CN1219850C - Desulfur method in coking process - Google Patents
Desulfur method in coking process Download PDFInfo
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- CN1219850C CN1219850C CN 03100343 CN03100343A CN1219850C CN 1219850 C CN1219850 C CN 1219850C CN 03100343 CN03100343 CN 03100343 CN 03100343 A CN03100343 A CN 03100343A CN 1219850 C CN1219850 C CN 1219850C
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- coke
- coking
- fixation agent
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- sulfur fixation
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Abstract
The present invention relates to a desulphurizing method in the process of coking, which comprises: solid organic substances and metallurgical solid waste which can be used as sulfur fixation agents are added in coking coal; the existing coking device and the existing coking technology are adopted for coking. The method realizes the synchronous desulphurization of coal gas and coke in the process of coking, the investment for devices and the cost are reduced, and the desulphurization effect of coal gas and coke is superior to those of separate coal gas desulphurization and separate coke desulphurization. Because metallurgical solid waste and the organic waste are used as used raw materials, the comprehensive utilization of the waste is realized, and the environmental pollution is reduced.
Description
Technical field
The invention belongs to the coking technology field, the method for coke-oven gas and coke synchronized desulfuring in particularly a kind of process of coking.
Background technology
In the process of coking, the whereabouts of sulphur mainly contains two portions in the coking coal: a part is with H
2S, COS, CS
2, C
2H
2The form of gaseous sulphides such as SH enters in the coke-oven gas, and another part is with FeS, CaS, S
2Deng form residue in the coke or be deposited on water coolant and tar in, if do not take required measure, will inevitably cause detrimentally affect to coal gas, coke and environmental quality.Traditional method is coke-oven gas to be carried out individual curing reach the desulfurization purpose mostly, but this method exists complex technical process, facility investment big, accounts for gross investment 15%, takes up an area of shortcoming such as wide, working cost height; Or in coking coal, add calcium base sulfur fixation agents such as lime, Wingdale and produce the sulfur bound coke charcoal, this method technology is simple, and expense is cheap, but sulphur content height in the coke, intensity difference can not be accepted by the user, more can not solve coke-oven gas sulphur pollution problem.
For the exploitation of coal gas of high temperature sulfur fixation agent, very extensive studies has been carried out in countries in the world.Chinese patent 99109834.X adopts industrial zinc oxide or/and contain ZnO, PbO and Fe
2O
3Industrial dust or mineral substance sulfur fixation agent sneak into method in the coking coal, realize the desulfurization of coal gas in coking or the gas production process.Though this method can obtain comparatively satisfied coal gas desulfurization effect, the sulphur content in the coke does not reduce, and does not promptly solve the synchronized desulfuring problem of coke-oven gas and coke.
Summary of the invention
The objective of the invention is in the prior art, the investment that the coking sulfur removal technology exists is big, complex technical process and can not realize coke-oven gas and the shortcoming of coke synchronized desulfuring, and the problems such as comprehensive utilization that are difficult to realize metallurgical solid waste and organic solid castoff, thereby under not changing existing coking equipment and coke making process condition, provide coke-oven gas and coke synchronized desulfuring method in a kind of process of coking.
Purpose of the present invention can realize by following measure:
Sulfur method in a kind of process of coking provided by the invention may further comprise the steps:
(1) coking coal, organism and sulfur fixation agent are mixed in proportion, wherein organic quality is the 2-15% of coking coal quality, and the formula of the quality of sulfur fixation agent is:
In the formula: R is the coefficient of excess of sulfur fixation agent;
(2) the above-mentioned mixture of being made up of coking coal, sulfur fixation agent and organism is added in the coke furnace carbonization chamber, be warming up to 950-1050 ℃ at 14-15 hour internal heating and carry out the coking coal pyrolysis, gaseous sulphide that the coking coal pyrolysis is produced and the reactive metal oxide in the sulfur fixation agent generate metallic sulfide and are deposited in stove dirt or the semicoke, realize coal gas desulfurization, obtain not sulfur compound or the lower coal gas of sulfide content;
(3) in coal gas desulfurization, form the high temperature section of coke in the semicoke charing of coke furnace carbonization chamber, this high temperature section initial temperature is 650 ℃, terminal temperature is 950-1050 ℃, with the H in the coke-oven gas
2Generate H with the organism cracking
2, reduzate such as CO and C is as reductive agent, the metal oxide in the reduction sulfur fixation agent and the metallic sulfide of step (1), the metal that reduction subsequently obtains is gasified, gaseous sulphide reaction in gaseous metal and the coal gas generates solid metal sulfide and is deposited in the stove dirt, realize coke desulfurating, obtain the coke of desulfurization;
(4) emit coke-oven gas from the stock gas outlet, emit coke from the furnace bottom coke export.
