CN103755926A - Condensed polynuclear polycyclic aromatic hydrocarbon resin and preparation method thereof - Google Patents

Condensed polynuclear polycyclic aromatic hydrocarbon resin and preparation method thereof Download PDF

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CN103755926A
CN103755926A CN201410021186.9A CN201410021186A CN103755926A CN 103755926 A CN103755926 A CN 103755926A CN 201410021186 A CN201410021186 A CN 201410021186A CN 103755926 A CN103755926 A CN 103755926A
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coal
resin
direct
dcl
liquefaction
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CN201410021186.9A
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CN103755926B (en
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李克健
周颖
章序文
程时富
常鸿雁
赵强
孙利
侯雨辰
舒成
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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 condensed polynuclear polycyclic aromatic hydrocarbon resin and a preparation method thereof. The preparation method comprises the following steps: (S1) deliming direct-coal-liquefaction residue, so as to obtain direct-coal-liquefaction high-temperature asphalt; (S2) adding a cross-linking agent and a catalyst into the direct-coal-liquefaction high-temperature asphalt to carry out cross-linking polymerization reaction, thereby obtaining the condensed polynuclear polycyclic aromatic hydrocarbon resin. According to the method, the direct-coal-liquefaction residue is utilized sufficiently and deeply, a new raw material and a new method which are used for preparing COPNA (Condensed Polynuclear Aromatics) resin are provided, and the prepared COPNA resin has the advantages of high beta-resin content and high resin-cured carbon residue ratio, can serve as a precursor for preparing a variety of carbon materials and has good application prospects in the fields of high-density and high-strength charcoal, charcoal/charcoal composite materials, brake braking wear-resistant materials, high heat-resistant fibers and the like. The process route is simple, the equipment is conventional, and reaction conditions are mild, thus a novel way for the high-added-value utilization of the direct-coal-liquefaction residue is provided.

Description

Condensation multinuclear polyaromatic hydrocarbon resin and preparation method thereof
Technical field
The present invention relates to coal directly-liquefied residue processing technology field, in particular to a kind of condensation multinuclear polyaromatic hydrocarbon resin and preparation method thereof.
Background technology
Condensation multinuclear polycyclic aromatic hydrocarbons (Condensed Polynuclear Aromatics, COPNA) resin claims again bituminous resins, is a kind of novel hot setting macromolecule resin take condensation polycyclic structure as main body.Copna resin mainly by as the aromatic compound such as phenanthrene, pyrene, naphthalene, anthracene and heavy oil residue, pitch, coal tar wet goods fragrance derivatives under the effect of bronsted acid catalyst, add thermal polycondensation with linking agent and form.Copna resin has excellent resistance to elevated temperatures, good formability and special electromagnetic property, has good avidity with Carbon Materials, becomes the hot subject of Carbon Materials research.Copna resin can be used as the presoma of the multiple Carbon Materials of preparation, is widely used in the fields such as carbon/carbon composite moulding, drag high-abrasive material and high heat resistance fiber simultaneously.
From people such as Otani, take pyrene and phenanthrene as monomer, terephthalyl alcohol is linking agent, and p-methyl benzenesulfonic acid is that catalyzer has synthesized B rank copna resin, has just obtained the extensive concern of Chinese scholars.Through development for many years, the synthesis material of copna resin is from initial aromatic compound, expand to gradually the relatively cheap arene derivatives of price, as coal tar, FCC slurry oil, heavy oil residue and petroleum pitch etc., prepared copna resin has better cohesiveness, dipping property and thermotolerance.
The method of preparing at present copna resin (pitch resinoid) is more, and at present disclosed as prepared the method for bituminous resins take heavy oil residue extract as raw material, gained resin is better than polyimide the high heat resistance of 800 ℃.The method of preparing condensation polycyclic polynuclear aromatic resins take petroleum residual oil or coal tar as raw material, prepared resin has good heat resistance, intensity high.The method of preparing polycyclic polynuclear aromatic resins with biomass material (bamboo tar), gained resin has good heat resistance, carbon yield high.With the method for the synthetic polycyclic polynuclear aromatic resins of catalytic cracking heavy oil, gained resin resistance toheat is good, and 10% thermal weight loss temperature is more than 380 ℃.But above-mentioned preparation method exists the problems such as complicated process of preparation.
