CN-117965190-B - Method for preparing bio-fuel oil by in-situ hydrogenation catalytic upgrading of sludge hydro-thermal crude oil

Abstract

The invention discloses a method for preparing bio-fuel oil by in-situ hydrocatalysis upgrading of sludge hydro-thermal crude oil, and relates to the field of sludge recycling treatment. According to the method for preparing the biofuel through in-situ hydrocatalytic upgrading of the sludge hydrothermal crude oil, provided by the invention, the long-chain alkane is added into the sludge hydrothermal crude oil to adjust the viscosity, so that the sludge hydrothermal crude oil can be fully mixed with the liquid hydrogen supply reagent and subjected to hydrodeoxygenation upgrading reaction, but both the long-chain alkane and the liquid hydrogen supply reagent not only influence the viscosity of the biofuel obtained through upgrading of the sludge hydrothermal crude oil, but also influence the calorific value of the biological fuel oil, so that the mass ratio between the sludge hydrothermal crude oil and the two reagents needs to be adjusted to be the sludge hydrothermal crude oil, wherein the hydrogen supply reagent is long-chain alkane=1 (1-10): 1-20.

Inventors

• YANG LE
• Liao Fanhui

Assignees

• 中山大学

Dates

Publication Date

20260508

Application Date

20231229

Claims (4)

1. 1. The method for preparing the biofuel from the sludge hydro-thermal crude oil through in-situ hydro-catalytic upgrading is characterized by comprising the following steps of: The sludge is subjected to hydrothermal treatment to obtain sludge hydrothermal crude oil, the sludge hydrothermal crude oil, a catalyst, a hydrogen supply reagent and long-chain alkane are fully mixed, and catalytic upgrading reaction of the sludge hydrothermal crude oil is carried out at a reaction temperature of 200-350 ℃, so that bio-fuel oil can be obtained after the reaction is completed; The mass ratio of the sludge hydro-thermal crude oil, the hydrogen supply reagent and the long-chain alkane is 1 (3-5) to 6; the hydrogen supply reagent is isopropanol; The long-chain alkane is n-dodecane.
2. 2. The method for preparing the biofuel from the sludge hydro-thermal crude oil through in-situ hydro-catalytic upgrading is characterized in that the mass ratio of the sludge hydro-thermal crude oil to the catalyst is 1 (0.05-1).
3. 3. The method for preparing the biofuel from the sludge hydro-thermal crude oil through in-situ hydro-catalytic upgrading is characterized in that the catalytic upgrading reaction of the sludge hydro-thermal crude oil is carried out for 1-12 hours.
4. 4. The method for preparing the biofuel from the sludge hydro-thermal crude oil through in-situ hydro-catalytic upgrading is characterized in that the catalytic upgrading reaction of the sludge hydro-thermal crude oil is carried out at the reaction temperature of 250-330 ℃.

Description

Method for preparing bio-fuel oil by in-situ hydrogenation catalytic upgrading of sludge hydro-thermal crude oil Technical Field The invention relates to the field of sludge recycling treatment, in particular to a method for preparing bio-fuel oil by in-situ hydrocatalytic upgrading of sludge hydro-thermal crude oil. Background With the development of socioeconomic and urban, the output of municipal sludge has increased year by year. The sludge contains organic matter components, and the organic matter components are recycled, so that the recycling of the sludge can be realized, and the pollution to the environment can be reduced. However, the current treatment methods for municipal sludge mainly comprise incineration and landfill, and means for recycling organic matters in the sludge are still to be developed. The sludge can be subjected to hydro-thermal treatment to obtain sludge hydro-thermal crude oil, wherein the main components are organic matter mixtures containing three elements of carbon, hydrogen and oxygen. The sludge hydro-thermal crude oil can be subjected to hydrodeoxygenation reaction under the catalysis of the catalyst, so that the quality is improved, and the sludge hydro-thermal crude oil is further converted into the bio-fuel oil with low oxygen content and high combustion value. However, in order to ensure that the hydrodeoxygenation reaction of the sludge hydro-thermal crude oil can be smoothly carried out, the hydrogen is always introduced into a reaction system, the initial hydrogen pressure is ensured to be 1-3 MPa, the reaction is usually carried out at about 300 ℃, the pressure of the reaction system can be increased to be twice or even more than the initial hydrogen pressure at the temperature, the pressure resistance requirement on production equipment is very high, and the treatment cost of the sludge hydro-thermal crude oil is increased by phase change. The prior art discloses a method for preparing bio-oil based on supercritical liquefaction of municipal sludge by in-situ hydrogen supply, which adopts methanol, ethanol and the like as a solvent and a hydrogen supply reagent simultaneously, directly liquefies the sludge by hydrothermal method to obtain the bio-oil, and explores the influence of the type of the hydrogen supply reagent on various performances of the bio-oil. However, the sludge hydro-thermal crude oil has complex components and high viscosity, the liquid is adopted to replace gas for supplying hydrogen source, and a large amount of liquid hydrogen-supplying reagent is required to be added to promote the hydrodeoxygenation reaction of the sludge hydro-thermal crude oil to be carried out smoothly, so that the ratio of the sludge hydro-thermal crude oil obtained by upgrading in a reaction system is reduced, and the calorific value of the finally obtained biofuel oil is reduced, and can only reach 36.32MJ/kg at most. Disclosure of Invention In order to solve the problem that the prior art cannot adopt a liquid hydrogen supply reagent to prepare the biofuel with high heat value from the sludge hydro-thermal crude oil, the invention provides a method for preparing the biofuel by in-situ hydro-catalytic upgrading of the sludge hydro-thermal crude oil, long-chain alkane is added into a system to adjust viscosity, and the viscosity of a reaction system can be in a proper range by adjusting the mass ratio of the liquid hydrogen supply reagent, the sludge hydro-thermal crude oil and the long-chain alkane, so that the sludge hydro-thermal crude oil can be fully contacted with the hydrogen supply reagent, and the sludge hydro-thermal crude oil can be extracted from the liquid hydrogen supply reagent to carry out hydro-deoxygenation upgrading reaction, so that the finally obtained biofuel has excellent heat value. The above object of the present invention is achieved by the following technical scheme: A method for preparing bio-fuel oil by in-situ hydrocatalytic upgrading of sludge hydro-thermal crude oil comprises the following steps: Fully mixing the sludge hydro-thermal crude oil, a catalyst, a hydrogen supply reagent and long-chain alkane, and carrying out catalytic upgrading reaction of the sludge hydro-thermal crude oil at a reaction temperature of 200-350 ℃, wherein the bio-fuel oil can be obtained after the reaction is completed; The mass ratio of the sludge hydro-thermal crude oil, the hydrogen supply reagent and the long-chain alkane is 1 (1-10) (1-20); The hydrogen supply reagent is fatty alcohol and/or fatty acid with carbon number of 1-12; the long-chain alkane is straight-chain alkane with 10-20 carbon atoms. In the specific embodiment of the invention, the sludge hydro-thermal crude oil can be prepared by carrying out a hydro-thermal reaction on sludge at 300-400 ℃ for 0.5-2 hours. In the specific embodiment of the invention, the mass ratio of water to sludge in the reaction system can be 10-15 mL/g. In a specific embodiment of the present invention, the sludge