CN114574255B - High-heat-stability high-heat-deposition fuel, preparation method and application thereof - Google Patents
High-heat-stability high-heat-deposition fuel, preparation method and application thereof Download PDFInfo
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- CN114574255B CN114574255B CN202210131571.3A CN202210131571A CN114574255B CN 114574255 B CN114574255 B CN 114574255B CN 202210131571 A CN202210131571 A CN 202210131571A CN 114574255 B CN114574255 B CN 114574255B
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- 239000000446 fuel Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 32
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 238000000151 deposition Methods 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000005336 cracking Methods 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 6
- 150000002978 peroxides Chemical class 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 18
- 229920002367 Polyisobutene Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- AAKTVNKKIZAFEN-UHFFFAOYSA-N methyl 2-(2-aminoethylamino)acetate Chemical compound COC(=O)CNCCN AAKTVNKKIZAFEN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002207 thermal evaporation Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- DZFGVGDQHQHOKZ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C(O)=O DZFGVGDQHQHOKZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 heteroatom compound Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920002557 polyglycidol polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a high heat stability and high heat deposition fuel, which comprises medium-chain alkane not less than 35wt%, naphthenic hydrocarbon not less than 60wt%, aromatic hydrocarbon content less than 2wt%, peroxide value less than 0.8ppm, acid value less than 0.002mgKOH/g, and total content of heteroatom compounds except carbon and hydrogen less than 0.7ppm; the heat stability temperature of the high heat stability and high heat sink fuel is not lower than 450 ℃, and the heat sink temperature at 760 ℃ is not lower than 3.5MJ/kg. The invention also provides a preparation method of the fuel with high thermal stability and high heat sink and application of the fuel in aerospace aircraft fuels. The preparation method comprises the following steps: adding hydrogenation catalyst into jet fuel to make hydrogenation reaction, and adding bifunctional additive with cleaning dispersion action and cracking initiation action so as to obtain the invented high-heat stability high-heat-deposition fuel.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a high-heat-stability high-heat-deposition fuel, a preparation method and application thereof.
Background
Supersonic aircrafts are one of the important strategic development directions in the aerospace field. Hydrocarbon fuel is the energy source of supersonic aircraft, and also as coolant to exchange heat with the high temperature parts of the aircraft.
With the increase of the flying speed, the temperature of the fuel gradually rises and the fuel is converted from physical heat exchange to chemical heat absorption, and the fuel application mainly faces two problems:
firstly, when the aircraft flies at the conventional sound velocity (below 3 Mach), the fuel is in physical heat exchange (< 480 ℃), and in the process, the fuel reacts with trace dissolved oxygen (70 mg/L), solid-phase sediments are possibly generated to block a fuel conveying system, so that the heat stability of the fuel is required to be improved;
secondly, when the aircraft flies at hypersonic speed, the aircraft is at the limit temperature (> 480 ℃), and the fuel needs to absorb heat chemically through thermal cracking so as to reduce the heat load of the aircraft.
In order to prepare fuels with high thermal stability, jet A, JP-TS, JP-7 and the like are prepared in the beginning of the sixties of the last century in the United states, but the large-scale application of the fuels is limited by the higher cost.
In order to reduce the cost, the composite additive is added on the basis of JP-8 in the United states, and the thermal oxidation stability temperature of the fuel is increased by 56 ℃ (Edwards T. Journal of Engineering for Gas Turbines & Power,2005,129 (1): 121-139).
In recent years, researchers have also produced coal-based JP-900 fuels with high thermal stability that remain stable at high temperatures of 482 ℃ (Balster L M, corporan E, dewitt M J, et al. Fuel Processing Technology,2008,89 (4): 364-378).
However, the high thermal stability fuel is only used for flying an aircraft with a flying speed below 3Mach, and the flying requirement of a hypersonic aircraft (5 Mach) cannot be met.
