CN110982549B - Low-temperature preparation method of modified asphalt - Google Patents
Low-temperature preparation method of modified asphalt Download PDFInfo
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- CN110982549B CN110982549B CN201911005356.3A CN201911005356A CN110982549B CN 110982549 B CN110982549 B CN 110982549B CN 201911005356 A CN201911005356 A CN 201911005356A CN 110982549 B CN110982549 B CN 110982549B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/04—Working-up tar by distillation
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Abstract
The invention relates to a low-temperature preparation method of modified asphalt. The technical scheme is as follows: placing 100 parts by mass of medium-temperature coal pitch into a reaction kettle with a distillation device, and heating to 105-115 ℃; adding 0.2-0.3 part by mass of binuclear cobalt phthalocyanine into the reaction kettle under the stirring condition, heating to 280-290 ℃, and preserving heat for 150-200 min; and then distilling for 25-35 min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain the modified asphalt. The medium-temperature coal pitch: the softening point is 80-90 ℃; the content of toluene insoluble substances is 15-25 wt%; the content of quinoline insoluble substances is 7-9 wt%; ash content is 0.24-0.27 wt%. The rotating speed of the stirring is 200-300 rpm. The method has the characteristics of simple process, low energy consumption, environmental protection and low cost, and the reaction kettle is not easy to coke, the service cycle of the equipment is long and the maintenance amount is small; the prepared modified asphalt reaches the first-grade index of the national standard.
Description
Technical Field
The invention belongs to the technical field of modified asphalt. In particular to a low-temperature preparation method of modified asphalt.
Background
The modified asphalt is also called graphite electrode asphalt, electrode bonding asphalt and high-quality asphalt, is mostly used as an ultrahigh power electrode or a high power electrode for electric furnace steel making, and is also used as an anode paste for electrolytic aluminum and a binder for carbon products. The modified asphalt contains higher Toluene Insoluble (TI), certain Quinoline Insoluble (QI), lower volatile content, higher resin content and the like, so that the carbon product produced by using the modified asphalt as a binder raw material has the advantages of small resistance, good conductivity, large capacitance density, low power consumption, high strength, no slag drop, long service life, small thermal expansion and the like. With the adjustment of the structure of steel and aluminum products, the demand of ultra-high power electrodes and high power electrodes is increasing day by day, and the demand of modified asphalt is increasing year by year.
The production method of the modified asphalt mainly comprises the following steps: a crosslinking agent addition method; oxidative thermal polymerization and high temperature thermal polymerization.
The method of adding a crosslinking agent. The method adds an aldehyde crosslinking agent into the medium-temperature coal pitch, and carries out crosslinking reaction under the catalysis of acid, such as the patent technology of 'modified pitch and preparation method thereof' (CN201410021224.0), although the technology can increase the content of beta resin of the modified pitch and enhance the cohesiveness, the graphitizable degree of the modified pitch can be reduced to a certain degree, so that the conductivity of the prepared carbon product is reduced.
Thermal oxidative polymerization. The method is that air or oxygen is introduced into the medium temperature coal pitch under the condition of more than 250 ℃, and the generated oxygen free radicals promote the polymerization of low molecular aromatic hydrocarbon in the medium temperature pitch, so that the molecular weight is increased. Although the method is simple in process and low in production cost, a large amount of non-condensable gas is generated, asphalt smoke is carried and discharged, the production environment is severe, the environmental protection pressure of enterprises is high, and the quality of the modified asphalt is difficult to control (Zhang Heman. research on the production process of the modified asphalt by the thermal polycondensation method [ D ]. academic papers of university of graduate, 2005).
