CN104449818B - Cyclopentadiene high density liquid hydrocarbon fuel and synthetic method thereof - Google Patents
Cyclopentadiene high density liquid hydrocarbon fuel and synthetic method thereof Download PDFInfo
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000000446 fuel Substances 0.000 title claims abstract description 39
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 33
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- -1 dimethyl tetrahydro dicyclopentadiene Chemical compound 0.000 claims abstract description 17
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 241001597008 Nomeidae Species 0.000 claims abstract description 8
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 229920002959 polymer blend Polymers 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000007039 two-step reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000006073 displacement reaction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/50—Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The open a kind of cyclopentadiene high density liquid hydrocarbon fuel of the present invention and synthetic method thereof, its weight percentages of components is dimethyl tetrahydro dicyclopentadiene 11 19%, tetrahydro-dicyclopentadiene 18 6%, methyl tetrahydro-dicyclopentadiene 45 57% and tetrahydrochysene three cyclopentadiene derivant 5 18%, density 0.94 0.96g/cm3.The present invention is by two-step reaction synthesis target product: the first step, and cyclopentadiene and methyl cyclopentadiene are carried out Diels-Alder additive reaction, and product is cyclopentadiene polymer mixture；Second step, carries out catalytic hydrogenation by above-mentioned cyclopentadiene polymer mixture, it is thus achieved that cyclopentadiene high density liquid hydrocarbon fuel.The hydrocarbon fuel density of the present invention is high, heat energy value is high, can meet the aircraft engine demand to high-density hydrocarbons；Method synthetic route is simple, environmental pollution is little for it, yield is high.
Description
Technical field
The present invention relates to a kind of novel cyclopentadiene high density liquid hydrocarbon fuel and synthetic method thereof, belong to the technology of preparing of novel space flight and aviation fuel.
Background technology
Development along with Modern High-Tech, the speed of aircraft, voyage are all greatly improved, higher requirement is it is also proposed simultaneously for the fuel system used, for meeting the aircraft height speed of a ship or plane, the demand of oceangoing voyage journey, in addition to using advanced engine configuration design to improve engine efficiency to greatest extent, the entrained density of fuel of raising, volume combustion calorific value are the emphasis of various countries' research.In the case of aircraft given volume, fuel density is the biggest, and the fuel being carried by is the most, and the energy that the highest volumetric fuel of volume combustion calorific value is provided that is the biggest, the most favourable for improving the performance of aircraft.High energy density fuel generally refers to density more than 0.8g/cm3, composition can be pure component or the mixture of multiple hydro carbons.Since the sixties in last century starts to develop high density carbon hydrogen species fuel, many countries achieve notable achievement in this field.Patent US [P] 4086284, US [P] 4288644, US [P] 4401837 etc. report the synthesis of conventional high density liquid hydrocarbon fuel JP-10, RJ-4, RJ-5, its synthetic route is typically obtained by techniques such as addition, hydrogenation, isomerization and separating-purifyings, wherein isomerization reaction uses catalyst, equipment corrosion and the environmental pollutions such as aluminum chloride serious.Fuel compound be take into account density while improve the effective means of high-density hydrocarbons cryogenic properties, it was reported that the new generation of high density hydrocarbon fuel RJ-7 of U.S.'s exploitation be made up of tetrahydrochysene three cyclopentadiene, hydrogenated cyclopentadiene/indenes addition product, three kinds of components of hanging type tetrahydrochysene dicyclopentadiene (JP-10) (Energy & Fuels,
1999,13,641-649), in such fuel process, each component needs to be respectively synthesized, purify, and causes its preparation cost high.
Summary of the invention
It is an object of the invention to provide and a kind of meet re-entry space vehicle electromotor to the demand of high-density hydrocarbons, the cyclopentadiene high density liquid hydrocarbon fuel of high density, high heat energy value.
It is a further object of the present invention to provide the synthetic method of the cyclopentadiene high density liquid hydrocarbon fuel that a kind of synthetic route is simple, environmental pollution is little, yield is high.
The technical scheme is that cyclopentadiene high density liquid hydrocarbon fuel components by weight percent includes: dimethyl tetrahydro dicyclopentadiene 11 ~ 19%, tetrahydro-dicyclopentadiene 18 ~ 26%, methyl tetrahydro-dicyclopentadiene 45 ~ 57%, tetrahydrochysene three cyclopentadiene derivant 5 ~ 18%.
