CN108203600A - A kind of method for improving kerosene oxidation stability - Google Patents

A kind of method for improving kerosene oxidation stability Download PDF

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Publication number
CN108203600A
CN108203600A CN201611170674.1A CN201611170674A CN108203600A CN 108203600 A CN108203600 A CN 108203600A CN 201611170674 A CN201611170674 A CN 201611170674A CN 108203600 A CN108203600 A CN 108203600A
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hydrogen
hydrogenation
oil
pipe
oxidation stability
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马守涛
孙发民
王刚
张全国
吴显军
张文成
赵野
刘龙
靳丽丽
倪术荣
孟祥彬
李凤铉
夏恩冬
李瑞峰
王锐
姜维
葛冬梅
张铁珍
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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Priority to CN201611170674.1A priority Critical patent/CN108203600A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A kind of method for improving kerosene oxidation stability, includes the following steps：Oil product and hydrogen are carried out being mixed to form hydrogen oil mixture, which are sent into hydrogenation reactor；Hydrogenation reaction is carried out to hydrogen oil mixture in hydrogenation reactor, obtains hydrogenation reaction product, is equipped with hydrogen make-up inner member in hydrogenation reactor, hydrogen make-up inner member makes the hydrogenation reaction region of hydrogenation reactor, and there are the dissolved hydrogens of content constant always；Hydrogenation reaction product is sent into fractionating system and carries out gas-liquid separation；Hydrogen make-up inner member includes：One empty circles, empty circles are equipped with an air inlet；Multiple transverse pipes, multiple transverse pipes are fixed on circle and are connected with circle, and multiple transverse pipes are mutually parallel and equidistantly distribute；And multiple longitudinal pipes, multiple longitudinal pipes be fixed on circle and be connected with circle and with multiple transverse pipe square crossings, multiple longitudinal pipes are mutually parallel and equidistantly distribute, and the upside tube wall of multiple transverse pipes and multiple longitudinal pipes is equipped with multiple trepannings.

Description

A kind of method for improving kerosene oxidation stability
Technical field
The present invention relates to hydrocarbon processing technology, for improving hydrocarbon-containing feedstock Oxidation Stability, more particularly to a kind of boat coal The technique that raw material hydrofinishing produces 3# jet fuels.
Background technology
In recent years, China's aircraft industry is fast-developing, and country's boat average annual consumption increase rate of coal is 10% or so, far above the world 5% growth level, it has also become annual consumption consumes big country up to 15,000,000 tons of aviation fuel.Domestic Hang Mei enterprises have 43 it More, total productive capacity is more than 10,000,000 tons/year.
National 3# jet fuels standard does not require the nitrogen in boat coal and basic nitrogen, but in fact, some boat coals The indexs such as component its mercaptan sulfur, smoke point and freezing point all meet the requirements, and since basic nitrogen is excessively high, on the one hand cause kerosene that can not grow Time, which preserves, to be used, and is on the other hand also easy to produce corrosion.Data of literatures shows that basic nitrogen compound is to cause jet fuel color And its most immediate cause of stability problem.Basic nitrogen and phenol oxygen can act synergistically, and cause the rapid decrease of color stability. It is generally acknowledged that the basic n content in jet fuel is more than 1 μ g/g, phenol oxygen content is more than 30 μ g/g, will pacify the color of oil product Qualitative variation.Since under hydro condition, oxide easily removes, therefore basic n content is less than 3 μ g/g under normal circumstances, just It can ensure the stabilization of oil product color.
The process for purification of country's boat coal is generally divided into two major class：One kind is clay-filtered for soda acid, and this method is with domestic medium and small Enterprise is using more.Its process conditions mitigates, and equipment is simple and construction investment expense is low, but the product quality produced is not high, receives Rate is low, and a large amount of acid sludge, alkaline residue and waste water are generated in production process, equipment seriously corroded.These shortcomings limit the work The development of skill, is gradually eliminated at present；Another kind of is hydrofinishing process, under the effect of the catalyst, is made each in oil product Class non-hydrocarbon compound occurs hydrogenolysis and then is removed from oil product, while make alkene, aromatic hydrogenation saturation.This method has liquid Body high income, good product quality, the advantages that not polluting, it has also become one of boat most important refined means of coal.
