CN110655949A

CN110655949A - Hydrogenation method of jet fuel rich in hydrogen

Info

Publication number: CN110655949A
Application number: CN201810715061.4A
Authority: CN
Inventors: 张锐; 习远兵; 李善清; 丁石; 刘锋; 鞠雪艳
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2018-06-29
Filing date: 2018-06-29
Publication date: 2020-01-07
Anticipated expiration: 2038-06-29
Also published as: CN110655949B

Abstract

The present disclosure relates to a hydrogen enriched jet fuel hydrogenation process, comprising: mixing kerosene extracted from the first line with hydrogen-containing gas, then sending the mixture into a hydrogenation reactor to contact with a hydrofining catalyst for hydrofining reaction, and carrying out product separation on the obtained product to obtain concentrated hydrogen and a refined aviation kerosene product; the hydrogen content of the hydrogen-containing gas is 40 to 85 vol%. The method can effectively reduce the energy consumption and investment of the device, can produce qualified refined aviation kerosene products, and can concentrate low-concentration hydrogen under the condition of not increasing the equipment investment and the operation cost.

Description

Hydrogenation method of jet fuel rich in hydrogen

Technical Field

The present disclosure relates to a hydrogen enriched jet fuel hydrogenation process.

Background

Currently, the air transportation industry in China keeps developing rapidly, annual aviation kerosene consumption exceeds two million tons, and the development of aviation kerosene technology is emphasized from the consideration of national energy strategic safety. At present, jet fuel (also called aviation kerosene, referred to as aviation kerosene for short) mainly comes from the common first-line fraction of an atmospheric distillation device. The main quality problems of straight run jet fuel fractions are that mercaptans are over-scaled, and acid number and color need to be improved. At present, the widely applied hydrofining technology of the jet fuel of the trickle bed in the refining process of the aviation kerosene fraction is a technology for hydrofining the jet fuel of the trickle bed, and the technology has the temperature of 230-300 ℃, the pressure of 0.7-1.6 MPa and the airspeed of 2-5 h^-1And carrying out hydrogenation treatment under the mild process condition that the volume ratio of hydrogen to oil is 30-100 (v/v), mainly reducing the mercaptan in the straight-run aviation kerosene fraction to be less than 20 mu g/g, and simultaneously improving the acid value and the color of the oil product.

The hydrogenation device of oil refinery, such as hydrofining, hydrocracking, catalytic reforming and other process devices, can discharge gas containing hydrogen in the production process, wherein the discharge amount of hydrogen with the hydrogen concentration of 40-80 percent is less, and 100Nm is less³100000Nm in each case³H is used as the reference value. The low-concentration hydrogen needs to be enriched or concentrated before being used. Pressure swing adsorption and membrane separation are mainly used for purifying/enriching hydrogen in industry. The pressure swing adsorption purification method utilizes a pressure swing adsorption process to replace three procedures of low-temperature transformation, decarbonization, methanation and the like in a chemical absorption purification method, so that the flow is simplified, and the purity of the obtained hydrogen can reach more than 99 percent; the membrane separation technology mainly utilizes the principle that a high-molecular hollow fiber tubular membrane has different permeability to different molecules to concentrate and purify gas. The hydrogen obtained by the two methods according to different working conditions canThe purification is carried out well, but the investment is high.

The normal line of the atmospheric distillation tower is pumped out and then directly enters a downstream jet fuel hydrogenation device or enters an intermediate storage tank as a raw material, and the hydrogenation device is generally provided with a new hydrogen compressor and/or a recycle hydrogen compressor and a reactor heating furnace. Therefore, the investment of equipment and equipment is high, the operation cost is high, and the energy consumption and the operation cost of the device are high.

CN201210357221.5 discloses a liquid-phase hydrofining method for aviation kerosene, which injects hydrogen into kerosene through a through hole with nanometer size without the aid of diluent or circulating oil, and belongs to a hydrogen dissolving device. And the method only provides enough hydrogen for reaction, and has no effect of concentrating hydrogen.

