CN101376826B - Hydrogenation technological process for long distillate coking kerosene - Google Patents
Hydrogenation technological process for long distillate coking kerosene Download PDFInfo
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- CN101376826B CN101376826B CN 200710012681 CN200710012681A CN101376826B CN 101376826 B CN101376826 B CN 101376826B CN 200710012681 CN200710012681 CN 200710012681 CN 200710012681 A CN200710012681 A CN 200710012681A CN 101376826 B CN101376826 B CN 101376826B
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Abstract
The invention discloses a hydrogenation technique method for long distillate coking kerosene. The operation conditions of the fractionating system of a coking device is regulated and delayed; a proper cutting point is adopted for cutting the long distillate coking kerosene into a hydrogenation device for carrying out hydrogenation refining. Compared with the respective hydrogenation or mixed hydrogenation of the existing various fraction oil, hydrogenation is independently carried out on the long distillate coking kerosene for producing jet fuel with higher price and improving the economic benefits of oil refinery enterprises in the invention.
Description
Technical field
The invention belongs to heat processing technique and hydroprocessing technique process integration technology.Specifically, be Technology with the associating of delay coking process and hydroprocessing technique.
Background technology
At present, the crude oil heaviness of refinery processing, the trend of in poor quality are day by day obvious, and along with socioeconomic development, the demand that light ends oil is particularly cleaned light ends oil progressively increases, and inferior, heavy feed stock need to be converted into cleaning light ends oil production.Delayed coking is the important means that realizes inferior heavy oil, residual oil weight-lightening, is widely used at refinery.
The product of delayed coker produces normally is cut into coker gasoline, coker gas oil and wax tailings in fractionating system, and the cut point of gasoline and diesel oil is generally about 180 ℃, and is relatively poor and do not produce kerosene because coking obtains the character of kerosene(oil)fraction.Coker gasoline cut wherein mainly contains following three kinds of processing modes: direct mediation charging as the pre-hydrogenation unit of catalytic reforming; After hydrotreatment as the mediation charging of the pre-hydrogenation unit of catalytic reforming; Raw material as preparing ethylene by steam cracking after hydrotreatment dispatches from the factory.The characteristics of Hydrogenation of Coker Gasoline process are vapour-phase reaction (raw material gasify under reaction conditions and is gas phase), and reaction temperature rising is large, the easy coking of beds, and device is short etc. running period.The coker gas oil part, because sulphur, nitrogen content are high, stability is poor, must pass through hydrotreatment could dispatch from the factory as diesel oil blending component.Coker gas oil and wax tailings hydrogenation are generally liquid phase reaction, owing to containing easy coking material in the coking product, still have the problem of the easy coking of beds.
Along with the fast development of civil aviation cause, the situation that supply falls short of demand has appearred in aviation kerosene, and market value is very high, and the price of diesel oil is then lower comparatively speaking.Therefore, oil refining enterprise rationally utilizes existing resource, and the higher aviation kerosene of production prices is the effective means that improves Business Economic Benefit to greatest extent.The main method of producing at present the boat coal is the shallow degree hydrogenation of virgin kerosene cut, removes the impurity such as mercaptan and obtains the product of coal that navigates.Hydrocracking process can obtain qualified boat product of coal in addition.
The respectively method of hydrogenation is generally adopted in existing coking distillate hydrotreatment, comprises Hydrogenation of Coker Gasoline, coker gas oil hydrogenation and wax tailings hydrogenation.Patent CN02109671.6 has introduced a kind of method, coker gasoline, coker gas oil, the wax tailings of delayed coker produces are carried out hydrogenation of total effluent, petroleum naphtha and diesel oil behind the hydrogenation directly dispatch from the factory, and the hydrogenation wax oil is as the mediation charging of fluid catalytic cracking or hydroeracking unit.The advantage of the method is that the product with delayed coking unit carries out hydrogenation of total effluent, and the device tricks is few; Shortcoming is that the device working pressure is high, air speed is low, plant construction is invested and process cost is high.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of coking kerosene cut fraction hydrogenation method, the low grade coal oil distillate that coking obtains is selected and suitable hydrogenation process and condition by suitable raw material boiling range scope, coking kerosene cut inferior can be processed as high-quality boat product of coal.
Coking kerosene hydrogenation technique provided by the invention comprises following content:
Adjust the operational condition of delayed coking unit fractionating system, take the cut point that suits, cut out long distillate coking kerosene and enter special hydrogenation unit and carry out hydrofining.Wherein the initial boiling point of long distillate coking kerosene is 120～200 ℃, is preferably 120～160 ℃, and final boiling point is 230～300 ℃, is preferably 260～300 ℃.Coking kerosene hydrogenation unit operational condition is:
Working pressure: 3.0～8.0MPa;
Reactor inlet temperature: 200～330 ℃, average reaction temperature: 230～360 ℃;
Volume space velocity: 1.0～5.0h
-1
Hydrogen to oil volume ratio: 100～1500.