Currently, kerosene hydrogenation generally use phase reaction (gas liquid solid body catalyst), such as traditional drip bed technique. In these systems, the continuous phase in reactor is gas phase, it usually needs a large amount of hydrogen is gas phase always in reactor to maintain Continuously.This is because, on the one hand, hydrogenation reaction is a micro- exothermic reaction, in order to maintain reaction temperature, needs excessive hydrogen Gas takes away reaction heat by catalyst bed；On the other hand, in the reaction of airwater mist cooling, higher hydrogen partial pressure is maintained to have Conducive to hydrogenation reaction, inhibit coke generation, extend catalyst life.Hydrogen more than needed usually after circulating hydrogen compressor is pressurized with New hydrogen mixing continues the hydrogen charging as reaction.This technical process can also be defined as gas phase cycle drip bed hydroprocessing work Skill.However, under this process conditions, bed Wen Sheng great, radial temperature difference are big, high energy consumption (more than 14 kilograms of mark oil/tons), increase throwing Money and operating cost.
For example, to provide and maintaining gas phase continuously required amount of hydrogen, hydrogenation reactor final effluent is generally separated Into the gaseous component and a liquid composition of a hydrogen.Gaseous component normally enters compressor, is then circulated back to reaction To help to provide a large amount of hydrogen, continuous gas phase is maintained with this for device entrance.Circulating hydrogen compressor is set as the key of hydrogenation process Standby, the ratio that investment accounts for entire hydrogenation plant cost is higher, and hydrogen heat-exchange system energy consumption is larger, if it is possible to will be in hydrogenation process Hydrogen flowing quantity reduce and save hydrogen gas circulating system and circulating hydrogen compressor, can be that enterprise reduce investment outlay cost.
Two-phase hydrogenation technique (for example, a liquid material and solid catalyst) is also to propose in some cases, will Certain hydrocarbon-bearing materials are converted to other more valuable hydro carbons.For example, by hydrogen presaturation, two-phase reactor reduction may be used Sulphur rather than the traditional three-phase system of use in certain hydrocarbon streams.
To Liquid-phase reactor other using being to be hydrocracked and the hydrotreating of hydrocarbon-bearing material.However, hydrotreating and Being hydrocracked needs a large amount of hydrogen that corresponding chemical conversion occurs.Therefore, even if these are reacted all in liquid phase systems, still Need a large amount of hydrogen.Therefore, it in order to maintain such a liquid-phase hydrogenatin processing or hydrocracking reaction, provides needed for reaction Hydrogen needs to introduce additional diluent or solvent in the raw material of existing liquid phase systems, comes relative to the amounts of hydrogen of dissolving It says, reactive component and reduction reactor Wen Sheng in main dilution charging.Then, for raw material, diluent and molten Agent provides the molten hydrogen concentration of a bigger, it is ensured that enough conversion ratios can occur in the liquid phase.Needed in these systems bigger, More complicated, more expensive Liquid-phase reactor, to realize required conversion.
Two-phase technique mainly has an IsoTherming technologies of DuPont at present, the said firm patent US6881326B2 and ZL200680018017.3 reports the molten hydrogen concentration that bigger is provided using diluent or solvent, using product as diluent or Solvent, due to being hydrocracked or hydrotreating reaction, hydrogen gas consumption is larger, causes product internal circulating load larger, therefore needs Increase the investment of liquid circulation pump.
