CN1304787A - Process for preparing SO2 desulfurizing agent-activated coke - Google Patents
Process for preparing SO2 desulfurizing agent-activated coke Download PDFInfo
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- CN1304787A CN1304787A CN 00124742 CN00124742A CN1304787A CN 1304787 A CN1304787 A CN 1304787A CN 00124742 CN00124742 CN 00124742 CN 00124742 A CN00124742 A CN 00124742A CN 1304787 A CN1304787 A CN 1304787A
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Abstract
A process for preparing SO2 desulfurizing agent-activated coke includes such steps as loading raw coal with 0.8-2.0 mm granularity to fluidized bed with nitrogen gas or the mixture of nitrogen gas and steam as fluidizing gas, heating to 600-900 deg.C by outer heater, and activating with the mixed gas of steam, oxygen and nitrogen as activating gas for 5-60 min. Its advantages include simple process, low cost, and greater specific surface area and high desulfurizing performance of obtained activated coke.
Description
The invention belongs to SO
2The preparation method of desulfurizing agent is specifically related to a kind of SO in the flue gas that removes
2Preparation method with desulfurizing agent-activated coke.
The method that removes sulfur dioxide of flue gases is a lot, but the technology of industrial applications maturation is limited, wherein mainly contains wet type lime/lime stone method, two alkaline process, sodium carbonate method, Ammonium Sulfite Method, activated coke and activated carbon method etc.Using at present maximum still is that still, these technology investments, maintenance cost are still higher with the various improvement technologies of lime/lime stone as absorbent, and secondary pollution is also more serious.
Little Songyuan City gram exhibition of Japan and white stone educate the husband wait by following process route prepare activated coke (will is assisted in combustion, 1985,64 (4): 255-262):
1. the coal that particle diameter is about 3.0mm carries out fluidized retoring under 400 ℃-700 ℃, time of staying 5-25min makes semicoke;
2. the semi-coke powder with the destructive distillation gained is broken to below the 1.0mm, adds feed coal (particle diameter is that 0.5mm is following) and maltha, and the water vapor mixing is after pan-type pelletizer is made diameter is 8.0mm, and length is the column moulding coke of 10.0mm-15.0mm;
3. moulding coke external-heat converter destructive distillation, pyrolysis temperature is 600 ℃-900 ℃, and programming rate is 1.5-15 ℃/min, and gas composition is during destructive distillation: water vapour 15%, surplus is nitrogen;
4. the moulding coke after the destructive distillation activates with identical converter, and activation temperature is 800 ℃-900 ℃, and gases used consisting of during activation: water vapour 80%, nitrogen 20% obtains activated coke.
The activated coke high specific surface area that utilizes this method to make is 340m
2/ g, maximum Sulfur capacity are 150mgSO
2/ gAC.
The preparation technology of this activated coke comprises that raw material pulverizing, drying, charing, semicoke are pulverized, mixed with binding agent, extruder grain, charing again, processes such as activation, complex process, the activated coke price comparison height that makes, and also specific area and Sulfur capacity are also big inadequately.
The objective of the invention is to develop that a kind of technology is simple, cheap, specific area is big, desulfurization performance SO preferably
2The preparation method of desulfurizing agent-activated coke,
Step of the present invention is as follows:
With particle diameter is that the feed coal of the selected coal of 0.8-2.0mm is packed in the fluid bed, fluidizing gas is the gaseous mixture (the two volume ratio is 1: 1) of nitrogen or steam and nitrogen, heater is set outside fluid bed, heating rate for heat up at a slow speed (heating rate be 10 ℃/min) or be rapidly heated (under activation temperature, coal directly being added in the fluidized bed plant), 600 ℃-900 ℃ activation down, soak time is 5-60min, activated gas consists of: water vapour 5-80%, oxygen content is 1-6%, and surplus is nitrogen.
Described coal is a Shaanxi Bin County coal, in preparation process, and the not fusion of outer surface of coal, coal particle shape shape is constant substantially before and after the processing.
The desulfurization performance of the activated coke that makes is as mentioned above measured by the following method: (it consists of: sulfur dioxide 1% with the activated coke of 0.9-2.0mm and simulated flue gas, water vapour 10%, oxygen 6%, surplus is nitrogen), at 100 ℃ of current downflow contact 4h, the sulfur content before and after the activated coke absorption is analyzed with the SC-444 Carbon-Sulfur Amalyzer that Leco company produces.Its specific area, pore volume, aperture etc. are measured with ASAP2000m gas absorption instrument.The Sulfur capacity computing formula of activated coke is:
The adsorbable SO of every gram activated coke sample
2Amount (mgSO
2/ gAC)=2000 (MK-mk)/m
Sample heavy (g) before the m=absorption
M=absorption back sample heavy (g)
The sulfur content (%) of K=absorption back sample
The sulfur content (%) of sample before the k=absorption
As mentioned above, the optimal activation temperature of utilizing this explained hereafter activated coke is 800 ℃-900 ℃, and soak time is 20-60min, and the concentration of water vapour is 30%-80%, and oxygen content is 1-6%, and surplus is nitrogen.
