CN103756703A - Modified asphalt, method for preparing modified asphalt by using direct liquefied coal residue in normal pressure continuous mode and application of modified coal residue - Google Patents
Modified asphalt, method for preparing modified asphalt by using direct liquefied coal residue in normal pressure continuous mode and application of modified coal residue Download PDFInfo
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Abstract
The invention discloses modified asphalt, a method for preparing the modified asphalt by using direct liquefied coal residues in a normal pressure continuous mode, and an application of the modified asphalt. The method comprises the following steps: 1, adding an extracting solvent into the direct liquefied coal residues for performing thermal dissolution extraction, solid-liquid separation and solvent recycling treatment in sequence so as to obtain a heavy dope with the extracting solvent; 2, adding a cross-linking agent into the heavy dope, stirring and mixing so as to obtain a first mixture; 3, adding a catalyst into the first mixture, heating at normal pressure to perform cross-linking polymerization so as to obtain the modified asphalt. According to the method, the modes that in the prior art, the direct liquefied coal residues are directly prepared into high-temperature asphalt firstly and subsequently heavy oil is added to perform cross-linking polymerization to modify the asphalt are abandoned, but the cross-linking agent is directly added into the heavy dope with the extracting solvent after distillation to polymerize at normal pressure so as to obtain a modified asphalt product with a low softening point and high beta resin content, and the modified asphalt is suitable for being used as middle/high-temperature binding asphalt and a raw material of dipping asphalt.
Description
Technical field
The present invention relates to coal liquefaction residue deep process technology field, in particular to a kind of modifying asphalt, utilize the serialization of coal directly-liquefied residue normal pressure to prepare method and the application thereof of modifying asphalt.
Background technology
Fast development along with national economy, modernization and social development process are constantly accelerated, and China constantly increases the consumption of petroleum products, have substantially exceeded the rate of growth of the crude production same period, cause us petroleum import amount all to increase year by year, and surpassed from output.And China is an oil-poor country of rich coal, make full use of abundant coal resources, the advanced persons' such as development of coal direct liquefaction clean coal technology is to reduce external crude oil to depend on unduly, alleviate one of important channel of China's oil shortage of resources, petroleum products supply and demand pressure, also be to improve our coal resources utilization ratio simultaneously, alleviate coal burning pollution, promote the Important Action of the energy, economy, harmonious development.
Coal direct liquefaction is that coal is passed through to high temperature, high pressure, and under catalyst action, hydrogenation directly changes into a kind of advanced person's of clean transport fuel (petroleum naphtha, diesel oil etc.) or industrial chemicals clean coal technology.The process of DCL/Direct coal liquefaction is generally that coal is crushed to the granularity below 0.15mm in advance, then is made into coal slurry with solvent, and under certain temperature (approximately 450 ℃) and high pressure hydrogenation, make the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process, except the liquiefied product that obtains needing, go back some hydrocarbon molecules of by-product, CO
xthe liquefaction residue (claiming again coal liquefaction residue) producing Deng gas, process water and solid-liquid separation process.Liquefied residue generally accounts for 30% left and right of coal input quantity.The utilization of coal liquefaction residue all has immeasurable impact to the economy of the efficiency of liquefaction process and whole liquefaction factory and environment protection etc.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts value product and has important practical significance to improving the economic benefit of direct liquefaction process.
Coal directly-liquefied residue is mainly comprised of inanimate matter and organic two portions, and organic matter comprises liquefaction heavy oil, bitumen and unconverted coal, and inorganic matter (being commonly referred to ash content) comprises mineral substance in coal and additional catalyzer.Liquefaction heavy oil and bitumen in organic material account for 50% of level of residue, and unconverted coal accounts for 30% of level of residue, and ash content accounts for 20% left and right.Therefore, by accounting for 50% bitumen and mink cell focus in liquefied residue, separate and carry out comprehensive development and utilization, it is feasible therefrom extracting or prepare more value product.