And kerosene belongs to light Fuel, sulphur nitrogen content is relatively low, and required amounts of hydrogen is smaller, therefore, for kerosene liquid-phase hydrogenatin The characteristics of, Chang Ling petrochemical industry develops tubular reactor, and [refinery boat coal tubular type liquid phase hydrogenation technology in Chang Ling realizes industrial applications, stone Oiling work, 2016 (3)：374], which obtains commercial Application in Chang Ling petrochemical industry and North Sea refinery.Although the technique does not need to The problems such as product recycles, but complicated there are structure of reactor, and Catalyst packing is time-consuming and laborious.
Although various technological processes, operating condition and catalyst have been used for industrial oil hydrocarbon conversion process, People always seek to be capable of providing more useful product and improve the new method and new process of product characteristic.In many cases, Even the minor change of technique or operating condition can also significantly affect product quality and selectivity.
Invention content
The purpose of the present invention is to provide a kind of methods for improving kerosene oxidation stability, include the following steps：
Oil product and hydrogen are carried out being mixed to form hydrogen oil mixture by step 1, which is sent into hydrogenation reaction Device；
Step 2 carries out hydrogenation reaction to hydrogen oil mixture in hydrogenation reactor, obtains hydrogenation reaction product, add hydrogen anti- It answers and hydrogen make-up inner member is equipped in device, hydrogen make-up inner member makes the hydrogenation reaction region of hydrogenation reactor, and there are contents always Constant dissolved hydrogen；And
Hydrogenation reaction product is sent into fractionating system and carries out gas-liquid separation by step 3；
Wherein, the hydrogen make-up inner member includes：
One empty circles, the empty circles are equipped with an air inlet；
Multiple transverse pipes, the multiple transverse pipe are fixed in the empty circles and are connected with the empty circles, The multiple transverse pipe is mutually parallel and equidistantly distributes；And
Multiple longitudinal pipes, the multiple longitudinal pipe be fixed in the empty circles and be connected with the empty circles and With multiple transverse pipe square crossings, the multiple longitudinal pipe is mutually parallel and equidistantly distributes, the multiple transverse pipe and multiple The upside tube wall of longitudinal pipe is equipped with multiple trepannings.
Further, the multiple transverse pipe is uniformly distributed with multiple trepannings on the multiple longitudinal pipe.
Further, diversion pipe is equipped in the multiple trepanning, the diversion pipe upper end closed, the both sides of diversion pipe are set There is opening.
Further, hydrogen reaches dissolving saturation state in the hydrogen oil mixture in step 1.
Further, in step 1 oil product be distillate, ranging from 100 DEG C~300 DEG C of the boiling range of the distillate.
Further, oil product is the boat coal component in straight-run diesel oil or straight-run diesel oil in step 1.
Further, hydrogenation conditions are in step 2：Reaction pressure 2.0MPa~5.0MPa, reaction temperature 220 DEG C~300 DEG C, volume space velocity 2.0h-1~6.0h-1。
Further, it is from hydrogenation reactor by the feeding manner of hydrogen oil mixture feeding hydrogenation reactor in step 1 Bottom is fed.
Further, hydrogenation reaction is Continuous Liquid Phase hydrogenation reaction in step 2.
Wherein, in step 1, the process that oil product and hydrogen are mixed is mixed for the gas-liquid before hydrogenation reactor It is carried out in clutch.The main function of air and liquid mixer is to make to reach dissolving saturation shape into the hydrogen in the distillate of reactor State.Experiment shows that the hydrogen needed for part reaction is made to be dissolved in feedstock oil in advance, can accelerate the rate of reaction, carry High reaction effect.
Wherein, in step 2, hydrogenation catalyst is placed in catalyst bed, hydrogen oil mixture is made to pass through from below to up It can react when catalyst bed；In addition, further including hydrogen make-up inner member in catalyst bed, pass through benefit Being flushed with hydrogen gas inner member, (hydrogen is still in the oil fully dissolved state after supplement, and what is supplemented herein is anti-to hydrogen oil mixture hydrogen make-up The hydrogen that should fall).The hydrogenation reactor of the present invention can set one or more catalyst beds according to the scale requirements of device Layer, hydrogen make-up inner member is installed on catalyst support plate.There are two aspect, (1) supplements molten hydrogen for the effect of inner member, and maintenance is anti- Answer device hydrogen partial pressure；(2) supplement is by the consumed hydrogen of previous bed reaction；(3) the partial reaction heat of a upper bed is absorbed, Reduce bed Wen Sheng.
