CN104388108B - Method for preparing catalytically hydrogenated biological asphalt - Google Patents

Abstract

The invention relates to a method for preparing catalytically hydrogenated bio-asphalt, comprising the following steps: 1) hydrogenating biomass pyrolysis oil under the action of a catalyst; 2) standing the product obtained in step 1), separating it, and taking the upper layer Extracting the oil phase to obtain an extract; 3) dehydrating and oxidizing the extract to obtain bio-asphalt. By adopting the preparation method of the present invention, not only the heavy components of biomass oil can be effectively utilized, turning waste into treasure, but also the catalytic hydrogenation of bio-asphalt can make the performance of bio-asphalt more stable and improve the quality of bio-asphalt. The bio-asphalt obtained by the preparation method of the present invention can reduce the demand of asphalt pavements for petroleum asphalt and alleviate the pressure brought about by the shortage of resources. At the same time, the bio-asphalt belongs to renewable resources and can realize the sustainable development of asphalt and roads.

Description

A kind of preparation method of catalytic hydrogenation bio-asphalt

technical field

The invention relates to a method for preparing catalytic hydrogenation bio-asphalt, which belongs to the technical field of asphalt materials.

Background technique

Biomass, as the main energy source that can be recycled, has attracted attention at home and abroad in recent years, especially with the continuous development of biomass pyrolysis technology, it has promoted the production of many biomass pyrolysis oil companies.

On the one hand, the current main use of biomass pyrolysis oil is to burn directly as primary fuel or to refine biodiesel. The former has a low calorific value due to the high moisture content of biomass pyrolysis oil, which in turn affects the selling price of the oil. , increasing the operating pressure of biomass pyrolysis oil enterprises. The latter has poor thermal stability due to the poor thermal stability of biomass pyrolysis oil, resulting in poor thermal stability of biodiesel refined from it, which requires further processing to barely meet the requirements, resulting in excessive cost of biomass diesel High, which in turn affects the demand for biomass pyrolysis oil, so it is urgent to expand the utilization of biomass pyrolysis oil.

On the other hand, with the rapid development of the national economy, the contradiction between human demand and energy supply has become increasingly serious. Petroleum, as the main fossil raw material, not only provides the main energy consumed by human beings, but also the remaining asphalt after refining is a necessary material for the road industry . However, with the continuous consumption of oil, especially the continuous reduction of high-quality oil sources, the contradiction between supply and demand of asphalt has been increasing, and the price of asphalt has been rising, which has caused great troubles to the development of the road industry. Since 2011, our research group has carried out a lot of research work on the preparation of bio-asphalt from biomass pyrolysis oil, and has published invention patents "Modified bio-asphalt material, bio-asphalt mixture, its preparation method and application", "Bio-asphalt , Bio-asphalt Composition and Its Preparation Method" and "A Bio-asphalt and Its Preparation Method", but in the research, it was found that the bio-asphalt prepared directly from biomass pyrolysis oil had poor low-temperature ductility to varying degrees. Therefore, how to obtain a preparation method to improve the low-temperature performance of bio-asphalt has become one of the problems that need to be solved urgently.

Contents of the invention

In order to solve the above problems, the present invention proposes a new bio-asphalt preparation process, the low-temperature ductility of the obtained bio-asphalt is significantly improved, and it has good thermal stability and road performance, thereby reducing the demand for petroleum asphalt on asphalt roads , to achieve sustainable development of asphalt and asphalt roads.

In order to achieve the above object, the present invention adopts the following technical solutions:

A method for preparing catalytically hydrogenated bio-asphalt, comprising the steps of:

1) The biomass pyrolysis oil undergoes a hydrogenation reaction under the action of a catalyst;

2) The product obtained in step 1) is left to stand, separated, and the upper oil phase is extracted to obtain the extract;

3) Dehydrating and oxidizing the extract to obtain bio-asphalt.

In the above preparation method, in step 1), the amount of the catalyst added is 0.5%-10% of the mass of the biomass pyrolysis oil, preferably 5%.

In the above preparation method, in step 1), the hydrogenation reaction temperature is 150-300°C, preferably 200°C.

In the above preparation method, in step 1), the hydrogenation reaction time is 30-90 min; preferably 60 min.

In the above preparation method, in step 1), the hydrogenation reaction pressure is 4-10 MPa, preferably 6 MPa.

In the above preparation method, in step 1), the catalyst is a platinum-based catalyst or an iron-based catalyst, preferably a platinum-based catalyst, more preferably Pt/γ-Al ₂ O ₃ .

