CN103756707B - Modified asphalt and preparation method thereof - Google Patents
Modified asphalt and preparation method thereof Download PDFInfo
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- CN103756707B CN103756707B CN201410021221.7A CN201410021221A CN103756707B CN 103756707 B CN103756707 B CN 103756707B CN 201410021221 A CN201410021221 A CN 201410021221A CN 103756707 B CN103756707 B CN 103756707B
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Abstract
The invention discloses modified asphalt and a preparation method thereof. The method comprises the following steps: S1, mixing high-temperature asphalt and heavy oil to form a first mixture, wherein the softening point of the high-temperature asphalt is 115-160 DEG C, the beta resin content is 5-15 wt%, and the ash content is no more than 0.5 wt%; S2, mixing the first mixture, crosslinking agent and a catalyst to form a second mixture; and S3, performing crosslinking polymerization reaction on the second mixture at 80-120 DEG C to obtain the modified asphalt. According to the invention, the high-temperature asphalt used as a raw material and the heavy oil are thoroughly mixed and molten, are thoroughly mixed with the crosslinking agent and the catalyst, and are subjected to crosslinking polymerization reaction at a low temperature, thus preparing the modified asphalt which has low softening point and increased beta resin content and can meet the requirements of the market for medium-and-high-temperature modified asphalt; and the modified asphalt has favorable binding property and can be used as medium-and-high-temperature binding agent asphalt and impregnated asphalt required in the market.
Description
Technical field
The present invention relates to pitch deep process technology field, in particular to a kind of modified pitch and preparation method thereof.
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.
DCL/Direct coal liquefaction is by coal by high temperature, high pressure, and under catalyst action, hydrogenation directly changes into the clean coal technology of a kind of advanced person of clean transport fuel (petroleum naphtha, diesel oil etc.) or industrial chemicals.The process of DCL/Direct coal liquefaction is generally granularity coal being crushed in advance below 0.15mm, then is made into coal slurry with solvent, and under certain temperature (about 450 DEG C) and high pressure hydrogenation, make the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process except obtaining the liquiefied product of needs, go back some hydrocarbon molecules of by-product, CO
xdeng the liquefaction residue (also known as coal liquefaction residue) that gas, process water and solid-liquid separation process produce.Liquefied residue generally accounts for about the 30wt% 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 the 50wt% of level of residue, and unconverted coal accounts for the 30wt% of level of residue, and ash content accounts for about 20wt%.Therefore, the bitumen and mink cell focus that account for 50wt% in liquefied residue are separated and carry out comprehensive development and utilization, it is feasible for therefrom extracting or prepare more value product.
Now the traditional methods such as boiler oil, coking liquefaction, gasification hydrogen-producing are mainly used in the technology that utilizes of coal liquefaction residue.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 semicoke and coke also have a large amount of ash contents and sulphur to have influence on its purposes.The method of liquefied residue being carried out gasification hydrogen-producing is a kind of effective extensive approach utilized, but is embodied the high value added utilization potentiality of the bitumen in residue and mink cell focus.
Up to now, have both at home and abroad and much changed Quality Research report about bitumen, as adopted oxidation thermal polymerization method, heated polymerizable method, pressurization thermal polymerization method.Oxidation thermal polymerization method is that asphalt stock intermittent type is added thermal still, then passes into pressurized air and carry out heated oxide, and temperature in the kettle generally maintains 340 ~ 360 DEG C, till pitch softening point can be brought up to required point by the air capacity passed into; The domestic coke-oven plant had adopts heated polymerizable method, and mid-temperature pitch softening temperature can be brought up to 120 DEG C, toluene insolubles value brings up to about 30wt%; Osaka, Japan Gas Company adopts pressurization thermal polymerization method, and find that pitch β proportion of resin present normal heating polymerization wants high, waterside town Iron And Steel Company of China coke-oven plant's this method has generated qualified modified pitch.
Although these asphalt modifier methods are adopted by domestic and international manufacturer, and all produce middle high-temperaturebitumen always, such as, softening temperature is at 75 ~ 120 DEG C, and β resin content is at 16 ~ 35wt%, and ash content is lower than high-temperaturebitumen in 0.5wt%.But these asphalt modifier methods are all for softening temperature lower (75 ~ 95 DEG C), β resin content is at the petroleum pitch of about 20wt% or coal tar system pitch, and mainly softening temperature is brought up to the standard of above-mentioned middle high-temperaturebitumen, and relevant high softening-point (115 ~ 160 DEG C), the hard pitch of low β resin content (5 ~ 15wt%) changes Quality Research does not have report so far, because there is the too poor inferior position of cohesiveness in the too high hard pitch of this softening temperature, product development suitability is not strong, be not suitable as tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, the raw material of waterproof paint etc., therefore need to continue to be carried out modification to meet needed for market.
