CN103756705B - Modified asphalt and preparation method thereof - Google Patents
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- CN103756705B CN103756705B CN201410020608.0A CN201410020608A CN103756705B CN 103756705 B CN103756705 B CN 103756705B CN 201410020608 A CN201410020608 A CN 201410020608A CN 103756705 B CN103756705 B CN 103756705B
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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, heavy oil, crosslinking agent and a catalyst to form a mixture, wherein the softening point of the high-temperature asphalt is 115-160 DEG C, the beta resin content value is 5-15 wt%, and the ash content value is no more than 0.5 wt%; S2, heating to melt the mixture, thus obtaining a molten mixture; and S3, performing crosslinking polymerization on the molten mixture at 80-120 DEG C to obtain the modified asphalt. According to the invention, the heavy oil and crosslinking agent are added into the high-temperature asphalt used as a raw material, slow heating is performed to obtain molten asphalt, and then, crosslinking polymerization reaction is performed on the high-temperature asphalt under the action of the catalyst, thus obtaining the modified asphalt which has low softening point and high beta resin content; and the modified asphalt having high beta resin content 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 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 for softening temperature lower (75 ~ 95 DEG C), β resin content.And do not have report so far about the hard pitch of high softening-point (115-160 DEG C), low β resin content (5 ~ 15wt%) changes Quality Research, 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 the raw material of tamping coking, gac and Graphite Electrodes binding agent, waterproof roll, 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.
In the another kind of typical embodiment of the present invention, additionally provide a kind of modified pitch prepared by aforesaid method, softening temperature can be prepared in prior art at 75 ~ 120 DEG C by preparation method of the present invention, β resin content is 16 ~ 35wt%, the modified pitch of ash oontent≤0.5wt%, this modified pitch has lower softening temperature and higher β resin content.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 78 ~ 116 DEG C, β resin content value is 17 ~ 27wt%, ash oontent value≤0.45wt%, 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, is raw material, and improves the performance of its pitch with hard 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, hard pitch to be mixed with mink cell focus, linking agent, catalyzer, obtain mixture, the softening temperature of hard pitch is at 115 ~ 160 DEG C, and β resin content value is 5 ~ 15wt%, ash oontent value≤0.5wt%; S2, by mixture through intensification melting, obtain molten mixture; And S3, make molten mixture carry out crosslinking polymerization at 80 ~ 120 DEG C, obtain modified pitch.
Further, above-mentioned steps S2 comprises: melt temperature mixture being warming up to 120 ~ 180 DEG C, and heat-up rate is 1 ~ 10 DEG C/min preferably; To stir the mixture 10 ~ 60min with the stirring velocity of 100 ~ 300r/min under melt temperature, obtain molten mixture.
Further, above-mentioned steps S3 comprises: molten mixture is cooled to 80 ~ 120 DEG C, and cooling rate is 1 ~ 10 DEG C/min preferably; Make molten mixture carry out crosslinking polymerization at 80 ~ 120 DEG C, obtain modified pitch.
Further, above-mentioned catalyzer is p-methyl benzenesulfonic acid.
Further, the consumption of above-mentioned catalyzer is 1 ~ 50wt% of hard pitch, preferably 15 ~ 35wt%.
Further, above-mentioned linking agent is selected from one or more in trioxymethylene, paraformaldehyde and phenyl aldehyde.
Further, the consumption of above-mentioned linking agent is 1 ~ 50wt% of described hard pitch, preferably 15 ~ 35wt%.
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, above-mentioned steps S1, S2 and S3 carry out in inert gas atmosphere or nitrogen atmosphere.
Further, the pulverizing pitch of above-mentioned hard pitch to be particle diameter be 0.2 ~ 5mm.
Further, also comprise the preparation process of described hard pitch in above-mentioned steps S1, 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 will be stated carry out underpressure distillation and obtain hard pitch.
Another aspect of the present invention also provides a kind of modified pitch obtained by above-mentioned preparation method, and the softening temperature of preferred above-mentioned modified pitch is at 78 ~ 116 DEG C, and β resin content is 17 ~ 27wt%, ash oontent≤0.45wt%.
Apply technical scheme of the present invention and provide a kind of modified pitch and preparation method thereof, high with softening temperature, the hard pitch that β resin content is low is raw material, formerly add after mink cell focus and linking agent carry out slowly heating up and obtain the pitch of melting, carry out under the effect of catalyzer again cross-linking polymerization the softening temperature of hard pitch is reduced to meet background technology to be mentioned in the requirement of high-temperaturebitumen, β resin content also brings up to the requirement that can meet above-mentioned middle high-temperaturebitumen, it is good that this β resin content improves modified pitch adhesive property, 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.