Wherein, the catalyst used in hydrogenation reaction is non-precious metal catalyst.
This method is the oxidation stability for improving hydrocarbon raw material.This method is utilized in a Continuous Liquid Phase reaction zone to be added Hydrogen reaction carries out the denitrogenation of hydrocarbon raw material and Porous deproteinized bone reacts rather than one needs a large amount of high pressure hydrogens to maintain gas phase continuous Three-phase reaction system.Referring herein to liquid-phase reaction system in a certain amount of hydrogen is mixed into hydrocarbon raw material, to add hydrogen The reaction rate of the condition of one Continuous Liquid Phase of holding and continuous equilibrium in conversion zone.
This method at least reduces one in nitrogen in hydrocarbon raw material, alkali nitrogen, aromatic hydrocarbons by Continuous Liquid Phase hydrogenation process Numerical value.Can be hydrogen and hydrocarbon raw material respectively enters hydroconversion reaction zone before hydrogenation reaction, hydrogen is mixed into hydrocarbon raw material, Full of in Continuous Liquid Phase hydroconversion reaction zone, while keep continuing liquid-phase condition；Can also be that hydrogen is first mixed into hydrocarbon raw material Hydrogen in saturated hydrocarbons raw material, then, hydrocarbon raw material are directly entered Continuous Liquid Phase hydroconversion reaction zone.In the region, hydro carbons Raw material (or part) is reacted to generate nitrogen, alkali nitrogen, aromatic hydrocarbons under Hydrofinishing conditions at least one hydrogenation catalyst At least one of relatively low hydrocarbon products.
In addition, state of the art form may be used in the hydrocarbon raw material hydrogenation technique of the present invention, such as single hop plus hydrogen work Skill carries out hydrofinishing (hydrogenation reactor), one-stage serial hydrogenation technique carries out hydrofinishing --- post-refining (two Hydrogenation reactor).
The present invention has no hydrogen gas bubbles in the reactor or hydrogen gas exists, but dissolved state.In the prior art In, in Chinese patent CN103119133A disclosure of that, including narration：" hydrogen is with strip (slug) or the shape of bubble Formula is present in the outside or inside that liquid is full of space region ", " hydrogen should exist to ensure to add hydrogen behaviour with sufficiently low concentration Make the Continuous Liquid Phase in reactor, but concentration will be high enough to provide enough hydrogen for hydroprocessing hydrocarbon feed ".It is above old It is there is (difference for having essence with the present invention) with gas or bubble shape to state bright hydrogen in that patent, and bubble form is deposited Hydrogen, it is described to illustrate that technology such as background of invention one that the patent uses saves, needs using circulating hydrogen compressor, band Come larger cost problem or directly outer row, a large amount of hydrogen is caused to waste, increase operating cost.In addition, Chinese patent There is " Liquid product recycle oil " a kind of vocabulary in CN103805240A disclosure of that, but CN103805240A is that gas-liquid is inverse The product circulation of flow reactor.Also, second reactor is not Liquid-phase reactor in CN103805240A, is gas-liquid conversed The reactor of flowing, therefore, final reaction product property and reaction condition and pure Liquid-phase reactor are differentiated. It can be seen that the features of the present invention from description of the invention：The circulating hydrogen compressor of conventional hydro is eliminated, while is also cancelled Conventional liquid phase adds the product of hydrogen to recycle, and by the technique of the present invention, can significantly reduce cost of investment and operating cost.
