CN116179787A - Blast furnace gas recycling system and method - Google Patents
Blast furnace gas recycling system and method Download PDFInfo
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- CN116179787A CN116179787A CN202111424180.2A CN202111424180A CN116179787A CN 116179787 A CN116179787 A CN 116179787A CN 202111424180 A CN202111424180 A CN 202111424180A CN 116179787 A CN116179787 A CN 116179787A
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000004064 recycling Methods 0.000 title abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 213
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002893 slag Substances 0.000 claims abstract description 72
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 67
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 61
- 239000010959 steel Substances 0.000 claims abstract description 61
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 31
- 230000018044 dehydration Effects 0.000 claims abstract description 30
- 238000010248 power generation Methods 0.000 claims abstract description 29
- 239000003546 flue gas Substances 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 230000001089 mineralizing effect Effects 0.000 claims abstract description 24
- 238000007664 blowing Methods 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 239000000779 smoke Substances 0.000 claims abstract description 19
- 238000000746 purification Methods 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 17
- 238000009628 steelmaking Methods 0.000 claims abstract description 13
- 238000005261 decarburization Methods 0.000 claims abstract description 12
- 239000004566 building material Substances 0.000 claims abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 16
- 238000005262 decarbonization Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003463 adsorbent Substances 0.000 claims description 11
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 claims description 10
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 20
- 239000000571 coke Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/30—Regulating or controlling the blowing
- C21C5/34—Blowing through the bath
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Combustion & Propulsion (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
Abstract
The invention relates to the technical field of metallurgy, in particular to a blast furnace gas recycling system and method. The system comprises: the decarburization unit is used for separating the blast furnace gas to obtain a first gas and a second gas rich in carbon dioxide; a dehydration unit for removing moisture in the first gas; the converter uses the first gas dehydrated by the dehydration unit as bottom blowing steel making to obtain converter tail gas; the power generation unit is used for combusting the tail gas of the converter to generate power so as to obtain smoke; the mineralizing unit is used for mineralizing the steel slag and the flue gas to obtain a building material; and the carbon monoxide purification unit is used for separating and purifying the second gas to obtain a gas rich in carbon monoxide and a mixed gas comprising hydrogen and nitrogen. The system and the method can obviously improve the utilization rate of blast furnace gas and the conversion rate of the mineralization process of the steel slag, and achieve the purposes of energy conservation and emission reduction.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a blast furnace gas recycling system and method.
Background
In the steel smelting process, the waste gas such as the flue gas generated by an iron-making blast furnace, a hot blast furnace, the converter flue gas, the lime roasting flue gas, the steel rolling heating furnace flue gas and the like contains a large amount of CO 2 These gases are emitted into the atmosphere to assist in the greenhouse effect. According to statistics, the carbon dioxide emission in the steel industry is inferior to that in the power generation industry and the petrochemical industry, and has become a third greenhouse gas emission source in China. In particular blast furnace gas produced in iron-making process, wherein the gas is other than CO 2 In addition, contains high concentrations of CO and H 2 Valuable gases are directly used as fuel gas to burn, so that huge waste of resources is caused.
On the other hand, a large amount of steel slag is produced in the blast furnace ironmaking, converter, electric furnace and refining processes, a large-scale treatment method is not currently available, and in the existing technology for fixing carbon dioxide in the steel slag, the conversion rate is low in the mineralization process, namely the carbonation process of the steel slag. The main components of the steel slag comprise alkaline components such as calcium oxide, magnesium oxide and the like besides silicon oxide, ferric oxide and aluminum oxide, and the alkaline components can be mixed with CO under certain conditions 2 Reaction to generate MgCO 2 And CaCO (CaCO) 3 Not only fix CO 2 And the mechanical property of the steel slag as a building material is improved, the energy conservation and emission reduction of the steel industry are realized, and the effect of treating waste by waste is achieved.
