CN108004362A - Troilite prepares sulfuric acid and the method and system of direct reduced iron - Google Patents
Troilite prepares sulfuric acid and the method and system of direct reduced iron Download PDFInfo
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- CN108004362A CN108004362A CN201711341385.8A CN201711341385A CN108004362A CN 108004362 A CN108004362 A CN 108004362A CN 201711341385 A CN201711341385 A CN 201711341385A CN 108004362 A CN108004362 A CN 108004362A
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- pelletizing
- troilite
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- sulfur
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- 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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/008—Use of special additives or fluxing agents
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses troilite to prepare sulfuric acid and the method and system of direct reduced iron, and wherein method includes：(1) fine grinding processing is carried out to troilite, to obtain troilite powder；(2) troilite powder and water, binding agent and additive are subjected to mixed-forming processing, to obtain mixing pelletizing；(3) the mixing pelletizing is supplied to drying grate is dried, the first preheating and second preheats, to obtain preheated pellets；(4) preheated pellets are supplied to rotary kiln and carries out oxidizing roasting processing, to obtain oxidizing roasting pelletizing and sulfur-containing smoke gas；(5) the sulfur-containing smoke gas relieving haperacidity is utilized, to obtain sulfuric acid and deacidification flue gas；(6) the oxidizing roasting pelletizing is supplied to direct-reduction processing is carried out with reducing gas in gas-based shaft kiln, to obtain flue gas containing zinc and direct reduced iron product.Sulfur recovery rate in troilite can be effectively improved using this method, shortens technological process, roasting rear oxidation pelletizing production high-quality direct reduced iron is efficiently used, improves resource utilization, to produce high-end casting, high-grade steel provides quality raw materials.
Description
Technical field
The invention belongs to field of chemical metallurgical technology, specifically, prepares sulfuric acid the present invention relates to troilite and directly goes back
The method and system of former iron.
Background technology
It is increasing to the demand of mineral resources with the progress and development of modern industrial technology, but mineral resources are
Non-renewable, continuous due to exploitation carries out, and mineral resources are increasingly exhausted.The contradiction that resource exhaustion and resource requirement increase is got over
More to protrude, so, efficiently use the important topic that existing mineral resources are current social developments.
Troilite is made of iron and sulphur, and under prior art economic condition, what can be efficiently used is sulphur therein, and
Iron therein becomes sulfate slag while using sulphur, and the content of iron is differed from 30% to 65% in slag, and this sulfate slag can be with
Raw material as ironmaking.Because containing a certain number of zinc and sulphur in sulfate slag, and zinc and sulphur are to endanger spy to blast furnace ironmaking process
Not big harmful element, thus application range and quantity of the sulfate slag as iron-smelting raw material are limited, prior art sulfate slag adds
Dosage is no more than iron ore 15%.Raw materials for production and noxious waste pollution environment of most of sulfate slag as cement plant,
Waste substantial amounts of valuable iron resource, the iron ore resource wretched insufficiency in another aspect China, it is annual need from foreign countries into
Mouthful 1,000,000,000 tons of iron ores are to meet the needs of Iron and Steel Enterprises in China.China's iron ore (A+B+C+D) resource reserves 463.7 hundred million
Ton, 152.95 hundred million tons of ferrous metal, wherein A+B+C grades of 7,300,000,000 tons of iron in ore amount of metal.4,600,000,000 tons of troilite reserves, wherein
Comprising 2,000,000,000 tons of ferrous metals, while using sulphur in troilite, as can comprehensively utilize iron resource therein, equivalent to for China
Add 30% and possess iron ore deposit, there is good economic and social benefit.
The content of the invention
It is contemplated that solve at least some of the technical problems in related technologies.For this reason, the present invention
One purpose is to propose that a kind of troilite prepares sulfuric acid and the method and system of direct reduced iron, can using this method and system
To effectively improve sulfur recovery rate in troilite, shorten technological process, efficiently use fired slags production high-quality direct reduced iron, carry
High resource utilization, to produce high-end casting, high-grade steel provides quality raw materials.
According to an aspect of the present invention, the present invention proposes the side that a kind of troilite prepares sulfuric acid and direct reduced iron
Method, according to a particular embodiment of the invention, this method include：
(1) fine grinding processing is carried out to troilite, to obtain troilite powder；
(2) troilite powder and water, binding agent and additive are subjected to mixed-forming processing, to obtain mixing ball
Group；
(3) the mixing pelletizing is supplied to drying grate is dried, the first preheating and second preheats, to be preheated
Pelletizing；
(4) by the preheated pellets supply to rotary kiln carry out oxidizing roasting processing, so as to obtain oxidizing roasting pelletizing and
Sulfur-containing smoke gas；
(5) the sulfur-containing smoke gas relieving haperacidity is utilized, to obtain sulfuric acid and deacidification flue gas；
(6) the oxidizing roasting pelletizing is supplied to carrying out direct-reduction processing with reducing gas in gas-based shaft kiln, so as to
Obtain flue gas containing zinc and direct reduced iron product.
Thus the method that sulfuric acid and direct reduced iron are prepared using the troilite of the above embodiment of the present invention is passed through to preheating
Pelletizing supplies to rotary kiln and carries out oxidizing roasting processing, can improve the effusion rate of zinc sum, and wherein sulfur recovery rate can reach
More than 99%, and then reduce the content of sulphur and zinc in the oxidizing roasting pelletizing after roasting.Oxidizing roasting pelletizing is in gas-based shaft kiln
Handled by direct-reduction, can high efficiente callback ferro element, avoid and reduce the prior art processing troilite caused by sulphur, iron resource
Waste.High ferro high-sulfur grade ferro-sulphur ore is after the method processing of the above embodiment of the present invention, the direct reduced iron that finally obtains
Product can be as the quality raw materials of electric furnace steel making.Method processing of the low iron low-sulfur grade ferro-sulphur ore through the above embodiment of the present invention
Afterwards, blast furnace ironmaking raw material can be used as, iron coke per ton ratio can at least reduce 4%-6%, and yield at least improves 5%-7%.