In a kind of typical embodiment of the present invention, provide a kind of preparation method of modified pitch.This preparation method comprises the following steps: S1, mixed with mink cell focus, linking agent, catalyzer by hard pitch, and obtain mixture, the softening temperature of above-mentioned hard pitch is at 115 ~ 160 DEG C, and β resin content value is 5 ~ 15wt%, ash oontent value≤0.5wt%; S2, by said mixture through intensification melting, obtain molten mixture; And S3, make above-mentioned molten mixture carry out crosslinking 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 value is 5 ~ 15wt%, ash oontent value≤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 DCL/Direct coal liquefaction hard pitch is higher, β resin content is lower, cause adhesive property difference and suitability is not strong.
The present invention with above-mentioned hard pitch for raw material, dissolving using mink cell focus as solvent, and after adding linking agent and catalyzer formation mixture, the pitch of melting is first obtained through intensification melting, carry out the requirement that cross-linking polymerization makes the softening temperature of hard pitch be reduced to meet the middle high-temperaturebitumen that background technology is mentioned again at a lower temperature, β resin content also brings up to the requirement that can meet above-mentioned middle high-temperaturebitumen, wherein the raising of β resin content makes the modified pitch adhesive property that obtains 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 according to the making method of the performance requriements of modified pitch to prior art.
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 S2 also comprises: melt temperature said mixture being warming up to 120 ~ 180 DEG C, heat-up rate preferably 1 ~ 10 DEG C/min of intensification; Under above-mentioned melt temperature, stir said mixture 10 ~ 60min with the stirring velocity of 100 ~ 300r/min, obtain above-mentioned molten mixture.
In above-mentioned steps S2 of the present invention melt temperature be set to 120 ~ 180 DEG C, hard pitch can be carried out melting and obtain the good pitch of mobility, when melt temperature is lower than 120 DEG C, can not by complete for hard pitch melting; During higher than 180 DEG C, added linking agent and catalyzer can be made to volatilize and do not have corresponding effect in 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 pitch, be unlikely to again too fast linking agent and the catalyzer of causing of heat-up rate and volatilize.Stirring said mixture 10 ~ 60min with the stirring velocity of 100 ~ 300r/min, is also to obtain the good pitch of melting effect and keep good cross-linking catalyst ability simultaneously.
After by mixture, at 120 ~ 180 DEG C, melting forms molten mixture, molten mixture is made to carry out cross-linking polymerization, well known to a person skilled in the art and be, the temperature of crosslinking polymerization directly can affect softening temperature or the β resin content value of the modified pitch obtained, in order to obtain the modified pitch that softening temperature is lower, β resin content value is higher, above-mentioned steps S3 comprises: above-mentioned molten mixture is cooled to 80 ~ 120 DEG C, and preferably lowers the temperature with the cooling rate of 5 ~ 10 DEG C/min; Then make above-mentioned molten mixture carry out crosslinking polymerization at 80 ~ 120 DEG C, obtain above-mentioned modified pitch.The present invention preferably carries out crosslinking polymerization at 80 ~ 120 DEG C, make on softening temperature modifying process simple and convenient, the time that need not control reaction just can obtain the modified pitch of better performances, and, crosslinking polymerization is carried out again after the temperature of the molten mixture of high temperature being reduced, be conducive to being cross-linked between the aromatic hydrocarbons molecule in hard pitch and in mink cell focus, improve β resin content value in modified pitch further.The present invention preferably carries out cooling with the cooling rate of 1 ~ 10 DEG C/min can reduce the volatile quantity of linking agent and catalyzer to keep higher cross-linking catalyst efficiency as far as possible, can avoid again 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.
For the catalyzer in above-mentioned steps S1, 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.The application considers the factor of the aspect such as catalytic effect, operational characteristic, and preferred p-methyl benzenesulfonic acid is as catalyzer of the present invention.Equally, the consumption of catalyzer 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 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 15 ~ 35wt%.
