CN109957257B - Biomass asphalt modifier and preparation method and application thereof - Google Patents
Biomass asphalt modifier and preparation method and application thereof Download PDFInfo
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- CN109957257B CN109957257B CN201910197952.XA CN201910197952A CN109957257B CN 109957257 B CN109957257 B CN 109957257B CN 201910197952 A CN201910197952 A CN 201910197952A CN 109957257 B CN109957257 B CN 109957257B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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Abstract
The invention discloses a biomass asphalt modifier and a preparation method and application thereof, wherein the biomass asphalt modifier comprises the following raw materials: straw stalk, liquefying agent and catalyst. The biomass modifier prepared by the invention takes straw stalks as raw materials, and the straw stalks and the mixture of polyethylene glycol 400, glycerol and p-hydroxyphenylethanol are subjected to chemical reaction under the action of acid catalysis in a high-temperature and high-pressure environment to prepare the biomass modifier with better thermoplasticity; the biomass modifier is used for modifying the road matrix asphalt, and the low-temperature deformability of the matrix asphalt can be obviously improved on the premise of not changing the high-temperature performance of the matrix asphalt.
Description
Technical Field
The invention relates to the field of road engineering, in particular to a biomass asphalt modifier and a preparation method and application thereof.
Background
Along with the rapid development of highway traffic construction in China, people show a diversified trend on the service performance of asphalt pavements, wherein the requirements on the sustainable development and the economic and environmental protection of road asphalt materials are particularly critical. In recent years, high molecular polymers are utilized to modify matrix asphalt so as to improve the high-temperature rutting resistance, aging resistance and other relevant performances of the asphalt and meet the requirements of people on the use of asphalt pavements. However, the asphalt pavement material is seriously dependent on the petroleum energy which is gradually exhausted, and the mass production of the petroleum asphalt and the high polymer modifier causes serious environmental pollution, thereby restricting the sustainable development of road materials in China and hindering the construction of resource-saving and environment-friendly society. Therefore, accelerating the development of sustainable economic and environment-friendly road materials becomes a problem which needs to be solved at present.
The wood materials such as the straws and the like have excellent physicochemical properties, environmental characteristics and good mechanical properties, and are refractory and indissolvable natural composite materials, so that the wood materials are difficult to process and treat like glass and plastic by physical heating, pressurization and the like, and the recovery and utilization of wood resources are influenced. Wood liquefaction is a method for converting wood fiber from solid state to liquid state, i.e. a thermochemical process for converting wood into viscous fluid under certain chemical catalytic reaction conditions. Under the double pressure that the supply of asphalt is increasingly tense and functional asphalt is difficult to popularize, the invention utilizes the liquefied product of the straw stalk as the biomass asphalt modifier, expands the application field of wood biomass materials and relieves the energy shortage and environmental pollution caused by the production of asphalt pavement materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a biomass asphalt modifier and a preparation method and application thereof, wherein the biomass modifier takes straw as a raw material, and is subjected to chemical reaction with a mixture of polyethylene glycol 400, glycerol and p-hydroxyphenylethanol under the action of acid catalysis in a high-temperature and high-pressure environment to prepare the biomass modifier with better thermoplasticity; the biomass modifier is used for modifying the road matrix asphalt, and the low-temperature deformability of the matrix asphalt can be obviously improved on the premise of not changing the high-temperature performance of the matrix asphalt.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
The biomass asphalt modifier comprises the following raw materials: straw stalk, liquefying agent and catalyst.
Preferably, the liquefying agent comprises p-hydroxyphenylethanol, polyethylene glycol and glycerol.
Preferably, the catalyst comprises p-toluenesulfonic acid.
Preferably, the mass ratio of the straw stalks to the liquefying agent is 1: 3-1: 4.
Further preferably, the mass ratio of the p-hydroxyphenylethanol, the polyethylene glycol and the glycerol in the liquefying agent is 1 (1-2) to 2-3.
Preferably, the mass of the catalyst accounts for 5-10% of the mass of the liquefying agent.
(II) a preparation method of the biomass asphalt modifier, which comprises the following steps:
step 1, preliminarily crushing straw stalks to obtain fibrous stalks;
step 2, further crushing the fibrous straws, sieving, drying to constant weight, and cooling to obtain powdery straws;
and 3, adding the powdery straw, a liquefying agent and a catalyst into a reaction kettle, introducing nitrogen into the reaction kettle to discharge air in the reaction kettle, performing liquefaction reaction, discharging gas in the reaction kettle, and cooling to room temperature to obtain the biomass asphalt modifier.
Preferably, in the step 1, the length of the fibrous straw is 0.2-0.5 cm.
Preferably, in step 2, the maximum particle size of the powdered straw is 50 meshes.
Preferably, in the step 2, the drying temperature is 100-110 ℃, and the drying time is 22-26 h.