Can also have in addition, troilite according to the above embodiment of the present invention prepares sulfuric acid and the method for direct reduced iron
Additional technical characteristic as follows：
In some embodiments of the invention, particle diameter is that 45~75 microns of particle accounts for 60-78 weight % in troilite powder,
The particle that particle diameter is 75-150 microns accounts for 6-15 weight %, and particle diameter is that 10-45 microns of particle accounts for 16-25 weight %.
In some embodiments of the invention, the matter of the troilite powder, the water, the binding agent and the additive
Amount is than being 100：(4.5-11)：(0.5-1.5)：(0.5-1.5), preferably 100:(6-8)：(0.5-1.5)：(0.5-1.5).
In some embodiments of the invention, in step (2), the troilite powder, the water, the binding agent and described
The mass ratio of additive is 100：(4.5-11)：(0.5-1.5)：(0.5-1.5), preferably 100:(6-8)：(0.5-1.5)：
(0.5-1.5)。
In some embodiments of the invention, the part that particle diameter is 10-18mm in the mixing pelletizing is not less than 90 weights
% is measured, preferable particle size is that the part of 10-14mm is not less than 90 weight %.
In some embodiments of the invention, the additive is calcium oxide and/or calcirm-fluoride,
Optionally, the additive is calcium oxide and calcirm-fluoride, and the mass ratio of the calcium oxide and the calcirm-fluoride is
(4-7)：(1-3).
In some embodiments of the invention, in step (3),
The drying is to carry out completing for 5-10 minutes under 100-400 degrees Celsius；
First preheating is to carry out completing for 3-5 minutes under 400-600 degrees Celsius；
Second preheating is to carry out completing for 3-5 minutes under 600-1200 degrees Celsius；
The oxidizing roasting processing is to carry out completing for 5-10 minutes under 1150-1250 degrees Celsius.
In some embodiments of the invention, step (5) may further include：
(5-1) carries out waste heat recovery using air to the sulfur-containing smoke gas, to obtain high temperature air and containing after cooling
Sulphur flue gas；
(5-2) utilizes the sulfur-containing smoke gas relieving haperacidity after the cooling, to obtain sulfuric acid and deacidification flue gas；
(5-3) by the high temperature air supply to drying grate to it is described mixing pelletizing dried and first preheating.
In some embodiments of the invention, the cumulative volume of hydrogen and carbon monoxide is not less than in the reducing gas
80%.
In some embodiments of the invention, the charging temperature of the reducing gas is 750-900 degrees Celsius, the gas base
Pressure in shaft furnace is 0.1-0.45MPa, when the time of the direct-reduction processing is 3.5-5.5 small.
According to the second aspect of the invention, the invention also provides a kind of troilite for implementing preceding embodiment prepares sulfuric acid
And the system of the method for direct reduced iron, according to a particular embodiment of the invention, which includes：
There is troilite entrance and troilite powder to export for ore grinding device, the ore grinding device；
Mixing arrangement, the mixing arrangement have troilite powder entrance, water inlet, binding agent entrance, additive entrance and
Mixed material exports, and the troilite powder entrance is connected with troilite powder outlet；
Molding machine, the molding machine have mixed material entrance and the outlet of mixing pelletizing, the mixed material entrance
It is connected with mixed material outlet；
Drying grate, the drying grate have mixing pelletizing entrance and preheated pellets outlet, the mixing pelletizing entrance and institute
The outlet of mixing pelletizing is stated to be connected；
Rotary kiln, the rotary kiln has preheated pellets entrance, sulfur-containing smoke gas outlet and the outlet of oxidizing roasting pelletizing, described
Preheated pellets entrance is connected with preheated pellets outlet, and the sulfur-containing smoke gas outlet is connected with acid making system；
Gas-based shaft kiln, the gas-based shaft kiln have oxidizing roasting pelletizing entrance, reducing gas entrance, exhanst gas outlet containing zinc and
Direct reduced iron product exit, the oxidizing roasting pelletizing entrance are connected with oxidizing roasting pelletizing outlet.
Thus the system that sulfuric acid and direct reduced iron are prepared using the troilite of the above embodiment of the present invention is passed through to preheating
Pelletizing supplies to rotary kiln and carries out oxidizing roasting processing, can improve the effusion rate of zinc sum, and wherein sulfur recovery rate can reach
More than 99%, and then reduce the content of sulphur and zinc in the oxidizing roasting pelletizing after roasting.Oxidizing roasting pelletizing is in gas-based shaft kiln
Handled by direct-reduction, can high efficiente callback ferro element, avoid and reduce the prior art processing troilite caused by sulphur, iron resource
Waste.High ferro high-sulfur grade ferro-sulphur ore is after the system processing of the above embodiment of the present invention, the direct reduced iron that finally obtains
Product can be as the quality raw materials of electric furnace steel making.System processing of the low iron low-sulfur grade ferro-sulphur ore through the above embodiment of the present invention
Afterwards, blast furnace ironmaking raw material can be used as, iron coke per ton ratio can at least reduce 4%-6%, and yield at least improves 5%-7%.
Brief description of the drawings
Fig. 1 is the flow chart for the method that troilite according to an embodiment of the invention prepares sulfuric acid and direct reduced iron.
Fig. 2 is the structural representation for the system that troilite according to an embodiment of the invention prepares sulfuric acid and direct reduced iron
Figure.