Current is mainly some traditional methods to the utilization of coal liquefaction residue, as burning, coking liquefaction and gasification hydrogen-producing etc.As fuel, directly in boiler or kiln, burn, will affect the economy of gelatin liquefaction undoubtedly, and in liquefied residue, higher sulphur content will be brought the problem of environment aspect.Although coking liquefaction has increased the liquid oils yield of coal liquefaction craft, liquefied residue can not obtain the most reasonably utilizing, semicoke and coke utilize approach also very not clear and definite.The method of liquefied residue being carried out to gasification hydrogen-producing is a kind of effectively extensive approach utilizing, but the high value added utilization potentiality to the bitumen in residue and mink cell focus are embodied, and the ash content in residue is up to more than 20%, this bring very large impact will to the deslagging of vapourizing furnace.
Patent ZL200510047800.X discloses a kind ofly take coal hydroliquefaction residue and prepares the method for carbon nano-material as raw material plasma body.Patent ZL200610012547.9 discloses a kind of method using coal liquefaction residue as road asphalt modifier.ZL200910087907.5 discloses a kind of method of utilizing coal directly-liquefied residue to prepare asphalt base carbon fiber.Patent 200910086158.4 discloses a kind of method of preparing mesophase pitch with coal liquefaction residue.The bitumen that aforesaid method all be take in coal liquefaction residue is applied to carbon materials field as raw material, do not relate to coal directly-liquefied residue through hard pitch and modification work thereof in solvent oil extraction, solid-liquid separation, underpressure distillation preparation, and the extracting of residue medium pitch class material all to take expensive pure chemistry reagent be solvent, cost is relatively high.
Up to now, the research report of relevant asphalt modification is a lot of both at home and abroad, mainly adopts high temperature thermal polymerization method, distillation under vacuum, oxidation thermal polymerization method.Although these asphalt modifier methods are adopted by domestic and international manufacturer always, and all produce qualified modified pitch, but these asphalt modifiers are generally from coal directly-liquefied residue, first to prepare DCL/Direct coal liquefaction hard pitch, then from system, add wherein the materials such as some mink cell focuses, linking agent to carry out heating and pressurizing crosslinking polymerization, the method has increased the complicacy of operation, cannot carry out serialization production.
Summary of the invention
The present invention aims to provide a kind of modifying asphalt, utilizes the serialization of coal directly-liquefied residue normal pressure to prepare method and the application thereof of modifying asphalt, the method the obtains coal directly-liquefied residue heavy dope that contains extraction solvent at distilling period directly carries out crosslinking polymerization, has realized the object that modifying asphalt is produced in serialization.
To achieve these goals, according to an aspect of the present invention, a kind of method of utilizing the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt is provided, comprise the following steps: S1, in coal directly-liquefied residue, add extraction solvent, carry out successively thermosol extraction, solid-liquid separation and solvent recuperation and process, obtain the heavy dope that contains extraction solvent; S2, in heavy dope, add linking agent, be uniformly mixed, obtain the first mixture; And S3, in the first mixture, add catalyzer, under normal pressure, heat cross-linking polymerization, obtains modifying asphalt.
Further, the softening temperature of heavy dope is 20～115 ℃, and β resin content value is 1～15wt.%, ash oontent value≤0.5wt%.
Further, extraction solvent is that boiling range is the distillate of 150～405 ℃.
Further, extraction solvent is one or more in liquefied coal coil, coal tar and distillate thereof, vacuum residuum and catalytically cracked oil; Linking agent is terephthalyl alcohol.
Further, step S1 comprises: coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with extraction solvent, obtain mixed solution; And under inert atmosphere, with 10 ℃～30 ℃/h, mixed solution is warming up to 80 ℃～280 ℃, and under 0.1～1.0MPa, constant temperature stirs, and thermosol extraction obtains thermosol extraction mixture; The time of thermosol extraction is 5～60min, and the speed that constant temperature stirs is 50～300r/min.
