CN106276795A - A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases - Google Patents
A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases Download PDFInfo
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- CN106276795A CN106276795A CN201610627291.6A CN201610627291A CN106276795A CN 106276795 A CN106276795 A CN 106276795A CN 201610627291 A CN201610627291 A CN 201610627291A CN 106276795 A CN106276795 A CN 106276795A
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- gas
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- 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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing 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
- C01B2203/0405—Purification by membrane separation
-
- 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
- C01B2203/042—Purification by adsorption on solids
-
- 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
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Gases By Adsorption (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention belongs to metallurgical reduction gas preparation technique field, a kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases.The present invention is with coke-stove gas as raw material, through impurity such as the thick detar of preliminary clearning, naphthalenes, is then sequentially sent to gas holder buffering, compressor boost, deep purifying removing tar, naphthalene, sulfur, TSA operation removing benzene, ammonia, and membrance separation, PSA separates, the H respectively obtained2Can use as metallurgical reduction gas after being mixed in proportion with CO.The present invention makes full use of oven gas resource, cleaning procedure is reasonable, gas separating technology configuration is reasonable, meets different reduced iron technology to CO and H2Proportion requirement.
Description
Technical field
The invention belongs to metallurgical reduction gas preparation technique field, specially one and utilize coke-stove gas extraction metallurgy reducing gases
Group technology.
Background technology
DRI (DRI-Direct Reduced Iron) be essence iron powder or ferrum oxide in stove
Through the low-carbon (LC) cellular material that metallurgical reduction gas direct-reduction is formed, its chemical composition stability, impurity content is few, is replacing of steel scrap
One of Dai Pin.Metallurgical reduction gas be mainly composed of CO and H2, relative to traditional blast furnace ironmaking, use metallurgical reduction gas to ferrum
Ore is reduced directly, it is achieved that coke-free ironmaking, and carbon consumes low, CO2Discharge is few.Therefore, utilize metallurgical reduction gas ironmaking right
Reduce disposable fossil energy consumption, protection environment etc. to have very important significance.
The at present main source of extraction metallurgy reducing gases or natural gas or the reforming reaction of high methane gas, but natural
Countries and regions the method for gas scarcity of resources is difficulty with.China is coking big country, coking industry the most all can by-product a large amount of
Coke-stove gas.Coke-stove gas be coking coal in coke oven after high-temperature retorting, institute while output coke and tar product
A kind of imflammable gas produced, is the side-product of coking industry.Coke-stove gas be mainly composed of H2(55-60%), CH4(23-
27%), CO(5-8%), additionally contain the Hydrocarbon such as benzene.Coke-stove gas extraction metallurgy reducing gases is utilized then to seem meaning weight
Greatly.The existing method utilizing coke-stove gas extraction metallurgy reducing gases, " a kind of utilization Jiao of Application No. 201210000587.7
Producer gas produce sponge iron method " patent, disclosed method is: will purify after coke-stove gas preheat；After preheating
Coke-stove gas carry out imperfect combustion in fluid bed porch with the oxygen being passed through, and make containing CO+H2The temperature of reducing gases
Degree is increased to 900 DEG C-1000 DEG C, then carries out convection current reduction in fluid bed with Iron concentrate or iron mine, generates sponge iron.The method
Major defect be coke oven gas purification not to be systematically discussed；And for example " the one of Application No. 201410088900.6
Kind of coke-stove gas modification direct-reduction iron ore system and device and method " patent, disclosed method is: utilize high temperature desulfuration agent
(MO and CeO1.72) realize desulfurizing and purifying, at high temperature after then being mixed according to a certain ratio with reduction of iron ore tail gas by coke-stove gas
Catalytic bed carries out reforming reaction and obtains metallurgical reduction gas, be finally reduced directly iron ore, reduction of iron ore tail gas.The method
Major defect is that coke-stove gas processes totally, and follow-up workshop section can be impacted by the particularly process of sulfide.Above patent
Report is all the use of the reforming reaction of methane to produce metallurgical reduction gas, but the reforming reaction of methane needs newly-built large-scale
Reburner, which increases equipment power dissipation and product cost.