Fig. 3 is that the structure for the system that troilite in accordance with another embodiment of the present invention prepares sulfuric acid and direct reduced iron is shown
It is intended to.
Embodiment
The embodiment of the present invention is described below in detail, the example of embodiment is shown in the drawings, wherein identical from beginning to end
Or similar label represents same or similar element or has the function of same or like element.Retouched below with reference to attached drawing
The embodiment stated is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes the side that a kind of troilite prepares sulfuric acid and direct reduced iron
Method, according to a particular embodiment of the invention, this method include：(1) fine grinding processing is carried out to troilite, to obtain troilite
Powder；(2) troilite powder and water, binding agent and additive are subjected to mixed-forming processing, to obtain mixing pelletizing；(3) will be mixed
Pelletizing is closed to supply to drying grate is dried, the first preheating and second preheats, to obtain preheated pellets；(4) by preheated pellets
Supply to rotary kiln carries out oxidizing roasting processing, to obtain oxidizing roasting pelletizing and sulfur-containing smoke gas；(5) sulfur-containing smoke gas system is utilized
Acid, to obtain sulfuric acid and deacidification flue gas；(6) oxidizing roasting pelletizing is supplied to direct with reducing gas progress in gas-based shaft kiln
Reduction treatment, to obtain flue gas containing zinc and direct reduced iron product.
Thus the method that sulfuric acid and direct reduced iron are prepared using the troilite of the above embodiment of the present invention is passed through to preheating
Pelletizing supplies to rotary kiln and carries out oxidizing roasting processing, can improve the effusion rate of zinc sum, and wherein sulfur recovery rate can reach
More than 99%, and then reduce the content of sulphur and zinc in the oxidizing roasting pelletizing after roasting.Oxidizing roasting pelletizing is in gas-based shaft kiln
Handled by direct-reduction, can high efficiente callback ferro element, avoid and reduce the prior art processing troilite caused by sulphur, iron resource
Waste.High ferro high-sulfur grade ferro-sulphur ore is after the method processing of the above embodiment of the present invention, the direct reduced iron that finally obtains
Product can be as the quality raw materials of electric furnace steel making.Method processing of the low iron low-sulfur grade ferro-sulphur ore through the above embodiment of the present invention
Afterwards, blast furnace ironmaking raw material can be used as, iron coke per ton ratio can at least reduce 4%-6%, and yield at least improves 5%-7%.
The method for preparing sulfuric acid and direct reduced iron to the troilite of the specific embodiment of the invention below with reference to Fig. 1 carries out in detail
Thin description：
S100：Troilite pre-processes
According to a particular embodiment of the invention, fine grinding processing is carried out to troilite first, to obtain troilite powder.Specifically
Ground, the troilite powder of the different-grain diameter mass ratio handled by fine grinding, specifically, particle diameter is micro- for 45~75 in troilite powder
The particle of rice accounts for 60-78 weight %, and the particle that particle diameter is 75-150 microns accounts for 6-15 weight %, and particle diameter is 10-45 microns of
Grain accounts for 16-25 weight %.Handled from there through fine grinding, obtain the troilite powder of different-grain diameter proportioning, and then balling-up can be improved
Rate, and the effusion of follow-up zinc and sulphur, reduce zinc, sulfur content in end-product.In addition the size distribution may insure pelletizing material
Specific surface area and the relatively low porosity of pelletizing.
According to a particular embodiment of the invention, further, troilite powder is mixed with water, binding agent and additive
Forming processes, to obtain mixing pelletizing.
According to a particular embodiment of the invention, since troilite pelletizing oxidizing roasting processing procedure has a large amount of sulfur dioxide to escape
Go out and cause pellet strength low.Inventor has found for this, increases the intensity of pelletizing by adding a certain proportion of additive.Specifically
Ground, additive selective oxidation calcium and/or calcirm-fluoride, it is preferable that both additive selective oxidation calcium and calcirm-fluoride are used in mixed way effect
Fruit is optimal, and the optimum quality ratio of calcium oxide and calcirm-fluoride is (4-7)：(1-3)., can from there through above-mentioned additive is used
To significantly improve the mouldability of troilite powder and pellet strength, in addition, inventor also found, above-mentioned additive can be with sial shape
Into low melting point, oxidizing roasting process produces a large amount of holes that Partial Liquid Phase flowing filling is formed by sulfur dioxide effusion.
According to a particular embodiment of the invention, the mass ratio of troilite powder, water, binding agent and additive is 100：(4.5-
11)：(0.5-1.5)：(0.5-1.5), and then mixing pelletizing can effectively be prepared.Specific example according to the present invention, sulphur
Iron Ore Powder, water, the mass ratio of binding agent and additive are preferably 100:(6-8)：(0.5-1.5)：(0.5-1.5).Thus, prepare
The drop strength of obtained mixing pelletizing, which can arrive, is more than 3 times/0.5m, acid pellet intensity>2000N/, porosity>20%,
And then the quality requirement for meeting green-ball and acid pellet can be reached.
According to a particular embodiment of the invention, the portion that particle diameter is 10-18mm in the mixing pelletizing that the above method is prepared
Divide and be not less than 90 weight %, and then can ensure the ratio of briquetting of pelletizing.Specific example according to the present invention, adds when selection is optimal
When adding agent and mixing match, particle diameter can reach more excellent effect in the mixing pelletizing being prepared, wherein it is 10- to select particle diameter
The part of 14mm can reach not less than 90 weight %.It is possible thereby to further improve the homogeneity of mixing pelletizing particle diameter, avoid
Difference in size is excessive.
