CN103756705A - Modified asphalt and preparation method thereof - Google Patents
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- CN103756705A CN103756705A CN201410020608.0A CN201410020608A CN103756705A CN 103756705 A CN103756705 A CN 103756705A CN 201410020608 A CN201410020608 A CN 201410020608A CN 103756705 A CN103756705 A CN 103756705A
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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 China constantly increases the consumption of petroleum products, have substantially exceeded the rate of growth of the crude production same period, cause us petroleum import amount all to increase year by year, and exceeded from output.And China is an oil-poor country of rich coal, make full use of abundant coal resources, the advanced persons' such as development of coal direct liquefaction clean coal technology is to reduce external crude oil to depend on unduly, alleviate one of important channel of China's oil shortage of resources, petroleum products supply and demand pressure, also be to improve our coal resources utilization ratio simultaneously, alleviate coal burning pollution, promote the Important Action of the energy, economy, harmonious development.
DCL/Direct coal liquefaction is that coal is passed through to high temperature, high pressure, and under catalyst action, hydrogenation directly changes into a kind of advanced person's of clean transport fuel (petroleum naphtha, diesel oil etc.) or industrial chemicals clean coal technology.The process of DCL/Direct coal liquefaction is generally that coal is crushed to the granularity below 0.15mm in advance, then is made into coal slurry with solvent, and under certain temperature (approximately 450 ℃) and high pressure hydrogenation, make the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process, except the liquiefied product that obtains needing, go back some hydrocarbon molecules of by-product, CO
xthe liquefaction residue (claiming again coal liquefaction residue) producing Deng gas, process water and solid-liquid separation process.Liquefied residue generally accounts for the 30wt% left and right of coal input quantity.The economy of the efficiency of the utilization of coal liquefaction residue on liquefaction process and whole liquefaction factory and environment protection etc. all have immeasurable impact.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts value product the economic benefit that improves direct liquefaction process is had important practical significance.
Coal directly-liquefied residue is mainly comprised of inanimate matter and organic two portions, and organic matter comprises liquefaction heavy oil, bitumen and unconverted coal, and inorganic matter (being commonly referred to ash content) comprises mineral substance in coal and additional catalyzer.Liquefaction heavy oil in organic material 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 20wt% left and right.Therefore, by accounting for the bitumen of 50wt% and mink cell focus in liquefied residue, separate and carry out comprehensive development and utilization, it is feasible therefrom extracting or prepare more value product.
Now the technology of utilizing of coal liquefaction residue is mainly used in to the traditional methods such as boiler oil, coking liquefaction, gasification hydrogen-producing.As fuel, directly in boiler or kiln, burn, will affect the economy of gelatin liquefaction undoubtedly, and in liquefied residue, higher sulphur content will be brought the problem of environment aspect.Although coking liquefaction has increased the liquid oils yield of coal liquefaction craft, liquefied residue can not obtain the most reasonably utilizing, 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 to gasification hydrogen-producing is a kind of effectively extensive approach utilizing, but the high value added utilization potentiality of the bitumen in residue and mink cell focus are embodied.
Up to now, there have been much research reports about bitumen upgrading both at home and abroad, 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 to thermal still, then passes into pressurized air and carry out heated oxide, and temperature in the kettle generally maintains 340～360 ℃, till the air capacity passing into can be brought up to pitch softening point required point; The domestic coke-oven plant having adopts heated polymerizable method, mid-temperature pitch softening temperature can be brought up to 120 ℃, and toluene insolubles value is brought up to 30wt% left and right; Osaka, Japan Gas Company adopts pressurization thermal polymerization method, finds that pitch β proportion of resin present normal heating polymerization is high, and China waterside town Iron And Steel Company coke-oven plant has generated qualified modified pitch by this method.
Although these asphalt modifier methods are adopted by domestic and international manufacturer, and all produce middle high-temperaturebitumen always, for example, softening temperature is at 75～120 ℃, and β resin content is at 16～35wt%, and ash content is lower than the middle high-temperaturebitumen of 0.5wt%.But these asphalt modifier methods are all at petroleum pitch or the coal tar of 20wt% left and right, to be pitch, and to be mainly the standard of softening temperature being brought up to above-mentioned middle high-temperaturebitumen for softening temperature lower (75～95 ℃), β resin content.And there is not so far report about the research of the hard pitch upgrading of high softening-point (115-160 ℃), low β resin content (5～15wt%), 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 required to meet market.
