CN103740396B - The method of modifying of modifying asphalt, DCL/Direct coal liquefaction hard pitch and application thereof - Google Patents

The method of modifying of modifying asphalt, DCL/Direct coal liquefaction hard pitch and application thereof Download PDF

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CN103740396B
CN103740396B CN201410021555.4A CN201410021555A CN103740396B CN 103740396 B CN103740396 B CN 103740396B CN 201410021555 A CN201410021555 A CN 201410021555A CN 103740396 B CN103740396 B CN 103740396B
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modifying
dcl
coal liquefaction
direct coal
hard pitch
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CN201410021555.4A
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CN103740396A (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 a kind of modifying asphalt, the method for modifying of DCL/Direct coal liquefaction hard pitch and application thereof.This method of modifying comprises the following steps: S1, in DCL/Direct coal liquefaction hard pitch, add mink cell focus and linking agent, is uniformly mixed, obtains the first mixture; And S2, in the first mixture, adding catalyzer, heating and pressurizing is polymerized, and obtains DCL/Direct coal liquefaction modifying asphalt.By heating the gelatin liquefaction hard pitch of high softening-point, low β resin content, pressure polymerization reaction, obtain and there 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 comparatively strong, is the novel material of a kind of high-performance, high added value.This method of modifying operational path is simple, mild condition, equipment are conventional, be easy to the advantages such as amplification production, for the DCL/Direct coal liquefaction hard pitch modification of high softening-point, low β resin content, especially the deep exploitation of coal directly-liquefied residue provides a kind of new approach.

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 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 be generally by coal in advance powder to the granularity of below 0.15mm, then be 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.But aforesaid method all with the bitumen in coal liquefaction residue for raw material, do not relate to the modification of hard pitch and pitch in 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 modifier methods are all the principles adopting softening temperature and β resin content and carbon yield to become mutually to increase progressively relation, namely increase β resin content and carbon yield by improving pitch softening point.Can the hard pitch that obtains through solvent extraction of coal directly-liquefied residue, there is a kind of situation of runing counter to it: softening temperature is higher, β resin content is too low, and it is too wide in range that its reason is exactly the distribution of DCL/Direct coal liquefaction hard pitch molecular-weight average.So, while being difficult to accomplish DCL/Direct coal liquefaction hard pitch softening temperature to fall only 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 DEG C), low β resin content (5 ~ 15wt%) and is rarely had report.
Summary of the invention
The present invention aims to provide a kind of modifying asphalt, the method for modifying of DCL/Direct coal liquefaction hard pitch and application thereof, and the method obtains the modifying asphalt of low softening point and high β resin content, achieves 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, 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 is polymerized, and obtains DCL/Direct coal liquefaction modifying asphalt.
Further, mink cell focus comprise carbolineum, underpressure distillation residual oil, liquefaction heavy oil and catalytically cracked oil in one or more, linking agent is terephthalyl alcohol.
Further, with DCL/Direct coal liquefaction hard pitch for 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 an inert atmosphere.
Further, step S2 comprises: S21, the first mixture is warming up to preset temperature, and constant temperature stirs, and obtains the second mixture; And S22, in the second mixture, add catalyzer, be forced into predetermined pressure at a predetermined temperature, constant temperature crosslinking polymerization, obtain DCL/Direct coal liquefaction modifying asphalt.
Further, preset temperature is 120 DEG C ~ 350 DEG C, and temperature rise rate is 1 ~ 10 DEG C/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 DEG C ~ 200 DEG C, and temperature rise rate is 3 ~ 6 DEG C/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; With DCL/Direct coal liquefaction hard pitch for 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 any one DCL/Direct coal liquefaction hard pitch above-mentioned.
Further, the softening temperature of DCL/Direct coal liquefaction modifying asphalt is 90 ~ 110 DEG C, and β resin content value is 19 ~ 30wt%, ash oontent value≤0.2wt%.
According to another aspect of the invention, the application of any one DCL/Direct coal liquefaction modifying asphalt above-mentioned in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint is provided.