The technique preparing hard pitch in prior art has a lot, the application is in order to obtain the hard pitch with These characteristics, preferred above-mentioned steps S1 also comprises the preparation process of hard pitch, and this preparation process comprises: mixed with extraction agent by coal directly-liquefied residue, forms solidliquid mixture; Above-mentioned solidliquid mixture is carried out successively extract, solid-liquid separation is extracted liquid and extract remainder; Above-mentioned extraction liquid is carried out underpressure distillation and obtains hard pitch.Above-mentionedly prepare extraction solvent used in the process of hard pitch and be separated with hard pitch in vacuum distillation process, and then can be returned this prepare in the process of hard pitch and reuse, save the cost preparing hard pitch.
Above-mentioned steps S1 of the present invention, S2 and S3 preferably carry out under the protection of rare gas element or nitrogen, with isolated air, reaction is carried out in the absence of oxygen, avoids the existence of the gases such as oxygen to bring the insecurity of pyroreaction.
In the another kind of typical embodiment of the present invention, additionally provide a kind of modified pitch prepared by aforesaid method, this modified pitch has lower softening temperature and higher β resin content.Because its softening temperature can reach the softening point temperature of hard pitch on market, and β resin content improves greatly, and this modified pitch adhesive property is good, can be used as the middle high-temperature agglomerant pitch needed for market and impregnating pitch.
In another preferred embodiment of the present invention, the softening temperature of the modified pitch prepared by aforesaid method is at 81 ~ 113 DEG C, and β resin content is 18 ~ 28wt%, ash oontent≤0.42wt%.The adhesive property of the modified pitch that this softening temperature is low, β resin content is high is better, can obtain better effect when applying in high-temperature agglomerant pitch and impregnating pitch.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment.
Summary of the invention
The present invention aims to provide a kind of modified pitch and preparation method thereof, take hard pitch as raw material, and can improve the performance of its pitch.
To achieve these goals, according to an aspect of the present invention, provide a kind of preparation method of modified pitch, comprise the following steps: S1, mixed with mink cell focus by hard pitch, obtain the first mixture, the softening temperature of hard pitch is at 115 ~ 160 DEG C, β resin content is 5 ~ 15wt%, ash oontent≤0.5wt%; S2, is undertaken being mixed to get the second mixture by the first mixture and linking agent, catalyzer; And S3, make the second mixture carry out cross-linking polymerization at 80 ~ 120 DEG C, obtain modified pitch.
Further, above-mentioned steps S1 comprises: step S11, hard pitch and mink cell focus is warming up to 120 ~ 260 DEG C under agitation and obtains the first pre-composition, and the speed preferably stirred is 100 ~ 300r/min, and the speed preferably heated up is 1 ~ 10 DEG C/min; Step S12, obtains the first mixture after Keep agitation first pre-composition 15 ~ 120min.
Further, above-mentioned steps S2 comprises: step S21, at 80 ~ 120 DEG C, the first mixture and linking agent is stirred 30 ~ 180min under the stirring velocity of 100 ~ 300r/min, obtains the second pre-composition; Step S22, is undertaken being mixed to form the second mixture by the second pre-composition and catalyzer.
Further, above-mentioned catalyzer is sulfuric acid, and the concentration of preferably sulfuric acid is 10 ~ 98wt%, further preferred 30 ~ 55wt%, and linking agent is terephthalyl alcohol.
Further, above-mentioned catalyzer is p-methyl benzenesulfonic acid, and linking agent is selected from one or more in trioxymethylene, paraformaldehyde and phenyl aldehyde.
Further, the consumption of above-mentioned catalyzer is 1 ~ 50wt% of described hard pitch, preferably 10 ~ 30wt%, and the consumption of described linking agent is 1 ~ 50wt% of described hard pitch, preferably 10 ~ 30wt%.
Further, above-mentioned mink cell focus is the mink cell focus that initial boiling point is greater than 260 DEG C.