Based on the above, researchers developed a series of endothermic hydrocarbon fuels, including EHF-01, etc., but the conventional endothermic hydrocarbon fuels have low thermal cracking conversion rate, fail to provide sufficient heat sink, have poor thermal stability, and are prone to generate deposition in the low-temperature physical heat exchange process (< 480 ℃).
Therefore, the development of fuel with high thermal stability and high thermal deposition is the basis for developing a new generation of supersonic aircraft.
However, at present, there is no high heat stability and high heat deposition fuel at home and abroad.
Disclosure of Invention
Aiming at the technical problems, in order to develop the flight requirements capable of being simultaneously applied to aircrafts with low Mach number and high Mach number, the invention provides a high-heat-stability and high-heat-sink fuel, the heat-stability temperature of the fuel is equivalent to that of the coal-based high-heat-stability fuel JP-900 reported in the current literature, and the heat sink at 760 ℃ exceeds 3.5MJ/kg. The aviation fuel has the characteristics of high heat stability and high heat sink, and is simple in preparation method, wide in raw material source, simple in preparation method of the used bifunctional additive and prepared for the first time.
A high heat stability high heat deposition fuel, its composition medium chain alkane is not less than 35wt%, cycloalkane is not less than 60wt%, aromatic hydrocarbon content is less than 2wt%, peroxide value is less than 0.8ppm, acid value is less than 0.002mgKOH/g, except carbon, total content of heteroatom compound (sulphur, nitrogen, oxygen, etc.) is less than 0.7ppm;
the heat stability temperature of the high heat stability and high heat sink fuel is not lower than 450 ℃, and the heat sink temperature at 760 ℃ is not lower than 3.5MJ/kg.
Preferably, the fuel with high thermal stability and high thermal deposition has the composition also containing 100-20000 ppm of a bifunctional additive with a cleaning dispersion effect and a cracking initiation effect.
The bifunctional additive is a core-shell type bipolar macromolecular polymer with a polar core and a non-polar shell, the polar core is a hyperbranched polymer and is selected from at least one of hyperbranched polyamide-amine, hyperbranched polyglycidyl and polyethyleneimine, and the non-polar shell is an oil-soluble branched chain and is selected from at least one of a polyisobutylene chain and a normal alkyl chain.
Specifically exemplified, the bifunctional additives include polyisobutylene-modified hyperbranched polyamidoamines, polyisobutylene-modified hyperbranched polyglycidols, polyisobutylene-modified polyethyleneimines, and the like.
In the bifunctional additive, the grafting ratio of the oil-soluble branched chain is preferably not less than 40%, and the oil-soluble branched chain partially or completely wraps the hyperbranched polymer core.
The molecular weight of the bifunctional additive is preferably not less than 5000.
The bifunctional additive can be prepared by adopting the following preparation method: the hyperbranched polymer and a compound (such as polyisobutylene and the like) for providing the oil-soluble branched chain are mixed in a solvent and are heated and refluxed to react to obtain the bifunctional additive.
The hyperbranched polymers and the compounds used to provide the oil-soluble branches are either commercially available or prepared using existing techniques.
The high-heat-stability high-heat-sink fuel provided by the invention can simultaneously meet the flight use requirements of an aircraft on low Mach number and high Mach number, and the synthesis method is simple.
The invention also provides a preparation method of the high-heat stability and high-heat sink fuel, which comprises the following steps: adding a hydrogenation catalyst into jet fuel to carry out hydrogenation reaction to obtain the fuel with high thermal stability and high thermal deposition.
In a preferred embodiment, the jet fuel is RP-3, the hydrogenation catalyst can be a commercially available Pd-based catalyst (such as a commercial Pd/C catalyst), the reaction temperature of the hydrogenation reaction is 60-300 ℃, and the hydrogen pressure is 3-8 MPa.
Preferably, the preparation method comprises the steps of adding a bifunctional additive which has a cleaning and dispersing effect and a cracking initiating effect into a product after hydrogenation reaction to obtain the high-heat-stability high-heat-deposition fuel;
the content of the bifunctional additive in the high-heat-stability high-heat-deposition fuel is 100-20000 ppm.
