CN108977237A - A kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur - Google Patents
A kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur Download PDFInfo
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- CN108977237A CN108977237A CN201810828279.0A CN201810828279A CN108977237A CN 108977237 A CN108977237 A CN 108977237A CN 201810828279 A CN201810828279 A CN 201810828279A CN 108977237 A CN108977237 A CN 108977237A
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- converter
- blast furnace
- volume fraction
- gas
- furnace gas
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 54
- 239000011593 sulfur Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006392 deoxygenation reaction Methods 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 194
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000001301 oxygen Substances 0.000 claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 57
- 239000003034 coal gas Substances 0.000 claims abstract description 52
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 33
- 230000023556 desulfurization Effects 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 239000000428 dust Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 17
- 229960004424 carbon dioxide Drugs 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000001741 organic sulfur group Chemical group 0.000 claims description 5
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004781 supercooling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000008246 gaseous mixture Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 21
- 230000007062 hydrolysis Effects 0.000 description 21
- 238000006460 hydrolysis reaction Methods 0.000 description 21
- 230000003009 desulfurizing effect Effects 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
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
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- 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
-
- 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
-
- 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
- C10K1/028—Dust removal by electrostatic precipitation
-
- 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
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
Abstract
A kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur, includes the following steps: S1), desulfurization；S2), mix；S3), deoxidation；S4), blending and fine de-sulfur.Present invention process is simple, it is easy to operate, it is mixed using by the higher coal gas of the oxygen content qualified coal gas low with oxygen content, mixed coal gas is then passed through deoxidation reactor and carries out deoxidation treatment, obtains qualified regeneration gas, a part of coal gas is recycled through recycle compressor simultaneously, it is mixed for the higher coal gas of oxygen content, gaseous mixture, entire simple process is made, energy consumption is small, can real-time online continuously to coal gas carry out deoxidation treatment.
Description
Technical field
The present invention relates to field of gas purification, and in particular to a kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur.
Background technique
Steel mill turns, blast furnace gas is before recycling, to pass through electric precipitation workshop section, therefore in view of recycling safety, controls coal gas
Middle oxygen content index is less than 1%.Domestic major steel mill turns, for CO content in 40-50%, oxygen content is universal in blast furnace gas
Between 0.5~1.5%.Turn, the general service of blast furnace gas is to generate electricity or be used as other fuel therefore not do deoxidation substantially
Processing.With the propulsion that steel industry energy-saving and emission-reduction, depth are taped the latent power, tempering coproduction project gradually increases, the raw material of Chemical Manufacture
Gas is gradually substituted by coal gas by steel-making tail gas, and in order to be able to satisfy the needs of Chemical Manufacture, the oxygen content in unstripped gas needs
Removing and control.
Existing deoxidation mode, which has, carries out deoxidation treatment using deoxidation reactor or gas conversion technique, but due to turning, it is high
The too high oxygen level of producer gas directly takes conventional treatment means to will cause reactor temperature runaway, catalyst and deoxidier inactivation etc.
Accident, therefore, existing deoxidation mode can not be suitable for turn, blast furnace gas deoxidation.
Summary of the invention
Technology of the invention solves the problems, such as: overcoming the deficiencies of the prior art and provide a kind of converter and/or blast furnace gas removes
The method of oxygen fine de-sulfur.
The technical solution of the invention is as follows: a kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur, converter and/
Or in blast furnace gas, the volume fraction of oxygen is 0.6-1%, and the content of sulfide is 16-18mg/Nm3；It is characterized in that, packet
Include following steps:
S1), desulfurization
By converter and/or blast furnace gas desulfurization, organic sulfur and inorganic sulfur are removed；
S2), mix
It is 0.001-0.005% by the volume fraction of converter and/or blast furnace gas and oxygen after step S1 desulfurization
The mixing of deoxidation coal gas, control in mixed mixed gas, the volume fraction of oxygen is not more than 0.7%；
S3), deoxidation
Will be by the mixed mixed gas deoxidation of step S2, in the deoxidation coal gas after making deoxidation, the volume fraction of oxygen
For 0.001-0.005%；
S4), blending and fine de-sulfur
Deoxidation coal gas after step S3 deoxidation is shunted, the warp in deoxidation coal gas and step S2 after a part of deoxidation
Converter and/or blast furnace gas blending after crossing step S1 desulfurization, control in mixed mixed gas, the volume fraction of oxygen is not
Greater than 0.7%；Deoxidation coal gas after remaining deoxidation carries out fine de-sulfur, forms purified gas.