The beneficial effects of the invention are as follows：The hydrocarbon raw material hydrogenation technique of the present invention, can cancel circulating hydrogen compressor and oil Product circulating pump, oil hydrogenation technological process is simple, reduces cost of investment and operational risk.This method can be used for coal component of navigating Add hydrogen dealkalize nitrogen and/or aromatic hydrocarbons, improve the oxidation stability of 3# jet fuels.
Description of the drawings
Fig. 1 is hydrogenation technique flow diagram of the present invention.
Fig. 2 is hydrogen make-up inner member structure diagram of the present invention.
Wherein, reference numeral：
1st, hydrogen
2nd, feedstock oil
3rd, air and liquid mixer
4th, hydrogenation reactor
5th, fractionating system
6th, product
7th, hydrogen make-up inner member
8th, empty circles
9th, transverse pipe
10th, longitudinal pipe
11st, trepanning
Specific embodiment
Technical scheme of the present invention is described in detail below in conjunction with specific embodiment, and listed illustrative embodiments are only Make to illustrate and be used, be not intended as the limitation of the present invention.
A kind of method for improving kerosene oxidation stability, includes the following steps：
Oil product and hydrogen are carried out being mixed to form hydrogen oil mixture by step 1, which is sent into hydrogenation reaction Device；
Step 2 carries out hydrogenation reaction to hydrogen oil mixture in hydrogenation reactor, obtains hydrogenation reaction product, add hydrogen anti- It answers and hydrogen make-up inner member is equipped in device, hydrogen make-up inner member makes the hydrogenation reaction region of hydrogenation reactor, and there are contents always Constant dissolved hydrogen；And
Hydrogenation reaction product is sent into fractionating system and carries out gas-liquid separation by step 3；
Wherein, the hydrogen make-up inner member includes：
One empty circles, the empty circles are equipped with an air inlet；
Multiple transverse pipes, the multiple transverse pipe are fixed in the empty circles and are connected with the empty circles, The multiple transverse pipe is mutually parallel and equidistantly distributes；And
Multiple longitudinal pipes, the multiple longitudinal pipe be fixed in the empty circles and be connected with the empty circles and With multiple transverse pipe square crossings, the multiple longitudinal pipe is mutually parallel and equidistantly distributes, the multiple transverse pipe and multiple The upside tube wall of longitudinal pipe is equipped with multiple trepannings.
Further, the multiple transverse pipe is uniformly distributed with multiple trepannings on the multiple longitudinal pipe.
Further, diversion pipe is equipped in the multiple trepanning, the diversion pipe upper end closed, the both sides of diversion pipe are set There is opening.
Further, hydrogen reaches dissolving saturation state in the hydrogen oil mixture in step 1.
Further, in step 1 oil product be distillate, ranging from 100 DEG C~300 DEG C of the boiling range of the distillate.
Further, oil product is the boat coal component in straight-run diesel oil or straight-run diesel oil in step 1.
Further, hydrogenation conditions are in step 2：Reaction pressure 2.0MPa~5.0MPa, reaction temperature 220 DEG C~300 DEG C, volume space velocity 2.0h-1~6.0h-1。
Further, it is from hydrogenation reactor by the feeding manner of hydrogen oil mixture feeding hydrogenation reactor in step 1 Bottom is fed.
Further, hydrogenation reaction is Continuous Liquid Phase hydrogenation reaction in step 2.
