CN103740396A - Modified asphalt, modification method of direct coal liquefaction high-temperature asphalt and application thereof - Google Patents

Modified asphalt, modification method of direct coal liquefaction high-temperature asphalt and application thereof Download PDF

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CN103740396A
CN103740396A CN201410021555.4A CN201410021555A CN103740396A CN 103740396 A CN103740396 A CN 103740396A CN 201410021555 A CN201410021555 A CN 201410021555A CN 103740396 A CN103740396 A CN 103740396A
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modifying
coal liquefaction
dcl
direct coal
temperature
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CN201410021555.4A
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CN103740396B (en
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李克健
章序文
舒成
程时富
常鸿雁
周颖
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神华集团有限责任公司
中国神华煤制油化工有限公司
中国神华煤制油化工有限公司上海研究院
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Abstract

The invention discloses modified asphalt, a modification method of direct coal liquefaction high-temperature asphalt and application thereof. The modification method comprises the following steps: S1, adding heavy oil and a cross-linking agent to the direct coal liquefaction high-temperature asphalt, stirring and mixing, so as to obtain a first mixture; S2, adding a catalyst to the first mixture, carrying out heating and pressure polymerization, so as to obtain direct coal liquefaction modified asphalt. The modified asphalt with a low softening point, high beta resin content and low quinoline insoluble matter content is obtained by carrying out heating and pressure polymerization reaction on the coal liquefaction high-temperature asphalt with a high softening point and low beta resin content. The product is strong in development applicability, and is a novel material with high performance and high additional value. The modification method has the advantages of being simple in process route, mild in condition, conventional in equipment, easy to amplify and produce and the like, and a new path is provided for deep utilization of the direct coal liquefaction high-temperature asphalt with the high softening point and low beta resin content, especially the direct coal liquefaction residue.

Description

The method of modifying of modifying asphalt, DCL/Direct coal liquefaction hard pitch and application thereof
Technical field
The present invention relates to the deep process technology field of coal directly-liquefied residue, in particular to method of modifying and the application thereof of a kind of modifying asphalt, DCL/Direct coal liquefaction hard pitch.
Background technology
Along with the fast development of 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 exceeded 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 be generally by coal in advance powder to the granularity below 0.15mm, then be 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 economy of the efficiency of the utilization of coal liquefaction residue on liquefaction process and whole liquefaction factory and environment protection etc. all have immeasurable impact.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts value product the economic benefit that improves direct liquefaction process is had important practical significance.
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 of method of preparing carbon nano-material take coal hydroliquefaction residue 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.But aforesaid method is all take the bitumen in coal liquefaction residue as raw material, do not relate to the modification of hard pitch and pitch in preparation, and the extracting of residue medium pitch class material is all take expensive pure chemistry reagent as solvent, cost is relatively high.
Up to now, about the research report of asphalt modification is a lot, mainly adopt high temperature thermal polymerization method, distillation under vacuum, oxidation thermal polymerization method both at home and abroad.Although these asphalt modifier methods are adopted by domestic and international manufacturer always, and all produce qualified modified pitch, but these asphalt modifier methods are all to adopt softening temperature and β resin content and carbon yield to become mutually to increase progressively the principle of relation, by raising pitch softening point, increase β resin content and carbon yield., there is a kind of situation of runing counter to it: softening temperature is higher in the hard pitch can coal directly-liquefied residue obtaining through solvent extraction, β resin content is too low, and its reason is exactly that DCL/Direct coal liquefaction hard pitch molecular-weight average distributes too wide in range.So, when being only difficult to accomplish DCL/Direct coal liquefaction hard pitch softening temperature is fallen by above-mentioned three kinds of methods, improve again its β resin content and carbon yield.How cut-off so far, is carried out modification to the gelatin liquefaction hard pitch of high softening-point (115～160 ℃), low β resin content (5～15wt.%) and is rarely had report.