Further, in step S4, a part and the process in step S2 in the deoxidation coal gas after step S3 deoxidation
Before converter and/or blast furnace gas blending after step S1 desulfurization, successively through supercooling, gas-liquid separation, after pressurization and by step
Converter and/or blast furnace gas blending after S1 desulfurization；Liquids recovery after gas-liquid separation.
Further, in step S4, the deoxidation coal gas after remaining deoxidation carries out first and converter and/or blast furnace coal before fine de-sulfur
Gas heat exchange, using carrying out fine de-sulfur after cooling.
Further, converter and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, before step S1, heating converter and/
Or blast furnace gas；Before step S3, mixed mixed gas is heated；During normal production, stop heating converter and/or blast furnace coal
Gas and mixed mixed gas.
Further, converter and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, and control enters step the converter of S1
And/or the mass flow of blast furnace gas is not more than the limiting value that deoxidation reactor is born.
Further, in the effective component of converter and/or blast furnace gas, the volume fraction of carbon monoxide is 40-60%, two
The volume fraction of carbonoxide is 20-26%, and the volume fraction of nitrogen is 20-28%, and the volume fraction of hydrogen is 1-4%, oxygen
Volume fraction be 0.6-1%, the content of hydrogen phosphide is 100-250mg/kg, and the content of tar and dust is not higher than 0.1mg/
Nm3, the content of sulfide is 16-18mg/Nm3；
In the effective component after step S4, the volume fraction of carbon monoxide is 45- for converter and/or blast furnace gas
60%, the volume fraction of carbon dioxide is 20-26%, and the volume fraction of nitrogen is 20-28%, and the volume fraction of hydrogen is 1-
4%, the volume fraction of oxygen is 0.001-0.005%；The content of hydrogen phosphide is 100-250mg/kg, the content of tar and dust
Not higher than 0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3。
Further, in the effective component of converter and/or blast furnace gas, the volume fraction of carbon monoxide is 48%, dioxy
The volume fraction for changing carbon is 24.5%, and the volume fraction of nitrogen is 24.37%, and the volume fraction of hydrogen is 2%, the volume of oxygen
Point rate is 1%, and the content of hydrogen phosphide is 200mg/kg, and the content of tar and dust is not higher than 0.1mg/Nm3, the content of sulfide
For 17.7mg/Nm3；
In the effective component after step S4, the volume fraction of carbon monoxide is for converter and/or blast furnace gas
48.48%, the volume fraction of carbon dioxide is 24.75%, and the volume fraction of nitrogen is 24.62%, and the volume fraction of hydrogen is
2.02%, the volume fraction of oxygen is 0.003%；The content of hydrogen phosphide is 200mg/kg, and the content of tar and dust is not higher than
0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3。
Further, before step S1, converter and/or blast furnace gas are just purified by converter and/or blast furnace gas, converter
And/or blast furnace gas just purifies and includes the following steps:
S01), dedusting detar
To converter and/or dedusting of blast furnace gas and detar, make the dust and tar total amount in converter and/or blast furnace gas
Not higher than 3mg/Nm3；
S02), compress
The converter for passing through step S01 and/or blast furnace gas are compressed to 0.95-1Mpa；
S03), clean
The converter of step S02 and/or blast furnace gas are cleaned, keep the impurity content in converter and/or blast furnace gas not high
In 1mg/Nm3。
Further, in the effective component by converter and/or blast furnace gas before step S01, the volume of carbon monoxide
Dividing rate is 40-60%；The volume fraction of carbon dioxide is 20-26%, and the volume fraction of nitrogen is 20-28%, the volume of hydrogen
Dividing rate is 1-4%, and the volume fraction of oxygen is 0.6-1%, and the content of hydrogen phosphide is 100-250mg/kg, the content of tar and dust
For 0.01-0.02g/Nm3, the content of sulfide is 16-18mg/Nm3。
Further, in the effective component by converter and/or blast furnace gas before step S01, the volume of carbon monoxide
Dividing rate is 48%；The volume fraction of carbon dioxide is 24.5%, and the volume fraction of nitrogen is 24.37%, the volume fraction of hydrogen
It is 2%, the volume fraction of oxygen is 1%, and the content of hydrogen phosphide is 200mg/kg, and the content of tar and dust is 0.015g/Nm3,
The content of sulfide is 17.7mg/Nm3。
The advantages of the present invention over the prior art are that:
Present invention process is simple, easy to operate, using the qualified coal that the higher coal gas of oxygen content is low with oxygen content
Gas is mixed, and mixed coal gas is then passed through deoxidation reactor and carries out deoxidation treatment, obtains qualified regeneration gas, simultaneously
A part of coal gas is recycled through recycle compressor, is mixed for the higher coal gas of oxygen content, gaseous mixture is made,
Entire simple process, energy consumption is small, can real-time online continuously to coal gas carry out deoxidation treatment.