The design philosophy of the present invention is: first step cyclopentadiene and methyl cyclopentadiene carry out Diels-Alder additive reaction, and product is undersaturated cyclopentadiene polymer mixture；Above-mentioned undersaturated cyclopentadiene polymer mixture is carried out catalytic hydrogenation by second step, it is thus achieved that cyclopentadiene high density liquid hydrocarbon fuel.
Technical scheme includes following operation: A) Diels-Alder additive reaction: reaction raw materials is cyclopentadiene and methyl cyclopentadiene, and cyclopentadiene and methyl cyclopentadiene are dissolved in reaction dissolvent, reaction temperature 130 DEG C ~ 190 DEG C, 5 ~ 15 hours response time；B) catalytic hydrogenating reduction reaction: adding hydrogenation catalyst, reaction pressure is 1.5MPa ~ 6MPa, reaction temperature 130 DEG C ~ 230 DEG C, 8 ~ 20 hours response time.
Described cyclopentadiene is 33:20 ~ 33:80 with the mass ratio of methyl cyclopentadiene.
Described reaction dissolvent is one or more in pentane, normal hexane, normal octane, methyl cyclopentane, hexamethylene, hexahydrotoluene, normal heptane, isobutyltrimethylmethane., toluene.
Described reaction dissolvent is 1:1 ~ 3:1 with the mass ratio of reaction raw materials.
The preferable reaction temperature of Diels-Alder additive reaction of the present invention 150 DEG C ~ 180 DEG C.
Hydrogenation catalyst of the present invention is palladium carbon hydrogenation catalyst and Raney's nickel hydrogenation catalyst, and the consumption of hydrogenation catalyst is to add 1 ~ 10 gram in every 100 grams of reaction raw materials.
The palladium content of described palladium carbon hydrogenation catalyst is 5-10%(mass fraction).
The preferred Hydrogen Vapor Pressure of hydrogenation reduction of the present invention is 2MPa ~ 4MPa, reaction temperature 180 DEG C ~ 210 DEG C, 10 ~ 18 hours response time.
It is an advantage of the current invention that: (1). synthetic method is simple, only Diels-Alder additive reaction and reduction reaction, and the experiment of two steps operates at same dicyandiamide solution, and yield is high；(2). being made without molecular structure isomerization reaction, environmental pollution is little；(2). raw material sources is extensive, it is easy to obtain；(3). the cyclopentadiene high density liquid hydrocarbon fuel that a synthetically prepared class is novel, density 0.94 ~ 0.97g/cm3, it is in a liquid state at 40 DEG C, meets the re-entry space vehicle electromotor demand to high-density hydrocarbons.The present invention uses the cyclopentadiene of wide material sources and methyl cyclopentadiene to be the hydrocarbon fuel that raw material disposably prepares high-density component, is not required to rectification and purification, and preparation cost is low.
