA barren solution outlet of the barren solution buffer tank 133 is pressurized by the coke oven gas barren solution pump 141 and then divided into two paths, and one path is filtered by the coke oven gas solution filter 103 to remove impurities and then joins the other path to enter the coke oven gas absorption tower 111; the MDEA barren liquor from the second MDEA barren liquor outlet of the barren liquor buffer tank 133 is boosted by a converter and/or blast furnace gas barren liquor pump 191 and then divided into two paths, and one path is mixed with the other path to enter the converter and/or blast furnace gas absorption tower after impurities are filtered by a converter and/or blast furnace gas liquor filter 153. By arranging the MDEA barren solution filtering path, the quality of the MDEA barren solution is improved, the impurities of the MDEA barren solution are removed on line, and the efficiency is improved.
Preferably, in order to ensure the water balance of the system and facilitate the preparation and recovery of the solution, the device is provided with an underground storage tank and a solution storage tank. Completing the preparation of the solution through circulation between the underground storage tank and the solution storage tank at the initial stage of driving, and storing part of the solution in the underground storage tank and the solution storage tank for later use; the underground storage tank recovers the drained liquid of the decarburization system during starting and replenishes the solution to the system through a submerged pump so as to ensure the water balance of the system. In order to avoid the oxidation of the solution, nitrogen is introduced into the underground storage tank and the solution storage tank to form a nitrogen seal. Further preferably, in order to prevent the solution from foaming and quickly defoaming after foaming, a defoaming agent storage tank is provided, the defoaming agent stored in the storage tank can quickly enter the lean solution or the rich solution by gravity flow through static pressure difference or in a pressure driving mode, and the driving pressure is provided by nitrogen after decompression. Further preferably, the low-pressure steam required by the reboiler is supplied from the outside, and the steam condensate from the reboiler enters the low-pressure steam separator and returns to the outside.
The decarbonization method of the coke oven gas and the converter and/or blast furnace gas comprises the following steps:
the decarburization method comprises the following steps:
s1), filtering and removing impurities from the coke oven gas and the converter and/or blast furnace gas, and pressurizing MDEA barren solution
The primarily purified coke oven gas and the converter and/or blast furnace gas pass through a coke oven gas filter 101 and a converter and/or blast furnace gas filter 151 respectively to remove mechanical impurities and free liquid, MDEA barren solution discharged from a first MDEA barren solution outlet and a second MDEA barren solution outlet of a barren solution buffer tank 133 passes through a coke oven gas barren solution pump 141 and a converter and/or blast furnace gas barren solution pump 191 respectively to be boosted to 4-5Mpa, preferably 4.5Mpa, and the temperature of the MDEA barren solution is 50 ℃.
S2)、CO2Separation of
The coke oven gas from the step S1 enters from the bottom inlet of the coke oven gas absorption tower 111, the pressurized MDEA barren solution enters from the top inlet of the coke oven gas absorption tower 111, the coke oven gas passes through the coke oven gas absorption tower 111 from bottom to top and flows reversely and exchanges mass and heat with the pressurized MDEA barren solution from top to bottom on the surface of the filler in the coke oven gas absorption tower 111, and CO in the coke oven gas flows reversely and exchanges mass and heat with the filler surface in the coke oven gas absorption tower 1112The pressurized MDEA barren solution is absorbed into a liquid phase, and the unabsorbed components flow out from a gas outlet at the top of a coke oven gas absorption tower 111 along with the coke oven gas to absorb CO2The MDEA rich liquid flows out from a liquid outlet at the bottom of the coke oven gas absorption tower 111. Wherein CO is not absorbed2The activated MDEA solution becomes MDEA barren solution, and the activated MDEA solution is called MDEA rich solution after absorbing acid gas.
The converter and/or the blast furnace gas after the step S1 enters from the bottom inlet of the converter and/or the blast furnace gas absorption tower 161, the pressurized MDEA lean solution enters from the top inlet of the converter and/or the blast furnace gas absorption tower 161, the converter and/or the blast furnace gas passes through the converter and/or the blast furnace gas absorption tower 161 from bottom to top and flows against the top-down pressurized MDEA lean solution on the surface of the packing in the converter and/or the blast furnace gas absorption tower 161, the mass transfer and heat exchange are performed, and the CO in the converter and/or the blast furnace gas flows in the reverse direction2The pressurized MDEA barren solution is absorbed into liquid phase, and the unabsorbed components are mixed with converter and/or blast furnace coalThe gas flows out from a gas outlet at the top of the converter and/or blast furnace gas absorption tower 161 to absorb CO2The MDEA rich liquor is discharged from a liquid outlet at the bottom of the converter and/or blast furnace gas absorption tower 161.
S3), purifying coke oven gas and converter and/or blast furnace gas
S31), cooling the gas subjected to the step S2 and the converter and/or the blast furnace gas to 40 ℃ through a coke oven gas cooler 121 and the converter and/or the blast furnace gas cooler 161 respectively.
S32), the coke oven gas and the converter and/or the blast furnace gas which pass through the step S31 pass through a coke oven gas-gas separator 131 and a converter and/or a blast furnace gas-gas separator 181 respectively to complete gas-liquid separation.
S33), the coke oven gas and the converter and/or the blast furnace gas which pass through the step S32 respectively flow out from gas outlets at the tops of the coke oven gas separator 131 and the converter and/or the blast furnace gas separator 181 and respectively enter a coke oven gas tower top filter 102 at the top of the coke oven gas absorption tower 111 and a converter and/or a blast furnace gas tower top filter 152 at the top of the converter and/or the blast furnace gas absorption tower to separate mechanical impurities and free liquid, and decarburization of the coke oven gas and the converter and/or the blast furnace gas is completed. The flow rate of the coke oven gas after decarburization is 78000 and 80000Nm3H, the pressure is 3.5-4Mpa, and the temperature is 38-42 ℃; the effective components comprise methane 20-25%, hydrogen 57-62%, carbon monoxide 8-12%, oxygen 0.0005-0.0007%, carbon dioxide 0.0015-0.0019%, and tar and dust not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3. The flow rate of the converter and/or blast furnace gas after decarburization is 27000-28500Nm3H, the pressure is 0.7-0.8Mpa, and the temperature is 38-42 ℃; in the effective components, the volume fraction of carbon monoxide is 60-70%, the volume fraction of carbon dioxide is 0.0015-0.0019%, the volume fraction of nitrogen is 31-33%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%; the content of phosphine is 1-5PPM, and the total sulfur content is not higher than 0.1mg/Nm3。
S4), MDEA barren liquor circulation regeneration
S41), the liquid separated in step S32, and the mechanical impurities and free liquid separated in step S33 are mixed, and at the same time, the MDEA rich solution in step S2 is depressurized to 0.5Mpa through a pressure regulating valve.
S42), the liquid mixture of liquid and mechanical impurities and free liquid in step S41, and the depressurized MDEA rich liquid are all sent to the flash drum 132 for flashing.
S43), the gas flashed off due to depressurization in the flash tank 132 flows out from the top gas outlet of the flash tank 132, and is subjected to pressure control by a regulating valve and then is released by a release system; preferably, to ensure that the flash tank 132 pressure is stable and to avoid oxidation of the solution, nitrogen is introduced into the flash tank 132 to form a nitrogen seal. Liquid flowing out of a liquid outlet at the bottom of the flash tank 132 is filtered by a rich liquid filter 104 to remove mechanical impurities to form MDEA rich liquid, and the MDEA rich liquid and the MDEA lean liquid are heated to 98 ℃ through a lean rich liquid heat exchanger 122 and then enter the top of the regeneration tower 122.
S44) and the regeneration tower 122 completes the regeneration of the activated MDEA solution by adopting a positive pressure stripping mode, the specific process is that MDEA rich solution enters from a liquid inlet at the top of the regeneration tower 122, stripping steam enters from a steam inlet at the bottom of the regeneration tower 122, the MDEA rich solution passes through the regeneration tower 112 from top to bottom, the counter flow of the stripping steam from bottom to top is carried out on the surface of a filler in the regeneration tower 112, sufficient mass transfer and heat transfer are carried out, acid gas in the MDEA rich solution is largely resolved into a gas phase and flows out from a gas outlet at the top of the regeneration tower 112 along with the stripping steam, the resolved MDEA solution flows out from a liquid outlet at the bottom of the regeneration tower 112, and the primary resolution of the acid gas of the MDEA rich solution is completed.
S45), the MDEA solution obtained in the step S44 enters a reboiler 124 through a reboiler liquid inlet to be heated, acid gas in the MDEA rich solution is desorbed by steam in the reboiler, secondary desorption of the acid gas in the MDEA rich solution is completed, and an MDEA lean solution is formed; steam enters the regeneration tower 112 from a steam outlet at the top of the reboiler 124 to be used as stripping steam, gas flowing out from a gas outlet at the top of the regeneration tower 112 is cooled to 40 ℃ through a regeneration tower top cooler 123 at the top of the regeneration tower 112 and then enters a regeneration tower top gas-liquid separator 134 at the top of the regeneration tower 112 to be subjected to gas-liquid separation, the separated gas flows out from a gas outlet at the top of the regeneration tower top gas-liquid separator 134 to be discharged locally, the separated liquid flows out from a liquid outlet at the bottom of the regeneration tower top gas-liquid separator 134 to be pressurized to 0.55Mpa through a recovery pump 142 and then enters a flash drum 132 to be flashed. Preferably, to ensure the pressure in the regeneration column 112 is stable and to avoid oxidation of the solution, nitrogen is introduced into the top gas-liquid separator 134 of the regeneration column to form a nitrogen seal.
S46), the MDEA lean solution formed in step S45 is cooled by heat exchange with the rich solution through the lean-rich solution heat exchanger 122, and then cooled to room temperature through the lean solution cooler 125, and then enters the lean solution buffer tank 133.