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 has improved the performance of its pitch.
To achieve these goals, according to an aspect of the present invention, a kind of preparation method of modified pitch is provided, comprise the following steps: S1, hard pitch is mixed with mink cell focus, linking agent, catalyzer, obtain mixture, the softening temperature of hard pitch is at 115～160 ℃, 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 at 80～120 ℃, carry out crosslinking polymerization, obtain modified pitch.
Further, above-mentioned steps S2 comprises: mixture is warming up to the melt temperature of 120～180 ℃, heat-up rate is 1～10 ℃/min preferably; Under melt temperature, with the stirring velocity of 100～300r/min, the 10～60min that stirs the mixture, obtain molten mixture.
Further, above-mentioned steps S3 comprises: molten mixture is cooled to 80～120 ℃, and cooling rate is 1～10 ℃/min preferably; Make molten mixture at 80～120 ℃, carry out crosslinking polymerization, obtain modified pitch.
Further, above-mentioned catalyzer is p-methyl benzenesulfonic acid.
Further, 1～50wt% that the consumption of above-mentioned catalyzer is hard pitch, preferably 15～35wt%.
Further, above-mentioned linking agent is selected from one or more in trioxymethylene, paraformaldehyde and phenyl aldehyde.
Further, 1～50wt% that the consumption of above-mentioned linking agent is 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 ℃.
Further, above-mentioned mink cell focus is selected from one or more in carbolineum, vacuum residuum, liquefaction heavy oil, catalytically cracked oil.
Further, 5～100wt% that the consumption of above-mentioned mink cell focus is described hard pitch, preferably 40～70wt%.
Further, above-mentioned steps S1, S2 and S3 carry out in inert gas atmosphere or nitrogen atmosphere.
Further, above-mentioned hard pitch is that particle diameter is the pulverizing pitch of 0.2～5mm.
Further, also comprise the preparation process of described hard pitch in above-mentioned steps S1, this preparation process comprises: coal directly-liquefied residue is mixed with extraction agent, form solidliquid mixture; By solidliquid mixture extract successively, solid-liquid separation is extracted liquid and extract remainder; To state extraction liquid carries out underpressure distillation and obtains hard pitch.
Another aspect of the present invention also provides one by the prepared modified pitch of above-mentioned preparation method, and the softening temperature of preferred above-mentioned modified pitch is at 78～116 ℃, and β resin content is 17～27wt%, ash oontent≤0.45wt%.
Apply technical scheme of the present invention a kind of modified pitch and preparation method thereof is provided, high with softening temperature, the hard pitch that β resin content is low is raw material, formerly add mink cell focus and linking agent to carry out slowly heating up and obtaining after the pitch of melting, under the effect of catalyzer, carry out again the requirement that cross-linking polymerization is reduced to the softening temperature of hard pitch to meet the middle high-temperaturebitumen that background technology mentions, β resin content is also brought 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 market required middle high-temperature agglomerant pitch and impregnating pitch, thereby for the making of the modified pitch of prior art provides new raw material, and for hard pitch has found new application 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 shows the preparation flow schematic diagram of the modified pitch of a kind of exemplary embodiments according to the present invention.
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.
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, hard pitch is mixed with mink cell focus, linking agent, catalyzer, obtain mixture, the softening temperature of above-mentioned hard pitch is at 115～160 ℃, 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 at 80～120 ℃, carry out crosslinking polymerization, obtain modified pitch.
As background technology of the present invention is recorded, the softening temperature of the hard pitch of producing from coal directly-liquefied residue is 115～160 ℃, β resin content value is 5～15wt%, ash oontent value≤0.5wt% is low with respect to 75～95 ℃ high of softening temperatures, the β resin content 20wt% left and right of raw material of preparing modified pitch in prior art.Because the softening temperature of above-mentioned DCL/Direct coal liquefaction hard pitch is higher, β resin content is lower, cause that adhesive property is poor and suitability is not strong.