The invention can take the existing commercial jet fuel such as RP-3 as a raw material, remove unsaturated hydrocarbon and heteroatom compounds through deep hydrofining, simultaneously reduce peroxide value and acid value in the fuel, and add a novel bifunctional additive to finally prepare the high-heat stability and high-heat-deposition fuel.
The invention also provides application of the high-heat-stability high-heat-sink fuel in aerospace aircraft fuels.
Compared with the prior art, the invention has the main advantages that:
1. the heat stability temperature of the high heat stability and high heat sink fuel is not lower than 450 ℃, which is equivalent to the heat stability temperature of the JP-900 fuel with the best heat stability at present, and in addition, the 760 ℃ heat sink of the prepared fuel is not lower than 3.5MJ/kg, which can simultaneously meet the flight use requirements of the aircraft at low Mach number and high Mach number (> 5 Mach).
2. Compared with the prior art, the invention provides a novel method for preparing the fuel with ultrahigh thermal stability and high thermal stability by ultrahigh thermal oxidation, which has more obvious effect. In the practical application process, the use method is simple and the application is wide.
3. The preparation method of the high heat stability and high heat sink fuel uses the bifunctional additive with the functions of cleaning and dispersing and cracking initiation in the process of synthesizing the high heat stability and high heat sink fuel, adsorbs polar oxides generated in the process of physical heat exchange of the fuel, avoids the aggregation and deposition of the polar oxides, and is quickly decomposed at high temperature to initiate the cracking of the fuel, thereby improving the cracking depth and the heat sink, and ensuring the high heat sink while realizing the heat stability of the fuel. The additive is simple to prepare and use, and is provided for the first time and used for preparing the high-heat-stability high-heat-deposition fuel.
4. The preparation method of the high-heat-stability high-heat-still fuel has the advantages of simple process, wide raw material source, low cost and high economic value.
Drawings
FIG. 1 is a graph showing the molecular weight distribution of the bifunctional hyperbranched polymer additive prepared in example 1;
FIG. 2 is a photograph of the tube wall rating after JFTOT evaluation (450 ℃,2.5 h): (a) Is RP-3 jet fuel, (b) is the high thermal stability and high thermal precipitation fuel prepared in example 1;
fig. 3 is a heat sink curve of the high thermal stability high heat sink fuel prepared in example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
The present invention is further illustrated by the example of national commercial jet fuel (RP-3), which is intended to be illustrative and not limiting. Jet fuel RP-3 is very aromatic and contains a small amount of olefins.
Example 1
(1) The preparation method of the bifunctional hyperbranched polymer additive comprises the following specific steps:
(1) firstly, 1mol of ethylenediamine and 2mol of anhydrous methanol are added into a three-neck flask, then methyl acrylate is slowly dropped into the flask, the system temperature is controlled within the range of 25-45 ℃, and the mixture is continuously stirred for 40-48h, so that prepolymer N- (2-aminoethyl) glycine methyl ester is obtained. (2) The solvent methanol is completely distilled off at 60 ℃ under normal pressure to obtain the product N- (2-aminoethyl) glycine methyl ester. (3) The obtained N- (2-aminoethyl) glycine methyl ester is subjected to polycondensation reaction for 2-3h at 80, 100 and 120 ℃ respectively under the reduced pressure condition (-0.1 MPa) to obtain the hyperbranched polyamide-amine. (4) Polyisobutylene with equal mass is added into the obtained hyperbranched polyamide-amine, a certain amount of toluene is added as a solvent, and the mixture is refluxed at 150 ℃ to obtain polyisobutylene-modified hyperbranched polyamide-amine, the molecular weight distribution of which is shown in figure 1, and the polyisobutylene-modified hyperbranched polyamide-amine is used as a bifunctional hyperbranched polymer additive for preparing high-heat stability and high-heat-deposition fuels.
