CN101880542B - Method for removing organic sulfur in coal pitch - Google Patents
Method for removing organic sulfur in coal pitch Download PDFInfo
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- CN101880542B CN101880542B CN 201010211279 CN201010211279A CN101880542B CN 101880542 B CN101880542 B CN 101880542B CN 201010211279 CN201010211279 CN 201010211279 CN 201010211279 A CN201010211279 A CN 201010211279A CN 101880542 B CN101880542 B CN 101880542B
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Abstract
The invention discloses a method for removing organic sulfur in a coal pitch, which comprises the following steps of: adding a surfactant and an organic solvent into the coal pitch; then adding oxidants namely perchloric acid and hydrogen peroxide into the mixture; under the condition that the temperature is between 30 and 90 DEG C, using ultrasonic waves to perform continuous action for 20 to 80 minutes; adding alkaline solution and methanol to perform extraction and vacuum suction filtration so as to remove a sulfur component. The method is suitable for deep desulfurization of the sulfur-bearing coal pitch, can remove 94 percent of the organic sulfur in a raw material, has a simple process and is easy to operate.
Description
Technical field
The present invention relates to a kind of method that removes organic sulfur in coal pitch, a kind of by tensio-active agent, organic solvent, perchloric acid, hydrogen peroxide being added in the coal-tar pitch system of paramount aromaticity content organosulfur, through ul-trasonic irradiation, sulfur component after using alkaline methanol solution to oxidation extracts, and separates the method that removes organic sulfur in coal pitch by vacuum filtration.
Technical background
By product coal tar as coke in process of coking accounts for 3～5% of coke output.According to 3.4 hundred million tons of calculating of present annual output coke, can produce ten thousand tons of tar 1020-1700 every year.Tar is the very complicated mixture of a kind of composition, can obtain many value products by separating.But because of operational path complexity and Cost Problems, present most of enterprise only can isolate tens kinds of products, and such as naphthalene, methylnaphthalene, polyalkylbenzene, anthracene, acenaphthene etc., rest part is mainly deposited with the pitch form or piled up.Be coal-tar pitch to be exactly coal tar remove remaining residue behind the segregative part organic compound through steps such as high temperature, decompressions, account for 50%～60% of tar.Its chief component is the condensed ring compound fragrant hydrocarbon.At present, coal-tar pitch is mainly used in fuel, soaker, carbon fiber, coating, binding agent, paves the way and the preparation of needle coke etc.Different because of the place of production, sulphur content is different, usually between between 0.8-3.0%.Because higher sulphur content, affect its further deep processing and utilization, as most advanced and sophisticated Carbon Materials raw material such as the preparation needle coke, because the existence of organosulfur has a strong impact on the Carbon Materials Performance and quality, namely sulphur content is had strict demand, thereby removing of sulphur is very important.That is to say, realize the appreciation utilization of coal-tar pitch, at first sulphur should be down to below 0.3% or more low-level.In addition, along with day by day the improving and promote increasing of coal-tar pitch approach of environmental requirement, only have the sulphur with coal-tar pitch to take off to low to certain level, just can carry out follow-up many-sided utilization.Analyze from form, the contained sulphur of coal-tar pitch is mainly organosulfur; Structurally, these organosulfurs are mainly take the thiophene-structure unit as main and link to each other with the aromatic hydrocarbons structure and to present the structure of polycyclic aromatic hydrocarbons.And along with the increasing of fragrant number of rings, the difficulty that removes sulphur is also increasing what become.Existing many disclosed documents and materials have been reported about the removal methods to organosulfur in power fuel diesel oil, gasoline or the aviation fuel oil.The method of these organic sulfide removals is pressed desulphurization mechanism and is divided, and mainly contains two kinds of shortening and oxidation sweetenings.Wherein, hydrogenating desulfurization requires temperature and pressure all higher (temperature is 320-380 ℃, and pressure is 3-7Mpa), and this has not only increased desulphurization cost and equipment is had very high requirement, and has certain potential safety hazard.Oxidation sweetening be a kind of under normal pressure, adopt oxygenant with the organosulfur oxidation after, then carry out a kind of method of extracting and separating.This method has use temperature many (60-90 ℃) lower than hydrogenating desulfurization, and the advantages such as pressure low (carrying out under normal pressure), safety and easy handling are so oxidation desulfurizing method receives more and more investigators' concern.Yet the raw material the Nomenclature Composition and Structure of Complexes is different, and sulfur method is inevitable different.That is same sulfur method is used for different desulfurization objects, and the desulfuration efficiency that shows differs greatly.Be applied to remove organosulfur in the coal-tar pitch as removing the method for organosulfur in the liquid motor fuel, desulfurization degree only can reach 20-30%.Power fuel mainly is comprised of saturated hydrocarbons compound, and coal-tar pitch or coal tar mainly are comprised of compound fragrant hydrocarbon, and degree of unsaturation is very high.If oxygenant kind or with the material rate improper use tends to cause unsaturated hydrocarbons compounds generation polymerism in coal tar or the pitch, thereby causes larger difficulty to desulfurization.