In the inventive method, catalyzer comprises conventional Hydrobon catalyst, reaches the quality product requirement of aviation kerosene; Also can comprise the deep hydrofinishing catalyzer, further reduce alkene, aromaticity content in the oil product, improve oil property.
In the inventive method, the fractionating system of hydrogenation unit adopts the double tower fractionation process, and oil product carries out full cut stripping at stripping tower, then carries out fractionation in separation column, obtains the hydrogenation kerosene(oil)fraction at the bottom of the separation column tower.
The present invention has following several advantages:
1, the long distillate coking kerosene that utilizes delayed coking unit to provide, the aviation kerosene product that the quality of production is good to greatest extent, price is high improves the economic benefit of enterprise.
2, the device working pressure is low, and air speed is high, and plant investment is few.Only need adjust the operational condition of fractionating system for delayed coking unit, can realize easily the present invention program.
3, can utilize idle diesel hydrotreating unit, device is changed little.
4, for a person skilled in the art, it is generally acknowledged to be not suitable for the coking kerosene cut is processed as the boat product of coal, because it is second-rate, and boat product of coal specification of quality is higher.The coking kerosene cut fraction hydrogenation has the dual characteristics of Hydrogenation of Coker Gasoline and coker gas oil hydrogenation concurrently, different with both again, the characteristics that the present invention shows by research coking kerosene cut fraction hydrogenation process, the factors such as relation such as reaction temperature rising and material gasification, adjust targetedly, as adjust the boiling range scope etc. of raw material, and adopt simultaneously suitable process and condition to obtain the qualified boat product of coal of high-quality, obtained beyond thought technique effect.
Description of drawings
Fig. 1 is long distillate coking kerosene hydrogenation technique schematic flow sheet.
Wherein: 1 is long distillate coking kerosene, and 2 is the hydrogenation fresh feed pump, and 3 is interchanger, and 4 is process furnace, and 5 is hydrotreating reactor, and 6 is high-pressure separator, and 7 is light pressure separator, and 8 is stripping tower, and 9 is the hydrogenation products separation column, and 10 is new hydrogen, and 11 is recycle hydrogen.
Embodiment
Further specify technical process of the present invention below in conjunction with accompanying drawing.
As shown in Figure 1, the delayed coking unit separation column is taked Operating condition, obtains long distillate coking kerosene 1 from the separation column side line, enters hydrogenation unit.
Long distillate coking kerosene 1 mixes with recycle hydrogen 11 and new hydrogen 10 through hydrogenation fresh feed pump 2, enters hydrotreating reactor 5 through interchanger 3, process furnace 4, at 200～330 ℃ of reactor inlet temperatures, reaction pressure 3.0～8.0MPa, volume space velocity 1.0～5.0h
-1, under hydrogen to oil volume ratio 100～1500 processing condition, carry out hydrofining reaction.Reaction product enters high-pressure separator 6 through interchanger 3, air cooling, water-cooled and carries out gas-liquid separation, and gaseous product recycles behind circulating hydrogen compressor, and product liquid enters light pressure separator 7 and again carries out gas-liquid separation.A low minute liquid product enters stripping tower 8 and carries out full cut stripping, enters in the separation column 9 again, obtains the hydrogenation kerosene(oil)fraction at the bottom of the separation column tower.
The hydrotreating catalyst that uses in the hydrotreatment of the present invention reaction preferably includes two or more type catalyst, and reaction raw materials contacts with the larger hydrogenation protecting agent of pore volume etc. in the aperture first, and then contacts with main hydrotreating catalyst.Main hydrotreating catalyst accounts for 80%～100% of total catalyst volume, is preferably 90%～95%.Various catalyzer can be selected commercial catalyst, also can prepare according to this area scheme.The hydrotreating catalyst such as FZC-100, FZC-102B, FZC-103 with the commodity hydrogenation catalyst of larger aperture and pore volume such as Fushun Petrochemical Research Institute's development and production.Main hydrotreating catalyst can be the common hydrotreating catalyst in this area, such as FH-5, FH-5A, FH-98, FH-40A, the catalyzer such as FH-40B, FH-40C of Fushun Petrochemical Research Institute's development and production, also can be other similar catalyzer.The deep hydrofinishing catalyzer that can also comprise high metal content in the main hydrotreating catalyst is such as FH-FS Hydrobon catalyst of Fushun Petrochemical Research Institute's development and production etc.Adopt the high deep hydrofinishing catalyzer of metal content, can further reduce alkene, aromaticity content in the hydrogenated gasoline, improve oil property.The Deep Hydrotreating catalyzer accounts for 10%～50% of total catalyst volume, can load with common hydrotreating catalyst layering, also can mixed packing, preferentially be seated in after the common hydrotreating catalyst, be that reaction mass contacts with common hydrotreating catalyst first, then contact with the deep hydrofinishing catalyzer.Common hydrotreating catalyst generally one or more in W, Mo, Ni, the Co is generally 10%～40% as active metal component in the oxide compound active metallic content.Deep hydrogenation catalyst activity metal content is generally 45%～85%.Consisting of of a kind of concrete hydrotreating catalyst: Tungsten oxide 99.999 5%～25%, molybdenum oxide 2%～12%, nickel oxide 2%～10%, carrier are silicon-containing alumina.A kind of concrete deep hydrogenation catalyzer is by weight percentage: Tungsten oxide 99.999 25%～45%, and molybdenum oxide 10%～25%, nickel oxide 10%～25%, carrier are silicon-containing alumina.(catalyzer forms by weight)
The following examples will be elaborated to the inventive method, but the present invention is not subjected to the restriction of embodiment.
