阅读说明：本技术 一种大密度煤基航空煤油的制造方法 (Method for manufacturing high-density coal-based aviation kerosene ) 是由 李学兵 陈松 李广慈 范芮堃 陈磊 于 2020-06-17 设计创作，主要内容包括：本发明公开了一种大密度煤基航空煤油的制造方法,其通过包括(1)煤基热解油一段非贵金属催化加氢精制,(2)煤基热解油二段非贵金属催化选择性加氢裂化和后续的分馏过程,将煤基热解油高效转化为密度大(>0.87g/mL)、凝点低(<-60℃)、硫含量低(<5μg/g)、稳定性好的大密度航空煤油产品,该方法是以富含多环芳族的低品质煤热解油为原料进行的全馏分加氢处理工艺,具有原料利用率高、过程对环境友好、操作可靠、产品品质稳定、生产运行周期长等优势,可以为高性能航空航天飞行器提供充足可靠的燃料。(The invention discloses a method for manufacturing high-density coal-based aviation kerosene, which comprises the steps of (1) carrying out catalytic hydrofining on a first-stage non-noble metal of coal-based pyrolysis oil, and (2) carrying out catalytic selective hydrocracking and subsequent fractionation on a second-stage non-noble metal of the coal-based pyrolysis oil to efficiently convert the coal-based pyrolysis oil into a high-density aviation kerosene product with high density (>0.87g/mL), low condensation point (< 60 ℃), low sulfur content (<5 mu g/g) and good stability.)

1. A process for preparing high-density coal-base aviation kerosene features that the coal-base pyrolytic oil is used as raw material and two-stage continuous hydrocatalysis process of fixed bed in the presence of non-noble metal catalyst with large pore size is used.

2. The method for producing a high-density coal-based aviation kerosene according to claim 1, wherein said method comprisesCharacterized in that the two-stage continuous fixed bed hydrotreating process comprises the following steps: (1) the coal-based pyrolysis oil raw material is at 8-16 MPa, the reaction temperature is 250-400 ℃, and the liquid hourly space velocity is 0.3-1.0h^-1Hydrofining is carried out in the presence of a non-noble metal large-aperture hydrogenation catalyst; (2) the oil phase of the hydrorefining product is at 8-16 MPa, the reaction temperature is 300-450 ℃, and the liquid hourly space velocity is 0.3-1.0h^-1And hydrofining is carried out in the presence of a non-noble metal selective hydrocracking catalyst.

3. The method of claim 1, wherein the jet fuel has a density of not less than 0.83 g/mL.

4. The method for producing high-density coal-based aviation kerosene according to claim 1, wherein the coal-based pyrolysis oil raw material is one or more of high-temperature coal tar, medium-temperature coal tar and low-temperature coal tar obtained by pyrolysis and dry distillation of coal at 400-1400 ℃.

5. Non-noble metal large pore hydrogenation catalyst according to claims 1 and 2, characterized in that the catalyst is based on active Al₂O₃Is a carrier, contains 15 to 25 weight percent of VIB group metal and 2 to 4 weight percent of VIII group metal, the pore volume is more than 0.35mL/g, the specific surface area is more than 150m²(ii)/g; wherein the group VIB metal is selected from Mo or W, and the group VIII metal is selected from Co or Ni.

Technical Field

The invention relates to a method for manufacturing high-density coal-based aviation kerosene, and belongs to the technical field of coal chemical industry.

Background

Aviation kerosene is one of three major transportation fuels, and the demand of the aviation kerosene is remarkably increased along with the rapid development of the economic society and the transportation industry in China. At present, the main source of aviation kerosene is petroleum, but petroleum resources in China are not abundant, so that the contradiction between the continuous increase of aviation kerosene demand and the excessive consumption of petroleum resources is increasingly aggravated. Therefore, how to alleviate the contradiction between supply and demand has become one of the important research topics in the present stage.

The coal pyrolysis oil is a main liquid product in the coal dry distillation process, is a complex mixture of high-aromaticity hydrocarbons, is mostly polycyclic and condensed ring compounds with side chains or without side chains and heterocyclic compounds containing oxygen, sulfur and nitrogen, contains a small amount of aliphatic hydrocarbons, naphthenic hydrocarbons and unsaturated hydrocarbons, and has the average density of 1.18-1.23 g/mL. China has rich coal resources, high coal pyrolysis oil yield and low price. In addition, the coal pyrolysis oil has the characteristics of high density and a polycyclic structure, and a high-quality hydrocarbon product with high density, low heteroatom content and a plurality of naphthenic base components can be obtained after hydrotreating, so that the coal pyrolysis oil is very suitable to be used as a raw material for preparing high-density aviation kerosene.

Compared with the conventional low-density aviation kerosene, the high-density aviation kerosene can provide larger thrust and longer range for the aircraft under the same volume of filling amount, thereby not only improving the performance of the aircraft, but also reducing the use amount of fuel. Therefore, the use of the high-density aviation kerosene instead of the traditional aviation kerosene reduces the overall demand of the aviation kerosene in China to a certain extent, and has important significance for relieving the supply and demand tension condition.

CN 201110222378.2 discloses a method for producing coal-based high-density jet fuel. The raw material used by the method is light distillate oil generated by direct coal liquefaction, coal-based pyrolysis oil is not used as the raw material, the operation process is complex, and the density of the obtained jet fuel is relatively low (<0.85 g/mL).