Sulfur fixation agent in the described step (1) is to contain ZnO, Fe
2O
3, metal oxide such as PbO metallurgical solid waste, mineral.
Organic particle in the described step (1) is that grain diameter is≤plastic grain of 5mm, rubber grain.
Advantage of the present invention is:
(1) the present invention realizes coke-oven gas and the synchronous desulfurization of coke in the process of coking, has reduced facility investment, has reduced cost, has realized the comprehensive utilization of waste, has reduced environmental pollution.
(2) the present invention selects for use metallurgical solid waste as the sulfur fixation agent that directly adds in the coking coal.To have ZnO, Fe than high desulfurization activity
2O
3, metal oxides such as PbO, CaO are combined with each other, overcome to be used alone the shortcoming that metal oxide exists; And metallurgical solid waste is rich in the oxide compound, fine size, active high of Fe, Zn, Pb, Ca etc., thereby sweetening effectiveness effective than independent coal gas desulfurization or independent coke desulfurating.
(3) the present invention also according to the thermal decomposition characteristic of organic wastes such as plastics, uses it for process of coking, does not need increase equipment, can economize on resources again, not only solves " white pollution " problem that is on the rise, and has improved the sweetening effectiveness of metallurgical waste.Macromolecular hydrocarbon in the organic solid castoff split products such as plastics finally enters in the tar after cooling off with coal gas; Fixed carbon remains in the coke; H
2Can strengthen the necessary reducing atmosphere of system in the high temperature carbonization coking phase of process of coking with reducing gas such as CO, thereby reduce the content of harmful element such as sulphur, zinc in the coke effectively.
Description of drawings
Fig. 1 is H in the coke-oven gas
2The concentration curve of S gas and be the heating curve of process of coking.
The drawing explanation:
T is the heating curve of process of coking
O-does not add the H that process of coking produced of sulfur fixation agent and organic solid castoff in coking coal
2The detected result curve of S concentration;
The H that process of coking produced that in coking coal, adds sulfur fixation agent and waste plastic among the 1-embodiment 1
2The detected result curve of S concentration;
The H that process of coking produced that in coking coal, adds sulfur fixation agent and waste plastic among the 2-embodiment 2
2The detected result curve of S concentration;
The H that process of coking produced that in coking coal, adds sulfur fixation agent and waste plastic among the 3-embodiment 3
2The detected result curve of S concentration; And
The H that process of coking produced that in coking coal, adds sulfur fixation agent and waste plastic among the 4-embodiment 4
2The detected result curve of S concentration.
Embodiment
Embodiment 1:
Adopt existing general pit kiln as coking equipment, adopt existing processes condition and step to carry out coking, realize coke-oven gas and coke synchronized desulfuring, concrete steps are as follows:
(1) batching:
The weight percentage of getting sulphur is 0.62%, the evaporation rate of sulphur is 40% coking coal 1t under the coking condition, the weight percentage of getting sulphur is 4.33%, the waste plastic particle 0.02t of the evaporation rate of sulphur about 100% under the coking condition (be coking coal 2%), wherein, the plastic grain median size is 1.5mm, and maximum particle diameter is 3mm.
Getting sulfur fixation agent is that ZnO content is 90% industrial zinc oxide slag (ignoring other metal oxide), and its consumption can calculate according to following formula:
The molar mass of sulphur is 32g/mol; The zinc oxide molar mass is 81g/mol; Sulfur fixation agent coefficient of excess R gets 1.2.In the above-mentioned formula of above-mentioned each data substitution, the consumption that calculates required sulfur fixation agent is 0.011t.
Above-mentioned raw material is even with the stirrer thorough mixing.
(2) raw material that step (1) is mixed adds in the coking chamber of pit kiln, in 14 hours, heat temperature raising to 950～1050 ℃, the gaseous sulphide reaction that oxide compound in the sulfur fixation agent and coking coal pyrolysis are produced generates the higher metallic sulfide of stability and is deposited in stove dirt or the semicoke, in finishing pyrogenic process gradually, realize coal gas desulfurization, obtain not sulfur compound or the lower coal gas of sulfide content.
