CN104611057A - Direct distillation kerosene hydrogenation method - Google Patents
Direct distillation kerosene hydrogenation method Download PDFInfo
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- CN104611057A CN104611057A CN201310540398.3A CN201310540398A CN104611057A CN 104611057 A CN104611057 A CN 104611057A CN 201310540398 A CN201310540398 A CN 201310540398A CN 104611057 A CN104611057 A CN 104611057A
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- kerosene
- hydrogenation
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- normal pressure
- hydrogenation method
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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
- C10G67/14—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 including at least two different refining steps in the absence of hydrogen
Abstract
The present invention discloses a direct distillation kerosene hydrogenation method. According to the method, the kerosene side stream of a normal pressure tower is provided with a liquid-phase hydrogenation reactor, the normal pressure first side extracting kerosene distillate is directly mixed with a small amount of pipeline network hydrogen gas in a static mixer or is subjected to heat exchange and then mixed with a small amount of pipeline network hydrogen gas in a static mixer, the obtained mixture enters the liquid-phase hydrogenation reactor to carry out a hydrorefining reaction under the effect of a hydrogenation catalyst, and the separated liquid product is adopted as the product kerosene after being subjected to steam stripping and then is discharged out of the apparatus. Compared with the method in the prior art, the method of the present invention has the following characteristics that: the rich heat of the normal pressure tower and the low hydrogen consumption of the kerosene hydrogenation are completely utilized so as to achieve the combination of the normal pressure tower and the kerosene hydrogenation process, the equipment investment can be reduces, the heat of the normal pressure tower can be reasonably utilized, and the energy consumption and the investment of the apparatus are effectively reduced.
Description
Technical field
The present invention relates to a kind of hydrofinishing process of kerosene, specifically relate to a kind of crude oil atmospheric distillation tower straight run kerosene fraction/or under liquid-phase hydrogenatin condition, carry out the method for hydrotreating that hydro-sweetening, deacidification value and color of improving produce qualified rocket engine fuel after directly mixing with a small amount of hydrogen after heat exchange.
Background technology
At present worldwide, the trend of crude oil heaviness and in poor quality is accelerated, in addition the sustainable development of world economy and the increasingly stringent of environmental regulation, need to produce a large amount of light clean fuel, these all require to improve existing oil Refining Technologies, produce satisfactory product with minimum cost.
General crude oil is divided into the material that petroleum naphtha, boat coal cut, diesel oil distillate, hydrocracking material (LVGO), fcc raw material hydrotreated feed (HVGO), coking raw material (VR) etc. meet following process matching requirements after desalting and dewatering, air distillation, underpressure distillation.The main Quality of straight run boat coal cut is that mercaptan exceeds standard, and acid number and color need to improve, and the process for refining of straight run boat coal mainly comprises and faces hydrogen and non-hydrogen technology two class.One class is the method for non-hydrogen, i.e. catalytic oxidation, and mercaptan is changed into two mercaptan, investment cost is lower, but the environmental pollution of various degrees, and poor to the adaptability of material composition change, and during the raw material of working properties difference, the qualification rate of product is low.An other class is method of hydrotreating, namely with virgin kerosene component for raw material, mix with hydrogen and be heated to enter reactor after temperature of reaction through process furnace, under special-purpose catalyst effect, remove thio-alcohol sulfide wherein, other sulfide and oxide compound.Reacted product, through condensation and Hydrogen Separation, enters stripping tower, removes hydrogen sulfide and the water of hydrogenation generation, obtains the jet fuel product meeting 3# rocket engine fuel quality index.
Conventional its reaction pressure of kerosene hydrogenation process for refining, temperature and hydrogen-oil ratio are higher, thus its investment and process cost also higher, and it is less to be specifically designed to the device of kerosene hydrogenation in China, adopt the technique of diesel oil, the processing of boat coal interruption more, because raw material is frequently changed, device displacement will lose part boat coal cut, and very easily cause the fluctuation of quality product.