Summary of the invention
The present invention aims to provide method of modifying and the application thereof of a kind of modifying asphalt, DCL/Direct coal liquefaction hard pitch, and the method has obtained the modifying asphalt of low softening point and high β resin content, has realized the high value added utilization of coal directly-liquefied residue.
To achieve these goals, according to an aspect of the present invention, provide a kind of method of modifying of DCL/Direct coal liquefaction hard pitch, comprised the following steps: S1, in DCL/Direct coal liquefaction hard pitch, added mink cell focus and linking agent, be uniformly mixed, obtain the first mixture; And S2, in the first mixture, adding catalyzer, heating and pressurizing polymerization, obtains DCL/Direct coal liquefaction modifying asphalt.
Further, mink cell focus comprises one or more in carbolineum, underpressure distillation residual oil, liquefaction heavy oil and catalytically cracked oil, and linking agent is terephthalyl alcohol.
Further, take DCL/Direct coal liquefaction hard pitch as benchmark, the addition of mink cell focus is 5～100wt%, and the addition of linking agent is 1～50wt%, and preferably, the addition of mink cell focus is 70～80wt%, and the addition of linking agent is 10～20wt%.
Further, step S2 carries out under inert atmosphere.
Further, step S2 comprises: S21, the first mixture is warming up to preset temperature, constant temperature stirs, and obtains the second mixture; And S22, in the second mixture, add catalyzer, and under preset temperature, being forced into predetermined pressure, constant temperature crosslinking polymerization, obtains DCL/Direct coal liquefaction modifying asphalt.
Further, preset temperature is 120 ℃～350 ℃, and temperature rise rate is 1～10 ℃/min, and the time that constant temperature stirs is 0.5～2 hour; Predetermined pressure is 0.01～10MPa, and the time of crosslinking polymerization is 0.5～36 hour.
Further, preset temperature is 160 ℃～200 ℃, and temperature rise rate is 3～6 ℃/min, and the time that constant temperature stirs is 1～1.5 hour; Predetermined pressure is 1～5MPa, and the time of crosslinking polymerization is 6～10 hours.
Further, catalyzer is sulfuric acid; Take DCL/Direct coal liquefaction hard pitch as benchmark, the add-on of catalyzer 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 DCL/Direct coal liquefaction modifying asphalt, this DCL/Direct coal liquefaction modifying asphalt is prepared from by the method for modifying of above-mentioned any DCL/Direct coal liquefaction hard pitch.
Further, the softening temperature of DCL/Direct coal liquefaction modifying asphalt is 90～110 ℃, and β resin content value is 19～30wt.%, ash oontent value≤0.2wt%.
According to another aspect of the invention, provide the application of above-mentioned any DCL/Direct coal liquefaction modifying asphalt in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint.
Apply technical scheme of the present invention, by the gelatin liquefaction hard pitch of high softening-point, low β resin content is heated, pressure polymerization reaction, obtained thering is the modifying asphalt that softening temperature is low, β resin content is high and quinoline insolubles content is low, the exploitation suitability of product is stronger, being suitable as the raw materials such as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, is the novel material of a kind of high-performance, high added value.Method of modifying for DCL/Direct coal liquefaction hard pitch provided by the present invention has that operational path is simple, mild condition, equipment routine, be easy to amplify the advantages such as production, for the DCL/Direct coal liquefaction hard pitch modification of high softening-point (115～160 ℃), low β resin content (5～15wt.%), especially 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 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, the feature in embodiment and 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 DCL/Direct coal liquefaction hard pitch " mentioned in the present invention refers to the low ash content heavy of the one dope that coal directly-liquefied residue obtains through solvent extraction, solid-liquid separation, underpressure distillation, prepares the method comparative maturity of DCL/Direct coal liquefaction hard pitch.
For to the DCL/Direct coal liquefaction hard pitch modification better with high softening-point (115～160 ℃), low β resin content (5～15wt.%), the invention provides a kind of method of modifying of DCL/Direct coal liquefaction hard pitch, as shown in Figure 1, comprise the following steps: S1, in DCL/Direct coal liquefaction hard pitch, add mink cell focus and linking agent, be uniformly mixed, obtain the first mixture; And S2, in the first mixture, adding catalyzer, heating and pressurizing polymerization, obtains DCL/Direct coal liquefaction modifying asphalt.