CN20130540398.3 discloses a straight-run kerosene hydrogenation method, which is to directly extract the kerosene side line of an atmospheric distillation tower, mix the extracted kerosene side line with hydrogen in a static mixer, and then enter a liquid phase hydrogenation reactor to perform hydrofining reaction. The method mainly carries out hydrogenation sweetening and decoloring reactions of kerosene, is a hydrogenation process with low hydrogen consumption and low energy consumption, and has no effect of enriching hydrogen.

Chemical engineering technology 2003,11(3) P29-31 discloses a straight-run aviation kerosene low-pressure hydrogenation technology, which mainly aims at removing mercaptan and improving properties such as color and acid value.

The RHSS technology is developed by petrochemical science research institute in 1999, adopts a special hydrodethiol catalyst, has mild process conditions, is mainly used for the mercaptan removal, deacidification, desulfurization and denitrification of straight-run aviation kerosene fractions, improves the color of products and properly improves the smoke point of the products, and has the characteristics of low hydrogen consumption in the process and basically keeping the straight-run fractions of the products. The RHSS technology does not involve the adaptation of hydrogen enrichment and optimization of process conditions.

Disclosure of Invention

The present disclosure provides a hydrogen-enriched jet fuel hydrogenation method, which aims at the defects of complex operation, high cost and high equipment investment of a jet fuel hydrorefining device in the existing refinery low-concentration hydrogen concentration technology.

To achieve the above objects, the present disclosure provides a hydrogen-enriched jet fuel hydrogenation method, comprising:

mixing kerosene extracted from the first line with hydrogen-containing gas, then sending the mixture into a hydrogenation reactor to contact with a hydrofining catalyst for hydrofining reaction, and carrying out product separation on the obtained product to obtain concentrated hydrogen and a refined aviation kerosene product; the hydrogen content of the hydrogen-containing gas is 40 to 85 vol%.

Optionally, the method further comprises: firstly, the kerosene extracted from the normal line and the hydrogen-containing gas are sent into a hydrogen mixer to be fully mixed and then sent into the hydrogenation reactor.

Optionally, the hydrogenation reactor is an upflow hydrogenation reactor.

Optionally, a gas-liquid contact strengthening component is arranged in the hydrogenation reactor, and the gas-liquid contact strengthening component is a cold hydrogen box, a hydrogen mixer, a bubble cap tray or a porous medium, or a combination of two or three of the components.

Optionally, the hydrogen content of the hydrogen-containing gas is 40-80 vol%.

Optionally, the hydrogen-containing gas is from at least one of a hydrofinishing unit, a hydrocracking unit, and a catalytic reforming unit.

Optionally, the hydrofining catalyst comprises a carrier and an active metal component responsible for being on the carrier, wherein the carrier is an inorganic oxide, and the active metal component is a group VIB metal and/or a group VIII metal.

Alternatively, the step of preparing the hydrofinishing catalyst comprises:

(1) impregnating a carrier with a first impregnation liquid, drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;

(2) dipping the semi-finished catalyst obtained in the step (1) by using a second dipping solution, and then drying without roasting;

the first impregnation liquid is an acidic aqueous solution containing a water-soluble compound of an active metal component and a first organic complexing agent, and the second impregnation liquid is an alkaline aqueous solution containing a second organic complexing agent;

further preferably, the first organic complexing agent is at least one selected from the group consisting of C2-C7 fatty acids; the second organic complexing agent is at least one selected from organic amine of C2-C7 and organic ammonium salt of C2-C7; the molar ratio of the first organic complexing agent to the second organic complexing agent is 1: (0.25-4).

Optionally, the distillation range of the kerosene extracted from the normal line is 140-260 ℃.

Alternatively, the conditions of the hydrofinishing reaction include: the reaction temperature is 200-300 ℃, preferably 220-260 ℃; the reaction pressure is 1.0-4.0 MPa, preferably 2.0-4.0 MPa; the liquid hourly space velocity is 0.5-10.0 h^-1Preferably 3.0 to 6.0 hours^-1(ii) a The volume ratio of hydrogen to oil is 40-300 Nm³/m³Preferably 50 to 200Nm³/m³。

Optionally, the method further comprises: and (3) carrying out heat exchange on the kerosene extracted from the normal line to 200-260 ℃, and then mixing the kerosene with the hydrogen-containing gas.

