CN101747977A - Desulfurization method for adding addition agent into coking coal - Google Patents
Desulfurization method for adding addition agent into coking coal Download PDFInfo
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- CN101747977A CN101747977A CN 200810229580 CN200810229580A CN101747977A CN 101747977 A CN101747977 A CN 101747977A CN 200810229580 CN200810229580 CN 200810229580 CN 200810229580 A CN200810229580 A CN 200810229580A CN 101747977 A CN101747977 A CN 101747977A
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Abstract
The invention discloses a desulfurization method for adding addition agent into coking coal, which is used for effectively separating out sulfur in the coking coal in the high-temperature dry distillation process and has a desulfurization function to both organic sulfur and inorganic sulfur. The desulfurization method comprises the following steps: preparation of addition agents: preparing three addition agents, namely, AlCl3 aqueous solution, H3BO3 aqueous solution and MgCl2 aqueous solution; preparation of coking coal: drying and crushing coking coal; adding of addition agent: mixing any one or two or all of the prepared addition agents with the prepared coal powder uniformly; high-temperature dry distillation: performing dry distillation to the coal powder mixed with the addition agents in a heating furnace. The addition agents used in the method has remarkable effect to the dry distillation and the desulfurization of coking coal, and the desulfurization percent of single coal is averagely increased by over 10 percent that the desulfurization percent of single coal without the addition agents. The desulfurization method can be widely applied in the desulfurization process of gas coal, fat coal, charred coal and 1/3 charred coal.
Description
Technical field
The present invention relates to a kind of sulfur method that in coking coal, adds additive.
Background technology
Because the fast development of Iron And Steel Industry, the metallurgical coke demand heightens.But high-quality caking coal resource undersupply.Coking coal resource accounts for 35.3% of coal resources total amount, and the high-sulfur coking coal accounts for 17.13%, and wherein the sulphur content of strong agglutinating value(of coal) main body coking coal is higher in gas-fat coal, rich coal and the coking coal etc.Gas-fat coal sulfur-bearing about 3.41%, rich coal 1.68%, coking coal sulfur-bearing 1.45%, the higher coking coal of these sulfur-bearings is generally better because of the general agglutinating value(of coal) of coal-forming environmental factors or coking property, therefore how effectively to utilize this part coal resources to be used for high-temperature coking, significant to the coal resources Sustainable development.
Consult pertinent literature, find one piece and be entitled as the article of " the laboratory pyrolysis desulfurizations of No. 8 coals in mining area, Gujiao City ", author Wang Hongdong, " Chinese coal field geology " 2004,16 (4), 34-36.Article has been introduced No. 8 coals in mining area, Gujiao City and has not been added catalyzer and the laboratory pyrolysis desulfurization test situation that adds under two kinds of conditions of catalyzer.The result shows, when add catalyst A lCl in raw coal
3And NH
4During Cl, desulfidation is preferably arranged, ash content does not obviously improve yet in the coke.This article desulfurization program is that experimental installation proposes with the tube furnace, also has very big distance with industrial coking.
Summary of the invention
The invention provides a kind of sulfur method that in coking coal, adds additive, the sulphur in the coking coal is effectively separated out in the high temperature carbonization process, organosulfur and inorganic sulfur are all had desulfidation.
Coking coal additive sulfur method provided by the invention may further comprise the steps:
A. additive preparation: prepare three kinds of additives, with AlCl
3Add the aqueous solution that water is made into 0.50～1.00mol/L; H
3BO
3Add the aqueous solution that water is made into 1.50～1.90mol/L; MgCl
2Add the aqueous solution that water is made into 0.60～1.00mol/L;
B. the preparation of coking coal: earlier with coking coal dry 2～3h under 105～110 ℃, again through being ground into granularity for reaching 85% coal dust less than the 3mm amount;
C. doping: with prepare among a any one additive solution, or any two kinds of additive solutions that mix, or three kinds of additive solutions that mix, coal dust uniform mixing with above-mentioned preparation, the addition of additive is counted 1.0～4.0% of coal dust weight with metal quality, places the dry 2～3h of 105～110 ℃ of drying plants then;
D. high temperature carbonization: carry out destructive distillation with above-mentioned with additive mixture of coal temperature rise rate with 3～12 ℃/min in process furnace, the whole temperature of destructive distillation is 600～900 ℃, and the residence time is 10～40min;
Said any two kinds of additive solutions mix or three kinds of additive solutions mixing among the above-mentioned steps c, and two kinds of additive solution blended ratios are 1: 1, and three kinds of additive solution blended ratios are 1: 1: 1.