" chemical science and technology " 2003,11(3) P29 ~ 31 disclose a kind of straight run boat coal low pressure hydrofining technology, and its main purpose removes mercaptan, improves the character such as color and acid number.US4087353 discloses a kind of method of kerosene hydrogenation desulfurization.CN03126437.9 mono-kind removes the method for aromatic hydrocarbons in kerosene, but can not solve etching problem, but also reduces the productive rate of boat coal.CN1324918 discloses a kind of hydrofining technology method simultaneously can producing qualified rocket engine fuel and diesel product from the coal diesel oil distillate of sulphur-bearing crude, can on the basis of existing Model of Diesel Hydrogenation Refining flow process, increase a kerosene hydrogenation refining reaction device and corresponding high and low pressure separator, share a set of new hydrogen and recycle hydrogen system, to realize in a device coal, diesel oil respectively hydrogenation produce the object of qualified rocket engine fuel and diesel product simultaneously.CN102465017A discloses a kind of gasoline and kerosene combined hydrogenation technique, comprising: FCC gasoline obtains gently through fractionation, heavy constituent; The mixing raw material of kerosene and hydrogen first through interchanger heat exchange, then mixes with heavy constituent and carries out hydrogenation after heating, and separating reaction effluent obtains gas phase and liquid phase, carries out fractionation, obtain qualified gasoline and kerosene fuel product after liquid phase mixes with FCC gasoline light constituent.CN101376827 discloses a kind of coker gasoline and virgin kerosene mixed hydrogenation process, coker gasoline mixes with virgin kerosene, and hydrogenation unit carries out deep hydrofinishing, the operational condition of adjustment separation column, take the cut point be suitable for, obtain up-to-standard hydrotreated naphtha and hydrotreated kerosene.
In above-mentioned patent or document, crude oil atmospheric distillation tower to be extracted out after straight run kerosene fraction directly or is entered downstream kerosene hydrogenation refining plant as raw material after entering relay tank, hydrogenation unit generally needs to arrange new hydrogen machine and/or circulating hydrogen compressor and reactor process furnace, so not only the facility investment of device and process cost higher, and the energy consumption of device and running cost also higher.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of kerosene hydrogenation process for purification, the method can effectively reduce the facility investment of kerosene hydrogenation device, Appropriate application heat, reduces overall energy consumption and the process cost of device.
A kind of virgin kerosene method of hydrotreating provided by the invention, comprises the steps:
(1) one liquid phase hydrogenation reactor is set at the kerosene side line of crude oil atmospheric tower, the normal line of atmospheric tower extracts kerosene(oil)fraction out directly or after heat exchange, enter liquid phase hydrogenation reactor after mixing in static mixer with a small amount of pipe network hydrogen, under the effect of hydrogenation catalyst, carry out the hydrofining reactions such as mercaptan removal, deolefination, depickling, desulfurization, denitrogenation, deoxidation;
(2) kerosene(oil)fraction visual response condition extracted out by a normal line of step (1) atmospheric tower, enters liquid phase hydrogenation reactor react as needed heat exchange after atmospheric tower heat can being utilized to carry out heat exchange to proper temperature;
(3) the liquid phase hydrogenation reactor effluent that step (1) obtains enters separator and carries out gas-liquid separation, being separated a small amount of gas obtained can as other low-voltage device of refinery as the hydrogen make-up of reformation pre-reactor, the hydrogen source of PSA device or other unit furnace fuel, be separated the liquid product obtained and go out device as product kerosene after stripping.
In the inventive method, the temperature that kerosene(oil)fraction extracted out by the normal line of described atmospheric tower is 170 ~ 220 DEG C.
The operational condition of the reaction of liquid-phase hydrogenatin described in step (2) is generally: reaction pressure 0.5MPa ~ 5.0MPa, volume space velocity is 1.0h
-1~ 10.0h
-1, average reaction temperature 50 DEG C ~ 350 DEG C.Preferred Hydroprocessing conditions is: reaction pressure 1.0MPa ~ 4.0MPa, volume space velocity 2.0h
-1~ 7.0h
-1, average reaction temperature 180 DEG C ~ 260 DEG C.
In the inventive method, the carrier of described Hydrobon catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., other auxiliary agent can be contained in carrier simultaneously, as one or more in P, Si, B, Ti and Zr, hydrogenation active component is generally base metal, comprise the metal of at least one VI B race and at least one VIII race, as metals such as Mo, W, Co, Ni.Described non-noble metal hydrogenation catalyst can adopt commercial catalyst, also can prepare satisfactory catalyzer by the existing method in this area.Catalyzer such as Fushun Petrochemical Research Institute (FRIPP) develops FH-40A, FH-40B, FH-40C catalyzer.
In the inventive method, base metal oxidation state hydrogenation catalyst or preloading sulfur catalyst before use, need, with hydrogen at the temperature of 150 DEG C ~ 300 DEG C, to use after preferably carrying out prevulcanized process or activation treatment under the condition of 200 DEG C ~ 280 DEG C.