(3) in coal gas desulfurization, form the high temperature section (650-950 ℃) of coke in the semicoke charing of coke furnace carbonization chamber, with the H in the coke-oven gas
2Generate H with plastic cracking
2, reduzate such as CO and C is as the reductive agent of reaction system, make in the sulfur fixation agent metal oxide and early stage the metallic sulfide in the sulfur product reduced and gasified, gaseous sulphide reaction in gaseous metal and the coal gas generates solid metal sulfide and is deposited in the stove dirt, realize coke desulfurating, obtain the low high grade coke of sulphur content.
(4) emit coke-oven gas from the stock gas outlet, emit coke from the furnace bottom coke export.
In process of coking to the H in the coke-oven gas
2S concentration detects, and draws out H
2S concentration is seen the curve 1 in the accompanying drawing 1 with the graphic representation that temperature and time changes; The heating curve figure of process of coking sees the curve T in the accompanying drawing 1; Detect the sulphur content and the zinc content of the coke of last coking gained, the sulphur content that draws coke is 0.408%, and zinc content is 0.351%, and the residual rate of zinc is 34.94%.
Control experiment: adopt same equipment and technology,, but do not add sulfur fixation agent and organic solid castoff carries out coking with same coking coal and consumption.Simultaneously to H in the coke-oven gas
2S concentration detects, and draws H
2S concentration is seen the curve 0 in the accompanying drawing 1 with the graphic representation that temperature and time changes; Detect the sulphur content of coking gained coke, the sulphur content that draws coke is 0.43%.
Implementation result:
Find out from the data of accompanying drawing 1 curve and gained:
When (1) carrying out coking with the coking coal that does not add sulfur fixation agent and organic solid castoff, H in institute's producing coal gas
2S concentration reaches as high as 11100mg/m
3And use to add coking coal behind sulfur fixation agent and the plastic waste when carrying out coking, H in institute's producing coal gas
2S concentration is the highest has only 3500mg/m
3, obviously to carry out the sulfur content in gas that coking obtains low than not adding sulfur fixation agent and plastic waste.
(2) add sulphur content in the coke of sulfur fixation agent and waste plastic coking gained and descended 5.12% than the sulphur content of the coke that does not add sulfur fixation agent and waste plastic gained.Tiing up element sulphur zinc content in the coke is 0.351%, and the zinc residual rate is 34.94%.
(3) desulphurization cost is starkly lower than other method.
Embodiment 2:
The batching of step (1), coking coal composition and consumption are with embodiment 1, and organic solid castoff granulometric composition and particle size are with embodiment 1, and its add-on is 15.0% of a coking coal weight; The component of sulfur fixation agent is with embodiment 1, and sulfur fixation agent coefficient of excess R gets 1.7; Calculate the consumption of sulfur fixation agent according to the formula of embodiment 1, and raw material is even with the stirrer thorough mixing; The heating-up time of step (2) is 15 hours; The temperature of step (3) high temperature section is 650～1050 ℃.Other are with embodiment 1
Implementation result:
(1) H in the coking institute producing coal gas
2The detected result of S concentration is seen curve 2 in the accompanying drawing 1.As seen, H in the coal gas
2S content is very low, in addition detect less than.
(2) sulphur content is 0.453% in the coke, compares when not adding sulfur fixation agent with plastics, slightly raises.
(3) solid element sulphur zinc content is 0.76% in the coke, and the zinc residual rate is 39.81%.
(4) desulphurization cost is starkly lower than additive method.
Embodiment 3:
The consumption of coking coal and composition are with embodiment 1.The organic solid castoff particle is got the plastic waste particle, and this waste plastic does not contain hazardness elements such as S, Cl, and the particle median size is 3mm, and maximum particle diameter is 5mm.Sulfur fixation agent is by industrial ZnO slag and contain ZnO, Fe
2O
3, PbO etc. metallurgical waste mix, its quality percentage composition is ZnO 29.02%, Fe
2O
316.99%, PbO 1.58%, C 17.42%, H
2O 2.26%, other 32.73%.The plastic waste addition is 10% of a coking coal weight; Sulfur fixation agent coefficient of excess R gets 1.0, calculates the consumption of sulfur fixation agent according to the formula of embodiment 1; The high temperature section of step (3) is 650-1000 ℃.Other are with embodiment 1.
Implementation result:
(1) H in the coking institute producing coal gas
2The detected result of S concentration is seen curve 3 in the accompanying drawing 1, promptly almost detects less than H
2S.
