CN103756703B - Modifying asphalt, the serialization of coal directly-liquefied residue normal pressure is utilized to prepare method and the application thereof of modifying asphalt - Google Patents
Modifying asphalt, the serialization of coal directly-liquefied residue normal pressure is utilized to prepare method and the application thereof of modifying asphalt Download PDFInfo
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Abstract
The invention discloses 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.The method comprises the following steps: S1, in coal directly-liquefied residue, add extraction solvent, carries out thermosol extraction, solid-liquid separation and solvent recuperation process successively, obtains the heavy dope containing extraction solvent; S2, in heavy dope, add linking agent, be uniformly mixed, obtain the first mixture; And S3, in the first mixture, adding catalyzer, heat cross-linking polymerization at ambient pressure, obtains 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 the mode of mink cell focus crosslinking polymerization to asphalt modification, but be polymerized containing adding linking agent in the heavy dope of extraction solvent directly to after distillation under normal pressure, obtain the modified bitumen product of low softening point, high β resin content, be suitable as the raw material of medium and high temperature binder pitch and impregnating pitch.
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
Along with the fast development of national economy, modernization and social development process are constantly accelerated, and the consumption of China to petroleum products constantly increases, and greatly exceed the rate of growth of the crude production same period, cause us petroleum import amount all to increase year by year, and exceeded from output.And the country that to be a rich coal oil-poor of China, make full use of abundant coal resources, the clean coal technology of the advanced person such as development of coal direct liquefaction reduces to depend on unduly external crude oil, one of important channel of alleviation China's oil shortage of resources, petroleum products supply and demand pressure, also be 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 by coal by high temperature, high pressure, and under catalyst action, hydrogenation directly changes into the clean coal technology of a kind of advanced person of clean transport fuel (petroleum naphtha, diesel oil etc.) or industrial chemicals.The process of DCL/Direct coal liquefaction is generally granularity coal being crushed in advance below 0.15mm, then is made into coal slurry with solvent, and under certain temperature (about 450 DEG C) and high pressure hydrogenation, make the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process except obtaining the liquiefied product of needs, go back some hydrocarbon molecules of by-product, CO
xdeng the liquefaction residue (also known as coal liquefaction residue) that gas, process water and solid-liquid separation process produce.Liquefied residue generally accounts for about 30% of coal input quantity.The economy and environment protection etc. of utilization on the efficiency of liquefaction process and whole liquefaction factory of coal liquefaction residue all have immeasurable impact.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts value product and has important practical significance to the economic benefit improving direct liquefaction process.
Coal directly-liquefied residue is primarily of inanimate matter and organic two portions composition, 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 in organic species and bitumen account for 50% of level of residue, and unconverted coal accounts for 30% of level of residue, and ash content accounts for about 20%.Therefore, the bitumen and mink cell focus that account for 50% in liquefied residue are separated and carry out comprehensive development and utilization, it is feasible for therefrom extracting or prepare more value product.
Current utilization mainly some traditional methods to coal liquefaction residue, as burning, coking liquefaction and gasification hydrogen-producing etc.Directly burn in boiler or kiln as fuel, will the economy of gelatin liquefaction be affected undoubtedly, and sulphur content higher in liquefied residue will bring the problem of environment aspect.Although coking liquefaction adds the liquid oil yield of coal liquefaction craft, liquefied residue can not obtain the most reasonably utilizing, and the utilization ways of semicoke and coke is very not clear and definite yet.The method of liquefied residue being carried out gasification hydrogen-producing is a kind of effective extensive approach utilized, but the high value added utilization potentiality of the bitumen in residue and mink cell focus are embodied, and the ash content in residue is up to more than 20%, this brings very large impact will to the deslagging of vapourizing furnace.
