CN104556029A - Preparation of active carbon and fuel oil by use of petroleum residue and tar residue together - Google Patents
Preparation of active carbon and fuel oil by use of petroleum residue and tar residue together Download PDFInfo
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- CN104556029A CN104556029A CN201410794351.4A CN201410794351A CN104556029A CN 104556029 A CN104556029 A CN 104556029A CN 201410794351 A CN201410794351 A CN 201410794351A CN 104556029 A CN104556029 A CN 104556029A
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- active carbon
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- tar refuse
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Abstract
The invention relates to a method for preparing granular active carbon and fuel oil by mixing petroleum residue and tar residue. The obtained active carbon has a highly developed pore structure and a huge specific surface area, and the fuel oil can be applied to an industrial boiler. The active carbon can be applied to the refining and separation of gas and liquid, water treatment, air purification and the like as a porous carbon material. Meanwhile, according to the method provided by the invention, by controlling the ratio of the petroleum residue to the tar residue, the viscosity of oil is reduced, and the asphaltene in the oil is dissolved; and meanwhile, by adding a stabilizer and a dispersing agent, the oil contained in the tar residue and petroleum residue can be sufficiently mixed to achieve an aim of preparing fuel oil. The residue left after the preparation of fuel oil is activated by use of air and phosphoric acid together to obtain active carbon different in specific surface area and pore size distribution. According to the method provided by the invention, by adopting the tar residue and petroleum residue as raw materials, the aim of utilizing the waste and turning the waste into wealth can be achieved, and the environmental pollution can be reduced.
Description
Technical field
The present invention relates to a kind of method that petroleum residual oil and coke tar refuse are mixed with granulated active carbon, oil fuel, gained gac has highly developed pore texture and huge specific surface area, and oil fuel can be used for Industrial Boiler; The invention belongs to trade waste and utilize field.
Background technology
Coke tar refuse is the residue composition that coke-oven plant's tar ammonia clarifying tank is separated and produces in crude benzol operation revivifier; For the coke-oven plant producing 2500000 tons, coke per year, coke tar refuse 1100 can be produced every year; Containing a considerable amount of polycyclic aromatic hydrocarbons in coke tar refuse volatile matter, having carcinogenesis to humans and animals, particularly Benzpyrene wherein, is the carcinogens of generally acknowledging in the world, very harmful; Plant area is stacked by current most producer, and rainfall can cause groundwater pollution; Along with volatile matter effusion in carbide slag, atmospheric pollution can be caused again; Some factories normally sell neighbouring resident and to do manual labour fuel, or make the fuel of baking bricks, and large quantity of exhaust gas enters air, causes severe contamination; Therefore how turning waste into wealth, turn harm into good, is a urgent task.
Petroleum residual oil is oil remaining residue after distillation processing, its ratio accounts for 50% before refining of petroleum, because residual oil is of poor quality, impurity and imperfect component content high, difficulty of processing is large, cause residual oil Zeng Zuowei to bring disaster upon stove fuel to be burnt, not only waste limited resources, and pollution is caused to environment.
Containing a large amount of unburnt carbon and coal tar and light component in coke tar refuse and petroleum residual oil; Can be used as the quality matetrial preparing gac, oil fuel; By the associating proportioning of coke tar refuse and petroleum residual oil, oily component is brought together according to the similar principle that mixes, by cheap, efficiently method process further, produce oil fuel.
Phosphoric acid as novel activated dose, the gac that the material of many carbon containings can be made to activate obtain high-specific surface area and receive the concern of countries in the world; Refine light component to low-quality coal-tar residue and petroleum residual oil at present, the method that remaining residue carries out phosphoric acid-air associating activation treatment has no report; Gac produced by coke tar refuse and petroleum residual oil is all generally carry out chemical activation with the chemical agent such as sodium hydroxide and potassium hydroxide, but pollutes larger; And various industrial chemicals is extracted from coke tar refuse, cost is higher, complex process, the more difficult grasp of returned enterprise; This research is using coal-tar residue and petroleum residual oil as raw material, with the treatment process reining fuel oil of two kinds of proportioning raw materials, carry out associating activation with air and phosphoric acid and prepare gac, for the problem solving coal-tar residue and petroleum residual oil recycling proposes a good solution.
