CN101385966A - Load metal ball shaped active carbon material and preparation, use method thereof - Google Patents
Load metal ball shaped active carbon material and preparation, use method thereof Download PDFInfo
- Publication number
- CN101385966A CN101385966A CNA2008101577097A CN200810157709A CN101385966A CN 101385966 A CN101385966 A CN 101385966A CN A2008101577097 A CNA2008101577097 A CN A2008101577097A CN 200810157709 A CN200810157709 A CN 200810157709A CN 101385966 A CN101385966 A CN 101385966A
- Authority
- CN
- China
- Prior art keywords
- active carbon
- carbon material
- metal ball
- shaped active
- ball shaped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a gasoline desulfurizer adsorbent loaded metal spherical active carbon material, a preparation method of the active carbon material and an application method of the active carbon material. The technical proposal comprises the steps as follows: the loaded metal spherical active carbon material of sulphonium compound such as thiophene in the gasoline is removed; ion exchanging resin is taken as raw material to carry out metal ion exchanging; subsequently, the charring and activation under nitrogen atmosphere are carried out; the metal loading quantity is 5-15%; the charring temperature is 600-800 DEG C, and the activation temperature is 800-900 DEG C; the adsorbent can adsorb and remove the thiophene compound in the gasoline, with the removing rate more than 80%; furthermore, the efficiency is basically unchangeable during the process of circulation usage.
Description
Technical field
The present invention relates to charcoal absorption material and preparation, application process, relate in particular to a kind of load metal ball shaped active carbon material that is used for removing the gasoline thiophenes and preparation, application process.
Background technology
Contain multiple sulfur-containing compound in the gasoline, comprise mercaptan, thioether, disulphide and thiophene and benzothiophene derivative etc., the sulfur dioxide that the burning back generates etc. are except that causing the parts corrosion and poisoning the motor-vehicle tail-gas reforming catalyst, also can cause serious environmental problem such as acid rain, therefore, the gasoline desulfur research as fuel for motor vehicle has great importance.
In multiple gasoline desulfating method, adsorption desulfurize is a kind of cost processing method lower, easy and simple to handle.Employing has the porous adsorbent of special surface chemical property, as silica gel, molecular sieve and active carbon etc., the optionally sulfur-containing compound in the adsorbing and removing gasoline.Wherein absorbent charcoal material is because have special pore structure and a surface chemical property, the thiophenes that can the traditional hydrodesulfurizationprocess process of adsorbing and removing is difficult to remove, thereby have reasonable application prospect.Yet, the influence of materials such as alkene that the adsorption capacity of common absorbent charcoal material and adsorptive selectivity are subjected to containing in the gasoline and aromatic hydrocarbons, thereby adsorption capacity and adsorptive selectivity are not high.
Summary of the invention
The objective of the invention is at the existing defective of existing absorbent charcoal material thiophenes in adsorbed gasoline, on the basis by theoretical research and repetition test, the spherical activated charcoal material of finding carried metal is because the complexing of metal and thiophenes, can reduce the competition effect that competitive Adsorption such as alkene and aromatic hydrocarbons material adsorbs thiophene in the gasoline, improve thiophene adsorptive selectivity and adsorption capacity, thereby a kind of load metal ball shaped active carbon material that removes thiophenes in the gasoline and preparation thereof, application process are provided.
The present invention is to be raw material with ion exchange resin, and the spherical activated charcoal material profile that makes is loaded in the adsorption column for spherical, can reduce bed resistance, is convenient to the contact mass transfer of adsorption process material and adsorbent.Adopt the ion-exchange carried metal on active carbon, load capacity is controlled.Resin after the ion-exchange through charing and activation process, can prepare the porous carbon material of pore structure prosperity under blanket of nitrogen, improve the contact area of reactive metal and material.