Detailed description of the invention
Embodiment 1:
Take 50 grams of cyclopentadiene, 61 grams of methyl cyclopentadienes are dissolved in 200 grams of normal hexane and add autoclave, air three times in logical nitrogen displacement still, at 750 revs/min, react 5 hours under 130 DEG C of temperature conditionss, then reaction system is down to room temperature, adding 2 grams of palladium content is 5%(mass fraction) palladium carbon hydrogenation catalyst, it is passed through hydrogen after air three times in nitrogen displacement still, Hydrogen Vapor Pressure 3MPa, at 1000 revs/min, stop after reacting 15 hours under the conditions of 160 DEG C being passed through hydrogen, it is filtered to remove hydrogenation catalyst after being cooled to room temperature, solvent hexane is distilled off and obtains product 102 grams.Through examination of infrared spectrum contrast hydrogenation after 1610,1450,756cm-1Neighbouring strong double bond absorption peak disappears, and shows that hydrogenation reaction is carried out fully and completely.Product carries out MS-HPLC analysis and characterization, and product contains dimethyl tetrahydro dicyclopentadiene 15.9%, tetrahydro-dicyclopentadiene 22.5%, methyl tetrahydro-dicyclopentadiene 56.1% and tetrahydrochysene three cyclopentadiene derivant 5.3%.Density during this hydrocarbon fuel 25 DEG C is 0.94g/cm3。
Embodiment 2:
Take 62 grams of cyclopentadiene, 50 grams of methyl cyclopentadienes are dissolved in 250 grams of hexamethylene and add autoclave, air three times in logical nitrogen displacement still, at 750 revs/min, react 10 hours under 170 DEG C of temperature conditionss, then reaction system is down to room temperature, adding 3 grams of palladium content is 10%(mass fraction) palladium carbon hydrogenation catalyst, it is passed through hydrogen after air three times in nitrogen displacement still, Hydrogen Vapor Pressure 1.5MPa, at 1000 revs/min, stop after reacting 20 hours under the conditions of 210 DEG C being passed through hydrogen, it is filtered to remove hydrogenation catalyst after being cooled to room temperature, solvent hexane is distilled off and obtains product 105 grams.Through examination of infrared spectrum contrast hydrogenation after 1610,1450,756cm-1Neighbouring strong double bond absorption peak disappears, and shows that hydrogenation reaction is carried out fully and completely..Product carries out MS-HPLC analysis and characterization, and product contains dimethyl tetrahydro dicyclopentadiene 11.9%, tetrahydro-dicyclopentadiene 25.1%, methyl tetrahydro-dicyclopentadiene 45.9% and tetrahydrochysene three cyclopentadiene derivant 11.6%.25 DEG C of density of this hydrocarbon fuel are 0.95g/cm3。
Embodiment 3:
Take 40 grams of cyclopentadiene, 72 grams of methyl cyclopentadienes are dissolved in 200 grams of normal octanes and add autoclave, air three times in logical nitrogen displacement still, at 750 revs/min, react 10 hours under 160 DEG C of temperature conditionss, then reaction system is down to room temperature, adding 6 grams of palladium content is 5%(mass fraction) palladium carbon hydrogenation catalyst, it is passed through hydrogen after air three times in nitrogen displacement still, Hydrogen Vapor Pressure 2MPa, at 1000 revs/min, stop after reacting 15 hours under the conditions of 180 DEG C being passed through hydrogen, it is filtered to remove hydrogenation catalyst after being cooled to room temperature, solvent hexane is distilled off and obtains product 104 grams.Through examination of infrared spectrum contrast hydrogenation after 1610,1450,756cm-1Neighbouring strong double bond absorption peak disappears, and shows that hydrogenation reaction is carried out fully and completely.Product carries out MS-HPLC analysis and characterization, and product contains dimethyl tetrahydro dicyclopentadiene 18.3%, tetrahydro-dicyclopentadiene 18.9%, methyl tetrahydro-dicyclopentadiene 51.4% and tetrahydrochysene three cyclopentadiene derivant 17.1%.25 DEG C of density of this hydrocarbon fuel are 0.96g/cm3。
Embodiment 4:
Take 66 grams of cyclopentadiene, 40 grams of methyl cyclopentadienes are dissolved in 200 grams of normal heptane and add autoclave, air three times in logical nitrogen displacement still, at 750 revs/min, react 15 hours under 180 DEG C of temperature conditionss, then reaction system is down to room temperature, add 5 Cray Buddhist nun's nickel hydrogenation catalysts, sealed reactor, it is passed through hydrogen after air three times in logical nitrogen displacement still, Hydrogen Vapor Pressure 3MPa, at 1000 revs/min, stop after reacting 13 hours under the conditions of 230 DEG C being passed through hydrogen, it is filtered to remove hydrogenation catalyst after being cooled to room temperature, solvent hexane is distilled off and obtains product 101 grams.Through examination of infrared spectrum contrast hydrogenation after 1610,1450,756cm-1Neighbouring strong double bond absorption peak disappears, and shows that hydrogenation reaction is carried out fully and completely.Product carries out MS-HPLC analysis and characterization, and product contains dimethyl tetrahydro dicyclopentadiene 15.3%, tetrahydro-dicyclopentadiene 15.5%, methyl tetrahydro-dicyclopentadiene 51.8% and tetrahydrochysene three cyclopentadiene derivant 17.7%.Density during this hydrocarbon fuel 25 DEG C is 0.96g/cm3。