High temperature thermal polymerization process. The method is that the medium temperature coal pitch is put into a polymerization reaction kettle and is kept for a certain time under a certain pressure and temperature for thermal polymerization, so that various indexes of the coal pitch reach the quality requirements. Under the condition of polymerization temperature of 380-400 ℃, polycyclic aromatic hydrocarbons generate free radicals to synthesize relatively large polymeric polycyclic aromatic hydrocarbons, so that toluene insoluble substances and quinoline insoluble substances are increased, the modified asphalt has certain cohesiveness and strength, and reaches the standard of the modified asphalt (Zhanfan yoga, comparison and application of the production process of the modified asphalt [ J ]. coal chemical industry, 2010, 1: 52-55). The quality of the modified asphalt produced by the method mainly depends on the reaction temperature and the residence time, and qualified modified asphalt products are obtained by increasing the reaction temperature or the residence time. However, the medium temperature coal pitch has the characteristics of high viscosity and easy coking at high temperature, so the high temperature thermal polymerization method also has the process limitation. In the polymerization reaction process, on one hand, the coal pitch has long retention time in a reaction kettle, light components of the pitch are evaporated, high carbon components are increased, the viscosity is increased, the fluidity of the pitch is reduced, the reaction kettle is easy to coke, pipelines are easy to block, and the long-period production of equipment is not facilitated; on the other hand, the high-temperature polymerization reaction not only has large energy consumption, but also releases more toxic and harmful gases, brings unsafe factors to production, and is not beneficial to environmental protection.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a low-temperature preparation method of modified asphalt, which has the advantages of simple process, low energy consumption, environmental protection, difficult coking of a reaction kettle, long service cycle of equipment and low cost.
In order to achieve the purpose, the invention adopts the technical scheme that: placing 100 parts by mass of medium-temperature coal pitch into a reaction kettle with a distillation device, and heating to 105-115 ℃; adding 0.2-0.3 part by mass of binuclear cobalt phthalocyanine into the reaction kettle under the stirring condition, heating to 280-290 ℃, and preserving heat for 150-200 min; and then distilling for 25-35 min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain the modified asphalt.
The medium-temperature coal pitch: the softening point is 80-90 ℃; the content of toluene insoluble substances is 15-25 wt%; the content of quinoline insoluble substances is 7-9 wt%; ash content is 0.24-0.27 wt%.
The rotating speed of the stirring is 200-300 rpm.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the preparation of the modified asphalt by a high-temperature thermal polymerization method relates to two aspects, on one hand, the distillation of light components is carried out; on the other hand, the carbon-hydrogen bond is broken and dehydrogenated at high temperature to generate polycyclic aromatic hydrocarbon free radicals, and the polycyclic aromatic hydrocarbon free radicals collide with each other and are polymerized into relatively large molecules, so that the softening point, the toluene insoluble substances and the quinoline insoluble substances are increased to obtain the modified asphalt. Under the action of no catalyst, the carbon-hydrogen bond energy of the aromatic hydrocarbon is large, and the carbon-hydrogen bond can be promoted to be broken to generate free radicals under the high-temperature condition of 380-400 ℃. The invention adopts binuclear cobalt phthalocyanine as a catalyst for polymerization, belongs to free radical reaction, and has the main catalytic action that pi electron cloud of polycyclic aromatic hydrocarbon in medium-temperature coal pitch is complexed with central cobalt ion, feedback electrons of cobalt enter into an anti-bond orbit of a carbon-hydrogen bond, so that the carbon-hydrogen bond can be weakened, the carbon-hydrogen bond of the polycyclic aromatic hydrocarbon is activated, the carbon-hydrogen bond can be broken at a lower temperature of 280-290 ℃ to generate aromatic hydrocarbon free radical, polymerization reaction is promoted to occur, low-temperature polymerization is realized, production energy consumption is reduced, and productivity is improved.
2. In the high-temperature thermal polymerization process, the temperature of a hearth of a reaction kettle is 380-400 ℃, and excessive polymerization is generated by overheating the kettle wall of the reaction kettle to form ultrahigh molecular weight cokes. The invention adopts a low-temperature polymerization process at 280-290 ℃, has low energy consumption, remarkably reduces the release of toxic and harmful gases, and is beneficial to environmental protection; meanwhile, the coking of the kettle wall of the reaction kettle is less, the pressure in the kettle is small, the long-period operation of the equipment is facilitated, and the maintenance cost is low.
3. The invention puts the medium temperature coal pitch into a reaction kettle with a distilling device, heats, adds the binuclear cobalt phthalocyanine under the stirring condition, heats, preserves the temperature, and then carries out reduced pressure distillation under the same condition to prepare the modified pitch, and the invention has simple process and low production cost.
The modified asphalt prepared by the invention comprises the following components: the softening point is 106-111 ℃; TI is 25-32%, and QI is 8-11%; the coking value is 53-56.8%; ash content 0.26%; reaches the first grade index of the national standard.
