CN102604712B - Steel slag composite desulfurizer for desulfurizing pulverized coal during combustion and desulfurization method using same - Google Patents
Steel slag composite desulfurizer for desulfurizing pulverized coal during combustion and desulfurization method using same Download PDFInfo
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Abstract
The invention provides a steel slag composite desulfurizer for desulfurizing pulverized coal during combustion, which comprises 50 to 100 parts by weight of steel slag, 45 to 85 parts by weight of limestone and 21 to 37 parts by weight of alumina; and the steel slag composite desulfurizer also comprises the following components: 37 to 45 percent by weight of calcium oxide, 8 to 24 percent by weight of alumina, 4 to 14 percent by weight of ferric oxide and 3 to 11 percent by weight of silicon oxide. The steel slag composite desulfurizer adopts the industrial waste steel slag and the limestone as main materials, and the mixture of alumina powder, which contains the calcium oxide, the alumina, the ferric oxide and the silicon oxide is added, a high-calcium-to-sulfur ratio and low-heat consumption formula is adopted, high sulfur fixation efficiency (60 to 80 percent) is achieved, and after desulfurization during combustion, sulfur-fixed slag can be directly recycled as cement clinker substitute for recycling. The invention also provides a desulfurization method using the steel slag composite desulfurizer.
Description
Technical field
The present invention relates to the sweetening agent that the coal dust furnace of boiler, power industry uses, relate in particular to a kind of slag composite desulfurizing agent and use its sulfur method.
Background technology
The desulfurization research of high sulphur coal is important topic in environmental pollution control research always for a long time, and high-efficiency desulfurization technology is also coal and environmentalist's study hotspot always.According to EPA's statistics, the SO of countries in the world exploitation, research, use
2control techniques is kind more than 200 nearly.Wherein combustion desulfurizing method, because not needing to increase extra sweetener, reduced investment, is subject to many investigators and pays close attention to.Coal dust firing sulfur method adds certain sweetening agent in coal, and the oxysulfide that coal combustion process is produced is fixed in coal ash with reactive desulfurizing agent generation vitriol or sulfide in coal.
Calcium-based desulfurizing agent is the at present domestic and international maximum class sweetening agent of study and use, it is ripe that its desulphurization during combustion theory has been tending towards, and fluid-bed sweetening combustion technology has started to use in Chinese large-sized power station, but due to the complicacy of desulfurization reaction process, and the decomposing again of vitriol under high temperature, make the effective rate of utilization of desulphurization during combustion agent and desulfurization efficiency generally lower.For improving desulfurization efficiency, investigator adds various auxiliary agents, to improve desulfurization product CaSO
4high-temperature decomposition temperature.Experimental study shows, the element compounds such as Na, K, Fe, Mn, Sr, as auxiliary agent, can make CaO and SO in sweetening agent
2reaction easily carry out, and easily form composite minerals, make CaSO
4high-temperature decomposition temperature improve.But in reality, taking calcium sulfate as main sulfur-bearing ore deposit phase, it will decompose below 1100 DEG C in coal dust firing operating mode, therefore cause desulfurization efficiency many lower than 50%.In addition, the calcium sulfur ratio of controlling when current combustion desulfurization is generally 2～3, main mine in desulfurization product (Gu sulphur slag) is calcium sulfate, gehlenite, calcium aluminate, Dicalcium Phosphate (Feed Grade), free oxide (calcium oxide, silicon oxide or aluminum oxide) etc. mutually, due to the variation of coal ash composition and the fluctuation of combustion conditions, Gu the ore deposit phase composite of sulphur slag changes greatly, free oxide is many, except the utilization of fly ash as general, does not substantially directly realize recycling.
Summary of the invention
The object of the present invention is to provide the slag composite desulfurizing agent that is applicable to coal dust firing desulfurization that a kind of desulfurization efficiency is high and use its sulfur method.
Technical scheme of the present invention is as follows:
For the slag composite desulfurizing agent of coal dust firing desulfurization, it is characterized in that, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 50～100 parts, 45～85 parts and 21～37 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 37～45wt%, the aluminum oxide of 8～24wt%, the ferric oxide of 4～14wt% and the silicon oxide of 3～11wt%.