DCL/Direct coal liquefaction be by solid coal under suitable temperature and pressure condition, directly catalytic hydrocracking, makes the technological process that its degraded and hydrocracking are liquid oil, broadly comprises direct liquefaction and the indirect liquefaction of coal.Coal directly-liquefied residue is inevitable a kind of by product in coal direct liquefaction process, account for 20~30% of liquefaction feed coal total amount, unconverted organism, inorganic mineral and additional deliquescence accelerant in coal in direct liquefaction process, formed the main body of coal liquefaction residue, it is the material of a kind of high charcoal, high ash and high-sulfur, its productive rate is generally 30% left and right of liquefaction raw coal total amount, and its calorific value is in 7000 kcal/kg left and right.Therefore efficient and rational resource utilization and the economy of approach to liquefaction process of utilizing of developing coal liquefaction residue is significant.
Summary of the invention
The present invention aims to provide a kind of condensation multinuclear polyaromatic hydrocarbon resin and preparation method thereof, and this condensation multinuclear polyaromatic hydrocarbon resin has the advantage such as carbon yield height after β-resin content and resin solidification.
In order to make full use of coal directly-liquefied residue and to achieve these goals, according to an aspect of the present invention, a kind of preparation method of condensation multinuclear polyaromatic hydrocarbon resin is provided, comprise the steps: S1, coal directly-liquefied residue is carried out to deliming processing, obtain DCL/Direct coal liquefaction hard pitch; And S2, in DCL/Direct coal liquefaction hard pitch, adding linking agent and catalyzer, cross-linking polymerization, obtains condensation multinuclear polyaromatic hydrocarbon resin.
Further, the softening temperature that coal is directly changed modifying asphalt is 115~160 ℃, and β resin content value is 5~15wt.%, ash oontent value≤0.5wt%.
Further, step S2 comprises: S21, in DCL/Direct coal liquefaction hard pitch, add linking agent, be warming up to preset temperature, obtain the first mixture; And S22, in the first mixture, adding catalyzer, constant temperature cross-linking polymerization, obtains condensation multinuclear polyaromatic hydrocarbon resin.
Further, preset temperature is 120 ℃~180 ℃, and temperature rise rate is 1~10 ℃/min, and the time of constant temperature cross-linking polymerization is 0.5~24 hour.
Further, preset temperature is 140 ℃~160 ℃, and temperature rise rate is 3~6 ℃/min, and the time of constant temperature cross-linking polymerization is 2~5 hours.
Further, linking agent is selected from one or more in terephthalyl alcohol, phenyl aldehyde and paraformaldehyde.
Further, take DCL/Direct coal liquefaction hard pitch as benchmark, the addition of linking agent is 5~50wt%, is preferably 10~20wt%.
Further, take DCL/Direct coal liquefaction hard pitch as benchmark, the addition of catalyzer is 3~30wt%, is preferably 4%~8wt%.
Further, catalyzer is bronsted acid catalyst.
Further, bronsted acid catalyst is p-methyl benzenesulfonic acid and/or sulfuric acid; The concentration of sulfuric acid is 10~98wt%.
Further, cross-linking polymerization carries out under inert atmosphere, and the flow of rare gas element is 100~500ml/min.
Further, the step of in step S1, coal directly-liquefied residue being carried out to deliming processing comprises: coal directly-liquefied residue is mixed with extraction solvent, and thermosol extraction, solid-liquid separation, obtains DCL/Direct coal liquefaction hard pitch.
Further, extraction solvent is selected from one or more in tetrahydrofuran (THF), quinoline, gelatin liquefaction light oil, middle distillate from coal liquefaction and coal tar.
According to a further aspect in the invention, provide a kind of condensation multinuclear polyaromatic hydrocarbon resin, this condensation multinuclear polyaromatic hydrocarbon resin is to adopt above-mentioned any method to be prepared from.