Preferably, before step S1, the converter and/or blast furnace gas is subjected to coarse decarburization and phosphine removal by a pressure swing adsorption coarse decarburization device in a pressure swing adsorption mode, so that the volume fraction of carbon dioxide in the converter and/or blast furnace gas subjected to pressure swing adsorption is 5.8-6.2%, and the content of phosphine is 1-5PPM, wherein the flow rate of the converter and/or blast furnace gas before coarse decarburization and phosphine removal is 28000-30000 Nm-3H, the pressure is 0.8-0.85Mpa, and the temperature is 38-42 ℃; the effective components comprise carbon monoxide 45-60% by volume, carbon dioxide 20-26% by volume, nitrogen 20-28% by volume, hydrogen 1-4% by volume and oxygen 0.001-0.005% by volume; the content of phosphine is 100-250mg/kg, and the total sulfur content is not higher than 0.1mg/Nm3。
The pressure swing adsorption coarse decarburization device comprises a gas-liquid separator 11, an adsorption tower set, a purified gas buffer tank 13, 2 pressure equalizing tanks 14 connected in parallel, a water ring vacuum pump 15, a gas supply path, a vacuum pumping path, a purified gas buffer path, a pressure equalizing path and corresponding valve sets; the adsorption tower group comprises 8 adsorption towers 12 connected in parallel; one end of the gas supply path and one end of the vacuum pumping path are both communicated with the bottom of each adsorption tower 12, and one end of the purified gas buffer path and one end of the uniform pressure path are both communicated with the top of each adsorption tower 12; the gas outlet of the gas-liquid separator 11 is communicated with the other end of the gas supply path, and the liquid outlet is communicated with the liquid recovery device; the water ring vacuum pump 15 is communicated with the other end of the vacuumizing path; the inlet of the purified gas buffer tank 13 is communicated with the other end of the purified gas buffer circuit, and the outlet is communicated with the MDEA solution adsorption fine decarburization device; each pressure equalizing tank 14 is communicated with the other end of the pressure equalizing roller. Preferably, the adsorption tower 12 is a composite bed adsorption tower mixed with a conventional adsorbent and a carbon dioxide adsorbent, a special adsorbent for removing heavy hydrocarbons, phosphine and macromolecular impurities is arranged at the lower part of the adsorption tower, and a carbon dioxide adsorbent is arranged at the upper part of the adsorption tower. Further preferably, the carbon dioxide adsorbent is a zeolite type molecular sieve. The long-term stable operation of the carbon dioxide adsorbent on the upper part of the adsorption tower is ensured by the arrangement of the composite bed layer.
The converter and/or blast furnace gas coarse decarburization and phosphine removal specifically comprises the following steps:
s051), gas-liquid separation of the converter and/or blast furnace gas is completed by the gas-liquid separator 11, the separated liquid is recovered by the liquid recovery device, and the separated converter and/or blast furnace gas enters the absorption tower group.
S052) and the adsorption tower group comprises 8 adsorption towers which are connected in parallel, the adsorption towers are used for adsorption in a two-tower adsorption mode, when in adsorption, the converter and/or blast furnace gas which passes through the step S051 enters the adsorption tower 12 from an inlet at the lower part of the adsorption tower 12, the converter and/or blast furnace gas passes through the adsorption bed from bottom to top, impurity components are selectively adsorbed by the adsorbent, and in the adsorption period, H in the converter and/or blast furnace gas is adsorbed by the adsorbent2、N2、CO、CH4The weakly adsorbed components firstly pass through the adsorption bed from bottom to top and flow out from the upper part of the adsorption tower, the decarbonized purified gas is sent to an MDEA solution adsorption fine decarbonization device, and CO in the raw material gas2Phosphine and other impurity components with stronger adsorptivity than CO are adsorbed, and the adsorbed impurities are used as CO in the adsorption tower2When the concentration reaches a preset value, preferably 98%, the adsorption towers are automatically switched, the adsorption tower which works previously is depressurized and enters a depressurization regeneration state, and the adsorption tower which is regenerated enters an adsorption state.
The regeneration of the adsorption tower adopts a five-time pressure-equalizing evacuation process, and specifically comprises the following steps:
s0521), first-stage pressure equalization reduction (1D, for short, all reduction)
And after the adsorption is finished, stopping the adsorption tower from entering the converter and/or blast furnace gas, and connecting the adsorption tower with the adsorption tower which finishes the two uniform lifting steps through an outlet end to perform first pressure equalization.
S0522), 2 nd level pressure balance drop (2D, two average drop for short)
After the equalization reduction is completed, the outlet end of the adsorption tower is connected with the equalization tank 14 to perform the second equalization reduction of pressure.
S0523), 3 rd level pressure balance drop (3D, three drop for short)
After the second average pressure drop is finished, the outlet end of the adsorption tower is connected with the inlet end of the adsorption tower which finishes the average lifting step to perform third pressure drop.
S0524), 4 th level pressure balance drop (4D, four drop for short)
And after the third uniform pressure reduction is finished, the outlet end of the adsorption tower is connected with the inlet end of the adsorption tower which finishes the uniform pressure reduction step for the fourth time.
S0525), 5 th level pressure balance drop (5D, five drop for short)
And after the fourth step of pressure equalization, connecting the outlet end of the adsorption tower with the inlet end of the adsorption bed which finishes the step of pressure equalization to perform the fifth pressure equalization.
S0526), reverse pressure relief (D, reverse for short)
After the fourth step of reducing, the adsorbent in the adsorption tower is saturated by impurities, residual gas in the bed is discharged from the inlet end in a forward direction through a reverse pressure reduction step, the pressure of the adsorption tower is reduced to be close to the atmospheric pressure, and preferably, the pressure of the adsorption tower is reduced to 0.02 MPa.
S0527), evacuation (V)
And (3) continuously reducing the pressure of the bed layer of the adsorption tower by adopting a desorption mode of vacuumizing by a water ring vacuum pump 15, so that the impurity components adsorbed by the adsorbent are further desorbed, and the adsorbent achieves the aim of complete desorption and regeneration.
S0528), pressure equalization rising from fifth level to first level (5 ~ 1R, five-one uniform rising for short)
And connecting the adsorption tower with the pressurized adsorption tower at an outlet end to perform fifth-time pressure equalization, and recovering effective gas CO components in a dead space of a bed layer in the adsorption tower for the first-fifth times while pressurizing until the pressure is balanced.
S0529), final boost (FR, Final boost for short)
Finally, partial adsorption waste gas produced in the adsorption step of other adsorption towers is utilized to pressurize the adsorption towers to a working pressure value, preferably 0.82 MPa.
The flows of 2-tower adsorption, 5-time pressure equalization, 1-time reverse discharge and 2-time vacuum pumping of the 8 parallel adsorption towers are shown in the following table:
preferably, before step S1, the coke oven gas is primarily purified by using a coke oven gas primary purification device, and the flow rate of the coke oven gas before primary purification is 80000 and 85000Nm3H, the pressure is 0.004-0.006Mpa, and the temperature is 18-22 ℃; the effective components comprise methane 20-25% by volume, hydrogen 60-65% by volume, carbon monoxide 8-12% by volume, oxygen 0.5-0.9% by volume, carbon dioxide 2-4% by volume, and tar and dust 0.14-0.16g/Nm3The content of hydrogen sulfide is 50-150mg/Nm3The content of other sulfides is 150-160mg/Nm3。
The coke oven gas primary purification device comprises a dust removal and tar removal device, a compressor, a desulfurization device, a TSA adsorption device and a compressor which are sequentially connected; preferably, the dust removal and tar removal device is an electrical tar precipitator, a compressor between the dust removal and tar removal device and the desulfurization device is a screw compressor, the desulfurization device is a desulfurization device using iron oxide as a desulfurizing agent, and the compressor between the TSA adsorption device and the oxygen removal fine desulfurization device is a centrifugal compressor.
The primary purification of the coke oven gas comprises the following steps:
s01), dedusting and detarring
Dedusting and detarring the coke oven gas by using a dedusting and detarring device, preferably an electric tar precipitator, so that the total amount of dust and tar in the coke oven gas is not higher than 3mg/Nm3。
S02), compression
The coke oven gas after the step S01 is compressed to 0.58-0.62MPa by using a compressor, preferably a screw compressor, because the coke oven gas after the step S01 still contains tar, the tar in the coke oven gas can cause the damage of the compressor by using other types of compressors, and the occurrence of the above situation can be avoided by using the screw compressor.
S03), crude desulfurization
The coke oven gas after the step S02 is roughly desulfurized by using a desulfurizer, preferably a desulfurizer using iron oxide as a desulfurizing agent, to thereby desulfurize H in the coke oven gas2S content not higher than 1mg/Nm3。
S04), removing impurities
Removing impurities from the coke oven gas in the step S03 by using a TSA adsorption device to ensure that the content of the impurities in the coke oven gas is not higher than 0.1mg/Nm3(ii) a The impurities are one or more of arsenic, tar, dust, naphthalene, benzene, hydrocyanic acid and ammonia.
S05), secondary compression
The coke oven gas after the step S04 is compressed by a compressor, preferably a centrifugal compressor, to 4-4.2Mpa, preferably 4Mpa, to improve the pressure of the coke oven gas in the subsequent processes, such as when the subsequent processes include oxygen-removing fine desulfurization and cryogenic separation, which helps to improve the effect and efficiency of the oxygen-removing fine desulfurization and cryogenic separation.
S06), oxygen-removing fine desulfurization
And (4) carrying out oxygen removal and fine desulfurization on the coke oven gas subjected to the step S05 by using a coke oven gas oxygen removal fine desulfurization device, so that the total sulfur content in the coke oven gas is not higher than 0.1PPM and the oxygen content is not higher than 1 PPM.
The device comprises a first heat exchanger 610, a pre-hydrogenation reaction device 100, a first-stage hydrogenation reactor 200, a first-stage desulfurization reaction device 300, a second heat exchanger 620, a second-stage hydrogenation reactor 400, a second-stage fine desulfurization reaction device 500, a third heat exchanger 630 and a branch pipeline 700 which are sequentially communicated through a pipeline; the pre-hydrogenation reaction device 100 comprises a pre-hydrogenation reactor I110 and a pre-hydrogenation reactor II 120 which are connected in parallel and have the same structure; the primary desulfurization reaction device 300 comprises a primary desulfurization reactor I310, a primary desulfurization reactor II 320 and a primary desulfurization reactor III 330 which are connected in parallel and have the same structure; the second-stage fine desulfurization reaction device 500 comprises two-stage desulfurization reactors I51 which are connected in parallel and have the same structure0 and a secondary desulfurization reactor II 520; the structure of the pre-hydrogenation reactor I110, the structure of the pre-hydrogenation reactor II 120, the structure of the primary hydrogenation reactor 200 and the structure of the secondary hydrogenation reactor 400 are the same; the first-stage desulfurization reactor I310, the first-stage desulfurization reactor II 320, the first-stage desulfurization reactor III 330, the second-stage desulfurization reactor I510 and the second-stage desulfurization reactor II 520 are identical in structure, two ends of the branch pipeline 700 are respectively communicated with a pipeline communicated with the first-stage hydrogenation reactor 200 and the first-stage desulfurization reactor 300 and a pipeline communicated with the second-stage hydrogenation reactor 400 and the second-stage fine desulfurization reactor 500, a part of coke oven gas subjected to first-stage hydroconversion is introduced into the coke oven gas before second-stage hydrogenation through the branch pipeline 700 and mixed through the branch pipeline 700, and the total sulfur of the coke oven gas before second-stage hydrogenation is controlled to be 10-15mg/m3So as to maintain the dynamic sulfur balance of the second-stage hydrogenation catalyst and ensure the high-efficiency hydrogenation conversion activity of the second-stage hydrogenation catalyst.