Since in the preparation process of activated coke, selected fluid technology, so the coal grain conducts heat, mass transfer rate is fast, the temperature homogeneous, the particle rate of heat addition is fast, and material activating is even.By the selection of coal and determining of production technology, selected feed coal can directly be heated to activation temperature and activate, thereby simplified preparation technology, shorten preparation time, reduce the cost of activated coke greatly, production capacity improves, simultaneously, the specific area of gained activated coke is bigger, and desulfurization performance is better.
Embodiments of the invention are:
Embodiment 1:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 800 ℃, feed activated gas, activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 40min.
Embodiment 2:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 20min.
Embodiment 3:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 30%, surplus is nitrogen.Soak time is 40min.
Embodiment 4:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 30%, oxygen 1%, surplus is nitrogen.Soak time is 20min.
Embodiment 5:
With the 100g particle diameter is that the feed coal of 1.6mm-2.0mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 40min.
Embodiment 6:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 50%, oxygen 6%, surplus is nitrogen.Soak time is 5min.
Embodiment 7:
With the 100g particle diameter is that the feed coal of the 1.0mm-1.25mm temperature of directly packing into is in 850 ℃ the fluidized bed plant that feeds activated gas, makes it to be rapidly heated, and activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 40min.
Embodiment 8:
With the 100g particle diameter is that the feed coal of 0.8mm-0.9mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 40min.
Embodiment 9:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 900 ℃, feed activated gas, activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 40min.
Embodiment 10:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 60min.
Embodiment 11:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is a nitrogen, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 80%, surplus is nitrogen.Soak time is 40min.
Embodiment 12:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is the gaseous mixture (volume ratio of steam and nitrogen is 1: 1) of nitrogen and steam, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 50%, surplus is nitrogen.Soak time is 5min.
Embodiment 13:
With the 100g particle diameter is that the feed coal of 1.0mm-1.25mm is packed in the fluidized bed plant, and fluidized gas is the gaseous mixture (volume ratio of steam and nitrogen is 1: 1) of nitrogen and steam, and heating rate is 10 ℃/min.When temperature is raised to 850 ℃, feed activated gas, activated gas consists of: water vapour 30%, surplus is nitrogen.Soak time is 20min.
Comparative Examples:
Be above-mentioned prior art.
Character and Sulfur capacity thereof as embodiment 1-13 and Comparative Examples gained activated coke are listed in table 1.
The activated coke of table 1 gained and the character of Comparative Examples and Sulfur capacity thereof
| Project | The BET specific area ( 2/g) | Pore volume (cm 3/g) | Average pore size (nm) | Iodine number (mg/g) | The yield of activated coke (%) | Activated coke Sulfur capacity (mgSO 2/gAC) |
| Comparative Examples | Be 340 to the maximum | ???-- | ??-- | ??-- | ?????-- | Be 150 to the maximum |
| Embodiment 1 | ??438.68 | ??0.2001 | ??0.49 | ?573.04 | ????64.4 | ????174.44 |
| Embodiment 2 | ??436.48 | ??0.2002 | ??0.48 | ?578.97 | ????64.0 | ????177.55 |
| Embodiment 3 | ??499.31 | ??0.2269 | ??0.47 | ?617.68 | ????59.8 | ????179.67 |
| Embodiment 4 | ?????-- | ????-- | ??-- | ?557.80 | ????61.1 | ????163.32 |
| Embodiment 5 | ??475.46 | ??0.2136 | ??0.48 | ?637.81 | ????57.0 | ????195.54 |
| Embodiment 6 | ??371.82 | ??0.1769 | ??0.53 | ?486.28 | ????63.3 | ????151.18 |
| Embodiment 7 | ??491.51 | ??0.2482 | ??0.53 | ?610.86 | ????52.0 | ????207.43 |
| Embodiment 8 | ??506.89 | ??0.2306 | ??0.46 | ?651.79 | ????58.9 | ????206.24 |
| Embodiment 9 | ??774.04 | ??0.3865 | ??0.51 | ?805.62 | ????46.2 | ????275.90 |
| Embodiment 10 | ??604.73 | ??0.2732 | ??0.49 | ?769.57 | ????53.2 | ????228.33 |
| Embodiment 11 | ??625.12 | ??0.2827 | ??0.48 | ?724.54 | ????55.3 | ????218.85 |
| Embodiment 12 | ??458.09 | ??0.2074 | ??0.48 | ?607.90 | ????61.5 | ????177.13 |
| Embodiment 13 | ????-- | ????-- | ??-- | ?577.42 | ????60.7 | ????181.81 |
The AC--activated coke
Obviously, activated coke of the present invention has higher specific surface area, bigger absorption sulfur capacity.
Claims (3)
1. SO
2The preparation method of desulfurizing agent-activated coke, it is characterized in that: with particle diameter is that the feed coal of the selected coal of 0.8-2.0mm is packed in the fluid bed, fluidizing gas is the gaseous mixture (the two volume ratio is 1: 1) of nitrogen or steam and nitrogen, heater is set outside fluid bed, heating rate for heat up at a slow speed (heating rate be 10 ℃/min) or be rapidly heated (under activation temperature, coal directly being added in the fluidized bed plant), 600 ℃-900 ℃ activation down, soak time is 5-60min, activated gas consists of: water vapour 5-80%, oxygen content is 1-6%, and surplus is nitrogen.