Disclosure of Invention
The invention aims to solve the problems of low utilization rate of blast furnace gas and low conversion rate of a steel slag mineralization process in the prior art, and provides a system and a method for recycling the blast furnace gas, which can remarkably improve the utilization rate of the blast furnace gas and the conversion rate of the steel slag mineralization process and achieve the purposes of energy conservation and emission reduction.
In order to achieve the above object, an aspect of the present invention provides a blast furnace gas recycling system, comprising:
the decarburization unit is used for separating the blast furnace gas to obtain a first gas and a second gas rich in carbon dioxide;
a dehydration unit for removing moisture in the first gas;
the converter uses the first gas dehydrated by the dehydration unit as bottom blowing steel making to obtain converter tail gas;
the power generation unit is used for combusting the tail gas of the converter to generate power so as to obtain smoke;
the mineralizing unit is used for mineralizing the steel slag and the flue gas to obtain a building material;
the carbon monoxide purification unit is used for separating and purifying the second gas to obtain a gas rich in carbon monoxide and a mixed gas comprising hydrogen and nitrogen; wherein the carbon monoxide rich gas is recycled back to the blast furnace; the mixed gas comprising hydrogen and nitrogen is sent to a power generation unit for combustion power generation.
The second aspect of the invention provides a blast furnace gas recycling method, which is carried out in the system and comprises the following steps:
1) Decarbonizing the blast furnace gas to obtain a first gas rich in carbon dioxide and a second gas containing carbon monoxide, hydrogen and nitrogen;
2) The first gas is dehydrated and then used as converter bottom blowing, the obtained converter tail gas is used for combustion power generation to generate smoke, and the smoke is used for mineralization reaction of steel slag to obtain a building material;
3) And purifying the second gas to obtain a gas rich in carbon monoxide and a mixed gas of nitrogen and hydrogen, wherein the gas rich in carbon monoxide is recycled to the blast furnace, and the mixed gas of nitrogen and hydrogen is used for combustion power generation.
Through the technical scheme, the invention has the following advantages:
1. according to the system and the method provided by the invention, the carbon dioxide in the blast furnace gas is used as the converter bottom blowing gas to replace expensive argon and nitrogen, and the flue gas generated by the combustion and power generation of the converter tail gas is used for mineralizing the steel slag, so that the steel-making cost and the energy consumption are saved, and the conversion rate of the mineralizing process of the steel slag is improved;
2. by the system and the method provided by the invention, carbon monoxide in the blast furnace gas is returned to the blast furnace to reduce the coke ratio, so that the steelmaking carbon consumption is reduced, and the steelmaking cost is saved;
3. by the system and the method provided by the invention, other gases in the blast furnace gas for removing carbon monoxide and carbon dioxide are used for combustion power generation, so that the energy consumption is saved;
in conclusion, the blast furnace gas is utilized to the maximum extent through the invention, and the aims of saving energy, reducing emission and treating waste with waste are realized in the true sense.
Drawings
Fig. 1 is a schematic diagram of a system configuration of a preferred embodiment of the present invention.
Description of the reference numerals
1-decarbonization unit; 9-steel slag;
2-a first gas; 10-building materials;
a 3-dehydration unit; 11-a second gas;
4-a converter; a 12-carbon monoxide PSA purification unit;
5-converter tail gas; 13-a carbon monoxide rich gas stream;
6-a power generation unit; 14-a mixed gas stream comprising hydrogen and nitrogen.
7-flue gas;
8-mineralization units;
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a blast furnace gas recycling system, which comprises:
the decarburization unit is used for separating the blast furnace gas to obtain a first gas and a second gas rich in carbon dioxide;
a dehydration unit for removing moisture in the first gas;
the converter uses the first gas dehydrated by the dehydration unit as bottom blowing steel making to obtain converter tail gas;
the power generation unit is used for combusting the tail gas of the converter to generate power so as to obtain smoke;
the mineralizing unit is used for mineralizing the steel slag and the flue gas to obtain a building material;
the carbon monoxide purification unit is used for separating and purifying the second gas to obtain a gas rich in carbon monoxide and a mixed gas comprising hydrogen and nitrogen; wherein the carbon monoxide rich gas is recycled back to the blast furnace; the mixed gas comprising hydrogen and nitrogen is used for being sent into a power generation unit to burn and generate power.