Preferably, the pre-hydrogenation reactor I110 comprises a hydrogenation reactor shell 101, a hydrogenation reactor gas inlet 102, a hydrogenation reactor gas outlet 103, a hydrogenation reactor lower catalyst discharge opening 104-1, a hydrogenation reactor upper catalyst discharge opening 104-2, a hydrogenation reactor lower hydrogenation agent layer 105-1, a hydrogenation reactor upper hydrogenation agent layer 105-2, a hydrogenation reactor first grid plate 106-1, a hydrogenation reactor second grid plate 106-2, a hydrogenation reactor first wire mesh layer 107-1, a hydrogenation reactor second wire mesh layer 107-2, a hydrogenation reactor third wire mesh layer 107-3, a hydrogenation reactor fourth wire mesh layer 107-4, a hydrogenation reactor first ceramic ball transition layer 108-1, a hydrogenation reactor second ceramic ball transition layer 108-2 and a hydrogenation reactor third ceramic ball transition layer 108-3, a fourth porcelain ball transition layer 108-4 of the hydrogenation reactor, a fifth porcelain ball transition layer 108-5 of the hydrogenation reactor, a sixth porcelain ball transition layer 108-6 of the hydrogenation reactor, a seventh porcelain ball transition layer 108-7 of the hydrogenation reactor, an eighth porcelain ball transition layer 108-8 of the hydrogenation reactor, a lower manhole 109-1 of the hydrogenation reactor and an upper manhole 109-2 of the hydrogenation reactor. The hydrogenation reactor shell 101 comprises an upper end enclosure, a cylindrical main body and a lower end enclosure which are fixedly connected in sequence; the gas inlet 102 of the hydrogenation reactor is arranged on the outer surface of the lower end socket and is communicated with the inner cavity of the lower end socket, the gas outlet 103 of the hydrogenation reactor is arranged on the outer surface of the upper end socket and is communicated with the inner cavity of the upper end socket, and a first grid plate 106-1 of the hydrogenation reactor, a first wire mesh layer 107-1 of the hydrogenation reactor, a second wire mesh layer 107-2 of the hydrogenation reactor, a second grid plate 106-2 of the hydrogenation reactor, a third wire mesh layer 107-3 of the hydrogenation reactor and a fourth wire mesh layer 107-4 of the hydrogenation reactor are fixedly connected in the cylindrical main body from bottom to top in sequence; the first porcelain ball transition layer 108-1 of the hydrogenation reactor and the second porcelain ball transition layer 108-2 of the hydrogenation reactor are sequentially arranged from bottom to top, the first porcelain ball transition layer 108-1 of the hydrogenation reactor is arranged on the first wire mesh layer 107-1 of the hydrogenation reactor, and the lower hydrogenation agent layer 105-1 of the hydrogenation reactor is arranged between the second porcelain ball transition layer 108-2 of the hydrogenation reactor and the second wire mesh layer 107-2 of the hydrogenation reactor; the third ceramic ball transition layer 108-3 of the hydrogenation reactor and the fourth ceramic ball transition layer 108-4 of the hydrogenation reactor are sequentially arranged from bottom to top, and the third ceramic ball transition layer 108-3 of the hydrogenation reactor is arranged on the second wire mesh layer 107-2 of the hydrogenation reactor; the fifth ceramic ball transition layer 108-5 of the hydrogenation reactor and the sixth ceramic ball transition layer 108-6 of the hydrogenation reactor are sequentially arranged from bottom to top, the fifth ceramic ball transition layer 108-5 of the hydrogenation reactor is arranged on the third wire mesh layer 107-3 of the hydrogenation reactor, and the upper hydrogenation agent layer 105-2 of the hydrogenation reactor is arranged between the sixth ceramic ball transition layer 108-6 of the hydrogenation reactor and the fourth wire mesh layer 107-4 of the hydrogenation reactor; the seventh ceramic ball transition layer 108-7 of the hydrogenation reactor and the eighth ceramic ball transition layer 108-8 of the hydrogenation reactor are sequentially arranged from bottom to top, and the seventh ceramic ball transition layer 108-7 of the hydrogenation reactor is arranged on the fourth wire mesh layer 107-4 of the hydrogenation reactor; the lower catalyst discharge opening 104-1 of the hydrogenation reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with the lower hydrogenation agent layer 105-1 of the hydrogenation reactor; the upper catalyst discharge opening 104-2 of the hydrogenation reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with the upper hydrogenation agent layer 105-2 of the hydrogenation reactor; the hydrogenation agent is loaded and unloaded through a lower catalyst discharge opening 104-1 of the hydrogenation reactor and an upper catalyst discharge opening 104-2 of the hydrogenation reactor respectively; the lower manhole 109-1 of the hydrogenation reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with the space between the fourth ceramic ball transition layer 108-4 of the hydrogenation reactor in the cylindrical main body and the second grid plate 106-2 of the hydrogenation reactor; the upper manhole 109-2 of the hydrogenation reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with the space between the eighth ceramic ball transition layer 108-8 of the hydrogenation reactor in the cylindrical main body and the upper end enclosure, and the ceramic balls are loaded and unloaded through the lower manhole 109-1 of the hydrogenation reactor and the upper manhole 109-2 of the hydrogenation reactor respectively. When a hydrogenation agent bed is too high, the gas in the reactor is unevenly distributed, and after the hydrogenation agent bed is divided into a plurality of beds, the gas can be further uniformly distributed through the adjustment of the grid plate and the wire mesh, so that the utilization rate of the hydrogenation agent in the reactor is improved, and the service cycle of the hydrogenation agent is prolonged. Therefore, the hydrogenation agent layer of the hydrogenation reactor of the present application may be provided as a plurality of layers, and herein, preferably two layers.
Preferably, the first wire mesh layer 107-1, the second wire mesh layer 107-2, the third wire mesh layer 107-3 and the fourth wire mesh layer 107-4 of the hydrogenation reactor are two wire meshes, and the two wire meshes play a role in supporting a ceramic ball transition layer of the hydrogenation reactor on one hand and realize uniform distribution of gas on the other hand.
The working principle of the hydrogenation reactor is that gas enters from a gas inlet 102 at the bottom of the reactor, and then uniformly enters a first grid plate 106-1 of the hydrogenation reactor, a first silk screen layer 107-1 of the hydrogenation reactor, a first ceramic ball transition layer 108-1 and a second ceramic ball transition layer 108-2 of the hydrogenation reactor, and then uniformly enters a lower hydrogenation agent layer 105-1 of the hydrogenation reactor, and after the gas and a hydrogenation agent are subjected to physical and chemical reactions in the lower hydrogenation agent layer 105-1 of the hydrogenation reactor, the gas sequentially passes through a second silk screen layer 107-2 of the hydrogenation reactor, a third ceramic ball transition layer 108-3 of the hydrogenation reactor, a fourth ceramic ball transition layer 108-4 of the hydrogenation reactor, a second grid plate 106-2 of the hydrogenation reactor, a third silk screen layer 107-3 of the hydrogenation reactor, a fifth ceramic ball transition layer 108-5 of the hydrogenation reactor and a sixth ceramic ball transition layer 108-6 of the hydrogenation reactor, and then more uniformly enters an upper hydrogenation agent layer 105 of And 2, carrying out a physical and chemical reaction with a hydrogenation agent, and discharging the reacted gas from a gas outlet 103 of the hydrogenation reactor through a fourth wire mesh layer 107-4 of the hydrogenation reactor, a seventh ceramic ball transition layer 108-7 of the hydrogenation reactor and an eighth ceramic ball transition layer 108-8 of the hydrogenation reactor.
Preferably, the first-stage desulfurization reactor I310 comprises a desulfurization reactor shell 301, a desulfurization reactor gas inlet 302, a desulfurization reactor gas outlet 303, a desulfurization reactor lower catalyst discharge opening 304-1, a desulfurization reactor upper catalyst discharge opening 304-2, a desulfurization reactor lower desulfurizer layer 305-1, a desulfurization reactor upper desulfurizer layer 305-2, a desulfurization reactor first grid plate 306-1, a desulfurization reactor second grid plate 306-2, a desulfurization reactor first wire mesh layer 307-1, a desulfurization reactor second wire mesh layer 307-2, a desulfurization reactor third wire mesh layer 307-3, a desulfurization reactor fourth wire mesh layer 307-4, a desulfurization reactor first ceramic ball transition layer 308-1, a desulfurization reactor second ceramic ball transition layer 308-2, a desulfurization reactor third ceramic ball transition layer 308-3, a fourth porcelain ball transition layer 308-4 of the desulfurization reactor, a fifth porcelain ball transition layer 308-5 of the desulfurization reactor, a sixth porcelain ball transition layer 308-6 of the desulfurization reactor, a seventh porcelain ball transition layer 308-7 of the desulfurization reactor, an eighth porcelain ball transition layer 308-8 of the desulfurization reactor, a lower manhole 309-1 of the desulfurization reactor and an upper manhole 309-2 of the desulfurization reactor. The desulfurization reactor shell 301 comprises an upper end enclosure, a cylindrical main body and a lower end enclosure which are fixedly connected in sequence; the gas inlet 302 of the desulfurization reactor is arranged on the outer surface of the lower end socket and is communicated with the inner cavity of the lower end socket, the gas outlet 303 of the desulfurization reactor is arranged on the outer surface of the upper end socket and is communicated with the inner cavity of the upper end socket, and a first grid plate 306-1 of the desulfurization reactor, a first wire mesh layer 307-1 of the desulfurization reactor, a second wire mesh layer 307-2 of the desulfurization reactor, a second grid plate 306-2 of the desulfurization reactor, a third wire mesh layer 307-3 of the desulfurization reactor and a fourth wire mesh layer 307-4 of the desulfurization reactor are fixedly connected in the cylindrical main body from bottom to top in sequence; the desulfurization reactor first ceramic ball transition layer 308-1 and the desulfurization reactor second ceramic ball transition layer 308-2 are sequentially arranged from bottom to top, the desulfurization reactor first ceramic ball transition layer 308-1 is arranged on the desulfurization reactor first wire mesh layer 307-1, and the desulfurization reactor lower desulfurizer layer 305-1 is arranged between the desulfurization reactor second ceramic ball transition layer 308-2 and the desulfurization reactor second wire mesh layer 307-2; the third ceramic ball transition layer 308-3 of the desulfurization reactor and the fourth ceramic ball transition layer 308-4 of the desulfurization reactor are sequentially arranged from bottom to top, and the third ceramic ball transition layer 308-3 of the desulfurization reactor is arranged on the second wire mesh layer 307-2 of the desulfurization reactor; the fifth ceramic ball transition layer 308-5 of the desulfurization reactor and the sixth ceramic ball transition layer 308-6 of the desulfurization reactor are sequentially arranged from bottom to top, the fifth ceramic ball transition layer 308-5 of the desulfurization reactor is arranged on the third wire mesh layer 307-3 of the desulfurization reactor, and the upper desulfurizer layer 305-2 of the desulfurization reactor is arranged between the sixth ceramic ball transition layer 308-6 of the desulfurization reactor and the fourth wire mesh layer 307-4 of the desulfurization reactor; the seventh ceramic ball transition layer 308-7 of the desulfurization reactor and the eighth ceramic ball transition layer 308-8 of the desulfurization reactor are sequentially arranged from bottom to top, and the seventh ceramic ball transition layer 308-7 of the desulfurization reactor is arranged on the fourth wire mesh layer 307-4 of the desulfurization reactor; the lower catalyst discharge opening 304-1 of the desulfurization reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with the lower desulfurizing agent layer 305-1 of the desulfurization reactor; the upper catalyst discharge opening 304-2 of the desulfurization reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with an upper desulfurizer layer 305-2 of the desulfurization reactor; the desulfurizer is loaded and unloaded through a lower catalyst discharge opening 304-1 of the desulfurization reactor and an upper catalyst discharge opening 304-2 of the desulfurization reactor respectively; the lower manhole 309-1 of the desulfurization reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with a space between the fourth ceramic ball transition layer 308-4 of the desulfurization reactor in the cylindrical main body and the second grid plate 306-2 of the desulfurization reactor; the upper manhole 309-2 of the desulfurization reactor is fixedly connected with the outer surface of the cylindrical main body and is communicated with the space between the eighth porcelain ball transition layer 308-8 of the desulfurization reactor in the cylindrical main body and the upper end socket, and porcelain balls are loaded and unloaded through the lower manhole 309-1 of the desulfurization reactor and the upper manhole 309-2 of the desulfurization reactor respectively. When a desulfurizer bed layer is too high, the gas in the reactor is unevenly distributed, and after the desulfurizer bed layer is divided into a plurality of bed layers, the gas can be further uniformly distributed through the adjustment of the grid plate and the silk screen, so that the utilization rate of the desulfurizer in the reactor is improved, and the service cycle of the desulfurizer is prolonged. Therefore, the desulfurization reactor desulfurization agent layer of the present application may be provided in multiple layers, and herein, two layers are preferred.