The present invention is take above-mentioned hard pitch as raw material, using mink cell focus, as solvent, dissolving, and after adding linking agent and catalyzer formation mixture, first through intensification melting, obtain the pitch of melting, at lower temperature, carry out again the requirement that cross-linking polymerization is reduced to the softening temperature of hard pitch to meet the middle high-temperaturebitumen that background technology mentions, β resin content is also brought 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 market required middle high-temperature agglomerant pitch and impregnating pitch, thereby for the making of the modified pitch of prior art provides new raw material, and for hard pitch has found new application approach.And, while making modified pitch take above-mentioned hard pitch as raw material, controlling on the basis of melting and polymeric reaction temperature, adopt existing common process flow process, making method is simple, and those skilled in the art can improve the making method of prior art 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 mixes more even, the effect of crosslinking polymerization is by better, for the molten mixture that makes the thorough melting of hard pitch and obtain mixing, those skilled in the art can, controlling on the basis of melt temperature and heat-up rate, suitably adjust the molten mixture that stirring velocity and churning time can obtain mixing.In a kind of preferred embodiment of the present invention, above-mentioned steps S2 also comprises: said mixture is warming up to the melt temperature of 120～180 ℃, the heat-up rate of intensification is 1～10 ℃/min preferably; Stirring velocity with 100～300r/min under above-mentioned melt temperature stirs said mixture 10～60min, obtains above-mentioned molten mixture.
In above-mentioned steps S2 of the present invention melt temperature be made as 120～180 ℃, hard pitch can be carried out to melting and obtain the good pitch of mobility, when melt temperature is during lower than 120 ℃, can not be by complete hard pitch melting; During higher than 180 ℃, can make added linking agent and catalyzer volatilize and in follow-up cross-linking polymerization, not have corresponding effect.Select the heat-up rate of 1～10 ℃/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 velocity with 100～300r/min stirs said mixture 10～60min, is also in order to obtain the good pitch of melting effect and to keep preferably crosslinked catalytic capability simultaneously.
Mixture melting at 120～180 ℃ is formed after molten mixture, make molten mixture carry out cross-linking polymerization, well known to a person skilled in the art and be, softening temperature or the β resin content value of the temperature of the crosslinking polymerization modified pitch that directly impact obtains, 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 ℃, and preferably with the cooling rate of 5～10 ℃/min, lowers the temperature; Then make above-mentioned molten mixture at 80～120 ℃, carry out crosslinking polymerization, obtain above-mentioned modified pitch.The present invention preferably carries out crosslinking polymerization at 80～120 ℃, 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, after being reduced, the temperature of the molten mixture of high temperature carries out again crosslinking polymerization, be conducive to being cross-linked between the aromatic hydrocarbons molecule in hard pitch and in mink cell focus, further improve β resin content value in modified pitch.The present invention preferably with the cooling rate of 1～10 ℃/min lower the temperature can reduce linking agent and catalyzer as far as possible volatile quantity to keep higher crosslinked catalytic efficiency, can avoid again causing because cooling rate is too fast in molten mixture each composition because rapid cooling causes performance degradation and then cross-linking polymerization is had a negative impact.
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 can promote the catalyzer of polyreaction all to can be applicable to the present invention, such as protonic acids such as sulfuric acid, trifluoroacetic acid, p-methyl benzenesulfonic acids.The application considers the factor of the aspects such as catalytic effect, operational characteristic, and preferably p-methyl benzenesulfonic acid is as catalyzer of the present invention.Equally, the consumption of catalyzer also can require to determine to speed of response, effect etc. according to concrete those skilled in the art, in another preferred embodiment of the present invention, guaranteeing on the basis of 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 the aromatic hydrocarbons molecule in hard pitch and mink cell focus to be cross-linked to form the high molecular polymer with tridimensional network, with this, improve the β resin content in modified pitch.Therefore, in prior art, can promote that hard pitch and mink cell focus are cross-linked, and the linking agent that completes 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 further to optimize cross-linking effect, effectively control the β resin content in modified pitch, preferably one or more in use trioxymethylene, phenyl aldehyde and paraformaldehyde are as linking agent, above-mentioned linking agent and Catalyzed by P-Toluenesulfonic Acid agent are used in conjunction with, crosslinking polymerization effective, mainly because trioxymethylene, phenyl aldehyde and polyformaldehyde reaction activity are high, utilize slightly acidic and the low hydrogen supply capacity of p-methyl benzenesulfonic acid, can effectively 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, by market, is bought.