Therefore, the method has the characteristics of simple process, low energy consumption, environmental protection and low cost, and the reaction kettle is not easy to coke, the service cycle of the equipment is long, and the maintenance amount is small; the prepared modified asphalt reaches the first-grade index of the national standard.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope:
in this embodiment:
the medium temperature asphalt: the softening point is 80-90 ℃; the content of toluene insoluble substances is 15-25 wt%; the content of quinoline insoluble substances is 7-9 wt%; ash content is 0.24-0.27 wt%.
The rotating speed of the stirring is 200-300 rpm.
The detailed description is omitted in the embodiments.
Example 1
A low-temperature preparation method of modified asphalt. The preparation method in this example is:
placing 100 parts by mass of medium-temperature coal pitch into a reaction kettle with a distillation device, and heating to 105-115 ℃; adding 0.2 part by mass of binuclear cobalt phthalocyanine into the reaction kettle under the stirring condition, heating to 280-290 ℃, and preserving heat for 150 min; then distilling for 35min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain modified asphalt.
The low temperature-based modified asphalt prepared in this example: the softening point is 107 ℃; TI is 25%; QI 8%; the coking value is 53%; the ash content was 0.26%.
Example 2
A low-temperature preparation method of modified asphalt. The preparation method in this example is:
placing 100 parts by mass of medium-temperature coal pitch into a reaction kettle with a distillation device, and heating to 105-115 ℃; adding 0.22 part by mass of binuclear cobalt phthalocyanine into the reaction kettle under the stirring condition, heating to 280-290 ℃, and preserving heat for 160 min; then distilling for 33min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain modified asphalt.
The low temperature-based modified asphalt prepared in this example: the softening point is 109 ℃; TI is 28%; QI 9%; the coking value is 55%; the ash content was 0.26%.
Example 3
A low-temperature preparation method of modified asphalt. The preparation method in this example is:
placing 100 parts by mass of medium-temperature coal pitch into a reaction kettle with a distillation device, and heating to 105-115 ℃; adding 0.26 part by mass of binuclear cobalt phthalocyanine into the reaction kettle under the stirring condition, heating to 280-290 ℃, and preserving heat for 180 min; then distilling for 30min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain modified asphalt.
The low temperature-based modified asphalt prepared in this example: the softening point is 110 ℃; TI is 29%; QI is 10%; the coking value is 56%; the ash content was 0.26%.
Example 4
A low-temperature preparation method of modified asphalt. The preparation method in this example is:
placing 100 parts by mass of medium-temperature coal pitch into a reaction kettle with a distillation device, and heating to 105-115 ℃; adding 0.3 part by mass of binuclear cobalt phthalocyanine into the reaction kettle under the stirring condition, heating to 280-290 ℃, and preserving heat for 200 min; then distilling for 25min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain modified asphalt.
The low temperature-based modified asphalt prepared in this example: the softening point is 111 ℃; TI is 32%; QI 11%; the coking value is 56.8%; the ash content was 0.26%.
Compared with the prior art, the specific implementation mode has the following advantages:
1. the preparation of the modified asphalt by a high-temperature thermal polymerization method relates to two aspects, on one hand, the distillation of light components is carried out; on the other hand, the carbon-hydrogen bond is broken and dehydrogenated at high temperature to generate polycyclic aromatic hydrocarbon free radicals, and the polycyclic aromatic hydrocarbon free radicals collide with each other and are polymerized into relatively large molecules, so that the softening point, the toluene insoluble substances and the quinoline insoluble substances are increased to obtain the modified asphalt. Under the action of no catalyst, the carbon-hydrogen bond energy of the aromatic hydrocarbon is large, and the carbon-hydrogen bond can be promoted to be broken to generate free radicals under the high-temperature condition of 380-400 ℃.
The polymerization belongs to free radical reaction by adopting binuclear cobalt phthalocyanine as a catalyst, the main catalytic action is that pi electron cloud of polycyclic aromatic hydrocarbon in the medium-temperature coal pitch is complexed with central cobalt ions, feedback electrons of cobalt enter an anti-bond orbit of a carbon-hydrogen bond, so that the carbon-hydrogen bond can be weakened, the carbon-hydrogen bond of the polycyclic aromatic hydrocarbon is activated, the carbon-hydrogen bond can be broken at a lower temperature of 280-290 ℃ to generate aromatic hydrocarbon free radicals, the polymerization reaction is promoted to occur, the low-temperature polymerization is realized, the production energy consumption is reduced, and the productivity is improved.