Summary of the invention
Present invention aims to the weak point of existing coke-stove gas extraction metallurgy reducing gases method, propose one
Utilize the group technology of coke-stove gas extraction metallurgy reducing gases, i.e. use coke oven gas purification-separation group technology to produce smelting
High methane gas is obtained while gold reducing gases.I.e. by membrance separation and PSA technology, isolated H2, CH4And CO.H2Permissible with CO
By different ratio, and then meet the reducing gases composition needed for all kinds of iron-smelting process.CH4Can be according to demand as returning coke oven
Combustion gas or on-site boiler combustion etc. use, make full use of methyl hydride combustion heat.This group technology is particularly suitable for China, print
Spend this type of coking big country, lack area and the country of natural gas resource simultaneously.
The object of the invention is realized by following technical proposals:
A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases, with coke-stove gas as raw material, enters after preliminary clearning
Gas holder, then after compressor supercharging, deep purifying, temp.-changing adsorption, carry out membrance separation and obtain hydrogen, the gas after membrance separation carries hydrogen
Body enter pressure-swing absorption apparatus, methane, nitrogen are separated with CO, it is thus achieved that CO and H2Can use as reducing gases, and methane rich
Gas then can use as combustion gas or the on-site boiler combustion etc. returning coke oven according to demand, makes full use of methyl hydride combustion
Heat.
Specifically comprising the following steps that of described method
(1) preliminary clearning
First the unstripped gas coke-stove gas that pressure is 7-10kPa being entered preliminary clearning device, described preliminary clearning is at depurator
Middle filling coke, utilizes the tar in the adsorptivity removing coke-stove gas of coke, naphthalene impurity, and tar content is down to 4mg/Nm3With
Under, naphthalene content is down to 10mg/Nm3Hereinafter, specifically require to carry out flexibly according to selected compressor pattern and compressor producer
Regulation.
(2) gas holder
After (1st) step completes, coke-stove gas enters gas holder.Described gas holder is to make for the composition tolerance fluctuation of coke-stove gas source of the gas
For cushioning effect.
(3) compression
(2nd) step gas holder coke-stove gas out is pressurized to 0.2MPa through compressor, reaches subsequent operation unit to material pressure
The requirement of power.In addition to the pressure loss of technological process itself, the operation pressure of subsequent handling is all carried out under this pressure.
(4) deep purifying
After (3rd) step completes, coke-stove gas carries out deep purifying again.Described deep purifying mainly includes two parts, first
Divide and use carbon-based adsorbent to remove tar, naphthalene further so that it is removing index respectively reaches tar less than 1mg/Nm3, naphthalene index
Less than 1mg/Nm3.Part II uses the thick desulfurization of wet desulphurization, by H2The sulfur content of S and organic sulfur is reduced to 10mg/Nm3, slightly
Sulfur removal technology is according to device unstripped gas sulfur content and the process program of the preferred economical rationality of unstripped gas scale.
(5) temp.-changing adsorption
After (4th) step completes, coke-stove gas enters temperature swing adsorption unit.This unit uses room temperature absorption, the operation of desorption by heating
Method makes the content of the benzene in unstripped gas and ammonia less than 10mg/Nm3.Adsorbent uses modified silica-gel and the compound suction of special typed active carbon
Attached dose, it is room temperature that described temp.-changing adsorption purifies adsorption operations temperature, and adsorbent reactivation needs heating.
(6) membrance separation
After (5th) step completes, coke-stove gas carries out membrance separation.Membrane separation device utilizes original pressure as motive force, makes hydrogen
Low-pressure side at film is enriched with, and the CO that a part obtains with pressure-variable adsorption operation mixes, and obtains can be directly used for the metallurgy of reduced iron
Reducing gases, another part is transported to the entrance that user needs.
(7) pressure-variable adsorption
Through (6th) step process after gas enter PSA device, methane, nitrogen are separated by PSA with CO, it is thus achieved that CO and H2Can make
Being used in mixed way for reducing gases, high methane gas then can be according to demand as combustion gas or the combustion of on-site boiler returning coke oven
Burnings etc. use, and make full use of methyl hydride combustion heat.
The positive effect of the present invention is:
(1) in coke-stove gas, impurity removal is more thorough.During coke oven gas purification, first through preliminary clearning thick detar naphthalene, then
Through deep purifying, temp.-changing adsorption, it is to avoid the impurity impact on equipment, the metallurgical reduction gas produced fully meets various reduction
The requirement of ferrum technology.