In addition, those skilled in the art should clearly, if make linking agent performance 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 adding in step S1 of the present invention, has certain viscosity, can be used as solvent hard pitch is dissolved, and forms mobility, the slurries that have good stability, and it is fully contacted with catalyzer with linking agent with hard pitch.Wherein, in order to realize the solvency action to hard pitch, the mink cell focus that preferably initial boiling point is greater than 260 ℃, 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, make the reactant that participates in cross-linking polymerization can under reaction conditions, keep enough liquid phases, and mink cell focus can be given full play to solvent heat transmission function.
In another preferred embodiment of the present invention, during 5～100wt% that in said mixture, the consumption of mink cell focus is hard pitch, dissolving and degree of steeping to hard pitch are higher, more preferably, the consumption of mink cell focus is 40～70wt% of hard pitch, and dissolving and the degree of steeping of the mink cell focus consumption of this scope to hard pitch is higher.Consumption is very few can not dissolve and flood above-mentioned hard pitch completely; 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, to completely cut off air, reaction are carried out under the condition of anaerobic, avoid the existence of the gases such as oxygen to bring the insecurity of pyroreaction.
For above-mentioned hard pitch can be dissolved in mink cell focus more fully, so increase and linking agent, catalyzer contact area, so that cross-linking polymerization is thorough, the pulverizing pitch that above-mentioned hard pitch preferable particle size is 0.2～5mm.
The technique of preparing hard pitch in prior art has a lot, the application is in order to obtain having the hard pitch of These characteristics, preferably above-mentioned steps S1 also comprises the preparation process of hard pitch, and this preparation process comprises: coal directly-liquefied residue is mixed with extraction agent, form solidliquid mixture; By above-mentioned solidliquid mixture extract successively, solid-liquid separation is extracted liquid and extract remainder; Above-mentioned extraction liquid is carried out to underpressure distillation and obtain hard pitch.Above-mentioned to prepare extraction solvent used in the process of hard pitch separation with hard pitch in vacuum distillation process, and then can return in this process of preparing hard pitch and reuse, and saved the cost of preparing hard pitch.
In the another kind of typical embodiment of the present invention, a kind of modified pitch of being prepared by aforesaid method is also provided, by preparation method of the present invention, can prepare in prior art softening temperature at 75～120 ℃, 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 market required middle high-temperature agglomerant pitch and impregnating pitch.
In another preferred embodiment of the present invention, the softening temperature of the modified pitch of being prepared by aforesaid method is at 78～116 ℃, 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, while applying in high-temperature agglomerant pitch and impregnating pitch, can obtain better effect.
Below in conjunction with specific embodiment, further illustrate beneficial effect of the present invention.
In embodiment 1～6 and comparative example 1～2, raw materials used hard pitch is all according to the schematic flow sheet of preparing modified pitch shown in accompanying drawing 1, first coal directly-liquefied residue mixes with extraction agent, extract successively afterwards, 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.Certainly those skilled in the art also can buy hard pitch from other producers, as long as the hard pitch using meets softening temperature, are that 115～160 ℃, β resin content value are that the condition of 5～15wt%, ash oontent value≤0.5wt% all can be used for the present invention.
Embodiment 1
The above-mentioned hard pitch that is 0.2mm by particle diameter is added in stirring tank together with the proportioning in table 1 with carbolineum, trioxymethylene, p-methyl benzenesulfonic acid, under nitrogen atmosphere protection, with the heat-up rate (V1) of 1 ℃/min, be warming up to 120 ℃ (T1) and carry out melting, and stir 60min with the stirring velocity of 100r/min, obtain molten mixture; Then with the cooling rate (V2) of 1 ℃/min, be cooled to 80 ℃ (T2), and at this temperature, carry out crosslinking polymerization to material cannot stir time, stop heating, obtain the modified pitch of embodiment 1.
Embodiment 2
The above-mentioned hard pitch that is 5mm by particle diameter is added in stirring tank together with the proportioning in table 1 with catalytically cracked oil, paraformaldehyde, p-methyl benzenesulfonic acid; under nitrogen atmosphere protection; according to being prepared with the parameter in table 1 as the step of embodiment 1, obtain the modified pitch of embodiment 2.
