CN116355646B - Method for synthesizing high-energy-density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon - Google Patents
Method for synthesizing high-energy-density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon Download PDFInfo
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- CN116355646B CN116355646B CN202310405423.0A CN202310405423A CN116355646B CN 116355646 B CN116355646 B CN 116355646B CN 202310405423 A CN202310405423 A CN 202310405423A CN 116355646 B CN116355646 B CN 116355646B
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- aromatic hydrocarbon
- polycyclic aromatic
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- aviation fuel
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 60
- 239000000446 fuel Substances 0.000 title claims abstract description 53
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 35
- 238000007142 ring opening reaction Methods 0.000 claims description 27
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000013459 approach Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 38
- -1 polycyclic alkane Chemical class 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- BOYDUSQXWHQREG-UHFFFAOYSA-N 1,2,4,5-tetraethylcyclohexane Chemical compound CCC1CC(CC)C(CC)CC1CC BOYDUSQXWHQREG-UHFFFAOYSA-N 0.000 description 1
- HBIKNLNXSSBQCT-UHFFFAOYSA-N 1,2,5,7-tetramethyladamantane Chemical compound C1C(C2)(C)CC3(C)CC1C(C)C2(C)C3 HBIKNLNXSSBQCT-UHFFFAOYSA-N 0.000 description 1
- BWGAFPQRFLNCLN-UHFFFAOYSA-N 1,2,5-trimethyladamantane Chemical compound C1C(C2)CC3(C)CC1C(C)C2(C)C3 BWGAFPQRFLNCLN-UHFFFAOYSA-N 0.000 description 1
- LIZRGEMTDKSQRZ-UHFFFAOYSA-N 1,2-dimethyl-3,5-di(propan-2-yl)cyclohexane Chemical compound CC(C)C1CC(C)C(C)C(C(C)C)C1 LIZRGEMTDKSQRZ-UHFFFAOYSA-N 0.000 description 1
- UJSORZVCMMYGBS-UHFFFAOYSA-N 1,3,5,7-tetramethyladamantane Chemical compound C1C(C2)(C)CC3(C)CC1(C)CC2(C)C3 UJSORZVCMMYGBS-UHFFFAOYSA-N 0.000 description 1
- WCACLGXPFTYVEL-UHFFFAOYSA-N 1,3,5-trimethyladamantane Chemical compound C1C(C2)CC3(C)CC1(C)CC2(C)C3 WCACLGXPFTYVEL-UHFFFAOYSA-N 0.000 description 1
- XHQDEOWLMBIVBU-UHFFFAOYSA-N 1,3-diethyladamantane Chemical compound C1C(C2)CC3CC1(CC)CC2(CC)C3 XHQDEOWLMBIVBU-UHFFFAOYSA-N 0.000 description 1
- HJXAJTBTOWMAIA-UHFFFAOYSA-N 1-(cyclohexylmethyl)-2-methylcyclohexane Chemical compound CC1CCCCC1CC1CCCCC1 HJXAJTBTOWMAIA-UHFFFAOYSA-N 0.000 description 1
- WSKOAXCLFMOIHR-UHFFFAOYSA-N 1-cyclopentyl-4-propan-2-ylcyclohexane Chemical compound C1CC(C(C)C)CCC1C1CCCC1 WSKOAXCLFMOIHR-UHFFFAOYSA-N 0.000 description 1
- FTNPDAKMYKMVKB-UHFFFAOYSA-N 1-ethyl-3,5-dimethyladamantane Chemical compound C1C(C2)CC3(C)CC2(C)CC1(CC)C3 FTNPDAKMYKMVKB-UHFFFAOYSA-N 0.000 description 1
- VYMIQGUNEIJWAR-UHFFFAOYSA-N 2-butyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2CC(CCCC)CCC21 VYMIQGUNEIJWAR-UHFFFAOYSA-N 0.000 description 1
- IBLVSWYGUFGDMF-UHFFFAOYSA-N 2-cyclohexylethylcyclohexane Chemical compound C1CCCCC1CCC1CCCCC1 IBLVSWYGUFGDMF-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000011269 tar Substances 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing high-energy density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon, which comprises the following steps of catalyst preparation and fuel synthesis: (1) Screening a proper molecular sieve carrier and measuring the saturated water absorption capacity of the molecular sieve carrier; (2) Preparing an active metal precursor solution, and adjusting the pH to 9-13; wherein the mass of water in the solution is equal to the saturated water absorption of the molecular sieve carrier used; (3) Adding a molecular sieve into the active metal precursor solution, uniformly mixing, and performing ultrasonic treatment for a period of time; (4) high temperature calcination; (5) The catalyst is made into particles, fixed in a reaction tube and then installed on a fixed bed reactor; (6) introducing hydrogen for reduction; (7) Inputting a polycyclic aromatic hydrocarbon solution serving as a reaction raw material into a reaction tube; adjusting reaction conditions; (8) And obtaining the high-energy-density heat-absorbing aviation fuel after the reaction reaches a steady state. The invention develops a technical approach for synthesizing high-energy-density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing high-energy-density heat-absorbing aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon.