In the invention, carbon dioxide in blast furnace gas is used as converter bottom blowing to replace expensive argon and nitrogen, and flue gas generated by the combustion of converter tail gas for mineralizing steel slag is used for saving steel-making cost and energy consumption and improving the conversion rate of the mineralizing process of the steel slag; carbon monoxide in the blast furnace gas is returned to the blast furnace to reduce the coke ratio, reduce the steelmaking carbon consumption and save the steelmaking cost; other gases in the blast furnace gas for removing carbon monoxide and carbon dioxide are used for combustion power generation, so that the energy consumption is saved; the blast furnace gas is utilized to the maximum, and the aims of saving energy, reducing emission and treating waste by waste are realized in the true sense.
According to a preferred embodiment of the invention, the power generation unit comprises at least one of a boiler, a steam turbine, a generator.
The invention provides a blast furnace gas recycling method, which is carried out in the system and comprises the following steps:
1) Decarbonizing the blast furnace gas to obtain a first gas rich in carbon dioxide and a second gas containing carbon monoxide, hydrogen and nitrogen;
2) The first gas is dehydrated and then used as converter bottom blowing, the obtained converter tail gas is used for combustion power generation to generate smoke, and the smoke is used for mineralization reaction of steel slag to obtain a building material;
3) And purifying the second gas to obtain a gas rich in carbon monoxide and a mixed gas of nitrogen and hydrogen, wherein the gas rich in carbon monoxide is recycled to the blast furnace, and the mixed gas of nitrogen and hydrogen is used for combustion power generation.
In the invention, carbon dioxide in blast furnace gas is used as converter bottom blowing to replace expensive argon and nitrogen, and flue gas generated by the combustion of converter tail gas for mineralizing steel slag is used for saving steel-making cost and energy consumption and improving the conversion rate of the mineralizing process of the steel slag; carbon monoxide in the blast furnace gas is returned to the blast furnace to reduce the coke ratio, reduce the steelmaking carbon consumption and save the steelmaking cost; other gases in the blast furnace gas for removing carbon monoxide and carbon dioxide are used for combustion power generation, so that the energy consumption is saved; the blast furnace gas is utilized to the maximum, and the aims of saving energy, reducing emission and treating waste by waste are realized in the true sense.
In the present invention, there is no particular requirement as long as the object of the present invention can be achieved, and the composition of the blast furnace gas, according to a preferred embodiment of the present invention, contains CO:24% -26%, CO 2 ：21％-23％，N 2 ：47％-50％，H 2 ：2％-4％。
In the present invention, as long as the object of the present invention can be achieved, there is no particular requirement for the decarburization conditions, and according to a preferred embodiment of the present invention, the decarburization conditions include: the temperature is 30-50deg.C, and the pressure is 0.8-1.2 MPaA. By adopting the preferable scheme, the energy consumption and the operation cost can be reduced, and the utilization rate of blast furnace gas and the conversion rate of steel slag in subsequent treatment are improved.
In the present invention, the method of separating the blast furnace gas by the decarburization unit may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the method of separating the blast furnace gas by the decarburization unit is selected from at least one of the MDEA method and the NHD method. By adopting the preferable scheme, the solvent loss can be reduced, and the regenerated CO can be improved 2 Purity of the product and minimize CO removal 2 And the influence of other components on the bottom blowing effect of the converter can improve the utilization rate of blast furnace gas and the conversion rate of steel slag in subsequent treatment.
According to a preferred embodiment of the invention, the carbon dioxide content of the first gas is greater than 90%, preferably 94% -96%.
According to a preferred embodiment of the present invention, the content of carbon dioxide in the first gas after dehydration by the dehydration unit is not less than 99.9% and the water content is less than 10ppm. By adopting the preferable scheme, the byproducts generated in the bottom blowing process of the converter by moisture can be reduced to the greatest extent, and the utilization rate of blast furnace gas and the conversion rate of steel slag in subsequent treatment are further improved.