Preferably, in the step 3, the initial pressure of the reaction kettle is 4-5 MPa.
Preferably, in the step 3, the temperature of the liquefaction reaction is 150-200 ℃, and the time of the liquefaction reaction is 120-180 min.
(III) the biomass modified asphalt comprises the following raw materials: biomass asphalt modifier and matrix asphalt.
Preferably, the mass of the biomass asphalt modifier accounts for 5-20% of the mass of the matrix asphalt.
(IV) a preparation method of biomass modified asphalt, which comprises the following steps:
step 1, heating matrix asphalt for standby;
and 2, adding the biomass asphalt modifier into the matrix asphalt, stirring and developing to obtain the biomass modified asphalt.
Preferably, in the step 1, the heating matrix asphalt is heated to 120-140 ℃.
Preferably, in the step 2, the stirring temperature is 120-135 ℃, and the stirring time is 30-60 min.
Preferably, in the step 2, the development temperature is 120-130 ℃, and the development time is 90-180 min.
Compared with the prior art, the invention has the beneficial effects that:
1) the straw stalk is dry natural straw stalk, is a waste renewable material, has the characteristics of natural degradation, easy recovery and the like, and can be subjected to chemical reaction with a mixture of polyethylene glycol 400, glycerol and p-hydroxyphenylethanol under the action of acid catalysis in a high-temperature and high-pressure environment, so that the natural straw stalk is converted into a dark brown viscous liquid substance with certain reaction activity, namely the biomass asphalt modifier.
2) The method is carried out in a high-temperature and oxygen-free environment, so that high-temperature oxidation and carbonization of the rice straws are avoided; the obtained liquefied product is a thermoplastic material, is brown viscous liquid at normal temperature and has good plasticity; the liquidity of the liquefied product is increased along with the rise of the temperature, and the liquefied product is cooled to normal temperature and then is recovered, and the liquefied product has the properties similar to petroleum asphalt.
3) The invention relates to a road engineering asphalt, belonging to a liquid with complex composition and extremely high viscosity, wherein the product obtained by liquefying straw stalks is used for modifying asphalt, and the obtained biomass modified asphalt has excellent performance and low cost, solves the problems of difficult utilization or low utilization rate of the straw stalks, improves the use value and applicability of waste straws, and widens the application field of waste wood materials.
4) The straw stalk liquefying process has the advantages of low liquefying agent consumption and good reproducibility, and avoids secondary environmental pollution in the liquefying process. Therefore, the biomass asphalt modifier can be effectively popularized, and the dependence of road engineering on petroleum asphalt and natural asphalt is relieved.
5) The biomass asphalt modifier provided by the invention has a remarkable improvement effect on the low-temperature deformability of asphalt on the premise of not changing the high-temperature performance of the asphalt.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a biomass asphalt modifier comprises the following steps:
step 1, primarily crushing the dried straw stalks to obtain fibrous stalks with the length of 0.2-0.5 cm.
And 2, further crushing the fibrous straws by using a miniature plant crusher, sieving the fibrous straws by using a 50-mesh sieve, drying the powdery straws passing through the sieve pores in a drying box at 105 ℃ for 24 hours, and cooling to room temperature to obtain completely dried powdery straws for later use.
And 3, adding 10g of powdery straw, 35g of liquefying agent (the mass ratio of the p-hydroxyphenylethanol to the polyethylene glycol 400 to the glycerol in the liquefying agent is 1:1.5:2.5) and 2.8g of p-toluenesulfonic acid into a reaction kettle, simultaneously opening a vent valve and an exhaust valve of the reaction kettle, and continuously introducing nitrogen for 1min to remove air in the reaction kettle. And closing the exhaust valve, and continuously filling nitrogen until the pressure in the reaction kettle reaches 4.5MPa, and then closing the vent valve. Starting the reaction kettle, carrying out liquefaction reaction at 175 ℃ for 160min, discharging gas in the reaction kettle after the reaction is finished, taking out a liquefied product, and cooling to room temperature to obtain the biomass asphalt modifier.
The obtained biomass asphalt modifier is used for modifying 90# matrix asphalt for road engineering, and the specific modification method comprises the following steps:
step 1, heating the shell 90# base asphalt to 130 ℃ for standby.
And 2, respectively adding 25g and 50g of biomass asphalt modifier into 500g of heated 90# matrix asphalt, mechanically stirring for 40min at 130 ℃ at 600r/min, and then putting into a drying oven at 120 ℃ for 90min to respectively obtain biomass modified asphalt A and modified asphalt B.
The properties of 90# matrix asphalt, modified asphalt A and modified asphalt B, such as softening point, penetration degree, ductility, viscosity and the like, are tested, the specific test method refers to T0604-.