By the gelatin liquefaction hard pitch of high softening-point, low β resin content is heated, pressure polymerization reaction, obtained thering is the modifying asphalt that softening temperature is low, β resin content is high and quinoline insolubles content is low, the exploitation suitability of product is stronger, being suitable as the raw materials such as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, is the novel material of a kind of high-performance, high added value.Method of modifying for DCL/Direct coal liquefaction hard pitch provided by the present invention has that operational path is simple, mild condition, equipment routine, be easy to amplify the advantages such as production, for the DCL/Direct coal liquefaction hard pitch modification of high softening-point (115～160 ℃), low β resin content (5～15wt.%), especially 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.
In order to reduce DCL/Direct coal liquefaction hard pitch softening temperature, the present invention adopts need to add mink cell focus in gelatin liquefaction hard pitch, its effect of the mink cell focus adding is as solvent, DCL/Direct coal liquefaction hard pitch to be dissolved, and then form mobility, the slurries that have good stability with DCL/Direct coal liquefaction hard pitch, and it is fully contacted with catalyzer with linking agent.Preferably, mink cell focus comprises one or more in carbolineum, underpressure distillation residual oil, liquefaction heavy oil and catalytically cracked oil.The heavy oil that wherein liquefies is that boiling point is 260 ℃ of above oil; Linking agent is terephthalyl alcohol.Different cross-linking systems should be selected different linking agents and catalyzer, it is linking agent that the present invention selects terephthalyl alcohol, can promote the aromatic hydrocarbons molecule in DCL/Direct coal liquefaction hard pitch and mink cell focus to be cross-linked to form the high molecular polymer with tridimensional network, with this, improve the β resin content in modified pitch.
A preferred embodiment of the invention, take DCL/Direct coal liquefaction hard pitch as benchmark, the addition of mink cell focus is 5～100wt%, the addition of linking agent is 1～50wt%.When the addition of mink cell focus is during lower than 5wt%, its effective solvability to gelatin liquefaction hard pitch reduces, and when the addition of mink cell focus is higher than 100wt%, is unfavorable for improving production economy; When the addition of linking agent is during lower than 1wt%, can reduce the degree of crosslinking polymerization between the aromatic hydrocarbons molecule in DCL/Direct coal liquefaction hard pitch and mink cell focus; When the addition of linking agent is during higher than 50wt%, be unfavorable for improving the economy of producing.Further preferably, the addition of mink cell focus is 70～80wt%, and the addition of linking agent is 10～20wt%.
According to a kind of exemplary embodiment of the present invention, as shown in Figure 1, step S2 comprises: S21, the first mixture is warming up to preset temperature, constant temperature stirs, and obtains the second mixture; And S22, in the second mixture, add catalyzer, and under preset temperature, being forced into predetermined pressure, constant temperature crosslinking polymerization, obtains DCL/Direct coal liquefaction modifying asphalt.For fear of the existence of the gases such as oxygen, bring the insecurity of pyroreaction, preferably, step S2 carries out under inert atmosphere, inert atmosphere preferred nitrogen or argon gas in the present invention.
A preferred embodiment of the invention, preset temperature is 120～350 ℃, and temperature rise rate is 1～10 ℃/min, and the time that constant temperature stirs is 0.5～2 hour; Predetermined pressure is 0.01～10MPa, 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 the gasification of reactant light constituent, heavy component coking phenomenon, cause pitch and mink cell focus to produce polyreaction with linking agent, be 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 enhancing productivity; 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; If predetermined pressure lower than 0.01MPa, can easily occur that linking agent at high temperature gasifies, cause pitch and mink cell focus that crosslinking reaction can not occur, be unfavorable for the polymerization of reaction; If predetermined pressure higher than 10MPa, there will be reaction pressure too high, cause the increase of reactor manufacturing cost and production danger coefficient too high, be unfavorable for the carrying out producing.Therefore, through considering, the present invention carries out cooperate optimization selection to preset temperature, temperature rise rate, churning time and predetermined pressure, 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 3～6 ℃/min, and the time that constant temperature stirs is 1～1.5 hour; Predetermined pressure is 1～5MPa, and the time of crosslinking polymerization is 6～10 hours.Most preferably, preset temperature is 180 ℃, and temperature rise rate is 5 ℃/min, and the time that constant temperature stirs is 1 hour; Predetermined pressure is 2MPa, and the time of crosslinking polymerization is 6 hours.
