CN105712347A - Method for preparing sulfur-rich activated carbon from high-sulfur petroleum coke - Google Patents
Method for preparing sulfur-rich activated carbon from high-sulfur petroleum coke Download PDFInfo
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- CN105712347A CN105712347A CN201610249895.1A CN201610249895A CN105712347A CN 105712347 A CN105712347 A CN 105712347A CN 201610249895 A CN201610249895 A CN 201610249895A CN 105712347 A CN105712347 A CN 105712347A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Abstract
The invention discloses a method for preparing sulfur-rich activated carbon from high-sulfur petroleum coke. The method comprises the following steps: (10) raw material mixing: proportionally mixing potassium hydroxide solid powder and high-sulfur petroleum coke particles, and stirring uniformly; (20) calcination activation: carrying out calcination activation on the mixture, collecting hydrogen sulfide gas generated in the calcination activation process, cooling the solid, washing with water, and drying to obtain powdery activated carbon; (30) petroleum coke combustion: combusting high-sulfur petroleum coke particles to generate sulfur dioxide gas; (40) simple substance sulfur generation: mixing the hydrogen sulfide gas with the sulfur dioxide gas, and reacting to obtain the simple substance sulfur; and (50) carbon particle immersion: immersing the activated carbon particles in an immersion solution prepared from the simple substance sulfur for 0.1-72 hours, and drying to obtain the sulfur-rich activated carbon. The method can greatly lower the manufacturing cost of the activated carbon and reduce the environmental pollution caused by the high-sulfur petroleum coke, thereby achieving the goal of sulfur fixation and demercuration.
Description
Technical field
The invention belongs to high sulfur petroleum coke recovery and utilization technology field, particularly a kind of method utilizing the rich sulfur activated carbon of high sulfur petroleum coke preparation.
Background technology
In recent years, China's rapid economic development, electricity needs is significantly increased so that the coal demand as the main primary energy of China steeply rises.But, environmental conservation is proposed huge challenge by utilizing in a large number of coal.The constituent of coal is complicated, can produce the flue gas containing a large amount of particulate matters, dust, harmful gas and trace element etc., environmental and human health impacts has serious harm when it burns in a large number.Wherein the harm of trace element is paid attention to by people day by day, and ecological environment and human health, as one of harmful element most in coal, even if aggregate amount is only small, also can be caused huge harm by hydrargyrum.Therefore, flue gas demercuration is at home and abroad obtained for general attention.
In demercuration methods numerous at present, absorption method demercuration is comparatively effective and more promising controls hydrargyrum technology.Sorbent used specifically include that activated carbon, zeolite, calcio activated carbon and flying dust etc..Activated carbon has good adsorption effect for being most difficult to removing and very harmful gaseous elemental mercury in flue gas.But commercial activated carbons utilization rate is low, consumption big, directly adopt active carbon adsorption high cost.
Therefore, prior art there is the problem that the activated carbon cost for absorption method demercuration is high.
Summary of the invention
The method that it is an object of the invention to provide the rich sulfur activated carbon of a kind of high sulfur petroleum coke preparation, is greatly reduced the manufacturing cost of activated carbon, reduces the high sulfur petroleum coke pollution to environment simultaneously.
The technical solution realizing the object of the invention is:
A kind of method utilizing the rich sulfur activated carbon of high sulfur petroleum coke preparation, comprises the steps:
(10) raw material mixing: by potassium hydroxide pressed powder and particle diameter be 60～120 orders, sulfur content be higher than 4% high sulfur petroleum coke granule mix by proportioning, stir；
Preferably, the mass ratio of high sulfur petroleum coke and potassium hydroxide is 1:3～8, and the best is 1:5.
(20) calcining and activating: by potassium hydroxide and high sulfur petroleum coke granulate mixture calcining and activating 3～6 hours at 500～800 DEG C; collect the hydrogen sulfide gas produced in calcining and activating process; solid cooled is taken out to room temperature, through washing, dries, obtains powdered active carbon；
Preferably, calcining and activating temperature is 600 DEG C, and the time is 4 hours.
(30) petroleum coke combustion: additionally burning high sulfur petroleum coke particles, provides activation energy for (20) calcining and activating step, collects the sulfur dioxide gas generated；
(40) elemental sulfur generates: is mixed with sulfur dioxide gas by hydrogen sulfide gas, is obtained by reacting elemental sulfur；
(50) carbon granule dipping: activated carbon granule be impregnated in the dipping solution prepared by elemental sulfur after 0.1～72 hour, dry, obtain rich sulfur activated carbon.
Preferably, dipping temperature is 25～100 DEG C；Dip time is 0.1～25 hour；The mass concentration of dipping solution is 1%～50%；Baking temperature is 60～180 DEG C, and drying time is 2～20 hours.