Preferably, the first wire mesh layer 307-1, the second wire mesh layer 307-2, the third wire mesh layer 307-3 and the fourth wire mesh layer 307-4 of the desulfurization reactor are two wire meshes, and the two wire meshes play a role in supporting a ceramic ball transition layer of the desulfurization reactor and realize uniform distribution of gas.
The working principle of the desulfurization reactor is that gas enters from a gas inlet 302 at the bottom of the reactor, and then uniformly enters a first grid plate 306-1 of the desulfurization reactor, a first wire mesh layer 307-1 of the desulfurization reactor, a first ceramic ball transition layer 308-1 and a second ceramic ball transition layer 308-2 of the desulfurization reactor, and then uniformly enters a lower desulfurizer layer 305-1 of the desulfurization reactor, and after the gas and a desulfurizer undergo a physical and chemical reaction, the gas sequentially passes through a second wire mesh layer 307-2 of the desulfurization reactor, a third ceramic ball transition layer 308-3 of the desulfurization reactor, a fourth ceramic ball transition layer 308-4 of the desulfurization reactor, a second grid plate 306-2 of the desulfurization reactor, a third wire mesh layer 307-3 of the desulfurization reactor, a fifth ceramic ball transition layer 308-5 of the desulfurization reactor and a sixth ceramic ball transition layer 308-6 of the desulfurization reactor, and then more uniformly enters an upper desulfurizer 305-6 of the desulfurization reactor And-2, performing a physical and chemical reaction with a desulfurizer, and discharging the gas after the reaction through a fourth wire mesh layer 307-4 of the desulfurization reactor, a seventh ceramic ball transition layer 308-7 of the desulfurization reactor and an eighth ceramic ball transition layer 308-8 of the desulfurization reactor from a gas outlet 303 of the desulfurization reactor.
Preferably, the heights of the second porcelain ball transition layer 108-2 of the hydrogenation reactor, the third porcelain ball transition layer 108-3 of the hydrogenation reactor, the sixth porcelain ball transition layer 108-6 of the hydrogenation reactor, the seventh porcelain ball transition layer 108-7 of the hydrogenation reactor, the second porcelain ball transition layer 308-2 of the desulfurization reactor, the third porcelain ball transition layer 308-3 of the desulfurization reactor, the sixth porcelain ball transition layer 308-6 of the desulfurization reactor and the seventh porcelain ball transition layer 308-7 of the desulfurization reactor are 100mm, the diameter of the adopted porcelain ball is 6mm, the first porcelain ball transition layer 108-1 of the hydrogenation reactor, the fourth porcelain ball transition layer 108-4 of the hydrogenation reactor, the fifth porcelain ball transition layer 108-5 of the hydrogenation reactor, the eighth porcelain ball transition layer 108-8 of the hydrogenation reactor and the first porcelain ball transition layer 308-1 of the desulfurization reactor, the layer heights of the fourth porcelain ball transition layer 308-4 of the desulfurization reactor, the fifth porcelain ball transition layer 308-5 of the desulfurization reactor and the eighth porcelain ball transition layer 308-8 of the desulfurization reactor are 100-200mm, and the diameter of the adopted porcelain ball is 13mm or 25 mm; the ceramic balls of each layer contacting the hydrogenation agent or the catalyst are set to be small-diameter ceramic balls, so that the gas is further uniformly distributed, and the reaction efficiency and the utilization rate of the hydrogenation agent or the catalyst are further improved.
The method for removing oxygen and fine sulfur comprises the following steps:
s1), heat exchange and temperature rise
The heat exchange of the compressed coke oven gas is carried out by using a first heat exchanger 610, and the temperature is raised to 180-300 ℃;
s2), pre-hydroconversion and primary hydroconversion
Performing pre-hydrogenation conversion and primary hydrogenation conversion on the coke oven gas subjected to heat exchange and temperature rise sequentially through a pre-hydrogenation reaction device 100 and a primary hydrogenation reactor 200, converting organic sulfur in the coke oven gas subjected to heat exchange and temperature rise into hydrogen sulfide, removing oxygen in the coke oven gas subjected to heat exchange and temperature rise by hydrogenation, performing hydrogenation saturation on unsaturated hydrocarbons in the coke oven gas subjected to heat exchange and temperature rise, and removing impurities in the coke oven gas subjected to heat exchange and temperature rise; the organic sulfur is COS and CS2、CH3SSCH3One or more of methyl mercaptan; the impurities are one or more of arsenic, tar, dust, benzene, naphthalene, ammonia and hydrocyanic acid.
S3), primary desulfurization
And (4) performing primary desulfurization on the coke oven gas subjected to the step S2 through a primary desulfurization reaction device 300 to remove inorganic sulfur and hydrogen chloride. Preferably, the primary desulfurization reaction device 300 is a medium-temperature desulfurization tank, and removes inorganic sulfur and hydrogen chloride in the coke oven gas after the primary hydrogenation; the inorganic sulfur is hydrogen sulfide.
S4), secondary heat exchange and temperature rise
The coke oven gas passing through S3 is heated to 280 ℃ and 340 ℃ through heat exchange by a second heat exchanger 620.
S5), secondary hydroconversion
Performing secondary hydrogenation reaction on the coke oven gas subjected to the S4 through a secondary hydrogenation reactor 400, deeply hydrogenating and converting organic sulfur, unsaturated hydrocarbon and oxygen remained in the coke oven gas subjected to the S4, namely converting the organic sulfur in the coke oven gas subjected to secondary heat exchange and temperature rise into hydrogen sulfide, hydrogenating and removing the oxygen in the coke oven gas subjected to secondary heat exchange and temperature rise, and hydrogenating and saturating the unsaturated hydrocarbon in the coke oven gas subjected to secondary heat exchange and temperature rise.
S6), secondary fine desulfurization
And (3) performing secondary fine desulfurization on the coke oven gas subjected to secondary hydroconversion through a secondary fine desulfurization reaction device 500, controlling the total sulfur removal in the gas to be not higher than 0.1PPM, and heating to the temperature required by the subsequent process through a third heat exchanger 630.
Preferably, a part of coke oven gas after primary hydrogenation conversion is introduced into the coke oven gas before secondary hydrogenation through a branch pipeline 700 and mixed, and the total sulfur of the coke oven gas before secondary hydrogenation is controlled to be 10-15mg/m3Preferably 12mg/m3So as to maintain the dynamic sulfur balance of the second-stage hydrogenation catalyst and ensure the high-efficiency hydrogenation conversion activity of the second-stage hydrogenation catalyst.
Preferably, before the coarse decarbonization and the dehydrophosphorization of the converter and/or blast furnace gas by adopting the pressure swing adsorption method, the converter and/or blast furnace gas is primarily purified by using the converter and/or blast furnace gas primary purification device, and the flow rate of the converter and/or blast furnace gas before primary purification is 28000-3H, the pressure is 0.003 to 0.005Mpa, and the temperature is 18 to 22 ℃; in the effective components, the volume fraction of carbon monoxide is 40-60%, the volume fraction of carbon dioxide is 20-26%, the volume fraction of nitrogen is 20-28%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.6-1%; the content of phosphine is 100-250mg/kg, and the content of tar and dust is 0.01-0.02g/Nm3The content of sulfide is 16-18mg/Nm3。
The converter and/or blast furnace gas primary purification device comprises a dust removal and tar removal device, a compressor, a TSA adsorption device and an oxygen removal and fine desulfurization device which are connected in sequence; preferably, the dust removal and tar removal device is an electrical tar precipitator, the compressor is a reciprocating compressor, and the TSA adsorption device is a temperature swing carbon adsorption device.
The primary purification of the converter and/or blast furnace gas comprises the following steps:
s01), dedusting and detarring
Use of dust-removing and tar-removing device, excellenceThe electricity selecting tar precipitator removes dust and tar from the converter and/or blast furnace gas to ensure that the total amount of dust and tar in the converter and/or blast furnace gas is not higher than 3mg/Nm3。
S02), compression
The converter and/or blast furnace gas that has passed through step S01 is compressed to 0.95-1Mpa using a compressor, preferably a reciprocating compressor.
S03), removing impurities
Removing impurities from the converter and/or blast furnace gas of step S02 using a TSA adsorption device, preferably a temperature swing carbon adsorption device, such that the impurities content in the converter and/or blast furnace gas is not higher than 0.1mg/Nm3. The impurities are tar and/or dust.