Apply technical scheme of the present invention, by heating the gelatin liquefaction hard pitch of high softening-point, low β resin content, pressure polymerization reaction, obtain and there 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 conventional, is easy to amplify the advantages such as production, for the DCL/Direct coal liquefaction hard pitch modification of high softening-point (115 ~ 160 DEG C), low β resin content (5 ~ 15wt%), especially for the deep exploitation of 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 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 DCL/Direct coal liquefaction hard pitch " mentioned in the present invention refers to the one low ash content heavy dope that coal directly-liquefied residue obtains through solvent extraction, solid-liquid separation, underpressure distillation, and the Measures compare of preparation DCL/Direct coal liquefaction hard pitch is ripe.
In order to the DCL/Direct coal liquefaction hard pitch modification better with high softening-point (115 ~ 160 DEG C), 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 is polymerized, and obtains DCL/Direct coal liquefaction modifying asphalt.
By heating the gelatin liquefaction hard pitch of high softening-point, low β resin content, pressure polymerization reaction, obtain and there 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 conventional, is easy to amplify the advantages such as production, for the DCL/Direct coal liquefaction hard pitch modification of high softening-point (115 ~ 160 DEG C), low β resin content (5 ~ 15wt%), especially for the deep exploitation of 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.
In order to reduce DCL/Direct coal liquefaction hard pitch softening temperature, the present invention adopts to be needed to add mink cell focus in gelatin liquefaction hard pitch, its effect of the mink cell focus added is dissolved DCL/Direct coal liquefaction hard pitch as solvent, and then the slurries forming mobility, have good stability with DCL/Direct coal liquefaction hard pitch, and it is made fully to contact 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.Wherein liquefy heavy oil to be boiling point be the oil of more than 260 DEG C; Linking agent is terephthalyl alcohol.Different cross-linking systems should select different linking agents and catalyzer, the present invention selects terephthalyl alcohol to be linking agent, can promote that the aromatic hydrocarbons molecule in DCL/Direct coal liquefaction hard pitch and mink cell focus is cross-linked to form the high molecular polymer with tridimensional network, improve the β resin content in modified pitch with this.
A preferred embodiment of the invention, with DCL/Direct coal liquefaction hard pitch for benchmark, the addition of mink cell focus is 5 ~ 100wt%, and the addition of linking agent is 1 ~ 50wt%.When the addition of mink cell focus is lower than 5wt%, it reduces effective solvability of gelatin liquefaction hard pitch, when the addition of mink cell focus is higher than 100wt%, is unfavorable for improving production economy; When the addition of linking agent is lower than 1wt%, the degree of crosslinking polymerization between the aromatic hydrocarbons molecule in DCL/Direct coal liquefaction hard pitch and mink cell focus can be reduced; When the addition of linking agent is 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, and constant temperature stirs, and obtains the second mixture; And S22, in the second mixture, add catalyzer, be forced into predetermined pressure at a predetermined temperature, constant temperature crosslinking polymerization, obtain DCL/Direct coal liquefaction modifying asphalt.Existence in order to avoid gases such as oxygen brings the insecurity of pyroreaction, and preferably, step S2 carries out under an inert atmosphere, the inert atmosphere preferred nitrogen in the present invention or argon gas.
A preferred embodiment of the invention, preset temperature is 120 ~ 350 DEG C, and temperature rise rate is 1 ~ 10 DEG C/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 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 pitch and mink cell focus cannot produce polyreaction with linking agent, 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 enhancing productivity; 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; If predetermined pressure is lower than 0.01MPa, then can easily occur that linking agent at high temperature gasifies, cause pitch and mink cell focus crosslinking reaction can not occur, be unfavorable for the polymerization of reacting; If predetermined pressure is higher than 10MPa, then there will be reaction pressure too high, cause the increase of reactor manufacturing cost and produce danger coefficient too high, be unfavorable for the carrying out produced.Therefore, through considering, the present invention carries out cooperate optimization selection to preset temperature, temperature rise rate, churning time and predetermined pressure, 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 3 ~ 6 DEG C/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 DEG C, and temperature rise rate is 5 DEG C/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 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 (pitch and mink cell focus) there occurs electrophilic substitution reaction, improves crosslinking polymerization degree.