S200：Pre- hot mixing pelletizing
According to a particular embodiment of the invention, the mixing pelletizing that above-described embodiment is prepared is supplied to drying grate and carried out
Drying, the first preheating and the second preheating, to obtain preheated pellets., can by the way that mixing pelletizing is dried and preheated in advance
To improve the efficiency that oxidizing roasting processing is carried out in follow-up rotary kiln.
According to a particular embodiment of the invention, above-mentioned drying is to carry out completing for 5-10 minutes under 100-400 degrees Celsius；
Above-mentioned first preheating is to carry out completing for 3-5 minutes under 400-600 degrees Celsius；Above-mentioned second preheating is Celsius in 600-1200
Degree is lower to carry out what is completed within 3-5 minutes.Thus the drying to mixing pelletizing can prevent pelletizing with pre- using gradually incremental temperature
In water removal and oxidizing process explosion and dusting, it is ensured that pellet strength is more than 2000N.
S300：Oxidizing roasting is handled
According to a particular embodiment of the invention, preheated pellets are supplied to rotary kiln and carries out oxidizing roasting processing, so as to
To oxidizing roasting pelletizing and sulfur-containing smoke gas.Specific example according to the present invention, oxidizing roasting processing is at 1150-1250 degrees Celsius
What lower progress was completed for 5-10 minutes.
According to a particular embodiment of the invention, preheated pellets carried out in rotary kiln oxidizing roasting processing specifically occur it is following
Reaction：
FeS2+O2=Fe2O3+SO2；
ZnS+O2=ZnO+SO2↑。
Oxidizing roasting processing produces the flue gas containing sulfur dioxide and solid oxidation pelletizing, CaO, CaF shape during pellet roasting
Into the component of fusible slag, fusible slag flowing is filled into because of a large amount of holes that sulfur dioxide escapes and is formed, and improves pelletizing pressure resistance
Degree and the control suitable porosity of pelletizing.
Thus, oxidizing roasting 5-10 minutes is carried out under 1150-1250 degrees Celsius, calcination temperature is high, and zinc effusion rate is high, sulphur
The rate of recovery more than 99%, advantageously reduces sulphur, the content of zinc in the iron content acid pellet after roasting.
S400：Sulfur-containing smoke gas relieving haperacidity
According to a particular embodiment of the invention, using sulfur-containing smoke gas relieving haperacidity, to obtain sulfuric acid and deacidification flue gas.It is and then right
The a large amount of sulphur contained in troilite carry out recycling.
S500：Oxidizing roasting pelletizing carries out direct-reduction processing
According to a particular embodiment of the invention, oxidizing roasting pelletizing is supplied to straight with reducing gas progress in gas-based shaft kiln
Reduction treatment is connect, to obtain flue gas containing zinc and direct reduced iron product.
According to a particular embodiment of the invention, hydrogen and carbon monoxide is total in the reducing gas that direct-reduction processing uses
Volume is not less than 80%.Carbon monoxide and hydrogen are the available gas for being reduced directly gas, the two cumulative volume is high, gas reduction
By force, be conducive to improve pelletizing reduction rate and productivity, reduce energy consumption.
According to a particular embodiment of the invention, the charging temperature of reducing gas is 750-900 degrees Celsius, in gas-based shaft kiln
Pressure is 0.1-0.45MPa, when the time for being reduced directly processing is 3.5-5.5 small.Thus, by right under the above-described reaction conditions
Oxidizing roasting pelletizing carries out direct-reduction processing, can reduce Zn content, the direct reduced iron production of acquisition with high efficiente callback ferro element
Thing can be as the excellent raw material of electric furnace steel making.
S600：The UTILIZATION OF VESIDUAL HEAT IN of sulfur-containing smoke gas
According to a particular embodiment of the invention, the troilite of the above embodiment of the present invention prepares sulfuric acid and direct reduced iron
Method further comprises：Waste heat recovery is carried out to sulfur-containing smoke gas using air, to obtain the sulfur-bearing after high temperature air and cooling
Flue gas；Using the sulfur-containing smoke gas relieving haperacidity after cooling, to obtain sulfuric acid and deacidification flue gas；High temperature air is supplied to drying grate pair
Mixing pelletizing carries out drying and the first preheating.From there through the sulfur-containing smoke gas of the high temperature produced to rotary kiln internal oxidition calcination process
Waste heat utilized, and the high temperature air after preheating dries mixing pelletizing and the first preheating, and then can be reduced
Drying and pre- thermal energy consumption.
According to the second aspect of the invention, the invention also provides a kind of troilite for implementing preceding embodiment prepares sulfuric acid
And the system of the method for direct reduced iron, according to a particular embodiment of the invention, which includes：Ore grinding device 100, mixing dress
Put 200, molding machine 300, drying grate 400, rotary kiln 500, gas-based shaft kiln 600.
Thus, fine grinding processing is carried out to troilite first with ore grinding device 100, to obtain troilite powder；Using mixed
Attach together put 200 and molding machine 300 troilite powder and water, binding agent and additive are subjected to mixed-forming processing, to obtain
Mix pelletizing；Mixing pelletizing is supplied to drying grate 400 is dried, the first preheating and second preheats, to obtain pre- hot-bulb
Group；Preheated pellets are supplied to rotary kiln 500 and carry out oxidizing roasting processing, to obtain oxidizing roasting pelletizing and sulfur-containing smoke gas；
Using sulfur-containing smoke gas relieving haperacidity, to obtain sulfuric acid and deacidification flue gas；Oxidizing roasting pelletizing is supplied interior with going back to gas-based shaft kiln 600
Raw-gas carries out direct-reduction processing, to obtain flue gas containing zinc and direct reduced iron product.