S04), oxygen-removing fine desulfurization
Using an oxygen-removing fine desulfurization device to remove oxygen and fine desulfurize the converter and/or blast furnace gas subjected to the step S03 so that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3The volume fraction of oxygen is 0.001-0.005%.
The oxygen-removing fine desulfurization device comprises a converter gas heat exchanger 301, a start-up heater 302, a circulating gas water cooler 303, a purified gas water cooler 304, a hydrolysis desulfurization start-up heater 305, a hydrolysis desulfurization tower, a fine desulfurization tower, a deoxygenation reactor 350, a converter and/or blast furnace gas circulating compressor 360 and a circulating gas liquid separation tank 370, wherein the hydrolysis desulfurization tower comprises a first hydrolysis desulfurization tower 310 and a second hydrolysis desulfurization tower 320 which have the same structure, the first hydrolysis desulfurization tower 310 and the second hydrolysis desulfurization tower 320 can be arranged in series or in parallel, the normal production is a series flow, when the catalyst is replaced, a parallel operation is adopted, the fine desulfurization tower includes a first fine desulfurization tower 330 and a first fine desulfurization tower 340 having the same structure, the first fine desulfurization tower 330 and the first fine desulfurization tower 340 are arranged in parallel, one is opened and the other is prepared, and fine desulfurization agents are filled in the towers to remove residual mercaptan and dimethyl disulfide in gas.
The converter and/or blast furnace gas holder is sequentially communicated with a converter gas heat exchanger 301, a hydrolysis desulfurization tower and a deoxygenation reactor 350, wherein the deoxygenation reactor 350 comprises a shell 351, an upper sealing head 352-1, a lower sealing head 352-2, a plurality of heat exchange tubes 353, a gas distributing cylinder 354, a manhole pipe opening 355, a catalyst self-discharging opening 356, a gas inlet 357, a gas outlet 358 and a pressure release valve 359; the shell 351 is connected with the upper seal head 352-1 and the lower seal head 352-2 to form a pressed shell; the plurality of heat exchange tubes 353 are arranged in the shell 351 and fixedly connected with the gas cylinder 354, the gas cylinder 354 is fixedly connected with the inside of the lower sealing head 352-2, the gas inlet 357, the gas outlet 358 and the catalyst self-discharging port 356 are respectively and fixedly connected with the outer surface of the lower sealing head 352-2, the gas inlet 357 is communicated with the inlet of the gas cylinder 354, the outlet of the gas cylinder 354 is communicated with the plurality of heat exchange tubes 353, the gas outlet 358 and the catalyst self-discharging port 356 are communicated with the inside of the lower sealing head 352-2, and the manhole pipe orifice 355 and the pressure relief valve 359 are respectively and fixedly connected with the outer surface of the upper sealing head 352-1 and communicated with the inside of the upper sealing head 352. The deoxygenation catalyst is loaded from a manhole pipe opening 355 of an upper sealing head 352-1 at the top of the deoxygenation reactor 350, is arranged among a plurality of heat exchange pipes 353 and is discharged from a catalyst self-discharging opening 356 of a lower sealing head 352-2 at the bottom of the deoxygenation reactor 350, and further preferably, the number of the catalyst self-discharging openings 356 is 2, and the catalyst self-discharging openings are arranged at two sides of the lower sealing head 352-2. Further preferably, the operating pressure of the deoxygenation reactor 350 is 0.95-1.05Mpa, preferably 1Mpa, the operating temperature is 50-160 ℃, preferably 56 ℃, the particle size of the packed catalyst particles is phi 3-4mm, the inner diameter of the shell 351 is 3700mm, and the overall height of the deoxygenation reactor 350 is 8000 mm. The outlet of the deoxidation reactor 350 is provided with two branches, one branch is communicated with a pipeline communicated with the outlet of the hydrolysis desulfurization tower and the inlet of the deoxidation reactor 350, and a circulating gas water cooler 303, a circulating gas liquid separation tank 370 and a converter and/or blast furnace gas circulating compressor 360 are sequentially arranged on the branch in the direction from the outlet of the deoxidation reactor 350 to the pipeline communicated with the outlet of the hydrolysis desulfurization tower and the inlet of the deoxidation reactor 350; the other branch is communicated with the converter gas heat exchanger 301, the purified gas water cooler 304 and the inlet of the fine desulfurization tower in sequence; a start-up branch is arranged on a pipeline for communicating the inlet of the hydrolysis desulfurization tower with a converter and/or a blast furnace gas holder, the hydrolysis desulfurization start-up heater 305 is arranged on the start-up branch, a hydrolysis desulfurization start-up branch is arranged on a pipeline for communicating the outlet of the hydrolysis desulfurization tower with the inlet of the deoxidation reactor 350, and the start-up heater 302 is arranged on the hydrolysis desulfurization start-up branch.
The oxygen-removing fine desulfurization comprises the following steps:
s041), desulfurization
The converter and/or blast furnace gas is subjected to heat exchange with deoxidized gas with the volume fraction of oxygen being not more than 0.7% through a converter gas heat exchanger 301, the temperature is raised to 55-65 ℃, and then the converter and/or blast furnace gas enters a hydrolysis desulfurization tower to remove organic sulfur and inorganic sulfur, wherein the specific process is that the converter and/or blast furnace gas is subjected to organic sulfur hydrolysis catalyst in the hydrolysis desulfurization tower to hydrolyze COS in the converter and/or blast furnace gas to convert COS in the converter and/or blast furnace gas into H2S, then entering a fine desulfurizing agent bed layer of a hydrolysis desulfurizing tower to remove H in gas2S and other sulfides including one or more of dimethyl sulfide, methyl mercaptan and thiophene. The desulfurization treatment is carried out before the deoxidation of the converter and/or blast furnace gas, so that the problem that the deoxidization catalyst fails due to the reaction of sulfides in the converter and/or blast furnace gas and the deoxidization catalyst in the deoxidization reactor is avoided. Before the converter and/or blast furnace gas is desulfurized, the converter and/or blast furnace gas is subjected to heat exchange and temperature rise, so that the desulfurization effect of the converter and/or blast furnace gas is improved.
S042) mixing
And (3) mixing the converter and/or blast furnace gas desulfurized in the step S041 with the deoxidation circulating gas with the volume fraction of oxygen of 0.001-0.005%, and controlling the volume fraction of the oxygen in the mixed gas to be not more than 0.7%.
S043), deoxidation
And (3) deoxidizing the mixed gas mixed in the step S042, wherein the volume fraction of oxygen in the deoxidized coal gas is 0.001-0.005%.
The deoxidation process specifically comprises the steps that the mixed coal gas mixed in the step S042 enters the gas distributor 354 from the gas inlet 357 of the lower end enclosure 352-2 at the bottom of the deoxidation reactor 350 and is distributed to the plurality of heat exchange tubes 353, the mixed coal gas mixed in the step S042 exchanges heat with the deoxidation catalyst between the heat exchange tubes 353 from bottom to top, the mixed coal gas mixed in the step S042 after heat exchange exits the heat exchange tubes 353 and then passes through the deoxidation catalyst between the heat exchange tubes 353 from top to bottom to perform deoxidation reaction, and after the deoxidation reaction, gas is discharged from the gas outlet 358. Preferably, when the deoxygenation reactor 350 exceeds a safe value, the pressure relief valve 359 is automatically opened, and the gas in the deoxygenation reactor 350 is discharged through the pressure relief valve 359. The deoxidation reactor adopts the gas distributor 354 and the uniformly distributed heat exchange tubes, ensures that the mixed gas deoxidation and the deoxidation catalyst after the mixing in the step S042 are uniformly distributed, improves the deoxidation efficiency, ensures the uniform temperature in the whole deoxidation reactor, realizes the self-unloading of the deoxidation catalyst by arranging the catalyst self-unloading opening, and reduces the labor intensity of the unloading of the deoxidation catalyst.
S044), blending and fine desulfurization
The flow of the deoxidized coal gas subjected to deoxidation in the step S043 is divided into two steps, wherein one part of the deoxidized coal gas is cooled to 35-45 ℃ through a circulating gas water cooler 303 and then subjected to gas-liquid separation through a circulating gas liquid separation tank 370, the gas subjected to gas-liquid separation is pressurized to 0.93-0.98Mpa through a converter and/or a blast furnace gas circulating compressor and then is used as the deoxidized circulating coal gas in the step S042 to be mixed with the converter and/or blast furnace gas desulfurized in the step S041, the volume fraction of oxygen in the mixed coal gas is ensured to be not more than 0.7%, and the liquid after gas-liquid separation is recovered; taking the other part of deoxidized coal gas as deoxidized coal gas with the volume fraction of 0.001-0.005% of oxygen in the step S041, performing heat exchange between the deoxidized coal gas and converter and/or blast furnace gas through a converter gas heat exchanger 301, cooling to 130-150 ℃, cooling to 35-45 ℃ through a purified gas water cooler 304, entering a fine desulfurization tower for desulfurization, removing residual mercaptan and dimethyl disulfide in the gas, and forming purified gas, wherein the total sulfur content of the purified gas is not higher than 0.1mg/Nm3。
Preferably, a circulating fan is arranged and is connected in parallel with the converter and/or blast furnace gas circulating compressor 360, the volume fraction of oxygen in the mixed gas after mixing is controlled to be not more than 0.7%, and the temperature of the deoxidized gas after deoxidation in the step S043 is not higher than 160 ℃. Because the converter gas has higher oxygen content and larger oxygen content fluctuation, the circulating fan is arranged to reduce the oxygen content at the inlet and realize the long-term stable operation of the deoxidization catalyst in the deoxidization reactor at lower temperature.
Preferably, when the converter and/or blast furnace gas oxygen removal fine desulfurization is started, before the step S041, the converter and/or blast furnace gas is heated to 55-65 ℃ so as to improve the desulfurization effect of the converter and/or blast furnace gas; before the step S043, heating the mixed gas to 55-65 ℃ to improve the deoxidation effect; and stopping heating the converter and/or blast furnace gas and the mixed gas in normal production.
Preferably, when the converter and/or the blast furnace gas oxygen removal fine desulfurization is started, the mass flow of the converter and/or the blast furnace gas entering the step S041 is controlled not to be greater than the limit value borne by the deoxygenation reactor, and herein, the mass flow of the converter and/or the blast furnace gas is 56791 and 88422kg/h, so as to ensure that when the converter and/or the blast furnace gas oxygen removal fine desulfurization is started, the mass flow of the converter and/or the blast furnace gas entering the step S041 is controlled not to be greater than the limit value borne by the deoxygenation reactor.