Existing document, publication number is CN1191217, reported " a kind of aromatic adsorption desulfurizing method ", the method that has proposed to adopt the amorphous alloy adsorbent that formed by nickel, aluminium, iron and other metallic copper, zinc, cobalt, molybdenum etc. that content in the aromatic hydrocarbons of benzene,toluene,xylene or C9-C11 is removed at the organosulfur of 0.1-200ppm.Be not difficult to find, this summary of the invention is difficult to be applied in high sulfur content of the present invention and the raw material composition is mainly condensed-nuclei aromatics class material coal-tar pitch, and adopt absorption method to be used for removing the sulphur of the very high coal-tar pitch of viscosity, also certainly exist the difficulty that is difficult to carry out in the operation.
Existing document, publication number is CN100366708C, " a kind of method to deeply de-aromatizing and desulfurizing solvent oil " proposed, the mixed catalyst that the method uses zeolite-loaded precious metals pt, Pd, Ru and hydrogen zeolite auxiliary agent to form takes off aromatic hydrocarbons and desulfurization by the principle of hydrogenation, and applicable object is that the solvent oil boiling point is lower than 120 ℃, benzene content is lower than 1000ppm and sulphur content is lower than 10ppm.Not only there is complicated catalyst preparation technology in this method and uses precious metal to increase extra desulphurization cost problem, and because being only suitable for all lower systems of benzene content and sulphur content, the condensed-nuclei aromatics content that at all can't be applied to indication of the present invention can account for 40-50%, sulphur content is the coal-tar pitch system of 0.8-3.0%.Verified by great many of experiments, the method that removes organosulfur in the dynamic fuel oil is used for removing the organosulfur of coal-tar pitch, sweetening effectiveness only can reach the degree of 20-30%, is difficult to realize the target of deep desulfuration.
Coal-tar pitch is except obvious different dynamic oil fuel on forming, even viscosity is still much higher than power fuel oil viscosity under 50-90 ℃ temperature, this phenomenon also causes certain difficulty to desulfurization.For this reason, the tensio-active agent and the organic solvent that add by the present invention can greatly improve this situation, and the Effective Raise oxygenant is to the oxidation effectiveness of organosulfur, by further extraction and fractionation, can make that sulphur content is reduced to a certain degree in the coal-tar pitch.
Summary of the invention
The problem to be solved in the present invention is by adding tensio-active agent and organic solvent, oxygenant and organosulfur are interacted, realization is carried out deep desulfuration to organic sulfur in coal pitch, solving the restriction coal-tar pitch affects it as the key issue of most advanced and sophisticated Carbon Materials because sulphur content is higher, and a kind of method that removes organic sulfur in coal pitch is provided.
