CN101724440B - Method for deodorizing aviation kerosene - Google Patents
Method for deodorizing aviation kerosene Download PDFInfo
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- CN101724440B CN101724440B CN 200810228407 CN200810228407A CN101724440B CN 101724440 B CN101724440 B CN 101724440B CN 200810228407 CN200810228407 CN 200810228407 CN 200810228407 A CN200810228407 A CN 200810228407A CN 101724440 B CN101724440 B CN 101724440B
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Abstract
The invention discloses a method for deodorizing aviation kerosene. Raw oil and hydrogen gas are mixed, a catalyst bed is hydrofined under a hydrogenation process condition by non-noble metal, a hydrogen gas circulation system is not arranged, and the use quantity of the hydrogen gas is 1-4 times the quantity of dissolved hydrogen in a reaction system under an increased reaction condition on the basis of the chemical hydrogen consumption in the reaction process. The method is a gas, liquid and solid three-phase hydrogenation process with very low hydrogen-to-oil ratio, and the low hydrogen-to-oil ratio can remove a circulating hydrogen system in the hydrogenation process, lowers the equipment investment and the operation cost greatly and also does not influence the effect of the deodorization reaction of the aviation kerosene and the running stability.
Description
Technical field
The present invention relates to a kind of method for deodorizing aviation kerosene, particularly adopt method of hydrotreating to carry out the method for deodorizing aviation kerosene.
Background technology
Along with growth and the development of aviation of national economy, the demand of rocket engine fuel is increased rapidly.The output of estimating boat coal in 2010 will reach 1,600 ten thousand tons.The average potential content of straight run boat coal cut is about 8% in the domestic crude oil, and the average potential content of straight run boat coal cut is about 8%～15% in the high-sulfur crude oil of import.At present, the output of China's boat coal accounts for below 4% of crude runs, the straight run boat coal cut that main source obtains for crude oil being carried out air distillation, and the boat output of coal of secondary processing accounts for less share.The process for refining of straight run boat coal mainly comprises and faces hydrogen and non-hydrogen technology two classes.Common hydrofining technology generally adopts the non-noble metal hydrogenation catalyst for refining, but needs reaction pressure, temperature and hydrogen-oil ratio higher, thereby its investment and process cost are also higher; Perhaps use noble metal catalyst, can reduce the severity of operational condition, but noble metal catalyst cost height is easily mended the sulfide poisoning, be affected running period.
Proportion, freezing point, smoke point and the sulphur content of the straight run of main oils boat coal cut meet boat product of coal index request substantially both at home and abroad, but mercaptan sulfur is generally higher, and portioned product acidity is also higher.Because the compatibleness of naturally occurring sulfide and rocket engine fuel cut is better, keeping it, an amount of to exist the anti-ablation property of protection fuel be needs, so the navigate hydrogenation purpose of coal cut of straight run is to remove mercaptan, improve acid number and color.In various hydrofining reactions, hydro-sweetening, depickling are the reactions that is easier to take place, and can finish under the reaction conditions that relaxes.At present, domestic straight run boat coal hydrogenation device generally adopts the non-noble metal hydrogenation catalyst for refining, lower pressure (～1.6MPa) and hydrogen-oil ratio (50-200:1) and suitable air speed (2.0～4.0h
-1) realize the purpose of refining boat coal under the condition.
The fixed bed hydrogenation technological process normally in order to remove from the sulphur in the raw material of crude oil, nitrogen, oxygen, metal impurities, or reduces the size of raw molecule and the catalytic reaction process that carries out.Hydrogenation technique process itself, because want unsaturated components such as saturated aromatic hydrocarbons, alkene, and the hydrogenation that removes impurity, need to consume a certain amount of hydrogen, referred to herein as the chemistry consumption hydrogen of hydrogenation reaction.Its chemical hydrogen consumption of the hydrogenation technique process of different material is different, can measure by experiment or calculate by experimental formula.This area be it is generally acknowledged, in the hydrogenation technique process, need operate under the condition of the amounts of hydrogen that consumes far above chemical hydrogen, and main purpose is to improve speed of response and avoid catalyst deactivation, guarantees certain running period.In the hydrogenation technique, hydrogen usage is generally represented with the volume ratio of hydrogen under the standard state and stock oil, is called for short hydrogen-oil ratio.
When hydrogenation technique adopts bigger hydrogen-oil ratio, after finishing, hydrogenation reaction must have a large amount of hydrogen more than needed.These hydrogen more than needed all mix back continuation as the hydrogen feed of reaction with new hydrogen by hydrogen cycle process usually after the circulating hydrogen compressor supercharging.