In such scheme, described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
The sulfur method that uses above-mentioned slag composite desulfurizing agent, is characterized in that, it comprises the following steps:
1) choosing of raw material: be respectively by weight 50～100 parts, 45～85 parts and 21～37 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get the slag in the step 1) of aluminum oxide in the step 1) of Wingdale in the step 1) of 80wt%, 80wt% and 10wt%, after mixing with 100 parts of coal dusts, grind, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then the compound after screening is sprayed in roasting kiln by coal burner;
3) will after the slag mixing of the aluminum oxide of remaining Wingdale, remainder and remainder, grind, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in roasting kiln by the stuff-spraying pipe of coal burner bottom, described coal burner and stuff-spraying pipe are arranged in parallel up and down.
In such scheme, described step 2) in milling time be 6～10 hours.
In such scheme, the milling time in described step 3) is 8～12 hours.
In such scheme, the width between centers of described coal burner and stuff-spraying pipe is 300～1200mm.
In such scheme, the width between centers of described coal burner and stuff-spraying pipe is 500mm.
In such scheme, the flame temperature of described roasting kiln is controlled at 950 DEG C～1250 DEG C, is oxydizing flame atmosphere.
The mechanism of action of sweetening agent of the present invention is: in slag, be rich in calcium oxide, silicon oxide, its crystalline phase state with Dicalcium Phosphate (Feed Grade), tricalcium silicate exists, and generates more multi-silicate dicalcium, tricalcium silicate and has played nucleus inducing action for component in coal ash participates in solid state reaction at a lower temperature; And in slag, be also rich in the oxide compound such as ferric oxide, magnesium oxide, to sulfureous phase, (1000 DEG C of left and right), wide temperature range (950 DEG C-1250 DEG C) calcium sulphoaluminate from calcium sulfate to high-temperature stable transforms at a lower temperature, iron phase sosoloid forms and (the 1050 DEG C of left and right) formation at a lower temperature of promotion Dicalcium Phosphate (Feed Grade) all has very great help.Because this composite desulfurizing agent is taking industrial waste slag as one of main raw material, wherein calcium oxide content reaches 40%, the required calcium source of cement clinker mineral that generates can be provided, amount of lime only needs to meet the required active calcium oxide of desulphurization during combustion, and due to behavior of sulfation product at high temperature, the reduction of cement clinker ore deposit phase formation temperature, and most of solid state reactions are thermopositive reaction, in desulphurization during combustion process, can not improve because of the raising of calcium oxide hear rate, therefore can adopt high calcium sulfur ratio, also ensure thus silicon oxide in enough calcium sources and slag, the water generation reaction mud grog ore deposit phases such as aluminum oxide.
Beneficial effect of the present invention is: this slag composite desulfurizing agent is taking industrial waste slag, Wingdale as main raw material, the auxiliary mixture that contains calcium oxide, aluminum oxide, ferric oxide, silicon oxide that adds aluminum oxide powder, adopt high calcium sulfur ratio, low heat dissipation formula, reach high desulfurization efficiency (60～80%), the solid sulphur slag after desulphurization during combustion can be directly as cement clinker surrogate by recycling.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
The slag using in all embodiment is below selected from the steelmaking slag of wuhan iron & steel croup co., and its composition is in table 1.Be understandable that, the slag of other type is also applicable to the present invention.
Table 1 slag chemical composition (by weight percentage):
| SiO 2 | Al 2O 3 | CaO | Fe 2O 3 | MgO | f-CaO |
| 13.7% | 0.8% | 41.7% | 17.4% | 6.7% | <0.04% |
The technical analysis of the high sulphur coal using in all embodiment is below to carry out experiment test with reference to GB GB212-91.
The measuring method of sulfur-fixing rate is as follows:
Adopt barium sulfate weighting method (GB/T176-1996) to measure the sulphur content in calcining material, obtain sulfur-fixing rate according to formula (1-1).