A kind of method that removes organic sulfur in coal pitch, the method at first are by 1-5: 1 mass ratio joins organic solvent in the coal-tar pitch, and the 0.2-1.0% that presses again the coal-tar pitch quality adds tensio-active agent, and stirring and dissolving is warming up to 30-60 ℃; Secondly, by weight, add each 0.2-5 part of hydrogen peroxide of 72% perchloric acid and 30% and 0.5-5 part in a coal-tar pitch to above-mentioned system, the temperature rise rate with per minute 2-5 ℃ under ultrasonication is warming up to 65-95 ℃ with reaction system, continues to use ul-trasonic irradiation 20-80min; Then, by every part of coal-tar pitch quality, adding 2-6 part concentration is the basic solution of 0.02-5.0% and the methyl alcohol of 1-3 part, mixes, extracts, and vacuum filtration is removed organic solvent and alkali lye, makes the sweetening solid coal-tar pitch.
In technique scheme, organic solvent of the present invention is one or more of benzene, toluene and dimethylbenzene; Described tensio-active agent is one or both of hexadecanol and sodium stearate.
A kind of method that removes organic sulfur in coal pitch of the present invention, by adding tensio-active agent and organic solvent, its oxygenant and organosulfur are fully acted on, realized the deep desulfuration to organic sulfur in coal pitch, having solved in the restriction coal-tar pitch affects it as the key issue of most advanced and sophisticated Carbon Materials because sulphur content is higher.Adopt German Elementar Vario EL elemental analyser that the coal-tar pitch sulphur content is measured, its organic sulfur removal rate reaches 87.5-94%.
After adopting the inventive method that coal-tar pitch is carried out desulfurization, can be used as most advanced and sophisticated Carbon Materials raw material that sulphur content is had a higher restriction as for the preparation of needle coke, electrode material for super capacitor or hydrogen storage material etc.; Further processing by to coal-tar pitch can also prolong the industry chain (supply chain) of coal chemical enterprise derived product, promotes the service efficiency of disposable fossil resource.
The inventive method is low for equipment requirements, process is easy to realize that used organic solvent is reusable through Distillation recovery.The deep processing of coal-tar pitch and utilization thereof belong to environment protection and the preferential project of supporting of chemical material field.
Embodiment
Further describe the specific embodiment of the present invention below in conjunction with specific embodiment, the technician of this professional domain can be realized.
The present invention removes the method for organic sulfur in coal pitch, the method is by using a kind of tensio-active agent and organic solvent to increase dispersion and the emulsification degree of oxygenant in the coal-tar pitch system, improve the effect of oxygenant oxidation organic sulfur in coal pitch, oxidized sulfide is extracted and further remove by vacuum filtration the extraction liquid realization deep desulfuration of sulfur-bearing by the hybrid extraction liquid of methyl alcohol and diluted alkaline composition.At first with organic solvent and coal-tar pitch by 1-5: 1 mass ratio adds to organic solvent in the coal-tar pitch, the amount of pressing again the 0.2-1.0% of coal-tar pitch quality adds tensio-active agent, mechanical stirring makes its dissolving, be warming up to 30-60 ℃, by each the 0.2-5 part of hydrogen peroxide that adds 72% perchloric acid and 30% in a coal-tar pitch and 0.5-5 part (by weight) to above-mentioned system, temperature rise rate with per minute 2-5 ℃ under ultrasonication is warming up to 65-95 ℃ with reaction system, continue to use ul-trasonic irradiation 20-80min, then in every part of coal-tar pitch, add 2-6 part, concentration is the basic solution of 0.02-5.0% and the methyl alcohol of 1-3 part, through fully mixing, extraction, with the mode of vacuum filtration organic solvent and alkali lye are removed again, obtained the solid coal-tar pitch of deep desulfuration.
In above-mentioned embodiment, described tensio-active agent is hexadecanol or sodium stearate and has emulsification and the material of dissemination, and organic solvent can be that benzene, toluene or dimethylbenzene and other boiling points are not less than 60 ℃ but also be not higher than 200 ℃ aromatic hydrocarbon solvent; Used coal-tar pitch is not limited by kind; Described basic solution can be prepared with potassium hydroxide, also can with sodium hydroxide or other have can and the alkaline matter that reacts of acidic substance prepare.