In the boat coal hydrogenation process unit, the investment of hydrogen recycle link accounts for the significant proportion of whole process cost.If can save hydrogen gas circulating system and circulating hydrogen compressor, can reduce investment and the process cost of hydrogenation technique device greatly, and then reduce the cost of product, improve the market competitiveness of enterprise.
Chinese patent CN1361229A discloses a kind of selectively mercaptan-eliminating catalyst for aviation fuel and preparation method thereof, and hydrogen to oil volume ratio is 100-200:1; Chinese patent CN101089134A discloses a kind of boat coal fraction hydroupgrading process, hydrogen to oil volume ratio 300-2000:1; " refining of petroleum and chemical industry " 2002,33 (5) P28～30 disclose the industrial application that rocket engine fuel faces the hydrogen mercaptan removal technique, and its purpose mainly is to remove mercaptan, improve character such as color and acid number, and hydrogen to oil volume ratio 55:1 adopts the hydrogen recycle compressor; " chemical science and technology " 2003,11 (3) P29～31 disclose a kind of straight run boat coal low pressure hydrofining technology, and its purpose mainly is to remove mercaptan, improve character such as color and acid number, hydrogen to oil volume ratio 80-150:1.The characteristics of these technology are to have higher hydrogen-oil ratio, therefore must adopt hydrogen recycle link and circulating hydrogen compressor.
Summary of the invention
Deficiency at existing deodorizing aviation kerosene technology the invention provides a kind of hydrogenation method that need not use the hydrogen recycle link, reduces cost of investment and the process cost of hydrogenation technique.
Method for deodorizing aviation kerosene of the present invention comprises following content, boat coal stock oil mixes with hydrogen, process non-noble metal hydrogenation catalyst for refining bed under hydrogenation deodorizing technology condition, hydrogen usage is to increase 1～4 times of reactive system dissolved hydrogen amount under the reaction conditions on reaction process chemistry hydrogen consumption basis, preferably increases 1～2 times of dissolved hydrogen amount.Because amounts of hydrogen seldom, does not arrange hydrogen gas circulating system.
In the inventive method, technology contents such as concrete hydrogenation technique condition and selection of catalysts can be determined according to the conventional knowledge in this area according to feedstock property and quality product requirement.The dissolved hydrogen amount can measuring under the chemical hydrogen consumption of reaction process and the reaction conditions, can calculate according to the experimental formula that this area document provides, can estimate that also above-mentioned experimental formula and empirical value can be with reference to " hydroprocessing technique and engineering " book associated visceras of Sinopec press publication in 2004 according to the empirical value that this area document provides.Determination of test method chemistry hydrogen consumption and reactive system dissolved hydrogen amount are technological methods well known to those skilled in the art, as on testing apparatus, adopt the condition identical with reaction process, when reaching suitable reaction result, measure chemical hydrogen consumption and system dissolves hydrogen amount.
In the inventive method, though the amounts of hydrogen of using is excessive less a little more than the chemical hydrogen consumption of reaction, the recycle hydrogen system need be set, can save hydrogen recycle link necessary in the conventional hydrotreatment process and circulating hydrogen compressor etc.
In the inventive method, the raw material that the hydrogenation technique process is used is the straight run coal that navigates.The inventive method also is applicable to the hydrogenation deodorising process of virgin naphtha.
In the hydrogenation process of the present invention, because therefore the amounts of hydrogen of using, does not need hydrogen gas circulating system far below the hydrogen usage of prior art.
In the inventive method, the best hydrogenation conditions of deodorizing aviation kerosene is: temperature of reaction is 150～320 ℃, and reaction pressure is 0.5～6.0MPa, and volume space velocity is 0.3～14.0h during liquid
-1Preferred reaction conditions is: temperature of reaction is 180～260 ℃, and reaction pressure is 0.8～3.0MPa, and volume space velocity is 4.0～8.0h during liquid
-1Catalyzer is the common non-noble metal hydrogenation catalyst for refining in this area, base metal is generally one or more among W, Mo, Ni and the Co, in oxide compound, the base metal weight content is generally 5%～35%, and is preferred 15%～25%, and support of the catalyst is generally aluminum oxide, can contain conventional auxiliary agent, the non-noble metal hydrogenation catalyst for refining can the commodity in use catalyzer, also can be by existing method preparation, as adopting immersion process for preparing etc.