Apply technical scheme of the present invention, by the DCL/Direct coal liquefaction hard pitch that coal directly-liquefied residue is obtained after deliming is processed, mix with linking agent, and under the acting in conjunction of associated catalysts thermal treatment crosslinking polymerization, the copna resin material of preparation has the high advantage of carbon yield after β-resin content and resin solidification.The present invention has not only carried out the utilization of the abundant degree of depth to coal directly-liquefied residue, and a kind of new raw material and method are provided for preparing copna resin, the copna resin of preparing can be used as the presoma of the multiple carbon materials of preparation, has a good application prospect in fields such as high-density high-strength charcoal, carbon/carbon composite, drag high-abrasive material and high heat resistance fibers simultaneously.Operational path provided by the present invention is simple, equipment is conventional, reaction conditions is gentle, is suitable for batch production, for the high value added utilization of coal hydroliquefaction residue provides a new approach.
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 is that the coal directly-liquefied residue that utilizes of a kind of exemplary embodiments according to the present invention is produced the process flow diagram of copna resin; And
Fig. 2 is the thermogravimetric curve after the copna resin prepared in embodiment 1 solidifies.
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 main literature that at present relevant coal liquefied residue utilizes is more, but does not all relate to the technology of utilizing coal directly-liquefied residue to prepare condensation multinuclear polycyclic aromatic hydrocarbons (Condensed Polynuclear Aromatics is called for short COPNA) resin.For coal directly-liquefied residue is made full use of, and a kind of new raw material and method are provided for preparing copna resin, the invention provides a kind of preparation method of condensation multinuclear polyaromatic hydrocarbon resin, as shown in Figure 1, comprise the steps: S1, coal directly-liquefied residue is carried out to deliming processing, obtain DCL/Direct coal liquefaction hard pitch; And S2, in DCL/Direct coal liquefaction hard pitch, adding linking agent and catalyzer, cross-linking polymerization, obtains condensation multinuclear polyaromatic hydrocarbon resin.
By the DCL/Direct coal liquefaction hard pitch that coal directly-liquefied residue is obtained after deliming is processed, mix with linking agent, and under the acting in conjunction of associated catalysts thermal treatment crosslinking polymerization, the copna resin material of preparation has after the high and resin solidification of β resin content the advantages such as carbon yield height, β resin content is higher shows that the adhesive property of copna resin is better, has good thermotolerance and high-temperature oxidation resistance; The higher explanation copna resin of carbon yield and Carbon Materials have good affinity, can be used as good carbon-carbon composites binding agent.The present invention has not only carried out the utilization of the abundant degree of depth to coal directly-liquefied residue, and a kind of new raw material and method are provided for preparing copna resin, the copna resin of preparing can be used as the presoma of the multiple carbon materials of preparation, has a good application prospect in fields such as high-density high-strength charcoal, carbon/carbon composite, drag high-abrasive material and high heat resistance fibers simultaneously.Operational path provided by the present invention is simple, equipment is conventional, reaction conditions is gentle, is suitable for batch production, for the high value added utilization of coal hydroliquefaction residue provides a new approach.
Wherein deliming treatment step is a kind of relatively method of conventional ripening, a preferred embodiment of the invention, as shown in Figure 1, the step of in step S1, coal directly-liquefied residue being carried out to deliming processing comprises: coal directly-liquefied residue is mixed with extraction solvent, thermosol extraction, solid-liquid separation, obtains DCL/Direct coal liquefaction hard pitch.Wherein, extraction solvent is selected from one or more in tetrahydrofuran (THF), quinoline, gelatin liquefaction light oil, middle distillate from coal liquefaction and coal tar.
At present for coal directly-liquefied residue, by solvent extraction and solid-liquid separation, obtaining the extract of different components for the preparation of the material of high added value, is an important topic of the high-effective classifying integrated utilization of coal directly-liquefied residue.The present invention preferably but be not limited to above-mentioned deliming treatment process, can also adopt other treatment process of the prior art to process coal directly-liquefied residue.The product obtaining after coal directly-liquefied residue deliming is processed is a kind of gelatin liquefaction heavy organism of rich aromatic hydrocarbon, owing to having experienced the processing of high temperature, high pressure in liquefaction process, make the heavy organism of this class coal liquefaction on the Nomenclature Composition and Structure of Complexes, have the different of essence from the heavy organism producing under other condition, through suitable modulation, can become the desirable feedstock of preparing copna resin.