According to a preferred embodiment of the present invention, the second gas comprises, in mole percent: CO:38% -42%, H 2 ：6％～10％，N 2 :48% -54%. By adopting the preferable scheme, the purity and the recovery rate of the CO product can be improved, the recycling is facilitated, and the utilization rate of blast furnace gas is improved.
According to a preferred embodiment of the present invention, the carbon monoxide rich gas has a carbon monoxide content of 50% to 70%. By adopting the preferable scheme, the efficiency of reducing the coke ratio of the CO-rich gas during recycling can be improved, the consumption of coal is reduced, and the utilization rate of blast furnace gas is improved.
According to a preferred embodiment of the invention, the converter tail gas comprises the following components in mole percent: 60% -80% of CO and 15% -20% of CO 2 . By adopting the preferable scheme, the hair can be maximally sent outCO volatilizing 2 As the effect of bottom blowing, the heat value of the converter tail gas is improved, expensive Ar gas is replaced, and the utilization rate of blast furnace gas and the conversion rate of steel slag in subsequent treatment are improved.
According to a preferred embodiment of the invention, the flue gas comprises, in mole percent: 99.9% or more of CO 2 . By adopting the preferable scheme, the CO can be improved 2 The purity is improved, and the mineralization reaction rate and conversion rate of the steel slag are improved.
In the present invention, the steel slag is subjected to grinding and pulverizing treatment before mineralization, and according to a preferred embodiment of the present invention, the grain size of the steel slag is 10 μm to 100 μm. By adopting the preferable scheme, the size of the steel slag can be reduced and the specific surface area of the steel slag and the mineralization reaction conversion rate can be improved as far as possible without greatly increasing the grinding cost.
According to a preferred embodiment of the present invention, the steel slag is at least one selected from the group consisting of converter slag, refining slag and electric slag.
In the invention, as long as the aim of the invention can be achieved, the mass ratio of the steel slag to the smoke in the mineralizing unit is not particularly required, and according to a preferred embodiment of the invention, the mass ratio of the steel slag to the smoke is 5:1-1:1. By adopting the preferable scheme, CO can be achieved 2 The optimal reaction proportion of the active components of the steel slag improves the mineralization reaction rate and the conversion rate.
In the present invention, as long as the object of the present invention can be achieved, in the mineralization unit, the operating conditions may be conventional choices in the art, and according to a preferred embodiment of the present invention, the operating conditions include: the pressure is 1.0-4.0MPaA, and the temperature is 140-200 ℃. By adopting the preferable scheme, the mineralization reaction rate and conversion rate can be improved, the material residence time can be reduced, and the equipment volume can be reduced.
In the present invention, the method for removing moisture from the first gas by the dehydration unit may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the method for removing moisture from the first gas by the dehydration unit is selected from at least one of molecular sieve dehydration, triethylene glycol dehydration, and silica gel dehydration. By adopting the preferable scheme, the operation cost can be reduced, the dehydration efficiency can be improved, and the utilization rate of blast furnace gas and the conversion rate of steel slag in subsequent treatment can be improved.
In the present invention, the method for purifying the second gas by the carbon monoxide purification unit may be a conventional choice in the art, and according to a preferred embodiment, the method for purifying the second gas by the carbon monoxide purification unit is selected from at least one of a PSA method, a copper ammonia absorption method and a membrane separation method, preferably a PSA method.
According to a preferred embodiment of the present invention, the adsorption material used in the PSA method is at least one of Cu (I) -activated carbon adsorbent and Cu (I) -molecular sieve adsorbent. By adopting the preferable scheme, the recovery rate of CO can be improved, the operation cost is reduced, and the utilization rate of blast furnace gas is improved.
According to a preferred embodiment of the present invention, the conditions for the purification include: the pressure was 0.7MPaA-0.9MPaA. By adopting the preferable scheme, the energy consumption and the operation cost in the CO purification process can be reduced as much as possible, and the utilization rate of blast furnace gas can be improved.