In the above preparation method, in step 1), the biomass pyrolysis oil is an oily product obtained after pyrolysis of one or more of corn stalks, rice husks, wood chips or bamboo chips.

In the above preparation method, in step 1), the reaction pressure is controlled by the amount of hydrogen gas introduced.

In the above preparation method, in step 2), the extraction solvent is water.

In the above preparation method, in step 2), the extraction process is to mix and stir the upper layer oil and water at a volume ratio of 1:3-10 at 5-30°C, and then filter or centrifuge to obtain a water-insoluble extract.

In the above preparation method, in step 3), the dehydration oxidation temperature is 90-110°C.

In the above preparation method, in step 3), the dehydration oxidation time is 30-90min.

The present invention also provides the biological asphalt obtained by the above preparation method.

By adopting the preparation method of the present invention, not only the heavy components of biomass oil can be effectively utilized, turning waste into treasure, but also the catalytic hydrogenation of bio-asphalt can make the performance of bio-asphalt more stable and improve the quality of bio-asphalt. The bio-asphalt obtained by the preparation method of the present invention can reduce the demand of asphalt pavements for petroleum asphalt and alleviate the pressure brought about by the shortage of resources. At the same time, the bio-asphalt belongs to renewable resources and can realize the sustainable development of asphalt and roads.

detailed description

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

The raw materials used in this embodiment are all commercially available products.

Example 1 A preparation method of catalytic hydrogenation bio-asphalt

A method for preparing catalytically hydrogenated bio-asphalt, comprising the steps of:

1) In the Parr high-pressure reactor in the United States, the pressure inside the reactor is controlled by passing hydrogen to 10MPa, and under the condition of 150°C, the biomass pyrolysis oil undergoes a hydrogenation reaction under the action of the catalyst Pt/γ-Al ₂ O ₃ , and the reaction time is 90 minutes;

Among them, biomass pyrolysis oil is an oily product obtained after pyrolysis of corn stalks, which was purchased from a bioenergy company.

Catalyst selects commercially available product for use.

Wherein, the addition amount of the catalyst is 10% of the mass of the biomass pyrolysis oil.

2) Leave the product obtained in step 1) to stand, the upper layer is the oil phase, and the lower layer is the water phase. After separation, take the upper layer oil phase and water at a volume ratio of 1:10, mix and stir at 5°C, and filter and separate to obtain water insoluble extract.

3) The extract was dehydrated and oxidized at a temperature of 110° C. for 30 minutes to obtain catalytic hydrogenation bio-asphalt 1 .

Example 2 A preparation method of catalytic hydrogenation bio-asphalt

1) In the Parr high-pressure reactor in the United States, hydrogen was introduced to control the internal pressure of the reactor to 4MPa, and under the condition of 300°C, the biomass pyrolysis oil underwent hydrogenation reaction under the action of the catalyst Pt/γ-Al ₂ O ₃ , and the reaction time was 30 minutes;

Among them, biomass pyrolysis oil is an oily product obtained after pyrolysis of wood chips, which was purchased from a bioenergy company.

Catalyst selects commercially available product for use.

Wherein, the addition amount of the catalyst is 0.5% of the mass of the biomass pyrolysis oil.

2) Put the product obtained in step 1) to stand, the upper layer is the oil phase, and the lower layer is the water phase. After separation, take the upper layer oil phase and water at a volume ratio of 1:3 and mix and stir at 30°C, and then filter and separate to obtain water insoluble extract.

3) The extract was dehydrated and oxidized at a temperature of 110° C. for 30 minutes to obtain catalytic hydrogenation bio-asphalt 2 .

Example 3 A preparation method of catalytic hydrogenation bio-asphalt

1) In the Parr high-pressure reactor in the United States, hydrogen was introduced to control the pressure inside the reactor to 6MPa. Under the condition of 200°C, the biomass pyrolysis oil underwent hydrogenation reaction under the action of the catalyst Pt/γ-Al ₂ O ₃ , and the reaction time was 60 minutes;

Among them, biomass pyrolysis oil is an oily product obtained after pyrolysis of bamboo chips, which was purchased from a bioenergy company.

Catalyst selects commercially available product for use.

Wherein, the amount of catalyst added is 5% of the mass of biomass pyrolysis oil.

2) Leave the product obtained in step 1) to stand, the upper layer is the oil phase, and the lower layer is the water phase. After separation, take the upper layer oil phase and water at a volume ratio of 1:10, mix and stir at 5°C, and filter and separate to obtain water insoluble extract.