η=S
1×M
1/(S
0×M
0)×100% （1-1）
In formula: η---sulfur-fixing rate, %;
M
0, M
1---the quality before sample calcining and after calcining, g;
S
0, S
1---the sulphur content (being scaled the mass percent of sulphur trioxide) before sample calcining and after calcining, %.
embodiment mono-:
For the slag composite desulfurizing agent of coal dust firing desulfurization, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 50 parts, 45 parts and 21 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 39～45wt%, the aluminum oxide of 17～21wt%, the ferric oxide of 6～9wt% and the silicon oxide of 4～7wt%.Described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
The sulfur method that uses above-mentioned slag composite desulfurizing agent, it comprises the following steps:
1) choosing of raw material: be respectively by weight 50 parts, 45 parts and 21 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get 36 parts of Wingdales, 16.8 parts of aluminum oxide and 5 parts of slags (being rich in calcium oxide, aluminum oxide), after mixing with 100 parts of high-sulfur coal dusts, pack in ball mill and grind, the time of grinding is 8 hours, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then by the compound after screening by coal burner spray in roasting kiln burn, desulfurization, make sulphur in flue gas be desulfurized the directed quick adsorption of agent.Roasting kiln should ensure that coal dust burns, and is oxydizing flame atmosphere, and the temperature control of flame is at 950 DEG C～1250 DEG C;
3) will after 45 parts of (being rich in slag) mixing of the slag of 4.2 parts, the aluminum oxide of 9 parts, remaining Wingdale, remainder and remainder, pack in ball mill and grind, the time of grinding is 12 hours, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in stove by the stuff-spraying pipe of coal burner bottom, can be subject to the heating of combustion flame, under roasting kiln Working environment, in solid sulphur slag, between compound, there is rapidly solid state reaction, form cement clinker ore deposit phase.Described coal burner and stuff-spraying pipe are arranged in parallel up and down, both width between centers is 300-1200mm, this distance can be determined according to the diameter of the size of roasting kiln, burner and stuff-spraying pipe, guarantees that the material that both spray does not intersect mutually, in order to avoid affect coal dust firing.In the present embodiment, both width between centers is 500 mm.
Coal dust is sprayed in stove and is burnt by burner with the sweetening agent fine powder that is rich in calcium oxide, aluminum oxide, the S that calcium oxide, aluminum oxide discharge during by coal dust firing catches, form calcium sulfate, calcium sulphoaluminate thing phase, thereafter jointly falling into below with high temperature ash content is together sprayed into and the heated slag fine powder that is rich in, in this process, calcium sulfate continues to react the calcium sulphoaluminate that generates high-temperature stable with aluminum oxide, and in mixture, each component continues reaction and forms the main hydrate phase such as Dicalcium Phosphate (Feed Grade), tricalcium silicate.By all lime-ash product collections, the levigate solid sulphur slag that can be used as cement clinker surrogate and utilize material that just can obtain containing the main thing phase such as calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate.Desulfurization degree reaches more than 70%.
The Analysis Values of the high sulphur coal in the present embodiment is in table 2, and coal ash chemical composition is in table 3
.
The technical analysis of table 2 coal and S analytical results (wt%):
| Coal | W ad | V ad | A ad | FC ad | S ad |
| High sulphur coal 1 | 2.08 | 13.34 | 18.23 | 66.26 | 3.34 |
Table 3 coal ash chemical composition (wt%):
| Raw material composition | SiO 2 | Al 2O 3 | CaO | Fe 2O 3 | MgO |
| High sulphur coal 1 | 54.43 | 26.9 | 9.64 | 2.5 | 1.93 |
embodiment bis-:
For the slag composite desulfurizing agent of coal dust firing desulfurization, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 50 parts, 82 parts and 37 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 38～42wt%, the aluminum oxide of 20～24wt%, the ferric oxide of 4～7wt% and the silicon oxide of 3～6wt%.Described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
The sulfur method that uses above-mentioned slag composite desulfurizing agent, it comprises the following steps:
1) choosing of raw material: be respectively by weight 50 parts, 82 parts and 37 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get 65.6 parts of Wingdales, 29.6 parts of aluminum oxide and 5 parts of slags (being rich in calcium oxide, aluminum oxide), after mixing with 100 parts of high-sulfur coal dusts, pack in ball mill and grind, the time of grinding is 8 hours, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then by the compound after screening by coal burner spray in roasting kiln burn, desulfurization, make sulphur in flue gas be desulfurized the directed quick adsorption of agent.Roasting kiln should ensure that coal dust burns, and is oxydizing flame atmosphere, and the temperature control of flame is at 950 DEG C～1250 DEG C;
3) will after 45 parts of (being rich in slag) mixing of the slag of 7.4 parts, the aluminum oxide of 16.4 parts, remaining Wingdale, remainder and remainder, pack in ball mill and grind, the time of grinding is 12 hours, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in stove by the stuff-spraying pipe of coal burner bottom, can be subject to the heating of combustion flame, under roasting kiln Working environment, in solid sulphur slag, between compound, there is rapidly solid state reaction, form cement clinker ore deposit phase.Described coal burner and stuff-spraying pipe are arranged in parallel up and down, both width between centers is 300-1200mm, this distance can be determined according to the diameter of the size of roasting kiln, burner and stuff-spraying pipe, guarantees that the material that both spray does not intersect mutually, in order to avoid affect coal dust firing.In the present embodiment, both width between centers is 500 mm.