Comparative example of a process for the preparation of modified bitumen: placing the medium-temperature coal pitch into a reaction kettle with a distillation device, heating to 105-115 ℃, uniformly stirring, heating to 280-290 ℃, and preserving heat for 200 min; then distilling for 35min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain modified asphalt. The prepared modified asphalt comprises the following steps: the softening point is 85 ℃; TI is 20%; QI is 7%; the coking value is 45.6%; the ash content was 0.26%. The results show that: the indexes of the modified asphalt prepared by the comparative example are not obviously changed compared with the indexes of the medium-temperature coal asphalt used in the embodiment. The situation that the polymerization reaction degree is low without adding a binuclear cobalt phthalocyanine catalyst under the same condition is shown; the binuclear cobalt phthalocyanine has obvious catalytic action on the used medium-temperature coal pitch under the reaction condition of 280-290 ℃.
2. In the high-temperature thermal polymerization process, the temperature of a hearth of a reaction kettle is 380-400 ℃, and excessive polymerization is generated by overheating the kettle wall of the reaction kettle to form ultrahigh molecular weight cokes. The specific implementation mode adopts a low-temperature polymerization process at 280-290 ℃, so that the energy consumption is low, the release of toxic and harmful gases is obviously reduced, and the environment is protected; meanwhile, the coking of the kettle wall of the reaction kettle is less, the pressure in the kettle is small, the long-period operation of the equipment is facilitated, and the maintenance cost is low.
3. The specific embodiment is that the medium-temperature coal pitch is placed in a reaction kettle with a distillation device, heated, added with the binuclear cobalt phthalocyanine under stirring, heated, insulated, and then distilled under the same conditions under reduced pressure to prepare the modified pitch, and the modified pitch has the advantages of simple process and low production cost.
The modified asphalt prepared by the embodiment comprises the following components: the softening point is 106-111 ℃; TI is 25-32%, and QI is 8-11%; the coking value is 53-56.8%; ash content 0.26%; reaches the first grade index of the national standard.
Therefore, the specific implementation mode has the characteristics of simple process, low energy consumption, environmental protection and low cost, and the reaction kettle is not easy to coke, the service cycle of the equipment is long, and the maintenance amount is small; the prepared modified asphalt reaches the first-grade index of the national standard.
Claims (3)
1. A low-temperature preparation method of modified asphalt is characterized by comprising the following steps: placing 100 parts by mass of medium-temperature coal pitch into a reaction kettle with a distillation device, and heating to 105-115 ℃; adding 0.2-0.3 part by mass of binuclear cobalt phthalocyanine into the reaction kettle under the stirring condition, heating to 280-290 ℃, and preserving heat for 150-200 min; and then distilling for 25-35 min under the conditions of continuous stirring, same temperature and vacuum degree of-0.09 Mpa to obtain the modified asphalt.
2. The low-temperature production method of the upgraded pitch of claim 1, wherein the medium-temperature coal pitch: the softening point is 80-90 ℃; the content of toluene insoluble substances is 15-25 wt%; the content of quinoline insoluble substances is 7-9 wt%; ash content is 0.24-0.27 wt%.
3. The low-temperature production method of the modified asphalt according to claim 1, wherein the rotation speed of the stirring is 200 to 300 rpm.
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| CN103059893A (en) * | 2013-01-14 | 2013-04-24 | 太原理工大学 | Method for preparing mesophase pitch by utilizing electrochemical catalysis |
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| CN103059893A (en) * | 2013-01-14 | 2013-04-24 | 太原理工大学 | Method for preparing mesophase pitch by utilizing electrochemical catalysis |
Non-Patent Citations (2)
| Title |
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| Reductive hydrogenation of polycyclic aromatic hydrocarbons catalyzed by metalloporphyrins;Elza Nelkenbaum;《Chemosphere》;20070301;第68卷(第2期);第210-217页 * |
| 平面双核金属酞菁衍生物的催化氧化性能;陈文兴;《化工学报》;20040630;第55卷(第6期);第924-928页 * |
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