Concrete technical scheme comprises:
Load metal ball shaped active carbon material is a carried metal nickel on spherical activated charcoal, and its load capacity is 5-15wt%.Described metallic nickel is the simple substance state, and the BET specific area is 500-800m
2/ g, metal average crystal grain particle diameter is 10-20nm.The diameter 200-400 μ m of described spherical activated charcoal, the BET specific area is 500-800m
2/ g, total hole volume are 0.4-0.6cm
3/ g.
The preparation method of load metal ball shaped active carbon material carries out as follows: (1) is dissolved in the 1g Nickelous nitrate hexahydrate in 20-40mL deionized water, makes nickel nitrate solution; (2) nickel nitrate solution is regulated the pH value to 7.0-8.0 with ammoniacal liquor; (3) will soak 2-4 hour in the 1g ion exchange resin immersion 10-20mL nickel nitrate solution; (4) ion exchange resin leaches from solution, with the washing of 10-20mL deionized water, filtration; (5) gained ion exchange resin sample is put into retort, under blanket of nitrogen in 600-800 ℃ of calcining at constant temperature 2-4 hours; (6) continue to be warming up to 800-900 ℃, feeding flow is the steam of 10-40mL/min, handles after 1-3 hour, is cooled to room temperature under blanket of nitrogen, obtains load metal ball shaped active carbon material.Described ion exchange resin is H type faintly acid phenolic type cation exchange resin, ion exchange capacity 〉=4mmol/g, water content 60-80%, granularity 0.315-1.25mm 〉=95%.
The application process of load metal ball shaped active carbon material is to carry out as follows: (1) every 1g load metal ball shaped active carbon material is handled the proportioning of 10-20mL gasoline; (2) load metal ball shaped active carbon material is packed into and is used in the adsorption column, and adsorption column is of a size of internal diameter and pipe range than being 6:450; (3) temperature constant of adsorption column is at 20-40 ℃, and gasoline flows through adsorption column under the promotion of plunger displacement pump.
The renovation process of load metal ball shaped active carbon material of the present invention is: with the absorbent charcoal material that the lost efficacy tube furnace of packing into, be warming up to 200-400 ℃ and handled 1-3 hour under blanket of nitrogen.
The present invention compares with prior art has outstanding feature and progress:
1. the preparation process that removes the load metal ball shaped active carbon material of thiophenes in the gasoline of the present invention is simple, and the spherical activated charcoal material metal load capacity that obtains after resin charing and the activation is controlled.
2. the adsorptive selectivity height of this spherical activated charcoal material, the thiophenes in the adsorbing and removing gasoline easily.
3. this spherical activated charcoal is reusable, and its adsorption capacity remains unchanged substantially.
4. with the carrier of raw material of wood-charcoal material as reactive metal, improved metal dispersity, its thiophene adsorption capacity is higher than traditional absorbent charcoal material.
The specific embodiment
The invention will be further described below in conjunction with example:
Embodiment 1: take by weighing the 582g Nickelous nitrate hexahydrate, be dissolved in the 20L deionized water, the dissolving back adds ammoniacal liquor, and regulating the pH value is 8.0; Take by weighing 1Kg H type faintly acid phenolic type cation exchange resin, add in the nickel nitrate solution, soak after 4 hours and filter; with the washing of 25L deionized water, dry after the filtration, put into retort; heating rate with 5 ℃/min under the condition that feeds nitrogen is warming up to 800 ℃; constant temperature 2 hours is warming up to 850 ℃ again, feeds the steam of 40L/min; activate 1.5 hours; under nitrogen protection, be cooled to room temperature, from retort, take out, obtain load metal ball shaped active carbon material.Handling sulfur content by every 1kg load metal ball shaped active carbon material is the proportioning of the gasoline 12L of 500 μ g/g, and load metal ball shaped active carbon material is packed into and used in the adsorption column, and adsorption column is of a size of internal diameter and pipe range than being 6:450; In temperature is to flow through adsorption column under the promotion of gasoline at plunger displacement pump with 12L under 25 ℃, and it is 65 μ g/g that the gasoline of outflow detects sulfur content, and desulfurization degree is 87.5%.
