CN103725322B - Method for preparing aviation fuel oil by adopting alpha-alkene - Google Patents
Method for preparing aviation fuel oil by adopting alpha-alkene Download PDFInfo
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- CN103725322B CN103725322B CN201310680364.4A CN201310680364A CN103725322B CN 103725322 B CN103725322 B CN 103725322B CN 201310680364 A CN201310680364 A CN 201310680364A CN 103725322 B CN103725322 B CN 103725322B
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Abstract
The invention discloses a method for preparing aviation fuel oil by adopting alpha-alkene. The method comprises the steps as follows: (1), the alpha-alkene is added to a sealed reactor and then reacts with introduced hydrogen under the action of a catalyst below 10 MPa pressure and at a temperature below 400 DEG C; (2), a cracking product obtained in the step (1) is subjected to gas-liquid separation, obtained liquid is rectified to obtain an aviation petrol component, an aviation kerosene component and a diesel oil component, the obtained aviation petrol component and the aviation kerosene component are collected as aviation fuel oil products, while the obtained diesel oil component returns to the step (1) and is used as a raw material to perform a reaction. The method for preparing the aviation fuel oil by using the alpha-alkene adopts the alpha-alkene as the raw material, and prepares the qualified aviation fuel oil by using the catalyst with the specifity to perform selective catalyzation under the catalysis of a special catalyst, and finally the produced diesel oil and dry gas parts can be both recycled. No waste is discharged during the whole process, the utilization ratio of energy is high, and the investment cost is low.
Description
Technical field
The invention belongs to derived energy chemical technical field, specifically relate to a kind of method that alpha-olefin prepares Aviation Fuel.
Background technology
Aviation Fuel, also known as aviation biofuel, refer to that some are aircraft and the fuel oil type established specially, the fuel oil that quality uses than heating system and automobile is high, usually all contains different additives and freezes and Yin Gaowen and the risk of exploding to lower.Aviation Fuel is divided into two large classes: aviation spirit (AviationGasoline, Avgas), for the aircraft of reciprocator.Aviation kerosene (Jet fuel), for the aircraft of jet engine.
Aviation kerosene is mainly used in the jet plane of high airflight, general requirement appropriate density, good combustionproperty, good low-temperature fluidity, good heat-resistant quality and anti-oxidative stability.Tradition aviation kerosene is formed by the additive mediation of the components such as the straight run in refining of petroleum, hydrocracking and hydrofining and necessity, the mixture be made up of different hydrocarbons compound, chemical formula is CH3 (CH2) nCH3 (n is 8 ~ 16).Using bio-aviation fuel to substitute or supplement fossil aviation fuel is the effective measure reducing air system greenhouse gas emission, reply European Union collection carbon emission expense.Publication number is that the preparation method that patent document discloses a kind aviation kerosene or diesel oil of CN103087748A comprises: (1) is under acid catalyst existent condition, with platform chemicals and the furans platform chemicals containing carbonyl in lignocellulose based platform compound for raw material, reacted by acid catalyzed alkyation and produce the oxygen-containing organic compound of carbon chain lengths between 8 to 16; (2) by carrying out hydrogenation to the product of alkylated reaction, effectively removing carbon-to-carbon double bond wherein and carbon-oxygen double bond, producing saturated oxygen-containing organic compound; (3) adopt metal-solids acid dual-function catalyst to the alkylation reaction product hydrogenation deoxidation after hydrogenation, thus obtain the biomass aviation kerosene with more high-energy-density and stability of carbon chain lengths between 8 to 16 or higher-grade diesel oil.
At present, the production technique of aviation biofuel comprises F-T synthesis, hydrogenation deoxidation and fast pyrogenation three kinds.F-T synthesis refers under high temperature, high pressure, biomass are converted into synthetic gas by thermochemical processes, and (main component is H, and CO), synthetic gas generates various hydro carbons and oxygen-containing organic compound by Fischer-Tropsch synthesis process, and namely products obtained therefrom can be made into aviation biofuel by further hydrogenation deoxidation process.Hydrogenation deoxidation explained hereafter aviation biofuel is that Vegetable oil lipoprotein or animal grease are generated hydrogenation deoxidation oil by deep hydrogenation.This technique is made up of two-step reaction: (1) first removes the Sauerstoffatom in grease by the reaction of grease and hydrogen, and makes all conversion of olefiness become paraffinic hydrocarbon.The Sauerstoffatom removed in stock oil improves the combustion heat of fuel, and removes thermostability and the oxidative stability that alkene improves fuel; (2) paraffinic hydrocarbon of diesel range is made to be converted into the paraffinic hydrocarbon of jet fuel range by hygrogenating isomerization reaction.The finished product are biologically-derived synthesis paraffinic base kerosene, and it contains the molecule with the identical type of conventional oil base rocket engine fuel.Biomass pyrolytic refers to biomass rapid decomposes under anaerobic or anoxia condition, finally generates the thermochemical process of charcoal, bio oil and non-condensable gases.Pyrolytic process can process nearly all dried biomass raw material.Fast pyrolysis technology combines with catalysis technique usually, reacts and completes in several seconds, and temperature rise rate is 103 ~ 104 DEG C/S, and temperature of reaction is about 500 DEG C, and gas residence time is no more than 2S.In usual product, biological carbon accounts for 12% (W), and the bio oil obtained is above the mixture of 300 kinds of liquefied hydrocarbons, in acid, has higher water content.