The present invention for raw material, adopts the process of two kinds of raw material mixing match with coal-tar residue and petroleum residual oil, extracts light component meets industrial furnace burning oil fuel in order to preparation; Remaining residue can adopt phosphoric acid and air-activated process, prepares the gac of high-ratio surface, coal-tar residue and petroleum residual oil is used as a valuable energy, reaches the object turning waste into wealth, turn harm into good; Up to the present, the relevant report producing gac and oil fuel do not combined by petroleum residual oil with coke tar refuse.
Summary of the invention
The object of the invention is to provide a kind of and produces oil fuel with underpressure distillation and phosphoric acid-air combines the method that activation coke tar refuse produces active carbon with high specific surface area; Comprise the following steps.
1. coke tar refuse and petroleum residual oil are carried out certain proportioning mixing, carry out underpressure distillation at a certain temperature, filter, underpressure distillation component is as preparation of fuels oil raw material.
2., with solvend in the remaining residue of dissolution with solvents, collect solute.
3. mixed with the oil of collecting in advance by above light component, add the solvent of 5 ~ 30%, solvent is respectively benzene solvent oil, coke-oven plant's washing oil and carbolineum, dissolves the bituminous matter in oil; Solvent is stirred and fragmentation, make it fully to mix, obtained oil fuel.
4. take out cooling after residue drying, add phosphate impregnation.
5. after phosphate impregnation, material activates in atmosphere at horizontal retort, and activation temperature is 400-1000 DEG C, extremely neutral with deionized water wash after cooling; After sample roasting at 120 DEG C is dry, obtained granular active carbon.
6. the viscosity of pair product, density, toluene insolubles, thermal value, flash-point and sulphur content carry out analyzing and testing, and carry out oil product stability experiment; By adjusting kind, the consumption of additive, coke tar refuse oil fuel can be made cold oil spout or hot oil spout.
7. pair gac specific surface area and pore size distribution are analyzed; The conditions such as adjustment activator proportioning, activation temperature, soak time and dipping temperature, obtain the gac producing different specific surface area and pore size distribution.
The key issue that emphasis solves is the proportioning of petroleum residual oil and coke tar refuse, the addition of phosphoric acid activation agent, the determination of air-activated temperature; By measuring nitrogen adsorption isotherm and the carbon dioxide adsorption thermoisopleth of gac, analyzing the pore texture of gac, and adopting the surface functional group content of Boehm determination of acid-basetitration gac; Obtain the impact that experiment condition distributes on activated carbon pore size.And the pore texture of gac and surface chemical property can be regulated and controled by phosphoric acid concentration during change dipping and activation temperature.
Activated carbon granule degree can be divided into 100-320 order on request, activates by level; The gac index of preparation is contemplated to: specific surface area 800-3000m
2/ g.
The expectation index preparing oil fuel is: thermal value is higher than 30MJ/kg; Flash-point is higher than 100 DEG C.
The present invention mainly with petroleum residual oil and coke tar refuse for raw material, adopt underpressure distillation with according to the similar principle that mixes of oily component contained in petroleum residual oil and coke tar refuse, can oil fuel be extracted.Remaining ingredient (residue) combines activation by phosphoric acid-air, produces gac; This research is for exploration petroleum residual oil and coke tar refuse produces oil fuel and gac provides Research foundation.
Embodiment
Embodiment 1.
Coke tar refuse and petroleum residual oil are carried out the mixing of 1:1 proportioning, at 350 DEG C, carries out underpressure distillation, filter, isolate light component as preparation of fuels oil raw material.
Residual residue collected, add the solvent of 20%, solvent is benzene solvent oil, dissolves the bituminous matter in oil, is mixed by liquid after solid-liquor separation with above-mentioned light component.
Remaining residue is added 20% phosphoric acid solution and floods 2 hours.
Carbon after dipping activates with horizontal retort in atmosphere, and activation temperature is 820 DEG C, extremely neutral with deionized water wash after cooling.After sample roasting at 120 DEG C is dry, obtained granular active carbon.
Embodiment 2.
Coke tar refuse and petroleum residual oil are carried out the mixing of 1:3 proportioning, at 340 DEG C, carries out underpressure distillation, filter, isolate light component as preparation of fuels oil raw material.
Residual residue collected, add the solvent of 10%, solvent is coke-oven plant's washing oil and carbolineum, dissolves the bituminous matter in oil, is mixed by liquid after solid-liquor separation with above-mentioned light component.
Remaining residue is added 30% phosphoric acid solution and floods 6 hours.