Handle 50L amount back desulfurization degree and obviously be reduced to the absorbent charcoal material 10% below tube furnace of packing into, under blanket of nitrogen, be warming up to 300 ℃ of processing after 2 hours, can reuse.
Embodiment 2: take by weighing the 291g Nickelous nitrate hexahydrate, be dissolved in the 20L deionized water, the dissolving back adds ammoniacal liquor, and regulating the pH value is 7.0; Take by weighing 1Kg H type faintly acid phenolic type cation exchange resin, add in the nickel nitrate solution, soak after 4 hours and filter; with the washing of 20L deionized water, dry after the filtration, put into retort; heating rate with 5 ℃/min under the condition that feeds nitrogen is warming up to 800 ℃; constant temperature 2 hours is warming up to 850 ℃ again, feeds the steam of 34L/min; activate 1.5 hours; under nitrogen protection, be cooled to room temperature, from retort, take out, obtain load metal ball shaped active carbon material.Handling sulfur content by every 1kg load metal ball shaped active carbon material is the proportioning of the gasoline 12L of 500 μ g/g, and load metal ball shaped active carbon material is packed into and used in the adsorption column, and adsorption column is of a size of internal diameter and pipe range than being 6:450; In temperature is to flow through adsorption column under the promotion of gasoline at plunger displacement pump with 12L under 25 ℃, and it is 156 that the gasoline of outflow detects sulfur content
μ g/g, desulfurization degree are 68.8%.
Handle 50L amount back desulfurization degree and obviously be reduced to the absorbent charcoal material 10% below tube furnace of packing into, under blanket of nitrogen, be warming up to 300 ℃ of processing after 2 hours, can reuse.
Embodiment 3: take by weighing the 582g Nickelous nitrate hexahydrate, be dissolved in the 20L deionized water, the dissolving back adds ammoniacal liquor, and regulating the pH value is 7.5; Take by weighing 1Kg ion exchange resin, add in the nickel nitrate solution, soak after 4 hours and filter; with the washing of 30L deionized water, dry after the filtration, put into retort; heating rate with 5 ℃/min under the condition that feeds nitrogen is warming up to 700 ℃; constant temperature 2 hours is warming up to 850 ℃ again, feeds the steam of 34L/min; activate 1.5 hours; under nitrogen protection, be cooled to room temperature, from retort, take out, obtain load metal ball shaped active carbon material.Handling sulfur content by every 1kg load metal ball shaped active carbon material is the proportioning of the gasoline 12L of 500 μ g/g, and load metal ball shaped active carbon material is packed into and used in the adsorption column, and adsorption column is of a size of internal diameter and pipe range than being 6:450; In temperature is to flow through adsorption column under the promotion of gasoline at plunger displacement pump with 12L under 25 ℃, and it is 233 μ g/g that the gasoline of outflow detects sulfur content, and desulfurization degree is 534%.
Handle 50L amount back desulfurization degree and obviously be reduced to the absorbent charcoal material 10% below tube furnace of packing into, under blanket of nitrogen, be warming up to 300 ℃ of processing after 2 hours, can reuse.
Embodiment 4: take by weighing the 582g Nickelous nitrate hexahydrate, be dissolved in the 20L deionized water, the dissolving back adds ammoniacal liquor, and regulating the pH value is 8.0; Take by weighing 1Kg ion exchange resin, add in the nickel nitrate solution, soak after 4 hours and filter; with the washing of 40L deionized water, dry after the filtration, put into retort; heating rate with 5 ℃/min under the condition that feeds nitrogen is warming up to 800 ℃; constant temperature 2 hours is warming up to 900 ℃ again, feeds the steam of 40L/min; activate 1.5 hours; under nitrogen protection, be cooled to room temperature, from retort, take out, obtain load metal ball shaped active carbon material.Handling sulfur content by every 1kg load metal ball shaped active carbon material is the proportioning of the gasoline 12L of 500 μ g/g; Load metal ball shaped active carbon material is packed into and is used in the adsorption column, and adsorption column is of a size of internal diameter and pipe range than being 6:450; In temperature is to flow through adsorption column under the promotion of gasoline at plunger displacement pump with 12L under 25 ℃, and it is 197 μ g/g that the gasoline of outflow detects sulfur content, and desulfurization degree is 60.6%.