Embodiment 1
The present embodiment provides a kind of methods for improving kerosene oxidation stability, include the following steps：
1) the normal line diesel oil of raw material A and hydrogen 1 are carried out mixing in air and liquid mixer 3 makes hydrogen 1 reach dissolving saturation State forms the hydrogen oil mixture of pure liquid state, and the hydrogen oil mixture is sent into hydrogenation reactor 4 from bottom；
2) in hydrogenation reactor 4, hydrogenation reaction is carried out to the hydrogen oil mixture, obtains hydrogenation reaction product, it is described Hydrogenation reactor 4 include a catalyst bed and filling kerosene hydrogenation catalyst PHK-101, in the catalyst bed Including hydrogen make-up inner member 7；The hydrogen make-up inner member 7 includes：One empty circles 8, the empty circles 8 are equipped with one Air inlet (is not drawn into) in figure；Three transverse pipes 9, three transverse pipes 9 be fixed in the empty circles 8 and with the sky Heart circle 8 is connected, and three transverse pipes 9 are mutually parallel and equidistantly distribute, equidistant equipped with more in each transverse pipe 9 A trepanning 11, the distance between two neighboring trepanning 11 in same transverse pipe 9 and the distance phase between two adjacent transverse pipes 9 Together；And three longitudinal pipes 10, three longitudinal pipes 10 be fixed in the empty circles 8 and with 8 phase of empty circles Connection and with three 9 square crossings of transverse pipe, three longitudinal pipes 10 are mutually parallel and equidistantly distribute, longitudinally in each pipe 10 On it is equidistant be equipped with multiple trepannings 11, distance between two neighboring trepanning 11 on same longitudinal pipe 10 and adjacent two it is vertical Distance between pipe 10 is identical.The hydrogenation reaction process conditions are：Reaction pressure 5.0MPa, reaction temperature are 300 DEG C, body Product air speed is 3.0h-1；
3) hydrogenation reaction product is sent into fractionating system 5.
2 property of feedstock oil is listed in table 1, and 6 property of product is listed in table 2.
As can be seen from Table 2, using the technology, basic nitrogen is less than 3 μ g/g, can improve boat oxidation of coal stability.
Embodiment 2
The present embodiment provides a kind of methods for improving kerosene oxidation stability, include the following steps：
1) by raw material B straight run boat coal component (boiling range range：180~300 DEG C) and hydrogen 1 carried out in air and liquid mixer 3 Mixing makes hydrogen reach dissolving saturation state, forms the hydrogen oil mixture of pure liquid state, which is sent from bottom Enter hydrogenation reactor 4；
2) in hydrogenation reactor 4, hydrogenation reaction is carried out to the hydrogen oil mixture, obtains hydrogenation reaction product, it is described Hydrogenation reactor 4 include three catalyst beds and filling kerosene hydrogenation catalyst PHK-101, in the catalyst bed Including hydrogen make-up inner member 7；The hydrogen make-up inner member 7 includes：One empty circles 8, the empty circles 8 are equipped with one Air inlet；Five transverse pipes 9, five transverse pipes 9 are fixed in the empty circles 8 and are connected with the empty circles 8 Logical, five transverse pipes 9 are mutually parallel and equidistantly distribute, equidistant in each transverse pipe 9 to be equipped with multiple trepannings 11, together The distance between two neighboring trepanning 11 in one transverse pipe 9 is identical with the distance between two adjacent transverse pipes 9；And five vertical To pipe 10, five longitudinal pipes 10 be fixed in the empty circles 8 and be connected with the empty circles 8 and with five horizontal strokes To 9 square crossing of pipe, five longitudinal pipes 10 are mutually parallel and equidistantly distribute, equidistant on pipe 10 longitudinally in each to be equipped with Multiple trepannings 11, the distance between two neighboring trepanning 11 on same longitudinal pipe 10 and the distance between adjacent two longitudinal pipes 10 It is identical.The hydrogenation reaction process conditions are：Reaction pressure 4.0MPa, reaction temperature are 245 DEG C, volume space velocity 4.0h-1；
3) hydrogenation reaction product is sent into fractionating system 5.
2 property of feedstock oil is listed in table 1, and 6 property of product is listed in table 2.
As can be seen from Table 2, using the technology, basic nitrogen is less than 3 μ g/g, can improve boat oxidation of coal stability.