Embodiment 5:
Take 33 grams of cyclopentadiene, 80 grams of methyl cyclopentadienes are dissolved in 300 grams of hexahydrotoluenes and add autoclave, air three times in logical nitrogen displacement still, at 750 revs/min, react 15 hours under 140 DEG C of temperature conditionss, then reaction system is down to room temperature, add 10 Cray Buddhist nun's nickel hydrogenation catalysts, sealed reactor, it is passed through hydrogen after air three times in logical nitrogen displacement still, Hydrogen Vapor Pressure is to 6MPa, at 1000 revs/min, stop after reacting 10 hours under the conditions of 190 DEG C being passed through hydrogen, it is filtered to remove hydrogenation catalyst after being cooled to room temperature, solvent hexane is distilled off and obtains product 106 grams.Through examination of infrared spectrum contrast hydrogenation after 1610,1450,756cm-1Neighbouring strong double bond absorption peak disappears, and shows that hydrogenation reaction is carried out fully and completely.Product carries out MS-HPLC analysis and characterization, and product contains dimethyl tetrahydro dicyclopentadiene 16.5%, tetrahydro-dicyclopentadiene 24.1%, methyl tetrahydro-dicyclopentadiene 51.5% and tetrahydrochysene three cyclopentadiene derivant 7.3%.Density during this hydrocarbon fuel 25 DEG C is 0.94g/cm3。
Claims (9)
1. a cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: components by weight percent includes dimethyl tetrahydro dicyclopentadiene 11 ~ 19%, tetrahydro-dicyclopentadiene 18 ~ 26%, methyl tetrahydro-dicyclopentadiene 45 ~ 57%, tetrahydrochysene three cyclopentadiene derivant 5 ~ 18%.
2. the synthetic method of cyclopentadiene high density liquid hydrocarbon fuel described in a claim 1, it is characterized in that including following operation: A) Diels-Alder additive reaction: reaction raw materials is cyclopentadiene and methyl cyclopentadiene, cyclopentadiene and methyl cyclopentadiene are dissolved in reaction dissolvent, reaction temperature 130 DEG C ~ 190 DEG C, 5 ~ 15 hours response time；B) catalytic hydrogenating reduction reaction: adding hydrogenation catalyst, Hydrogen Vapor Pressure is 1.5MPa ~ 6MPa, reaction temperature 130 DEG C ~ 230 DEG C, 8 ~ 20 hours response time.
3. according to claim2The synthetic method of described cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: described cyclopentadiene is 33:20 ~ 33:80 with the mass ratio of methyl cyclopentadiene.
4. according to claim2The synthetic method of described cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: reaction dissolvent is one or more in pentane, normal hexane, normal octane, methyl cyclopentane, hexamethylene, hexahydrotoluene, normal heptane, isobutyltrimethylmethane., toluene.
5. according to claim2The synthetic method of described cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: reaction dissolvent is 1:1 ~ 3:1 with the mass ratio of reaction raw materials.
6. according to claim2The synthetic method of described cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: Diels-Alder additive reaction reaction temperature 150 DEG C ~ 180 DEG C.
7. according to claim2The synthetic method of described cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: hydrogenation catalyst is palladium carbon hydrogenation catalyst and Raney's nickel hydrogenation catalyst, and the consumption of hydrogenation catalyst is to add 1 ~ 10 gram in every 100 grams of reaction raw materials.
8. according to claim7The synthetic method of described cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: the palladium content of described palladium carbon hydrogenation catalyst is 5-10% mass fraction.
9. according to claim2The synthetic method of described cyclopentadiene high density liquid hydrocarbon fuel, it is characterised in that: the Hydrogen Vapor Pressure of hydrogenation reduction is 2MPa ~ 4MPa, reaction temperature 180 DEG C ~ 210 DEG C, 10 ~ 18 hours response time.
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| CN105567318A (en) * | 2016-01-13 | 2016-05-11 | 山东联星能源集团有限公司 | Synthetic method for high-density hydrocarbon military fuel |
| CN107879872B (en) * | 2017-11-09 | 2021-06-01 | 湖北航天化学技术研究所 | The density is more than 1g/cm3Method for synthesizing high-density liquid hydrocarbon fuel |
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