Further, above-mentioned mink cell focus is selected from one or more in carbolineum, vacuum residuum, liquefaction heavy oil, catalytically cracked oil.
Further, the consumption of above-mentioned mink cell focus is 5 ~ 100wt% of described hard pitch, preferably 40 ~ 70wt%.
Further, the pulverizing pitch of above-mentioned hard pitch to be particle diameter be 0.2 ~ 5mm.
Further, above-mentioned preparation method also comprises the preparation process of described hard pitch, and this preparation process comprises: mixed with extraction agent by coal directly-liquefied residue, forms solidliquid mixture; Solidliquid mixture is carried out successively extract, solid-liquid separation is extracted liquid and extract remainder; Extraction liquid is carried out underpressure distillation and obtains hard pitch.
Further, above-mentioned steps S1, S2 and S3 carry out in inert gas atmosphere or nitrogen atmosphere.
Another aspect of the present invention also provides a kind of modified pitch obtained by aforesaid method, and its softening temperature is at 81 ~ 113 DEG C, and β resin content is 18 ~ 28wt%, ash oontent≤0.42wt%.
Apply a kind of modified pitch of technical scheme of the present invention and preparation method thereof, by taking hard pitch as raw material, form the first mixture of the good melting of mobility after carry out dissolving also fully melting using mink cell focus as solvent after, again the first mixture and linking agent and catalyzer are fully mixed rear formation second mixture, then the second mixture is made to carry out cross-linking polymerization at a lower temperature, the softening temperature of hard pitch can be made to be reduced to meet the requirement of the middle high-temperaturebitumen that background technology is mentioned, β resin content also brings up to the requirement that can meet above-mentioned middle high-temperaturebitumen, this softening temperature is lower, the modified pitch that β resin content improves, adhesive property is good, can be used as the middle high-temperature agglomerant pitch needed for market and impregnating pitch, thus provide new raw material for the making of modified pitch of prior art, and for hard pitch have found new application approach.
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 the preparation flow schematic diagram of the modified pitch according to 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 invention provides a kind of preparation method of modified pitch, the method comprises the following steps: S1, is mixed by hard pitch with mink cell focus, obtain the first mixture, the softening temperature of this hard pitch is at 115 ~ 160 DEG C, and β resin content is 5 ~ 15wt%, ash oontent≤0.5wt%; S2, is undertaken being mixed to get the second mixture by the first mixture and linking agent, catalyzer; And S3, make the second mixture carry out cross-linking polymerization at 80 ~ 120 DEG C, obtain modified pitch.
Described in background technology of the present invention, the softening temperature of the hard pitch produced from coal directly-liquefied residue is 115 ~ 160 DEG C, β resin content is 5 ~ 15wt%, ash oontent≤0.5wt% is high relative to the softening temperature 75 ~ 95 DEG C of the raw material preparing modified pitch in prior art, about 20wt% is low for β resin content.Because the softening temperature of above-mentioned hard pitch is higher, β resin content is lower, cause its adhesive property difference and suitability is not strong.
The present invention with above-mentioned hard pitch for raw material, form the first mixture of the good melting of mobility after carry out dissolving also fully melting using mink cell focus as solvent after, again the first mixture and linking agent and catalyzer are fully mixed rear formation second mixture, then the second mixture is made to carry out cross-linking polymerization at a lower temperature, the softening temperature of hard pitch can be made to be reduced to meet the requirement of the middle high-temperaturebitumen that background technology is mentioned, β resin content also brings up to the requirement that can meet above-mentioned middle high-temperaturebitumen, this softening temperature is lower, the modified pitch that β resin content improves, adhesive property is good, can be used as the middle high-temperature agglomerant pitch needed for market and impregnating pitch, thus provide new raw material for the making of modified pitch of prior art, and for hard pitch have found new application approach.And, during with above-mentioned hard pitch for raw material making modified pitch, on the basis controlling melting and polymeric reaction temperature, adopt existing conventional flowsheet, making method is simple, and those skilled in the art can improve making method according to the performance requriements of modified pitch.