Thus the system that sulfuric acid and direct reduced iron are prepared using the troilite of the above embodiment of the present invention is passed through to preheating
Pelletizing supplies to rotary kiln and carries out oxidizing roasting processing, can improve the effusion rate of zinc sum, and wherein sulfur recovery rate can reach
More than 99%, and then reduce the content of sulphur and zinc in the oxidizing roasting pelletizing after roasting.Oxidizing roasting pelletizing is in gas-based shaft kiln
Handled by direct-reduction, can high efficiente callback ferro element, avoid and reduce the prior art processing troilite caused by sulphur, iron resource
Waste.High ferro high-sulfur grade ferro-sulphur ore is after the system processing of the above embodiment of the present invention, the direct reduced iron that finally obtains
Product can be as the quality raw materials of electric furnace steel making.System processing of the low iron low-sulfur grade ferro-sulphur ore through the above embodiment of the present invention
Afterwards, blast furnace ironmaking raw material can be used as, iron coke per ton ratio can at least reduce 4%-6%, and yield at least improves 5%-7%.
The system for preparing sulfuric acid and direct reduced iron to the troilite of the specific embodiment of the invention below with reference to Fig. 2 carries out in detail
Thin description：
According to a particular embodiment of the invention, ore grinding device 100 has troilite entrance 110 and troilite powder outlet 120.
Fine grinding processing is carried out to troilite using ore grinding device 100, to obtain troilite powder.Specifically, it is thin using ore grinding device 100
The troilite powder for the different-grain diameter mass ratio that mill is handled, specifically, particle diameter is 45~75 microns of particle in troilite powder
60-78 weight % are accounted for, the particle that particle diameter is 75-150 microns accounts for 6-15 weight %, and particle diameter is that 10-45 microns of particle accounts for 16-25
Weight %.Handled from there through fine grinding, obtain different-grain diameter distribution and proportioning troilite powder, and then can improve balling ratio and
The effusion of follow-up zinc and sulphur is improved, reduces zinc, sulfur content in end-product.
According to a particular embodiment of the invention, mixing arrangement 200 has troilite powder entrance 210, water inlet 220, bonds
Agent entrance 230, additive entrance 240 and mixed material outlet 250, troilite powder entrance 210 are connected with troilite powder outlet
120；Molding machine 300 has mixed material entrance 310 and mixing pelletizing outlet 320, mixed material entrance 310 and mixed material
Outlet 250 is connected.Thus, using mixing arrangement 200 and molding machine 300 by troilite powder and water, binding agent and additive into
Row mixed-forming processing, to obtain mixing pelletizing.It is possible thereby to it is easy to subsequent oxidation calcination process.
According to a particular embodiment of the invention, since troilite powder is not easily molded, pelletizing tool acquires a certain degree of difficulty.For this
Inventor has found, can improve the mouldability of troilite powder by adding a certain proportion of additive, and can also increase ball
The intensity of group.Specifically, additive selective oxidation calcium and/or calcirm-fluoride, it is preferable that additive selective oxidation calcium and calcirm-fluoride two
Person is used in mixed way best results, and the optimum quality ratio of calcium oxide and calcirm-fluoride is (4-7)：(1-3).From there through using upper
Additive is stated, mouldability, pellet strength and the porosity of troilite powder can be significantly improved.
According to a particular embodiment of the invention, the mass ratio of troilite powder, water, binding agent and additive is 100：(4.5-
11)：(0.5-1.5)：(0.5-1.5), and then mixing pelletizing can effectively be prepared.Specific example according to the present invention, sulphur
Iron Ore Powder, water, the mass ratio of binding agent and additive are preferably 100:(6-8)：(0.5-1.5)：(0.5-1.5).Thus, prepare
The drop strength of obtained mixing pelletizing, which can arrive, is more than 3 times/0.5m, acid pellet intensity>2000N/, porosity>20%,
And then the quality requirement for meeting green-ball and acid pellet can be reached.
According to a particular embodiment of the invention, the portion that particle diameter is 10-18mm in the mixing pelletizing that said system is prepared
Divide and be not less than 90 weight %, and then can ensure the ratio of briquetting of pelletizing.Specific example according to the present invention, adds when selection is optimal
When adding agent and mixing match, particle diameter can reach more excellent effect in the mixing pelletizing being prepared, wherein it is 10- to select particle diameter
The part of 14mm can reach not less than 90 weight %.It is possible thereby to further improve the homogeneity of mixing pelletizing particle diameter, avoid
Difference in size is excessive.
According to a particular embodiment of the invention, drying grate 400 has mixing pelletizing entrance 410 and preheated pellets outlet 420,
Mixing pelletizing entrance 410 is connected with mixing pelletizing outlet 320.Drying grate 400 is suitable for be prepared in above-mentioned molding machine 300
Mixing pelletizing dried, first preheating and second preheating, to obtain preheated pellets.By being carried out in advance to mixing pelletizing
Drying and preheating, can improve the efficiency that oxidizing roasting processing is carried out in follow-up rotary kiln.
According to a particular embodiment of the invention, there is rotary kiln 500 preheated pellets entrance 510, sulfur-containing smoke gas to export 520 and
Oxidizing roasting pelletizing outlet 530, preheated pellets entrance 510 are connected with preheated pellets outlet 420, sulfur-containing smoke gas outlet 520 and system
Acid system is connected.Rotary kiln 500 is suitable for the preheated pellets that preheating obtains in drying grate 400 carrying out oxidizing roasting processing, so as to
Obtain oxidizing roasting pelletizing and sulfur-containing smoke gas.
According to a particular embodiment of the invention, preheated pellets carry out the specific generation of oxidizing roasting processing in rotary kiln 500
Following reaction：
FeS2+O2=Fe2O3+SO2；
ZnS+O2=ZnO+SO2↑。
Oxidizing roasting processing produces the flue gas containing sulfur dioxide and solid oxidation pelletizing, CaO, CaF shape during pellet roasting
Component into fusible slag can suppress the expansion index of pelletizing, reduce pelletizing expansion rate, improve pelletizing compression strength.