Table 1 results of performance testing
As can be seen from table 1, compared with the base asphalt, the modified asphalt a and the modified asphalt B have no significant change in softening point, but have significantly increased penetration and ductility and reduced viscosity; the biomass asphalt modifier has no influence on the high-temperature performance of the matrix asphalt basically, but can increase the low-temperature deformability of the matrix asphalt. Namely, after the biomass asphalt modifier is doped into the matrix asphalt, the function similar to that of the light component in the matrix asphalt is achieved, so that the asphalt is softened, the consistency is reduced, and the low-temperature anti-cracking performance of the asphalt is better facilitated.
Meanwhile, the penetration degree and the ductility of the modified asphalt B are higher than those of the modified asphalt A, which shows that the penetration degree and the ductility are increased along with the increase of the mixing amount of the biomass asphalt modifier, and the higher the mixing amount of the biomass asphalt modifier is, the more favorable the low-temperature deformation capability of the asphalt is. The viscosity difference between the modified asphalt B and the modified asphalt A is not large, which shows that the influence of the mixing amount of the biomass asphalt modifier on the asphalt viscosity is limited.
In conclusion, the biomass asphalt modifier obtained by the invention has a good modification effect on the low-temperature deformability of the asphalt on the premise of not changing the high-temperature performance of the asphalt, and has a wide application prospect in cold regions.
Example 2
A preparation method of a biomass asphalt modifier comprises the following steps:
step 1, primarily crushing the dried straw stalks to obtain fibrous stalks with the length of 0.2-0.5 cm.
And 2, further crushing the fibrous straws by using a miniature plant crusher, sieving the fibrous straws by using a 50-mesh sieve, drying the powdery straws passing through the sieve pores in a drying box at the temperature of 100 ℃ for 26 hours, and cooling to room temperature to obtain completely dried powdery straws for later use.
And 3, adding 10g of powdery straw, 30g of liquefying agent (the mass ratio of the p-hydroxyphenylethanol to the polyethylene glycol 400 to the glycerol in the liquefying agent is 1:2:3) and 1.5g of p-toluenesulfonic acid into a reaction kettle, simultaneously opening a vent valve and an exhaust valve of the reaction kettle, and continuously introducing nitrogen for 1min to remove air in the reaction kettle. And closing the exhaust valve, and continuously filling nitrogen until the pressure in the reaction kettle reaches 5MPa, and then closing the vent valve. Starting the reaction kettle, carrying out liquefaction reaction for 180min at 150 ℃, discharging gas in the reaction kettle after the reaction is finished, taking out a liquefied product, and cooling to room temperature to obtain the biomass asphalt modifier.
The obtained biomass asphalt modifier is used for modifying 90# matrix asphalt for road engineering, and the specific modification method comprises the following steps:
step 1, heating the shell 90# base asphalt to 120 ℃ for standby.
Step 2, adding a biomass asphalt modifier into the heated 90# matrix asphalt, mechanically stirring for 60min at the temperature of 120 ℃ and at the speed of 600r/min, and then putting the mixture into a drying oven at the temperature of 125 ℃ to develop for 130min to obtain biomass modified asphalt; wherein, the mixing amount of the biomass asphalt modifier is 20 percent of the mass of the 90# base asphalt.
Example 3
A preparation method of a biomass asphalt modifier comprises the following steps:
step 1, primarily crushing the dried straw stalks to obtain fibrous stalks with the length of 0.2-0.5 cm.
And 2, further crushing the fibrous straws by using a miniature plant crusher, sieving the fibrous straws by using a 50-mesh sieve, drying the powdery straws passing through the sieve pores in a drying box at the temperature of 110 ℃ for 22 hours, and cooling to room temperature to obtain completely dried powdery straws for later use.
And 3, adding 10g of powdery straw, 40g of liquefying agent (the mass ratio of the p-hydroxyphenylethanol to the polyethylene glycol 400 to the glycerol in the liquefying agent is 1:1:2) and 4g of p-toluenesulfonic acid into the reaction kettle, simultaneously opening a vent valve and an exhaust valve of the reaction kettle, and continuously introducing nitrogen for 1min to remove air in the reaction kettle. And closing the exhaust valve, and continuously filling nitrogen until the pressure in the reaction kettle reaches 4MPa, and then closing the vent valve. Starting the reaction kettle, carrying out liquefaction reaction at 200 ℃ for 120min, discharging gas in the reaction kettle after the reaction is finished, taking out a liquefied product, and cooling to room temperature to obtain the biomass asphalt modifier.
The obtained biomass asphalt modifier is used for modifying 90# matrix asphalt for road engineering, and the specific modification method comprises the following steps:
step 1, heating the shell 90# base asphalt to 140 ℃ for later use.