Those skilled in the art are noted that, in the mixture of above-mentioned embodiment, each material mixing is more even, the effect of crosslinking polymerization is by better, in order to make the thorough melting of hard pitch and obtain the molten mixture that mixes, those skilled in the art can on the basis controlling melt temperature and heat-up rate, and suitable adjustment stirring velocity and churning time can obtain the molten mixture mixed.In a kind of preferred embodiment of the present invention, above-mentioned steps S1 also comprises: step S11, above-mentioned hard pitch and mink cell focus are warming up to 120 ~ 260 DEG C under agitation and obtain the first pre-composition, the speed of preferred above-mentioned stirring is 100 ~ 300r/min, and the speed of preferred above-mentioned intensification is 1 ~ 10 DEG C/min; Step S12, obtains above-mentioned first mixture after the above-mentioned first pre-composition 15 ~ 120min of Keep agitation.
In above-mentioned steps S11 of the present invention melt temperature be set to 120 ~ 260 DEG C, hard pitch can be carried out melting and obtain the good molten asphalt of mobility, when melt temperature is lower than 120 DEG C, can not by complete for hard pitch melting; During higher than 260 DEG C, easily make mink cell focus solvent become gaseous state and vapor away, reactant can not be made to keep good liquid phase state and affect follow-up cross-linking polymerization.Select the heat-up rate of 1 ~ 10 DEG C/min both can make the abundant melted by heating of hard pitch, be unlikely to again the too fast linking agent that not only causes of heat-up rate to volatilize, also there will be reactant is heated uneven, causes the reactant coking of reactor wall place or gasification, is unfavorable for homogeneous reaction.Stirring above-mentioned first pre-composition 15 ~ 120min with the stirring velocity of 100 ~ 300r/min, is also to obtain thorough melting and have the hard pitch of better mobility and keep good cross-linking catalyst ability simultaneously.
Under guidance of the present invention, those skilled in the art just can obtain the modified pitch that softening temperature is lower, β resin content is higher by the temperature suitably adjusting crosslinking polymerization.In a kind of preferred embodiment of the present invention, above-mentioned steps S2 comprises: step S21, at 80 ~ 120 DEG C, above-mentioned first mixture and above-mentioned linking agent is stirred 30 ~ 180min under the stirring velocity of 100 ~ 300r/min, obtains the second pre-composition; Step S22, is undertaken being mixed to form above-mentioned second mixture by above-mentioned second pre-composition and above-mentioned catalyzer.
The present invention preferably carries out crosslinking polymerization at 80 ~ 120 DEG C, makes on softening temperature modifying process simple and convenient, and the time that need not control reaction just can obtain the modified pitch of better performances.The present invention preferably mixes with catalyzer after stirring 30 ~ 180min under the stirring velocity of 100 ~ 300r/min again, not only makes the full cross-linked formation reticulated structure of the aromatic hydrocarbons macromole in the pitch of melting, increases the β resin content in modified pitch; And the volatile quantity that can reduce linking agent and catalyzer is to keep higher cross-linking catalyst efficiency, can also avoid causing each composition in molten mixture cause performance degradation due to rapid cooling and then have a negative impact to cross-linking polymerization because cooling rate is too fast as far as possible.
For the catalyzer in above-mentioned steps S2 and linking agent, those skilled in the art are noted that the use of catalyzer just promotes the generation of polyreaction, therefore, it is possible to promote that the catalyzer of polyreaction all can be applicable to the present invention, the protonic acids such as such as sulfuric acid, trifluoroacetic acid, p-methyl benzenesulfonic acid.As long as linking agent can promote that the aromatic hydrocarbons molecule in hard pitch and mink cell focus is cross-linked to form the high molecular polymer with tridimensional network, the linking agent of the β resin content improved in modified pitch with this all can be used for the present invention.The application considers the factor of the aspects such as cross-linking effect, catalytic effect and operational characteristic, when selecting sulfuric acid as catalyzer of the present invention, preferred terephthalyl alcohol is arranged in pairs or groups as linking agent and sulfuric acid catalyst and is used, utilize the strongly-acid of sulfuric acid to activate terephthalyl alcohol linking agent reactive behavior, and then improve linking agent and hard pitch, the crosslinking polymerization speed of mink cell focus and degree, and sulfuric acid has advantage that is cheap, wide material sources.Its reaction principle is: add sulfuric acid catalyst and terephthalyl alcohol linking agent in above-mentioned first mixture after, the aromatic hydrocarbons of the phenmethyl positively charged ion that terephthalyl alcohol linking agent generates under the highly acid katalysis of sulfuric acid and mink cell focus and pitch there occurs electrophilic substitution reaction, improves crosslinking polymerization degree.Further preferred concentration is 10 ~ 98wt%, and more preferably the concentration of sulfuric acid is 30 ~ 55wt%.When selecting p-methyl benzenesulfonic acid as catalyzer, one or more in preferred trioxymethylene, phenyl aldehyde and paraformaldehyde are mated use as linking agent.This is mainly high due to trioxymethylene, phenyl aldehyde and polyformaldehyde reaction activity, utilizes the slightly acidic of p-methyl benzenesulfonic acid and low hydrogen supply capacity, effectively can control the crosslinking polymerization speed of aromatic hydrocarbons in linking agent and pitch and mink cell focus.Above-mentioned various raw material does not need special preparation, is bought by market.