Preferably, coal directly-liquefied residue is mixed according to mass ratio 1:1~1:10 with extraction solvent, obtain mixed solution; And under inert atmosphere, with 10 ℃~30 ℃/h, mixed solution is warming up to 80 ℃~280 ℃, and under 0.1~1.0MPa, constant temperature stirs, and thermosol extraction obtains thermosol extraction mixture; The time of thermosol extraction is 5~60min, and the speed that constant temperature stirs is 50~300r/min.Coal directly-liquefied residue is mixed according to mass ratio 1:1~1:10 with extraction solvent, can guarantee effect of extracting and recovery rate of extraction solvent, if the mass ratio of coal directly-liquefied residue and extraction solvent is higher than 1:1, may there is the situation that extraction solvent can not dissolve coal directly-liquefied residue completely, cause extraction thorough not; If the mass ratio of coal directly-liquefied residue and extraction solvent lower than 1:10, can cause extraction solvent waste, increase the cost recovery of follow-up extraction solvent.Consider that high temperature mink cell focus and bitumen reaction entrained air easily catch fire, dangerous, the present invention passes into N2 and first gets rid of reactor as the air in stirring tank in reaction forward direction mixed solution, and reaction is carried out under the condition of anaerobic.
Particularly, solid-liquid separation adopts the mode of thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, centrifugation, gravity settling separation and fractionation by distillation to carry out, 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 reaches required effect.When adopting the mode of thermal air pressure filtration to carry out solid-liquid separation, the temperature of thermal air pressure filtration is 50 ℃~210 ℃, is preferably 150 ℃~200 ℃; The pressure of thermal air pressure filtration is 0.02~101.3KPa or 0.2MPa~1.0MPa.Adopt in said temperature and pressure range and carry out thermal air pressure filtration, can largely solid-liquid be separated.Except thermal air pressure filtration, when solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 ℃~250 ℃, and inlet pressure is 0.2MPa~0.6MPa.
After solid-liquid separation, in order rationally to reuse extraction solvent, to the extraction liquid after solid-liquid separation, adopt the mode of distillation or evaporation to carry out solvent recuperation processing, preferably adopt air distillation or underpressure distillation.By distilling or evaporating, can make extraction solvent return to thermosol extraction step and recycle.
Preferably, the softening temperature that the coal that coal directly-liquefied residue obtains after deliming is processed is directly changed hard pitch is 115~160 ℃, and β resin content value is 5~15wt.%, ash oontent value≤0.5wt%.By the DCL/Direct coal liquefaction hard pitch of high softening-point, low β resin content is carried out to heat cross-linking polyreaction, just can obtain having the copna resin that softening temperature is low, β resin content is high and quinoline insolubles content is low, the exploitation suitability of product is stronger, can be used as the presoma of the multiple carbon material of preparation, in fields such as high-density high-strength charcoal, carbon/carbon composite, drag high-abrasive material and high heat resistance fibers, have a good application prospect simultaneously.
After adding linking agent in DCL/Direct coal liquefaction hard pitch, mix, and carry out crosslinking polymerization under the condition existing at catalyzer, particularly, step S2 comprises: S21, in DCL/Direct coal liquefaction hard pitch, add linking agent, be warming up to preset temperature, obtain the first mixture; And S22, in the first mixture, adding catalyzer, constant temperature cross-linking polymerization, obtains condensation multinuclear polyaromatic hydrocarbon resin.
