阅读说明：本技术 一种煤油混合原料制备高热值高密度喷气燃料的方法 (Method for preparing high-calorific-value high-density jet fuel from kerosene mixed raw material ) 是由 张轩 扈广法 蒋中山 黄传峰 常方圆 韩信有 杨涛 刘亚青 朱永红 王亦颿 王维 于 2020-12-27 设计创作，主要内容包括：一种煤油混合原料制备高热值高密度喷气燃料的方法,(1)将煤粉通过筛分机筛选出合适粒径的煤粉；(2)将重油、步骤(1)获得的煤粉和浆态床催化剂置于恒温原料罐进行混合；(3)将步骤(2)获得的混合原料与氢气加氢裂化反应；(4)将步骤(3)获得的产物油先进行闪蒸一次,然后轻馏分进入分馏系统；(5)将步骤(4)得到的柴油馏分进入固定床加氢精制和加氢裂化反应区；(6)将步骤(5)获得的裂化柴油馏分油进入分馏系统；(7)将步骤(4)得到的喷气燃料馏分油和步骤(5)得到的喷气燃料馏分油混合进入补充加氢精制反应区,得到煤-油混合基喷气燃料。本发明解决了石油资源的短缺、重质化和纯煤基喷气燃料安定性差的问题。(A method for preparing jet fuel with high calorific value and high density by using kerosene mixed raw materials comprises (1) screening coal dust with a proper particle size by using a screening machine; (2) placing heavy oil, the coal powder obtained in the step (1) and a slurry bed catalyst in a constant-temperature raw material tank for mixing; (3) carrying out hydrocracking reaction on the mixed raw material obtained in the step (2) and hydrogen; (4) flashing the product oil obtained in the step (3) once, and then feeding the light fraction into a fractionation system; (5) feeding the diesel fraction obtained in the step (4) into a fixed bed hydrofining and hydrocracking reaction zone; (6) feeding the cracked diesel distillate oil obtained in the step (5) into a fractionation system; (7) and (3) mixing the jet fuel distillate oil obtained in the step (4) and the jet fuel distillate oil obtained in the step (5) and entering a supplementary hydrofining reaction zone to obtain the coal-oil mixed base jet fuel. The invention solves the problems of shortage of petroleum resources, heavy oil and poor stability of pure coal-based jet fuel.)

1. A method for preparing jet fuel with high calorific value and high density by using kerosene mixed raw materials is characterized by comprising the following steps;

step (1), preparing coal powder with proper particle size:

screening the pulverized coal with proper particle size by a screening machine;

preparing mixed raw materials in the step (2):

putting heavy oil, the coal powder obtained in the step (1) and a catalyst in a constant-temperature raw material tank according to a certain proportion, and uniformly mixing to obtain a mixed raw material;

hydrocracking in step (3):

mixing the mixed raw material obtained in the step (2) with hydrogen, entering a slurry bed hydrocracking reaction zone, carrying out hydrocracking reaction, cracking macromolecular hydrocarbons, and removing partial sulfur and nitrogen heteroatoms to obtain cracked product oil;

step (4), distillation and cutting:

flashing the product oil obtained in the step (3) once, and then feeding the light fraction into a fractionation system for oil product distillation and segmentation to respectively obtain naphtha fraction, jet fuel fraction and diesel fraction;

step (5) hydrofining and cracking:

enabling the diesel oil fraction obtained in the step (4) to enter a fixed bed hydrofining and hydrocracking reaction zone to obtain cracked diesel oil distillate;

and (6) distilling and cutting:

feeding the cracked diesel distillate oil obtained in the step (5) into a fractionation system, and distilling and cutting to obtain jet fuel distillate oil;

and (7) supplementary refining:

and (3) mixing the jet fuel distillate oil obtained in the step (4) and the jet fuel distillate oil obtained in the step (5) and entering a supplementary hydrofining reaction zone to obtain the coal-oil mixed base jet fuel.

2. The method for preparing high heating value and high density jet fuel from kerosene mixture raw material according to claim 1, wherein the heavy oil in step (2) is one or more of atmospheric residue, vacuum residue and catalytic cracking slurry oil, and the pulverized coal is bituminous coal or lignite.

3. The method for preparing the high-calorific-value high-density jet fuel from the kerosene mixture raw materials according to claim 1, wherein the particle size range of the pulverized coal in the step (1) is 20-200 μm, and the particle size distribution of the pulverized coal is in normal distribution.