Coal dust is sprayed in stove and is burnt by burner with the sweetening agent fine powder that is rich in calcium oxide, aluminum oxide, the S that calcium oxide, aluminum oxide discharge during by coal dust firing catches, form calcium sulfate, calcium sulphoaluminate thing phase, thereafter jointly falling into below with high temperature ash content is together sprayed into and the heated slag fine powder that is rich in, in this process, calcium sulfate continues to react the calcium sulphoaluminate that generates high-temperature stable with aluminum oxide, and in mixture, each component continues reaction and forms the main hydrate phase such as Dicalcium Phosphate (Feed Grade), tricalcium silicate.By all lime-ash product collections, the levigate solid sulphur slag that can be used as cement clinker surrogate and utilize material that just can obtain containing the main thing phase such as calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate.Desulfurization degree reaches more than 60%.
The Analysis Values of the high sulphur coal in the present embodiment is in table 4, and coal ash chemical composition is in table 5
.
The technical analysis of table 4 coal and S analytical results (wt%):
| Coal | W ad | V ad | A ad | FC ad | S ad |
| High sulphur coal 3 | 2.08 | 13.43 | 28.23 | 56.26 | 5.64 |
Table 5 coal ash chemical composition (wt%):
| Raw material composition | SiO 2 | Al 2O 3 | CaO | Fe 2O 3 | MgO |
| High sulphur coal 3 | 54.43 | 26.59 | 9.64 | 2.5 | 1.93 |
embodiment tri-:
For the slag composite desulfurizing agent of coal dust firing desulfurization, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 70 parts, 77 parts and 37 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 37～41wt%, the aluminum oxide of 19～24wt%, the ferric oxide of 6～9wt% and the silicon oxide of 4～7wt%.Described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
The sulfur method that uses above-mentioned slag composite desulfurizing agent, it comprises the following steps:
1) choosing of raw material: be respectively by weight 70 parts, 77 parts and 37 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get 61.6 parts of Wingdales, 29.6 parts of aluminum oxide and 7 parts of slags (being rich in calcium oxide, aluminum oxide), after mixing with 100 parts of high-sulfur coal dusts, pack in ball mill and grind, the time of grinding is 8 hours, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then by the compound after screening by coal burner spray in roasting kiln burn, desulfurization, make sulphur in flue gas be desulfurized the directed quick adsorption of agent.Roasting kiln should ensure that coal dust burns, and is oxydizing flame atmosphere, and the temperature control of flame is at 950 DEG C～1250 DEG C;
3) will after 63 parts of (being rich in slag) mixing of the slag of 7.4 parts, the aluminum oxide of 15.4 parts, remaining Wingdale, remainder and remainder, pack in ball mill and grind, the time of grinding is 12 hours, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in stove by the stuff-spraying pipe of coal burner bottom, can be subject to the heating of combustion flame, under roasting kiln Working environment, in solid sulphur slag, between compound, there is rapidly solid state reaction, form cement clinker ore deposit phase.Described coal burner and stuff-spraying pipe are arranged in parallel up and down, both width between centers is 300-1200mm, this distance can be determined according to the diameter of the size of roasting kiln, burner and stuff-spraying pipe, guarantees that the material that both spray does not intersect mutually, in order to avoid affect coal dust firing.In the present embodiment, both width between centers is 500 mm.