Preferably, preset temperature is 120 ℃~180 ℃, and temperature rise rate is 1~10 ℃/min, and the time of constant temperature cross-linking polymerization is 0.5~24 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 180 ℃, there will be a large amount of linking agents and catalyzer because of the high-temperature heating loss of gasifying, be unfavorable for that the polyreaction between DCL/Direct coal liquefaction hard pitch and linking agent is carried out smoothly.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.In addition, to the requirement of heating system power load, also can improve, also affect the work-ing life of reactor simultaneously.Therefore,, through considering, for cross-linking polymerization can be carried out smoothly, the present invention carries out cooperate optimization selection to preset temperature and temperature rise rate, and they are limited in above-mentioned scope, has improved production efficiency, has reduced severe reaction conditions degree.Further preferably, preset temperature is 140 ℃~160 ℃, and temperature rise rate is 3~6 ℃/min, and the time of constant temperature cross-linking polymerization is 2~5 hours.
When DCL/Direct coal liquefaction hard pitch is carried out to modification, different cross-linking systems is selected different linking agents and catalyzer, and preferably, the linking agent adopting in the present invention is selected from one or more in terephthalyl alcohol, phenyl aldehyde and paraformaldehyde.Preferably adopt terephthalyl alcohol as linking agent, mainly to consider that terephthalyl alcohol can promote the aromatic hydrocarbons molecule in DCL/Direct coal liquefaction hard pitch to be cross-linked to form the high molecular polymer with tridimensional network preferably, improves the β resin content in modified pitch with this.Take DCL/Direct coal liquefaction hard pitch as benchmark, the addition of linking agent is 5~50wt%.When the addition of linking agent is during lower than 5wt%, can reduce the degree of crosslinking polymerization between the aromatic hydrocarbons molecule in DCL/Direct coal liquefaction hard pitch; When the addition of linking agent is during higher than 50wt%, be unfavorable for improving the economy of producing.Preferably, the addition of linking agent is 10~20wt%.
The present invention, when DCL/Direct coal liquefaction hard pitch is carried out to cross-linking polymerization, need to add bronsted acid catalyst.Preferably, catalyzer is p-methyl benzenesulfonic acid and/or sulfuric acid, and the concentration of sulfuric acid is 10~98wt%.The present invention preferably adopts above-mentioned catalyzer, but is not limited to this, as long as contribute to the carrying out of cross-linking polymerization, the present invention adopts sulfuric acid to have high, the cheap advantage of catalytic efficiency as catalyzer.When adopting sulfuric acid as catalyzer, preferably adopt terephthalyl alcohol as linking agent.For a reaction system, the selection of linking agent and catalyzer is mutual, the present invention is when adopting terephthalyl alcohol as linking agent, preferably adopt sulfuric acid as catalyzer, mainly 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 polymerization degree of linking agent and DCL/Direct coal liquefaction hard pitch.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 (DCL/Direct coal liquefaction hard pitch), has improved crosslinking polymerization degree.
Take DCL/Direct coal liquefaction hard pitch as benchmark, the addition of catalyzer is 3~30wt%, is preferably 4~8wt%.Take DCL/Direct coal liquefaction hard pitch as benchmark, if the add-on of catalyzer, lower than 3wt%, can reduce catalytic efficiency, thereby reduce crosslinking polymerization degree; If the add-on of catalyzer higher than 30wt%, 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 concentration of preferably sulfuric acid is 10%~98wt%, more preferably 40~70wt%.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.
Consider that DCL/Direct coal liquefaction hard pitch class substance reaction entrained air easily catches fire, dangerous, the present invention passes into N2 and first gets rid of reactor as the air in stirring tank in reaction forward direction mixed solution, cross-linking polymerization is carried out in inert ambient environment, and the flow of rare gas element is 100~500ml/min.Wherein inert atmosphere is preferably nitrogen or argon gas.
According to a further aspect in the invention, provide a kind of condensation multinuclear polyaromatic hydrocarbon resin, this resin adopts above-mentioned any method to be prepared from.In condensation multinuclear polyaromatic hydrocarbon resin prepared by employing the method, β resin content is up to 58%, and wherein β-resin refers to that toluene insolubles deducts quinoline insolubles.β resin content is higher shows that the adhesive property of copna resin is better, and carbon yield is higher.The better explanation copna resin of adhesive property of copna resin has good thermotolerance and high-temperature oxidation resistance, and carbon yield high explanation copna resin and Carbon Materials have good affinity, can be used as good carbon-carbon composites binding agent.