In the mixture of step S1 of the present invention, add 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, improve the β resin content in modified pitch with this.Therefore, can promote in prior art that hard pitch and mink cell focus are cross-linked, and the linking agent completing polymeric modification under the effect of catalyzer all can be used for the present invention.In a kind of preferred embodiment of the present invention, in order to optimize cross-linking effect further, effectively control the β resin content in modified pitch, one or more in preferred use trioxymethylene, phenyl aldehyde and paraformaldehyde are as linking agent, above-mentioned linking agent and Catalyzed by P-Toluenesulfonic Acid agent with the use of, crosslinking polymerization effective, mainly because trioxymethylene, phenyl aldehyde and polyformaldehyde reaction activity are high, utilize 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.
In addition, those skilled in the art should clearly, if make linking agent play effect preferably, need to control the consumption of linking agent, in the another kind of preferred embodiment of the present invention, the consumption of above-mentioned linking agent is 1 ~ 50wt% of DCL/Direct coal liquefaction hard pitch, more preferably 15 ~ 35wt%.
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.
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 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 1.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 value is 5 ~ 15wt%, the condition of ash oontent value≤0.5wt% all can be used for the present invention.
Embodiment 1
Be that the above-mentioned hard pitch of 0.2mm is added in stirring tank with carbolineum, trioxymethylene, p-methyl benzenesulfonic acid together with the proportioning in table 1 by particle diameter, under nitrogen atmosphere protection, be warming up to 120 DEG C (T1) with the heat-up rate of 1 DEG C/min (V1) and carry out melting, and stir 60min with the stirring velocity of 100r/min, obtain molten mixture; Then be cooled to 80 DEG C (T2) with the cooling rate of 1 DEG C/min (V2), and carry out crosslinking polymerization to material at such a temperature when cannot stir, stop heating, obtain the modified pitch of embodiment 1.
Embodiment 2
Be that the above-mentioned hard pitch of 5mm is added in stirring tank with catalytically cracked oil, paraformaldehyde, p-methyl benzenesulfonic acid together with the proportioning in table 1 by particle diameter; under nitrogen atmosphere protection; be prepared with the parameter in table 1 according to the step of such as embodiment 1, obtain the modified pitch of embodiment 2.
Embodiment 3
Be that the above-mentioned hard pitch of 2.5mm is added in stirring tank with vacuum residuum, trioxymethylene, p-methyl benzenesulfonic acid together with the proportioning in table 1 by particle diameter; under argon gas atmosphere protection; be prepared with the parameter in table 1 according to the step of such as embodiment 1, obtain the modified pitch of embodiment 3.
Embodiment 4
The above-mentioned hard pitch of particle diameter 0.5mm is added in stirring tank together with liquefaction heavy oil, phenyl aldehyde, p-methyl benzenesulfonic acid; under the argon gas atmosphere protection passed into; be prepared with the parameter in table 1 according to the step of such as embodiment 1, obtain the modified pitch of embodiment 4.
Embodiment 5
The above-mentioned hard pitch of particle diameter 0.5mm is added in stirring tank with carbolineum together with pressurize residual oil, paraformaldehyde, p-methyl benzenesulfonic acid; under the argon gas atmosphere protection passed into; be prepared with the parameter in table 1 according to the step of such as embodiment 1, obtain the modified pitch of embodiment 5.
Embodiment 6
Be that the above-mentioned hard pitch of 2.5mm is added in stirring tank with carbolineum, paraformaldehyde together with phenyl aldehyde, p-methyl benzenesulfonic acid by particle diameter; under the nitrogen atmosphere protection passed into; be prepared with the parameter in table 1 according to the step of such as embodiment 1, obtain the modified pitch of embodiment 6.
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.
To above-described embodiment 1 ~ 8 and the obtained modified pitch of comparative example 1 ~ 2 softening temperature adopt standard A STMD3461-83 to measure, ash oontent value adopts standard GB/T212 to measure successively, toluene insolubles content adopts standard GB/T2293-1997 test, quinoline insolubles content adopts standard GB/T2292-1997 test, and the difference that toluene insolubles content deducts quinoline insolubles content gained is β resin content.Test result is in table 2.
