阅读说明：本技术 一种过热水蒸气辅助生物油脂催化裂解的方法 (Method for assisting biological oil catalytic cracking by superheated steam ) 是由 徐俊明 龙锋 蒋霞 蒋剑春 翟巧龙 于 2020-03-11 设计创作，主要内容包括：本发明公开了一种过热水蒸气辅助生物油脂催化裂解的方法,属于生物质能源高值化利用技术领域。在过热水蒸气的辅助下对生物油脂进行催化裂解制备烯烃含量较高的生物燃油；所述过热水蒸气的温度为500～600℃。本发明催化裂解过程中使用过热水蒸气一方面为生物油脂的催化裂解提供热源,过热水蒸气传热性能较好,有利于提高生物油脂的催化裂解转化率；另一方面过热水蒸气热解产生质子氢,可以辅助烯烃的形成,提高烯烃和烷烃的得率。(The invention discloses a superheated steam assisted biological oil catalytic cracking method, and belongs to the technical field of high-value utilization of biomass energy. Carrying out catalytic cracking on the biological grease under the assistance of superheated steam to prepare the biological fuel oil with higher olefin content; the temperature of the superheated steam is 500-600 ℃. The superheated steam is used in the catalytic cracking process, so that on one hand, a heat source is provided for the catalytic cracking of the biological oil, the superheated steam has good heat transfer performance, and the catalytic cracking conversion rate of the biological oil is improved; on the other hand, the superheated steam is pyrolyzed to generate proton hydrogen, so that the formation of olefin can be assisted, and the yield of olefin and alkane is improved.)

1. A superheated steam-assisted biological oil catalytic cracking method is characterized in that biological oil is catalytically cracked under the assistance of superheated steam to prepare biofuel oil with high olefin content; the temperature of the superheated steam is 500-600 ℃.

2. A superheated steam-assisted biological oil and fat catalytic cracking method as claimed in claim 1, which is characterized by comprising the following steps:

(1) adding a catalyst into a catalyst cage of a cracking reaction kettle, and starting stirring;

(2) the cracking reaction kettle is hermetically connected with a superheated steam generating device, a gas valve on the superheated steam generating device is opened to introduce superheated steam into the cracking reaction kettle, and the flow rate of the superheated steam is adjusted according to the set temperature in the cracking reaction kettle;

(3) opening a feeding valve on the cracking reaction kettle, introducing biological grease into the kettle, and starting catalytic cracking reaction; when the main component of the condensed liquid is water, stopping introducing the superheated steam, and finishing the reaction.

3. A superheated steam-assisted biological oil catalytic cracking method as claimed in claim 1 or 2, wherein the set temperature in the cracking reaction kettle is 400-500 ℃.

4. A superheated steam-assisted catalytic cracking method of biological oil and fat according to claim 1 or 2, wherein the catalyst is an alkali catalyst.

5. A superheated steam-assisted catalytic cracking method of biological oil and fat according to claim 1 or 2, wherein the catalyst is sodium carbonate.

6. A superheated steam-assisted biological oil and fat catalytic cracking method as claimed in claim 1 or 2, wherein the amount of the catalyst is 5-15% of the mass of the biological oil and fat.

7. A superheated steam-assisted catalytic cracking method of biological oil and fat according to claim 1 or 2, wherein the biological oil and fat is any one of soybean oil, palm oil, acidified oil, illegal cooking oil or rubber seed oil.

8. A superheated steam-assisted catalytic cracking method for biological oil and fat according to claim 1 or 2, wherein the feeding rate of the biological oil and fat is 5-6 g/s.

Technical Field

The invention belongs to the technical field of high-value utilization of biomass energy, and particularly relates to a superheated steam-assisted catalytic cracking method for biological oil.

Background

At present, the utilization of renewable energy is more and more researched, and the research of preparing the biofuel oil by taking the biological grease as the raw material is concerned by many researchers. There are several ways to utilize biological oils: first, the transesterification process produces first generation biodiesel, and the fatty acid esters formed by transesterification in the presence of acid and base catalysts can be combusted in an engine to provide heat. Secondly, the bio-fuel oil is prepared by catalytic cracking of the grease, and under the condition of an external heat source, the fatty acid can be effectively deoxidized by utilizing the catalytic action of an alkali metal or molecular sieve catalyst, so that a series of hydrocarbons are obtained, the molecular distribution of the molecular structure of the hydrocarbons distributed in petroleum components is very similar, and the hydrocarbons can also be used as a good fuel. In particular, after aromatization or isomerization, various fuels can be produced, including: bio-aviation kerosene, bio-gasoline, bio-diesel, and the like. Thirdly, the fatty acid raw material can be deoxidized to form a carbon chain distributed in C under the action of hydrogen and a hydrogenation catalyst₁₅-C₁₈The left and right alkanes can be directly used as diesel oil.