Coking coal additive sulfur method provided by the invention, compared with prior art beneficial effect is remarkable, adopts SDSM2000 type sulphur detector that each coal sample and burnt sample are carried out the mensuration of full sulphur, and instrumental resolution is 0.01%, experiment is 40-60mg with test specimens weight, and the test duration is＜the 8min/ sample.When the whole temperature of destructive distillation is that 900 ℃, temperature rise rate are 12 ℃/min, the coking coal sweetening effectiveness was better when the residence time was 10min.Work as AlCl
3Loading be 1.0～4.0% o'clock, the bottle coal desulfurization degree is 63.67～68.37%, and the rich coal desulfurization degree is 54.04～65.21%, and the coking coal desulfurization degree is 55.11～66.58%, the desulfurization degree of 1/3 coking coal is 36.97～50.89%, and each single coal sample desulfurization degree of planting is than not adding AlCl
3Additive increases by 3.59～18.64 percentage points.Work as H
3BO
3Loading be 1.0～4.0% o'clock, the bottle coal desulfurization degree is 52.37～58.13%, the rich coal desulfurization degree is 52.62～58.23%, the coking coal desulfurization degree is that 55.02～59.60%, 1/3 coking coal desulfurization degree is 35.87～41.78%, each single coal sample desulfurization degree of planting is than not adding H
3BO
3Additive increases by 1.33～9.53 percentage points.By above-mentioned steps each coal sample is carried out the destructive distillation desulfurization, work as MgCl
2Loading be 1.0～4.0% o'clock, the bottle coal desulfurization degree is 64.62～71.21%, and the rich coal desulfurization degree is 54.06～63.93%, and the coking coal desulfurization degree is 55.40～61.47%, 1/3 coking coal desulfurization degree is 37.57～52.06%, and each single coal sample desulfurization degree of planting increases by 3.61～20.17 percentage points.When selecting AlCl for use
3, H
3BO
3, MgCl
2In two kinds of additives or three kinds of additive combinations when using, each single coal sample desulfurization degree of planting slightly increases, comparable independent use increases by 2.01～4.63 percentage points.
Embodiment
Below by embodiment the present invention is described in further detail.
Embodiment 1
With the laboratory lab scale is example:
(1) additive preparation: AlCl
3Add water and be mixed with the solution that concentration is 0.50～1.00mol/L;
(2) preparation of coal sample:, be crushed to granularity again for reaching 85% less than the 3mm amount earlier with each coal sample dry 2～3h under 105～110 ℃;
(3) doping: with the additive solution uniform mixing of above-mentioned coal sample, make metallic element support quality between 1.0～4.0%, place the dry 2～3h of 105～110 ℃ of baking ovens then with (1) middle preparation;
(4) high temperature carbonization: take by weighing 1～2 part of the above-mentioned coal sample temperature rise rate with 3～12 ℃/min in 1.5 kilograms of experimental furnaces and carry out destructive distillation, the whole temperature of destructive distillation is 600～900 ℃, and the residence time is 10～40min;
By above-mentioned steps each coal sample is carried out destructive distillation desulfurization, AlCl
3Obvious to the equal effect of each coking coal destructive distillation desulfurization, work as AlCl
3Loading be 1.0～4.0% o'clock, bottle coal (V
DafBe 37～42%, G
RIBeing 50～65) desulfurization degree is 63.67～68.37%, rich coal (V
DafBe 20～37%, G
RIBeing 85～92) desulfurization degree is 54.04～65.21%, coking coal (V
DafBe 20～28%, G
RIBeing 62～69) desulfurization degree is 55.11～66.58%, 1/3 Jiao (V
DafBe 28～37%, G
RIBeing 65～71) desulfurization degree of coal is 36.97～50.89%, each single coal sample desulfurization degree of planting is than not adding AlCl
3Additive increases by 3.59～18.64 percentage points.