The invention provides a blast furnace gas recycling system, as shown in fig. 1, which comprises a decarburization unit 1, a dehydration unit 3, a converter 4, a power generation unit 6 and a mineralization unit 8 which are sequentially connected, and a carbon monoxide PSA purification unit 12 connected with the decarburization unit, wherein the decarburization unit 1 is used for separating blast furnace gas to obtain a first gas 2 rich in carbon dioxide and a second gas 11 containing carbon monoxide, hydrogen and nitrogen, the first gas 2 is sent into the dehydration unit 3 to be dehydrated and then used as bottom blowing of the converter 4, converter tail gas 5 obtained by the converter 4 is sent into the power generation unit 6 to be used for combustion power generation, and generated flue gas 7 is sent into the mineralization unit 8 to be mineralized with steel slag 9 to generate a building material 10; the second gas 11 is introduced into a carbon monoxide PSA purification unit 12 to obtain a gas stream 13 rich in carbon monoxide and a mixed gas stream 14 comprising hydrogen and nitrogen, wherein the gas stream 13 rich in carbon monoxide is recycled to the blast furnace, and the mixed gas stream 14 comprising hydrogen and nitrogen is introduced into the power generation unit 6 for combustion power generation.
The present invention will be described in detail by examples.
Example 1
CO content of blast furnace gas of certain steel mill is 25mol percent and CO 2 Content of 22mol%, N 2 Content of 50mol%, H 2 3mol% of CO is desorbed by decarbonization by MDEA method (pressure is 0.8MPaA, temperature is 30 ℃), the concentration of CO is 95mol% 2 CO after passing through molecular sieve dehydration unit 2 The content is increased to 99.94%, the water content is 10ppm, the converter tail gas is used as converter bottom blowing gas and is sent to a boiler to generate electricity (the generated energy is 4kg tail gas/kWh), and the smoke (the composition is CO) 2 、CO，CO 2 99.90 percent) enters a mineralizing unit to react with a mixture of converter slag and refining slag (the weight ratio of flue gas to steel slag is 1:3) which are ground to 30 mu m at 2.0MPa and 180 ℃, and the conversion rate is 85 percent; the CO content in the tail gas after decarbonization of blast furnace gas is 39mol percent, H 2 Content of 8mol%, N 2 The content of 53mol percent is fed into a carbon monoxide PSA purifying unit, the purifying pressure is 0.7Mpa A, cu (I) -activated carbon adsorbent is adopted for CO purification, the purity of the purified CO is 60 percent, the purified CO is recycled to a blast furnace to reduce the coke ratio, and PSA tail gas is sent to a boiler to generate power for recovering heat.
Example 2
Blast furnace gas CO content of 24mol% and CO of certain steel mill 2 Content of 25mol%, N 2 Content of 47mol%, H 2 After decarbonization by MDEA (pressure 1MPaA, temperature 40 ℃) the CO with concentration of 96mol% was desorbed 2 CO after passing through molecular sieve dehydration unit 2 The content is increased to 99.90 percent, the water content is 5ppm, the converter tail gas is used as the converter bottom blowing gas and is sent to a boiler to generate electricity (the generated energy is 6kg tail gas/kWh), the smoke (the composition is CO) 2 、CO，CO 2 99.93 percent) enters a mineralizing unit to react with a mixture of converter slag and electric furnace slag (the weight ratio of flue gas to steel slag is 1:1) which are ground to 10 mu m at the temperature of 140 ℃ under the pressure of 1.0MPa, and the conversion rate is 88 percent; CO content 38mol% and H in tail gas after decarbonization of blast furnace gas 2 Content of 8mol%, N 2 The mixture with the content of 54mol percent enters a carbon monoxide PSA purifying unit, the purifying pressure is 0.8Mpa A, the Cu (I) -molecular sieve adsorbent is adopted for CO purification, and the purified CO with the purity of 55 percent is recycled to the blast furnaceAnd the coke ratio is reduced, and the PSA tail gas is sent to a boiler to generate power and recycle heat.