The investigation and application of bio-aviation fuel is still in test and safety evaluation stage at present, and production cost is higher, fails to realize large-scale commercial and produces, so the biological Aviation Fuel production technology developing new low cost is absolutely necessary.
Summary of the invention
The invention provides a kind of method that alpha-olefin prepares Aviation Fuel, the method adopts alpha-olefin to be raw material, under the catalysis of special catalyst, prepares qualified Aviation Fuel, and no waste discharge, energy utilization rate is high, and input cost is low.
Alpha-olefin prepares a method for Aviation Fuel, comprising:
(1) join in the reactor of sealing by alpha-olefin, pass into dry gas, at below pressure 10MPa, temperature less than 400 DEG C, reacts under catalyst action; Described catalyzer is metal carrying catalyst, and in this catalyzer, metal ingredient comprises nickel, tungsten, molybdenum, platinum, target; At least one in platinum, target; Described alpha-olefin is C
14~ C
18alpha-olefin; Described dry gas is C
1~ C
4alkane;
(2) cracked product that step (1) obtains is carried out gas-liquid separation:
The gas (dry gas) obtained passes into and reacts as raw material to step (1) reactor;
The liquid obtained obtains aviation spirit, aviation kerosene and diesel component after rectifying, using the aviation spirit component that obtains and aviation kerosene component as Aviation Fuel product-collecting, is back to by the diesel component obtained in step (1) and reacts as raw material.
Under the effect of hydrogen and catalyst activity component, long-chain CH compound generation intermolecular breaks, unsaturated C=C key is by the saturated generation alkane of hydrogen simultaneously.Molecule is in diffusion process, and branched paraffin, under catalyst action, isomery occurs.Meanwhile, first split product may contact catalyst and hydrogen again, secondary cracking occurs, generates small molecules CH compound, cause kerosene component yield to decline, by-product gasoline and C
4following gas.
Product degasification after hydrocracking takes away methane, ethane, propane and butane (being referred to as dry gas) outward mutually, it is a large amount of positive structure, the isoparaffin that normal temperature arrives in positive structure octadecane boiling spread that liquid product comprises boiling point, need by the separating substances within the scope of gasoline boiling range and kerosene boiling range out, remaining diesel component reenters reactor cycles cracking.Dry gas part returns in step (1) simultaneously and participates in the addition reaction of unsaturated C=C key and intermolecular reforming reaction.
For improving the productive rate of object product, as preferably, the temperature of reaction of step (1) is 300 ~ 400 DEG C, more preferably 300 ~ 350 DEG C.When temperature is too high, alpha-olefin easily carries out transition cracking, generates a large amount of dry gas components, causes the productive rate of target product significantly to reduce.When temperature is too low, anyway speed is comparatively slow, production cost is higher.
Experiment shows, reaction pressure is also the factor affecting products collection efficiency, and reaction pressure is too high, is unfavorable for the desorption of target product, and what cause target product proceeds cracking reaction, generates by product, reduces the productive rate of target product.As preferably, in step (1), reaction pressure is 7 ~ 9MPa.
Described catalyzer is metal carrying catalyst, and this catalyzer can adopt existing method to prepare, and such as can adopt by carrier impregnation and containing in the solution of metal ion, then dry, calcining can obtain metal carrying catalyst.Charge capacity≤1% of metal ingredient in described catalyzer.As preferred further, in described catalyzer, the charge capacity of metal ingredient is 0.1 ~ 0.3%.The add-on of the catalyzer described in during actual use is 0.01 ~ 0.08% of alpha-olefin weight, and the usage quantity of catalyzer is less.And can be recycled after catalyst upon activation, use cost is lower.