Detailed description of the invention
Fig. 1 is the flow chart of converter of the invention and/or blast furnace gas deoxygenation desulfurizing process.
Fig. 2 is the schematic diagram of converter of the invention and/or blast furnace gas deoxygenation fine de-sulfur device.
Fig. 3 is the structural schematic diagram of deoxidation reactor of the invention.
Specific embodiment
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside", " up time
The orientation or positional relationship of the instructions such as needle ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " be orientation based on the figure or
Positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device or element of indication or suggestion meaning must
There must be specific orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.In addition, limit
There is the feature of " first ", " second " to can explicitly or implicitly include one or more of the features surely.Of the invention
In description, unless otherwise indicated, the meaning of " plurality " is two or more.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
As shown in Figure 1-3, a kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur, the converter and/or blast furnace coal
The flow of gas is 28000-30000Nm3/ h, pressure 0.95-1Mpa, temperature are 38-42 DEG C；In effective component, carbon monoxide
Volume fraction be 40-60%, the volume fraction of carbon dioxide is 20-26%, and the volume fraction of nitrogen is 20-28%, hydrogen
Volume fraction be 1-4%, the volume fraction of oxygen is 0.6-1%, and the content of hydrogen phosphide is 100-250mg/kg, tar and ash
The content of dirt is not higher than 0.1mg/Nm3, the content of sulfide is 16-18mg/Nm3.Using deoxygenation fine de-sulfur device to the converter
And/or blast furnace gas deoxygenation fine de-sulfur.
The deoxygenation fine de-sulfur device includes coal gas of converter heat exchanger 301, and go into operation heater 302, circulating air water cooler
303, purified gas water cooler 304, hydrolysis desulfurization goes into operation heater 305, hydrolyzes desulfurizing tower, fine de-sulfur tower, deoxidation reactor 350,
Converter and/or blast furnace gas recycle compressor 360, circulating air liquid separation tank 370, wherein the hydrolysis desulfurizing tower includes structure phase
Same the first hydrolysis desulfurizing tower 310 and the second hydrolysis desulfurizing tower 320, the first hydrolysis desulfurizing tower 310 and the second hydrolysis desulfurization
Tower 320 is normally produced as serial flow using that can go here and there and can and be arranged, and when more catalyst changeout using parallel operation, the essence is de-
Sulphur tower includes identical first fine de-sulfur tower 330 of structure and the first fine de-sulfur tower 340, first fine de-sulfur tower 330 and first
Fine de-sulfur tower 340 is arranged in parallel, and one opens one standby, and tower is provided with desulfurizing agent, removes mercaptan and dimethyl two remaining in gas
Sulfide.
Converter and/or blast furnace gas gas holder hydrolyze desulfurizing tower, deoxidation reactor 350 successively with coal gas of converter heat exchanger 301
Connection, the deoxidation reactor 350 include shell 351, upper cover 352-1, lower head 352-2, and several heat exchanger tubes 353 divide gas
Cylinder 354, manhole pipe orifice 355, catalyst self-unloading mouth 356, air inlet 357, gas outlet 358 and relief valve 359；The shell 351
Pressure shell is connected and composed with upper cover 352-1 and lower head 352-2；Several heat exchanger tubes 353 are set to the shell 351
Interior and be fixedly connected with the atmolysis cylinder 354, the atmolysis cylinder 354 is fixedly connected in the lower head 352-2, the air inlet
Mouth 357, gas outlet 358 and catalyst self-unloading mouth 356 are respectively fixedly connected in the outer surface the lower head 352-2, the air inlet
Mouthfuls 357 be connected tos with 354 entrance of atmolysis cylinder, and the atmolysis cylinder 354 is exported and is connected to several heat exchanger tubes 353, it is described out
It is connected to inside port 358 and catalyst self-unloading mouth 356 and the lower head 352-2, the manhole pipe orifice 355 and relief valve 359
It is fixedly connected with the outer surface the upper cover 352-1 and is connected to the inside upper cover 352-1 respectively.Deoxidation catalyst is from de-
The manhole pipe orifice 355 of the upper cover 352-1 at 350 top of oxygen reactor is packed into, between several heat exchanger tubes 353 and anti-by deoxidation
356 discharging of catalyst self-unloading mouth for answering the lower head 352-2 of 350 bottom of device, it is further preferred that the catalyst self-unloading mouth