According to a particular embodiment of the invention, there is gas-based shaft kiln 600 oxidizing roasting pelletizing entrance 610, reducing gas to enter
Mouth 620, exhanst gas outlet containing zinc 630 and direct reduced iron product exit 640, oxidizing roasting pelletizing entrance 610 and oxidizing roasting ball
Group outlet 530 is connected.Gas-based shaft kiln 600 is suitable for carrying out direct-reduction processing to oxidizing roasting pelletizing and reducing gas, so as to
To flue gas containing zinc and direct reduced iron product.
Specific example according to the present invention, is reduced directly in processing procedure, the charging temperature of reducing gas is taken the photograph for 750-900
Family name's degree, the pressure in gas-based shaft kiln is 0.1-0.45MPa, be reduced directly time of processing for 3.5-5.5 it is small when.
Specifically, the reduction reaction occurred in gas-based shaft kiln includes：
Fe2O3+H2(CO) ↑=Fe+H2O(CO2)↑；
ZnO+H2(CO)=Zn ↑+H2O(CO2)。
Direct reduced iron can be come out of the stove using after hot wafering, heat discharging or cooling and be used as blast furnace ironmaking, electric furnace steel making etc. after reduction
Raw material.
According to a particular embodiment of the invention, as shown in figure 3, the troilite of above-described embodiment prepares sulfuric acid and direct-reduction
The system of iron further comprises：
There is sulfur-containing smoke gas entrance 710, air intake 720, high temperature air to export 730 and for heat-exchanger rig 700, heat-exchanger rig
Low temperature sulfur-containing smoke gas outlet 740, sulfur-containing smoke gas entrance 710 are connected with sulfur-containing smoke gas outlet 520, high temperature air outlet 730 and chain
Comb machine 400 is connected.Thus waste heat recovery is carried out to sulfur-containing smoke gas using air, to obtain the sulfur-bearing after high temperature air and cooling
Flue gas；By high temperature air supply to drying grate to mixing pelletizing dried and first preheating.From there through to oxygen in rotary kiln
The waste heat of sulfur-containing smoke gas for changing the high temperature that calcination process produces is utilized, and by the high temperature air after preheating to mixing pelletizing into
Row drying and the first preheating, and then drying and pre- thermal energy consumption can be reduced.
The troilite of the above embodiment of the present invention prepares the method and system of sulfuric acid and direct reduced iron at least with following
One of advantage：
(1) calcination temperature is high, and zinc effusion rate is high, sulfur recovery rate more than 99%, is conducive to the iron content acid pellet after roasting
Sulphur, Zn content are low, and roasting rear oxidation pelletizing is used to be reduced directly, high efficiente callback ferro element, avoid and reduce prior art processing
The waste of sulphur, iron resource caused by troilite.
(2) after high ferro high-sulfur grade ferro-sulphur ore is processed by the invention, ferrous material can be as the quality raw materials of electric furnace steel making.
After low iron low-sulfur grade ferro-sulphur ore is processed by the invention, blast furnace ironmaking raw material can be used as, iron coke per ton ratio can at least reduce 4%-
6%, yield at least improves 5%-7%.
(3) troilite production sulfur dioxide process is combined into one with pelletizing oxidizing roasting, reduces enterprise's production occupation of land face
Product, equipment investment reduce by more than 10%.Chemical industry and metallurgical production are organically combined, 1 ton of troilite at least increases by 35 yuan of economic effects
Benefit.
Embodiment 1
Troilite fine grinding after selected is accounted for more than 60% to -200 mesh, troilite, water, binding agent bentonite after fine grinding,
Additive calcium oxide is with mass ratio 100：8：0.83：0.77 mixes pelletizing, and pelletizing particle diameter 10-18mm accounts for 90%, the ball that will have been made
Group is transported to grate kiln in 8min, 400-600 DEG C of preheating 5min of 250 DEG C of drying, 600-1200 DEG C of preheating after screening
4min, 1200-1250 DEG C of oxidizing roasting 8min, oxidizing roasting principle：FeS2+O2=Fe2O3+SO2, ZnS+O2=ZnO+SO2↑ roasting
Burn and produce flue gas and solid oxidation pelletizing, SO2Relieving haperacidity is recycled from flue gas, acid pellet is sent into gas-based shaft kiln and is carried out directly also
Original, reducing gas main component H2+ CO contents 80%, reducing gas temperature are heated to 950 DEG C, enter reduction shaft furnace section temperature 900
DEG C, erect furnace pressure control 0.44MPa, recovery time 3.9h.Reduction principle：Fe2O3+H2(CO) ↑=Fe+H2O(CO2) ↑, ZnO+
H2(CO)=Zn ↑+H2O(CO2), rate 95.22% direct reduced iron in reducing metal is come out of the stove after can cooling down, hot wafering, heat discharge
Take out and be used as high-quality steelmaking feed.Compared with prior art, sulphur oxidation generation SO2Relieving haperacidity, sulfur recovery rate improve 9%, iron recycling
Rate improves 95%.