Before the converter and/or blast furnace gas oxygen removal fine desulfurization device is started, the oxygen removal catalyst needs to be reduced before being normally used, and the specific process is as follows:
A) and starting the converter and/or blast furnace gas circulating compressor 360 to perform nitrogen circulation, wherein the circulation flow is that the converter and/or blast furnace gas circulating compressor 360 → the converter gas heat exchanger 301 → the hydrolysis desulfurization start heater 305 → the hydrolysis desulfurization tower → the start heater 302 → the deoxidation reactor 350 → the circulating gas water cooler 303 → the circulating gas liquid separation tank 370 and then returns to the converter and/or blast furnace gas circulating compressor 360.
B) And heating the nitrogen to 170-180 ℃ by using a start-up heater 302, finally heating the oxygen-removing catalyst to 170 ℃, keeping the temperature constant, and gradually adding converter and/or blast furnace gas.
Preferably, the hydrolysis desulfurization start-up heater 305 is heated by steam to raise the temperature of the hydrolysis desulfurization tower to 60 ℃ before supplementing the converter and/or blast furnace gas, then the temperature is raised to 180 ℃, the content of CO entering the deoxidation reactor 350 is controlled until the volume fraction of CO is 3-4% and the content of CO at the inlet and outlet is not changed, and the reduction is finished.
C) After reduction, the temperature of the deoxygenation reactor is reduced to 80 ℃, the gas quantity of the raw materials is adjusted, and normal production is started.
When the converter and/or blast furnace gas oxygen removal fine desulfurization device stops, the number of the converter and/or blast furnace gas entering the device is gradually reduced until the converter and/or blast furnace gas entering the device is stopped, the circulating fan is started, the circulating amount is increased, the deoxidation reactor 350 is changed into a circulating flow, and the circulating flow is that the converter and/or blast furnace gas circulating compressor 360 → the converter gas heat exchanger 301 → the hydrolysis desulfurization start heater 305 → the hydrolysis desulfurization tower → the start heater 302 → the deoxidation reactor 350 → the circulating gas water cooler 303 → the circulating gas liquid separation tank 370 returns to the converter and/or blast furnace gas circulating compressor 360, the system pressure is maintained, the temperature of the oxygen removal catalyst is gradually reduced to the normal temperature, and the circulating fan is.
Example 1
A method for decarbonizing coke oven gas and converter and/or blast furnace gas comprises the following steps:
s0), primary purification of coke oven gas and converter and/or blast furnace gas
The flow rate of the coke oven gas before primary purification is 83052Nm3H, the pressure is 0.005Mpa, and the temperature is 20 ℃; the effective components contained methane at 20.8% by volume, hydrogen at 60.31% by volume, carbon monoxide at 8.9% by volume, oxygen at 0.82% by volume, carbon dioxide at 2.58% by volume, and tar and dust at 0.015g/Nm3The content of hydrogen sulfide is 50mg/Nm3The content of other sulfides was 155.2mg/Nm3(ii) a The flow rate of the converter and/or blast furnace gas before the preliminary cleaning is 29000Nm3H, the pressure is 0.005Mpa, and the temperature is 20 ℃; in the effective components, the volume fraction of carbon monoxide was 48%, the volume fraction of carbon dioxide was 24.5%, the volume fraction of nitrogen was 24.37%, the volume fraction of hydrogen was 2%, and the volume fraction of oxygen was 1%; the content of phosphine was 200mg/kg, and the content of tar and dust was 0.015g/Nm3The content of sulfide was 17.7mg/Nm3。
The coke oven gas purification comprises the following steps:
s01), dedusting and detarring
Using an electrical tar precipitator for saidRemoving dust and tar from coke oven gas to make the total amount of dust and tar in the coke oven gas not higher than 3mg/Nm3。
S02), compression
And (4) compressing the coke oven gas subjected to the step S01 to 0.6MPa by using a screw compressor.
S03), crude desulfurization
The coke oven gas after the step S02 is roughly desulfurized by using a desulfurizer which takes ferric oxide as a desulfurizer, so that H in the coke oven gas is removed2S content not higher than 1mg/Nm3。
S04), removing impurities
Removing impurities from the coke oven gas in the step S03 by using a TSA adsorption device to ensure that the content of the impurities in the coke oven gas is not higher than 0.1mg/Nm3(ii) a The impurities are one or more of arsenic, tar, dust, naphthalene, benzene, hydrocyanic acid and ammonia.
S05), secondary compression
And (4) compressing the coke oven gas subjected to the step S04 to 4MPa by using a centrifugal compressor.
S06), oxygen-removing fine desulfurization
S061), heat exchange and temperature rise
The compressed coke oven gas is subjected to heat exchange by using a first heat exchanger 610 and is heated to 250 ℃;
s062), pre-hydroconversion and first hydroconversion
Performing pre-hydrogenation conversion and primary hydrogenation conversion on the coke oven gas subjected to heat exchange and temperature rise sequentially through a pre-hydrogenation reaction device 100 and a primary hydrogenation reactor 200, converting organic sulfur in the coke oven gas subjected to heat exchange and temperature rise into hydrogen sulfide, removing oxygen in the coke oven gas subjected to heat exchange and temperature rise by hydrogenation, performing hydrogenation saturation on unsaturated hydrocarbons in the coke oven gas subjected to heat exchange and temperature rise, and removing impurities in the coke oven gas subjected to heat exchange and temperature rise; the organic sulfur is COS and CS2、CH3SSCH3One or more of methyl mercaptan; the impurities are one or more of arsenic, tar, dust, benzene, naphthalene, ammonia and hydrocyanic acid.
S063), primary desulfurization
And (3) performing primary desulfurization on the coke oven gas subjected to the step S062 by using a primary desulfurization reaction device 300 to remove inorganic sulfur and hydrogen chloride. Preferably, the primary desulfurization reaction device 300 is a medium-temperature desulfurization tank, and removes inorganic sulfur and hydrogen chloride in the coke oven gas after the primary hydrogenation; the inorganic sulfur is hydrogen sulfide.
S064), secondary heat exchange and temperature rise
The coke oven gas after S063 is heated to 320 ℃ through heat exchange of the second heat exchanger 620.
S065), two-stage hydroconversion
Performing secondary hydrogenation reaction on the coke oven gas subjected to the S064 by a secondary hydrogenation reactor 400, deeply hydrogenating and converting organic sulfur, unsaturated hydrocarbon and oxygen remained in the coke oven gas subjected to the S064, namely converting the organic sulfur in the coke oven gas subjected to secondary heat exchange and temperature rise into hydrogen sulfide, hydrogenating and removing the oxygen in the coke oven gas subjected to secondary heat exchange and temperature rise, and hydrogenating and saturating the unsaturated hydrocarbon in the coke oven gas subjected to secondary heat exchange and temperature rise.
S066), secondary fine desulfurization
And (3) performing secondary fine desulfurization on the coke oven gas subjected to secondary hydroconversion through a secondary fine desulfurization reaction device 500, controlling the total sulfur removal in the gas to be not higher than 0.1PPM, and heating to the temperature required by the subsequent process through a third heat exchanger 630.
The flow rate of the coke oven gas after the step S066 is 79161Nm3H, the pressure is 3.8Mpa, and the temperature is 40 ℃; the effective components comprise methane 21.31% by volume, hydrogen 58.46% by volume, carbon monoxide 9.12% by volume, oxygen 0.0006% by volume, carbon dioxide 2.64% by volume, and tar and dust not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3。
The primary purification of the converter and/or blast furnace gas comprises the following steps:
s01), dedusting and detarring
Dedusting and detarring the converter and/or blast furnace gas by using an electric tar precipitator, so that the total amount of dust and tar in the converter and/or blast furnace gas is not higher than 3mg/Nm3。
S02), compression
The converter and/or blast furnace gas having passed through step S01 was compressed to 1Mpa using a reciprocating compressor.
S03), removing impurities
Removing impurities from the converter and/or blast furnace gas in the step S02 by using a temperature swing carbon adsorption device, so that the content of the impurities in the converter and/or blast furnace gas is not higher than 0.1mg/Nm3。
S04), oxygen-removing fine desulfurization
Using an oxygen-removing fine desulfurization device to remove oxygen and fine desulfurize the converter and/or blast furnace gas subjected to the step S03 so that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3The volume fraction of oxygen was 0.003%.
The oxygen-removing fine desulfurization comprises the following steps:
s041), desulfurization
The converter and/or blast furnace gas is subjected to heat exchange with deoxidized gas with the volume fraction of oxygen being not more than 0.7% through a converter gas heat exchanger 301, the temperature is raised to 60 ℃, and then the converter and/or blast furnace gas enters a hydrolysis desulfurizing tower to remove organic sulfur and inorganic sulfur.
S042) mixing
And (3) mixing the converter and/or blast furnace gas desulfurized in the step S041 with the deoxygenation circulating gas with the volume fraction of oxygen of 0.003%, and controlling the volume fraction of the oxygen in the mixed gas to be not more than 0.7%.
S043), deoxidation
The mixed gas mixed in the step S042 is deoxidized so that the volume fraction of oxygen in the deoxidized gas is 0.003%.
S044), blending and fine desulfurization
The flow of the deoxidized coal gas after the deoxidation in the step S043 is divided into two steps, wherein one part of the deoxidized coal gas is cooled to 40 ℃ by a circulating gas water cooler 303 and then is subjected to gas-liquid separation by a circulating gas liquid separation tank 370, the gas after the gas-liquid separation is pressurized to 0.95Mpa by a converter and/or blast furnace gas circulating compressor and is used as the deoxidized circulating coal gas in the step S042 to be mixed with the converter and/or blast furnace gas desulfurized in the step S041, and the volume fraction of oxygen in the mixed coal gas is ensured to be not greater than that in the mixed coal gasAt 0.7%, recovering the liquid after gas-liquid separation; the other part of deoxidized coal gas is used as deoxidized coal gas with the volume fraction of 0.003 percent of oxygen in the step S041, the deoxidized coal gas is subjected to heat exchange with a converter and/or blast furnace gas through a converter gas heat exchanger 301, cooled to 140 ℃, cooled to 40 ℃ through a purified gas water cooler 304, and then enters a fine desulfurization tower for desulfurization, residual mercaptan and dimethyl disulfide in the gas are removed, and purified gas is formed, wherein the total sulfur content of the purified gas is not higher than 0.1mg/Nm3。
The flow rate of the converter and/or blast furnace gas after the primary cleaning is 29000Nm3H, the pressure is 0.82Mpa, and the temperature is 40 ℃; the effective components comprise 48.48% of carbon monoxide by volume, 24.75% of carbon dioxide by volume, 24.62% of nitrogen by volume, 2.02% of hydrogen by volume and 0.003% of oxygen by volume; the content of phosphine is 200mg/kg, and the total sulfur content is not higher than 0.1mg/Nm3。
S1), coarse decarburization of the converter and/or blast furnace gas
And (3) carrying out coarse decarburization and hydrogen phosphide removal on the converter and/or blast furnace gas by using a pressure swing adsorption coarse decarburization device, so that the volume fraction of carbon dioxide of the converter and/or blast furnace gas subjected to pressure swing adsorption is 6%, and the content of hydrogen phosphide is 3 PPM.