Carbon after dipping activates with horizontal retort in atmosphere, and activation temperature is 800 DEG C, extremely neutral with deionized water wash after cooling.After sample roasting at 120 DEG C is dry, obtained granular active carbon.
Embodiment 3.
Coke tar refuse and petroleum residual oil are carried out the mixing of 3:1 proportioning, at 350 DEG C, carries out underpressure distillation, filter, isolate light component as preparation of fuels oil raw material.
Residual residue collected, add the solvent of 20%, solvent is coke-oven plant's washing oil and 18 alkyl polyoxyethylene ethers, dissolves the bituminous matter in oil, is mixed by liquid after solid-liquor separation with above-mentioned light component.
Remaining residue is added 15% phosphoric acid solution and floods 4 hours.
Carbon after dipping activates with horizontal retort in atmosphere, and activation temperature is 800 DEG C, extremely neutral with deionized water wash after cooling.After sample roasting at 120 DEG C is dry, obtained granular active carbon.
Embodiment 4.
Coke tar refuse and petroleum residual oil are carried out the mixing of 1:2 proportioning, at 340 DEG C, carries out underpressure distillation, filter, isolate light component as preparation of fuels oil raw material.
Residual residue collected, add the solvent of 15%, solvent is coke-oven plant's washing oil and carbolineum, dissolves the bituminous matter in oil, is mixed by liquid after solid-liquor separation with above-mentioned light component.
Remaining residue is added 20% phosphoric acid solution and floods 2 hours.
Carbon after dipping activates with horizontal retort in atmosphere, and activation temperature is 840 DEG C, extremely neutral with deionized water wash after cooling.After sample roasting at 120 DEG C is dry, obtained granular active carbon.
Embodiment 5.
Coke tar refuse and petroleum residual oil are carried out the mixing of 2:1 proportioning, at 340 DEG C, carries out underpressure distillation, filter, isolate light component as preparation of fuels oil raw material.
Residual residue collected, add the solvent of 15%, solvent is carbolineum, dissolves the bituminous matter in oil, is mixed by liquid after solid-liquor separation with above-mentioned light component.
Remaining residue is added 20% phosphoric acid solution and floods 4 hours.
Carbon after dipping activates with horizontal retort in atmosphere, and activation temperature is 830 DEG C, extremely neutral with deionized water wash after cooling.After sample roasting at 120 DEG C is dry, obtained granular active carbon.
Claims (5)
1. coke tar refuse and petroleum residual oil are carried out certain proportioning mixing, carry out underpressure distillation at a certain temperature, filter, underpressure distillation component is as preparation of fuels oil raw material; With solvend in the remaining residue of dissolution with solvents, collect solute; Above light component is mixed with the oil of collecting in advance, add the thinner of 5 ~ 30%, the stable dispersant of 10 ~ 60%, thinner is respectively benzene solvent oil, coke-oven plant's washing oil and carbolineum, dissolve the bituminous matter in oil, solvent is stirred and fragmentation, make it fully to mix, obtained oil fuel; Take out cooling after residue drying, add phosphoric acid and activate; After phosphoric acid activation, material activates in atmosphere at horizontal retort, and activation temperature is 400-1000 DEG C, extremely neutral with deionized water wash after cooling; After sample roasting at 120 DEG C is dry, obtained granular active carbon; Analyzing and testing is carried out to the viscosity of product, density, toluene insolubles, thermal value, flash-point and sulphur content, and carries out oil product stability experiment; By adjusting kind, the consumption of additive, coke tar refuse oil fuel can be made cold oil spout or hot oil spout; Gac specific surface area and pore size distribution are analyzed; The conditions such as adjustment activator proportioning, activation temperature, soak time and dipping temperature, obtain the gac producing different specific surface area and pore size distribution.
2. require that described a kind of petroleum residual oil and coke tar refuse are mixed with granulated active carbon, oil fuel according to right 1, it is characterized in that the addition of the proportion relation of petroleum residual oil and coke tar refuse, activator, the determination of activation temperature; The pore texture of gac and surface chemical property can be regulated and controled by phosphoric acid concentration, soak time and activation temperature during change dipping.
3. require that described a kind of petroleum residual oil and coke tar refuse are mixed with granulated active carbon, oil fuel according to right 1, it is characterized in that the addition of the proportion relation of petroleum residual oil and coke tar refuse, activator, the determination of activation temperature; The pore texture of gac and surface chemical property can be regulated and controled by phosphoric acid concentration, soak time and activation temperature during change dipping.