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.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 (pitch and mink cell focus), has improved crosslinking polymerization degree.
Take DCL/Direct coal liquefaction hard pitch as benchmark, the add-on of catalyzer is 1～50wt%, is preferably 10～20wt%.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.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 further aspect in the invention, provide a kind of DCL/Direct coal liquefaction modifying asphalt, this DCL/Direct coal liquefaction modifying asphalt is to adopt above-mentioned any method of modifying of DCL/Direct coal liquefaction hard pitch to be prepared from.Preferably, the softening temperature of DCL/Direct coal liquefaction modifying asphalt is 90～110 ℃, and β resin content value is 19～30wt%, ash oontent value≤0.2wt%.
According to another aspect of the invention, provide the application of above-mentioned any DCL/Direct coal liquefaction modifying asphalt in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint.
Below in conjunction with specific embodiment, further illustrate beneficial effect of the present invention:
Embodiment 1
Get coal directly-liquefied residue through thermosol extraction, solid-liquid separation, underpressure distillation processing, obtain DCL/Direct coal liquefaction hard pitch, its ash content is 0.45wt.%, and β resin content is 7wt.%, and softening temperature is 130 ℃.
1) 200Kg DCL/Direct coal liquefaction hard pitch is added in stirring tank together with carbolineum, linking agent terephthalyl alcohol, be uniformly mixed, obtain the first mixture.The carbolineum that wherein added is the 70wt% of DCL/Direct coal liquefaction hard pitch, and terephthalyl alcohol is the 10wt% of DCL/Direct coal liquefaction hard pitch.The first mixture is placed under nitrogen atmosphere protection, with the heat-up rate of 5 ℃/min, is warming up to 160 ℃, constant temperature stirs 1 hour, obtains the second mixture.
2) at 160 ℃, then in the second mixture, add the sulfuric acid (concentration is 70wt%) that accounts for DCL/Direct coal liquefaction hard pitch 10wt%, be forced into subsequently 1Mpa constant temperature cross-linking polymerization 10 hours, stop heating, take out, obtain product DCL/Direct coal liquefaction modifying asphalt.
The operation steps of embodiment 2 to 7 and comparative example 1 and 2 is identical with embodiment 1, and difference is specifically in Table 1.Wherein the DCL/Direct coal liquefaction hard pitch in table 1 is referred to as hard pitch, and DCL/Direct coal liquefaction modifying asphalt is referred to as modifying asphalt.
Wherein, 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, and β resin content is the difference of toluene insolubles and quinoline insolubles.
Table 1
Data from table 1 can be found out, adopt the modified technique of normal pressure or atmospheric low-temperature to compare with comparative example 1 and comparative example 2, in embodiments of the invention 1 to 7, adopt the mode of heating and pressurizing to carry out modification to the intermediate product DCL/Direct coal liquefaction hard pitch of coal directly-liquefied residue, having obtained softening temperature and be 90～110 ℃, β resin content value is the DCL/Direct coal liquefaction modifying asphalt of 19～30wt% and ash oontent value≤0.2wt%.Especially in embodiment 1 and embodiment 2, modified technique is optimized, the weight to added mink cell focus, linking agent and catalyzer and Heating temperature, pressure are in optimized selection, and have obtained the DCL/Direct coal liquefaction modifying asphalt that softening temperature is lower, β resin content is higher.Visible, adopt the exploitation suitability of modified bitumen product prepared by method of modifying of the present invention stronger, be suitable as the raw materials such as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, be the novel material of a kind of high-performance, high added value.