Equally, the consumption of catalyzer and linking agent also can require speed of response, effect etc. according to concrete those skilled in the art and determine, in another preferred embodiment of the present invention, on the basis ensureing crosslinked and catalytic effect, consume the catalytic effect that alap cost is realized ideal, the consumption of preferred catalyst is 1 ~ 50wt% of hard pitch, more preferably 10 ~ 30wt%.The consumption of preferred linking agent is 1 ~ 50wt% of hard pitch, more preferably 10 ~ 30wt%.
The mink cell focus added in step S1 of the present invention, has certain viscosity, can dissolve as solvent to hard pitch, the slurries forming mobility with hard pitch, have good stability, and makes it fully contact with catalyzer with linking agent.Wherein, in order to realize the solvency action to hard pitch, the mink cell focus that preferred initial boiling point is greater than 260 DEG C, more preferably one or more in carbolineum, vacuum residuum, liquefaction heavy oil or catalytically cracked oil, above-mentioned mink cell focus can make follow-up cross-linking polymerization process keep good mobility, enable the liquid phase that the reactant of participation cross-linking polymerization keeps enough at reaction conditions, and mink cell focus can give full play to solvent heat transmission function.
In another preferred embodiment of the present invention, when in said mixture, the consumption of mink cell focus is 5 ~ 100wt% of hard pitch, to the dissolving of hard pitch and degree of steeping higher, more preferably, the consumption of mink cell focus is 40 ~ 70wt% of hard pitch, the mink cell focus consumption of this scope to the dissolving of hard pitch and degree of steeping higher.Consumption is very few can not be dissolved completely and flood above-mentioned hard pitch; When consumption is too much, not only increase production cost, and cause the wasting of resources.
In order to enable above-mentioned hard pitch be dissolved in mink cell focus more fully, and then increase and linking agent, catalyst exposure area, so that cross-linking polymerization is thorough, above-mentioned hard pitch preferable particle size is the pulverizing pitch of 0.2 ~ 5mm.
In embodiment 1 ~ 6 and comparative example 1 ~ 2, raw materials used hard pitch is all according to the schematic flow sheet preparing modified pitch shown in accompanying drawing 1, first coal directly-liquefied residue mixes with extraction agent, carry out successively afterwards extracting, solid-liquid separation, underpressure distillation obtain hard pitch, in embodiment 1 ~ 6 and comparative example 1 ~ 2, the key parameter of hard pitch is in table 2.Certain those skilled in the art also can buy hard pitch from other producers, as long as the hard pitch used meets, softening temperature is 115 ~ 160 DEG C, β resin content is 5 ~ 15wt%, the condition of ash oontent≤0.5wt% all can be used for the present invention.
Embodiment 1
According to the preparation flow shown in accompanying drawing 1, be that the above-mentioned hard pitch 50g of 0.2mm mixes with 2.5g carbolineum by particle diameter, obtain the first mixture; First mixture is added in stirring tank, under nitrogen atmosphere protection, is warming up to 120 DEG C (T1) with the heat-up rate of 1 DEG C/min (V1) and obtains the first pre-composition, and stir stirring first pre-composition 60min with the speed of 100r/min, obtain the first mixture;
Then at the temperature of 80 DEG C (T2), in the first mixture, add 0.5g trioxymethylene, and to stir 30min under the stirring velocity of 100r/min, obtain the second pre-composition, in the second pre-composition, add 0.5g p-methyl benzenesulfonic acid again to mix, obtain the second mixture;
Carry out at such a temperature crosslinking polymerization to material cannot by stirring time, stop heating, obtain the modified pitch of embodiment 1.