Handle 50L amount back desulfurization degree and obviously be reduced to the absorbent charcoal material 10% below tube furnace of packing into, under blanket of nitrogen, be warming up to 300 ℃ of processing after 2 hours, can reuse.
Claims (6)
1, a kind of load metal ball shaped active carbon material is characterized in that: carried metal nickel on spherical activated charcoal, its load capacity are 5-15wt%.
2, load metal ball shaped active carbon material as claimed in claim 1 is characterized in that: described metallic nickel is the simple substance state, and the BET specific area is 500-800m
2/ g, metal average crystal grain particle diameter is 10-20nm.
3, load metal ball shaped active carbon material as claimed in claim 1 or 2 is characterized in that: the diameter 200-400 μ m of described spherical activated charcoal, the BET specific area is 500-800m
2/ g, total hole volume are 0.4-0.6cm
3/ g.
4, as the preparation method of each described load metal ball shaped active carbon material of claim 1-3, it is characterized in that carrying out as follows: (1) is dissolved in the 1g Nickelous nitrate hexahydrate in 20-40mL deionized water, makes nickel nitrate solution; (2) nickel nitrate solution is regulated the pH value to 7.0-8.0 with ammoniacal liquor; (3) will soak 2-4 hour in the 1g ion exchange resin immersion 10-20mL nickel nitrate solution; (4) ion exchange resin leaches from solution, with the washing of 10-20mL deionized water, filtration; (5) gained ion exchange resin sample is put into retort, under blanket of nitrogen in 600-800 ℃ of calcining at constant temperature 2-4 hours; (6) continue to be warming up to 800-900 ℃, feeding flow is the steam of 10-40mL/min, handles after 1-3 hour, is cooled to room temperature under blanket of nitrogen, obtains load metal ball shaped active carbon material.
5, the preparation method of load metal ball shaped active carbon material as claimed in claim 4, it is characterized in that: described ion exchange resin is H type faintly acid phenolic type cation exchange resin, ion exchange capacity 〉=4mmol/g, water content 60-80%, granularity 0.315-1.25mm 〉=95%.
6,, it is characterized in that carrying out as follows as the application process of each described load metal ball shaped active carbon material of claim 1-3:
(1) every 1g load metal ball shaped active carbon material is handled the proportioning of 10-20mL gasoline; (2) load metal ball shaped active carbon material is packed into and is used in the adsorption column, and adsorption column is of a size of internal diameter and pipe range than being 6:450; (3) temperature constant of adsorption column is at 20-40 ℃, and gasoline flows through adsorption column under the promotion of plunger displacement pump.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101577097A CN101385966B (en) | 2008-10-16 | 2008-10-16 | Load metal ball shaped active carbon material and preparation, use method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101577097A CN101385966B (en) | 2008-10-16 | 2008-10-16 | Load metal ball shaped active carbon material and preparation, use method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101385966A true CN101385966A (en) | 2009-03-18 |
| CN101385966B CN101385966B (en) | 2011-04-27 |
Family
ID=40475754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101577097A Expired - Fee Related CN101385966B (en) | 2008-10-16 | 2008-10-16 | Load metal ball shaped active carbon material and preparation, use method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101385966B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041788A (en) * | 2012-12-17 | 2013-04-17 | 沈阳化工大学 | Adsorbent for removing thiophene-type sulfides in gasoline and preparation method thereof |