It take coal hydroliquefaction residue as the method that raw material plasma body prepares carbon nano-material that patent ZL200510047800.X discloses a kind of.Patent ZL200610012547.9 discloses a kind of using the method for coal liquefaction residue as road asphalt modifier.ZL200910087907.5 discloses a kind of method utilizing coal directly-liquefied residue to prepare asphalt base carbon fiber.Patent 200910086158.4 discloses a kind of method preparing mesophase pitch with coal liquefaction residue.Aforesaid method all with the bitumen in coal liquefaction residue for raw material is applied to carbon materials field, do not relate to coal directly-liquefied residue 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 with expensive pure chemistry reagent for solvent, cost is relatively high.
Up to now, the research report both at home and abroad about asphalt modification is a lot, main employing 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 first prepare DCL/Direct coal liquefaction hard pitch from coal directly-liquefied residue, then from system, add some materials such as mink cell focus, linking agent wherein carry out heating and pressurizing crosslinking polymerization, this method increase the complicacy of operation, cannot continuous prodution be carried out.
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 heavy dope containing extraction solvent that coal directly-liquefied residue obtains at distilling period is directly carried out crosslinking polymerization by the method, achieves the object of continuous prodution modifying asphalt.
To achieve these goals, according to an aspect of the present invention, provide a kind of method 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 thermosol extraction, solid-liquid separation and solvent recuperation process successively, obtain the heavy dope containing extraction solvent; S2, in heavy dope, add linking agent, be uniformly mixed, obtain the first mixture; And S3, in the first mixture, adding catalyzer, heat cross-linking polymerization at ambient pressure, obtains modifying asphalt.
Further, the softening temperature of heavy dope is 20 ~ 115 DEG C, and β resin content value is 1 ~ 15wt.%, ash oontent value≤0.5wt%.
Further, extraction solvent to be boiling range the be distillate of 150 ~ 405 DEG C.
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: mixed according to mass ratio 1:1 ~ 1:10 with extraction solvent by coal directly-liquefied residue, obtain mixed solution; And under an inert atmosphere, with 10 DEG C ~ 30 DEG C/h, mixed solution is warming up to 80 DEG C ~ 280 DEG C, under 0.1 ~ 1.0MPa, constant temperature stirs, and thermosol extracts, and obtains thermosol extraction mixture; The time of thermosol extraction is 5 ~ 60min, and the speed that constant temperature stirs is 50 ~ 300r/min.
Further, adopt thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation in step S1, the mode of gravity settling separation and fractionation by distillation carries out solid-liquid separation.
Further, adopt the mode of distillation or evaporation to carry out solvent recuperation process to the extraction liquid after solid-liquid separation in step S1, preferably adopt air distillation or underpressure distillation.
Further, with heavy dope for benchmark, the addition of linking agent is 1 ~ 50wt%, and preferably, the addition of linking agent is 10 ~ 20wt%.
Further, in step S3, the first mixture adding catalyzer is warming up to preset temperature, constant temperature normal pressure crosslinking polymerization.
Further, preset temperature is 120 ~ 350 DEG C, and temperature rise rate is 1 ~ 10 DEG C/min, and the time of crosslinking polymerization is 0.5 ~ 36 hour; Preferably, preset temperature is 160 ~ 200 DEG C, and temperature rise rate is 5 ~ 7 DEG C/min, and the time of crosslinking polymerization is 6 ~ 10 hours.
Further, catalyzer is sulfuric acid, and with heavy dope for benchmark, 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 adopt any one method utilizing the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt above-mentioned to be prepared from.
Further, the softening temperature of modifying asphalt is 75 DEG C ~ 120 DEG C, and β resin content value is 16 ~ 35wt%, and ash oontent value is≤0.5wt.%.
According to another aspect of the invention, the application of any one modifying asphalt above-mentioned in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, high-temperature agglomerant pitch and impregnating pitch is provided.