Embodiment 3
The above-mentioned hard pitch that is 2.5mm by particle diameter is added in stirring tank together with the proportioning in table 1 with vacuum residuum, trioxymethylene, p-methyl benzenesulfonic acid; under argon gas atmosphere protection; according to being prepared with the parameter in table 1 as the step of 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 passing into; according to being prepared with the parameter in table 1 as the step of 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 together with pressurization residual oil, paraformaldehyde, p-methyl benzenesulfonic acid with carbolineum; under the argon gas atmosphere protection passing into; according to being prepared with the parameter in table 1 as the step of embodiment 1, obtain the modified pitch of embodiment 5.
Embodiment 6
By particle diameter, be that the above-mentioned hard pitch of 2.5mm is added in stirring tank together with carbolineum, paraformaldehyde and phenyl aldehyde, p-methyl benzenesulfonic acid; under the nitrogen atmosphere protection passing into; according to being prepared with the parameter in table 1 as the step of embodiment 1, obtain the modified pitch of embodiment 6.
Comparative example 1
In the preparation process of comparative example 1 except be cooled to 60 ℃ carry out polyreaction when material cannot stir, stop heating, 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 be cooled to 150 ℃ carry out polyreaction when material cannot stir, stop heating, all the other steps are prepared according to the parameter identical with embodiment 2, obtain the modified pitch of comparative example 2.
The modified pitch that above-described embodiment 1～8 and comparative example 1～2 are made 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/℃ | 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, above-described embodiment 1～6 utilize modified pitch provided by the invention method can be by high softening-point, the hard pitch of low β resin content is prepared into softening temperature at 75～120 ℃, β resin content is at the middle high-temperaturebitumen of 16～35wt%, the softening temperature being 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 gentleness, 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 modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (15)
1. a preparation method for modified pitch, is characterized in that, described preparation method comprises the following steps:
S1, hard pitch is mixed with mink cell focus, linking agent, catalyzer, obtain mixture, the softening temperature of described hard pitch is at 115～160 ℃, 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 at 80～120 ℃, carry out crosslinking polymerization, 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 ℃, the speed of described intensification is 1～10 ℃/min preferably;
Under described melt temperature, with the stirring velocity of 100～300r/min, stir described mixture 10～60min, obtain described molten mixture.
3. preparation method according to claim 2, is characterized in that, described step S3 comprises:
Described molten mixture is cooled to 80～120 ℃, and the speed of described cooling is 1～10 ℃/min preferably;
Make described molten mixture at 80～120 ℃, carry out crosslinking polymerization, obtain described modified pitch.
4. preparation method according to claim 1, is characterized in that, described catalyzer is p-methyl benzenesulfonic acid.
5. according to the preparation method described in claim 1 or 4, it is characterized in that 1～50wt% that the consumption of described catalyzer is described hard pitch, preferably 15～35wt%.
6. 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.
7. according to the preparation method described in claim 1 or 6, it is characterized in that 1～50wt% that the consumption of described linking agent is described hard pitch, preferably 15～35wt%.
8. preparation method 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 ℃.
9. preparation method according to claim 8, is characterized in that, described mink cell focus is selected from one or more in carbolineum, vacuum residuum, liquefaction heavy oil, catalytically cracked oil.
10. according to the preparation method described in claim 1 or 8, it is characterized in that 5～100wt% that the consumption of described mink cell focus is described hard pitch, preferably 40～70wt%.
11. 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.
12. preparation methods according to claim 1, is characterized in that, described hard pitch is that particle diameter is the pulverizing pitch of 0.2～5mm.
13. 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, form solidliquid mixture;
By described solidliquid mixture extract successively, solid-liquid separation is extracted liquid and extract remainder;
Described extraction liquid is carried out to underpressure distillation and obtain described hard pitch.
14. 1 kinds of modified pitches, is characterized in that, described modified pitch adopts the preparation method described in any one in claim 1 to 13 to be prepared from.
15. modified pitches according to claim 14, the softening temperature of described modified pitch is at 78～116 ℃, and β resin content value is 17～27wt%, ash oontent value≤0.45wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745219A (en) * | 2015-03-23 | 2015-07-01 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN105273421A (en) * | 2014-07-23 | 2016-01-27 | 中国石油大学(华东) | Catalytic slurry oil utilization method |
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| CN104745219A (en) * | 2015-03-23 | 2015-07-01 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103756705B (en) | 2015-06-03 |
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