| CN108472626A (en) * | 2015-10-28 | 2018-08-31 | 阿彻丹尼尔斯米德兰德公司 | Porous, shaped metal-carbon product |
| CN108609714A (en) * | 2018-03-21 | 2018-10-02 | 四川大学 | A method of removing incretion interferent in water removal using carbon-based magnetic metal composite material catalyzing activation persulfate |
| CN109012716A (en) * | 2018-06-25 | 2018-12-18 | 浙江工业大学 | A kind of sulphur carbon ball supported precious metal catalyst and its preparation and the application in synthesis N, N '-dibenzyl-ethylenediamin |
| CN110028982A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | Biomass pyrolysis liquid boiling bed hydrogenation dehydrogenation catalyst and its preparation method and application |
| CN110182797A (en) * | 2019-03-19 | 2019-08-30 | 杭州电子科技大学 | A kind of preparation method of the new modified absorbent charcoal material for capacitive deionization technology |
| CN110559994A (en) * | 2019-09-09 | 2019-12-13 | 西安石油大学 | Load type adsorbent for adsorbing thiophene sulfides in oil and preparation method thereof |
| US11253839B2 (en) | 2014-04-29 | 2022-02-22 | Archer-Daniels-Midland Company | Shaped porous carbon products |
| CN114099715A (en) * | 2021-11-22 | 2022-03-01 | 郑州大学 | Preparation method of magnetic carbon ball for tracing sentinel lymph nodes |
-
2008
- 2008-10-16 CN CN2008101577097A patent/CN101385966B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041788A (en) * | 2012-12-17 | 2013-04-17 | 沈阳化工大学 | Adsorbent for removing thiophene-type sulfides in gasoline and preparation method thereof |
| US11253839B2 (en) | 2014-04-29 | 2022-02-22 | Archer-Daniels-Midland Company | Shaped porous carbon products |
| CN108472626A (en) * | 2015-10-28 | 2018-08-31 | 阿彻丹尼尔斯米德兰德公司 | Porous, shaped metal-carbon product |
| CN113769749A (en) * | 2015-10-28 | 2021-12-10 | 阿彻丹尼尔斯米德兰德公司 | Porous shaped metal-carbon product |
| CN108472626B (en) * | 2015-10-28 | 2021-10-01 | 阿彻丹尼尔斯米德兰德公司 | Porous shaped metal-carbon product |
| CN108609714B (en) * | 2018-03-21 | 2020-07-24 | 四川大学 | Method for removing endocrine disruptors in water by catalytically activating persulfate through carbon-based magnetic metal composite material |
| CN108609714A (en) * | 2018-03-21 | 2018-10-02 | 四川大学 | A method of removing incretion interferent in water removal using carbon-based magnetic metal composite material catalyzing activation persulfate |
| CN109012716A (en) * | 2018-06-25 | 2018-12-18 | 浙江工业大学 | A kind of sulphur carbon ball supported precious metal catalyst and its preparation and the application in synthesis N, N '-dibenzyl-ethylenediamin |
| CN110182797A (en) * | 2019-03-19 | 2019-08-30 | 杭州电子科技大学 | A kind of preparation method of the new modified absorbent charcoal material for capacitive deionization technology |
| CN110028982B (en) * | 2019-04-26 | 2021-08-31 | 河南百优福生物能源有限公司 | Biomass pyrolysis liquid fluidized bed hydrodeoxygenation catalyst and preparation method and application thereof |
| CN110028982A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | Biomass pyrolysis liquid boiling bed hydrogenation dehydrogenation catalyst and its preparation method and application |
| CN110559994A (en) * | 2019-09-09 | 2019-12-13 | 西安石油大学 | Load type adsorbent for adsorbing thiophene sulfides in oil and preparation method thereof |
| CN114099715A (en) * | 2021-11-22 | 2022-03-01 | 郑州大学 | Preparation method of magnetic carbon ball for tracing sentinel lymph nodes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101385966B (en) | 2011-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101385966B (en) | Load metal ball shaped active carbon material and preparation, use method thereof | |