Embodiment 1
Be 1.2% in sulphur content, quality is in the 100g coal-tar pitch, add 50g dimethylbenzene, 50g toluene and 0.4g hexadecanol, mechanical stirring makes its dissolving, be warming up to 50 ℃, add again 72% perchloric acid and 30% each 20g of hydrogen peroxide and 100g, after under ultrasonication, reaction system being warming up to 95 ℃ with the temperature rise rate of 2 ℃ of per minutes, continue to use ul-trasonic irradiation 50min, then add concentration and be 0.02% potassium hydroxide solution 200g, methyl alcohol 300g, fully stir and extract, use the mode of vacuum filtration with organic solvent and alkali lye elimination, the coal-tar pitch sulphur content that obtains is 0.15% again, and desulfurization degree is 87.5%.
Embodiment 2
Be 1.15% at sulfur-bearing, quality is in the 100g coal-tar pitch, add 150g dimethylbenzene, 1.0g sodium stearate and 0.5g hexadecanol, mechanical stirring makes its dissolving, be warming up to 30 ℃, add again 72% perchloric acid and 30% each 500g of hydrogen peroxide and 250g, after under ultrasonication, reaction system being warming up to 85 ℃ with the temperature rise rate of 2 ℃ of per minutes, continue to use ul-trasonic irradiation 60min, then adding concentration and be 3% sodium hydroxide solution 400g and methyl alcohol 100g extracts, use again the mode of vacuum filtration with organic solvent and alkali lye elimination, the coal-tar pitch sulphur content that obtains is 0.09%, and desulfurization degree is 92.1%.
Embodiment 3
Getting sulphur content is 0.9%, quality is the coal-tar pitch of 100g, add 500g benzene, 0.4g sodium stearate and 0.2g hexadecanol, mechanical stirring makes its dissolving, be warming up to 25 ℃, add again 72% perchloric acid and 30% each 300g of hydrogen peroxide and 500g, after under ultrasonication, reaction system being warming up to 65 ℃ with the temperature rise rate of 2 ℃ of per minutes, continue to use ul-trasonic irradiation 80min, then adding concentration and be 0.5% potassium hydroxide solution 600g and 100g methyl alcohol extracts, use again the mode of vacuum filtration with organic solvent and alkali lye elimination, the coal-tar pitch sulphur content that obtains is 0.07%, and desulfurization degree can reach 92.2%.
Embodiment 4
Getting sulphur content is 1.5%, quality is the coal-tar pitch of 100g, add 300g toluene, 50g dimethylbenzene and 0.2g hexadecanol, mechanical stirring makes its dissolving, be warming up to 50 ℃, add again 72% perchloric acid and 30% each 400g of hydrogen peroxide and 50g, after under ultrasonication, reaction system being warming up to 90 ℃ with the temperature rise rate of 5 ℃ of per minutes, continue to use ul-trasonic irradiation 40min, then adding concentration and be 0.5% sodium hydroxide solution 500g and methyl alcohol 300g extracts, use again the mode of vacuum filtration with organic solvent and alkali lye elimination, the coal-tar pitch sulphur content that obtains is 0.09%, and desulfurization degree can reach 94%.
Embodiment 5
Getting sulphur content is 1.8%, quality is the coal-tar pitch of 100g, add 200g toluene, 150g ethyltoluene and 1.0g Span60 SP-60, mechanical stirring makes its dissolving, be warming up to 60 ℃, add again 72% perchloric acid and 30% each 200g of hydrogen peroxide and 300g, after under ultrasonication, reaction system being warming up to 95 ℃ with the temperature rise rate of 4 ℃ of per minutes, continue to use ul-trasonic irradiation 20min, then adding concentration and be 0.5% barium hydroxide solution 400g and methyl alcohol 300g extracts, use again the mode of vacuum filtration with organic solvent and alkali lye elimination, the coal-tar pitch sulphur content that obtains is 0.17%, and desulfurization degree can reach 90.6%.
