阅读说明：本技术 一种液态催化剂生产第二代生物柴油的方法 (Method for producing second-generation biodiesel by liquid catalyst ) 是由 陈松 王康县 李广慈 李学兵 林冠楠 范芮堃 宋彦超 王�忠 于 2020-10-10 设计创作，主要内容包括：本发明公开了一种液态催化剂生产第二代生物柴油的方法,该方法采用含有一种和/或多种过渡金属的液态催化剂,在加氢条件下利用连续式悬浮床反应器,将生物质原料转化为高十六烷值生物柴油。和传统的固定床加氢工艺相比,采用悬浮床加氢工艺能够显著提高对废弃油脂原料的处理能力,有效避免了固体颗粒催化剂破损失活的问题。该方法适用于包括植物油和/或动物脂肪及其它可再生生物质油脂的加氢处理,生物柴油产品十六烷值普遍在85以上,具有催化剂用量少、催化效率高、便于处理废渣等特点,特别适合于第二代生物柴油的大规模推广生产。(The invention discloses a method for producing second-generation biodiesel by using a liquid catalyst, which adopts the liquid catalyst containing one and/or a plurality of transition metals and converts a biomass raw material into the biodiesel with high cetane number by using a continuous suspension bed reactor under the hydrogenation condition. Compared with the traditional fixed bed hydrogenation process, the suspended bed hydrogenation process can obviously improve the processing capacity of the waste oil raw material, and effectively avoids the problem of damage and inactivation of the solid particle catalyst. The method is suitable for the hydrotreatment of vegetable oil and/or animal fat and other renewable biomass grease, the cetane number of the biodiesel product is over 85 commonly, and the method has the characteristics of small catalyst consumption, high catalytic efficiency, convenience in waste residue treatment and the like, and is particularly suitable for large-scale popularization and production of second-generation biodiesel.)

1. A method for producing second-generation biodiesel by using a liquid catalyst is characterized by comprising the following steps: the biomass raw material is converted into second-generation biodiesel with high cetane number by adopting a liquid catalyst containing one or more transition metals and under the hydrogenation condition in the presence of hydrogen.

2. The method for producing the second-generation biodiesel by using the liquid catalyst according to claim 1, wherein the liquid catalyst comprises the following components: the liquid catalyst comprises a liquid artificially synthesized catalyst of VB, VIB and VIII element components.

3. The method for producing the second-generation biodiesel by using the liquid catalyst according to claim 1, wherein the liquid catalyst comprises the following components: the hydrogenation condition is a hydrogenation process in which the reaction pressure is 2-20 MPa of hydrogen pressure, the reaction temperature is 200-400 ℃, hydrogen, a liquid catalyst and the raw material pass through a continuous hydrogenation reactor together and are kept for reaction residence time of 0.1-5 hours, preferably 0.3-3 hours.

4. The method for producing the second-generation biodiesel by using the liquid catalyst according to claim 1, wherein the liquid catalyst comprises the following components: the biomass raw material comprises vegetable oil and/or animal fat and other renewable biomass grease, and the second-generation biodiesel refers to diesel fraction with the cetane number not less than 70 prepared by hydrodeoxygenation.

5. The method for producing the second-generation biodiesel by using the liquid catalyst according to claim 1, wherein the liquid catalyst comprises the following components: the continuous hydrogenation reactor comprises a suspension slurry bed, a suspension boiling bed or a full back-mixing suspension bed hydrogenation reactor.

Technical Field

The invention relates to a method for producing second-generation biodiesel, belonging to the field of renewable energy sources.

Background

The continuous increase of human industrialization and globalization process leads to the dramatic increase of global demand on fossil energy, the development of energy directly affects the sustainable development, stability and the like of various countries, in order to relieve the global dependence on fossil fuel, solve environmental problems and climatic problems, the development and development of renewable new energy are not slow, and the biomass energy has the advantages of being renewable, clean, pollution-free, wide in source and the like, and is considered as renewable energy with great potential and application prospect.

Biomass energy has wide sources and various varieties, and oil and fat are important one of the biomass energy. At present, the development and utilization means of grease is generally to prepare fatty acid methyl ester through ester exchange or enzyme catalysis, and the fatty acid methyl ester is a main component of first-generation biodiesel, but the fatty acid methyl ester has the defects of large viscosity and poor low-temperature fluidity, and the existence of oxygen atoms in the fatty acid methyl ester causes higher freezing point, poor fluidity and lower heat value, so that the application range of the fatty acid methyl ester is limited. Subsequent development has therefore consisted in converting the first generation biodiesel to paraffinic biodiesel (second generation biodiesel) by various hydrodeoxygenation means.

The production of the second generation biodiesel is mainly developed on the basis of the oxygenation refining of the petroleum diesel, adopts the raw materials which are completely the same as the first generation, and mainly comprises animal and vegetable oil, fatty acid and the like. Compared with fatty acid methyl ester, the second-generation biodiesel is completely the same as petroleum diesel in chemical structure, has low content of O, S and other elements, has similar Dian degree, lower density and higher cetane number as diesel, has higher calorific value of the same mass unit, good compatibility with the petroleum diesel, wider application range and can be added into the petroleum diesel in a larger proportion. Therefore, the fatty acid methyl ester is further converted into the second-generation biodiesel by a catalytic means, and the method has important significance for improving the quality and the application range of the biomass fuel.