With DCL/Direct coal liquefaction hard pitch for 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 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.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 further aspect in the invention, provide a kind of DCL/Direct coal liquefaction modifying asphalt, this DCL/Direct coal liquefaction modifying asphalt is adopt any one the method for modifying of DCL/Direct coal liquefaction hard pitch above-mentioned to be prepared from.Preferably, the softening temperature of DCL/Direct coal liquefaction modifying asphalt is 90 ~ 110 DEG C, and β resin content value is 19 ~ 30wt%, ash oontent value≤0.2wt%.
According to another aspect of the invention, the application of any one DCL/Direct coal liquefaction modifying asphalt above-mentioned in high-temperature agglomerant, tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, waterproof paint is provided.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1
Get coal directly-liquefied residue through thermosol extraction, solid-liquid separation, underpressure distillation process, obtain DCL/Direct coal liquefaction hard pitch, its ash content is 0.45wt%, β resin content is 7wt%, and softening temperature is 130 DEG C.
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.Wherein added carbolineum is the 70wt% of DCL/Direct coal liquefaction hard pitch, and terephthalyl alcohol is the 10wt% of DCL/Direct coal liquefaction hard pitch.Under first mixture being placed in nitrogen atmosphere protection, with the heat-up rate of 5 DEG C/min, be warming up to 160 DEG C, constant temperature stirs 1 hour, obtains the second mixture.
2) at 160 DEG C, in the second mixture, then add the sulfuric acid (concentration is 70wt%) accounting for DCL/Direct coal liquefaction hard pitch 10wt%, be forced into 1Mpa constant temperature cross-linking polymerization 10 hours subsequently, stop heating, take out, obtain product DCL/Direct coal liquefaction modifying asphalt.
Embodiment 2 to 7 and comparative example 1 identical with embodiment 1 with the operation steps of 2, difference is specifically in table 1.DCL/Direct coal liquefaction hard pitch wherein 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 obtaining, and namely β resin content is the difference of toluene insolubles and quinoline insolubles.
Table 1
Data as can be seen from table 1, the modified technique of normal pressure or atmospheric low-temperature is adopted to compare with comparative example 1 and comparative example 2, adopt the intermediate product DCL/Direct coal liquefaction hard pitch of the mode of heating and pressurizing to coal directly-liquefied residue to carry out modification in embodiments of the invention 1 to 7, obtain that softening temperature is 90 ~ 110 DEG C, β resin content value is 19 ~ 30wt% and the DCL/Direct coal liquefaction modifying asphalt of ash oontent value≤0.2wt%.Especially in embodiment 1 and embodiment 2, modified technique is optimized, namely the weight of added mink cell focus, linking agent and catalyzer and Heating temperature, pressure are in optimized selection, obtain the DCL/Direct coal liquefaction modifying asphalt that softening temperature is lower, β resin content is higher.Visible, the exploitation suitability of the modified bitumen product adopting method of modifying of the present invention to prepare is comparatively strong, and 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.
Below in conjunction with embodiment 8 to 10 further illustrate adopt modified technique of the present invention can to having different softening point, the DCL/Direct coal liquefaction hard pitch of β resin content value carries out modification preferably.
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%, β resin content is 5wt%, and softening temperature is 115 DEG C.
1) above-mentioned for 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 DEG C/min, be warming up to 200 DEG C and carry out constant temperature stirring, obtain the second mixture.
2) at 200 DEG C, in the second mixture, add the sulfuric acid 2Kg that concentration is 98wt%, be forced into 10Mpa subsequently and react 36h, stop heating, take out and obtain DCL/Direct coal liquefaction modifying asphalt.The softening temperature recording DCL/Direct coal liquefaction modifying asphalt is 117 DEG C, 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%, β resin content is 15wt%, and softening temperature is 160 DEG C.
1) above-mentioned for 200Kg gelatin liquefaction hard pitch is added in stirring tank together with 200Kg vacuum residuum, 100Kg terephthalyl alcohol, obtains the first mixture.Under first mixture being placed in nitrogen atmosphere protection, with the heat-up rate of 10 DEG C/min, being warming up to 350 DEG C and carrying out constant temperature stirring, obtain the second mixture.