Apply technical scheme of the present invention, by carrying out thermosol extraction, solid-liquid separation and distillation to coal directly-liquefied residue, obtain the DCL/Direct coal liquefaction heavy dope containing partial extraction solvent, under the effect of catalyzer, just can make to remain in the extraction solvent in heavy dope and heavy dope crosslinking polymerization by the mode of normal heating, thus 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 mink cell focus is added in hard pitch, asphalt modification is carried out again by crosslinking polymerization, but select at ambient pressure directly to distillation process section obtain containing partial extraction solvent heavy dope in add linking agent, obtain equally through crosslinking polymerization and there is 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, waterproof paint and the raw material such as the middle high-temperature agglomerant pitch needed for market and impregnating pitch.Continuous modification method technique provided by the present invention is simple, mild condition, equipment are conventional, be easy to amplification produces, deep exploitation for coal directly-liquefied residue provides a kind of new approach, reduce 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 forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows and prepares the schematic flow sheet of modifying asphalt according to the coal directly-liquefied residue normal pressure serialization that utilizes of a kind of exemplary embodiments of the present invention.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
" the heavy dope " mentioned in the present invention refers to the low ash content heavy dregs of fat that coal liquefaction residue obtains through solvent extraction, solid-liquid separation, underpressure distillation, be the intermediate product obtained in coal directly-liquefied residue treating processes, main component is extraction solvent and gelatin liquefaction bitumen.
There is the problems such as intermittent production to solve in prior art, improve production economy efficiency, the invention provides a kind of method 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 thermosol extraction, solid-liquid separation and solvent recuperation process successively, obtain the heavy dope containing extraction solvent; S2, in heavy dope, add linking agent, be uniformly mixed, obtain the first mixture; And S3, in the first mixture, adding catalyzer, heat cross-linking polymerization at ambient pressure, obtains modifying asphalt.
Extraction solvent contained in heavy dope 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 height of extraction solvent directly affects softening temperature and the β resin content value of heavy dope, if the higher increase of the content of extraction solvent, then the softening temperature of heavy dope reduces, and β resin content value reduces; If the content of extraction solvent reduces, then 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, needing to control the content of the extraction solvent in heavy dope, making it be in certain scope.Preferably, when the softening temperature of heavy dope is 20 ~ 115 DEG C, β resin content value is 1 ~ 15wt.%, during ash oontent value≤0.5wt%, has preferably performance after being now cross-linked with the extraction solvent contained by it in heavy dope.Technique provided by the present invention is adopted only to need crosslinking polymerization under normal pressure just can obtain 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 carrying out thermosol extraction, solid-liquid separation and distillation to coal directly-liquefied residue, obtain the DCL/Direct coal liquefaction heavy dope containing partial extraction solvent, under the effect of catalyzer, just can make to remain in the extraction solvent in heavy dope and heavy dope crosslinking polymerization by the mode of normal heating, thus 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 mink cell focus is added in hard pitch, asphalt modification is carried out again by crosslinking polymerization, but select at ambient pressure directly to distillation process section obtain containing partial extraction solvent heavy dope in add linking agent, obtain equally through crosslinking polymerization and there is 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, waterproof paint and the raw material such as the middle high-temperature agglomerant pitch needed for market and impregnating pitch.Continuous modification method technique provided by the present invention is simple, mild condition, equipment are conventional, be easy to amplification produces, deep exploitation for coal directly-liquefied residue provides a kind of new approach, reduce 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 the raw material additionally adding crosslinking polymerization, and only need to utilize extraction solvent contained in heavy dope just can reach the object of crosslinking polymerization modifying asphalt, this just there are certain requirements the character of extraction solvent.Preferably, extraction solvent to be boiling range the be distillate of 150 ~ 405 DEG C.Preferred 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 thereto, above-mentioned extraction solvent is adopted to be because above-mentioned extraction solvent can either dissolve coal directly-liquefied residue, cross-linking polymerization can be there is with heavy dope under the effect of linking agent and catalyzer again, thus reach the object of modifying asphalt.