By discovering, in the boat coal hydrogenation deodorising process that uses the non-noble metal hydrogenation catalyst for refining, hydrogen to oil volume ratio is also incomplete same to influence and other hydrogenation process of reaction effect, and shows unique characteristics.When hydrogen to oil volume ratio was big, when namely amounts of hydrogen was excessive far away, hydrogen to oil volume ratio was similar to other hydrogenation process to the influence of boat coal hydrogenation deodorising process; But when hydrogen to oil volume ratio was low, hydrogen to oil volume ratio was to influence and other hydrogenation process and inequality of boat coal hydrogenation deodorising process.By discovering, in the deodorizing aviation kerosene reaction process of using the non-noble metal hydrogenation catalyst for refining, as long as there is a spot of gas phase hydrogen, just can guarantee reactive behavior and catalyzer work-ing life, be not as other hydrogenation process, to need a large amount of excessive hydrogens.Therefore, in the hydrogenation process of the present invention, the amounts of hydrogen of using is for increasing the dissolved hydrogen amount of the system that is slightly more than on chemical hydrogen consumption basis, this scheme can guarantee that slightly a small amount of gas phase hydrogen exists in the reactive system, guarantee that reactive system is in the gas, liquid, solid three-phase state, reaches good reaction effect.In the hydrogenation process of condition of the present invention, the required hydrogen of hydrogenation reaction is mainly derived from the hydrogen that adds, because it is considerably less that straight run boat coal removes the hydrogen of mercaptan consumption, so the gas (as hydrogen sulfide and ammonia) that reactive system generates can be ignored, and does not need to set up exhaust system and hydrogen gas circulating system.
Description of drawings
Fig. 1 is processing method schematic flow sheet of the present invention.
1-fresh feed, 2-feedstock pump, 3-process furnace, 4-hydrogen, 5-mixing tank, 6-hydrogenator, 7-separator, 8-gas, 9-liquid product.
Embodiment
Characteristics of the present invention are to reduce hydrogen-oil ratio greatly in fixed bed three-phase hydrotreatment process, thus necessary hydrogen recycle link and circulating hydrogen compressor in can the present conventional hydrotreatment process of cancellation.
Fixed bed three-phase hydrotreatment process of the present invention, material enters from reactor top, after the beds in the reactor of flowing through carries out the hydrotreatment reaction, discharges through the outlet of reactor lower part.
For ease of further specifying clear hydrogenation technique process of the present invention, here process of the present invention is described.As shown in Figure 1, fresh feed 1 heats by process furnace 3 after fresh feed pump 2 pressurizations, enters after mixing tank 5 is forced to stir with new hydrogen 4 and removes thiol reactant in the hydrogenator.Reaction product enters separator 7.In separator 7, a small amount of gas 8 is emitted system, and liquid product 9 enters fractionating system.
Embodiment 1
Boat coal hydrogenation refining desulfurization alcohol, catalyzer is the FH-40A catalyzer of Fushun Petrochemical Research Institute's development and production.Chemical hydrogen consumption and the system dissolves hydrogen amount of elder generation's test determination reaction are carried out the inventive method process then.Condition 1 amounts of hydrogen is chemical hydrogen consumption adding system dissolved hydrogen amount.Condition 2 amounts of hydrogen are 2 times of chemical hydrogen consumption adding system dissolved hydrogen amount.The catalyzer main character sees Table 1, principal reaction condition and the results are shown in Table 2.
After 3000 hours, reaction effect does not have obviously to descend in 1 time steady running of condition, and is suitable under catalyst activity stability and the common high hydrogen oil volume condition.
Comparative example 1
According to 1 operation of embodiment 1 condition, the amounts of hydrogen that only is to use is the chemical hydrogen consumption of this reaction process, and the refined oil mercaptan sulfur content is 30.2 μ g.g
-1
Comparative example 2
According to 1 operation of embodiment 1 condition, the amounts of hydrogen that only is to use is the popular response hydrogen to oil volume ratio, be that hydrogen to oil volume ratio is 50:1 (is equivalent to chemical hydrogen consumption and adds about 50 times of dissolved hydrogen amount), excessive hydrogen uses the recycle hydrogen system, and the refined oil mercaptan sulfur content is 6.2 μ g.g
-1
Boat coal hydrogenation refining desulfurization alcohol, catalyzer is the FH-UDS catalyzer of Fushun Petrochemical Research Institute's development and production.Chemical hydrogen consumption and the system dissolves hydrogen amount of elder generation's test determination reaction are carried out the inventive method process then.Condition 1 amounts of hydrogen is chemical hydrogen consumption adding system dissolved hydrogen amount 2.Condition 2 amounts of hydrogen are 3 times of chemical hydrogen consumption adding system dissolved hydrogen amount.The catalyzer main character sees Table 3, principal reaction condition and the results are shown in Table 4.