Optionally, the method further comprises: the enriched hydrogen is used as make-up hydrogen for a hydrofinishing process and/or a hydrocracking process.

Through the technical scheme, the kerosene extracted from the normal line of the crude oil atmospheric distillation tower is mixed with the low-concentration hydrogen to carry out hydrofining reaction, the heat of the atmospheric tower can be fully utilized, in addition, a circulating hydrogen system in a conventional jet fuel hydrogenation device is also cancelled, the energy consumption and investment of the device are effectively reduced, qualified refined aviation kerosene products can be produced, meanwhile, the low-concentration hydrogen can be concentrated under the condition that the equipment investment and the operation cost are not increased, the obtained concentrated hydrogen can be further utilized, and the hydrofining process is advanced, integrated, low in energy consumption and high in efficiency.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:

fig. 1 is a schematic flow diagram of a method provided by the present disclosure.

Description of the reference numerals

1 atmospheric distillation tower 2 normal line extraction kerosene

3 hydrogen mixer 4 hydrogen mixing reactant stream

5 hydrogenation reactor for hydrogen-containing gas 6

7 gas-liquid contact strengthening component 8 hydrogenation reaction product

9 separator 10 liquid fraction

11-concentrated hydrogen 12 fractionating tower

13 refining the aviation kerosene product with overhead gas 14

Detailed Description

The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

In the present disclosure, the use of directional words such as "upper and lower" generally means upper and lower in the operating state of the device, unless stated to the contrary.

The present disclosure provides a hydrogen enriched jet fuel hydrogenation process, comprising: mixing kerosene extracted from the first line with hydrogen-containing gas, then sending the mixture into a hydrogenation reactor to contact with a hydrofining catalyst for hydrofining reaction, and carrying out product separation on the obtained product to obtain concentrated hydrogen and a refined aviation kerosene product; the hydrogen content of the hydrogen-containing gas is 40 to 85 vol%.

According to the present disclosure, the conditions of the jet fuel hydrorefining reaction are mild, and the requirements of the reaction temperature can be met generally at 220-280 ℃. The method takes kerosene extracted from a normal line of an atmospheric distillation tower as a raw material, and can fully utilize the heat of the atmospheric tower, thereby reducing the energy consumption of the device. In the present disclosure, the distillation range of the kerosene extracted from the normal line is generally 140 to 260 ℃, and the distillation temperature can be 180 to 240 ℃. Further, where needed, the method may further include: the kerosene extracted from the normal line is subjected to heat exchange to 200-260 ℃, and then is mixed with the hydrogen-containing gas; thus, the kerosene is extracted from the heat exchange line to meet the requirement of the feeding temperature of the hydrofining reaction.

According to the present disclosure, the hydrogen-containing gas may be from a hydrorefining unit, a hydrocracking unit, a catalytic reforming unit, and the like, and the hydrogen-containing gas produced by these units has a low hydrogen content, and generally includes hydrocarbons of C1 to C4, and the like, and is particularly suitable for the method of the present disclosure to enrich hydrogen. In order to further obtain a desired hydrogen concentration effect, the hydrogen content of the hydrogen-containing gas may be 40 to 80 vol%.

In accordance with the present disclosure, to further improve the quality of the refined aviation kerosene product and achieve the desired hydrogen concentration effect, the method may further comprise: firstly, the kerosene extracted from the normal line and the hydrogen-containing gas are sent into a hydrogen mixer to be fully mixed and then sent into the hydrogenation reactor. In this way, the pre-mixing of the normal-line drawn kerosene and the hydrogen-containing gas in the hydrogen mixer enables the hydrogen-containing gas to be better dispersed in the normal-line drawn kerosene, and has a more excellent reaction effect than when the hydrogen-containing gas and the hydrogen-containing gas are directly fed to the hydrogenation reactor. The hydrogen mixer may be of a conventional type commercially available, for example, a model FITS type hydrogen mixer manufactured by Changling petrochemical technology development, Inc. of Hunan.