2) then in the second mixture, add the sulfuric acid 200Kg that concentration is 40wt%, be forced into 5Mpa subsequently and react 10h, stop heating, take out gained gelatin liquefaction modifying asphalt.The softening temperature recording product is 112 DEG C, 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 DEG C.
1) above-mentioned for 200Kg gelatin liquefaction hard pitch and 150Kg being liquefied together with heavy oil, 50Kg terephthalyl alcohol is added in stirring tank, obtains the first mixture.Under argon gas atmosphere protection, by the first mixture with the heat-up rate of 5 DEG C/min, be warming up to 180 DEG C and carry out constant temperature stirring, obtain the second mixture.
2) then in the second mixture, add the sulfuric acid 60Kg that concentration is 10wt%, be forced into 2Mpa subsequently and react 0.5h, stop heating, take out gained gelatin liquefaction modifying asphalt.The softening temperature recording product is 90 DEG C, β resin content 19wt%, and ash value is 0.31wt%.
To sum up, the present invention achieves following beneficial effect: by heating the gelatin liquefaction hard pitch of high softening-point, low β resin content, pressure polymerization reaction, obtain and there 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 conventional, is easy to amplify the advantages such as production, for the DCL/Direct coal liquefaction hard pitch modification of high softening-point (115 ~ 160 DEG C), low β resin content (5 ~ 15wt%), especially for the deep exploitation of 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 (14)

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 first mixture, add catalyzer, heating and pressurizing is polymerized, and obtains DCL/Direct coal liquefaction modifying asphalt; Wherein, described step S2 comprises:
S21, described first mixture is warming up to preset temperature, constant temperature stirs, and obtains the second mixture; And
S22, in described second mixture, add catalyzer, under described preset temperature, be forced into predetermined pressure, constant temperature crosslinking polymerization, obtain described DCL/Direct coal liquefaction modifying asphalt, described catalyzer is sulfuric acid.
2. method of modifying according to claim 1, is characterized in that, described mink cell focus comprise carbolineum, underpressure distillation residual oil, liquefaction heavy oil and catalytically cracked oil in one or more, described linking agent is terephthalyl alcohol.
3. method of modifying according to claim 1, is characterized in that, with described DCL/Direct coal liquefaction hard pitch for benchmark, the addition of described mink cell focus is 5 ~ 100wt%, and the addition of described linking agent is 1 ~ 50wt%.
4. method of modifying according to claim 3, is characterized in that, with described DCL/Direct coal liquefaction hard pitch for benchmark, the addition of described mink cell focus is 70 ~ 80wt%, and the addition of described linking agent is 10 ~ 20wt%.
5. method of modifying according to claim 1, is characterized in that, described step S2 carries out under an inert atmosphere.
6. method of modifying according to claim 1, is characterized in that,
Described preset temperature is 120 DEG C ~ 350 DEG C, and temperature rise rate is 1 ~ 10 DEG C/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 DEG C ~ 200 DEG C, and temperature rise rate is 3 ~ 6 DEG C/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 1, is characterized in that, with described DCL/Direct coal liquefaction hard pitch for benchmark, the add-on of described catalyzer is 1 ~ 50wt%.
9. method of modifying according to claim 8, is characterized in that, with described DCL/Direct coal liquefaction hard pitch for benchmark, the add-on of described catalyzer is 10 ~ 20wt%.
10. method of modifying according to claim 1, is characterized in that, the mass percent concentration of described sulfuric acid is 10% ~ 98%.
11. method of modifying according to claim 10, is characterized in that, the mass percent concentration of described sulfuric acid is 40 ~ 70%.
12. 1 kinds of modifying asphalts, is characterized in that, adopt the method for modifying of the DCL/Direct coal liquefaction hard pitch according to any one of claim 1 to 11 to be prepared from.
13. modifying asphalts according to claim 12, is characterized in that, the softening temperature of describedization modifying asphalt is 90 ~ 110 DEG C, and β resin content value is 19 ~ 30wt%, ash oontent value≤0.2wt%.
The application of modifying asphalt described in 14. 1 kinds of claims 12 or 13 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
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
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
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
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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