(2) comprehensive utilization of industrial discharge gas is realized, economic and environment-friendly.Whole technical process is without continuous pollutant emission, sulfur, Jiao
Oil and dust all obtain solidification and collect.Device has stable, the advantage that reliability is high, heat utilization ratio is high, reaches industry
Effluent gas recovery utilization, energy-saving and emission-reduction, the effect that turns waste into wealth.
(3) H obtained by new group technology2Can close according to the requirement to reducing gases of any metallurgical technology with CO
Reason proportioning, reaches optimum reduction effect.
(4) high methane gas obtained by PSA, high methane gas can be as fuel, it is also possible to former as methane reforming
Material, sufficiently make use of each important component in coke-stove gas.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention.
Detailed description of the invention
All features disclosed in this specification, or disclosed all methods or during step, except mutually exclusive
Feature and/or step beyond, all can combine by any way.
Any feature disclosed in this specification (including any accessory claim, summary), unless specifically stated otherwise,
By other equivalences or there is the alternative features of similar purpose replaced.I.e., unless specifically stated otherwise, each feature is a series of
An example in equivalence or similar characteristics.
Embodiment 1:
A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases, specifically comprising the following steps that of described technique
(1) preliminary clearning
Coke gas flow is 30000Nm3/ h, wherein, with volume basis, H2Content is 57.5%, and CO content is 7%, CH4Content
It is 24.4%, CO2Content is 2.3%, N2Content is 5%, and many carbon hydrocarbon content is 3.5%, O2Content is 0.3%, cumulative volume percentage composition
Sum is 100%.Impurity content is: benzene, toluene level about 3500mg/Nm3, naphthalene content about 200mg/Nm3, tar and dust content
About 110mg/Nm3, ammonia content about 48mg/Nm3, H2S content about 200mg/Nm3, organic sulfur content about 200mg/Nm3.This composition
Raw coke oven gas temperature 40 DEG C, pressure 7kPa, enter preliminary clearning device, utilize the adsorptivity of coke to be down to by tar content
4mg/Nm3Hereinafter, naphthalene content is down to 10mg/Nm3Below.
(2) gas holder
After (1st) step completes, coke-stove gas enters gas holder.Described gas holder is to make for the composition tolerance fluctuation of coke-stove gas source of the gas
For cushioning effect.
(3) compression
(2nd) step gas holder coke-stove gas out is pressurized to 0.2MPa through compressor, reaches subsequent operation unit to material pressure
The requirement of power.In addition to the pressure loss of technological process itself, the operation pressure of subsequent handling is all carried out under this pressure.
(4) deep purifying
After (3rd) step completes, coke-stove gas carries out deep purifying again.Described deep purifying mainly includes two parts, first
Divide and use carbon-based adsorbent to remove tar, naphthalene further so that it is removing index respectively reaches tar less than 1mg/Nm3, naphthalene index
Less than 1mg/Nm3.Part II uses the thick desulfurization of wet desulphurization, by H2The sulfur content of S and organic sulfur is reduced to 10mg/Nm3, slightly
Sulfur removal technology is according to device unstripped gas sulfur content and the process program of the preferred economical rationality of unstripped gas scale.
(5) temp.-changing adsorption
After (4th) step completes, coke-stove gas enters temperature swing adsorption unit.This unit uses room temperature absorption, the operation of desorption by heating
Method makes the content of the benzene in unstripped gas and ammonia less than 10mg/Nm3.Adsorbent uses modified silica-gel and the compound suction of special typed active carbon
Attached dose, it is room temperature that described temp.-changing adsorption purifies adsorption operations temperature, and adsorbent reactivation needs heating.
(6) membrance separation
After (5th) step completes, coke-stove gas carries out membrance separation.Membrane separation device utilizes original pressure as motive force, obtains richness
Hydrogen 14663Nm3/h.Wherein, the amounts of hydrogen that the CO obtained with pressure-variable adsorption operation mixes is 3080Nm3/ h, obtaining after mixing can
It is directly used in the metallurgical reduction gas of reduced iron, remains 11583Nm3/ h hydrogen is transported to the entrance that user needs.
(7) pressure-variable adsorption
Gas after (6th) step processes enters PSA device, and methane, nitrogen are separated by PSA with CO, it is thus achieved that 1596Nm3/ h's
CO, the H obtained with membrance separation2Can be used in mixed way as reducing gases, obtain 9120Nm simultaneously3The high methane gas of/h.