4. require by determining instruments such as viscosity, density, toluene insolubles, thermal value, flash-point and sulphur content according to right 1, measure the combustionproperty of oil fuel, change the addition of the proportion relation of petroleum residual oil and coke tar refuse, thinner and dispersion agent, obtain the oil fuel meeting industrial furnace burning.
5. require that described a kind of petroleum residual oil and coke tar refuse are mixed with the method for granulated active carbon, oil fuel according to right 2, it is characterized in that preparing granulated active carbon, oil fuel, activate by level; The gac index of preparation is contemplated to: specific surface area 800-3000m
2/ g; The expectation index preparing oil fuel is: thermal value is higher than 30MJ/kg; Flash-point is higher than 100 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410794351.4A CN104556029B (en) | 2014-12-21 | 2014-12-21 | Petroleum residual oil is combined with tar slag and prepares activated carbon and fuel oil |
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| CN201410794351.4A CN104556029B (en) | 2014-12-21 | 2014-12-21 | Petroleum residual oil is combined with tar slag and prepares activated carbon and fuel oil |
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| CN104556029B CN104556029B (en) | 2017-03-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668567A (en) * | 2016-04-15 | 2016-06-15 | 太原理工大学 | Method for preparing magnetic powdered activated carbon from gasified coal tar waste residues |
| CN114192555A (en) * | 2021-10-11 | 2022-03-18 | 北京清新环境技术股份有限公司 | Method for recycling and comprehensively utilizing high-carbon-content hazardous solid wastes, product and application thereof |
| CN114804074A (en) * | 2022-05-13 | 2022-07-29 | 太原理工大学 | Method for preparing carbon nano tube by low-pressure combustion of coking crude benzene |
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| JP2004044074A (en) * | 2002-06-17 | 2004-02-12 | Sgl Carbon Ag | Activated carbon fiber and method for producing the same |
| CN102275915A (en) * | 2011-05-30 | 2011-12-14 | 大连理工大学 | Preparation method of high specific surface area scalar porous active carbon material |
| CN102381705A (en) * | 2011-07-27 | 2012-03-21 | 西南科技大学 | Method for producing activated carbon by thermally activating coal tar dreg/ sludge fermentation body by using microwaves |
| CN102807216A (en) * | 2012-09-13 | 2012-12-05 | 山东大学 | Method for preparing activated carbon with high specific surface area utilizing wood tar |
| CN103626175A (en) * | 2013-12-17 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Method for preparing activated carbon from coal tar residues and application thereof |
-
2014
- 2014-12-21 CN CN201410794351.4A patent/CN104556029B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186043A (en) * | 1996-12-24 | 1998-07-01 | 中国科学院山西煤炭化学研究所 | Method for producing activated carbon with high specific surface area from asphalt |
| JP2004044074A (en) * | 2002-06-17 | 2004-02-12 | Sgl Carbon Ag | Activated carbon fiber and method for producing the same |
| CN102275915A (en) * | 2011-05-30 | 2011-12-14 | 大连理工大学 | Preparation method of high specific surface area scalar porous active carbon material |
| CN102381705A (en) * | 2011-07-27 | 2012-03-21 | 西南科技大学 | Method for producing activated carbon by thermally activating coal tar dreg/ sludge fermentation body by using microwaves |
| CN102807216A (en) * | 2012-09-13 | 2012-12-05 | 山东大学 | Method for preparing activated carbon with high specific surface area utilizing wood tar |
| CN103626175A (en) * | 2013-12-17 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Method for preparing activated carbon from coal tar residues and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668567A (en) * | 2016-04-15 | 2016-06-15 | 太原理工大学 | Method for preparing magnetic powdered activated carbon from gasified coal tar waste residues |
| CN114192555A (en) * | 2021-10-11 | 2022-03-18 | 北京清新环境技术股份有限公司 | Method for recycling and comprehensively utilizing high-carbon-content hazardous solid wastes, product and application thereof |
| CN114804074A (en) * | 2022-05-13 | 2022-07-29 | 太原理工大学 | Method for preparing carbon nano tube by low-pressure combustion of coking crude benzene |
| CN114804074B (en) * | 2022-05-13 | 2023-10-20 | 太原理工大学 | Method for firing carbon nano tube by coking crude benzol under low pressure |
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