Embodiment 3
The present embodiment provides a kind of methods for improving kerosene oxidation stability, include the following steps：
1) by raw material C straight run boat coal component (boiling range range：180~240 DEG C) and hydrogen 1 carried out in air and liquid mixer 3 Mixing makes hydrogen reach dissolving saturation state, forms the hydrogen oil mixture of pure liquid state, which is sent from bottom Enter hydrogenation reactor 4；
2) in hydrogenation reactor 4, hydrogenation reaction is carried out to the hydrogen oil mixture, obtains hydrogenation reaction product, it is described Hydrogenation reactor 4 include two catalyst beds and filling kerosene hydrogenation catalyst PHK-101, in the catalyst bed Including hydrogen make-up inner member 7；The hydrogen make-up inner member 7 includes：One empty circles 8, the empty circles 8 are equipped with one Air inlet；Five transverse pipes 9, five transverse pipes 9 are fixed in the empty circles 8 and are connected with the empty circles 8 Logical, five transverse pipes 9 are mutually parallel and equidistantly distribute, equidistant in each transverse pipe 9 to be equipped with multiple trepannings 11, together The distance between two neighboring trepanning 11 in one transverse pipe 9 is identical with the distance between two adjacent transverse pipes 9；And five vertical To pipe 10, five longitudinal pipes 10 be fixed in the empty circles 8 and be connected with the empty circles 8 and with five horizontal strokes To 9 square crossing of pipe, five longitudinal pipes 10 are mutually parallel and equidistantly distribute, equidistant on pipe 10 longitudinally in each to be equipped with Multiple trepannings 11, the distance between two neighboring trepanning 11 on same longitudinal pipe 10 and the distance between adjacent two longitudinal pipes 10 It is identical.It is equipped with diversion pipe (in figure for draw) in trepanning 11 in transverse pipe 9 and longitudinal pipe 10, end seal on the diversion pipe It closes, the both sides of diversion pipe are equipped with opening.The hydrogenation reaction process conditions are：Reaction pressure 4.0MPa, reaction temperature 220 DEG C, volume space velocity 4.0h-1；
3) hydrogenation reaction product is sent into fractionating system 5.
2 property of feedstock oil is listed in table 1, and 6 property of product is listed in table 2.
As can be seen from Table 2, using the technology, basic nitrogen is less than 3 μ g/g, can improve boat oxidation of coal stability.
Comparative example 1
The boat coal raw material D of same nature is handled, using this process and conventional single stage process, correction data is shown in Table 3. As can be seen from Table 3, comparable in process conditions, the indices for generating oil are substantially suitable, but this process institute 76% is saved with the more conventional method of amounts of hydrogen.
The property of the raw materials used oil of 1 Examples 1 to 3 of table
2 Examples 1 to 3 result of the test of table
Project Embodiment 1 Embodiment 2 Embodiment 3
Total nitrogen, μ g/g 8.9 3.3 3.1
Alkali nitrogen, μ g/g 2.3 2.4 2.0
Aromatic hydrocarbons, ω % 3.5 3.2 1.6
3 comparative example of table, 1 raw material oil nature and result of the test
As can be seen from the above embodiments, hydrocarbon raw material hydrogenation technique of the invention can cancel circulating hydrogen compressor and oil Product circulating pump, oil hydrogenation technological process is simple, reduces cost of investment and operational risk.This method can be used for coal component of navigating Add hydrogen dealkalize nitrogen and/or aromatic hydrocarbons, improve the oxidation stability of 3# jet fuels.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art The protection domain of the claims in the present invention should all be belonged to.