Compared with prior art, its remarkable advantage is the present invention:
The manufacturing cost of activated carbon is greatly reduced, reduces the high sulfur petroleum coke pollution to environment simultaneously.The present invention adopts low value garbage high sulfur petroleum coke to be presoma, method with potassium hydroxide base activation, prepare high-ratio surface, high absorption demercuration activated carbon, the hydrogen sulfide gas that activation process the produces sulfur dioxide gas precursor reactant produced that directly burns with high sulfur petroleum coke is utilized to generate elemental sulfur, elemental sulfur is carried on activated carbon surface and improves its absorption demercuration ability further, reduce the preparation cost of activated carbon.While realizing high sulfur petroleum coke recycling and high value added utilization, the sulphur pollution caused when reducing high sulfur petroleum coke burning.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the method flow diagram that the present invention utilizes the rich sulfur activated carbon of high sulfur petroleum coke preparation.
Fig. 2 is the process chart that the present invention utilizes the rich sulfur activated carbon of high sulfur petroleum coke preparation.
Detailed description of the invention
Following embodiment all adopts the step identical with technique scheme to carry out, in order to contrast.
Material, equipment used by each embodiment are commercially available without special instruction.Detection method is conventional method without special instruction.
Embodiment one
Choose 60 order high sulfur petroleum cokes, weigh potassium hydroxide, mix and blend for 1:5 in mass ratio.Mixture is calcining and activating 3 hours at 600 DEG C, take out after being cooled to room temperature, through washing, obtain powdered active carbon product after drying, collect the hydrogen sulfide gas produced in calcining and activating process.Choose high sulfur petroleum coke directly to burn, collect the sulfur dioxide gas produced in combustion process.By two kinds of gas hybrid reactions, it is thus achieved that elemental sulfur product.Elemental sulfur is configured to the impregnation liquid that mass concentration is 10%, activated carbon is impregnated 3 hours.After having impregnated, dry 3 hours in 60 DEG C, prepare rich sulfur activated carbon.Demercuration rate reaches 91%.
Embodiment two
Choose 60 order high sulfur petroleum cokes, weigh potassium hydroxide, mix and blend for 1:5 in mass ratio.Mixture is calcining and activating 4 hours at 600 DEG C, are cooled to room temperature and take out, and through washing, obtain powdered active carbon product after drying, collect the hydrogen sulfide gas produced in calcining and activating process.Choose high sulfur petroleum coke directly to burn, collect the sulfur dioxide gas produced in combustion process.By two kinds of gas hybrid reactions, it is thus achieved that elemental sulfur product.Elemental sulfur is configured to the impregnation liquid that mass concentration is 20%, activated carbon is impregnated 3 hours.After having impregnated, dry 4 hours in 80 DEG C, prepare rich sulfur activated carbon.Demercuration rate reaches 95%.
Embodiment three
Choose 80 order high sulfur petroleum cokes, weigh potassium hydroxide, mix and blend for 1:5 in mass ratio.Mixture is calcining and activating 3 hours at 600 DEG C, are cooled to room temperature and take out, and through washing, obtain powdered active carbon product after drying, collect the hydrogen sulfide gas produced in calcining and activating process.Choose high sulfur petroleum coke directly to burn, collect the sulfur dioxide gas produced in combustion process.By two kinds of gas hybrid reactions, it is thus achieved that elemental sulfur is configured to the impregnation liquid that mass concentration is 30% by elemental sulfur product, activated carbon is impregnated 2 hours.After having impregnated, dry 6 hours in 80 DEG C, prepare rich sulfur activated carbon.Demercuration rate reaches 93%.
Embodiment four
Choose 100 order high sulfur petroleum cokes, weigh potassium hydroxide, mix and blend for 1:5 in mass ratio.Mixture is calcining and activating 3 hours at 600 DEG C, are cooled to room temperature and take out, and through washing, obtain powdered active carbon product after drying, collect the hydrogen sulfide gas produced in calcining and activating process.Choose high sulfur petroleum coke directly to burn, collect the sulfur dioxide gas produced in combustion process.By two kinds of gas hybrid reactions, it is thus achieved that elemental sulfur product.Elemental sulfur is configured to the impregnation liquid that mass concentration is 20%, activated carbon is impregnated 3 hours.After having impregnated, dry 4 hours in 80 DEG C, prepare rich sulfur activated carbon.Demercuration rate reaches 91%.
Embodiment five
Choose 120 order high sulfur petroleum cokes, weigh potassium hydroxide, mix and blend for 1:5 in mass ratio.Mixture is calcining and activating 3 hours at 600 DEG C, are cooled to room temperature and take out, and through washing, obtain powdered active carbon product after drying, collect the hydrogen sulfide gas produced in calcining and activating process.Choose high sulfur petroleum coke directly to burn, collect the sulfur dioxide gas produced in combustion process.By two kinds of gas hybrid reactions, it is thus achieved that elemental sulfur product.Elemental sulfur is configured to the impregnation liquid that mass concentration is 40%, activated carbon is impregnated 3 hours.After having impregnated, dry 5 hours in 120 DEG C, prepare rich sulfur activated carbon.Demercuration rate reaches 90%.