Prove through overtesting, as preferably, described metal ingredient is at least one in nickel, tungsten, molybdenum.The carrier of described catalyzer can select common catalyst support material, such as, can select one or more in gac, aluminum oxide, molecular sieve, diatomite, carbon nanotube.
For realizing utilization to biomaterial, reduce input cost further, as preferably, described alpha-olefin is C
16~ C
18alpha-olefin.C
16~ C
18alpha-olefin biofuel can be adopted to prepare, raw material sources are extensive, with low cost.
The product liquid that hydrocracking obtains comprises from C
5to C
18positive structure and isoparaffin.C
5~ C
8component is mainly gasoline component, and rectification temperature is 40 ~ 140 DEG C; And C
9~ C
14component is kerosene component, and rectification temperature is 150 ~ 300 DEG C; All the other high boiling cuts are diesel component, participate in cracking and reforming reaction as the raw material in step (1).
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) alpha-olefin of the present invention prepares the method employing alpha-olefin of Aviation Fuel is raw material, under the catalysis of special catalyst, utilize the narrow spectrum selective catalysis of catalyzer, prepare qualified Aviation Fuel, the diesel oil finally produced and dry gas part are all recycled, whole process no waste is discharged, and energy utilization rate is high, and input cost is low.
(2) the present invention adopts C
16~ C
18alpha-olefin as raw material time, this raw material can adopt the waste oil etc. of the huge biofuel of reserves, sewer oil or other field to prepare, and raw material sources are extensive, with low cost.
Embodiment
Following examples are only and further illustrate technical scheme of the present invention, can not be interpreted as the restriction to protection scope of the present invention.
Embodiment 1
(1) by 1kg C
18alpha-olefin (the 1-octadecylene purchased from upper Shanghai's style Qi Ao Trade Co., Ltd.) join in the reactor of sealing, add the aluminium oxide catalyst (charge capacity 0.3%) of 0.5g tungsten load, tungsten is by carrier impregnation and containing in the solution of tungsten ion, and then dry, calcining can obtain tungsten load catalyzer.Then, pass into methane gas, pressure 7MPa, temperature 350 DEG C, carries out reaction 24h under catalyst action.
(2) cracked product that step (1) obtains is carried out gas-liquid separation, gas can be used as the raw material reuse of step (1): the liquid obtained obtains aviation spirit (rectification temperature is 40 ~ 140 DEG C) 300g, aviation kerosene (rectification temperature is 150 ~ 300 DEG C) 560g after rectifying, rest part collects 80g as diesel component, using the aviation spirit component that obtains and aviation kerosene component as Aviation Fuel product-collecting, using the diesel component that obtains as material collection.
(3) after testing, produce the aviation kerosene performance obtained and meet GB6537-2006 national standard.
Embodiment 2
(1) by 1kg C
16alpha-olefin (the 1-hexadecylene purchased from lark prestige Science and Technology Ltd.) and embodiment 1 collect 80g diesel oil heavy constituent join in the tubular reactor of sealing, add the aluminium oxide catalyst (charge capacity 0.2%) of 0.8g molybdenum load, molybdenum is by carrier impregnation and containing in the solution of molybdenum ion, and then dry, calcining can obtain molybdenum supported catalyst.Pass into butane gas, pressure 8MPa, temperature 350 DEG C, carries out reaction 24h under catalyst action.
(2) cracked product that step (1) obtains is carried out gas-liquid separation, gas can be used as the raw material reuse of step (1): the liquid obtained obtains aviation spirit (rectification temperature is 40 ~ 140 DEG C) 305g, aviation kerosene (rectification temperature is 150 ~ 300 DEG C) 580g after rectifying, rest part collects 78g as diesel component, using the aviation spirit component that obtains and aviation kerosene component as Aviation Fuel product-collecting, using the diesel component that obtains as material collection.
(3) utilize the method to produce the aviation kerosene performance obtained after testing and meet GB6537-2006 national standard.
Embodiment 3
(1) by 1kg C
16alpha-olefin+C
18alpha-olefin (alpha-olefin+C
18the source of alpha-olefin with embodiment 1 and embodiment 2, both mass ratioes are 1:1) join in the tubular reactor of sealing, add the aluminium oxide catalyst (charge capacity 0.3%) of 0.3g Ni, nickel is by carrier impregnation and containing in the solution of molybdenum ion, and then dry, calcining can obtain molybdenum supported catalyst.Pass into butane gas, pressure 7MPa, temperature 350 DEG C, carries out reaction 24h under catalyst action.