Embodiment 2
With the laboratory lab scale is example:
(1) additive preparation: H
3BO
3Add water and be mixed with the solution that concentration is 1.50～1.90mol/L;
(2) preparation of coal sample: earlier with each coal sample dry 2～3h under 105～110 ℃, again through being crushed to granularity for reaching 85% less than the 3mm amount;
(3) doping: with the additive solution uniform mixing of above-mentioned coal sample, make metallic element support quality between 1.0～4.0%, place the dry 2～3h of 105～110 ℃ of baking ovens then with (1) middle preparation;
(4) high temperature carbonization: take by weighing 1～2 part of the above-mentioned coal sample temperature rise rate with 3～12 ℃/min in 1.5 kilograms of experimental furnaces and carry out destructive distillation, the whole temperature of destructive distillation is 600～900 ℃, and the residence time is 10～40min;
By above-mentioned steps each coal sample is carried out the destructive distillation desulfurization, work as H
3BO
3Loading be 1.0～4.0% o'clock, bottle coal (V
DafBe 37～42%, G
RIBeing 50～65) desulfurization degree is 52.37～58.13%, rich coal (V
DafBe 20～37%, G
RIBeing 85～92) desulfurization degree is 52.62～58.23%, coking coal (V
DafBe 20～28%, G
RIBeing 62～69) desulfurization degree is 55.02～59.60%, 1/3 coking coal (V
DafBe 28～37%, G
RIBeing 65～71) desulfurization degree is 35.87～41.78%, each single coal sample desulfurization degree of planting is than not adding H
3BO
3Additive increases by 1.33～9.53 percentage points.
Embodiment 3
With the laboratory lab scale is example:
(1) additive preparation: MgCl
2Add water and be mixed with the solution that concentration is 0.60～1.00mol/L;
(2) preparation of coal sample: earlier with each coal sample dry 2～3h under 105～110 ℃, again through being crushed to granularity for reaching 85% less than the 3mm amount;
(3) doping: with the additive solution uniform mixing of above-mentioned coal sample, make metallic element support quality between 1.0～4.0% earlier, place the dry 2～3h of 105～110 ℃ of baking ovens then with (1) middle preparation;
(4) high temperature carbonization: take by weighing 1～2 part of the above-mentioned coal sample temperature rise rate with 3～12 ℃/min in 1.5 kilograms of experimental furnaces and carry out destructive distillation, the whole temperature of destructive distillation is 600～900 ℃, and the residence time is 10～40min;
By above-mentioned steps each coal sample is carried out the destructive distillation desulfurization, work as MgCl
2Loading be 1.0～4.0% o'clock, bottle coal (V
DafBe 37～42%, G
RIBeing 50～65) desulfurization degree is 64.62～71.21%, rich coal (V
DafBe 20～37%, G
RIBeing 85～92) desulfurization degree is 54.06～63.93%, coking coal (V
DafBe 20～28%, G
RIBeing 62～69) desulfurization degree is 55.40～61.47%, 1/3 coking coal (V
DafBe 28～37%, G
RIBeing 65～71) desulfurization degree is 37.57～52.06%, each single coal sample desulfurization degree of planting increases by 3.61～20.17 percentage points.