356 dischargings are 2, are arranged in the two sides the lower head 352-2.It is further preferred that the operation pressure of the deoxidation reactor 350
Power is 0.95-1.05Mpa, preferably 1Mpa, and operation temperature is 50-160 DEG C, and preferably 56 DEG C, catalyst filling particle diameter is ф 3-
4mm, 351 internal diameter of shell are 3700mm, and 350 whole height of deoxidation reactor is 8000mm.The outlet of deoxidation reactor 350 is set
Two branches are set, a branch hydrolyzes the pipeline connection of desulfurizing tower outlet and 350 entrance of deoxidation reactor with being connected to, in the branch
On, it is exported in connection hydrolysis desulfurizing tower outlet and the pipeline direction of 350 entrance of deoxidation reactor from deoxidation reactor 350, according to
It is secondary to be provided with circulating air water cooler 303, circulating air liquid separation tank 370 and converter and/or blast furnace gas recycle compressor 360；It is another
Successively with coal gas of converter heat exchanger 301, purified gas water cooler 304 is connected to the entrance of fine de-sulfur tower for branch；It is connected to the water
It solves and is provided with the branch that goes into operation on the entrance and the pipeline of converter and/or blast furnace gas gas holder of desulfurizing tower, the hydrolysis desulfurization goes into operation
The setting of heater 305 goes into operation on branch road described, is connected to the pipeline of hydrolysis desulfurizing tower outlet and 350 entrance of deoxidation reactor
On be provided with hydrolysis desulfurization and go into operation branch, the setting of heater 302 that goes into operation goes into operation on branch road in the hydrolysis desulfurization.
The method of deoxygenation fine de-sulfur includes the following steps:
S1), desulfurization
The converter and/or blast furnace gas are little by coal gas of converter heat exchanger 301 and the volume fraction of oxygen after deoxidation
In 0.7% the heat exchange of deoxidation coal gas be warming up to 55-65 DEG C after enter hydrolysis desulfurizing tower removing organic sulfur and inorganic sulfur, specific mistake
Journey is that converter and/or blast furnace gas will be in converters and/or blast furnace gas by the organic sulfur hydrolyst of hydrolysis desulfurizing tower
COS hydrolysis is H2S removes the H in gas subsequently into the desulfurizing agent bed of hydrolysis desulfurizing tower2S and other sulfide,
Other sulfide include dimethyl disulfide, one of methyl mercaptan and thiophene or multiple combinations.In converter and/or blast furnace gas deoxidation
Preceding carry out desulfurization process, the deoxidation catalyst avoided in the sulfide and deoxidation reactor in converter and/or blast furnace gas are anti-
It answers so that deoxidation catalyst fails.Before converter and/or blast furnace gas desulfurization, converter and/or blast furnace gas heat exchange are heated up, improved
The desulfurization effect of converter and/or blast furnace gas.
S042), mix
It is 0.001-0.005% by the volume fraction of converter and/or blast furnace gas and oxygen after step S1 desulfurization
The mixing of deoxidation circulating gas, control in mixed mixed gas, the volume fraction of oxygen is not more than 0.7%.
S043), deoxidation
The mixed mixed gas deoxidation of step S2, the volume fraction of the oxygen of the deoxidation coal gas after making deoxidation will be passed through
0.001-0.005%.
Deoxidation process is specially to pass through the mixed mixed gas of step S2 by 350 bottom lower head 352- of deoxidation reactor
Distribution is described to pass through the mixed mixed gas of step S2 to several heat exchanger tubes 353 after 2 air inlet 357 enters atmolysis cylinder 354
From bottom to top the deoxidation catalyst heat exchange between heat exchanger tube 353, the mixed mixed gas of process step S2 after heat exchange go out
The deoxidation catalyst across heat exchanger tube 353 carries out deoxygenation reaction from top to bottom after heat exchanger tube 353, after deoxygenation reaction, gas
It is discharged by gas outlet 358.Preferably, when the deoxidation reactor 350 exceeds safety value, relief valve 359 is automatically opened, deoxidation
Gas in reactor 350 is discharged by relief valve 359.The deoxidation reactor uses atmolysis cylinder 354 and uniformly distributed several heat exchange
Pipe guarantees to be evenly distributed by the mixed mixed gas deoxidation of step S042 and deoxidation catalyst, improves oxygen removal efficiency
Temperature simultaneously in entire deoxidation reactor is uniform, by the way that catalyst self-unloading mouth is arranged, realizes the self-unloading of deoxidation catalyst, subtracts
The labor intensity of deoxidation catalyst discharging is lacked.