Example 3
CO content of blast furnace gas of certain steel mill is 26mol percent and CO 2 Content of 22mol%, N 2 Content of 50mol%, H 2 After decarbonization by MDEA (pressure 0.9MPaA, temperature 50 ℃) at a content of 2mol%, CO with a concentration of 96.3mol% was desorbed 2 CO after passing through molecular sieve dehydration unit 2 The content is increased to 99.96%, the water content is 8ppm, the converter tail gas is used as converter bottom blowing gas and is sent to a boiler to generate electricity (the generated energy is 5kg tail gas/kWh), and the smoke (the composition is CO) 2 、CO，CO 2 99.95 percent) enters a mineralizing unit to react with a mixture of converter slag and refining slag (the weight ratio of flue gas to steel slag is 1:5) which is ground to 50 mu m at the temperature of 190 ℃ under the pressure of 3.0MPa, and the conversion rate is 78 percent; CO content 42mol% and H in tail gas after decarbonizing blast furnace gas 2 Content of 8mol%, N 2 The carbon monoxide with the content of 50mol percent enters a carbon monoxide PSA purifying unit, the purifying pressure is 0.8Mpa A, the Cu (I) -activated carbon adsorbent is adopted for CO purification, the purity of the purified CO is 65 percent, the purified CO is recycled to a blast furnace to reduce the coke ratio, and the PSA tail gas is sent to a boiler to generate power to recycle heat.
Example 4
Blast furnace gas CO content of 24mol% and CO of certain steel mill 2 Content of 23mol%, N 2 Content of 49mol%, H 2 After decarbonization by MDEA (pressure 1.2MPaA, temperature 45 ℃) the CO was desorbed at a concentration of 96.0mol% 2 CO after passing through molecular sieve dehydration unit 2 The content is increased to 99.91 percent, the water content is 3ppm, the converter tail gas is used as the blowing gas of the converter bottom, the converter tail gas is sent to a boiler to generate electricity (the generated energy is 5.5kg tail gas/kWh), and the smoke (the composition is CO) 2 、CO，CO 2 99.96 percent) enters a mineralizing unit to react with a mixture of converter slag and refining slag (the weight ratio of flue gas to steel slag is 1:4) which are ground to 100 mu m at 4.0MPa and 200 ℃, and the conversion rate is 84 percent; the CO content in the tail gas after decarbonization of blast furnace gas is 39mol percent, H 2 Content of 10mol%, N 2 The mixture with the content of 51mol percent enters a carbon monoxide PSA purifying unit, the purifying pressure is 1.0MpaA, and a Cu (I) -molecular sieve adsorbent is adopted for CO purification, so that the purity of the purified CO is improvedAnd (5) recycling 70% of the waste gas to the blast furnace to reduce the coke ratio, and sending the PSA tail gas to a boiler to generate electricity and recycle heat.
Example 5
CO content of blast furnace gas of certain steel mill is 25mol percent and CO 2 Content of 22mol%, N 2 Content of 50mol%, H 2 3mol% of CO is desorbed by decarbonization by MDEA method (pressure is 1.1MPaA, temperature is 42 ℃), the concentration is 94.0mol% 2 CO after passing through molecular sieve dehydration unit 2 The content is increased to 99.92%, the water content is 7ppm, the converter tail gas is used as converter bottom blowing gas, the converter tail gas is sent to a boiler to generate electricity (the generated energy is 4.8kg tail gas/kWh), and the smoke (the composition is CO2, CO and CO) 2 99.91 percent of the mixture enters a mineralizing unit to react with a mixture of converter slag and refining slag (the weight ratio of flue gas to steel slag is 1:3) which are ground to 80 mu m at the temperature of 3.5MPa and 185 ℃, and the conversion rate is 87 percent; CO content 40mol% and H in tail gas after decarbonization of blast furnace gas 2 Content of 10mol%, N 2 The carbon monoxide with the content of 50mol percent enters a carbon monoxide PSA purifying unit, the purifying pressure is 0.95Mpa A, a Cu (I) -molecular sieve adsorbent is adopted for CO purification, the purity of the purified CO is 65 percent, the purified CO is recycled to a blast furnace to reduce the coke ratio, and PSA tail gas is sent to a boiler to generate power to recycle heat.