(2) Preparing high-heat stability and high-heat sink fuel: 1.2L of jet fuel RP-3 as a raw material and 3wt% of a commercially available Pd/C catalyst were charged into a 2L pressure reactor, and hydrofinishing saturation was carried out at 140 ℃ for 10 hours. And after the reaction is finished, cutting the fraction of the product to obtain an intermediate product with the distillation range of 150-220 ℃. Subsequently, 500ppm of the bifunctional hyperbranched polymer additive prepared in the step (1) is added into the intermediate product. The properties of the feedstock RP-3 used in the experiment and the prepared high heat stability and high heat sink fuels are shown in Table 1. FIG. 2 is a photograph of the tube wall rating after JFTOT evaluation (450 ℃,2.5 h): wherein (a) is raw material RP-3 jet fuel, and (b) is high heat stability fuel prepared in example 1. As can be seen from Table 1 and FIG. 2, the contents of aromatic hydrocarbon and olefin in the obtained fuel with high thermal stability are very low, and the peroxide number, acid number and total heteroatom compounds (sulfur, nitrogen, oxygen, etc.) are all significantly reduced. The heat stability of the fuel is greatly improved, and the heat stability can be evaluated by jet fuel thermal oxidation stability (JFTOT) of 450 ℃ multiplied by 2.5h, and is equivalent to the heat stability temperature of the currently known JP-900 fuel with the best heat stability, and the heat sink of the fuel at 760 ℃ is not lower than 3.5MJ/kg.
The heat sink curve of the high heat stability high heat sink fuel prepared in example 1 is shown in fig. 3.
TABLE 1 comparison of the physicochemical Properties of RP-3 jet fuels and of the fuels of high thermal stability obtained in example 1
Examples 2 to 4
Example 2 preparation of bifunctional hyperbranched polymer additives:
(1) firstly, 1mol of ethylenediamine and 2mol of anhydrous methanol are added into a three-neck flask, then 2mol of methyl acrylate is slowly dripped into the flask, the system temperature is controlled within the range of 25-45 ℃, and the mixture is continuously stirred for 36-40h, so that prepolymer N- (2-aminoethyl) glycine methyl ester is obtained. (2) The solvent methanol is completely distilled off at 60 ℃ under normal pressure to obtain the product N- (2-aminoethyl) glycine methyl ester. (3) And carrying out polycondensation reaction on the obtained N- (2-aminoethyl) glycine methyl ester at the reduced pressure condition (-0.1 MPa) at the temperatures of 80, 100 and 120 ℃ for 2-3h respectively to obtain the hyperbranched polyamide-amine. (4) Adding polyisobutene with double mass into the obtained hyperbranched polyamide-amine, adding a certain amount of toluene as a solvent, refluxing at 150 ℃ to obtain polyisobutene modified hyperbranched polyamide-amine, and using the polyisobutene modified hyperbranched polyamide-amine as a bifunctional hyperbranched polymer additive for preparing high-heat stability and high-heat-sink fuels.
Example 3 preparation of bifunctional hyperbranched polymer additives:
(1) 4g of potassium methoxide dissolved in 2ml of anhydrous methanol was added to the three-necked flask, and the atmosphere in the flask was purged with nitrogen. Then 4g trimethylolpropane is added to the bottle and heated to 60 ℃ to dissolve. Magnetically stirring for 30min, and vacuumizing to remove methanol. (2) And continuously dripping glycidol for 12 hours by using a peristaltic pump under the protection of nitrogen, and stopping the reaction after continuously reacting for 24 hours. (3) Adding 50ml of anhydrous methanol, neutralizing by a cation exchange resin column, removing most of methanol by rotary evaporation, pouring into 200ml of acetone, and magnetically stirring for half an hour to obtain a viscous polymer. The acetone is discarded and repeated, and then dissolved in methanol and collected in a pear-shaped bottle. Spin-drying at 60 ℃ under vacuum to obtain the hyperbranched polyglycidyl glycerol. (4) Adding equal amount of polyisobutene into the obtained hyperbranched polyglycidyl glycerol, adding a certain amount of toluene as a solvent, refluxing at 150 ℃ to obtain polyisobutene modified hyperbranched polyamide-amine, and using the polyisobutene modified hyperbranched polyamide-amine as a bifunctional hyperbranched polymer additive for preparing high-heat stability and high-heat-sink fuels.