The physico-chemical property of table 1 FH-40A catalyzer
| Catalyzer | FH-40A |
| Reactive metal | Mo-Ni-Co |
| Pore volume/mL.g -1 | ≮0.40 |
| Specific surface area/m 2.g -1 | ≮200 |
| Side pressure strength/N.cm -1 | ≮150 |
| Packing density/g.cm -3 | 0.67～0.73 |
Table 2 embodiment 1 deodorizing aviation kerosene condition and result
| Processing condition | Condition 1 | |
|
| Reaction pressure, MPa | 1.8 | 2.5 | |
| Temperature of reaction, ℃ | 220 | 240 | |
| Volume space velocity, h -1 | 6.6 | 8.0 | |
| Oil property | Boat coal raw material | Treated oil | Treated oil |
| Density (20 ℃)/g.cm -3 | 0.7876 | 0.7891 | 0.7893 |
| Boiling range/℃ IBP/EBP | 146/231 | 142/232 | 148/231 |
| Sulphur/μ g.g -1 | 1258 | 1088 | 1091 |
| The doctor test | By | By | |
| Mercaptan sulfur/μ g.g -1 | 99.7 | 6.5 | 5.8 |
Table 3 FH-UDS catalyst property
| Catalyzer | FH-UDS |
| Chemical constitution, quality % | |
| WO 3 | 13.0～16.0 |
| MoO 3 | 8.5～11.0 |
| NiO | 1.8～2.8 |
| CoO | 2.3～3.3 |
| Pore volume, ml/g | ≮0.33 |
| Specific surface area, m 2/g | ≮200 |
| Tap density, g/ml | 0.87～0.96 |
| Side pressure strength, N/cm | 160 |
Table 4 embodiment 2 deodorizing aviation kerosene condition and results
| Processing condition | Condition 1 | |
|
| Reaction pressure, MPa | 1.0 | 3.0 | |
| Temperature of reaction, ℃ | 200 | 270 | |
| Volume space velocity, h -1 | 5.0 | 10.0 | |
| Oil property | Boat coal raw material | Treated oil | Treated oil |
| Density (20 ℃)/g.cm -3 | 0.7876 | 0.7892 | 0.7891 |
| Boiling range/℃ IBP/EBP | 146/231 | 142/232 | 148/231 |
| Sulphur/μ g.g -1 | 1258 | 1072 | 1083 |
| The doctor test | By | By | |
| Mercaptan sulfur/μ g.g -1 | 99.7 | 6.2 | 5.5 |
Claims (6)
1. method for deodorizing aviation kerosene, it is characterized in that: boat coal stock oil mixes with hydrogen, through non-noble metal hydrogenation catalyst for refining bed, hydrogen usage be 1～4 times of reactive system dissolved hydrogen amount under reaction process chemistry hydrogen consumption basis increase reaction conditions under hydrogenation deodorizing technology condition; The support of the catalyst of non-noble metal hydrogenation catalyst for refining is aluminum oxide, and base metal is 5%～35% in the oxide compound weight content; Reaction pressure is 0.5～6.0MPa, and temperature of reaction is 150～320 ℃, and volume space velocity is 0.3～14.0h during liquid
-1
2. it is characterized in that in accordance with the method for claim 1: hydrogen usage is 1～2 times of reactive system dissolved hydrogen amount under reaction process chemistry hydrogen consumption basis increase reaction conditions.
3. it is characterized in that in accordance with the method for claim 1: reactive system does not arrange hydrogen gas circulating system.
4. in accordance with the method for claim 1, it is characterized in that: the deodorizing aviation kerosene reaction conditions is: temperature of reaction is 180～260 ℃, and reaction pressure is 0.8～3.0MPa, and volume space velocity is 4.0～8.0h during liquid
-1
5. it is characterized in that in accordance with the method for claim 1: the base metal of described non-noble metal hydrogenation catalyst for refining is one or more among W, Mo, Ni and the Co.
6. it is characterized in that in accordance with the method for claim 1: the base metal in the non-noble metal hydrogenation catalyst for refining is 15%～25% in the oxide compound weight content.
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| CN 200810228407 CN101724440B (en) | 2008-10-29 | 2008-10-29 | Method for deodorizing aviation kerosene |
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| CN101724440B true CN101724440B (en) | 2013-08-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870626A (en) * | 1973-02-27 | 1975-03-11 | Gulf Research Development Co | Method for reducing the mercaptan content of a middle distillate oil |
| CN1229838A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工集团公司 | Conversion process of hydrocarbon oil |
| CN101089134A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aviation kerosene fraction hydroupgrading process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141363C (en) * | 2001-04-28 | 2004-03-10 | 中国石油化工股份有限公司 | Process for selectively removing thiol from light oil |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870626A (en) * | 1973-02-27 | 1975-03-11 | Gulf Research Development Co | Method for reducing the mercaptan content of a middle distillate oil |
| CN1229838A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工集团公司 | Conversion process of hydrocarbon oil |
| CN101089134A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aviation kerosene fraction hydroupgrading process |
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| CN101724440A (en) | 2010-06-09 |
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