Cut out the coking kerosene cut from the separation column of delayed coking unit, hydrogenation kerosene dispatches from the factory as aviation kerosene.
Stock oil character sees Table 1, and operational condition sees Table 2, and hydrogenated products character sees Table 3.
Table 1 stock oil character
Table 2 operational condition
Table 3 product property
Embodiment 2
Cut out the long distillate coking kerosene cut from the separation column of delayed coking unit, hydrogenation kerosene dispatches from the factory as aviation kerosene.
Stock oil character sees Table 4, and operational condition sees Table 5, and hydrogenated products character sees Table 6.
Table 4 stock oil character
Table 5 operational condition
Table 6 product property
Claims (7)
1. hydrogenation technological process for long distillate coking kerosene, comprise following content: the operational condition of adjusting the delayed coking unit fractionating system, take the cut point that suits, cutting out long distillate coking kerosene enters hydrogenation unit and carries out hydrofining, wherein the initial boiling point of long distillate coking kerosene is 120～200 ℃, and final boiling point is 230～300 ℃; Coking kerosene hydrogenation unit operational condition is:
Working pressure: 3.0～8.0MPa;
Reactor inlet temperature: 200～330 ℃, average reaction temperature: 230～360 ℃;
Volume space velocity: 1.0～5.0h
-1
Hydrogen to oil volume ratio: 100～1500.
2. in accordance with the method for claim 1, the initial boiling point that it is characterized in that described long distillate coking kerosene is 120～160 ℃, and final boiling point is 260～300 ℃.
3. in accordance with the method for claim 1, it is characterized in that the catalyzer that described hydrofining is used comprises conventional Hydrobon catalyst, perhaps comprises the deep hydrofinishing catalyzer.
4. in accordance with the method for claim 1, it is characterized in that the fractionating system of described hydrogenation unit adopts the double tower fractionation process, oil product carries out full cut stripping at stripping tower, then carries out fractionation in separation column, obtains the hydrogenation kerosene(oil)fraction at the bottom of the separation column tower.
5. in accordance with the method for claim 3, it is characterized in that described deep hydrofinishing catalyzer accounts for 10%～50% of total catalyst volume, with conventional Hydrobon catalyst layering filling, perhaps mixed packing.
6. in accordance with the method for claim 5, it is characterized in that reaction mass contacts with conventional Hydrobon catalyst first, then contacts with the deep hydrofinishing catalyzer.
7. in accordance with the method for claim 3, it is characterized in that one or more in W, Mo, Ni, the Co of described conventional Hydrobon catalyst are as active metal component, take the oxide compound active metallic content as 10%～40%; Described deep hydrofinishing catalyst activity metal content is 45%～85%.
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| CN101514294B (en) * | 2009-03-31 | 2012-11-07 | 中国石油化工集团公司 | Method for reducing aviation kerosene corrosion |
| CN101942334B (en) * | 2009-07-09 | 2013-10-09 | 中国石油化工股份有限公司 | Production method of molecular sieve dewaxing raw material |
| CN102465026B (en) * | 2010-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Hydroprocessing method for coking kerosene distillates |
Citations (2)
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|---|---|---|---|---|
| CN1458233A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for coking full fraction oil hydrogenation refining |
| CN1478867A (en) * | 2002-08-29 | 2004-03-03 | 中国石油化工股份有限公司 | Method of producing jet fuel from coking distillate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458233A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for coking full fraction oil hydrogenation refining |
| CN1478867A (en) * | 2002-08-29 | 2004-03-03 | 中国石油化工股份有限公司 | Method of producing jet fuel from coking distillate |
Non-Patent Citations (3)
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| 中国国家标准化管理委员会.3号喷气燃料.《GB6537-2006 3号喷气燃料》.中华人民共和国国家质量监督检验检疫总局,2006,表1. * |
| 党鸿瑞译.《煤及焦油的高压催化加氢》.《煤及焦油的高压催化加氢》.石油工业出版社出版,1958,第146页. * |
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