Claims (2)
1. method that removes organic sulfur in coal pitch, its method steps is as follows:
At first, by 1-5: 1 mass ratio is that one or more of benzene, toluene and dimethylbenzene join in the coal-tar pitch with organic solvent, and the 0.2-1.0% that presses again the coal-tar pitch quality adds tensio-active agent, and stirring and dissolving is warming up to 30-60 ℃;
Secondly, by weight, add each 0.2-5 part of hydrogen peroxide of 72% perchloric acid and 30% and 0.5-5 part in a coal-tar pitch to above-mentioned system, the temperature rise rate with per minute 2-5 ℃ under ultrasonication is warming up to 65-95 ℃ with reaction system, continues to use ul-trasonic irradiation 20-80min;
Then, by every part of coal-tar pitch quality, adding 2-6 part concentration is the basic solution of 0.02-5.0% and the methyl alcohol of 1-3 part, mixes, extracts, and vacuum filtration is removed organic solvent and alkali lye, makes the sweetening solid coal-tar pitch.
2. the method for claim 1, its tensio-active agent is one or both of hexadecanol and sodium stearate.
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| CN106675683B (en) * | 2017-01-12 | 2020-06-30 | 安徽理工大学 | Microwave-assisted low-quality coal desulfurization method |
| CN108949212B (en) * | 2018-08-01 | 2020-11-13 | 国家能源投资集团有限责任公司 | Preparation method and preparation device of coal liquefied asphalt and coal liquefied asphalt |
| CN108998064B (en) * | 2018-08-01 | 2021-04-27 | 济宁碳素集团有限公司 | Method for removing aluminum trichloride in naphthalene pitch |
| CN113046023A (en) * | 2021-03-11 | 2021-06-29 | 山西中科化美科技有限责任公司 | Preparation method and application of environment-friendly asphalt |
| CN113046109B (en) * | 2021-03-11 | 2021-12-07 | 山西中科化美科技有限责任公司 | Preparation method and application of low-sulfur low-nitrogen environment-friendly asphalt |
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|---|---|---|---|---|
| TW290586B (en) * | 1995-09-19 | 1996-11-11 | Defence Dept Chung Shan Inst | Process for preparing raw materials for high-density, high-strength carbon materials |
| EP1757672A2 (en) * | 2005-08-24 | 2007-02-28 | C. Hasse & Sohn Dachbaustoffwerk Uelzen Inh. E. Rädecke GmbH & Co. | Process for treating bituminous composite material |
| CN101220284A (en) * | 2007-12-14 | 2008-07-16 | 鞍钢股份有限公司 | Method for producing electrode impregnation asphalt |
| CN101475820A (en) * | 2009-01-23 | 2009-07-08 | 北京石油化工学院 | Purification method for coal pitch |
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| JPS5853036B2 (en) * | 1976-11-12 | 1983-11-26 | 新日鐵化学株式会社 | How to treat tar sludge |
| US7566394B2 (en) * | 2006-10-20 | 2009-07-28 | Saudi Arabian Oil Company | Enhanced solvent deasphalting process for heavy hydrocarbon feedstocks utilizing solid adsorbent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW290586B (en) * | 1995-09-19 | 1996-11-11 | Defence Dept Chung Shan Inst | Process for preparing raw materials for high-density, high-strength carbon materials |
| EP1757672A2 (en) * | 2005-08-24 | 2007-02-28 | C. Hasse & Sohn Dachbaustoffwerk Uelzen Inh. E. Rädecke GmbH & Co. | Process for treating bituminous composite material |
| CN101220284A (en) * | 2007-12-14 | 2008-07-16 | 鞍钢股份有限公司 | Method for producing electrode impregnation asphalt |
| CN101475820A (en) * | 2009-01-23 | 2009-07-08 | 北京石油化工学院 | Purification method for coal pitch |
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