1 troilite of table (butt) main component and content %
| Component | TFe | S | ∑ gangue |
| Content | 44.10 | 39.22 | 1.65 |
Table 2 roasts rear oxidation pelletizing main component and content, (90%)
| Component | TFe | Fe2O3 | S | ∑ gangue |
| Content | 66.88 | 95.07 | 0.037 | 4.39 |
3 DRI main components of table and content, %
| Component | TFe | MFe | FeO | S | ∑ gangue |
| Content | 92.37 | 87.95 | 5.68 | 0.051 | 6.32 |
Embodiment 2
Troilite fine grinding after selected is accounted for more than 60% to -200 mesh, troilite, water, binding agent bentonite after fine grinding,
Additive calcirm-fluoride is with mass ratio 100：6：0.62：0.98 mixes pelletizing, and pelletizing particle diameter 10-18mm accounts for 90%, the ball that will have been made
Group is transported to grate kiln and 3min, 400-600 DEG C of preheating 4min, 600-1200 DEG C of preheating is dried at 250 DEG C after screening
4min, 1200-1250 DEG C of oxidizing roasting 5min, oxidizing roasting principle：FeS2+O2=Fe2O3+SO2, ZnS+O2=ZnO+SO2↑ roasting
Burn and produce flue gas and solid oxidation pelletizing, SO2Relieving haperacidity is recycled from flue gas, acid pellet is sent into gas-based shaft kiln and is carried out directly also
Original, reducing gas main component H2+ CO contents more than 85%, reducing gas temperature are heated to 850 DEG C, enter reduction shaft furnace section temperature
800 DEG C, erect furnace pressure control 0.12MPa, recovery time 4.1h.Reduction principle：Fe2O3+H2(CO) ↑=Fe+H2O(CO2) ↑,
ZnO+H2(CO)=Zn ↑+H2O(CO2), rate 92.37% direct reduced iron in reducing metal is come out of the stove after can cooling down, hot wafering, heat
Discharging takes out and is used as blast furnace ironmaking, steelmaking feed and cooling agent.Compared with prior art, sulphur oxidation generation SO2Relieving haperacidity, sulfur recovery
Rate improves 7%, and iron recovery improves 96%.
4 troilite of table (butt) main component and content %
| Component | TFe | S | ∑ gangue |
| Content | 38.86 | 36.72 | 1.65 |
Table 5 roasts rear oxidation pelletizing main component and content, (90%)
| Component | TFe | Fe2O3 | S | ∑ gangue |
| Content | 56.79 | 57.56 | 0.037 | 17.72 |
6 DRI main components of table and content, %
| Component | TFe | MFe | FeO | S | ∑ gangue |
| Content | 74.98 | 69.26 | 7.36 | 0.048 | 23.32 |
Embodiment 3：Additive is calcium oxide and the mixture of calcirm-fluoride
As different from Example 2, the troilite after fine grinding, water, binding agent bentonite, additive calcium oxide and additive
Calcirm-fluoride is with mass ratio 100：6：0.8：0.87:0.33 mixes pelletizing, and pelletizing particle diameter 10-18mm accounts for 90%, the pelletizing that will have been made
Grate kiln is transported to after screening, and 3min, 400-600 DEG C of preheating 3min, 600-1200 DEG C of preheating are dried at 300 DEG C
3min, 1200-1250 DEG C of oxidizing roasting 5min, oxidizing roasting principle：FeS2+O2=Fe2O3+SO2, ZnS+O2=ZnO+SO2↑ roasting
Burn and produce flue gas and solid oxidation pelletizing, SO2Relieving haperacidity is recycled from flue gas, acid pellet is sent into gas-based shaft kiln and is carried out directly also
Original, reducing gas main component H2+ CO contents more than 85%, reducing gas temperature are heated to 900 DEG C, enter reduction shaft furnace section temperature
850 DEG C, erect furnace pressure control 0.257MPa, recovery time 4.6h.Reduction principle：Fe2O3+H2(CO) ↑=Fe+
H2O(CO2) ↑, ZnO+H2(CO)=Zn ↑+H2O(CO2), 94.68% direct reduced iron of reducing metal rate can be cold
But come out of the stove afterwards, hot wafering, heat discharge to take out and is used as blast furnace ironmaking, steelmaking feed and cooling agent.Compared with prior art, sulphur aoxidizes
Generate SO2Relieving haperacidity, sulfur recovery rate improve 5%, and iron recovery improves 96%.
4 troilite of table (butt) main component and content %
| Component | TFe | S | ∑ gangue |
| Content | 38.86 | 36.72 | 1.65 |
Table 5 roasts rear oxidation pelletizing main component and content, (90%)
| Component | TFe | Fe2O3 | S | ∑ gangue |
| Content | 56.79 | 57.56 | 0.045 | 17.72 |
7 DRI main components of table and content, %
| Component | TFe | MFe | FeO | S | ∑ gangue |
| Content | 75.67 | 71.64 | 5.18 | 0.048 | 23.18 |
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment of the present invention or example.In the present specification, schematic expression of the above terms is not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
Combined in an appropriate manner in a or multiple embodiments or example.In addition, without conflicting with each other, the technology of this area
Different embodiments or example described in this specification and different embodiments or exemplary feature can be combined by personnel
And combination.
Although the embodiment of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of method that troilite prepares sulfuric acid and direct reduced iron, it is characterised in that including：
(1) fine grinding processing is carried out to troilite, to obtain troilite powder；
(2) troilite powder and water, binding agent and additive are subjected to mixed-forming processing, to obtain mixing pelletizing；
(3) the mixing pelletizing is supplied to drying grate is dried, the first preheating and second preheats, to obtain pre- hot-bulb
Group；
(4) preheated pellets are supplied to rotary kiln and carries out oxidizing roasting processing, to obtain oxidizing roasting pelletizing and sulfur-bearing
Flue gas；
(5) the sulfur-containing smoke gas relieving haperacidity is utilized, to obtain sulfuric acid and deacidification flue gas；
(6) the oxidizing roasting pelletizing is supplied to direct-reduction processing is carried out with reducing gas in gas-based shaft kiln, to obtain
Flue gas containing zinc and direct reduced iron product.