Coal dust is sprayed in stove and is burnt by burner with the sweetening agent fine powder that is rich in calcium oxide, aluminum oxide, the S that calcium oxide, aluminum oxide discharge during by coal dust firing catches, form calcium sulfate, calcium sulphoaluminate thing phase, thereafter jointly falling into below with high temperature ash content is together sprayed into and the heated slag fine powder that is rich in, in this process, calcium sulfate continues to react the calcium sulphoaluminate that generates high-temperature stable with aluminum oxide, and in mixture, each component continues reaction and forms the main hydrate phase such as Dicalcium Phosphate (Feed Grade), tricalcium silicate.By all lime-ash product collections, the levigate solid sulphur slag that can be used as cement clinker surrogate and utilize material that just can obtain containing the main thing phase such as calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate.Desulfurization degree reaches more than 60%.
The high sulphur coal using in the present embodiment is identical with embodiment bis-.
embodiment tetra-:
For the slag composite desulfurizing agent of coal dust firing desulfurization, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 100 parts, 63 parts and 22 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 41～45wt%, the aluminum oxide of 11～15wt%, the ferric oxide of 9～12wt% and the silicon oxide of 7～10wt%.Described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
The sulfur method that uses above-mentioned slag composite desulfurizing agent, it comprises the following steps:
1) choosing of raw material: be respectively by weight 100 parts, 63 parts and 22 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get 50.4 parts of Wingdales, 17.6 parts of aluminum oxide and 10 parts of slags (being rich in calcium oxide, aluminum oxide), after mixing with 100 parts of high-sulfur coal dusts, pack in ball mill and grind, the time of grinding is 8 hours, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then by the compound after screening by coal burner spray in roasting kiln burn, desulfurization, make sulphur in flue gas be desulfurized the directed quick adsorption of agent.Roasting kiln should ensure that coal dust burns, and is oxydizing flame atmosphere, and the temperature control of flame is at 950 DEG C～1250 DEG C;
3) will after 90 parts of (being rich in slag) mixing of the slag of 4.4 parts, the aluminum oxide of 12.6 parts, remaining Wingdale, remainder and remainder, pack in ball mill and grind, the time of grinding is 12 hours, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in stove by the stuff-spraying pipe of coal burner bottom, can be subject to the heating of combustion flame, under roasting kiln Working environment, in solid sulphur slag, between compound, there is rapidly solid state reaction, form cement clinker ore deposit phase.Described coal burner and stuff-spraying pipe are arranged in parallel up and down, both width between centers is 300-1200mm, this distance can be determined according to the diameter of the size of roasting kiln, burner and stuff-spraying pipe, guarantees that the material that both spray does not intersect mutually, in order to avoid affect coal dust firing.In the present embodiment, both width between centers is 500 mm.
Coal dust is sprayed in stove and is burnt by burner with the sweetening agent fine powder that is rich in calcium oxide, aluminum oxide, the S that calcium oxide, aluminum oxide discharge during by coal dust firing catches, form calcium sulfate, calcium sulphoaluminate thing phase, thereafter jointly falling into below with high temperature ash content is together sprayed into and the heated slag fine powder that is rich in, in this process, calcium sulfate continues to react the calcium sulphoaluminate that generates high-temperature stable with aluminum oxide, and in mixture, each component continues reaction and forms the main hydrate phase such as Dicalcium Phosphate (Feed Grade), tricalcium silicate.By all lime-ash product collections, the levigate solid sulphur slag that can be used as cement clinker surrogate and utilize material that just can obtain containing the main thing phase such as calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate.Desulfurization degree reaches more than 65%.
The Analysis Values of the high sulphur coal in the present embodiment is in table 6, and coal ash chemical composition is in table 7
.