The converter and/or blast furnace gas coarse decarburization specifically comprises the following steps:
s11), gas-liquid separation of the converter and/or blast furnace gas is completed through the gas-liquid separator 11, the separated liquid is recovered through the liquid recovery device, and the separated converter and/or blast furnace gas enters the absorption tower group.
S12), the adsorption tower group comprises 8 adsorption towers which are connected in parallel, the adsorption towers adopt the adsorption mode of two towers, when in adsorption, the converter and/or blast furnace gas which passes through the step S11 enters the adsorption tower 12 from the inlet at the lower part of the adsorption tower 12 under the pressure of 0.82Mpa, the converter and/or blast furnace gas passes through the adsorption bed from bottom to top, the impurity components are selectively adsorbed by the adsorbent, and in the adsorption period, H in the converter and/or blast furnace gas2、N2、CO、CH4The weak adsorbate components firstly pass through the adsorption bed from bottom to top and flow out from the upper part of the adsorption tower,the decarbonized purified gas is sent to an MDEA solution adsorption fine decarbonization device, and CO in the raw material gas2Phosphine and other impurity components with adsorption property stronger than that of CO are adsorbed under the pressure of 0.82Mpa, and CO is adsorbed in the adsorption tower2When the concentration reaches 98%, the adsorption towers are automatically switched, the adsorption tower which works previously is depressurized and enters a depressurization regeneration state, and the adsorption tower which is regenerated enters an adsorption state.
After step S1, the flow rate of the converter and/or blast furnace gas is 18147Nm3H, the pressure is 0.8Mpa, and the temperature is 40 ℃; in the effective components, the volume fraction of carbon monoxide was 60.39%, the volume fraction of carbon dioxide was 6%, the volume fraction of nitrogen was 30.97%, the volume fraction of hydrogen was 2.55%, and the volume fraction of oxygen was 0.0038%; the content of phosphine is 3PPM, and the total sulfur content is not higher than 0.1mg/Nm3。
S2), decarburization of the Coke oven gas with converter and/or blast furnace gas
And (3) decarbonizing the primarily purified coke oven gas by using an MDEA solution adsorption decarbonization device, and decarbonizing the converter and/or blast furnace gas subjected to coarse decarbonization, so that the volume fraction of the carbon dioxide of the coke oven gas is 0.0018%, and the volume fraction of the carbon dioxide of the converter and/or blast furnace gas is 0.0017%.
The decarbonization of the coke oven gas and the converter and/or blast furnace gas specifically comprises the following steps:
s21), filtering and removing impurities from converter and/or blast furnace gas, and pressurizing MDEA barren solution
The primarily purified coke oven gas and the converter and/or blast furnace gas subjected to rough decarburization respectively pass through a coke oven gas filter 101 and a converter and/or blast furnace gas filter 151 to remove mechanical impurities and free liquid, MDEA barren solution discharged from a first MDEA barren solution outlet and a second MDEA barren solution outlet of a barren solution buffer tank 133 is respectively pressurized to 4.5Mpa through a coke oven gas barren solution pump 141 and a converter and/or blast furnace gas barren solution pump 191, and the temperature of the MDEA barren solution is 50 ℃.
S22)、CO2Separation of
The coke oven gas after the step S1 enters from the bottom inlet of the coke oven gas absorption tower 111, and the pressurized MDEA is poorThe liquid enters from the top inlet of the coke oven gas absorption tower 111, the coke oven gas passes through the coke oven gas absorption tower 111 from bottom to top and MDEA barren solution pressurized from top to bottom reversely flows on the surface of the filling material in the coke oven gas absorption tower 111, and the mass transfer and heat exchange are carried out, so that CO in the coke oven gas2The pressurized MDEA barren solution is absorbed into a liquid phase, and the unabsorbed components flow out from a gas outlet at the top of a coke oven gas absorption tower 111 along with the coke oven gas to absorb CO2The MDEA rich liquid flows out from a liquid outlet at the bottom of the coke oven gas absorption tower 111. Wherein CO is not absorbed2The activated MDEA solution becomes MDEA barren solution, and the activated MDEA solution is called MDEA rich solution after absorbing acid gas.
The converter and/or the blast furnace gas after the step S1 enters from the bottom inlet of the converter and/or the blast furnace gas absorption tower 161, the pressurized MDEA lean solution enters from the top inlet of the converter and/or the blast furnace gas absorption tower 161, the converter and/or the blast furnace gas passes through the converter and/or the blast furnace gas absorption tower 161 from bottom to top and flows against the top-down pressurized MDEA lean solution on the surface of the packing in the converter and/or the blast furnace gas absorption tower 161, the mass transfer and heat exchange are performed, and the CO in the converter and/or the blast furnace gas flows in the reverse direction2The pressurized MDEA lean solution is absorbed into a liquid phase, and the unabsorbed components flow out from a gas outlet at the top of a converter and/or blast furnace gas absorption tower 161 along with the converter and/or blast furnace gas to absorb CO2The MDEA rich liquor is discharged from a liquid outlet at the bottom of the converter and/or blast furnace gas absorption tower 161.
S23), gas purification
S231) and cooling the gas subjected to the step S22 and the converter and/or the blast furnace gas to 40 ℃ through the coke oven gas cooler 121 and the converter and/or the blast furnace gas cooler 161 respectively.
S232), the coke oven gas and the converter and/or the blast furnace gas which pass through the step S231 pass through a coke oven gas-gas separator 131 and a converter and/or a blast furnace gas-gas separator 181 respectively to complete gas-liquid separation.
S233), the coke oven gas and the converter and/or the blast furnace gas which are processed by the step S232 respectively flow out from gas outlets at the top of the coke oven gas separator 131 and the converter and/or the blast furnace gas separator 181 and respectively enter the top of the coke oven gas absorption tower 111The coke oven gas top filter 102 and the converter and/or blast furnace gas top filter 152 on the top of the converter and/or blast furnace gas absorption tower separate mechanical impurities and free liquid, and decarburization of the coke oven gas and the converter and/or blast furnace gas is completed. The flow rate of the coke oven gas after decarburization is 79113Nm3H, the pressure is 3.75Mpa, and the temperature is 40 ℃; the effective components comprise methane 22.27% by volume, hydrogen 61.1% by volume, carbon monoxide 9.53% by volume, oxygen 0.0006% by volume, carbon dioxide 0.0018% by volume, and tar and dust not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3. The flow rate of the converter and/or blast furnace gas after decarburization is 28147Nm3H, the pressure is 0.75Mpa, and the temperature is 40 ℃; in the effective components, the volume fraction of carbon monoxide is 64.24%, the volume fraction of carbon dioxide is 0.0017%, the volume fraction of nitrogen is 32.95%, the volume fraction of hydrogen is 2.72%, and the volume fraction of oxygen is 0.004%; the content of phosphine is 3PPM, and the total sulfur content is not higher than 0.1mg/Nm3。
S24), MDEA barren liquor circulation regeneration
S241), the liquid separated in step S232, and the mechanical impurities and the free liquid separated in step S233 are mixed, and at the same time, the MDEA rich solution in step S22 is depressurized to 0.5Mpa through a pressure regulating valve.
S242), the liquid mixture of liquid and mechanical impurities and free liquid in step S241 and the depressurized MDEA rich liquid are all sent to the flash drum 132 for flash evaporation.
S243), the gas flashed off due to depressurization in the flash tank 132 flows out from a top gas outlet of the flash tank 132, and is subjected to pressure control by a regulating valve and then is released by a release system; preferably, to ensure that the flash tank 132 pressure is stable and to avoid oxidation of the solution, nitrogen is introduced into the flash tank 132 to form a nitrogen seal. Liquid flowing out of a liquid outlet at the bottom of the flash tank 132 is filtered by a rich liquid filter 104 to remove mechanical impurities to form MDEA rich liquid, and the MDEA rich liquid and the MDEA lean liquid are heated to 98 ℃ through a lean rich liquid heat exchanger 122 and then enter the top of the regeneration tower 122.
S244) and the regeneration tower 122 completes the regeneration of the activated MDEA solution by adopting a positive pressure stripping mode, wherein the specific process is that MDEA rich solution enters from a liquid inlet at the top of the regeneration tower 122, stripping steam enters from a steam inlet at the bottom of the regeneration tower 122, the MDEA rich solution passes through the regeneration tower 112 from top to bottom, the surface of a filler in the regeneration tower 112 reversely flows with the stripping steam from bottom to top to perform sufficient mass and heat transfer, a large amount of acid gas in the MDEA rich solution is analyzed to a gas phase and flows out from a gas outlet at the top of the regeneration tower 112 along with the stripping steam, the analyzed MDEA solution flows out from a liquid outlet at the bottom of the regeneration tower 112, and the primary analysis of the acid gas in the MDEA rich solution is completed.
S245), the MDEA solution obtained in the step S244 enters a reboiler 124 through a reboiler liquid inlet to be heated, the acid gas in the MDEA rich solution is desorbed by steam in the reboiler, secondary desorption of the acid gas in the MDEA rich solution is completed, and an MDEA lean solution is formed; steam enters the regeneration tower 112 from a steam outlet at the top of the reboiler 124 to be used as stripping steam, gas flowing out from a gas outlet at the top of the regeneration tower 112 is cooled to 40 ℃ through a regeneration tower top cooler 123 at the top of the regeneration tower 112 and then enters a regeneration tower top gas-liquid separator 134 at the top of the regeneration tower 112 to be subjected to gas-liquid separation, the separated gas flows out from a gas outlet at the top of the regeneration tower top gas-liquid separator 134 to be discharged locally, the separated liquid flows out from a liquid outlet at the bottom of the regeneration tower top gas-liquid separator 134 to be pressurized to 0.55Mpa through a recovery pump 142 and then enters a flash drum 132 to be flashed. Preferably, to ensure the pressure in the regeneration column 112 is stable and to avoid oxidation of the solution, nitrogen is introduced into the top gas-liquid separator 134 of the regeneration column to form a nitrogen seal.