A preferred embodiment of the invention, step S1 comprises: mixed according to mass ratio 1:1 ~ 1:10 with extraction solvent by coal directly-liquefied residue, obtain mixed solution; And under an inert atmosphere, with 10 DEG C ~ 30 DEG C/h, mixed solution is warming up to 80 DEG C ~ 280 DEG C, under 0.1 ~ 1.0MPa, constant temperature stirs, and thermosol extracts, and 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, effect and the solvent recovering rate of extraction can be ensured, if the mass ratio of coal directly-liquefied residue and extraction solvent is higher than 1:1, then may occur that extraction solvent can not completely by the situation of coal directly-liquefied residue dissolving, cause extraction thorough not, and extraction solvent contained in heavy dope also can cause heavy dope softening temperature because content reduces; If the mass ratio of coal directly-liquefied residue and extraction solvent is lower than 1:10, then extraction solvent can be caused to 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 before the reaction in mixed solution
2first get rid of reactor as the air in stirring tank, reaction is carried out in the absence of oxygen.
Particularly, adopt thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation in step S1, the mode of gravity settling separation and fractionation by distillation carries out solid-liquid separation.The present invention preferably but be not limited to above-mentioned listed solid-liquid separation method, as long as solid-liquid fully can be 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 DEG C ~ 210 DEG C, is preferably 150 DEG C ~ 200 DEG C; 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 separated.Except thermal air pressure filtration, when solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 DEG C ~ 250 DEG C, and inlet pressure is 0.2MPa ~ 0.6MPa.
After solid-liquid separation, in order to rationally reuse extraction solvent, adopting the mode of distillation or evaporation to carry out solvent recuperation process to the extraction liquid after solid-liquid separation in step S1, preferably adopting air distillation or underpressure distillation.By distilling or evaporating, partial extraction solvent can be made to return thermosol extraction step and recycle, remaining extraction solvent has been stayed in heavy dope.
The present invention selects terephthalyl alcohol to be linking agent, and terephthalyl alcohol can form carbonium ion under acid catalyst effect, then with heavy dope cross-linking polymerization, improves the β resin content in modified pitch with this.With heavy dope for benchmark, the addition of linking agent is 1 ~ 50wt%, and preferably, the addition of linking agent is 10 ~ 20wt%.If the addition of linking agent is higher than 50wt%, then can cause the unnecessary wasting of resources, also can increase production cost; On the contrary, if the addition of linking agent is lower than 1wt%, then can reduces the degree of crosslinking polymerization between the aromatic hydrocarbons molecule in heavy dope and the extraction solvent contained by it, the quality standard of required modifying asphalt cannot be reached.Therefore, through considering, the addition of linking agent controls in the scope of 1 ~ 50wt% by the present invention, modification preferably can either be carried out preferably to DCL/Direct coal liquefaction intermediate product heavy dope, be met the medium and high temperature modifying asphalt of low softening point needed for application and high β resin content, and can conservative control production 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 thereto, 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 considers 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 linking agent and pitch, the crosslinking polymerization speed of mink cell focus and degree.After adding sulfuric acid, terephthalyl alcohol under the effect of an acidic catalyst, generate phenmethyl positively charged ion and rich aromatic hydrocarbons (heavy dope) there occurs electrophilic substitution reaction, improves crosslinking polymerization degree.
With heavy dope for benchmark, the add-on of catalyzer is 1 ~ 50wt%, is preferably 10 ~ 20wt%.With DCL/Direct coal liquefaction hard pitch for benchmark, if the add-on of catalyzer is lower than 1wt%, then can reduce catalytic efficiency, thus reduce crosslinking polymerization degree; If the add-on of catalyzer is higher than 50wt%, then catalytic can be made too fast, reaction is too violent, is unfavorable for the carrying out reacted, also can causes the waste of catalyzer in addition, add production cost.The mass percent concentration of preferably sulfuric acid is 10% ~ 98%, more preferably 40 ~ 70%.Through considering, the consumption of catalyzer and concentration limits fix in above-mentioned scope and contribute to steadily carrying out of reaction by the present invention.