Claims (8)
1. the method utilizing the rich sulfur activated carbon of high sulfur petroleum coke preparation, it is characterised in that comprise the steps:
(10) raw material mixing: by potassium hydroxide pressed powder and particle diameter be 60～120 orders, sulfur content be higher than 4% high sulfur petroleum coke granule mix by proportioning, stir；
(20) calcining and activating: by potassium hydroxide and high sulfur petroleum coke granulate mixture calcining and activating 3～6 hours at 500～800 DEG C; collect the hydrogen sulfide gas produced in calcining and activating process; solid cooled is taken out to room temperature, through washing, dries, obtains powdered active carbon；
(30) petroleum coke combustion: additionally burning high sulfur petroleum coke particles, provides activation energy for (20) calcining and activating step, collects the sulfur dioxide gas generated；
(40) elemental sulfur generates: is mixed with sulfur dioxide gas by hydrogen sulfide gas, is obtained by reacting elemental sulfur；
(50) carbon granule dipping: activated carbon granule be impregnated in the dipping solution prepared by elemental sulfur after 0.1～72 hour, dry, obtain rich sulfur activated carbon.
2. the method for the rich sulfur activated carbon of preparation according to claim 1, it is characterised in that in described (10) raw material blend step, the mass ratio of high sulfur petroleum coke and potassium hydroxide is 1:3～8.
3. the method for the rich sulfur activated carbon of preparation according to claim 1, it is characterised in that in described (10) raw material blend step, the mass ratio of high sulfur petroleum coke and potassium hydroxide is 1:5.
4. the method for the rich sulfur activated carbon of preparation according to claim 1, it is characterised in that in described (20) calcining and activating step, calcining and activating temperature is 600 DEG C, and the time is 4 hours.
5. the method for the rich sulfur activated carbon of preparation according to claim 1, it is characterised in that in described (50) carbon granule impregnation steps, dipping temperature is 25～100 DEG C.
6. the method for the rich sulfur activated carbon of preparation according to claim 1, it is characterised in that in described (50) carbon granule impregnation steps, dip time is 0.1～25 hour.
7. the method for the rich sulfur activated carbon of preparation according to claim 1, it is characterised in that in described (50) carbon granule impregnation steps, the mass concentration of dipping solution is 1%～50%.
8. the method for the rich sulfur activated carbon of preparation according to claim 1, it is characterised in that in described (50) carbon granule impregnation steps, baking temperature is 60～180 DEG C, and drying time is 2～20 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051391A (en) * | 2017-06-29 | 2017-08-18 | 安徽天顺环保设备股份有限公司 | One kind carries the sulfur-rich activated carbon flue gas demercuration adsorbent of bromine and preparation method |
| CN110783553A (en) * | 2019-11-26 | 2020-02-11 | 长虹格兰博科技股份有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN113120901A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Method for co-producing activated carbon and calcium oxide from petroleum coke and gypsum |
| CN114100592A (en) * | 2021-11-24 | 2022-03-01 | 中南大学 | Method for regenerating flue gas demercuration material and recovering elemental mercury |
| CN115282951A (en) * | 2022-07-18 | 2022-11-04 | 昆明理工大学 | Modification method of activated carbon for recovering gold in aqueous solution of thiosulfate |
-
2016
- 2016-04-21 CN CN201610249895.1A patent/CN105712347B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| 张勇: "制备方法对硫／活性炭复合材料性能的影响", 《矿冶工程》 * |
| 张永刚: "煅前∥段后石油焦制高比表面积活性炭的研究", 《炭素技术》 * |
| 张红波: "氢氧化钾/石油焦质量配比对活性炭性能的影响", 《功能材料》 * |
| 杜亚平: "石油焦基活性炭制备工艺对其吸附性能及孔结构的影响", 《新型炭材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051391A (en) * | 2017-06-29 | 2017-08-18 | 安徽天顺环保设备股份有限公司 | One kind carries the sulfur-rich activated carbon flue gas demercuration adsorbent of bromine and preparation method |
| CN110783553A (en) * | 2019-11-26 | 2020-02-11 | 长虹格兰博科技股份有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN113120901A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Method for co-producing activated carbon and calcium oxide from petroleum coke and gypsum |
| CN113120901B (en) * | 2019-12-31 | 2023-01-10 | 中国石油化工股份有限公司 | Method for co-producing activated carbon and calcium oxide from petroleum coke and gypsum |
| CN114100592A (en) * | 2021-11-24 | 2022-03-01 | 中南大学 | Method for regenerating flue gas demercuration material and recovering elemental mercury |
| CN115282951A (en) * | 2022-07-18 | 2022-11-04 | 昆明理工大学 | Modification method of activated carbon for recovering gold in aqueous solution of thiosulfate |
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