CN200410043708.1 discloses a process for producing high-quality gasoline, diesel oil and lubricating oil by hydrocracking high-temperature coal tar. The process comprises the steps of subjecting coal tar to hydrorefining, fractionating, allowing tail oil to enter a hydrocracking reactor, subjecting the tail oil to gas-liquid separation, and allowing the obtained liquid-phase product oil and hydrorefining product oil to enter a fractionating tower to obtain high-quality gasoline, diesel oil and lubricating oil products. Although the process can produce diesel oil products with higher density, the condensation point is too high (-10 ℃), and the requirements of aerospace aircrafts are difficult to meet.

CN201610036712.8 discloses a method for preparing high-density coal-based jet fuel by using anthracene oil as raw material. The method prepares the high-density coal-based jet fuel which has high density, high flash point, low freezing point and good stability and meets the No. 6 jet fuel standard through the anthracene oil two-stage hydrogenation process. However, the sulfur content of the obtained fuel is relatively high (200 mug/g), and the national requirements for ultra-low sulfur clean fuel at present and in future are difficult to meet.

Disclosure of Invention

In view of the defects of the prior art in the aspect of producing high-density aviation fuel, the invention aims to provide a method for producing ultralow-sulfur aviation kerosene with high density, high heat value and low condensation point from coal pyrolysis oil, which can meet the actual requirements of China on high-density aviation fuel and can also carry out high-value utilization on low-quality coal pyrolysis oil.

In order to achieve the purpose, the technical scheme adopted by the invention is a method for manufacturing high-density coal-based aviation kerosene, which comprises the following specific steps:

the coal-based pyrolysis oil is used as a raw material, and a hydrogenation catalytic process of two-section continuous fixed bed hydrogenation treatment is adopted in the presence of a non-noble metal large-aperture hydrogenation catalyst.

The method for manufacturing the high-density coal-based aviation kerosene is characterized in that the two-stage continuous fixed bed hydrotreatment process comprises the following steps: (1) the coal-based pyrolysis oil raw material is at 8-16 MPa, the reaction temperature is 250-400 ℃, and the liquid hourly space velocity is 0.3-1.0h^-1Hydrofining is carried out in the presence of a non-noble metal large-aperture hydrogenation catalyst; (2) the oil phase of the hydrorefining product is at 8-16 MPa, the reaction temperature is 300-450 ℃, and the liquid hourly space velocity is 0.3-1.0h^-1And hydrofining is carried out in the presence of a non-noble metal selective hydrocracking catalyst.

The manufacturing method of the high-density coal-based aviation kerosene is characterized in that the density of the aviation kerosene is not lower than 0.83 g/mL.

The method for preparing the high-density coal-based aviation kerosene is characterized in that the coal-based pyrolysis oil raw material is one or more of high-temperature coal tar, medium-temperature coal tar and low-temperature coal tar obtained by pyrolyzing and dry distilling coal at 400-1400 ℃.

Non-noble metal large pore hydrogenation catalyst according to claims 1 and 2, characterized in that the catalyst is based on active Al₂O₃Is a carrier containing 15-25 wt% of VIB group metal2-4 wt% of VIII group metal, pore volume of more than 0.35mL/g, specific surface area of more than 150m²(ii)/g; wherein the group VIB metal is selected from Mo or W, and the group VIII metal is selected from Co or Ni.

Compared with the prior art, the method provided by the invention has the following advantages:

1) the method provided by the invention takes low-quality coal-based pyrolysis oil as a raw material, aiming at the characteristic that a hydrogenation product of the low-quality coal-based pyrolysis oil has a large amount of naphthenic hydrocarbon and aromatic hydrocarbon, and aviation kerosene with high density, high calorific value, low freezing point and good stability is produced through continuous hydrogenation treatment, so that the volume calorific value is improved while the density is ensured to be more than 0.83g/mL, the content of heteroatoms such as sulfur, nitrogen and the like is reduced, and the utilization value of the raw material is improved.

2) The hydrogenation product of the coal pyrolysis oil contains a large amount of naphthenic hydrocarbon and aromatic hydrocarbon, and the hydrogenation product is very suitable for being used as a raw material for producing high-density aviation kerosene regardless of composition, structure, density and cost. In addition, the cycloparaffin has high-temperature pyrolysis thermal stability, so that the stability of the obtained fuel is high, the oil consumption ratio of an engine can be reduced, and the requirements of high navigational speed, large load and long range are met.

3) The large-aperture non-noble metal hydrogenation catalyst used in the invention has excellent mass transfer and carbon capacity, is very suitable for processing viscous raw materials with high C/H ratio and high polycyclic aromatic hydrocarbon content, improves the processing capacity of the catalyst, prolongs the service life of the catalyst, and effectively reduces the use cost of the catalyst and the equipment operation cost.

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.

The invention relates to a production method of high-density aviation kerosene, which is characterized in that coal pyrolysis oil with the density of 1.07-1.15 g/mL is used as a raw material, and different types of hydrofining catalysts are respectively adopted to carry out a two-stage continuous fixed bed hydrotreating process so as to obtain clean hydrocarbon fuel with high density, high heat value and low condensation point and hardly contains heteroatoms such as sulfur, nitrogen, oxygen, metal and the like. The properties of the coal pyrolysis oil feedstock used in the examples are shown in table 1.

TABLE 1 coal pyrolysis oil feedstock Properties