Further, in step S1, adopt the mode of thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation to carry out solid-liquid separation.
Further, in step S1, to the extraction liquid after solid-liquid separation, adopt the mode of distillation or evaporation to carry out solvent recuperation processing, preferably adopt air distillation or underpressure distillation.
Further, take heavy dope as benchmark, the addition of linking agent is 1～50wt%, and preferably, the addition of linking agent is 10～20wt%.
Further, in step S3, will add the first mixture of catalyzer to be warming up to preset temperature, constant temperature normal pressure crosslinking polymerization.
Further, preset temperature is 120～350 ℃, and temperature rise rate is 1～10 ℃/min, and the time of crosslinking polymerization is 0.5～36 hour; Preferably, preset temperature is 160～200 ℃, and temperature rise rate is 5～7 ℃/min, and the time of crosslinking polymerization is 6～10 hours.
Further, catalyzer is sulfuric acid, take heavy dope as benchmark, and the add-on of sulfuric acid is 1～50wt%, is preferably 10～20wt%.
Further, the mass percent concentration of sulfuric acid is 10%～98%, is preferably 40～70%.
According to a further aspect in the invention, provide a kind of modifying asphalt, this modifying asphalt is for adopting the above-mentioned method that any utilizes the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt to be prepared from.
Further, the softening temperature of modifying asphalt is 75 ℃～120 ℃, and β resin content value is 16～35wt%, and ash oontent value is≤0.5wt.%.
According to another aspect of the invention, provide the application of above-mentioned any modifying asphalt in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, high-temperature agglomerant pitch and impregnating pitch.
Apply technical scheme of the present invention, by coal directly-liquefied residue is carried out to thermosol extraction, solid-liquid separation and distillation, obtained the DCL/Direct coal liquefaction heavy dope that contains part extraction solvent, under the effect of catalyzer, mode by normal heating just can be so that remain in extraction solvent and the heavy dope crosslinking polymerization in heavy dope, thereby prepare the medium and high temperature gelatin liquefaction modifying asphalt of high added value.The present invention has abandoned in prior art and first coal directly-liquefied residue has been prepared into hard pitch, and then add mink cell focus in hard pitch, by crosslinking polymerization, carry out asphalt modification again, and be selected in the heavy dope that contains part extraction solvent directly obtaining to distillation process section under normal pressure, add linking agent, through crosslinking polymerization, obtained equally having low softening point, the high added value modified asphalt material of high β resin content, its cohesiveness is good, product development suitability is strong, be suitable as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, the raw materials such as the middle high-temperature agglomerant pitch that waterproof paint and market are required and impregnating pitch.Continuous modification method technique provided by the present invention is simple, mild condition, equipment are conventional, be easy to amplify and produce, for the deep exploitation of coal directly-liquefied residue provides a kind of new approach, reduced the pollution of coal directly-liquefied residue to environment, improve the economy of coal direct liquefaction, there is good market application foreground.
Accompanying drawing explanation
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the coal directly-liquefied residue normal pressure serialization that utilizes of a kind of exemplary embodiments according to the present invention and prepares the schematic flow sheet of modifying asphalt.
Embodiment
It should be noted that, in the situation that not conflicting, embodiment and the feature in embodiment in the application can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
" the heavy dope " mentioned in the present invention refers to that coal liquefaction residue is through solvent extraction, solid-liquid separation, the resulting low ash content heavy dregs of fat of underpressure distillation, be the intermediate product obtaining in coal directly-liquefied residue treating processes, main component is extraction solvent and gelatin liquefaction bitumen.
In order to solve in prior art problems such as having intermittent production, improve production economy efficiency, the invention provides a kind of method of utilizing the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt, comprise the following steps: S1, in coal directly-liquefied residue, add extraction solvent, carry out successively thermosol extraction, solid-liquid separation and solvent recuperation and process, obtain the heavy dope that contains extraction solvent; S2, in heavy dope, add linking agent, be uniformly mixed, obtain the first mixture; And S3, in the first mixture, add catalyzer, under normal pressure, heat cross-linking polymerization, obtains modifying asphalt.