S246), the MDEA lean solution formed in step S245 is subjected to heat exchange with the rich solution and temperature reduction through the lean-rich solution heat exchanger 122, and then is cooled to room temperature through the lean solution cooler 125, and then enters the lean solution buffer tank 133.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (9)
1. A method for decarbonizing coke oven gas and converter and/or blast furnace gas is characterized by comprising the following steps:
s0), primary purification of coke oven gas and converter and/or blast furnace gas
Coarse decarbonization and phosphine removal are carried out on the gas of the converter and/or the blast furnace in a pressure swing adsorption mode; the volume fraction of carbon dioxide of converter and/or blast furnace gas subjected to pressure swing adsorption is 5.8-6.2%, and the content of phosphine is 1-5 PPM;
s1), filtering and removing impurities from the coke oven gas and the converter and/or blast furnace gas, and pressurizing MDEA barren solution
Respectively filtering the coke oven gas and the converter and/or blast furnace gas, and removing impurities; simultaneously, pressurizing the MDEA solution;
S2)、CO2separation of
Respectively carrying out reverse flow and mass transfer heat exchange on the coke oven gas and the converter and/or the blast furnace gas which are processed by the step S1 and the pressurized MDEA barren solution, and absorbing CO in the coke oven gas and the converter and/or the blast furnace gas by the MDEA barren solution2Forming an MDEA rich solution;
s3), purifying coke oven gas and converter and/or blast furnace gas
S31), separating CO in the step S22Cooling the coke oven gas and the converter and/or blast furnace gas;
s32), respectively carrying out gas-liquid separation on the coke oven gas cooled in the step S31 and converter and/or blast furnace gas;
s33), respectively filtering the coke oven gas and the converter and/or blast furnace gas after gas-liquid separation in the step S32, separating mechanical impurities and free liquid, and finishing decarburization of the coke oven gas and the converter and/or blast furnace gas;
s4), MDEA barren liquor circulation regeneration
S41), respectively mixing the liquid obtained after gas-liquid separation in the step S32 with the mechanical impurities and free liquid obtained in the step S33, and reducing the pressure of the MDEA rich liquid in the step S2;
s42), the mixture of the liquid, the mechanical impurities and the free liquid in the step S41 and the MDEA rich solution after pressure reduction are flashed;
s43), conveying the flashed gas to a diffusing system for diffusing, filtering the flashed liquid to remove mechanical impurities to form MDEA rich liquid, and exchanging heat with MDEA barren liquid formed in the subsequent process to raise the temperature;
s44), carrying out reverse flow and mass transfer heat exchange on the MDEA rich solution subjected to heat exchange in the step S43 and stripping steam, resolving acid gas in the MDEA rich solution through the stripping steam, and completing primary resolution of the acid gas of the MDEA rich solution;
s45), heating the MDEA rich solution subjected to the primary analysis of the acid gas in the step S44, analyzing the acid gas in the MDEA rich solution through steam, and performing secondary analysis on the acid gas of the MDEA rich solution to form an MDEA barren solution; cooling the stripped steam, performing gas-liquid separation, discharging gas after gas-liquid separation into the atmosphere, boosting the pressure of liquid after gas-liquid separation, and flashing together with the liquid, the mechanical impurities, the free liquid mixture and the decompressed MDEA rich solution in the step S41;
s46), cooling the MDEA lean solution formed in step S45 after exchanging heat with the MDEA rich solution in step S43, and forming the MDEA lean solution in step S1.
2. The method of claim 1, wherein:
the method for the coarse decarburization and the removal of phosphine of the gas of the converter and/or the blast furnace by adopting a pressure swing adsorption mode comprises the following steps: the converter and/or blast furnace gas is subjected to gas-liquid separation to remove liquid, and then enters an adsorption tower group, the adsorption tower group comprises 8 adsorption towers which are connected in parallel, when the adsorption tower group is used for adsorption, a pumping-out process of two-tower adsorption and five-time pressure equalization is adopted, each adsorption tower sequentially undergoes the steps of adsorption, one-tower uniform reduction, two-tower uniform reduction, three-tower uniform reduction, four-tower uniform reduction, five-tower uniform reduction, reverse release, pumping-out, five-tower uniform rise, four-tower uniform rise, three-tower uniform rise, two-tower uniform rise, one-tower uniform rise and final rise, purified gas is obtained from the tower top, and decarbonized and decomposed gas is.
3. The method of claim 1, wherein:
pressurizing the MDEA solution, dividing the MDEA solution into 2 paths, removing impurities from one path, mixing the MDEA solution with the other path, and entering step S2.
4. The method of claim 1, wherein:
before step S1, the effective components of the coke oven gas comprise 20-25% of methane by volume, 55-60% of hydrogen by volume, 8-12% of carbon monoxide by volume, 0.0005-0.0007% of oxygen by volume, 2-4% of carbon dioxide by volume, and tar and dust content of not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3(ii) a In the effective components of the converter and/or blast furnace gas, the volume fraction of carbon monoxide is 55-65%, the volume fraction of carbon dioxide is 5.8-6.2%, the volume fraction of nitrogen is 28-32%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%; the content of phosphine is 1-5PPM, and the content of tar and dust is not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3；
After step S33, the effective components of the coke oven gas comprise 20-25% of methane by volume, 57-62% of hydrogen by volume, 8-12% of carbon monoxide by volume, 0.0005-0.0007% of oxygen by volume, 0.0015-0.0019% of carbon dioxide by volume, and tar and dust content not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3(ii) a In the effective components of the converter and/or blast furnace gas, the volume fraction of carbon monoxide is 60-70%, the volume fraction of carbon dioxide is 0.0015-0.0019%, the volume fraction of nitrogen is 31-33%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%; the content of phosphine is 1-5PPM, and the content of tar and dust is not higher than 0.1mg/Nm3Total sulfur content of not more than 0.1mg/Nm3。
5. The method of claim 1, wherein: introducing nitrogen gas for nitrogen sealing in the flash evaporation process and the gas-liquid separation process after cooling the stripping steam respectively.
6. The method of claim 1, wherein:
before the step S1, the coke oven gas is primarily purified by the coke oven gas, and the primary purification of the coke oven gas comprises the following steps:
s01), dedusting and detarring
Dust removal and tar removal are carried out on coke oven gas, so that the total amount of dust and tar in the coke oven gas is not higher than 3mg/Nm3；
S02), compression
Compressing the coke oven gas obtained in the step S01 to 0.58-0.62 Mpa;
s03), crude desulfurization
The coke oven gas after the step S02 is roughly desulfurized to make H in the coke oven gas2S content not higher than 1mg/Nm3；
S04), removing impurities
Removing impurities from the coke oven gas in the step S03 to ensure that the content of the impurities in the coke oven gas is not higher than 0.1mg/Nm3；
S05), secondary compression
Compressing the coke oven gas obtained in the step S04 to 4-4.2 Mpa;
s06), oxygen-removing fine desulfurization
The coke oven gas after the step S05 is deoxidized and refined desulfurized to ensure that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of not more than 1mg/Nm3。
7. The method of claim 2, wherein:
before the converter and/or blast furnace gas is subjected to coarse decarburization and phosphine removal by adopting a pressure swing adsorption mode, the converter and/or blast furnace gas is subjected to primary purification by the converter and/or blast furnace gas, and the primary purification of the converter and/or blast furnace gas comprises the following steps:
s01), dedusting and detarring
Dedusting and detarring the converter and/or blast furnace gas to ensure that the total amount of dust and tar in the converter and/or blast furnace gas is not higher than 3mg/Nm3；
S02), compression
Compressing the converter and/or blast furnace gas from step S01 to 0.95-1 MPa;
s03), removing impurities
Removing impurities from the converter and/or blast furnace gas in the step S02 to ensure that the impurity content in the converter and/or blast furnace gas is not higher than 1mg/Nm3；
S04), oxygen-removing fine desulfurization
The converter gas and/or the blast furnace gas after the step S03 are deoxidized and refined desulfurized to ensure that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of less than 30mg/Nm3。
8. The method of claim 6, wherein:
in step S06, the coke oven gas after the step S05 is deoxidized and refined desulfurized to ensure that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of not more than 1mg/Nm3The method comprises the following steps:
s061), heat exchange and temperature rise
Heating the compressed coke oven gas to 180-300 ℃ through heat exchange;
s062), pre-hydroconversion and first hydroconversion
Performing pre-hydrogenation conversion and primary hydrogenation conversion on the coke oven gas subjected to the step S061 in sequence to convert organic sulfur in the coke oven gas subjected to the step S061 into hydrogen sulfide, removing oxygen by hydrogenation, saturating unsaturated hydrocarbon by hydrogenation, and removing impurities;
s063), primary desulfurization
Performing primary desulfurization on the coke oven gas obtained in the step S062 to remove inorganic sulfur and hydrogen chloride;
s064), secondary heat exchange and temperature rise
Heating the coke oven gas subjected to S063 to 280-340 ℃ through heat exchange;
s065), two-stage hydroconversion
Carrying out secondary hydrogenation reaction on the coke oven gas subjected to S064, and deeply hydrogenating and converting organic sulfur, unsaturated hydrocarbon and oxygen remained in the coke oven gas subjected to S064;
s066), secondary fine desulfurization
And performing secondary fine desulfurization on the coke oven gas subjected to secondary hydroconversion.
9. The method of claim 7, wherein:
in step S04, the converter gas and/or the blast furnace gas after the step S03 is deoxidized and refined desulfurized to ensure that the total sulfur content in the coke oven gas is not higher than 0.1mg/Nm3Oxygen content of less than 30mg/Nm3The method comprises the following steps:
s041), desulfurization
Desulfurizing converter and/or blast furnace gas to remove organic sulfur and inorganic sulfur;
s042) mixing
Mixing the converter and/or blast furnace gas desulfurized in the step S041 with deoxygenated gas with the volume fraction of oxygen of 0.001-0.005%, and controlling the volume fraction of oxygen in the mixed gas to be not more than 0.7%;
s043), deoxidation
Deoxidizing the mixed gas mixed in the step S2 to ensure that the volume fraction of oxygen in the deoxidized coal gas is 0.001-0.005%;
s044), blending and fine desulfurization
Shunting the deoxidized coal gas deoxidized in the step S043, mixing a part of deoxidized coal gas with the converter and/or blast furnace gas desulfurized in the step S041 in the step S042, and controlling the volume fraction of oxygen in the mixed coal gas to be not more than 0.7%; and carrying out fine desulfurization on the rest deoxidized coal gas to form purified gas.
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| CN109609202A (en) * | 2019-01-17 | 2019-04-12 | 武汉禾谷环保有限公司 | A kind of blast furnace gas desulfurizing and purifying method |
| CN110387270B (en) * | 2019-08-09 | 2024-03-01 | 中冶赛迪技术研究中心有限公司 | Dry desulfurization system and method for blast furnace gas |
| CN112574788B (en) * | 2019-09-29 | 2021-12-10 | 中石化南京化工研究院有限公司 | Method for purifying blast furnace gas |
| CN113717758B (en) * | 2021-08-27 | 2024-02-09 | 山东津挚环保科技有限公司 | Desulfurization and decarbonization system for synthesis gas |
| CN114456854A (en) * | 2022-02-13 | 2022-05-10 | 新疆八一钢铁股份有限公司 | Method for removing CO in hydrogen-rich carbon circulating blast furnace gas2Of (2) a |
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