According to a kind of exemplary embodiment of the present invention, preset temperature is 120 ~ 350 DEG C, and temperature rise rate is 1 ~ 10 DEG C/min, and the time of crosslinking polymerization is 0.5 ~ 36 hour.If preset temperature is lower than 120 DEG C, then there will be reactant can not efficient melting, causes stirring uneven, is unfavorable for the quality uniformity of product; If preset temperature is higher than 350 DEG C, then there will be the gasification of reactant light constituent, heavy component coking phenomenon, cause the extraction solvent of heavy dope and its intension cannot polyreaction preferably, be unfavorable for the carrying out of crosslinking reaction.Equally, if temperature rise rate is lower than 1 DEG C/min, then 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 is higher than 10 DEG C/min, then there will be reactant and be heated uneven, 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, they is limited in above-mentioned scope, can enhances productivity, and reduces severe reaction conditions degree, contributes to the carrying out reacted.Further preferably, preset temperature is 160 ~ 200 DEG C, and temperature rise rate is 5 ~ 7 DEG C/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 adopt any one method utilizing the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt above-mentioned to be prepared from.The softening temperature of the modifying asphalt adopting the method to prepare is 75 ~ 120 DEG C, and β resin content value is 16 ~ 35wt.%, and ash oontent value is≤0.5wt.%.
According to another aspect of the invention, the application of any one modifying asphalt above-mentioned in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, high-temperature agglomerant pitch and impregnating pitch is provided.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1
1) 300Kg coal directly-liquefied residue and extraction solvent vacuum residuum (boiling range is 300-420 DEG C) are added to (weight ratio of coal directly-liquefied residue and vacuum residuum is 1:2.5) in stirring tank, stir with the speed of 60r/min, obtain mixed solution.N is filled in stirring tank
2rise to 0.1MPa to the pressure in stirring tank, after mixed solution being warming up to 150 DEG C with 20 DEG C/h, stir with 300r/min constant temperature, thermosol extraction 30min, is extracted mixture.
2) thermal air pressure filtration mode is adopted to carry out solid-liquid separation to extraction mixture.Wherein filtration temperature is 150 DEG C, and filter pressure is 0.3MPa, and the filter core aperture size of strainer is 30 μm.After filtering, extraction liquid and extract remainder is collected.
3) extraction liquid is sent into vacuum still and carry out vacuum distillation recovered solvent, column bottom temperature is 250 DEG C, tower top temperature is 90 DEG C, tower top pressure is 2KPa(absolute pressure), recovered overhead partial extraction solvent returns extraction step recycle, and tower bottom divides collects the gelatin liquefaction heavy dope containing extraction solvent that ash content is 0.35wt.%, after testing, the softening temperature of this heavy dope is 115 DEG C, and β resin content value is 13wt%, and ash oontent value is 0.35wt%.
4) that gets that 300Kg obtains through underpressure distillation is added in stirring tank containing the heavy dope of extraction solvent and 3Kg terephthalyl alcohol; under nitrogen atmosphere protection; 160 DEG C are warming up to the heat-up rate of 5 DEG C/min; then adding concentration is 10wt.% sulfuric acid 3Kg; at 160 DEG C of isothermal reaction 24h; stop heating, obtain modifying asphalt.The softening temperature recording product is 105 DEG C, 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 obtaining, namely β resin content is the difference of toluene insolubles and quinoline insolubles, and performance perameter is specifically in table 1.