2. according to the method described in claim 1, it is characterized in that, particle diameter is 45~75 microns of particle in the troilite powder
60-78 weight % are accounted for, the particle that particle diameter is 75-150 microns accounts for 6-15 weight %, and particle diameter is that 10-45 microns of particle accounts for 16-25
Weight %.
It is the troilite powder, the water, described viscous 3. according to the method described in claim 1, it is characterized in that, in step (2)
The mass ratio for tying agent and the additive is 100：(4.5-11)：(0.5-1.5)：(0.5-1.5), preferably 100:(6-8)：
(0.5-1.5)：(0.5-1.5).
4. according to the method described in claim 1, it is characterized in that, it is described mixing pelletizing in particle diameter be 10-18mm part not
Less than 90 weight %, preferable particle size is that the part of 10-14mm is not less than 90 weight %.
5. according to the method described in claim 1, it is characterized in that, the additive is calcium oxide and/or calcirm-fluoride,
Optionally, the additive is calcium oxide and calcirm-fluoride, and the mass ratio of the calcium oxide and the calcirm-fluoride is (4-
7)：(1-3).
6. according to the method described in claim 1, it is characterized in that, in step (3),
The drying is to carry out completing for 5-10 minutes under 100-400 degrees Celsius；
First preheating is to carry out completing for 3-5 minutes under 400-600 degrees Celsius；
Second preheating is to carry out completing for 3-5 minutes under 600-1200 degrees Celsius；
Optionally, in step (4), the oxidizing roasting processing is to carry out completing for 5-10 minutes under 1150-1250 degrees Celsius.
7. according to the method described in claim 1, it is characterized in that, step (5) may further include：
(5-1) carries out waste heat recovery using air to the sulfur-containing smoke gas, to obtain the sulfur-bearing cigarette after high temperature air and cooling
Gas；
(5-2) utilizes the sulfur-containing smoke gas relieving haperacidity after the cooling, to obtain sulfuric acid and deacidification flue gas；
(5-3) by the high temperature air supply to drying grate to it is described mixing pelletizing dried and first preheating.
8. the according to the method described in claim 1, it is characterized in that, cumulative volume of hydrogen and carbon monoxide in the reducing gas
Not less than 80%.
9. according to the method described in claim 1, it is characterized in that, the charging temperature of the reducing gas is Celsius for 750-900
Spend, the pressure in the gas-based shaft kiln is 0.1-0.45MPa, when the time of the direct-reduction processing is 3.5-5.5 small.
10. a kind of system implemented any one of the claim 1-9 troilite and prepare the method for sulfuric acid and direct reduced iron, its
It is characterized in that, including：
There is troilite entrance and troilite powder to export for ore grinding device, the ore grinding device；
Mixing arrangement, the mixing arrangement have troilite powder entrance, water inlet, binding agent entrance, additive entrance and mixing
Material outlet, the troilite powder entrance are connected with troilite powder outlet；
Molding machine, the molding machine have mixed material entrance and the outlet of mixing pelletizing, the mixed material entrance and institute
Mixed material outlet is stated to be connected；
Drying grate, the drying grate are mixed with mixing pelletizing entrance and preheated pellets outlet, the mixing pelletizing entrance with described
Pelletizing outlet is closed to be connected；
Rotary kiln, the rotary kiln have preheated pellets entrance, sulfur-containing smoke gas outlet and the outlet of oxidizing roasting pelletizing, the preheating
Pelletizing entrance is connected with preheated pellets outlet, and the sulfur-containing smoke gas outlet is connected with acid making system；
Gas-based shaft kiln, the gas-based shaft kiln have oxidizing roasting pelletizing entrance, reducing gas entrance, exhanst gas outlet containing zinc and directly
Reduced iron product exit, the oxidizing roasting pelletizing entrance are connected with oxidizing roasting pelletizing outlet.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711341385.8A CN108004362A (en) | 2017-12-14 | 2017-12-14 | Troilite prepares sulfuric acid and the method and system of direct reduced iron |
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|---|---|---|---|
| CN201711341385.8A CN108004362A (en) | 2017-12-14 | 2017-12-14 | Troilite prepares sulfuric acid and the method and system of direct reduced iron |
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ID=62058804
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| CN108893600A (en) * | 2018-07-09 | 2018-11-27 | 刘慧南 | A kind of method of troilite production iron acid pellet |
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| CN114107590A (en) * | 2021-11-26 | 2022-03-01 | 钢铁研究总院 | Pellet oxidizing roasting-pure hydrogen reduction cooling system and method |
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| CN108893600A (en) * | 2018-07-09 | 2018-11-27 | 刘慧南 | A kind of method of troilite production iron acid pellet |
| CN112322818A (en) * | 2020-10-29 | 2021-02-05 | 钢研晟华科技股份有限公司 | Full-oxygen melting reduction iron-making method for high-sulfur iron-containing raw material |
| CN115491454A (en) * | 2021-06-18 | 2022-12-20 | 宝山钢铁股份有限公司 | Iron ore microwave high-temperature sintering hydrogen cooling reduction device and method |
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| CN115491489B (en) * | 2021-06-18 | 2023-12-12 | 宝山钢铁股份有限公司 | Prereduced pellet preparation device and prereduced pellet preparation method based on grate-rotary kiln |
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| CN114107590A (en) * | 2021-11-26 | 2022-03-01 | 钢铁研究总院 | Pellet oxidizing roasting-pure hydrogen reduction cooling system and method |
| CN114107590B (en) * | 2021-11-26 | 2023-01-10 | 钢铁研究总院 | Pellet oxidizing roasting-pure hydrogen reduction cooling system and method |
| CN117535520A (en) * | 2024-01-09 | 2024-02-09 | 北京高能时代环境技术股份有限公司 | Method for smelting matte by reducing and producing iron powder internal circulation reinforced lead-containing waste residues |
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