The catalytic cracking of biological grease is another important way for producing renewable liquid fuel, the catalytic cracking can effectively remove oxygen in carboxylic acid, most products of the base catalytic cracking mainly comprise about 75% of liquid fuel, 2% -5% of water, 15% -20% of gas products and 5% -10% of solid products, wherein the components of the liquid fuel mainly comprise olefin and alkane, the percentage is 70% -80%, and a small part of aromatic hydrocarbon and olefin. Many researchers use supported molecular sieve catalysts to perform catalytic cracking on biological grease, for example, CaO/ZSM-5 is used to crack biological grease, so that more aromatic compounds can be obtained than alkali catalytic cracking, and thus, the liquid fuel is more suitable for the application of biological aviation fuel. But the cracking conversion is not substantially changed, except that the aromatization of the ZSM-5 causes the structural change of the hydrocarbons. Also, MgO (ZnO)/SBA-15 and MgO (ZnO, Al) are used₂O₃) The catalyst such as MCM-41 is used for cracking, the yield of cracked liquid can be effectively improved orThe acid value of the product becomes high, etc. However, these molecular sieve-supported catalysts are relatively expensive to prepare, and if industrialization of biolipid is considered, the cost of the catalyst needs to be considered, and most of high-temperature catalytic cracking uses basic catalysts (CaO, Na)₂CO₃And the like), the components of the liquid fuel obtained by catalytic cracking are very similar to those of petroleum, wherein the high-olefin and alkane components endow the liquid components with good physical and chemical properties, and various physical and chemical properties including condensation point, acid value, thermogravimetric, density, viscosity and freezing point are very similar to those of commercial fuel oil. The molecular composition structure of the cracked oil component is regulated after aromatization or isomerization and partial hydrogenation, and the oil product can be prepared to meet the use standard of commercial fuel oil.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method for assisting biological oil catalytic cracking by superheated steam, wherein efficient heat transfer is realized by using superheated steam for heat supply, the contents of alkane and olefin are increased under the action of superheated steam, and particularly the content of olefin is increased by nearly 10%.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

a superheated steam assisted biological oil catalytic cracking method, under the assistance of superheated steam, carries on the catalytic cracking to the biological oil to prepare the biofuel with higher olefin content; the temperature of the superheated steam is 500-600 ℃.

The superheated steam assisted biological oil catalytic cracking method specifically comprises the following steps:

(1) adding a catalyst into a catalyst cage of a cracking reaction kettle, and starting stirring;

(2) the cracking reaction kettle is hermetically connected with the superheated steam generating device, a gas valve on the superheated steam generating device is opened to introduce superheated steam into the cracking reaction kettle, and the flow speed of the superheated steam is adjusted according to the set temperature in the cracking reaction kettle: when the temperature in the cracking reaction kettle is lower than a set temperature, the flow rate of the superheated steam is increased, and when the temperature in the cracking reaction kettle is higher than the set temperature, the flow rate of the superheated steam is reduced, and the temperature in the cracking reaction kettle is controlled to be the set temperature; the function of providing a heat source for the cracking reaction kettle by superheated steam is realized, and energy is saved;

(3) opening a feeding valve on the cracking reaction kettle, introducing biological grease into the kettle, and starting catalytic cracking reaction; when the main component of the condensed liquid is water, stopping introducing the superheated steam, and finishing the reaction.

In the method for assisting the catalytic cracking of the biological oil and fat by using the superheated steam, the set temperature in the cracking reaction kettle is 400-500 ℃.

In the method for assisting the catalytic cracking of the biological oil and fat by superheated steam, the catalyst is an alkali catalyst.

The superheated steam-assisted biological oil catalytic cracking method is characterized in that the catalyst is sodium carbonate.

In the method for assisting the catalytic cracking of the biological oil by the superheated steam, the dosage of the catalyst is 5-15% of the mass of the biological oil.

In the superheated steam assisted biological oil catalytic cracking method, the biological oil is any one of soybean oil, palm oil, acidified oil, illegal cooking oil or rubber seed oil.

According to the superheated steam assisted biological oil catalytic cracking method, the feeding rate of the biological oil is 5-6 g/s.

Has the advantages that: compared with the prior art, the invention has the advantages that:

(1) the superheated steam is used in the catalytic cracking process, on one hand, a heat source is provided for the catalytic cracking of the biological oil, the superheated steam has good heat transfer performance, and the energy consumption of the cracking reaction can be reduced by comparing with electric heating. Secondly, superheated steam can effectively contact with the raw materials, so that the catalytic cracking conversion rate of the biological oil is improved; on the other hand, the superheated steam is pyrolyzed to generate proton hydrogen, so that the formation of olefin can be assisted, and the yield of olefin and alkane is improved.

(2) The method carries out catalytic cracking on the waste biological oil under the assistance of superheated steam to prepare the carbon chain with the length of C₆-C₂₄The biological fuel oil of the components is subjected to superheated steam assisted catalytic cracking, so that the deoxygenation cracking capability of the grease is improved, the yield of olefin is improved, and the selectivity of olefin and alkane in the product is improved.

Drawings

FIG. 1 is a GC-MS diagram of the cracked products of examples 1 and 2, wherein FIG. 1-1 is a GC-MS diagram of the cracked product of example 1, and FIG. 1-2 is a GC-MS diagram of the cracked product of example 2;

FIG. 2 is a GC-MS diagram of the cleavage products of examples 3 and 4, wherein FIG. 2-1 is a GC-MS diagram of the cleavage product of example 3, and FIG. 2-2 is a GC-MS diagram of the cleavage product of example 4;

FIG. 3 is a GC-MS diagram of the cleavage products of examples 5 and 6, wherein FIG. 3-1 is a GC-MS diagram of the cleavage product of example 5, and FIG. 3-2 is a GC-MS diagram of the cleavage product of example 6.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.