Below in conjunction with specific embodiment, further illustrate beneficial effect of the present invention:
Embodiment 1
By weight of oil in coal directly-liquefied residue and liquefaction than mixing for 1:1, with 10 ℃/h, mixed solution is warming up to 280 ℃, under 1.0MPa, with 300r/min constant temperature, stir, thermosol extraction 60min, obtain thermosol extraction mixture, thermosol is extracted to mixture solid-liquid separation, obtain DCL/Direct coal liquefaction hard pitch.This coal directly-liquefied residue is through thermosol extraction, solid-liquid separation, underpressure distillation processing, and obtaining softening temperature and be 115 ℃, β resin content is the DCL/Direct coal liquefaction hard pitch that 5wt.%, ash content are 0.35wt.%.
Take the above-mentioned DCL/Direct coal liquefaction hard pitch of 50g and 5g linking agent terephthalyl alcohol (addition of linking agent accounts for 10wt%) is placed in reactor, with the speed of 2 ℃/min, be warming up to 140 ℃, adding concentration is the sulfuric acid (accounting for the 4wt.% of coal directly-liquefied residue) of 70wt%, pass into the nitrogen that flow is 200ml/min simultaneously, at 140 ℃, react 2h, stop heating, finish reaction, obtain copna resin.
Copna resin is cured and is processed 2 hours at 200 ℃, obtain C stage resin.Adopt thermogravimetry to carry out thermogravimetric analysis to C stage resin, obtain the thermogravimetric curve of C stage resin, as shown in Figure 2.As can be seen from Figure 2,, when being heated to 465 ℃, the weightlessness of copna resin is 5wt.%; While continuing to be heated to 525 ℃, the weightlessness of copna resin is 10wt.%; When being heated to more than 800 ℃, carbon yield is 76wt.%.Illustrate that the copna resin that adopts technical scheme of the present invention to prepare has good thermotolerance and has good affinity with Carbon Materials, can be used as good carbon-carbon composites binding agent.
Embodiment 2 to 7
The operation steps of embodiment 2 to 7 and comparative example 1 to 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.Embodiment and comparative example are all to operate under normal pressure.
Wherein, adopt respectively standard A STMD3461-83, GB/T212 to measure softening temperature, the ash oontent value of DCL/Direct coal liquefaction modifying asphalt, employing standard GB/T2293-1997 tests toluene insolubles, employing standard GB/T2292-1997 test quinoline insolubles content, the difference of toluene insolubles and quinoline insolubles content is β resin content.Specifically in Table 1.
Table 1
As can be seen from Table 1, adopt technical scheme of the present invention, under Parameter Conditions in embodiment 3 and embodiment 4, β resin content and the higher copna resin of carbon yield have been obtained, especially in embodiment 1 and embodiment 2, by parameters such as the additions to linking agent addition, inert gas flow, temperature rise rate, preset temperature, crosslinking time and catalyzer, be optimized, finally obtained β resin content and carbon yield with respect to better copna resin in embodiment 3 and embodiment 4.
In embodiment 5, adopted p-methyl benzenesulfonic acid as catalyzer, due to the acidity of p-methyl benzenesulfonic acid a little less than, hydrogen supply capacity is low, when the low terephthalyl alcohol of reactive behavior is under its acid catalysis, slack-off with the crosslinking polymerization speed of aromatic hydrocarbons (DCL/Direct coal liquefaction hard pitch), the β resin content in the copna resin that its effect obtains when adopting sulfuric acid in embodiment 1 and embodiment 2 is high.
Compare with 2 with embodiment 1, the addition of addition, inert gas flow, temperature rise rate, preset temperature, crosslinking time and catalyzer to linking agent in embodiment 6 and 7 etc. changes, and the size of these parameter values is larger on the β resin content impact in copna resin.In embodiment 6, the addition of linking agent is 3wt%, because the addition of linking agent is less, makes reactant crosslinking polymerization degree step-down, and the β resin content of the copna resin obtaining reduces, and causes cohesiveness and carbon yield also to decrease.And the addition of embodiment 7 is 57wt%, because the addition of linking agent is too much, not only wasted raw material, and unnecessary linking agent can remain in product, affect the quality uniformity of copna resin.