4. The method for preparing high heating value and high density jet fuel by using the kerosene mixture raw material as claimed in claim 1, wherein the raw material mass mixing ratio in the step (2) is as follows: 85-65 wt% of heavy oil and 15-35 wt% of coal powder; the catalyst accounts for 1-4 wt% of the mixed raw materials.

5. The method for preparing high heating value and high density jet fuel from kerosene mixture raw material according to claim 1, wherein said slurry bed catalyst of step (2) is a carbon-based supported catalyst of iron-based, iron-copper-based, iron-nickel-based and iron-molybdenum-based.

6. The method for preparing high heating value high density jet fuel from kerosene mixture raw material according to claim 1, characterized in that the hydrocracking conditions of the step (3) are as follows: the reaction temperature is 440-470 ℃, the reaction pressure is 12-22 MPa, and the feeding volume space velocity is 0.5-1.4 h^-1The volume ratio of the light oil is 800-2000.

7. The method for preparing high-heating-value high-density jet fuel from kerosene mixture raw materials as claimed in claim 1, wherein the flash evaporation condition in step (4) is 370-390 ℃, and the further fractionation condition of the obtained light fraction is as follows: naphtha fraction is less than 180 ℃, jet fuel fraction is 180-280 ℃, and diesel fraction is 280-380 ℃.

8. The method for preparing high heating value high density jet fuel from kerosene mixture raw material according to claim 1, characterized in that the hydrofinishing reaction conditions in said step (5) are as follows: the reaction temperature is 320-350 ℃, the reaction pressure is 5-10 MPa, and the liquid volume space velocity is 2.0-3.0 h^-1Hydrogen-oil ratio of 500 to 1000, Al₂O₃The carrier nickel-molybdenum catalyst has the hydrocracking reaction conditions as follows: the reaction temperature is 350-410 ℃, the reaction pressure is 8-12 MPa, and the liquid volume space velocity is 1.0-2.0 h^-1The hydrogen-oil ratio is 600-1500, and the molecular sieve carrier is a nickel-cobalt-molybdenum catalyst.

9. The method for preparing high-heating-value high-density jet fuel from kerosene mixture raw material as defined in claim 1, wherein the distillation cutting conditions in step (6) are 190-300 ℃.

10. The method for preparing high heating value high density jet fuel from kerosene mixture raw material according to claim 1, characterized in that said hydrofinishing reaction conditions of step (7) are as follows: the reaction temperature is 230-290 ℃, the reaction pressure is 3-5 MPa, and the liquid volume space velocity is 2.0-5.0 h^-1Hydrogen-oil ratio of 60 to 100, Al₂O₃A supported nickel molybdenum catalyst.

Technical Field

The invention relates to the technical field of jet fuels, in particular to a method for preparing a high-calorific-value high-density jet fuel from a kerosene mixed raw material.

Background

With the continuous enlargement of the international air transportation industry, the global demand of jet fuel is increased year by year, and meanwhile, the rapid development of the national air transportation industry, the continuous service of novel aircrafts such as high-performance airplanes and supersonic fighters and the like, and the demand of the jet fuel with high heat value, high density and good thermal stability is more and more urgent. At present, the production of aviation jet fuel mainly takes petroleum-based raw materials as main raw materials, and in the oil refining process of petroleum, the fraction of the jet fuel only accounts for 4-8% of the total amount of crude oil, and in addition, the shortage of petroleum resources in China and the trend of crude oil heaving worldwide will cause the production difficulty and the supply shortage of high-quality jet fuel in China.

In recent years, the coal-based yield of China is increasing year by year (10% of increase rate every year), the annual yield is about 3000 ten thousand tons, and the research of coal-based jet fuel production is gradually hot. Compared with petroleum-based oil, the coal-based oil mainly has an aromatic ring structure, and is rich in a large amount of bicyclic aromatic hydrocarbon, hydrogenated aromatic hydrocarbon and naphthenic hydrocarbon, so that the coal-based oil has the characteristics of high heat value, high density, good thermal stability and the like, and is a preferred fuel for high-performance aircrafts. At present, the technology of taking coal-based oil as a raw material is to firstly carry out hydrofining or hydrocracking on the coal-based oil or distillate oil thereof, then carry out distillation cutting on a product, and cut a jet fuel characteristic fraction to be used as jet fuel or a jet fuel blending component. The problems of the technologies are that the utilization rate of raw materials is low, the yield of target products is low, meanwhile, because coal-based oil contains a large amount of phenolic substances, the stability of oil products is poor, and coal-based oil distillate oil does not meet the requirement of high stability of jet fuel and can not be directly used as the jet fuel.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a method for preparing high-calorific-value and high-density jet fuel from kerosene mixed raw materials, which solves the problems of shortage of petroleum resources, heavy fuel and poor stability of pure coal-based jet fuel, and the obtained mixed-base jet fuel has multiple characteristics of coal-based and petroleum-based fuel oil, and meets the requirements of future high-performance aircrafts.