Compared with existing kerosene hydrogenation technology, the inventive method has the following advantages:
The present invention sets up a liquid phase hydrogenation reactor and both subsidiary streams pipeline by the kerosene side line other at atmospheric tower, atmospheric distillation tower virgin kerosene overhead product/or directly carry out hydro-sweetening, deacidification value and color of improving after mixing with a small amount of pipe network hydrogen after heat exchange and produce qualified rocket engine fuel.Atmospheric distillation tower virgin kerosene overhead product temperature after heat exchange can meet the needs of hydrogenation reaction, and hydrogenator does not need to establish process furnace, does not also need to set up the make-up hydrogen compressor needed for conventional kerosene hydrogenation unit and/or circulating hydrogen compressor.Hydrogenator effluent enters separator and carries out gas-liquid separation, be separated the liquid product obtained and go out device as product kerosene after stripping, so not only can reduce the facility investment of device, also the heat of atmospheric tower reasonably be utilized, effectively reduce plant energy consumption and investment.
Accompanying drawing explanation
Fig. 1 is the principle flow chart of present invention process method.
Embodiment
Below in conjunction with the drawings and specific embodiments, more detailed description is done to method of the present invention.
As shown in Figure 1, the concrete technology flow process of the inventive method is as follows: on a normal line kerosene side line of atmospheric tower C-1, arrange a liquid phase hydrogenation reactor R-1, a normal line kerosene is through pipeline 1, after static mixing gas M-1 mixes, liquid phase hydrogenation reactor R-1 is entered through pipeline 3 with the hydrogen through pipeline 2, carry out catalytic hydrogenation reaction, remove mercaptan and other sulfide, deacidification value, improve product colour.The effluent that catalytic hydrogenation reaction device R-1 obtains enters separator S-1 through pipeline 4 and carries out gas-liquid separation.Separator S-1 obtains gas and leaves separator as other low-voltage device of refinery as the hydrogen make-up of reformation pre-reactor through pipeline 5, the hydrogen source of PSA device or other unit furnace fuel.The generation oil that separator S-1 obtains leaves reactor through pipeline 6, removes H through stripping tower
2can directly as boat product of coal after S.
Method of the present invention is further illustrated below by specific embodiment.
The present invention's normal line kerosene(oil)fraction character of atmospheric tower used is in table 1, and the FH-40B catalyzer of Fushun Petrochemical Research Institute's development and production selected by catalyzer, and catalyst property is in table 2.
The normal line kerosene character of table 1.
| Project | Data |
| Density, | 0.7938 |
| Boiling range, DEG C | |
| IBP | 139.5 |
| 10％ | 168.4 |
| 50％ | 182 |
| 90％ | 201 |
| EBP | 230 |
| Mercaptan sulfur, μ g/g | 52 |
| Freezing point, DEG C | -55.2 |
| Acidity, mgKOH/100mL | 12.9 |
| Sulphur, μ g/g | 900 |
| Alkali nitrogen, μ g/g | 2.5 |
Table 2 catalyst property.
| Project | FH-40B |
| Outward appearance | Light blue trifolium bar |
| Physical dimension, mm | Ф(1.4～1.6)×(2～8) |
| Carrier | γ-Al 2O 3 |
| Metallic state | Oxidation state |
| MoO 3，m% | 13.0~16.0 |
| CoO，m% | 3.5~4.5 |
| Surface-area, m 2/g | ≥200 |
| Pore volume, mL/g | ≥0.40 |
| Compressive strength, N/cm | ≥180 |
| Tap density, g/cm 3 | 0.68～0.72 |
Table 3 processing condition.
| Project | Embodiment 1 | Embodiment 2 |
| Hydrogenator | ||
| Temperature of reaction, DEG C | 240 | 260 |
| Reaction pressure, MPa | 1.8 | 1.8 |
| Volume space velocity, h -1 | 4.0 | 6.0 |
Table 4 product property.