Table 1
Table 2
| Softening temperature/DEG C | β resin content/wt% | TI/wt% | Ash oontent/wt% | |
| Embodiment 1 | 75 | 16 | 18 | 0.31 |
| Embodiment 2 | 120 | 35 | 36 | 0.07 |
| Embodiment 3 | 95 | 22 | 24 | 0.45 |
| Embodiment 4 | 88 | 20 | 22 | 0.18 |
| Embodiment 5 | 91 | 25 | 27 | 0.19 |
| Embodiment 6 | 97 | 26 | 28 | 0.37 |
| Comparative example 1 | 62 | 10 | 12 | 0.30 |
| Comparative example 2 | 147 | 39 | 40 | 0.06 |
From upper table 2, compare ratio 1 ~ 2, what above-described embodiment 1 ~ 6 utilized the method for modified pitch provided by the invention can by high softening-point, the hard pitch of low β resin content is prepared into softening temperature at 75 ~ 120 DEG C, β resin content high-temperaturebitumen in 16 ~ 35wt%, the softening temperature obtained by preparation method of the present invention is lower, and the adhesive property of the modified pitch that β resin content improves is good, can be used as middle high-temperature agglomerant pitch and impregnating pitch.In addition, preparation were established of the present invention simple,
Reaction conditions is gentle, is 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, mixed with mink cell focus, linking agent, catalyzer by hard pitch, obtain mixture, 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, by described mixture through intensification melting, obtain molten mixture; And
S3, make described molten mixture carry out crosslinking polymerization at 80 ~ 120 DEG C, obtain modified pitch.
2. preparation method according to claim 1, is characterized in that, described step S2 comprises:
Described mixture is warming up to the melt temperature of 120 ~ 180 DEG C;
Under described melt temperature, stir described mixture 10 ~ 60min with the stirring velocity of 100 ~ 300r/min, obtain described molten mixture.
3. preparation method according to claim 2, is characterized in that, the speed of described intensification is 1 ~ 10 DEG C/min.
4. preparation method according to claim 2, is characterized in that, described step S3 comprises:
Described molten mixture is cooled to 80 ~ 120 DEG C;
Make described molten mixture carry out crosslinking polymerization at 80 ~ 120 DEG C, obtain described modified pitch.
5. preparation method according to claim 4, is characterized in that, the speed of described cooling is 1 ~ 10 DEG C/min.
6. preparation method according to claim 1, is characterized in that, described catalyzer is p-methyl benzenesulfonic acid.
7. the preparation method according to claim 1 or 6, is characterized in that, the consumption of described catalyzer is 1 ~ 50wt% of described hard pitch.
8. the preparation method according to claim 1 or 6, is characterized in that, the consumption of described catalyzer is 15 ~ 35wt% of described hard pitch.
9. preparation method according to claim 1, is characterized in that, described linking agent is selected from one or more in trioxymethylene, paraformaldehyde and phenyl aldehyde.
10. the preparation method according to claim 1 or 9, is characterized in that, the consumption of described linking agent is 1 ~ 50wt% of described hard pitch.
11. preparation methods according to claim 1 or 9, it is characterized in that, the consumption of described linking agent is 15 ~ 35wt% 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 12, 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, described step S1, S2 and S3 carry out in inert gas atmosphere or nitrogen atmosphere.
17. 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.
18. preparation methods according to claim 1, is characterized in that, also comprise the preparation process of described hard pitch in described step S1, and 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.
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 78 ~ 116 DEG C, and β resin content value is 17 ~ 27wt%, ash oontent value≤0.45wt%.
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|---|---|---|---|---|
| CN1341696A (en) * | 2001-09-27 | 2002-03-27 | 石油大学(华东) | Method for preparing heat-resisting pitch resin by using heavy residuum as raw material |
| CN1760331A (en) * | 2005-10-27 | 2006-04-19 | 任利华 | Modified coal tar, and producing method |
| JP2009538970A (en) * | 2006-05-31 | 2009-11-12 | イノフォス インコーポレーテッド | Process for producing an improved bitumen by adding polyphosphoric acid and a crosslinkable polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060089429A1 (en) * | 2004-10-22 | 2006-04-27 | Fina Technology, Inc. | Use of inorganic acids with crosslinking agents in polymer modified asphalts |
| US8198350B2 (en) * | 2010-02-11 | 2012-06-12 | Icl Performance Products, Lp | Polymer-modified asphalt with a crosslinking agent and methods of preparing |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341696A (en) * | 2001-09-27 | 2002-03-27 | 石油大学(华东) | Method for preparing heat-resisting pitch resin by using heavy residuum as raw material |
| CN1760331A (en) * | 2005-10-27 | 2006-04-19 | 任利华 | Modified coal tar, and producing method |
| JP2009538970A (en) * | 2006-05-31 | 2009-11-12 | イノフォス インコーポレーテッド | Process for producing an improved bitumen by adding polyphosphoric acid and a crosslinkable polymer |
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