(2) cracked product that step (1) obtains is carried out gas-liquid separation, gas can be used as the raw material reuse of step (1): the liquid obtained obtains aviation spirit (rectification temperature is 40 ~ 140 DEG C) 310g, aviation kerosene (rectification temperature is 150 ~ 300 DEG C) 590g after rectifying, rest part collects 85g as diesel component, using the aviation spirit component that obtains and aviation kerosene component as Aviation Fuel product-collecting, using the diesel component that obtains as material collection.
(3) utilize the method to produce the aviation kerosene performance obtained after testing and meet GB6537-2006 national standard.
Claims (10)
1. alpha-olefin prepares a method for Aviation Fuel, comprising:
(1) join in the reactor of sealing by alpha-olefin, pass into dry gas, at below pressure 10MPa, temperature less than 400 DEG C, reacts under catalyst action; Described catalyzer is metal carrying catalyst, and in this catalyzer, metal ingredient comprises at least one in nickel, tungsten, molybdenum, platinum, palladium; Described alpha-olefin is C
14~ C
18alpha-olefin; Described dry gas is C
1~ C
4alkane;
(2) cracked product that step (1) obtains is carried out gas-liquid separation:
The liquid obtained obtains aviation spirit, aviation kerosene and diesel component after rectifying, using the aviation spirit component that obtains and aviation kerosene component as Aviation Fuel product-collecting, the diesel component obtained is back in step (1) and reacts as raw material.
2. alpha-olefin according to claim 1 prepares the method for Aviation Fuel, it is characterized in that, temperature of reaction is 300 ~ 400 DEG C.
3. alpha-olefin according to claim 1 prepares the method for Aviation Fuel, it is characterized in that, reaction pressure is 7 ~ 9MPa.
4. alpha-olefin according to claim 1 prepares the method for Aviation Fuel, it is characterized in that, charge capacity≤1% of metal ingredient in described catalyzer.
5. alpha-olefin according to claim 4 prepares the method for Aviation Fuel, it is characterized in that, in described catalyzer, the charge capacity of metal ingredient is 0.1 ~ 0.3%.
6. alpha-olefin according to claim 5 prepares the method for Aviation Fuel, it is characterized in that, the add-on of described catalyzer is 0.01 ~ 0.08% of alpha-olefin weight.
7. alpha-olefin according to claim 1 prepares the method for Aviation Fuel, it is characterized in that, described metal ingredient is at least one in nickel, tungsten, molybdenum.
8. the alpha-olefin according to the arbitrary claim of claim 4 ~ 7 prepares the method for Aviation Fuel, it is characterized in that, the carrier of described catalyzer is at least one in gac, aluminum oxide, molecular sieve, diatomite, carbon nanotube.
9. alpha-olefin according to claim 1 prepares the method for Aviation Fuel, it is characterized in that, described alpha-olefin is C
16~ C
18alpha-olefin.
10. alpha-olefin according to claim 1 prepares the method for Aviation Fuel, it is characterized in that, the dry gas that in step (2), gas-liquid separation obtains passes into and reacts as raw material to reactor in step (1).
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| CN201310680364.4A CN103725322B (en) | 2013-12-12 | 2013-12-12 | Method for preparing aviation fuel oil by adopting alpha-alkene |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704389A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Process for preparing propylene and ethylene by catalytic cracking of olefin |
| CN102227489A (en) * | 2008-11-26 | 2011-10-26 | 埃莱文斯可更新科学公司 | Methods of producing jet fuel from natural oil feedstocks through oxygen-cleaved reactions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1508555A1 (en) * | 2003-08-19 | 2005-02-23 | Total Petrochemicals Research Feluy | Production of olefins |
| US20110230333A1 (en) * | 2010-03-16 | 2011-09-22 | Uop Llc | Olefin Cracking Catalyst and Manufacturing Process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704389A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Process for preparing propylene and ethylene by catalytic cracking of olefin |
| CN102227489A (en) * | 2008-11-26 | 2011-10-26 | 埃莱文斯可更新科学公司 | Methods of producing jet fuel from natural oil feedstocks through oxygen-cleaved reactions |
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Inventor after: Zhu Cuihan Inventor after: Ji Jianbing Inventor after: Liu Xuejun Inventor after: Yu Xuegong Inventor before: Zhu Cuihan Inventor before: Fang Shi Inventor before: Yu Xuegong |
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Free format text: CORRECT: ADDRESS; FROM: 310003 HANGZHOU, ZHEJIANG PROVINCE TO: 102211 CHANGPING, BEIJING Free format text: CORRECT: INVENTOR; FROM: ZHU CUIHAN FANG SHI YU XUEGONG TO: ZHU CUIHAN JI JIANBING LIU XUEJUN YU XUEGONG |
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