S4), blending and fine de-sulfur
Deoxidation coal gas after step S3 deoxidation is divided into two steps point, and the deoxidation coal gas after a part of deoxidation is by following
Ring air water cooler 303, which cools, carries out gas-liquid separation by circulating air liquid separation tank 370 to after 35-45 DEG C, after gas-liquid separation
Gas is after converter and/or blast furnace gas recycle compressor are pressurized to 0.93-0.98Mpa as the deoxidation circulation in step S2
Coal gas and converter and/or blast furnace gas blending after step S1 desulfurization, guarantee in mixed mixed gas, the body of oxygen
Integration rate is not more than 0.7%, the liquids recovery after gas-liquid separation；Deoxidation coal gas after another part deoxidation is as in step S1
The deoxidation coal gas that the volume fraction of oxygen is 0.001-0.005% is by coal gas of converter heat exchanger 301 and converter and/or blast furnace coal
Gas heat exchange enters fine de-sulfur tower desulfurization after being cooled to 130-150 DEG C after purified gas water cooler 304 is cooled to 35-45 DEG C, takes off
Except mercaptan and dimethyl disulphide remaining in gas, purified gas is formed, the total sulfur content of the purified gas is not higher than
0.1mg/Nm3。
After step S4, the flow of converter and/or blast furnace gas is 28000- for converter and/or blast furnace gas
30000Nm3/ h, pressure 0.8-0.85Mpa, temperature are 38-42 DEG C；In effective component, the volume fraction of carbon monoxide is 45-
60%, the volume fraction of carbon dioxide is 20-26%, and the volume fraction of nitrogen is 20-28%, and the volume fraction of hydrogen is 1-
4%, the volume fraction of oxygen is 0.001-0.005%；The content of hydrogen phosphide is 100-250mg/kg, the content of tar and dust
Not higher than 0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3。
Preferably, circulating fan, the circulating fan and the converter and/or blast furnace gas recycle compressor are provided with
360 are arranged in parallel, and control in mixed mixed gas, and the volume fraction of oxygen is not more than 0.7%, by the deoxidation of step S3
Deoxidation gas temperature afterwards is not higher than 160 DEG C.Since coal gas of converter oxygen content is higher, and oxygen content fluctuation is larger, passes through setting
Circulating fan reduces entrance oxygen content, and the deoxidation catalyst realized in deoxidation reactor is long-term steady at a lower temperature
Fixed operation.
Preferably, converter and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, and before step S1, heat the converter
And/or blast furnace gas is to 55-65 DEG C, to improve the desulfurization effect of converter and/or blast furnace gas；Before step S3, heating mixing
Mixed gas afterwards is to 55-65 DEG C, to improve deoxidation effect；During normal production, stop heating the converter and/or blast furnace gas
With mixed mixed gas.
Preferably, furnace and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, control enter step S1 converter and/or
The mass flow of blast furnace gas is not more than the limiting value that deoxidation reactor is born, here, converter and/or the blast furnace gas of the application
Mass flow be 56791-88422kg/h, with guarantee and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, control enter
The converter of step S1 and/or the mass flow of blast furnace gas are not more than the limiting value that deoxidation reactor is born.
Before the converter and/or blast furnace gas deoxygenation fine de-sulfur device go into operation, needed before deoxidation catalyst normal use into
Row reduction, detailed process is as follows:
A), start converter and/or blast furnace gas recycle compressor 360 and carry out nitrogen circulation, circulation process be converter and/or
Blast furnace gas 360 → coal gas of converter of recycle compressor heat exchanger 301 → hydrolysis desulfurization go into operation heater 305 → hydrolysis desulfurizing tower →
Go into operation return after heater 302 → deoxidation reactor, 350 → circulating air water cooler 303 → circulating air liquid separation tank 370 converter and/or
Blast furnace gas recycle compressor 360.
B), nitrogen is heated to 170-180 DEG C using heater 302 is gone into operation, deoxidation catalyst is finally warming up to 170 DEG C
Constant temperature afterwards, then gradually fill into converter and/or blast furnace gas.
Preferably, the heater 305 that needs to go into operation to hydrolysis desulfurization before filling into converter and/or blast furnace gas passes through steam
Hydrolysis desulfurizing tower temperature is lifted temperature to 60 DEG C by heating, temperature is then lifted temperature to 180 DEG C, control enters deoxidation reactor 350
CO content, until the volume fraction of CO is to 3-4% and imports and exports CO content and does not change, reduction terminates.
C deoxidation reactor temperature is down to 80 DEG C after) reduction is good, adjusts material gas quantity, starts normal production.