The technical analysis of table 6 coal and S analytical results (wt%):
| Coal | W ad | V ad | A ad | FC ad | S ad |
| High sulphur coal 2 | 0.47 | 11.62 | 39.23 | 48.64 | 4.07 |
Table 7 coal ash chemical composition (wt%):
| Raw material composition | SiO 2 | Al 2O 3 | CaO | Fe 2O 3 | MgO |
| High sulphur coal 2 | 50.92 | 28.11 | 11.34 | 3.32 | 6.11 |
embodiment five:
For the slag composite desulfurizing agent of coal dust firing desulfurization, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 100 parts, 45 parts and 21 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 37wt%, the aluminum oxide of 8wt%, the ferric oxide of 14wt% and the silicon oxide of 11wt%.Described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
The sulfur method that uses above-mentioned slag composite desulfurizing agent, it comprises the following steps:
1) choosing of raw material: be respectively by weight 100 parts, 45 parts and 21 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get 36 parts of Wingdales, 16.8 parts of aluminum oxide and 10 parts of slags (being rich in calcium oxide, aluminum oxide), after mixing with 100 parts of high-sulfur coal dusts, pack in ball mill and grind, the time of grinding is 6 hours, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then by the compound after screening by coal burner spray in roasting kiln burn, desulfurization, make sulphur in flue gas be desulfurized the directed quick adsorption of agent.Roasting kiln should ensure that coal dust burns, and is oxydizing flame atmosphere, and the temperature control of flame is at 950 DEG C～1250 DEG C;
3) will after 90 parts of (being rich in slag) mixing of the slag of 4.2 parts, the aluminum oxide of 9 parts, remaining Wingdale, remainder and remainder, pack in ball mill and grind, the time of grinding is 12 hours, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in stove by the stuff-spraying pipe of coal burner bottom, can be subject to the heating of combustion flame, under roasting kiln Working environment, in solid sulphur slag, between compound, there is rapidly solid state reaction, form cement clinker ore deposit phase.Described coal burner and stuff-spraying pipe are arranged in parallel up and down, both width between centers is 300-1200mm, this distance can be determined according to the diameter of the size of roasting kiln, burner and stuff-spraying pipe, guarantees that the material that both spray does not intersect mutually, in order to avoid affect coal dust firing.In the present embodiment, both width between centers is 500 mm.
Coal dust is sprayed in stove and is burnt by burner with the sweetening agent fine powder that is rich in calcium oxide, aluminum oxide, the S that calcium oxide, aluminum oxide discharge during by coal dust firing catches, form calcium sulfate, calcium sulphoaluminate thing phase, thereafter jointly falling into below with high temperature ash content is together sprayed into and the heated slag fine powder that is rich in, in this process, calcium sulfate continues to react the calcium sulphoaluminate that generates high-temperature stable with aluminum oxide, and in mixture, each component continues reaction and forms the main hydrate phase such as Dicalcium Phosphate (Feed Grade), tricalcium silicate.By all lime-ash product collections, the levigate solid sulphur slag that can be used as cement clinker surrogate and utilize material that just can obtain containing the main thing phase such as calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate.Desulfurization degree reaches more than 70%.
The high sulphur coal using in the present embodiment is identical with embodiment mono-.
embodiment six:
For the slag composite desulfurizing agent of coal dust firing desulfurization, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 50 parts, 85 parts and 24 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 45wt%, the aluminum oxide of 13wt%, the ferric oxide of 4wt% and the silicon oxide of 3wt%.Described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
The sulfur method that uses above-mentioned slag composite desulfurizing agent, it comprises the following steps:
1) choosing of raw material: be respectively by weight 50 parts, 85 parts and 24 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get 68 parts of Wingdales, 19.2 parts of aluminum oxide and 5 parts of slags (being rich in calcium oxide, aluminum oxide), after mixing with 100 parts of high-sulfur coal dusts, pack in ball mill and grind, the time of grinding is 10 hours, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then by the compound after screening by coal burner spray in roasting kiln burn, desulfurization, make sulphur in flue gas be desulfurized the directed quick adsorption of agent.Roasting kiln should ensure that coal dust burns, and is oxydizing flame atmosphere, and the temperature control of flame is at 950 DEG C～1250 DEG C;
3) will after 45 parts of (being rich in slag) mixing of the slag of 4.8 parts, the aluminum oxide of 17 parts, remaining Wingdale, remainder and remainder, pack in ball mill and grind, the time of grinding is 8 hours, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in stove by the stuff-spraying pipe of coal burner bottom, can be subject to the heating of combustion flame, under roasting kiln Working environment, in solid sulphur slag, between compound, there is rapidly solid state reaction, form cement clinker ore deposit phase.Described coal burner and stuff-spraying pipe are arranged in parallel up and down, both width between centers is 300-1200mm, this distance can be determined according to the diameter of the size of roasting kiln, burner and stuff-spraying pipe, guarantees that the material that both spray does not intersect mutually, in order to avoid affect coal dust firing.In the present embodiment, both width between centers is 500 mm.