In heavy dope, contained extraction solvent plays the effect of dissolving gelatin liquefaction heavies on the one hand, on the other hand can with heavy dope crosslinking polymerization.Wherein, in heavy dope, the content of extraction solvent height directly affects softening temperature and the β resin content value of heavy dope, if the higher increase of the content of extraction solvent, the softening temperature of heavy dope reduces, and β resin content value reduces; If the content of extraction solvent reduces, the softening temperature of heavy dope improves, and β resin content value increases.In order to obtain the modifying asphalt of excellent properties after crosslinked, need to control the content of the extraction solvent in heavy dope, make it in certain scope.Preferably, when the softening temperature of heavy dope is 20～115 ℃, β resin content value is 1～15wt.%, and during ash oontent value≤0.5wt%, now in heavy dope, the extraction solvent contained with it has preferably performance after crosslinked.Adopt technique provided by the present invention only to need crosslinking polymerization under normal pressure just can access the medium and high temperature DCL/Direct coal liquefaction modifying asphalt of high added value.Owing to adopting normal pressure crosslinking polymerization, be convenient to production operation, process safety coefficient is high, can also reduce the manufacturing cost of reactor.
By coal directly-liquefied residue is carried out to thermosol extraction, solid-liquid separation and distillation, obtained the DCL/Direct coal liquefaction heavy dope that contains part extraction solvent, under the effect of catalyzer, mode by normal heating just can be so that remain in extraction solvent and the heavy dope crosslinking polymerization in heavy dope, thereby prepare the medium and high temperature gelatin liquefaction modifying asphalt of high added value.The present invention has abandoned in prior art and first coal directly-liquefied residue has been prepared into hard pitch, and then add mink cell focus in hard pitch, by crosslinking polymerization, carry out asphalt modification again, and be selected in the heavy dope that contains part extraction solvent directly obtaining to distillation process section under normal pressure, add linking agent, through crosslinking polymerization, obtained equally having low softening point, the high added value modified asphalt material of high β resin content, its cohesiveness is good, product development suitability is strong, be suitable as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, the raw materials such as the middle high-temperature agglomerant pitch that waterproof paint and market are required and impregnating pitch.Continuous modification method technique provided by the present invention is simple, mild condition, equipment are conventional, be easy to amplify and produce, for the deep exploitation of coal directly-liquefied residue provides a kind of new approach, reduced the pollution of coal directly-liquefied residue to environment, improve the economy of coal direct liquefaction, there is good market application foreground.
The present invention does not need additionally to add the raw material of crosslinking polymerization, only need to utilize extraction solvent contained in heavy dope just can reach the object of crosslinking polymerization modifying asphalt, and this just there are certain requirements the character of extraction solvent.Preferably, extraction solvent is that boiling range is the distillate of 150～405 ℃.Preferably extraction solvent is one or more in liquefied coal coil, coal tar and distillate thereof, vacuum residuum and catalytically cracked oil; Linking agent is terephthalyl alcohol.The preferred above-mentioned extraction solvent of the present invention and linking agent, but be not limited to this, above-mentioned extraction solvent adopt above-mentioned extraction solvent to be because can either dissolve coal directly-liquefied residue, can under the effect of linking agent and catalyzer, there is cross-linking polymerization with heavy dope again, thereby reach the object of modifying asphalt.