When the converter and/or blast furnace gas deoxygenation fine de-sulfur device are stopped work, gradually reduce and until stop converter and/or
Blast furnace gas enters device, starts circulating fan, increases internal circulating load, and deoxidation reactor 350 is changed to circulation process, and circulation process is
Converter and/or blast furnace gas 360 → coal gas of converter of recycle compressor heat exchanger 301 → hydrolysis desulfurization go into operation 305 → water of heater
It is returned after solution desulfurizing tower → heater 302 → deoxidation reactor, the 350 → circulating air water cooler 303 → circulating air liquid separation tank 370 that goes into operation
Rotary furnace and/or blast furnace gas recycle compressor 360 maintain system pressure, are then gradually down to deoxidation catalyst temperature often
Temperature stops circulating fan.
Preferably, before step S1, purification device at the beginning of using converter and/or blast furnace gas passes through converter and/or blast furnace gas
It crosses converter and/or blast furnace gas just purifies, just the flow of the converter before purification and/or blast furnace gas is 28000-30000Nm3/
H, pressure 0.003-0.005Mpa, temperature are 18-22 DEG C；In effective component, the volume fraction of carbon monoxide is 40-60%,
The volume fraction of carbon dioxide is 20-26%, and the volume fraction of nitrogen is 20-28%, and the volume fraction of hydrogen is 1-4%, oxygen
The volume fraction of gas is 0.6-1%；The content of hydrogen phosphide is 100-250mg/kg, and the content of tar and dust is 0.01-
0.02g/Nm3, the content of sulfide is 16-18mg/Nm3。
Just purification device includes sequentially connected dedusting detar device for the converter and/or blast furnace gas, compressor and
TSA adsorbent equipment；Preferably, the dedusting detar device is electrical tar precipitator, and the compressor is reciprocating compressor, institute
Stating TSA adsorbent equipment is alternating temperature carbon adsorption device.
Converter and/or blast furnace gas, which just purify, to be included the following steps:
S01), dedusting detar
Using dedusting detar device, preferably electrical tar precipitator to the converter and/or dedusting of blast furnace gas and detar,
Dust and tar total amount in the converter and/or blast furnace gas is set to be not higher than 3mg/Nm3。
S02), compress
Using compressor, preferably reciprocating compressor compresses the converter for passing through step S01 and/or blast furnace gas to 0.95-
1Mpa。
S03), clean
Using TSA adsorbent equipment, preferably alternating temperature carbon adsorption device, converter and/or blast furnace gas removal of impurities to step S02,
Make the impurity content in the converter and/or blast furnace gas not higher than 0.1mg/Nm3.The impurity is tar and/or dust.
Embodiment 1
A kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur,
Include the following steps:
S0), converter and/or the first purification of blast furnace gas
Just the flow of the converter before purification and/or blast furnace gas is 29000Nm3/ h, pressure 0.005Mpa, temperature 20
℃；In effective component, the volume fraction of carbon monoxide is 48%, and the volume fraction of carbon dioxide is 24.5%, the volume of nitrogen
Dividing rate is 24.37%, and the volume fraction of hydrogen is 2%, and the volume fraction of oxygen is 1%；The content of hydrogen phosphide is 200mg/kg,
The content of tar and dust is 0.015g/Nm3, the content of sulfide is 17.7mg/Nm3。
Converter and/or blast furnace gas, which just purify, to be included the following steps:
S01), dedusting detar
Using electrical tar precipitator to the converter and/or dedusting of blast furnace gas and detar, make the converter and/or blast furnace
Dust and tar total amount in coal gas are not higher than 3mg/Nm3。
S02), compress
The converter for passing through step S01 and/or blast furnace gas are compressed using reciprocating compressor to 1Mpa.
S03), clean
Using alternating temperature carbon adsorption device, converter and/or blast furnace gas removal of impurities to step S02 make the converter and/or height
Impurity content in producer gas is not higher than 0.1mg/Nm3。
The flow of first purified converter and/or blast furnace gas is 29000Nm3/ h, pressure 0.97Mpa, temperature 40
℃；The volume fraction of carbon monoxide is 48% in effective component；The volume fraction of carbon dioxide is 24.5%, the volume point of nitrogen
Rate is 24.37%, and the volume fraction of hydrogen is 2%, and the volume fraction of oxygen is 1%, and the content of hydrogen phosphide is 200mg/kg, tar
Content with dust is 0.015g/Nm3, the content of sulfide is 17.7mg/Nm3。
S01), desulfurization
The converter and/or blast furnace gas are little by coal gas of converter heat exchanger 301 and the volume fraction of oxygen after deoxidation
In 0.7% the heat exchange of deoxidation coal gas be warming up to 60 DEG C after enter hydrolysis desulfurizing tower removing organic sulfur and inorganic sulfur.