Example 4 preparation of bifunctional hyperbranched polymer additives:
(1) precursor DDMAT: 37g of n-dodecyl mercaptan, 107g of acetone and 3g of methyl trioctyl ammonium chloride are added into a round-bottom flask, mixed uniformly and cooled to 10 ℃. 16g of an aqueous sodium hydroxide solution (50 wt%) was added dropwise to the above system. Stirring is carried out at 10 ℃ for 30min, and a mixed solution of 14g of carbon disulfide and 19g of acetone is added dropwise into the system within 20min, and stirring is carried out continuously for 10min. Then, 33g of chloroform was added to the system at a time, and 74g of a 50wt% aqueous solution of sodium hydroxide was added dropwise thereto. After the reaction was allowed to proceed overnight, 300ml of water was added in one portion, and finally 50ml of hydrochloric acid was added dropwise until the pH of the system was close to 2. Collecting a solid product by suction filtration, adding the solid product into 300ml of 2-propanol, stirring vigorously, filtering out insoluble solids, carrying out spin drying on the filtrate to obtain a crude product, and recrystallizing the crude product in petroleum ether at 60-90 ℃ to obtain a yellow crystal, namely DDMAT. (2) Monomer ACDT: 1.7ml of thionyl chloride was dissolved in 5ml of dichloromethane and added dropwise to the flask by syringe with vigorous stirring. The flask was transferred to a 45 ℃ oil bath for reaction for 1.5h, and then dichloromethane and excess thionyl chloride were evaporated to give an orange-yellow liquid. The orange liquid was dissolved in 30ml of methylene chloride again and cooled to 0 ℃ and a mixed solution containing 1.6g of triethylamine, 2.4g of hydroxyethyl acrylate and 8ml of ethylenediamine was added dropwise thereto. After the reaction was stirred overnight, the mixture was washed with 1M hydrochloric acid solution (50 ml) and saturated brine, respectively, and then dried over anhydrous magnesium sulfate and filtered, and the solvent was removed by rotary evaporation to obtain a crude product, which was separated and purified by a silica gel column using petroleum ether/ethyl acetate (25) as an eluent to obtain an orange viscous liquid, i.e., ACDT. (3) Synthesizing a sulfur-containing block hyperbranched polymer SHPGMA: GMA and ACDT were dissolved in 1, 4-dioxane at a 1. After adding initiator AIBN, bubbling in ice bath for 30min to eliminate oxygen and ensure the effective proceeding of free radical reaction. Then the polymerization reaction is carried out in an oil bath at 75 ℃, and after the reaction system is stirred for 2 hours, the reaction is poured into liquid nitrogen for quenching. When the quenched system had thawed, 8ml of dioxane was added for solubilization. The solution was then poured into 200ml of chilled methanol and the precipitate was carefully collected and dried under vacuum at 45 ℃ to give the final product SHPGMA. (4) Adding equal amount of polyisobutene into the obtained sulfur-containing block hyperbranched polymer, adding a certain amount of toluene as a solvent, refluxing at 150 ℃ to obtain polyisobutene modified hyperbranched polyamide-amine, and using the polyisobutene modified hyperbranched polyamide-amine as a bifunctional hyperbranched polymer additive for preparing high-heat stability and high-heat-sink fuels.
Preparation of high heat stability and high heat sink fuels for examples 2-4: the procedure is as in example 1 except that the type and amount of the bifunctional additive are different. The type and amount of the bifunctional additive are shown in table 2, and the obtained fuel properties with high thermal stability and high heat sink and the heat sink are shown in table 2.