A preferred embodiment of the invention, step S1 comprises: coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with extraction solvent, obtain mixed solution; And under inert atmosphere, with 10 ℃～30 ℃/h, mixed solution is warming up to 80 ℃～280 ℃, and under 0.1～1.0MPa, constant temperature stirs, and thermosol extraction obtains thermosol extraction mixture; The time of thermosol extraction is 5～60min, and the speed that constant temperature stirs is 50～300r/min.Coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with extraction solvent, can guarantee effect and the solvent recovering rate of extraction, if the mass ratio of coal directly-liquefied residue and extraction solvent is higher than 1:1, may there is the situation that extraction solvent can not dissolve coal directly-liquefied residue completely, cause extraction thorough not, and in heavy dope, contained extraction solvent also can cause because content reduces heavy dope softening temperature; If the mass ratio of coal directly-liquefied residue and extraction solvent lower than 1:10, can cause extraction solvent waste, increase the cost recovery of follow-up extraction solvent.Consider that high temperature mink cell focus and bitumen reaction entrained air easily catch fire, dangerous, the present invention passes into N in reaction forward direction mixed solution
2first get rid of reactor as the air in stirring tank, reaction is carried out under the condition of anaerobic.
Particularly, in step S1, adopt the mode of thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation to carry out solid-liquid separation.The present invention preferably but be not limited to above-mentioned listed solid-liquid separation method, as long as can be by solid-liquid fully separated and reach required effect.When adopting the mode of thermal air pressure filtration to carry out solid-liquid separation, the temperature of thermal air pressure filtration is 50 ℃～210 ℃, is preferably 150 ℃～200 ℃; The pressure of thermal air pressure filtration is 0.02～101.3KPa or 0.2MPa～1.0MPa.Adopt in said temperature and pressure range and carry out thermal air pressure filtration, can largely solid-liquid be carried out to separation.Except thermal air pressure filtration, when solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 ℃～250 ℃, and inlet pressure is 0.2MPa～0.6MPa.
After solid-liquid separation, in order rationally to reuse extraction solvent, in step S1, to the extraction liquid after solid-liquid separation, adopt the mode of distillation or evaporation to carry out solvent recuperation processing, preferably adopt air distillation or underpressure distillation.By distilling or evaporating, can make part extraction solvent return to thermosol extraction step and recycle, remaining extraction solvent has been stayed in heavy dope.
It is linking agent that the present invention selects terephthalyl alcohol, and terephthalyl alcohol can form carbonium ion under acid catalyst effect, then, with heavy dope cross-linking polymerization, with this, improves the β resin content in modified pitch.Take heavy dope as benchmark, and the addition of linking agent is 1～50wt%, and preferably, the addition of linking agent is 10～20wt%.If the addition of linking agent, higher than 50wt%, can cause the unnecessary wasting of resources, also can increase production cost; On the contrary, if the addition of linking agent lower than 1wt%, can reduce the degree of crosslinking polymerization between the aromatic hydrocarbons molecule in heavy dope and its contained extraction solvent, cannot reach the quality standard of required modifying asphalt.Therefore, through considering, the present invention is controlled at the addition of linking agent in the scope of 1～50wt%, can either to DCL/Direct coal liquefaction intermediate product heavy dope, carry out modification preferably preferably, be met the required low softening point of application and the medium and high temperature modifying asphalt of high β resin content, and reasonable production control cost.
In order to make gelatin liquefaction hard pitch and mink cell focus cross-linking polymerization, also need to add catalyzer in the second mixture, preferably, catalyzer is sulfuric acid.The present invention preferably adopts above-mentioned catalyzer, but is not limited to this, as long as contribute to the carrying out of cross-linking polymerization, the present invention adopts sulfuric acid to have high, the cheap advantage of catalytic efficiency as catalyzer.When adopting sulfuric acid as catalyzer, preferably adopt terephthalyl alcohol as linking agent.The selection of linking agent terephthalyl alcohol is arranged in pairs or groups mutually with catalyst sulfuric acid, this is to consider that terephthalyl alcohol reactive behavior is low, need that the sour ability of this confession of sulfuric acid is strong, cheap, the catalyzer of wide material sources, to improve crosslinking polymerization speed and the degree of linking agent and pitch, mink cell focus.Add after sulfuric acid, terephthalyl alcohol under the effect of an acidic catalyst, generates phenmethyl positively charged ion and electrophilic substitution reaction has occurred rich aromatic hydrocarbons (heavy dope), has improved crosslinking polymerization degree.