Embodiment 4
With the laboratory lab scale is example:
(1) additive preparation: MgCl
2Add water and be mixed with the solution that concentration is 0.60～1.00mol/L, H
3BO
3Add water and be mixed with the solution that concentration is 1.50～1.90mol/L, AlCl
3Add water and be mixed with the solution that concentration is 0.50～1.00mol/L;
(2) preparation of coal sample: earlier with each coal sample dry 2～3h under 105～110 ℃, again through being crushed to granularity for reaching 85% less than the 3mm amount;
(3) doping: with any two kinds of mixing of additive of preparation in (1), the blended ratio is 1: 1, with above-mentioned coal sample and additive solution uniform mixing, make metallic element support quality between 1.0%～4.0% again, place the dry 2～3h of 105～110 ℃ of baking ovens then;
(4) high temperature carbonization: take by weighing 1～2 part of the above-mentioned coal sample temperature rise rate with 3～12 ℃/min in 1.5 kilograms of experimental furnaces and carry out destructive distillation, the whole temperature of destructive distillation is 600～900 ℃, and the residence time is 10～40min;
By above-mentioned steps each coal sample is carried out the destructive distillation desulfurization, when the loading of composite desulfurizing agent is 1.0～4.0%, bottle coal (V
DafBe 37～42%, G
RIBeing 50～65) desulfurization degree is 65.68～73.22%, rich coal (V
DafBe 20～37%, G
RIBeing 85～92) desulfurization degree is 56.54～67.71%, coking coal (V
DafBe 20～28%, G
RIBeing 62～69) desulfurization degree is 59.74～71.21%, 1/3 coking coal (V
DafBe 28～37%, G
RIBeing 65～71) desulfurization degree is 40.57～54.49%, each single coal sample desulfurization degree of planting increases by 6.09～22.24 percentage points.
Embodiment 5
With the laboratory lab scale is example:
In the foregoing description 4 steps (3), with three kinds of additives mixing of preparation, the blended ratio is 1: 1: 1, and with coal sample and additive solution uniform mixing, other testing sequences and result are with embodiment 4 again.
Claims (3)
1. the sulfur method of an adding addition agent into coking coal is characterized in that this method may further comprise the steps:
A. additive preparation: prepare three kinds of additives, with AlCl
3Add the aqueous solution that water is made into 0.50～1.00mol/L, H
3BO
3Add the aqueous solution that water is made into 1.50～1.90mol/L, MgCl
2Add the aqueous solution that water is made into 0.60～1.00mol/L;
B. the preparation of coking coal:, be coal dust through being ground into granularity again less than 3mm earlier with coking coal dry 2～3h under 105～110 ℃;
C. doping: with prepare among a any one additive solution, or any two kinds of additive solutions that mix, or three kinds of additive solutions that mix, coal dust uniform mixing with above-mentioned preparation, the addition of additive is counted 1.0～4.0% of coal dust weight with metal quality, places the dry 2～3h of 105～110 ℃ of drying plants then;
D. high temperature carbonization: carry out destructive distillation with above-mentioned with sweetening agent mixture of coal temperature rise rate with 3～12 ℃/min in process furnace, the whole temperature of destructive distillation is 600～900 ℃, and the residence time is 10～40min.
2. the sulfur method of adding addition agent into coking coal according to claim 1 is characterized in that said coking coal among this method steps b is ground into granularity and will reaches 85% for the amount less than the coal dust of 3mm.
3. the sulfur method of adding addition agent into coking coal according to claim 1, it is characterized in that said any two kinds of additive solution blending ratios that mix are 1: 1 among this method steps c, three kinds of additive solution blending ratios that mix are 1: 1: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421577A (en) * | 2012-11-30 | 2013-12-04 | 上海理工大学 | Quality improving method for high-sodium coal |
| CN106675683A (en) * | 2017-01-12 | 2017-05-17 | 安徽理工大学 | Method for carrying out microwave-assisted low-quality coal desulfurization |
-
2008
- 2008-12-11 CN CN 200810229580 patent/CN101747977A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421577A (en) * | 2012-11-30 | 2013-12-04 | 上海理工大学 | Quality improving method for high-sodium coal |
| CN106675683A (en) * | 2017-01-12 | 2017-05-17 | 安徽理工大学 | Method for carrying out microwave-assisted low-quality coal desulfurization |
| CN106675683B (en) * | 2017-01-12 | 2020-06-30 | 安徽理工大学 | Microwave-assisted low-quality coal desulfurization method |
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Application publication date: 20100623 |