S02), mix
The deoxidation for being 0.003% by the volume fraction of converter and/or blast furnace gas and oxygen after step S01 desulfurization
Circulating gas mixing, controls in mixed mixed gas, and the volume fraction of oxygen is not more than 0.7%.
S03), deoxidation
The mixed mixed gas deoxidation of step S02, the volume fraction of the oxygen of the deoxidation coal gas after making deoxidation will be passed through
It is 0.003%.
S04), blending and fine de-sulfur
Deoxidation coal gas after step S03 deoxidation is divided into two steps point, and the deoxidation coal gas after a part of deoxidation passes through
Circulating air water cooler 303 cools to after 40 DEG C and carries out gas-liquid separation by circulating air liquid separation tank 370, the gas after gas-liquid separation
Body after converter and/or blast furnace gas recycle compressor are pressurized to 0.95Mpa as in step S02 deoxidation circulating gas with
Converter and/or blast furnace gas blending after step S01 desulfurization, guarantee in mixed mixed gas, the volume point of oxygen
Rate is not more than 0.7%, the liquids recovery after gas-liquid separation；Deoxidation coal gas after another part deoxidation is as the oxygen in step S01
The deoxidation coal gas that the volume fraction of gas is 0.003% is dropped by coal gas of converter heat exchanger 301 and converter and/or blast furnace gas heat exchange
Temperature removes sulphur remaining in gas to fine de-sulfur tower desulfurization is entered after 140 DEG C after purified gas water cooler 304 is cooled to 40 DEG C
Alcohol and dimethyl disulphide, form purified gas, and the total sulfur content of the purified gas is not higher than 0.1mg/Nm3。
The flow of converter and/or blast furnace gas after step S04 is 29000Nm3/ h, pressure 0.82Mpa, temperature
It is 40 DEG C；In effective component, the volume fraction of carbon monoxide is 48.48%, and the volume fraction of carbon dioxide is 24.75%, nitrogen
The volume fraction of gas is 24.62%, and the volume fraction of hydrogen is 2.02%, and the volume fraction of oxygen is 0.003%；Hydrogen phosphide
Content is 200mg/kg, and the content of tar and dust is not higher than 0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3。
In the description of this specification, reference term " one embodiment ", " some embodiments ", " illustrative examples ",
The description of " example ", " specific example " or " some examples " etc. means specific features described in conjunction with this embodiment or example, knot
Structure, material or feature are included at least one embodiment or example of the invention.In the present specification, to above-mentioned term
Schematic representation may not refer to the same embodiment or example.Moreover, specific features, structure, material or the spy of description
Point can be combined in any suitable manner in any one or more of the embodiments or examples.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this
The range of invention is defined by the claims and their equivalents.
Claims (10)
1. a kind of method of converter and/or blast furnace gas deoxygenation fine de-sulfur, in converter and/or blast furnace gas, the volume point of oxygen
Rate is 0.6-1%, and the content of sulfide is 16-18mg/Nm3；It is characterized by comprising the following steps:
S1), desulfurization
By converter and/or blast furnace gas desulfurization, organic sulfur and inorganic sulfur are removed；
S2), mix
It is the de- of 0.001-0.005% by the volume fraction of converter and/or blast furnace gas and oxygen after step S1 desulfurization
Oxycoal gas mixing, controls in mixed mixed gas, and the volume fraction of oxygen is not more than 0.7%；
S3), deoxidation
Will be by the mixed mixed gas deoxidation of step S2, in the deoxidation coal gas after making deoxidation, the volume fraction of oxygen is
0.001-0.005%；
S4), blending and fine de-sulfur
Deoxidation coal gas after step S3 deoxidation is shunted, passing through in the deoxidation coal gas and step S2 after a part of deoxidation walks
Converter and/or blast furnace gas blending after rapid S1 desulfurization, control in mixed mixed gas, the volume fraction of oxygen is not more than
0.7%；Deoxidation coal gas after remaining deoxidation carries out fine de-sulfur, forms purified gas.
2. according to the method described in claim 1, it is characterized by:
In step S4, in the deoxidation coal gas after step S3 deoxidation a part with step S2 in after step S1 desulfurization
Before converter and/or blast furnace gas blending, successively through supercooling, gas-liquid separation, after pressurization with the converter after step S1 desulfurization
And/or blast furnace gas blending；Liquids recovery after gas-liquid separation.