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

a method for preparing jet fuel with high calorific value and high density by using kerosene mixed raw materials comprises the following steps;

step (1), preparing coal powder with proper particle size:

screening the pulverized coal with proper particle size by a screening machine;

preparing mixed raw materials in the step (2):

putting heavy oil, the coal powder obtained in the step (1) and a catalyst in a constant-temperature raw material tank according to a certain proportion, and uniformly mixing to obtain a mixed raw material;

hydrocracking in step (3):

mixing the mixed raw material obtained in the step (2) with hydrogen, entering a slurry bed hydrocracking reaction zone, carrying out hydrocracking reaction, cracking macromolecular hydrocarbons, and removing partial sulfur and nitrogen heteroatoms to obtain cracked product oil;

step (4), distillation and cutting:

performing flash evaporation on the product oil obtained in the step (3) for one time (the flash evaporation temperature is 370-390 ℃), then enabling the light fraction to enter a fractionation system, and performing oil product distillation and segmentation to respectively obtain a naphtha fraction (<180 ℃), a jet fuel fraction (180-280 ℃) and a diesel fraction (280-380 ℃);

step (5) hydrofining and cracking:

enabling the diesel oil fraction obtained in the step (4) to enter a fixed bed hydrofining and hydrocracking reaction zone to obtain cracked diesel oil distillate;

and (6) distilling and cutting:

and (3) feeding the cracked diesel distillate oil obtained in the step (5) into a fractionation system, and distilling and cutting to obtain jet fuel distillate oil (190-300 ℃).

And (7) supplementary refining:

and (3) mixing the jet fuel distillate oil obtained in the step (4) and the jet fuel distillate oil obtained in the step (5) and entering a supplementary hydrofining reaction zone to obtain the coal-oil mixed base jet fuel.

The heavy oil in the step (2) is one or a mixture of several of atmospheric residue, vacuum residue and catalytic cracking slurry oil, and the coal powder is bituminous coal or lignite.

The particle size range of the pulverized coal in the step (1) is 20-200 mu m, and the particle size distribution of the pulverized coal is in normal distribution.

The raw materials in the step (2) are mixed according to the mass ratio: 85-65 wt% of heavy oil and 15-35 wt% of coal powder; the catalyst accounts for 1-4 wt% of the mixed raw materials.

The slurry bed catalyst in the step (2) is an iron-based, iron-copper-based, iron-nickel-based or iron-molybdenum-based carbon-based carrier catalyst.

The hydrocracking conditions in the step (3) are as follows: the reaction temperature is 440-470 ℃, the reaction pressure is 12-22 MPa, and the feeding volume space velocity is 0.5-1.4 h^-1The volume ratio of the light oil is 800-2000.

The flash evaporation condition in the step (4) is 370-390 ℃, and the further fractionation condition of the obtained light fraction is as follows: naphtha fraction <180 ℃, jet fuel fraction 180-280 ℃, and diesel fraction 280-380 ℃;

the hydrofining reaction conditions in the step (5) are as follows: the reaction temperature is 320-350 ℃, the reaction pressure is 5-10 MPa, and the liquid volume space velocity is 2.0-3.0 h^-1Hydrogen-oil ratio of 500 to 1000, Al₂O₃A supported nickel molybdenum catalyst. The hydrocracking reaction conditions are as follows: inverse directionThe reaction temperature is 350-410 ℃, the reaction pressure is 8-12 MPa, and the liquid volume space velocity is 1.0-2.0 h^-1The hydrogen-oil ratio is 600-1500, and the molecular sieve carrier is a nickel-cobalt-molybdenum catalyst.

And (3) the distillation and cutting conditions in the step (6) are 190-300 ℃.

The hydrorefining reaction conditions in the step (7) are as follows: the reaction temperature is 230-290 ℃, the reaction pressure is 3-5 MPa, and the liquid volume space velocity is 2.0-5.0 h^-1Hydrogen-oil ratio of 60 to 100, Al₂O₃A supported nickel molybdenum catalyst.