Example 6
Blast furnace gas of a certain steel plant is 1.0MPaA, the temperature is 35 ℃, the CO content is 26mol percent, and the CO is 2 Content of 21mol%, N 2 Content of 50mol%, H 2 After decarbonization by MDEA (pressure 1.0MPaA, temperature 35 ℃) the CO was desorbed at a concentration of 94.0mol% 2 CO after passing through molecular sieve dehydration unit 2 The content is increased to 99.90 percent, the water content is 6.4ppm, the converter tail gas is used as the converter bottom blowing gas and is sent to a boiler to generate electricity (the generated energy is 5.4kg tail gas/kWh), and the smoke (the compositions are CO2, CO and CO) 2 99.94% of the concentration of the slag enters a slag mineralizing unit to react with a mixture of converter slag and refined slag (the weight ratio of flue gas to steel slag is 1:2) which is ground to 70 mu m at 2.5MPa and 160 ℃, and the conversion rate is 84%; CO content 42mol% and H in tail gas after decarbonization of blast furnace gas 2 Content of 10mol%, N 2 48mol% of the mixture enters a carbon monoxide PSA purifying unit, the purifying pressure is 0.85Mpa A, and Cu (I) -molecular sieve adsorbent is adopted for enteringAnd (3) purifying CO, wherein the purified CO with the purity of 75% is returned to a blast furnace to reduce the coke ratio, and the PSA tail gas is sent to a boiler to generate power and recycle heat.
Example 7
Blast furnace gas CO content of 24mol% and CO of certain steel mill 2 Content of 23mol%, N 2 Content of 50mol%, H 2 3mol% of CO is desorbed by decarbonization with MDEA method (pressure of 0.9MPaA, temperature of 42 ℃), the concentration of CO is 95.0mol% 2 CO after passing through molecular sieve dehydration unit 2 The content is increased to 99.94%, the water content is 5.5ppm, the converter tail gas is used as the converter bottom blowing gas, the converter tail gas is sent to a boiler to generate electricity (the generated energy is 5.9kg tail gas/kWh), and the smoke (the compositions are CO2, CO and CO) 2 99.93 percent of the mixture enters a mineralizing unit to react with a mixture of converter slag and refining slag (the weight ratio of flue gas to steel slag is 3:1) which are ground to 40 mu m at 2.0MPa and 150 ℃, and the conversion rate is 85 percent; the CO content in the tail gas after decarbonization of blast furnace gas is 41mol percent and H is 2 Content of 8mol%, N 2 The content of the carbon monoxide is 51mol%, the carbon monoxide enters a PSA purifying unit, the purifying pressure is 0.75Mpa A, a Cu (I) -activated carbon adsorbent is adopted for CO purification, the purity of the purified CO is 65 percent, the purified CO is recycled to a blast furnace to reduce the coke ratio, and PSA tail gas is sent to a boiler to generate power to recycle heat.
Example 8
The difference from example 1 is that the MDEA process was carried out at a pressure of 0.6MPaA and a temperature of 50℃and the converter tail gas was sent to a boiler for power generation (the power generation amount was 7kg tail gas/kWh), and the flue gas was reacted with the ground steel slag at 1.0MPa and 140℃with a conversion of 72%.
Example 9
The difference from example 1 is that the ratio of flue gas to steel slag is 2:1 and the conversion is 73%.
Comparative example 1
The difference with example 1 is that the blast furnace flue gas is decarbonized by a decarbonizing unit, dried and dehydrated by a molecular sieve and then directly sent into a carbon dioxide mineralizing unit, a converter and a power generating unit are not arranged, and the mineralizing conversion rate of the steel slag is 60%.