Embodiment 2
According to the preparation flow shown in accompanying drawing 1, selecting particle diameter to be the above-mentioned hard pitch of 0.5mm is raw material, select the mink cell focus of embodiment 2 in table 1, linking agent and catalyst type, be prepared according to the step of embodiment 1 with parameter corresponding in table 2, obtain the modified pitch of embodiment 2.
Embodiment 3
According to the preparation flow shown in accompanying drawing 1, selecting particle diameter to be the above-mentioned hard pitch of 5mm is raw material, select the mink cell focus of embodiment 3 in table 1, linking agent and catalyst type, be prepared according to the step of embodiment 1 with parameter corresponding in table 2, obtain the modified pitch of embodiment 3.
Embodiment 4
According to the preparation flow shown in accompanying drawing 1, selecting particle diameter to be the above-mentioned hard pitch of 2.5mm is raw material, select the mink cell focus of embodiment 4 in table 1, linking agent and catalyst type, be prepared according to the step of embodiment 1 with parameter corresponding in table 2, obtain the modified pitch of embodiment 4.
Embodiment 5
According to the preparation flow shown in accompanying drawing 1, selecting particle diameter to be the above-mentioned hard pitch of 2mm is raw material, select the mink cell focus of embodiment 5 in table 1, linking agent and catalyst type, be prepared according to the step of embodiment 1 with parameter corresponding in table 2, obtain the modified pitch of embodiment 5.
Embodiment 6
Embodiment 6 is different from embodiment 5 except the linking agent used and mink cell focus kind, selects outside kind shown in table 1 and embodiment 6, is prepared, obtains the modified pitch of embodiment 6 according to parameter corresponding in table 2 according to the step of embodiment 1.
Comparative example 1
In the preparation process of comparative example 1 except being cooled to 60 DEG C and carrying out stopping heating when polyreaction to material cannot stir, all the other steps are prepared according to the parameter identical with embodiment 1, obtain the modified pitch of comparative example 1.
Comparative example 2
In the preparation process of comparative example 2 except being cooled to 150 DEG C and carrying out stopping heating when polyreaction to material cannot stir, all the other steps are prepared according to the parameter identical with embodiment 2, obtain the modified pitch of comparative example 2.
ASTMD3461-83 standard testing softening temperature is pressed to the performance of the modified pitch that above-described embodiment 1 ~ 6 and comparative example 1 ~ 2 obtain, ash oontent employing standard GB/T212 measures, toluene insolubles adopts standard GB/T2293-1997 test, quinoline insolubles adopts standard GB/T2292-1997 test, β resin content is the difference that toluene insolubles content deducts quinoline insolubles content gained, and test result is in table 3.
Table 1
Table 2
Table 3
From upper table 3, what above-described embodiment 1 ~ 6 utilized the method for modified pitch provided by the invention can prepare softening temperature at 75 ~ 120 DEG C, β resin content more than 16% in high-temperaturebitumen, the requirement of current this area centering high-temperaturebitumen can be met completely, be applicable to needed for market; Comparative example 1 does not reach needed for market because β resin content is low, and comparative example 2 exists that softening temperature is too high also be can not meet needed for market.Because crosslinking polymerization temperature adopts 60 DEG C in comparative example 1, can not make the complete melting of the hard pitch in raw material, crosslinking polymerization degree is low, when crosslinking polymerization temperature is greater than 120 DEG C in same comparative example 2, causes finally being polymerized the pitch softening point obtained too high.Preparation were established of the present invention is simple, reaction conditions is gentle, and the adhesive property of the modifying asphalt obtained is relatively good, can be used as middle high-temperature agglomerant pitch and impregnating pitch, be suitable for suitability for industrialized production.
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 (20)
1. a preparation method for modified pitch, is characterized in that, described preparation method comprises the following steps:
S1, mixes hard pitch with mink cell focus, obtains the first mixture, and the softening temperature of described hard pitch is at 115 ~ 160 DEG C, and β resin content is 5 ~ 15wt%, ash oontent≤0.5wt%;
S2, is undertaken being mixed to get the second mixture by described first mixture and linking agent, catalyzer; And
S3, makes described second mixture carry out cross-linking polymerization at 80 ~ 120 DEG C, obtains modified pitch;
Wherein, described catalyzer is sulfuric acid, and linking agent is terephthalyl alcohol; Or catalyzer is p-methyl benzenesulfonic acid, and linking agent is selected from one or more in trioxymethylene, paraformaldehyde and phenyl aldehyde.