Embodiment 2
A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases, with embodiment 1, wherein:
In (1st) step, coke gas flow is 40000Nm3/ h, wherein, with volume basis, H2Content is 57.1%, and CO content is
7%, CH4Content is 24%, CO2Content is 2.5%, N2Content is 5%, and many carbon hydrocarbon content is 3.9%, O2Content is 0.5%, cumulative volume
Percentage composition sum is 100%.Impurity content is: benzene, toluene level about 3500mg/Nm3, naphthalene content about 150mg/Nm3, tar and
Dust content about 100mg/Nm3, ammonia content about 45mg/Nm3, H2S content about 180mg/Nm3, organic sulfur content about 200mg/Nm3。
The raw coke oven gas temperature of this composition 40 DEG C, pressure 7kPa, enter preliminary clearning device, utilize the adsorptivity of coke to be contained by tar
Amount is down to 4mg/Nm3Hereinafter, naphthalene content is down to 10mg/Nm3Below.
In (6th) step, coke-stove gas carries out membrance separation.Membrane separation device utilizes original pressure as motive force, obtains richness
Hydrogen 23158Nm3/h.Wherein, the amounts of hydrogen that the CO obtained with pressure-variable adsorption operation mixes is 4867Nm3/ h, obtaining after mixing can
It is directly used in the metallurgical reduction gas of reduced iron, remains 18291Nm3/ h hydrogen is transported to the entrance that user needs.
In (7th) step, the gas after (6th) step processes enters PSA device, and methane, nitrogen are separated with CO, obtains by PSA
Obtain 2433Nm3The CO of/h, the H obtained with membrance separation2Can be used in mixed way as reducing gases, obtain 14308Nm simultaneously3/ h is the richest in
Alkane gas.
The invention is not limited in aforesaid detailed description of the invention.The present invention expands to any disclose in this manual
New feature or any new combination, and the arbitrary new method that discloses or the step of process or any new combination.
Claims (6)
1. the group technology utilizing coke-stove gas extraction metallurgy reducing gases, it is characterised in that comprise the following steps: oven gas
Make it meet tar content through preliminary clearning and be down to 4mg/Nm3Hereinafter, naphthalene content is down to 10mg/Nm3Hereinafter, it is then fed into gas holder；
Gas holder coke-stove gas out carries out deep purifying removing tar, naphthalene after compressor supercharging, respectively reaches tar and is less than
1mg/Nm3, naphthalene index is less than 1mg/Nm3；
Use PDS desulfurization by H2The sulfur content of S and organic sulfur is reduced to 10mg/Nm3；
Coke-stove gas after desulfurization enters temperature swing adsorption unit, controls the content of benzene and ammonia less than 10mg/Nm3；
After TSA, gas enters film separation unit, and after isolating hydrogen, residue mixed gas enters PSA unit isolated
Carbon monoxide；
Hydrogen and carbon monoxide use as metallurgical reduction gas after being mixed in proportion.
The group technology utilizing coke-stove gas extraction metallurgy reducing gases the most according to claim 1, it is characterised in that: described
The pressure of coke-stove gas is 7-10kPa, and described preliminary clearning is filling coke in depurator, utilizes the adsorptivity of coke to remove
Tar in coke-stove gas, naphthalene impurity.
The group technology utilizing coke-stove gas extraction metallurgy reducing gases the most according to claim 1, it is characterised in that: described
Deep purifying include two parts, Part I uses carbon-based adsorbent to remove tar, naphthalene further, and Part II uses wet method
The thick desulfurization of desulfurization.
The group technology utilizing coke-stove gas extraction metallurgy reducing gases the most according to claim 1, it is characterised in that: described
Temperature swing adsorption unit use room temperature absorption and the operational approach of desorption by heating to make the benzene in unstripped gas and ammonia removal.
The group technology utilizing coke-stove gas extraction metallurgy reducing gases the most according to claim 1, it is characterised in that: described
The adsorbent of temp.-changing adsorption uses modified silica-gel and special typed active carbon compound adsorbent.
The group technology utilizing coke-stove gas extraction metallurgy reducing gases the most according to claim 1, it is characterised in that: described
The adsorbent reactivation of temp.-changing adsorption needs to be heated to 160 DEG C-220 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171848A (en) * | 2020-01-21 | 2020-05-19 | 太原理工大学 | System and method for producing high-purity steel and hydrogen |
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Application publication date: 20170104 |