Coal dust is sprayed in stove and is burnt by burner with the sweetening agent fine powder that is rich in calcium oxide, aluminum oxide, the S that calcium oxide, aluminum oxide discharge during by coal dust firing catches, form calcium sulfate, calcium sulphoaluminate thing phase, thereafter jointly falling into below with high temperature ash content is together sprayed into and the heated slag fine powder that is rich in, in this process, calcium sulfate continues to react the calcium sulphoaluminate that generates high-temperature stable with aluminum oxide, and in mixture, each component continues reaction and forms the main hydrate phase such as Dicalcium Phosphate (Feed Grade), tricalcium silicate.By all lime-ash product collections, the levigate solid sulphur slag that can be used as cement clinker surrogate and utilize material that just can obtain containing the main thing phase such as calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate.Desulfurization degree reaches more than 60%.
The Analysis Values of the high sulphur coal in the present embodiment is in table 8, and coal ash chemical composition is in table 9
.
The technical analysis of table 8 coal and S analytical results (wt%):
| Coal | W ad | V ad | A ad | FC ad | S ad |
| High sulphur coal 4 | 2.23 | 13.06 | 55.62 | 29.09 | 4.95 |
Table 9 coal ash chemical composition (wt%):
| Raw material composition | SiO 2 | Al 2O 3 | CaO | Fe 2O 3 | MgO |
| High sulphur coal 4 | 52.06 | 32.24 | 2.3 | 4.48 | 2.24 |
Each raw material that the present invention is cited, and the bound value of each raw material, with and interval value, can realize the present invention; And the bound value of each processing parameter (as time etc.), with and interval value, can realize the present invention, do not enumerate embodiment at this.
Claims (8)
1. for the slag composite desulfurizing agent of coal dust firing desulfurization, it is characterized in that, it is made up of slag, Wingdale and aluminum oxide, and the weight part of described slag, Wingdale and aluminum oxide is respectively 50～100 parts, 45～85 parts and 21～37 parts; Described slag composite desulfurizing agent meets composition range simultaneously: the calcium oxide of 37～45wt%, the aluminum oxide of 8～24wt%, the ferric oxide of 4～14wt% and the silicon oxide of 3～11wt%, the ore deposit phase composite in the solid sulfur mineral in the solid sulphur slag after coal dust firing desulfurization mainly comprises calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate and ferro-aluminate.
2. slag composite desulfurizing agent as claimed in claim 1, is characterized in that, described slag, Wingdale and aluminum oxide are crossed 120 mesh sieves after pre-grinding respectively, and screen over-size is 6%.
3. a sulfur method that uses slag composite desulfurizing agent as claimed in claim 1, is characterized in that, it comprises the following steps:
1) choosing of raw material: be respectively by weight 50～100 parts, 45～85 parts and 21～37 parts and choose slag, Wingdale and aluminum oxide, for subsequent use;
2) get the slag in the step 1) of aluminum oxide in the step 1) of Wingdale in the step 1) of 80wt%, 80wt% and 10wt%, after mixing with 100 parts of coal dusts, grind, the compound grinding is sieved, screen cloth is 180 orders, screen over-size is 3%, then the compound after screening is sprayed in roasting kiln by coal burner;
3) will after the slag mixing of the aluminum oxide of remaining Wingdale, remainder and remainder, grind, the compound grinding is sieved, screen cloth is 150 orders, screen over-size is 2%, then the compound after screening is added in roasting kiln by the stuff-spraying pipe of coal burner bottom, described coal burner and stuff-spraying pipe are arranged in parallel up and down, and the ore deposit phase composite in the solid sulfur mineral in the solid sulphur slag after coal dust firing desulfurization mainly comprises calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tricalcium silicate and ferro-aluminate.