3. according to the method described in claim 1, it is characterized by:
In step S4, the deoxidation coal gas after remaining deoxidation carries out first and converter and/or blast furnace gas heat exchange before fine de-sulfur, using
Fine de-sulfur is carried out after cooling.
4. according to the method described in claim 1, it is characterized by:
Converter and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, and before step S1, heat converter and/or blast furnace gas；?
Before step S3, mixed mixed gas is heated；During normal production, stop heating converter and/or blast furnace gas and mixed
Mixed gas.
5. according to the method described in claim 1, it is characterized by:
Converter and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, and control the converter and/or blast furnace gas for entering step S1
Mass flow is not more than the limiting value that deoxidation reactor is born.
6. according to the method described in claim 1, it is characterized by:
In the effective component of converter and/or blast furnace gas, the volume fraction of carbon monoxide is 40-60%, the volume of carbon dioxide
Dividing rate is 20-26%, and the volume fraction of nitrogen is 20-28%, and the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is
0.6-1%, the content of hydrogen phosphide are 100-250mg/kg, and the content of tar and dust is not higher than 0.1mg/Nm3, sulfide contains
Amount is 16-18mg/Nm3；
Converter and/or blast furnace gas be in the effective component after step S4, and the volume fraction of carbon monoxide is 45-60%, and two
The volume fraction of carbonoxide is 20-26%, and the volume fraction of nitrogen is 20-28%, and the volume fraction of hydrogen is 1-4%, oxygen
Volume fraction be 0.001-0.005%；The content of hydrogen phosphide is 100-250mg/kg, and the content of tar and dust is not higher than
0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3。
7. according to the method described in claim 6, it is characterized by:
In the effective component of converter and/or blast furnace gas, the volume fraction of carbon monoxide is 48%, the volume fraction of carbon dioxide
It is 24.5%, the volume fraction of nitrogen is 24.37%, and the volume fraction of hydrogen is 2%, and the volume fraction of oxygen is 1%, phosphatization
The content of hydrogen is 200mg/kg, and the content of tar and dust is not higher than 0.1mg/Nm3, the content of sulfide is 17.7mg/Nm3；
In the effective component after step S4, the volume fraction of carbon monoxide is 48.48%, two for converter and/or blast furnace gas
The volume fraction of carbonoxide is 24.75%, and the volume fraction of nitrogen is 24.62%, and the volume fraction of hydrogen is 2.02%, oxygen
Volume fraction be 0.003%；The content of hydrogen phosphide is 200mg/kg, and the content of tar and dust is not higher than 0.1mg/Nm3, always
Sulfur content is not higher than 0.1mg/Nm3。
8. according to the method described in claim 1, it is characterized by:
Before step S1, converter and/or blast furnace gas are just purified by converter and/or blast furnace gas, at the beginning of converter and/or blast furnace gas
Purification includes the following steps:
S01), dedusting detar
To converter and/or dedusting of blast furnace gas and detar, keep dust in converter and/or blast furnace gas and tar total amount not high
In 3mg/Nm3；
S02), compress
The converter for passing through step S01 and/or blast furnace gas are compressed to 0.95-1Mpa；
S03), clean
The converter of step S02 and/or blast furnace gas are cleaned, the impurity content in converter and/or blast furnace gas is not higher than
1mg/Nm3。
9. according to the method described in claim 8, it is characterized by:
In effective component by converter and/or blast furnace gas before step S01, the volume fraction of carbon monoxide is 40-60%；
The volume fraction of carbon dioxide is 20-26%, and the volume fraction of nitrogen is 20-28%, and the volume fraction of hydrogen is 1-4%, oxygen
Volume fraction be 0.6-1%, the content of hydrogen phosphide is 100-250mg/kg, and the content of tar and dust is 0.01-0.02g/
Nm3, the content of sulfide is 16-18mg/Nm3。
10. according to the method described in claim 9, it is characterized by:
In effective component by converter and/or blast furnace gas before step S01, the volume fraction of carbon monoxide is 48%；Two
The volume fraction of carbonoxide is 24.5%, and the volume fraction of nitrogen is 24.37%, and the volume fraction of hydrogen is 2%, the volume of oxygen
Point rate is 1%, and the content of hydrogen phosphide is 200mg/kg, and the content of tar and dust is 0.015g/Nm3, the content of sulfide is
17.7mg/Nm3。
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| CN111732976A (en) * | 2020-05-19 | 2020-10-02 | 福州大学 | Blast furnace gas desulfurization method and system |
| CN113968572A (en) * | 2021-10-21 | 2022-01-25 | 福州大学 | Blast furnace and converter gas mixed gas deoxidation hydrogen production system and process |
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