In a preferred embodiment of the present disclosure, the hydrogenation reactor is an upflow hydrogenation reactor. When the hydrogenation reactor is adopted, gas and liquid phases of reactant flow through the catalyst bed layer from bottom to top, so that the possibility of local accumulation of hydrogen-containing gas in the reactor is reduced, the distribution uniformity of the hydrogen-containing gas in liquid phase flow is further optimized, and the reaction effect is improved. Meanwhile, when the upflow hydrogenation reactor is adopted, the hydrogen-containing gas can be in a one-time flow process, and a hydrogen circulating compression system required in the conventional hydrogenation treatment process is omitted.

Further, a gas-liquid contact strengthening component can be arranged in the hydrogenation reactor to improve the contact surfaces of gas phase and liquid phase, so that the gas phase and the liquid phase are mixed strongly, and an ideal hydrogen concentration effect is obtained. The gas-liquid contact enhancing component may be a conventional component capable of achieving the above purpose, and may be, for example, a cold hydrogen tank, a hydrogen mixer, a bubble cap tray or a porous medium, or a combination of two or three of them. The position of the gas-liquid contact enhancement component is not particularly required, and can be arranged at any position of the hydrogenation reactor, preferably 1/2-2/3 of the total height of the catalyst bed layer along the flowing direction of the reactant flow.

According to the present disclosure, the conditions of the hydrofinishing reaction may be conventional, for example, the conditions of the hydrofinishing reaction may include: the reaction temperature is 200-300 ℃, preferably 220-260 ℃; the reaction pressure is 1.0-4.0 MPa, preferably 2.0-4.0 MPa; the liquid hourly space velocity is 0.5-10.0 h^-1Preferably 3.0 to 6.0 hours^-1(ii) a The volume ratio of hydrogen to oil (the volume ratio of hydrogen-containing gas to kerosene extracted from the normal line) is 40-300 Nm³/m³Preferably 50 to 200Nm³/m³。

The step of subjecting the resulting product to product isolation is conventional in the art in light of this disclosure and may be, for example: firstly, carrying out gas-liquid separation on the obtained product, wherein the separated gas is the concentrated hydrogen; and then the liquid phase fraction is sent into a fractionating tower for fractionation to remove impurities (such as hydrogen sulfide) and micromolecular hydrocarbons, and a refined aviation kerosene product is obtained at the bottom of the fractionating tower.

By adopting the method disclosed by the invention, the low-concentration hydrogen-containing gas produced by devices such as a refinery hydrofining device and the like can be enriched, and the hydrogen content of the obtained enriched hydrogen is 80-95 vol% and can be further utilized, so that the method can further comprise the following steps: the enriched hydrogen is used as make-up hydrogen for a hydrofinishing process and/or a hydrocracking process.

The hydrofinishing catalyst may be of any conventional kind well known to those skilled in the art in light of this disclosure, for example, the hydrofinishing catalyst may comprise a support, which may be an inorganic oxide (e.g., alumina, silica-alumina, etc.), and an active metal component responsible for the support, which may be a group VIB metal (e.g., molybdenum and/or tungsten) and/or a group viii metal (e.g., cobalt and/or nickel), such as a hydrofinishing catalyst developed by the institute of petrochemical science and technology under model number RSS-1A, RSS-2, etc.

According to the present disclosure, the object of the present disclosure can be achieved by using a conventional hydrofining catalyst, but the inventors of the present disclosure found in their research that a hydrofining catalyst prepared by a specific method has a higher activity, which is particularly advantageous for improving the quality of refined aviation kerosene products and obtaining a better hydrogen concentration effect.

Thus, in a preferred embodiment of the present disclosure, the step of preparing the hydrofinishing catalyst comprises:

(2) and (2) impregnating the semi-finished catalyst obtained in the step (1) by using a second impregnation solution, and then drying without roasting.

The first impregnation liquid is an acidic aqueous solution containing a water-soluble compound of an active metal component and a first organic complexing agent, and the second impregnation liquid is an alkaline aqueous solution containing a second organic complexing agent.