| CN102049179B (en) | Method for preparing supported iron oxide series desulfurizing agent | |
| Nguyen et al. | A novel removal of CO2 using nitrogen doped biochar beads as a green adsorbent | |
| CN100486689C (en) | Method for regenerating desulfurizing and denitrogenating adsorbant | |
| CN106118717B (en) | One kind is with Ag2O/SiO2Composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil | |
| US7625429B2 (en) | Zeolite adsorbent for desulfurization and method of preparing the same | |
| US20140231354A1 (en) | Heavy metal removal methods and systems | |
| CN102407094B (en) | Gasoline desulfurization adsorbent and preparation and application thereof | |
| CN101262928A (en) | Desulfurizing agent for removing organic sulfur compounds, preparation method thereof and method for removing organic sulfur compounds using the same | |
| CN105126788B (en) | A kind of high amino density cellular PEI solid amine absorption materials and its preparation method and application | |
| CN112619609B (en) | Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof | |
| CN110201637B (en) | Preparation method of adsorbent for removing organic sulfide in natural gas | |
| CN102093907A (en) | Method for desulphurizing gasoline | |
| Saliba et al. | Adsorption of heavy metal ions on virgin and chemically-modified lignocellulosic materials | |
| CN101323794B (en) | Spherical active carbon fuel oil adsorption desulfurizing agent and preparation thereof | |
| CN103506071A (en) | Purificant used for absorbing hydrogen sulfide and carbonyl sulfide in tail gas of natural gas and preparation method thereof | |
| CN104667861A (en) | Desulfurization adsorption agent used for gasoline and gasoline desulfurization method | |
| CN108893138B (en) | Ag2O/SiO2-ZrO2Method for removing thiophene sulfides in fuel oil by using composite aerogel as adsorbent | |
| CN101462041A (en) | Activated coal modified material for removing thiophen compounds in gasoline and method for preparing and using the same | |
| CN1952049A (en) | Modified active carbon FCC absorbent and desulfurizer for gasoline and diesel oil and its preparation method | |
| Ge et al. | Humidity swing adsorption of H2S by fibrous polymeric ionic liquids (PILs) | |
| CN1970696A (en) | Method for preparing active semicoking FCC gasoline and diesel oil adsorption desulfurizer | |
| CN101524640B (en) | On-line regenerating method of oil product desulfurizing and denitrifying absorbent | |
| Krishnan et al. | A Preliminary examination of the adsorption characteristics of Pb (II) ions using sulphurised activated carbon prepared from bagasse pith | |
| Janetaisong et al. | Pelletization of iron oxide based sorbents for hydrogen sulfide removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zheng Jingtang Inventor after: Liu Qian Inventor after: Jiang Bo Inventor after: Yu Weizhao Inventor after: Yang Zhe Inventor after: Wu Mingbo Inventor after: Li Shi Inventor after: Zhao Yucui Inventor after: Qu Xianfeng Inventor after: Sui Wubin Inventor after: Zhang Yuzhen Inventor before: Yu Weizhao Inventor before: Zhang Yuzhen Inventor before: Li Taojiang Inventor before: Zhao Yucui Inventor before: Qu Xianfeng Inventor before: Liu Ying Inventor before: Li Shi |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: YU WEIZHAO ZHANG YUZHEN LI TAOJIANG ZHAO YUCUI QU XIANFENG LIU YING LI SHITO: ZHENG JINGTANG YU WEIZHAO YANG ZHE WU MINGBO LI SHI ZHAO YUCUI QU XIANFENG SUI WUBIN ZHANG YUZHEN LIU QIAN JIANG BO |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110427 Termination date: 20131016 |