Below in conjunction with embodiment 8 to 10, further illustrate and adopt modified technique of the present invention to carry out preferably modification to the DCL/Direct coal liquefaction hard pitch with different softening point, β resin content value.
Embodiment 8
First utilize coal directly-liquefied residue to obtain DCL/Direct coal liquefaction hard pitch through thermosol extraction, solid-liquid separation, underpressure distillation, its ash content is 0.35wt.%, and β resin content is 5wt.%, and softening temperature is 115 ℃.
1) above-mentioned 200Kg gelatin liquefaction hard pitch is added in stirring tank together with 100Kg carbolineum, 2Kg terephthalyl alcohol, is uniformly mixed, obtain the first mixture.Under nitrogen atmosphere protection, with the heat-up rate of 1 ℃/min, be warming up to 200 ℃ and carry out constant temperature stirring, obtain the second mixture.
2) at 200 ℃, to adding concentration in the second mixture, be the sulfuric acid 2Kg of 98wt.%, be forced into subsequently 10Mpa reaction 36h, stop heating, take out and obtain DCL/Direct coal liquefaction modifying asphalt.The softening temperature that records DCL/Direct coal liquefaction modifying asphalt is 117 ℃, β resin content 30wt.%, and ash value is 0.29wt.%.
Embodiment 9
Utilize coal directly-liquefied residue to obtain DCL/Direct coal liquefaction hard pitch through thermosol extraction, solid-liquid separation, underpressure distillation, its ash content is 0.01wt.%, and β resin content is 15wt.%, and softening temperature is 160 ℃.
1) above-mentioned 200Kg gelatin liquefaction hard pitch is added in stirring tank together with 200Kg vacuum residuum, 100Kg terephthalyl alcohol, obtains the first mixture.The first mixture is placed under nitrogen atmosphere protection, with the heat-up rate of 10 ℃/min, is warming up to 350 ℃ and carries out constant temperature stirring, obtain the second mixture.
2) to adding concentration in the second mixture, be then the sulfuric acid 200Kg of 40wt%, be forced into subsequently 5Mpa reaction 10h, stop heating, take out gained gelatin liquefaction modifying asphalt.The softening temperature that records product is 112 ℃, β resin content 27wt.%, and ash value is 0.01wt.%.
Embodiment 10
First utilize coal directly-liquefied residue to obtain DCL/Direct coal liquefaction hard pitch through solvent extraction, solid-liquid separation, underpressure distillation, its ash content is 0.5wt%, β resin content 11.04wt.%, and softening temperature is 130 ℃.
1) above-mentioned 200Kg gelatin liquefaction hard pitch and 150Kg are liquefied together with heavy oil, 50Kg terephthalyl alcohol and be added in stirring tank, obtain the first mixture.Under argon gas atmosphere protection, the heat-up rate by the first mixture with 5 ℃/min, is warming up to 180 ℃ and carries out constant temperature stirring, obtains the second mixture.
2) to adding concentration in the second mixture, be then the sulfuric acid 60Kg of 10wt.%, be forced into subsequently 2Mpa reaction 0.5h, stop heating, take out gained gelatin liquefaction modifying asphalt.The softening temperature that records product is 90 ℃, β resin content 19wt.%, and ash value is 0.31wt.%.
To sum up, the present invention has obtained following beneficial effect: by the gelatin liquefaction hard pitch of high softening-point, low β resin content is heated, pressure polymerization reaction, obtained thering is the modifying asphalt that softening temperature is low, β resin content is high and quinoline insolubles content is low, the exploitation suitability of product is stronger, being suitable as the raw materials such as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint, is the novel material of a kind of high-performance, high added value.Method of modifying for DCL/Direct coal liquefaction hard pitch provided by the present invention has that operational path is simple, mild condition, equipment routine, be easy to amplify the advantages such as production, for the DCL/Direct coal liquefaction hard pitch modification of high softening-point (115～160 ℃), low β resin content (5～15wt.%), especially 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 (12)

1. a method of modifying for DCL/Direct coal liquefaction hard pitch, is characterized in that, comprises the following steps:
S1, in described DCL/Direct coal liquefaction hard pitch, add mink cell focus and linking agent, be uniformly mixed, obtain the first mixture; And
S2, in described the first mixture, add catalyzer, heating and pressurizing polymerization, obtains DCL/Direct coal liquefaction modifying asphalt.