Claims (9)

  1. A kind of 1. method for improving kerosene oxidation stability, which is characterized in that include the following steps：
    Oil product and hydrogen are carried out being mixed to form hydrogen oil mixture by step 1, which is sent into hydrogenation reactor；
    Step 2 carries out hydrogenation reaction to hydrogen oil mixture in hydrogenation reactor, obtains hydrogenation reaction product, hydrogenation reactor Interior to be equipped with hydrogen make-up inner member, hydrogen make-up inner member makes the hydrogenation reaction region of hydrogenation reactor, and there are content constants always Dissolved hydrogen；And
    Hydrogenation reaction product is sent into fractionating system and carries out gas-liquid separation by step 3；
    Wherein, the hydrogen make-up inner member includes：
    One empty circles, the empty circles are equipped with an air inlet；
    Multiple transverse pipes, the multiple transverse pipe is fixed in the empty circles and is connected with the empty circles, described Multiple transverse pipes are mutually parallel and equidistantly distribute；And
    Multiple longitudinal pipes, the multiple longitudinal pipe be fixed in the empty circles and be connected with the empty circles and with it is more A transverse pipe square crossing, the multiple longitudinal pipe are mutually parallel and equidistantly distribute, the multiple transverse pipe and multiple longitudinal directions The upside tube wall of pipe is equipped with multiple trepannings.
  2. 2. it is according to claim 1 improve kerosene oxidation stability method, which is characterized in that the multiple transverse pipe with Multiple trepannings on the multiple longitudinal pipe are uniformly distributed.
  3. 3. the method according to claim 1 for improving kerosene oxidation stability, which is characterized in that in the multiple trepanning Equipped with diversion pipe, the diversion pipe upper end closed, the both sides of diversion pipe are equipped with opening.
  4. 4. the method according to claim 1 for improving kerosene oxidation stability, which is characterized in that the hydrogen oil in step 1 mixes It closes hydrogen in object and reaches dissolving saturation state.
  5. 5. the method according to claim 1 for improving kerosene oxidation stability, which is characterized in that oil product is evaporates in step 1 Divide oil, ranging from 100 DEG C~300 DEG C of the boiling range of the distillate.
  6. 6. the method according to claim 1 for improving kerosene oxidation stability, which is characterized in that oil product is straight in step 1 Evaporate the boat coal component in diesel oil or straight-run diesel oil.
  7. 7. the method according to claim 1 for improving kerosene oxidation stability, which is characterized in that hydrogenation reaction in step 2 Condition is：Reaction pressure 2.0MPa~5.0MPa, reaction temperature are 220 DEG C~300 DEG C, volume space velocity 2.0h-1~6.0h-1。
  8. 8. the method according to claim 1 for improving kerosene oxidation stability, which is characterized in that mix hydrogen oil in step 1 It closes object and is sent into the feeding manner of hydrogenation reactor to be fed from hydrogenation reactor bottom.
  9. 9. the method according to claim 1 for improving kerosene oxidation stability, which is characterized in that hydrogenation reaction in step 2 For Continuous Liquid Phase hydrogenation reaction.
CN201611170674.1A 2016-12-16 2016-12-16 A kind of method for improving kerosene oxidation stability Pending CN108203600A (en)

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CN103666546A (en) * 2012-09-21 2014-03-26 中国石油化工股份有限公司 Liquid-phase hydrogenation refining method of aviation kerosene
CN103965953A (en) * 2013-01-30 2014-08-06 中国石油天然气股份有限公司 Distillate oil two-phase hydrogenation reactor and hydrogenation process
CN104232154A (en) * 2013-06-21 2014-12-24 中国石油天然气股份有限公司 Distillate oil hydro-upgrading method
CN105602619A (en) * 2015-12-18 2016-05-25 中国石油天然气股份有限公司 Liquid-phase hydrogenation heterogeneous system and process and application thereof
CN105733669A (en) * 2014-12-11 2016-07-06 中国石油天然气股份有限公司 Oil product hydrogenation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
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CN103666546A (en) * 2012-09-21 2014-03-26 中国石油化工股份有限公司 Liquid-phase hydrogenation refining method of aviation kerosene
CN103965953A (en) * 2013-01-30 2014-08-06 中国石油天然气股份有限公司 Distillate oil two-phase hydrogenation reactor and hydrogenation process
CN104232154A (en) * 2013-06-21 2014-12-24 中国石油天然气股份有限公司 Distillate oil hydro-upgrading method
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Application publication date: 20180626