2. the preparation method of activated coke as claimed in claim 1, the optimal activation temperature that it is characterized in that described activated coke is 800-900 ℃, soak time is 20-60min, the consisting of of activation gas: steam 30-80%, oxygen 1-6%, surplus is nitrogen.
3. method as claimed in claim 1 or 2 is characterized in that described coal is a Shaanxi Bin County coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00124742A CN1120746C (en) | 2000-09-14 | 2000-09-14 | Process for preparing SO2 desulfurizing agent-activated coke |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00124742A CN1120746C (en) | 2000-09-14 | 2000-09-14 | Process for preparing SO2 desulfurizing agent-activated coke |
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|---|---|
| CN1304787A true CN1304787A (en) | 2001-07-25 |
| CN1120746C CN1120746C (en) | 2003-09-10 |
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| CN00124742A Expired - Fee Related CN1120746C (en) | 2000-09-14 | 2000-09-14 | Process for preparing SO2 desulfurizing agent-activated coke |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408474C (en) * | 2006-08-01 | 2008-08-06 | 长春惠工净化工业有限公司 | Production method of desulfur denitrate dust collecting active coke |
| CN101862575A (en) * | 2010-06-24 | 2010-10-20 | 瓮福（集团）有限责任公司 | Method for reducing SO2 content in exhaust gas in production of sulfuric acid |
| CN101584958B (en) * | 2009-06-01 | 2011-07-06 | 上海克硫环保科技股份有限公司 | Movable desorption device of activated coke |
| CN101462040B (en) * | 2007-12-19 | 2013-07-17 | 张大伟 | Method and apparatus for regenerating activated coke after processing waste water and sewage water |
| CN101491754B (en) * | 2008-01-24 | 2013-07-17 | 张大伟 | Reactive coke regeneration method and device |
| CN103224235A (en) * | 2013-05-13 | 2013-07-31 | 山东大学 | Process and device for quickly preparing powdered active coke for desulfurization by utilizing pulverized coal |
| CN104261405A (en) * | 2014-09-24 | 2015-01-07 | 哈尔滨工业大学 | Preparation method of activated cokes with surface functional groups with directionally distributed polarities |
| CN104891487A (en) * | 2015-04-30 | 2015-09-09 | 山东大学 | Method for rapidly preparing powdery active coke |
| CN106311144A (en) * | 2016-09-19 | 2017-01-11 | 新奥科技发展有限公司 | Method for preparing active coke |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148752A (en) * | 1976-04-09 | 1979-04-10 | Bayer Aktiengesellschaft | Production of activated carbon in a reactor having a lower static layer and an upper fluidized layer |
| JPS61151012A (en) * | 1984-12-25 | 1986-07-09 | Mitsubishi Chem Ind Ltd | Method of activating carbide |
| CN1057745C (en) * | 1997-06-25 | 2000-10-25 | 宁夏万得活性炭有限公司 | Amorphous particulate active carbon made from antiracite and its producing method |
-
2000
- 2000-09-14 CN CN00124742A patent/CN1120746C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408474C (en) * | 2006-08-01 | 2008-08-06 | 长春惠工净化工业有限公司 | Production method of desulfur denitrate dust collecting active coke |
| CN101462040B (en) * | 2007-12-19 | 2013-07-17 | 张大伟 | Method and apparatus for regenerating activated coke after processing waste water and sewage water |
| CN101491754B (en) * | 2008-01-24 | 2013-07-17 | 张大伟 | Reactive coke regeneration method and device |
| CN101584958B (en) * | 2009-06-01 | 2011-07-06 | 上海克硫环保科技股份有限公司 | Movable desorption device of activated coke |
| CN101862575A (en) * | 2010-06-24 | 2010-10-20 | 瓮福（集团）有限责任公司 | Method for reducing SO2 content in exhaust gas in production of sulfuric acid |
| CN103224235A (en) * | 2013-05-13 | 2013-07-31 | 山东大学 | Process and device for quickly preparing powdered active coke for desulfurization by utilizing pulverized coal |
| CN103224235B (en) * | 2013-05-13 | 2015-07-29 | 山东大学 | A kind of coal dust that utilizes prepares the desulfurization technique of powder activated Jiao and device fast |
| CN104261405A (en) * | 2014-09-24 | 2015-01-07 | 哈尔滨工业大学 | Preparation method of activated cokes with surface functional groups with directionally distributed polarities |
| CN104261405B (en) * | 2014-09-24 | 2016-01-20 | 哈尔滨工业大学 | The activated coke preparation method of surface functional group polarity orientation distribution |
| CN104891487A (en) * | 2015-04-30 | 2015-09-09 | 山东大学 | Method for rapidly preparing powdery active coke |
| CN106311144A (en) * | 2016-09-19 | 2017-01-11 | 新奥科技发展有限公司 | Method for preparing active coke |
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| Publication number | Publication date |
|---|---|
| CN1120746C (en) | 2003-09-10 |
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