TABLE 2 comparison of reaction conditions for preparing fuels of high thermal stability and results of fuels of high thermal stability obtained in examples 2 to 4
The above examples illustrate that the fuel with high thermal stability and high thermal deposition obtained by the present invention has an aromatic hydrocarbon content of less than 2wt%, a peroxide value of less than 0.8ppm, an acid value of less than 0.002mgKOH/g, a total content of heteroatom compounds (sulfur, nitrogen, oxygen, etc.) of less than 0.7ppm, a thermal stability temperature of not less than 450 ℃, and a thermal deposition temperature of 760 ℃ of not less than 3.5MJ/kg.
Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention defined by the appended claims.
Claims (4)
1. A high heat stability and high heat deposition fuel is characterized in that the fuel has the components of medium-chain alkane not less than 35wt%, naphthenic hydrocarbon not less than 60wt%, aromatic hydrocarbon content less than 2wt%, peroxide value less than 0.8ppm, acid value less than 0.002mgKOH/g, and total content of heteroatom compounds except carbon and hydrogen less than 0.7ppm;
the heat stability temperature of the high heat stability and high heat sink fuel is not lower than 450 ℃, and the heat sink temperature at 760 ℃ is not lower than 3.5MJ/kg;
the fuel with high heat stability and high heat deposition also contains 100-20000 ppm of bifunctional additive with functions of cleaning and dispersing and cracking initiation;
the bifunctional additive is a core-shell bipolar macromolecular polymer with a polar core and a non-polar shell, the polar core is a hyperbranched polymer and is selected from at least one of hyperbranched polyamide-amine, hyperbranched polyglycidyl and polyethyleneimine, and the non-polar shell is an oil-soluble branched chain and is selected from at least one of a polyisobutylene chain and a normal alkyl chain;
in the bifunctional additive, the grafting ratio of the oil-soluble branched chain is not lower than 40%, and the oil-soluble branched chain partially or completely wraps the hyperbranched polymer core;
the molecular weight of the bifunctional additive is not less than 5000.
2. The method for preparing the fuel with high thermal stability and high heat sink according to claim 1, comprising the following steps: adding a hydrogenation catalyst into jet fuel to carry out hydrogenation reaction, and adding a bifunctional additive which has a cleaning and dispersing effect and a cracking initiating effect into a product after the hydrogenation reaction to obtain the high-heat-stability high-heat-deposition fuel.
3. The preparation method according to claim 2, wherein the jet fuel is RP-3, the hydrogenation catalyst is a Pd-based catalyst, the reaction temperature of the hydrogenation reaction is 60 to 300 ℃, and the hydrogen pressure is 3 to 8MPa.
4. The use of the high thermal stability high heat sink fuel of claim 1 in aerospace aircraft fuels.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504894A (en) * | 2011-11-21 | 2012-06-20 | 中国人民解放军空军油料研究所 | Additive with high heat stability for jet fuels |
| CN107868682A (en) * | 2017-07-24 | 2018-04-03 | 湖北航天化学技术研究所 | A kind of hypersonic aircraft high heat absorbing type fuel and preparation method |
| CN108795514A (en) * | 2018-07-12 | 2018-11-13 | 天津大学 | A kind of heat absorbing type aviation fuel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504894A (en) * | 2011-11-21 | 2012-06-20 | 中国人民解放军空军油料研究所 | Additive with high heat stability for jet fuels |
| CN107868682A (en) * | 2017-07-24 | 2018-04-03 | 湖北航天化学技术研究所 | A kind of hypersonic aircraft high heat absorbing type fuel and preparation method |
| CN108795514A (en) * | 2018-07-12 | 2018-11-13 | 天津大学 | A kind of heat absorbing type aviation fuel and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 提高烃类燃料热沉的研究进展;贺芳等;《化学进展》;20060831;第18卷(第7/8期);第1041-1048页 * |
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