Step 2, adding a biomass asphalt modifier into the heated 90# matrix asphalt, mechanically stirring for 45min at 120 ℃ at 600r/min, and then putting the mixture into a drying oven at 130 ℃ to develop for 90min to obtain biomass modified asphalt; wherein, the mixing amount of the biomass asphalt modifier is 12.5 percent of the mass of the 90# base asphalt.
Example 4
A preparation method of a biomass asphalt modifier comprises the following steps:
step 1, primarily crushing the dried straw stalks to obtain fibrous stalks with the length of 0.2-0.5 cm.
And 2, further crushing the fibrous straws by using a miniature plant crusher, sieving the fibrous straws by using a 50-mesh sieve, drying the powdery straws passing through the sieve pores in a drying box at 105 ℃ for 24 hours, and cooling to room temperature to obtain completely dried powdery straws for later use.
And 3, adding 10g of powdery straw, 40g of liquefying agent (the mass ratio of the p-hydroxyphenylethanol to the polyethylene glycol 400 to the glycerol in the liquefying agent is 1:1:3) and 2g of p-toluenesulfonic acid into the reaction kettle, simultaneously opening a vent valve and an exhaust valve of the reaction kettle, and continuously introducing nitrogen for 1min to remove air in the reaction kettle. And closing the exhaust valve, and continuously filling nitrogen until the pressure in the reaction kettle reaches 4.5MPa, and then closing the vent valve. Starting the reaction kettle, carrying out liquefaction reaction at 200 ℃ for 160min, discharging gas in the reaction kettle after the reaction is finished, taking out a liquefied product, and cooling to room temperature to obtain the biomass asphalt modifier.
The obtained biomass asphalt modifier is used for modifying 90# matrix asphalt for road engineering, and the specific modification method comprises the following steps:
step 1, heating the shell 90# base asphalt to 130 ℃ for standby.
Step 2, adding a biomass asphalt modifier into the heated 90# matrix asphalt, mechanically stirring for 30min at 135 ℃ at 600r/min, and then putting the mixture into a drying oven at 120 ℃ to develop for 180min to obtain biomass modified asphalt; wherein, the mixing amount of the biomass asphalt modifier is 5 percent of the mass of the 90# base asphalt.
In the above embodiments, the reaction kettle is a high-temperature high-pressure reaction kettle, which can provide a high-temperature and high-pressure reaction environment to realize solid-solid, solid-liquid and liquid-liquid reactions.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (3)
1. The biomass modified asphalt is characterized by comprising the following raw materials: matrix asphalt and biomass asphalt modifier; wherein the content of the first and second substances,
the preparation method of the biomass asphalt modifier comprises the following steps:
step 1, preliminarily crushing straw stalks to obtain fibrous stalks;
step 2, further crushing the fibrous straws, sieving, drying to constant weight, and cooling to obtain powdery straws;
step 3, adding the powdery straw, a liquefying agent and a catalyst into a reaction kettle, introducing nitrogen into the reaction kettle to discharge air in the reaction kettle, performing liquefaction reaction, discharging gas in the reaction kettle, and cooling to room temperature to obtain a biomass asphalt modifier; the initial pressure of the reaction kettle is 4-5 MPa; the temperature of the liquefaction reaction is 150-200 ℃, and the time of the liquefaction reaction is 120-180 min;
the biomass asphalt modifier comprises the following raw materials: straw stalks, a liquefying agent and a catalyst; wherein:
the liquefying agent is p-hydroxyphenylethanol, polyethylene glycol and glycerol; the catalyst is toluenesulfonic acid;
the mass ratio of the straw stalks to the liquefying agent is 1: 3-1: 4, and the mass of the catalyst accounts for 5-10% of that of the liquefying agent; wherein the mass ratio of the p-hydroxyphenylethanol to the polyethylene glycol to the glycerol in the liquefying agent is 1: 1-2: 2-3;
the mass of the biomass asphalt modifier accounts for 5-20% of the mass of the matrix asphalt;
the maximum grain size of the powdery straw is 50 meshes; the drying temperature is 100-110 ℃, and the drying time is 22-26 h.
2. The biomass modified asphalt according to claim 1, wherein in the step 1, the length of the fibrous straw is 0.2-0.5 cm.
3. A method of preparing the biomass-modified asphalt of claim 1, comprising the steps of:
step 1, heating matrix asphalt for standby;
step 2, adding a biomass asphalt modifier into the matrix asphalt, stirring and developing to obtain biomass modified asphalt;
the stirring temperature is 120-135 ℃, and the stirring time is 30-60 min; the development temperature is 120-130 ℃, and the development time is 90-180 min.
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| CN106279598B (en) * | 2016-08-22 | 2018-08-14 | 长安大学 | A kind of wooden base asphalt modifier and preparation method thereof |
| CN106317919A (en) * | 2016-08-22 | 2017-01-11 | 长安大学 | Environment-friendly asphalt modifier and preparation method thereof |
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