Wherein, preferably, the roasting condition in the step (1) is that the carbon content in the semi-finished catalyst is 0.04-0.4 wt% based on the total weight of the semi-finished catalyst; further preferably, the calcination conditions in step (1) are such that the amount of carbon in the semi-finished catalyst is 0.05 to 0.35 wt% based on the total amount of the semi-finished catalyst. The above-mentioned carbon content can be obtained by controlling the calcination temperature in the calcination conditions and the rate of introduction of an oxygen-containing gas, which may be one or more of various gases having an oxygen content of not less than 20% by volume, such as air, oxygen and a mixed gas thereof. The rate of introduction of the oxygen-containing gas is not less than 0.2 liter/hr per gram of the carrier. On one hand, the introduction of the oxygen-containing gas meets the combustion condition, so that the water-soluble compound of the active metal component is converted into oxide, and the organic complexing agent is converted into carbon; on the other hand, carbon dioxide and water formed by combustion and other components can be discharged to avoid the deposition on the catalyst to cause vacancy obstruction of the active phase. Preferably, the rate of introduction of the oxygen-containing gas is in the range of 0.2 to 20 liters/hour, more preferably 0.3 to 10 liters/hour, per gram of the carrier.

Further, the roasting temperature in the step (1) is 350-. Controlling the roasting temperature within the range can ensure that the organic complexing agent can form carbon on the carrier within the content range to obtain the semi-finished catalyst.

Wherein the molar ratio of the first organic complexing agent to the water-soluble compound of the active metal component, calculated as the metal element, may be (0.03-2): 1, preferably (0.08-1.5): 1.

Wherein the molar ratio of the first organic complexing agent to the second organic complexing agent may be 1: (0.25-4), preferably 1: (0.5-2).

Wherein, the first organic complexing agent and the second organic complexing agent can be the same or different. In order to further obtain a hydrofining catalyst with higher activity, preferably, the first organic complexing agent is at least one selected from organic acids, more preferably, the first organic complexing agent is at least one selected from fatty acids of C2-C7; the second organic complexing agent is at least one selected from organic amine and organic ammonium salt, and more preferably, the second organic complexing agent is at least one selected from organic amine of C2-C7 and organic ammonium salt of C2-C7.

The drying conditions are not particularly limited, and the drying conditions in step (1) and step (2) may be the same or different. Preferably, the drying temperature in the step (1) is 100-250 ℃, and the time is 1-12 h; the drying temperature in the step (2) is 100-200 ℃, and the time is 1-12 h.

The water-soluble compound of the hydrogenation metal active component can be various water-soluble compounds with the solubility meeting the loading requirement or can form the hydrogenation metal active component with the solubility meeting the requirement in water in the presence of a cosolvent, and can be one or more of nitrate, chloride, sulfate and carbonate, and nitrate is preferred. The concentration of the water-soluble compound of the hydrogenation metal active component may be 0.2 to 8mol/L, preferably 0.2 to 5mol/L, and more preferably 0.2 to 2mol/L in terms of the metal element. The concentrations herein are the respective concentrations of the water-soluble compounds of the various hydrogenation metal active components, not the total concentration.

Wherein, the dosage of the hydrogenation metal active component is 5-60 wt%, preferably 10-40 wt% calculated by oxide based on the total amount of the hydrofining catalyst.

Wherein, the hydrogenation metal active component comprises at least one selected from VIB group metal elements and at least one selected from VIII group metal elements; based on the total amount of the hydrofining catalyst, the content of the VIB group metal element is 4-50 wt%, preferably 8-35 wt%, and the content of the VIII group metal element is 1-10 wt%, preferably 2-5 wt%, calculated by oxide. Further, the group VIB metal element is preferably molybdenum and/or tungsten; the group VIII metal element is preferably cobalt and/or nickel.

Further, the water-soluble compound of the group VIB metal element may be one or more selected from the group consisting of ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide, and tungsten oxide. The water soluble compound of the group VIII metal element may be selected from, but is not limited to, one or more of nickel nitrate, nickel sulfate, nickel acetate, nickel hydroxycarbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt hydroxycarbonate, cobalt chloride, and nickel chloride.