(2) sulphur content is 0.435% in the coke, and is suitable substantially when not adding sulfur fixation agent and plastics.
(3) solid element sulphur zinc content is 0.137% in the coke, and the zinc residual rate is 34.89%.
(4) desulphurization cost is starkly lower than additive method.
Embodiment 4:
The source of coking coal and plastic waste and composition are with example 3.Just sulfur fixation agent is for containing ZnO, Fe
2O
3Etc. the metallurgical waste of various ingredients, its weight percentage is: ZnO 10.03%, Fe
2O
321.54%, PbO 2.01%, C 22.08%, H
2O 2.86%, other 41.48%.The plastic waste addition is 5.0% of a coking coal weight; Sulfur fixation agent coefficient of excess R gets 1.0.Other are with embodiment 1.
Implementation result:
(1) H in the coal gas2The testing result of S concentration is seen curve 4 in the accompanying drawing 1.
(2) sulfur content is 0.421% in the coke, compares when not adding sulfur fixation agent with plastics, and 2.09 % have descended.
(3) solid element sulphur zinc content is 0.064% in the coke, and the zinc residual rate is 33.45%.
(4) desulphurization cost is starkly lower than additive method.
The present invention directly adds to the sulfur fixation agent of super quality and competitive price in the coking coal, in process of coking, realize the synchronized desulfuring of coke-stove gas and coke, obtain simultaneously in the investment that reduces coke-stove gas and coke desulfurating process and consumption, the reduction coke harmfulness constituent content such as sulphur, reduce many-sided effects such as discharging of sulfide, thereby guarantee coke-stove gas, coke and atmosphere quality; Organic matter and sulfur fixation agent can be selected from respectively organic waste and Using Metallurgical Solid Wastes, not only economize on resources, and also can be the solution white pollution problems of appropriateness.
Claims (1)
1, the method for desulfurization in a kind of process of coking is characterized in that, may further comprise the steps:
(1) coking coal, organism and sulfur fixation agent are mixed in proportion, wherein organic quality is the 2-15% of coking coal quality, and the calculation formula of the quality of sulfur fixation agent is:
In the formula: R is the coefficient of excess of sulfur fixation agent;
(2) the above-mentioned mixture of being made up of coking coal, sulfur fixation agent and organism is added in the coke furnace carbonization chamber, be warming up to 950-1050 ℃ at 14-15 hour internal heating and carry out the coking coal pyrolysis, gaseous sulphide that the coking coal pyrolysis is produced and the reactive metal oxide in the sulfur fixation agent generate metallic sulfide and are deposited in stove dirt or the semicoke, realize coal gas desulfurization, obtain not sulfur compound or the lower coal gas of sulfide content;
(3) in coal gas desulfurization, in the coke furnace carbonization chamber, it is the charing coking phase of the semicoke of 650-950 ℃ or 1050 ℃ in temperature, with the H in the coke-oven gas
2Generate H with the organism cracking
2, reduzate such as CO and C is as reductive agent, the metal oxide in the reduction sulfur fixation agent and the metallic sulfide of step (1), the metal that reduction subsequently obtains is gasified, gaseous sulphide reaction in gaseous metal and the coal gas generates solid metal sulfide and is deposited in the stove dirt, realize coke desulfurating, obtain the coke of desulfurization;
(4) emit coke-oven gas from the stock gas outlet, emit coke from the furnace bottom coke export;
Contain metal oxide ZnO, Fe in the sulfur fixation agent in the described step (1)
2O
3, at least a among PbO, the CaO;
Organism in the described step (1) is plastic grain or the rubber grain of average grain particle diameter less than 5mm.
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|---|---|---|---|
| CN 03100343 CN1219850C (en) | 2003-01-14 | 2003-01-14 | Desulfur method in coking process |
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|---|---|---|---|
| CN 03100343 CN1219850C (en) | 2003-01-14 | 2003-01-14 | Desulfur method in coking process |
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| CN1219850C true CN1219850C (en) | 2005-09-21 |
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| CN105219408B (en) * | 2014-06-23 | 2018-12-04 | 宝山钢铁股份有限公司 | It is a kind of to reduce the device and method that sulphur improves coke quality in coke |
| CN107384503A (en) * | 2017-08-09 | 2017-11-24 | 昆明理工大学 | A kind of sulfur method of petroleum coke |
| CN111575039B (en) * | 2020-04-30 | 2021-07-16 | 中南大学 | Coking desulfurization method |
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