3) The extract was dehydrated and oxidized at a temperature of 90° C. for 90 minutes to obtain catalytic hydrogenation bio-asphalt 3 .

Example 4 A preparation method of catalytic hydrogenation bio-asphalt

1) In the Parr high-pressure reactor in the United States, hydrogen gas is introduced to control the internal pressure of 6MPa, and under the condition of 200°C, the biomass pyrolysis oil undergoes hydrogenation reaction under the action of the catalyst _FeS2 , and the reaction time is 60min;

Among them, biomass pyrolysis oil is an oily product obtained after pyrolysis of bamboo chips, which was purchased from a bioenergy company.

Catalyst selects commercially available product for use.

Wherein, the amount of catalyst added is 5% of the mass of biomass pyrolysis oil.

2) The product obtained in step 1) is left to stand, the upper layer is the oil phase, and the lower layer is the water phase. After separation, the upper layer oil phase and water are mixed and stirred at 15°C at a volume ratio of 1:6, and the water is separated by filtration. insoluble extract.

3) The extract was dehydrated and oxidized at a temperature of 100°C for 60 minutes to obtain catalytic hydrogenation bio-pitch 4.

Comparative example A kind of preparation method of bio-asphalt

1) The biomass pyrolysis oil and water are mixed and stirred at a volume ratio of 1:10 at 5°C, and separated by filtration to obtain a water-insoluble extract.

Among them, biomass pyrolysis oil is an oily product obtained after pyrolysis of bamboo chips, which was purchased from a bioenergy company.

2) The extract was dehydrated and oxidized at a temperature of 90°C for 90 minutes to obtain bio-pitch 5.

Performance test of bio-asphalt

1) Performance tests were carried out on the bio-asphalt obtained in Examples 1-4 and Comparative Examples, and the results are shown in Table 1.

Table 1 Road performance of bio-asphalt

It can be seen from Table 1 that compared with the comparative example, the bio-asphalt obtained in Examples 1-4 has significantly increased penetration, increased softening point, and significantly increased ductility. 》The requirements of No. 90 C grade petroleum asphalt in JTGF40-2004, especially in Example 3, the resulting bio-asphalt can meet the requirements of No. 90 A grade petroleum asphalt. It can be seen that the bio-asphalt obtained by adopting the preparation process of the present invention has better road performance, improved quality, and significantly improves the low-temperature ductility of the existing bio-asphalt.

Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of catalytic hydrogenation Biological asphalt, it is characterised in that comprise the steps：

1) be there is into hydrogenation reaction under catalyst action in biomass pyrolysis oil；

2) by step 1) products therefrom standing, separate, take upper oil phase extraction, obtain extract；

3) extract dehydration oxidation is obtained into Biological asphalt；

Step 1) in, the 0.5%-10% of the catalyst charge form biomass pyrolysis oil quality；The hydrogenation reaction temperature For 150-300 DEG C；The hydrogenation reaction time is 30-90min；The hydrogenation reaction pressure is 4-10MPa；The catalyst is Platinum group catalyst or Fe-series catalyst；

Step 3) in, the dehydration oxidizing temperature is 90-110 DEG C；The dehydration oxidization time is 30-90min.

2. the preparation method of Biological asphalt according to claim 1, it is characterised in that step 1) in, the catalyst adds Enter the 5% of amount form biomass pyrolysis oil quality.

3. the preparation method of Biological asphalt according to claim 1, it is characterised in that step 1) in, the hydrogenation reaction Temperature is 200 DEG C.

4. the preparation method of Biological asphalt according to claim 1, it is characterised in that step 1) in, the hydrogenation reaction Time is 60min.

5. the preparation method of Biological asphalt according to claim 1, it is characterised in that step 1) in, the hydrogenation reaction Pressure is 6MPa.

6. the preparation method of Biological asphalt according to claim 1, it is characterised in that step 1) in, the catalyst is Platinum group catalyst.

7. the preparation method of Biological asphalt according to claim 6, it is characterised in that step 1) in, the catalyst is Pt/γ-Al₂O₃。

8. the preparation method of Biological asphalt according to claim 1, it is characterised in that step 2) in, the extractant For water.

9. the preparation method of Biological asphalt according to claim 8, it is characterised in that step 2) in, the extraction process For：By upper oil phase and water with 1:The volume ratio of 3-10 is mixed in 5-30 DEG C, and Jing is filtered or to be centrifugally separating to obtain water insoluble Extract.

10. the Biological asphalt that the arbitrary preparation method of claim 1-9 is obtained.