Wherein the first impregnation liquid is an acidic aqueous solution, such as pH value of 2-6, preferably pH value of 3-5; the second impregnation liquid is an alkaline aqueous solution, for example, having a pH value of 7 to 14, preferably 8 to 11. For the aqueous solution after adding the water-soluble compound of the active metal component and the first organic complexing agent (or adding the second organic complexing agent), if the acidity or basicity is not satisfactory, the acidity or basicity of the aqueous solution can be adjusted by a conventional method, such as adding an acidic substance or a basic substance, specifically, for example, an acidic compound such as an appropriate amount of hydrochloric acid or phosphoric acid to obtain an acidic aqueous solution, and an alkaline compound such as an appropriate amount of ammonia, urea, soda ash, ammonium bicarbonate, or sodium hydroxide to obtain an alkaline aqueous solution.

The impregnation may be an equal volume impregnation or a supersaturated impregnation. The temperature of the impregnation is not particularly limited, and may be various temperatures that the impregnation solution can reach; the time for impregnation is also not particularly limited as long as the desired amount of the desired components can be supported, for example: the impregnation temperature may be 15-60 deg.C and the impregnation time may be 0.5-5 hours.

Among them, the carrier may be various shaped porous carriers commonly used in the art. Preferably, the support is a shaped inorganic refractory oxide. Wherein the term "inorganic refractory oxide" refers to an inorganic oxygen-containing compound having a decomposition temperature of not less than 300 ℃ in oxygen or an oxygen-containing atmosphere (e.g., a decomposition temperature of 300-1000 ℃). The shaped porous carrier may be formed of one kind of inorganic refractory oxide, or may be formed of two or more kinds of inorganic refractory oxides. Specifically, the inorganic heat-resistant oxide may be selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, for example. Preferably, the support comprises alumina and a large pore molecular sieve (i.e., an alumina-large pore molecular sieve), wherein the alumina is further preferably alumina obtained after calcination of a hydrated alumina (aluminum hydroxide) colloidal composite.

The hydrofinishing catalyst prepared by the above steps is pre-sulphided with sulphur, hydrogen sulphide or a sulphur-containing feedstock at a temperature of 140 ℃ and 370 ℃ before use, preferably in the presence of hydrogen, either ex situ or in situ, to convert it to the sulphidic form.

The method of the present disclosure is briefly described below in conjunction with fig. 1 to further illustrate the present disclosure, but is not limited thereto.

As shown in fig. 1, kerosene 2 (which may be subjected to heat exchange) extracted from a normal line extracted from an atmospheric distillation tower 1 is fully mixed with hydrogen-containing gas 5 in a hydrogen mixer 3, and a mixed hydrogen-mixed reactant flow 4 is conveyed to the bottom of a hydrogenation reactor 6 and passes through a hydrofining catalyst bed from bottom to top. A gas-liquid contact strengthening component 7 can be arranged in the hydrogenation reactor 6, so that the hydrogen distribution in oil products is improved, and the hydrogen is more effectively concentrated. The hydrogenation reaction product 8 flows out from the top of the hydrogenation reactor 6 and then enters a separator 9 for gas-liquid separation, and the separated gas is concentrated hydrogen 11 which can be used as supplementary hydrogen of other hydrogenation devices or a hydrogen source of a PSA device. The liquid phase fraction 10 flowing out from the bottom of the separator 9 enters a fractionating tower 12 for rectification to remove hydrogen sulfide and hydrocarbons (namely, the top gas 13) of C1-C4, and a refined aviation kerosene product 14 is obtained at the bottom of the tower.

The following examples further illustrate the present disclosure, but are not intended to limit the same.

The properties of the normal line draw kerosene used in the examples are shown in Table 1.