According to the embodiment and the comparative example, the invention can obviously improve the utilization rate of blast furnace gas and the conversion rate of the mineralization process of steel slag, and achieve the purposes of energy conservation and emission reduction.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A blast furnace gas recovery system, comprising:
the decarburization unit is used for separating the blast furnace gas to obtain a first gas and a second gas rich in carbon dioxide;
a dehydration unit for removing moisture in the first gas;
the converter uses the first gas dehydrated by the dehydration unit as bottom blowing steel making to obtain converter tail gas;
the power generation unit is used for combusting the tail gas of the converter to generate power so as to obtain smoke;
the mineralizing unit is used for mineralizing the steel slag and the flue gas to obtain a building material;
the carbon monoxide purification unit is used for separating and purifying the second gas to obtain a gas rich in carbon monoxide and a mixed gas comprising hydrogen and nitrogen; wherein the carbon monoxide rich gas is recycled back to the blast furnace; the mixed gas comprising hydrogen and nitrogen is sent to a power generation unit for combustion power generation.
2. A blast furnace gas recovery process, wherein the process is carried out in the system of claim 1, comprising:
1) Decarbonizing the blast furnace gas to obtain a first gas rich in carbon dioxide and a second gas containing carbon monoxide, hydrogen and nitrogen;
2) The first gas is dehydrated and then used as converter bottom blowing, the obtained converter tail gas is used for combustion power generation to generate smoke, and the smoke is used for mineralization reaction of steel slag to obtain a building material;
3) And purifying the second gas to obtain a gas rich in carbon monoxide and a mixed gas of nitrogen and hydrogen, wherein the gas rich in carbon monoxide is recycled to the blast furnace, and the mixed gas of nitrogen and hydrogen is used for combustion power generation.
3. The method of claim 2, wherein the blast furnace gas comprises, in mole percent, CO:24% -26%, CO 2 ：21％-23％，N 2 ：47％-50％，H 2 :2% -4%; and/or
The decarburization conditions include: the temperature is 30-50deg.C, and the pressure is 0.8-1.2 MPaA.
4. A method according to claim 2 or 3, wherein the decarbonization method is selected from at least one of MDEA and NHD.
5. The method according to any one of claims 2 to 4, wherein,
the content of carbon dioxide in the first gas is more than 90%, preferably 94% -96%; and/or
The content of carbon dioxide in the first gas dehydrated by the dehydration unit is not less than 99.9 percent, and the content of water is less than 10ppm.
6. The method according to any one of claims 2 to 5, wherein,
the second gas comprises the following components in mole percent: CO:38% -42%, H 2 ：6％～10％，N 2 :48% -54%; and/or
The carbon monoxide content in the carbon monoxide-rich gas is 50% -70%.
7. The method according to any one of claims 2-6, wherein,
the converter tail gas contains the following components in mole percentA meter, comprising: 60% -80% of CO and 15% -20% of CO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The flue gas comprises the following components in mole percent: 99.9% or more of CO 2 。
8. The method according to any one of claims 2 to 7, wherein the steel slag has a particle size of 10 μm to 100 μm, preferably at least one of converter slag, refining slag and electric slag.
9. The method of any one of claims 2-8, wherein the mass ratio of steel slag to flue gas in the mineralization unit is 5:1-1:1; and/or
The operating conditions include: the pressure is 1.0-4.0MPaA, and the temperature is 140-200 ℃.
10. The method according to any one of claims 2 to 9, wherein the method of removing moisture in the first gas by the dehydration unit is selected from at least one of molecular sieve dehydration, triethylene glycol dehydration, and silica gel dehydration.
11. The method according to any one of claims 2-10, wherein,
the method for purifying the second gas by the carbon monoxide purifying unit is at least one selected from a PSA (pressure swing adsorption) method, a cuprammonium absorption method and a membrane separation method, preferably a PSA method, wherein an adsorption material adopted in the PSA method is at least one of a Cu (I) -activated carbon adsorbent and a Cu (I) -molecular sieve adsorbent; and/or
The conditions for the purification include: the pressure was 0.7MPaA-0.9MPaA.
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