| Project | Embodiment 1 | Embodiment 2 |
| Density, | 0.7930 | 0.7932 |
| Boiling range, DEG C | ||
| IBP， | 137 | 137 |
| 10％ | 167 | 168 |
| 50％ | 181 | 181 |
| 90％ | 200 | 200 |
| EBP | 230 | 230 |
| Mercaptan sulfur, μ g/g | 4 | 6 |
| Freezing point, DEG C | -56 | -56 |
| Acidity, mgKOH/100mL | 0.006 | 0.010 |
| Sulphur, μ g/g | 150 | 200 |
| Alkali nitrogen, μ g/g | 1.5 | 1.7 |
As can be seen from embodiment 1,2, this technology can obtain the 3# rocket engine fuel of high-quality.Compared with existing kerosene hydrogenation technique, due to only hydrogenator need be arranged on the kerosene side line of atmospheric tower in the present invention, and reactor is coupled with atmospheric tower, thus the heat of atmospheric tower can be made full use of.Hydrogen consumption simultaneously due to mercaptan sulfur hydrogenation is lower, so without the need to newly-built hydrogen gas compressor, and less pipe network hydrogen only need be utilized can to realize the reaction such as hydro-sweetening, decolouring of kerosene, thus greatly reduce cost of investment and plant energy consumption.
Claims (7)
1. a kerosene hydrogenation method, comprises the steps:
(1) one liquid phase hydrogenation reactor is set at the kerosene side line of crude oil atmospheric tower, the normal line of atmospheric tower extracts kerosene(oil)fraction out directly or after heat exchange, enter liquid phase hydrogenation reactor after mixing in static mixer with a small amount of pipe network hydrogen, under the effect of hydrogenation catalyst, carry out hydrofining reaction;
(2) the liquid phase hydrogenation reactor effluent that step (1) obtains enters separator and carries out gas-liquid separation, be separated a small amount of gas obtained and be used as other low-voltage device hydrogen make-up or furnace fuel, be separated the liquid product obtained and go out device as product kerosene after stripping.
2. according to kerosene hydrogenation method according to claim 1, it is characterized in that, a normal line of step (1) is extracted out after kerosene(oil)fraction utilizes atmospheric tower heat to carry out heat exchange to proper temperature and is entered liquid phase hydrogenation reactor and react.
3. according to kerosene hydrogenation method according to claim 1, it is characterized in that, the temperature that kerosene(oil)fraction extracted out by the normal line of described atmospheric tower is 170 ~ 220 DEG C.
4. according to kerosene hydrogenation method according to claim 1, it is characterized in that, the operational condition of the reaction of liquid-phase hydrogenatin described in step (2) is: reaction pressure 0.5MPa ~ 5.0MPa, volume space velocity is 1.0h
-1~ 10.0h
-1, average reaction temperature 50 DEG C ~ 350 DEG C.
5. according to the kerosene hydrogenation method described in claim 1 or 4, it is characterized in that, described in step (2), the operational condition of liquid phase hydrogenation reactor is: reaction pressure 1.0MPa ~ 4.0MPa, volume space velocity 2.0h
-1~ 7.0h
-1, average reaction temperature 180 DEG C ~ 260 DEG C.
6. according to kerosene hydrogenation method according to claim 1, it is characterized in that, the carrier of described Hydrobon catalyst is one or more in aluminum oxide, amorphous silicon aluminium, silicon oxide or titanium oxide, hydrogenation active component is base metal, comprises the metal of at least one VI B race and at least one VIII race.
7., according to kerosene hydrogenation method according to claim 1, it is characterized in that, in described support of the catalyst simultaneously containing one or more in P, Si, B, Ti and Zr as auxiliary agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107792387A (en) * | 2016-08-30 | 2018-03-13 | 中国飞行试验研究院 | A kind of double atomizer water filling devices of piston type and application method |
| CN110408425A (en) * | 2019-07-12 | 2019-11-05 | 中石化广州工程有限公司 | A kind of boat coal liquid phase hydrogenating method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324918A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Simultaneous qualified coal and diesel oil producing process |
| CN101445747A (en) * | 2007-11-28 | 2009-06-03 | 中国石油化工集团公司 | Hydrofining process integration method |
| CN101684414A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid and high-calcium crude oil |
-
2013
- 2013-11-05 CN CN201310540398.3A patent/CN104611057A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324918A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Simultaneous qualified coal and diesel oil producing process |
| CN101445747A (en) * | 2007-11-28 | 2009-06-03 | 中国石油化工集团公司 | Hydrofining process integration method |
| CN101684414A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid and high-calcium crude oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107792387A (en) * | 2016-08-30 | 2018-03-13 | 中国飞行试验研究院 | A kind of double atomizer water filling devices of piston type and application method |
| CN110408425A (en) * | 2019-07-12 | 2019-11-05 | 中石化广州工程有限公司 | A kind of boat coal liquid phase hydrogenating method |
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Application publication date: 20150513 |