TABLE 1

Item	Kerosene extracted from the ordinary line
		Density (20 ℃ C.)/g.cm^-3	0.8074
Total sulfur content/μ g/g	1500
		Mercaptan sulfur content/. mu.g/g	108
Distillation range (ASTM D-86), deg.C	161～251

Preparation example

2000 g of aluminum hydroxide powder (dry rubber powder produced by catalyst factory of Changling division, 72 wt% of dry base) is weighed, extruded into butterfly-shaped strips with the circumscribed circle diameter of 1.3 mm by a strip extruder, the wet strips are dried for 4 hours at 120 ℃, and are roasted for 3 hours at 600 ℃ to obtain the alumina carrier Z1.

40 g of molybdenum trioxide, 21 g of basic nickel carbonate, 13 g of phosphoric acid and 30 g of citric acid are respectively weighed and placed into 140 g of deionized water, and the mixture is heated, stirred and dissolved to obtain a first impregnation solution, and the pH value is measured to be 4.0. 200 g of the alumina carrier Z1 was impregnated with the first impregnation solution by a saturated impregnation method for 2 hours, then dried at 150 ℃ for 2 hours, and then calcined under a condition of introducing air flow at 360 ℃ for 3 hours at an air introduction rate of 10 liters/hour per gram of the carrier, to obtain a semi-finished catalyst Z1-S1, wherein the carbon content of Z1-S1 was 0.35 wt%.

Putting 10 g of ethylenediamine into 150 g of deionized water, adding a proper amount of ammonia water to adjust the pH value of the solution to 10.5, stirring to obtain a second impregnation liquid, impregnating Z1-S1 by using the second impregnation liquid by a saturated impregnation method for 2 hours, and then drying at 150 ℃ for 3 hours to obtain the catalyst S1. In the catalyst S1, MoO was calculated as oxides based on the total amount of S1₃15.2 wt%, NiO 3.9 wt%, P₂O₅The content was 2.9% by weight.

Preparation of comparative example 1

A hydrorefining catalyst was prepared by the method of preparation example 1, except thatThe obtained catalyst S1 was calcined at 400 ℃ for 3 hours to obtain catalyst D1. In the catalyst D1, MoO was calculated as oxides based on the total amount of D1₃15.1 wt%, NiO 3.8 wt%, P₂O₅The content was 2.8% by weight.

Preparation of comparative example 2

A hydrorefining catalyst was prepared according to the method of preparation example 1, except that the first impregnation liquid contained no citric acid and the second impregnation liquid contained no ethylenediamine, to obtain catalyst D2. In the catalyst D2, MoO was calculated as oxides based on the total amount of D1₃15.2 wt%, NiO 3.8 wt%, P₂O₅The content was 2.9% by weight.

Example 1

Referring to the flow shown in fig. 1, kerosene is extracted from the normal line, heat exchanged to 240 ℃, and then sent to a hydrogen mixer (FITS, model number, manufactured by long ridge petrochemical technology and technology development limited, of the south of Hunan), and is fully mixed with hydrogen-containing gas discharged from a diesel hydrorefining device in the hydrogen mixer, and the mixed material flow is conveyed to an upstream hydrogenation reactor. The reactor was packed with hydrofining catalyst S1 and a gas-liquid contact enhancement assembly hydrogen mixing tank was placed between the catalyst beds. And separating the reaction product to obtain concentrated hydrogen and refined aviation kerosene. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

Comparative example 1

A refined aviation kerosene product was produced by following the procedure of example 1 except that the hydrogen-containing gas in example 1 was replaced with hydrogen gas having a hydrogen concentration of 86% by volume. The hydrogenation conditions, the properties of the product obtained and the composition of the concentrated hydrogen are shown in Table 2.

Example 2

Enriched hydrogen and refined aviation kerosene products were produced according to the method of example 1, except that the hydrogen-containing gas used was from a hydrogen grid, primarily hydrogen from a catalytic reformer. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

Example 3

Enriched hydrogen and refined aviation kerosene products were produced in accordance with the method of example 1, except that the hydrogen-containing gas used was from a residuum hydrogenation unit. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

Example 4

Concentrated hydrogen and refined aviation kerosene products were produced by following the procedure of example 1 except that the catalyst charged in the hydrogenation reactor was catalyst D1 prepared in comparative example 1. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

Example 5

Concentrated hydrogen and refined aviation kerosene products were produced by following the procedure of example 1 except that the catalyst charged in the hydrogenation reactor was catalyst D2 prepared in comparative example 2. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