In comparative example 1 and 2, adopted respectively naphthalene and anthracene to prepare copna resin as raw material, preparation technology parameter is specifically in Table 1.From Data Comparison, can find out, compared with adopting feed coal direct liquefaction hard pitch of the present invention, in comparative example 1 and 2, in the copna resin of preparation, β resin content reduces, and carbon yield is low.Visible, adopt copna resin material prepared by technical scheme of the present invention to there is the advantage such as carbon yield height after the high and resin solidification of β resin content, for preparing copna resin, provide a kind of new raw material and method.
Embodiment 8
200kg coal directly-liquefied residue is mixed by weight 1:10 with oil (boiling range is 150~310 ℃) in liquefaction, with 30 ℃/h, mixed solution is warming up to 80 ℃, fill under N2 to 0.1MPa and stir with 75r/min constant temperature, thermosol extraction 45min, obtain thermosol extraction mixture, thermosol is extracted to mixture cyclonic separation, and obtaining softening temperature and be 160 ℃, β resin content is the DCL/Direct coal liquefaction hard pitch that 15wt.%, ash content are 0.01wt.%.
Take gelatin liquefaction hard pitch 50g and phenyl aldehyde 25g in stirring tank, under flow 100ml/min argon gas atmosphere, with the temperature rise rate of 10 ℃/min, be warming up to 180 ℃, adding concentration is the sulfuric acid 1.5g of 98wt%, then 180 ℃ of constant temperature crosslinking polymerizations 24 hours, stop heating, finish reaction, obtain copna resin.
Embodiment 9
200kg coal directly-liquefied residue is mixed by weight 1:4 with carbolineum (boiling range is 220~405 ℃), with 20 ℃/h, mixed solution is warming up to 200 ℃, fill under N2 to 0.15MPa and stir with 85r/min constant temperature, thermosol extraction 27min, obtain thermosol extraction mixture, thermosol is extracted to mixture thermal air pressure filtration and separate, obtaining softening temperature and be 130 ℃, β resin content is the DCL/Direct coal liquefaction hard pitch that 11.04wt.%, ash content are 0.5wt.%.
Take gelatin liquefaction hard pitch 50g and paraformaldehyde 2.5g in stirring tank, under nitrogen atmosphere, with the temperature rise rate of 5 ℃/min, be warming up to 140 ℃, add 1.5g p-methyl benzenesulfonic acid; Then at 140 ℃ of constant temperature cross-linking polymerization 0.5h, stop heating, finish reaction, obtain copna resin.
Embodiment 10
350kg coal directly-liquefied residue and 1000kg dead oil (boiling range is 200~260 ℃) are added in stirring tank, with 15 ℃/h, mixed solution is warming up to 180 ℃, fill under N2 to 1.0MPa and stir with 55r/min constant temperature, thermosol extraction 50min, obtain thermosol extraction mixture, thermosol is extracted to mixture thermal air pressure filtration and separate, obtaining softening temperature and be 120 ℃, β resin content is the DCL/Direct coal liquefaction hard pitch that 7.44wt.%, ash content are 0.2wt.%.
Take gelatin liquefaction hard pitch 50g and trioxymethylene 10g in stirring tank, under argon gas atmosphere, take the temperature rise rate of 5 ℃/min, be warming up to and after 120 ℃, add the sulfuric acid of 15g concentration as 10wt%, at 120 ℃, react 6h, stop heating, finish reaction, obtain copna resin.
Adopt respectively standard A STMD3461-83, GB/T212 to measure softening temperature, the ash oontent value of DCL/Direct coal liquefaction modifying asphalt, employing standard GB/T2293-1997 tests toluene insolubles, employing standard GB/T2292-1997 test quinoline insolubles content, toluene insolubles content and quinoline insolubles content difference are β resin content.Specifically in Table 2.