Take heavy dope as benchmark, and the add-on of catalyzer is 1～50wt%, is preferably 10～20wt%.Take DCL/Direct coal liquefaction hard pitch as benchmark, if the add-on of catalyzer, lower than 1wt%, can reduce catalytic efficiency, thereby reduce crosslinking polymerization degree; If the add-on of catalyzer higher than 50wt%, can make catalytic too fast, react too violent, be unfavorable for the carrying out of reaction, also can cause in addition the waste of catalyzer, increased production cost.The mass percent concentration of preferably sulfuric acid is 10%～98%, more preferably 40～70%.Through considering, the present invention fixes on the consumption of catalyzer and concentration limits in above-mentioned scope, to contribute to steadily carrying out of reaction.
According to a kind of exemplary embodiment of the present invention, preset temperature is 120～350 ℃, and temperature rise rate is 1～10 ℃/min, and the time of crosslinking polymerization is 0.5～36 hour.If preset temperature lower than 120 ℃, there will be the reactant can not efficient melting, cause stirring inhomogeneous, be unfavorable for the quality uniformity of product; If preset temperature higher than 350 ℃, there will be reactant light constituent gasification, heavy component coking phenomenon, the extraction solvent that causes heavy dope and its intension is polyreaction preferably, is unfavorable for the carrying out of crosslinking reaction.Equally, if temperature rise rate lower than 1 ℃/min, there will be temperature rise rate excessively slow, cause the production time long, be unfavorable for the raising of production efficiency; If temperature rise rate, higher than 10 ℃/min, there will be reactant to be heated inhomogeneous, cause the reactant coking of reactor wall place or gasification, be unfavorable for homogeneous reaction.Therefore, through considering, the present invention carries out cooperate optimization selection to preset temperature, temperature rise rate, churning time, and they are limited in above-mentioned scope, can enhance productivity, and reduces severe reaction conditions degree, contributes to the carrying out of reaction.Further preferably, preset temperature is 160～200 ℃, and temperature rise rate is 5～7 ℃/min, and the time of crosslinking polymerization is 6～10 hours.
According to a further aspect in the invention, provide a kind of modifying asphalt, this modifying asphalt is for adopting the above-mentioned method that any utilizes the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt to be prepared from.The softening temperature of modifying asphalt prepared by employing the method is 75～120 ℃, and β resin content value is 16～35wt.%, and ash oontent value is≤0.5wt.%.
According to another aspect of the invention, provide the application of above-mentioned any modifying asphalt in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, high-temperature agglomerant pitch and impregnating pitch.
Below in conjunction with specific embodiment, further illustrate beneficial effect of the present invention:
Embodiment 1
1) 300Kg coal directly-liquefied residue and extraction solvent vacuum residuum (boiling range is 300-420 ℃) are added to (weight ratio of coal directly-liquefied residue and vacuum residuum is 1:2.5) in stirring tank, the speed stirring with 60r/min, obtains mixed solution.In stirring tank, fill N
2pressure to stirring tank rises to 0.1MPa, with 20 ℃/h, mixed solution is warming up to after 150 ℃, with 300r/min constant temperature, stirs, and thermosol extraction 30min, is extracted mixture.
2) adopt thermal air pressure filtration mode to carry out solid-liquid separation to extraction mixture.Wherein filtration temperature is 150 ℃, and filter pressure is 0.3MPa, and the filter core aperture size of strainer is 30 μ m.After filtering, collect extraction liquid and extract remainder.