Example 6

Concentrated hydrogen and refined aviation kerosene products were produced in the same manner as in example 1, except that the catalyst charged in the hydrogenation reactor was an RSS-2 type catalyst (Ni-Mo system aviation kerosene hydrofining catalyst) developed by the institute of petrochemical science and research. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

Example 7

The enriched hydrogen and refined aviation kerosene products were produced according to the method of example 1 except that the upstream hydrogenation reactor in example 1 was replaced with the downstream hydrogenation reactor. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

Example 8

The enriched hydrogen and refined aviation kerosene products were produced according to the method of example 1, except that no hydrogen mixer was provided, i.e., kerosene and hydrogen-containing gas taken out of the normal line were directly fed into the hydrogenation reactor, and no gas-liquid contact enhancing assembly was provided in the hydrogenation reactor. The initial composition of the hydrogen-containing gas, the hydrogenation reaction conditions, the properties of the product obtained and the composition of the enriched hydrogen are shown in table 2.

TABLE 2

As can be seen from Table 3, the refined aviation kerosene product meeting the 3# jet fuel quality standard (the standard number is GB 6537-. Further, as can be seen from comparison of examples 1 and 3 with example 2, when the hydrogen content of the hydrogen-containing gas is 40 to 80 vol%, the hydrogen enrichment effect can be further improved. As can be seen from the comparison between example 1 and examples 4-6, the hydrorefining catalyst prepared by the special method can further improve the quality of refined aviation kerosene products and obtain better hydrogen concentration effect. As can be seen from the comparison between the embodiment 1 and the embodiments 7 to 8, the quality of the refined aviation kerosene product can be further improved and a better hydrogen concentration effect can be obtained by adopting the upstream hydrogenation reactor or arranging the hydrogen mixer and the gas-liquid contact strengthening component.

The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims

1. A process for hydrogenating a hydrogen-enriched jet fuel, comprising:

2. The method of claim 1, wherein the method further comprises: firstly, the kerosene extracted from the normal line and the hydrogen-containing gas are sent into a hydrogen mixer to be fully mixed and then sent into the hydrogenation reactor.

3. The process of claim 1, wherein the hydrogenation reactor is an upflow hydrogenation reactor.

4. The process of claim 1 or 3, wherein a gas-liquid contact enhancement component is disposed within the hydrogenation reactor, the gas-liquid contact enhancement component being a cold hydrogen box, a hydrogen mixer, a bubble cap tray, or a porous media, or a combination of two or three thereof.

5. The method according to claim 1, wherein the hydrogen-containing gas has a hydrogen content of 40 to 80 vol%.

6. The method of claim 1, wherein the hydrogen-containing gas is from at least one of a hydrofinishing unit, a hydrocracking unit, and a catalytic reforming unit.

7. The process of claim 1, wherein the hydrofinishing catalyst comprises a support which is an inorganic oxide and an active metal component which is a group VIB metal and/or a group viii metal, which is responsible on the support.

8. The method of claim 7, wherein the step of preparing the hydrofinishing catalyst comprises:

9. The process according to claim 1, wherein the distillation range of the normal line draw kerosene is 140-260 ℃.

10. The method of claim 1, wherein the conditions of the hydrofinishing reaction include: the reaction temperature is 200-300 ℃, preferably 220-260 ℃; the reaction pressure is 1.0-4.0 MPa, preferably 2.0-4.0 MPa; the liquid hourly space velocity is 0.5-10.0 h^-1Preferably 3.0 to 6.0 hours^-1(ii) a The volume ratio of hydrogen to oil is 40-300 Nm³/m³Preferably 50 to 200Nm³/m³。

11. The method of claim 1, wherein the method further comprises: and (3) carrying out heat exchange on the kerosene extracted from the normal line to 200-260 ℃, and then mixing the kerosene with the hydrogen-containing gas.

12. The method of claim 1, wherein the method further comprises: the enriched hydrogen is used as make-up hydrogen for a hydrofinishing process and/or a hydrocracking process.