2. method of modifying according to claim 1, is characterized in that, described mink cell focus comprises one or more in carbolineum, underpressure distillation residual oil, liquefaction heavy oil and catalytically cracked oil, and described linking agent is terephthalyl alcohol.
3. method of modifying according to claim 1, it is characterized in that, take described DCL/Direct coal liquefaction hard pitch as benchmark, the addition of described mink cell focus is 5～100wt%, the addition of described linking agent is 1～50wt%, preferably, the addition of described mink cell focus is 70～80wt%, and the addition of described linking agent is 10～20wt%.
4. method of modifying according to claim 1, is characterized in that, described step S2 carries out under inert atmosphere.
5. method of modifying according to claim 1, is characterized in that, described step S2 comprises:
S21, described the first mixture is warming up to preset temperature, constant temperature stirs, and obtains the second mixture; And
S22, in described the second mixture, add catalyzer, under described preset temperature, be forced into predetermined pressure, constant temperature crosslinking polymerization, obtains described DCL/Direct coal liquefaction modifying asphalt.
6. method of modifying according to claim 5, is characterized in that,
Described preset temperature is 120 ℃～350 ℃, and temperature rise rate is 1～10 ℃/min, and the time that described constant temperature stirs is 0.5～2 hour;
Described predetermined pressure is 0.01～10MPa, and the time of described crosslinking polymerization is 0.5～36 hour.
7. method of modifying according to claim 6, is characterized in that,
Described preset temperature is 160 ℃～200 ℃, and temperature rise rate is 3～6 ℃/min, and the time that described constant temperature stirs is 1～1.5 hour;
Described predetermined pressure is 1～5MPa, and the time of described crosslinking polymerization is 6～10 hours.
8. method of modifying according to claim 5, is characterized in that, described catalyzer is sulfuric acid; Take described DCL/Direct coal liquefaction hard pitch as benchmark, the add-on of described catalyzer is 1～50wt%, is preferably 10～20wt%.
9. method of modifying according to claim 8, is characterized in that, the mass percent concentration of described sulfuric acid is 10%～98%, is preferably 40～70%.
10. a modifying asphalt, is characterized in that, adopts the method for modifying of the DCL/Direct coal liquefaction hard pitch described in any one in claim 1 to 9 to be prepared from.
11. modifying asphalts according to claim 10, is characterized in that, the softening temperature of describedization modifying asphalt is 90～110 ℃, and β resin content value is 19～30wt.%, ash oontent value≤0.2wt%.
The application of modifying asphalt described in 12. 1 kinds of claims 10 or 11 in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint.
CN201410021555.4A 2014-01-16 2014-01-16 The method of modifying of modifying asphalt, DCL/Direct coal liquefaction hard pitch and application thereof CN103740396B (en)

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CN106753654A (en) * 2016-11-24 2017-05-31 神雾环保技术股份有限公司 Improve high-temperature agglomerant of the jet coal with quick lime mixing pellet strength and its application
CN108585859A (en) * 2018-04-25 2018-09-28 国家能源投资集团有限责任公司 Carbon/carbon composite and preparation method thereof
CN108707450A (en) * 2018-03-30 2018-10-26 国家能源投资集团有限责任公司 Binder pitch and preparation method
CN109694482A (en) * 2017-10-23 2019-04-30 神华集团有限责任公司 Modified emulsifying asphalt and preparation method thereof and mist sealing material
CN110437627A (en) * 2018-05-04 2019-11-12 中国石油化工股份有限公司 A kind of modifying agent mother liquor and road asphalt and preparation method thereof

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