3) extraction liquid is sent into vacuum still and carried out vacuum distillation recovered solvent, column bottom temperature is 250 ℃, tower top temperature is 90 ℃, tower top pressure is 2KPa(absolute pressure), recovered overhead part extraction solvent returns to extraction step recycle, and tower bottom divides collects the gelatin liquefaction heavy dope that contains extraction solvent that ash content is 0.35wt.%, after testing, the softening temperature of this heavy dope is 115 ℃, and β resin content value is 13wt%, and ash oontent value is 0.35wt%.
4) getting the heavy dope that contains extraction solvent and the 3Kg terephthalyl alcohol that 300Kg obtains through underpressure distillation is added in stirring tank; under nitrogen atmosphere protection; heat-up rate with 5 ℃/min is warming up to 160 ℃; then adding concentration is 10wt.% sulfuric acid 3Kg; at 160 ℃ of isothermal reaction 24h; stop heating, obtain modifying asphalt.The softening temperature that records product is 105 ℃, β resin content 28wt.%, and ash value is 0.32wt.%.
The operation steps of embodiment 2 to 6 is identical with embodiment 1, and difference is specifically in Table 1.The softening temperature of modifying asphalt, ash oontent value adopt standard A STMD3461-83, GB/T212 to measure successively, β resin content adopts GB/T2293-1997 standard testing toluene insolubles, GB/T2292-1997 standard testing quinoline insolubles and obtains, be that β resin content is the difference of toluene insolubles and quinoline insolubles, performance perameter is specifically in Table 1.
Table 1
Data from table 1 can be found out, apply technical scheme of the present invention, coal directly-liquefied residue is carried out to hot melt extraction, after solid-liquid separation and solvent recuperation, having obtained softening temperature is 20 ℃～115 ℃, β resin content value is the heavy dope of 1～15wt.% and ash oontent value≤0.5wt%, under the effect of linking agent and catalyzer, mode by normal heating just can be so that softening temperature and the heavy dope of β resin content value in the above-mentioned scope extraction solvent crosslinking polymerization contained with it, thereby prepared softening temperature, it is 75 ℃～120 ℃, β resin content value be 16～35wt% and ash oontent value≤0.5wt.% high added value in, high-temperature coal liquefaction modifying asphalt.
The present invention has abandoned in prior art and first coal directly-liquefied residue has been prepared into hard pitch, and then add mink cell focus in hard pitch, by crosslinking polymerization, carry out asphalt modification again, and be selected in the heavy dope that contains part extraction solvent directly obtaining to distillation process section under normal pressure, add linking agent, through the crosslinked poly-low softening point that obtained equally having, the high added value modified asphalt material of high β resin content, its cohesiveness is good, product development suitability is strong, be suitable as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, the raw materials such as the middle high-temperature agglomerant pitch that waterproof paint and market are required and impregnating pitch.Continuous modification method technique provided by the present invention is simple, mild condition, equipment are conventional, be easy to amplify and produce, for the deep exploitation of coal directly-liquefied residue provides a kind of new approach, reduced the pollution of coal directly-liquefied residue to environment, improve the economy of coal direct liquefaction, there is good market application foreground.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (15)
1. utilize the serialization of coal directly-liquefied residue normal pressure to prepare a method for modifying asphalt, it is characterized in that, comprise the following steps:
S1, in described coal directly-liquefied residue, add extraction solvent, carry out successively thermosol extraction, solid-liquid separation and solvent recuperation and process, obtain the heavy dope that contains described extraction solvent;
S2, in described heavy dope, add linking agent, be uniformly mixed, obtain the first mixture; And
S3, in described the first mixture, add catalyzer, heat cross-linking polymerization under normal pressure, obtains described modifying asphalt.
2. method according to claim 1, is characterized in that, the softening temperature of described heavy dope is 20～115 ℃, and β resin content value is 1～15wt.%, ash oontent value≤0.5wt%.
3. method according to claim 1, is characterized in that, described extraction solvent is that boiling range is the distillate of 150～405 ℃.
4. method according to claim 1, is characterized in that, described extraction solvent is one or more in liquefied coal coil, coal tar and distillate thereof, vacuum residuum and catalytically cracked oil; Described linking agent is terephthalyl alcohol.