Table 1
Data as can be seen from table 1, apply technical scheme of the present invention, hot melt extraction is carried out to coal directly-liquefied residue, after solid-liquid separation and solvent recuperation, obtaining softening temperature is 20 DEG C ~ 115 DEG C, 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, softening temperature and the heavy dope of β resin content value in above-mentioned scope and the extraction solvent crosslinking polymerization contained by it just can be made by the mode of normal heating, thus to have prepared softening temperature be 75 DEG C ~ 120 DEG C, β resin content value is 16 ~ 35wt% and in the high added value of ash oontent value≤0.5wt.%, 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 mink cell focus is added in hard pitch, asphalt modification is carried out again by crosslinking polymerization, but select at ambient pressure directly to distillation process section obtain containing partial extraction solvent heavy dope in add linking agent, through crosslinked poly-obtaining equally, there is 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, waterproof paint and the raw material such as the middle high-temperature agglomerant pitch needed for market and impregnating pitch.Continuous modification method technique provided by the present invention is simple, mild condition, equipment are conventional, be easy to amplification produces, deep exploitation for coal directly-liquefied residue provides a kind of new approach, reduce 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 amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (18)
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 thermosol extraction, solid-liquid separation and solvent recuperation process successively, obtain the heavy dope containing described extraction solvent;
S2, in described heavy dope, add linking agent, be uniformly mixed, obtain the first mixture; And
S3, in described first mixture, add catalyzer, heat cross-linking polymerization at ambient pressure, obtains described modifying asphalt;
Wherein, described linking agent is terephthalyl alcohol; Described catalyzer is sulfuric acid; And with described heavy dope for benchmark, the addition of described linking agent is 1 ~ 50wt%, with described heavy dope for benchmark, the add-on of described sulfuric acid is 1 ~ 50wt%.
2. method according to claim 1, is characterized in that, the softening temperature of described heavy dope is 20 ~ 115 DEG C, 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 to be boiling range the be distillate of 150 ~ 405 DEG C.
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.
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, obtains mixed solution; And
Under an inert atmosphere, with 10 DEG C ~ 30 DEG C/h, described mixed solution is warming up to 80 DEG C ~ 280 DEG C, under 0.1 ~ 1.0MPa, constant temperature stirs, and thermosol extracts, and 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 thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, the mode of gravity settling separation and fractionation by distillation carries out solid-liquid separation in described step S1.
7. method according to claim 1, is characterized in that, adopts the mode of distillation or evaporation to carry out solvent recuperation process in described step S1 to the extraction liquid after solid-liquid separation.
8. method according to claim 7, is characterized in that, adopts the mode of air distillation or underpressure distillation to carry out solvent recuperation process in described step S1 to the extraction liquid after solid-liquid separation.
9. method according to claim 1, is characterized in that, with described heavy dope for benchmark, the addition of described linking agent is 10 ~ 20wt%.
10. method according to claim 1, is characterized in that, in described step S3, described first mixture adding described catalyzer is warming up to preset temperature, constant temperature normal pressure crosslinking polymerization.
11. methods according to claim 10, is characterized in that, described preset temperature is 120 ~ 350 DEG C, and temperature rise rate is 1 ~ 10 DEG C/min, and the time of described crosslinking polymerization is 0.5 ~ 36 hour.
12. methods according to claim 11, is characterized in that, described preset temperature is 160 ~ 200 DEG C, and temperature rise rate is 5 ~ 7 DEG C/min, and the time of described crosslinking polymerization is 6 ~ 10 hours.
13. methods according to claim 1, is characterized in that, with described heavy dope for benchmark, the add-on of described sulfuric acid is 10 ~ 20wt%.
14. methods according to claim 13, is characterized in that, the mass percent concentration of described sulfuric acid is 10% ~ 98%.
15. methods according to claim 14, is characterized in that, the mass percent concentration of described sulfuric acid is 40 ~ 70%.
16. 1 kinds of modifying asphalts, is characterized in that, adopt the method utilizing the serialization of coal directly-liquefied residue normal pressure to prepare modifying asphalt according to any one of claim 1 to 15 to be prepared from.
17. modifying asphalts according to claim 16, is characterized in that, the softening temperature of described modifying asphalt is 75 DEG C ~ 120 DEG C, and β resin content value is 16 ~ 35wt%, and ash oontent value is≤0.5wt.%.
The application of modifying asphalt described in 18. 1 kinds of claims 16 or 17 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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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