The core of the preparation of the second generation biodiesel of alkanes by the hydrodeoxygenation of fatty acid methyl ester is to find an efficient hydrodeoxygenation catalyst. In addition to high efficiency and high activity, the hydrodeoxygenation catalyst designed by research should have excellent thermal stability, hydrothermal stability and practical operation stability, so as to be expected for further industrial application. At present, the hydrodeoxygenation catalyst is mainly a load type catalyst of transition metal and noble metal, either sulfur pollution is easily caused to products and hydrogen consumption in the catalytic hydrogenation process is large, or the cost is high, the industrial popularization is not facilitated, and the heterogeneous catalysts generally have the problems of easy abrasion and inactivation and easy pulverization of treated biological oil, so that the large-scale production of the biodiesel is influenced.

Disclosure of Invention

In view of the problems of easy abrasion and inactivation and easy pulverization of the treated biological grease of the solid catalyst used for producing the second-generation biodiesel at present, the invention aims to provide a method for synthesizing the second-generation biodiesel by adopting a liquid catalyst.

In order to achieve the purpose, the invention adopts the technical scheme that:

provides a method for producing second-generation biodiesel by using a liquid catalyst, which is characterized by comprising the following steps: the biomass raw material is converted into second-generation biodiesel with high cetane number by adopting a liquid catalyst containing one or more transition metals and under the hydrogenation condition in the presence of hydrogen.

The liquid catalyst is a liquid artificially synthesized catalyst containing VB, VIB and VIII element components.

The hydrogenation condition is a hydrogenation process in which the reaction pressure is 2-20 MPa of hydrogen pressure, the reaction temperature is 200-400 ℃, hydrogen, a liquid catalyst and the raw material pass through a continuous hydrogenation reactor together and are kept for 0.1-5 hours, preferably 0.3-3 hours of reaction residence time.

The biomass raw material comprises vegetable oil and/or animal fat and other renewable biomass grease, and the second-generation biodiesel refers to diesel fraction with the cetane number not less than 70 prepared by hydrodeoxygenation.

The continuous hydrogenation reactor comprises a suspension slurry bed, a suspension boiling bed or a full back-mixing suspension bed hydrogenation reactor.

Compared with the prior art, the invention has the following advantages:

the adoption of the liquid homogeneous catalyst can increase the contact chance of materials and the active center of the catalyst, greatly improve the catalytic efficiency, greatly reduce the using amount of the catalyst and reduce the amount of waste residues to be treated after the reaction is finished.

Detailed Description

The present invention will be further explained with reference to specific examples, but the present invention is not limited to the following embodiments.

Example 1

Mixing 100g of soybean oil with 0.06g of liquid catalyst (containing Co and Mo components), passing the mixture and hydrogen through a suspension slurry bed reactor together, keeping the reaction pressure at 11MPa and the reaction temperature at 360 ℃ for 0.9h, keeping the reaction for a retention time, separating hydrogenation residues after the reaction, and collecting a liquid hydrogenation product. The yield of the diesel oil component is 80 percent, and the density is 0.7826g/cm³The sulfur content was 4.2mg/L, and the cetane number was 90.

Example 2

Mixing 120g of illegal cooking oil with 0.08g of liquid catalyst (containing Nb and Ni components), passing through a suspension boiling bed reactor together with hydrogen at the reaction pressure of 8MPa and the reaction temperature of 350 ℃, keeping the reaction temperature for 1.2h, separating hydrogenation residues after the reaction, and collecting liquid hydrogenation products. The yield of the diesel oil component is 78 percent, and the density is 0.7778g/cm³The sulfur content was 5.5mg/L, and the cetane number was 87.

Example 3

Mixing 150g of palm oil with 0.12g of liquid catalyst (containing W, Ni components), passing through a full back-mixing suspension bed reactor together with hydrogen at the reaction pressure of 8MPa and the reaction temperature of 380 ℃ for 2h, separating hydrogenation residues after reaction, and collecting liquid hydrogenation products. The yield of the diesel oil component is 76 percent, and the density is 0.7686g/cm³The sulfur content was 3.3mg/L, and the cetane number was 88.

Example 4

Mixing 100g of soybean oil with 0.06g of liquid catalyst (containing Co and W components), passing the mixture and hydrogen through a suspension slurry bed reactor together, keeping the reaction pressure at 11MPa and the reaction temperature at 360 ℃ for 0.9h, separating hydrogenation residues after the reaction, and collecting liquid hydrogenation products. The yield of the diesel oil component is 79 percent, and the density is 0.7846g/cm³Sulfur content4.4mg/L and a cetane number of 90.

Example 5

Mixing 120g of soybean oil with 0.08g of liquid catalyst (containing Ni, Mo and W components), passing through a suspension slurry bed reactor together with hydrogen at the reaction pressure of 11MPa and the reaction temperature of 350 ℃, keeping the reaction temperature for 1.6h, separating hydrogenation residues after the reaction, and collecting liquid hydrogenation products. The yield of the diesel oil component is 80 percent, and the density is 0.7821g/cm³The sulfur content was 3.8mg/L, and the cetane number was 91.