5. method according to claim 1, is characterized in that, described step S1 comprises:
Described coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with described extraction solvent, obtain mixed solution; And
Under inert atmosphere, with 10 ℃～30 ℃/h, described mixed solution is warming up to 80 ℃～280 ℃, under 0.1～1.0MPa, constant temperature stirs, and thermosol extraction obtains described thermosol extraction mixture;
The time of described thermosol extraction is 5～60min, and the speed that described constant temperature stirs is 50～300r/min.
6. method according to claim 1, is characterized in that, adopts the mode of thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation to carry out solid-liquid separation in described step S1.
7. method according to claim 1, is characterized in that, in described step S1, to the extraction liquid after solid-liquid separation, adopts the mode of distillation or evaporation to carry out solvent recuperation processing, preferably adopts air distillation or underpressure distillation.
8. method according to claim 1, is characterized in that, the described heavy dope of take is benchmark, and the addition of described linking agent is 1～50wt%, and preferably, the addition of described linking agent is 10～20wt%.
9. method according to claim 1, is characterized in that, in described step S3, will add described first mixture of described catalyzer to be warming up to preset temperature, constant temperature normal pressure crosslinking polymerization.
10. method according to claim 9, is characterized in that, described preset temperature is 120～350 ℃, and temperature rise rate is 1～10 ℃/min, and the time of described crosslinking polymerization is 0.5～36 hour; Preferably, described preset temperature is 160～200 ℃, and temperature rise rate is 5～7 ℃/min, and the time of described crosslinking polymerization is 6～10 hours.
11. methods according to claim 1, is characterized in that, described catalyzer is sulfuric acid, and the described heavy dope of take is benchmark, and the add-on of described sulfuric acid is 1～50wt%, is preferably 10～20wt%.
12. methods according to claim 11, is characterized in that, the mass percent concentration of described sulfuric acid is 10%～98%, is preferably 40～70%.
13. 1 kinds of modifying asphalts, is characterized in that, adopt the method for utilizing the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt described in any one in claim 1 to 12 to be prepared from.
14. modifying asphalts according to claim 13, is characterized in that, the softening temperature of described modifying asphalt is 75 ℃～120 ℃, and β resin content value is 16～35wt%, and ash oontent value is≤0.5wt.%.
The application of modifying asphalt described in 15. 1 kinds of claims 13 or 14 in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, high-temperature agglomerant pitch and impregnating pitch.
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| CN104745219A (en) * | 2015-03-23 | 2015-07-01 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
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| CN105778968A (en) * | 2016-04-08 | 2016-07-20 | 神华集团有限责任公司 | Method for preparing impregnating pitch, impregnating pitch and application thereof |
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| CN106753652A (en) * | 2016-11-24 | 2017-05-31 | 神雾环保技术股份有限公司 | High-temperature agglomerant and its method for improving jet coal and quick lime mixing pelletizing elevated temperature strength |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104745219A (en) * | 2015-03-23 | 2015-07-01 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN105443078A (en) * | 2015-11-09 | 2016-03-30 | 安东环保技术有限公司 | Oil-based drilling cutting innocent treatment and comprehensive utilization method and waterproof film |
| CN105778968A (en) * | 2016-04-08 | 2016-07-20 | 神华集团有限责任公司 | Method for preparing impregnating pitch, impregnating pitch and application thereof |
| CN105861014A (en) * | 2016-04-08 | 2016-08-17 | 神华集团有限责任公司 | Method for preparing impregnation pitch using direct coal liquefaction residue, impregnation pitch and application thereof |
| CN106753652A (en) * | 2016-11-24 | 2017-05-31 | 神雾环保技术股份有限公司 | High-temperature agglomerant and its method for improving jet coal and quick lime mixing pelletizing elevated temperature strength |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN111501134B (en) * | 2020-05-28 | 2022-05-06 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
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