Table 2
Data from table 1 and table 2 can be found out, 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.Adopt technical scheme of the present invention to obtain excellent effect:
1) the present invention has set forth a kind of method of utilizing deliming coal directly-liquefied residue to prepare copna resin, the raw material adopting is that DCL/Direct coal liquefaction hard pitch is the resistates that DCL/Direct coal liquefaction process produces, this preparation technology is simple, not high to equipment requirements, parameter easily controls, easy and simple to handle, be easy to amplify.
2) copna resin that adopts method of the present invention to prepare has good high-temperature oxidation resistance, and has good affinity with Carbon Materials.
3) deep exploitation that the present invention is coal directly-liquefied residue has been opened up a new approach, has reduced the pollution of coal directly-liquefied residue to environment, has improved the economy of coal direct liquefaction.
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 (14)

1. a preparation method for condensation multinuclear polyaromatic hydrocarbon resin, is characterized in that, comprises the steps:
S1, coal directly-liquefied residue is carried out to deliming processing, obtain DCL/Direct coal liquefaction hard pitch; And
S2, in described DCL/Direct coal liquefaction hard pitch, add linking agent and catalyzer, cross-linking polymerization, obtains described condensation multinuclear polyaromatic hydrocarbon resin.
2. preparation method according to claim 1, is characterized in that, the softening temperature that described coal is directly changed modifying asphalt is 115~160 ℃, and β resin content value is 5~15wt.%, ash oontent value≤0.5wt%.
3. preparation method according to claim 1, is characterized in that, described step S2 comprises:
S21, in described DCL/Direct coal liquefaction hard pitch, add linking agent, be warming up to preset temperature, obtain the first mixture; And
S22, in described the first mixture, add catalyzer, constant temperature cross-linking polymerization, obtains described condensation multinuclear polyaromatic hydrocarbon resin.
4. preparation method according to claim 3, is characterized in that, described preset temperature is 120 ℃~180 ℃, and temperature rise rate is 1~10 ℃/min, and the time of described constant temperature cross-linking polymerization is 0.5~24 hour.
5. preparation method according to claim 4, is characterized in that, described preset temperature is 140 ℃~160 ℃, and temperature rise rate is 3~6 ℃/min, and the time of described constant temperature cross-linking polymerization is 2~5 hours.
6. preparation method according to claim 1, is characterized in that, described linking agent is selected from one or more in terephthalyl alcohol, phenyl aldehyde and paraformaldehyde.
7. preparation method according to claim 1, is characterized in that, take described DCL/Direct coal liquefaction hard pitch as benchmark, the addition of described linking agent is 5~50wt%, is preferably 10~20wt%.
8. preparation method according to claim 1, is characterized in that, take described DCL/Direct coal liquefaction hard pitch as benchmark, the addition of described catalyzer is 3~30wt%, is preferably 4%~8wt%.
9. preparation method according to claim 1, is characterized in that, described catalyzer is bronsted acid catalyst.
10. preparation method according to claim 9, is characterized in that, described bronsted acid catalyst is p-methyl benzenesulfonic acid and/or sulfuric acid; The concentration of described sulfuric acid is 10~98wt%.
11. preparation methods according to claim 1, is characterized in that, described cross-linking polymerization carries out under inert atmosphere, and the flow of rare gas element is 100~500ml/min.
12. preparation methods according to claim 1, it is characterized in that, the step of in described step S1, described coal directly-liquefied residue being carried out to deliming processing comprises: described coal directly-liquefied residue is mixed to thermosol extraction with extraction solvent, solid-liquid separation, obtains described DCL/Direct coal liquefaction hard pitch.
13. preparation methods according to claim 12, is characterized in that, described extraction solvent is selected from one or more in tetrahydrofuran (THF), quinoline, gelatin liquefaction light oil, middle distillate from coal liquefaction and coal tar.
14. 1 kinds of condensation multinuclear polyaromatic hydrocarbon resins, is characterized in that, adopt any one method in claim 1 to 13 to be prepared from.
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