The invention has the beneficial effects that:

the process can take various inferior heavy oil and coal as raw materials, can effectively relieve the problems of shortage of domestic petroleum resources and global crude oil heaviness, has wide raw material sources and low cost, is easy to obtain, and can ensure the supply of production raw materials.

The jet fuel prepared by the method has the advantages of petroleum-based jet fuel and coal-based jet fuel. The coal in the mixed raw material is the main source of the cycloparaffin and the aromatic hydrocarbon, the cycloparaffin and the aromatic hydrocarbon have good pyrolysis stability and the advantages of high heat value and high density, and the heavy oil is doped mainly to reduce the contents of phenolic substances and sulfur and nitrogen heteroatoms in the mixed raw material, so that the stability of an oil product is enhanced, and simultaneously, the environment-friendly requirement of jet fuel tail gas emission can be well met.

The invention refines and then cracks the fractionated diesel fraction, and cuts the characteristic fraction of the cracked diesel fraction, thereby improving the overall yield of jet fuel, improving the utilization rate of raw materials, and converting more cheap raw materials into target products with high added values.

Drawings

FIG. 1 is a process flow diagram of an embodiment of the invention.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.

Example 1

(1) And (4) preparing mixed raw materials. Mixing 65% of catalytic cracking slurry oil, 35% of pulverized bituminous coal (particle size is 150-200 mu m) and 2% of slurry bed catalyst to prepare slurry, and obtaining a mixed raw material 1.

(2) And (4) hydrocracking. Mixing the mixed raw material 1 obtained in the step (1) with hydrogen 2, feeding the mixture into a slurry bed hydrocracking reaction device 3, and reacting at the temperature of 440 ℃, the reaction pressure of 20MPa and the liquid volume space velocity of 0.5h^-1And carrying out hydrocracking reaction under the condition of hydrogen-oil ratio of 2000 to obtain cracked product oil 4.

(3) And (5) distilling and cutting. And (3) feeding the cracked product oil 4 obtained in the step (2) into a flash tank 5 (at a flash evaporation temperature of 370-390 ℃), feeding the obtained light fraction 6 into a fractionation system 8, and performing oil distillation and segmentation to obtain a naphtha fraction 9 with a distillation range of <180 ℃, a jet fuel fraction 10 with a distillation range of 180-280 ℃ and a diesel fraction 11 with a distillation range of 280-380 ℃.

(4) Hydrorefining and cracking. And (4) feeding the diesel fraction 11 obtained in the step (3) into a fixed bed hydrofining and hydrocracking reaction device 12 for hydrofining and cracking reaction to obtain cracked diesel distillate 13. The hydrorefining reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 6MPa, and the liquid volume space velocity is 2.0h^-1Hydrogen to oil ratio 1100, Al₂O₃A supported nickel molybdenum catalyst. The hydrocracking reaction conditions are as follows: the reaction temperature is 400 ℃, the reaction pressure is 8MPa, and the liquid volume space velocity is 1.5h^-1Hydrogen-oil ratio 1000, molecular sieve carrier nickel-cobalt-molybdenum catalyst.

(5) And (5) distilling and cutting. And (3) feeding the cracked diesel distillate oil 13 obtained in the step (4) into a fractionation system 14, and distilling and cutting to obtain jet fuel distillate oil 16 with the distillation range of 190-300 ℃.

(6) And (5) supplementary refining. Mixing the jet fuel distillate oil 10 obtained in the step (3) and the jet fuel distillate oil 16 obtained in the step (5), and feeding the mixture into a supplementary hydrofining reaction device, wherein the reaction temperature is 230 ℃, the reaction pressure is 4MPa, and the liquid volume space velocity is 2.0h^-1Hydrogen to oil ratio of 60, Al₂O₃And carrying out refining reaction under the condition of a carrier nickel-molybdenum catalyst to obtain the coal-oil mixed base jet fuel oil 18. (as shown in FIG. 1)

The embodiment 2, the embodiment 3 and the embodiment 4 are realized by adjusting different coal powder adding proportions, coal powder particle size distribution, slurry bed catalysts and hydrogenation reaction conditions of each section.

TABLE 1 preparation conditions of the feedstock and the reaction conditions of the hydrogenation in each stage

TABLE 2 basic Properties of the raw materials

TABLE 3 basic Properties of the catalyst

Item	Catalyst A
		Specific surface area (m)2/g)	461
C/wt％	55.23
		H/wt％	1.18
S/wt％	1.76
		N/wt％	0.61
Fe/wt％	6.60

TABLE 4 properties of jet fuels obtained under different conditions