2. preparation method according to claim 1, is characterized in that, described step S1 comprises:
Step S11, is warming up to 120 ~ 260 DEG C under agitation by described hard pitch and described mink cell focus and obtains the first pre-composition;
Step S12, obtains described first mixture after first pre-composition 15 ~ 120min described in Keep agitation.
3. preparation method according to claim 2, is characterized in that, in described step S11, the speed of described stirring is 100 ~ 300r/min.
4. preparation method according to claim 2, is characterized in that, in described step S11, the speed of described intensification is 1 ~ 10 DEG C/min.
5. preparation method according to claim 1, is characterized in that, described step S2 comprises:
Step S21, at 80 ~ 120 DEG C, stirs 30 ~ 180min by described first mixture and described linking agent, obtains the second pre-composition under the stirring velocity of 100 ~ 300r/min;
Step S22, is undertaken being mixed to form described second mixture by described second pre-composition and described catalyzer.
6. preparation method according to claim 1, is characterized in that, described catalyst sulfuric acid concentration is 10 ~ 98wt%.
7. preparation method according to claim 1, is characterized in that, described catalyst sulfuric acid concentration is 30 ~ 55wt%.
8. preparation method according to claim 1, is characterized in that, the consumption of described catalyzer is 1 ~ 50wt% of described hard pitch, and the consumption of described linking agent is 1 ~ 50wt% of described hard pitch.
9. preparation method according to claim 1, is characterized in that, the consumption of described catalyzer is described hard pitch is 10 ~ 30wt%, and the consumption of described linking agent is 1 ~ 50wt% of described hard pitch.
10. preparation method according to claim 1, is characterized in that, the consumption of described catalyzer is described hard pitch is 1 ~ 50wt%, and the consumption of described linking agent is 10 ~ 30wt% of described hard pitch.
11. preparation methods according to claim 1, is characterized in that, the consumption of described catalyzer is described hard pitch is 10 ~ 30wt%, and the consumption of described linking agent is 10 ~ 30wt% of described hard pitch.
12. preparation methods according to claim 1, is characterized in that, described mink cell focus is the mink cell focus that initial boiling point is greater than 260 DEG C.
13. preparation methods according to claim 1 or 12, it is characterized in that, described mink cell focus is selected from one or more in carbolineum, vacuum residuum, liquefaction heavy oil, catalytically cracked oil.
14. preparation methods according to claim 1 or 12, it is characterized in that, the consumption of described mink cell focus is 5 ~ 100wt% of described hard pitch.
15. preparation methods according to claim 1 or 12, it is characterized in that, the consumption of described mink cell focus is 40 ~ 70wt% of described hard pitch.
16. preparation methods according to claim 1, is characterized in that, the pulverizing pitch of described hard pitch to be particle diameter be 0.2 ~ 5mm.
17. preparation methods according to claim 1, it is characterized in that, described preparation method also comprises the preparation process of described hard pitch, described preparation process comprises:
Coal directly-liquefied residue is mixed with extraction agent, forms solidliquid mixture;
Described solidliquid mixture is carried out successively extract, solid-liquid separation is extracted liquid and extract remainder;
Described extraction liquid is carried out underpressure distillation and obtains described hard pitch.
18. preparation methods according to claim 1, is characterized in that, described step S1, S2 and S3 carry out in inert gas atmosphere or nitrogen atmosphere.
19. 1 kinds of modified pitches, is characterized in that, described modified pitch adopts the preparation method according to any one of claim 1 to 18 to be prepared from.
20. modified pitches according to claim 19, the softening temperature of described modified pitch is at 81 ~ 113 DEG C, and β resin content is 18 ~ 28wt%, ash oontent≤0.42wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410021221.7A CN103756707B (en) | 2014-01-16 | 2014-01-16 | Modified asphalt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410021221.7A CN103756707B (en) | 2014-01-16 | 2014-01-16 | Modified asphalt and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN103756707A CN103756707A (en) | 2014-04-30 |
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| CN104593032B (en) * | 2015-01-12 | 2018-07-06 | 中钢集团鞍山热能研究院有限公司 | A kind of environmentally-friendly asphalt and preparation method thereof |
| 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 |
| CN111138670B (en) * | 2020-01-19 | 2022-05-31 | 济宁辰星碳素有限公司 | Preparation method of binder asphalt for low-cost high-performance prebaked anode |
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