4. sulfur method as claimed in claim 3, is characterized in that, described step 2) in milling time be 6～10 hours.
5. sulfur method as claimed in claim 3, is characterized in that, the milling time in described step 3) is 8～12 hours.
6. sulfur method as claimed in claim 3, is characterized in that, the width between centers of described coal burner and stuff-spraying pipe is 300～1200mm.
7. sulfur method as claimed in claim 6, is characterized in that, the width between centers of described coal burner and stuff-spraying pipe is 500mm.
8. sulfur method as claimed in claim 3, is characterized in that, the flame temperature of described roasting kiln is controlled at 950 DEG C～1250 DEG C, is oxydizing flame atmosphere.
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| CN104232231B (en) * | 2014-09-18 | 2016-08-24 | 济南宝华新能源技术有限公司 | A kind of biomass-based fuel and preparation method |
| CN105199806A (en) * | 2015-09-25 | 2015-12-30 | 江阴兴澄特种钢铁有限公司 | Combustion-supporting fire coal additive and use method thereof |
| CN105238479A (en) * | 2015-10-14 | 2016-01-13 | 华北理工大学 | Steel slag checking tailing-modified biomass molded charcoal |
| CN105238474B (en) * | 2015-10-14 | 2018-07-17 | 华北理工大学 | The clean type coal and preparation method of additive are done using slag final election tailings |
| CN105276576B (en) * | 2015-10-20 | 2017-11-07 | 张保森 | A kind of coal desulfurization technique |
| CN105199809B (en) * | 2015-10-20 | 2017-10-10 | 张保森 | A kind of fire coal sulphur-fixing agent and preparation method thereof |
| CN105176618B (en) * | 2015-10-20 | 2017-10-10 | 张保森 | A kind of Filter Tuber For Clean Coal and its production method |
| CN105400562A (en) * | 2015-10-30 | 2016-03-16 | 广西桂晟新能源科技有限公司 | Desulfurization method for coal burning process |
| CN107099355A (en) * | 2017-04-21 | 2017-08-29 | 雷笑天 | A kind of preparation method of coal sulphur-fixing agent |
| CN113388427A (en) * | 2021-06-22 | 2021-09-14 | 镇江市蓝火环保能源有限公司 | Energy-saving coal powder and production method thereof |
| CN114904377A (en) * | 2022-04-07 | 2022-08-16 | 珠海市胜彥节能环保科技有限公司 | Desulfurizing agent and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4262610A (en) * | 1978-02-18 | 1981-04-21 | Rheinisch-Westfalisches Elektrizitatswerk Ag | Method of reducing the sulfur emissions from boilers fired with brown coal and, more generally, from boilers fired with low-rank solid fossil fuels and used in the production of electric power |
| CN1053083A (en) * | 1989-12-25 | 1991-07-17 | 航空工业部南方动力机械公司科技开发部 | A kind of additive for fire coal and using method thereof |
| CN1594516A (en) * | 2004-01-19 | 2005-03-16 | 阎玉德 | Combustion coal desulfurizing agent |
| CN102114379A (en) * | 2009-12-30 | 2011-07-06 | 中国环境科学研究院 | Desulfurizing agent and preparation and application thereof |
Family Cites Families (1)
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|---|---|---|---|---|
| JPS63108097A (en) * | 1986-10-23 | 1988-05-12 | Nippon Kankyo Asesumento Center:Kk | Production of briquette |
-
2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4262610A (en) * | 1978-02-18 | 1981-04-21 | Rheinisch-Westfalisches Elektrizitatswerk Ag | Method of reducing the sulfur emissions from boilers fired with brown coal and, more generally, from boilers fired with low-rank solid fossil fuels and used in the production of electric power |
| CN1053083A (en) * | 1989-12-25 | 1991-07-17 | 航空工业部南方动力机械公司科技开发部 | A kind of additive for fire coal and using method thereof |
| CN1594516A (en) * | 2004-01-19 | 2005-03-16 | 阎玉德 | Combustion coal desulfurizing agent |
| CN102114379A (en) * | 2009-12-30 | 2011-07-06 | 中国环境科学研究院 | Desulfurizing agent and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP昭63-108097A 1988.05.12 * |
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