Background
As aerospace vehicles move faster, higher, and farther, thermal barrier and energy starvation problems are more pronounced, and there is a need to develop high performance aviation fuels with high heating value, high density, and high heat absorption. Conventional petroleum-based aviation fuels contain a large amount of paraffins, which have low energy density and thermal oxidation stability, and are difficult to maintain stable at higher temperatures. This is because an important role of aviation fuel is to cool structural parts of an aircraft that are subjected to dynamic heating due to friction with high-speed ram air flow, when the flying speed reaches mach 3, the temperature of the fuel may rise to 350 ℃ or higher, and paraffin is inevitably thermally cracked and dehydrogenated coked at such high temperature, so that it is difficult for conventional petroleum-based aviation fuel to satisfy the requirements of the development of modern aviation industry. The high-density aviation fuel is aviation fuel with density higher than 0.8g/mL, is a mixture of single-component or multi-component C8-C16 hydrocarbons, and is mainly applied to aircrafts such as rockets, missiles, satellites and the like. Compared with the conventional petroleum-based aviation fuel (such as RP-3), the high-energy-density heat-absorption aviation fuel has higher density, volume heat value and thermal oxidation stability, and can greatly improve the range of a missile and the flight distance and load of an aircraft under the limited volume of an oil tank.
Polycyclic aromatic hydrocarbon is the main component of petroleum refining residual oil and coal liquefaction tar, such as naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene and alkyl substitutes thereof, the carbon number is similar to that of aviation fuel, and the high-energy density aviation fuel with the density of more than or equal to 0.90g/mL can be prepared by performing one-step hydroconversion on the polycyclic aromatic hydrocarbon, wherein the content of polycyclic alkane in the fuel is more than or equal to 95wt%, and the polycyclic aromatic hydrocarbon has high density, high heat value and high thermal oxidation stability. Applicant 2021 discloses a method for preparing high density aviation fuel by using hollow molecular sieve catalyst for catalyzing polycyclic aromatic hydrocarbon hydrogenation, see patent CN113368891a, and the obtained fully saturated polycyclic alkane shows excellent fuel property; but the performance of the product can be further enhanced, namely, the fully saturated polycyclic alkane can further undergo hydroisomerization, skeleton rearrangement, selective ring opening and other reactions to form alkyladamantane (PSA) and selective ring opening products (SRO), and the carbon atoms of the PSA and the SRO are consistent with those of the saturated polycyclic alkane, so that the resource waste is reduced. Wherein, the selective ring-opening reaction refers to the ring opening of one or two rings of saturated polycyclic alkane, and the carbon number of the polycyclic alkane is kept unchanged. PSA has higher fuel density, volumetric heating value and thermo-oxidative stability than saturated multicycloparaffins; while SRO has a slightly lower heating value than adamantane, but it has excellent heat absorbing capacity, the formation of coke by cracking of the product is greatly reduced, and a higher heat sink is exhibited. PSA and SRO are therefore more excellent high energy density endothermic aviation fuel components. In the industry, PSA and SRO are generally produced by two-step catalytic reaction, wherein a hydrotreating catalyst is adopted in the first step, and polycyclic aromatic hydrocarbon is firstly hydrogenated and saturated to form polycyclic alkane; and then in the second step, a catalyst with isomerism and ring opening properties is adopted, and the saturated polycyclic alkane undergoes isomerism and ring opening reaction under the action of the catalyst. The production method has complicated reaction steps, different catalysts are needed in different reaction stages, and the cost is high. Therefore, the synthesis of high-energy-density endothermic aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon by adopting a multifunctional catalyst is a hot spot of current research.
At present, the research of one-step hydroconversion of polycyclic aromatic hydrocarbon is mainly focused on hydroisomerization and selective ring-opening reaction of bicycloalkane decalin and derivatives thereof, but the catalytic research of tricyclic and above aromatic hydrocarbon is less. Therefore, polycyclic aromatic hydrocarbon with the ring number more than or equal to 3 is used as a raw material, and the high-energy-density heat-absorbing aviation fuel containing PSA and SRO is synthesized by one-step hydroconversion, so that the method has more attractive force and application prospect. Wherein the key point is in the design of the multifunctional catalyst; because the multifunctional catalyst needs to have excellent deep hydrogenation capability and excellent hydroisomerization, rearrangement and selective ring opening properties at the same time. Patent CN112341307A discloses a method for preparing alkyladamantane from phenanthrene in coal tar, wherein mesoporous Y molecular sieve is adopted to load Pt catalyst, and a high-pressure reaction kettle is used for catalytic reaction; however, the highest yield of alkyladamantane in this patent is only 6.5wt% and is obtained at a high temperature of 280 ℃; in addition, the autoclave is a batch reaction, which is disadvantageous for continuous operation. Patent CN112851459a further uses USY molecular sieve supported Pt-Pd catalyst to catalyze fused ring alkane to prepare alkyladamantane, but the patent still uses high pressure reactor to react, the hydrogenation temperature is up to 280 ℃, and the alkyladamantane product contains a large amount of 1,3, 5-trimethyladamantane and 1,3, 4-trimethyladamantane with reduced carbon number, which causes great energy waste, and the yield of alkyladamantane is only 6.72wt% at most under optimal condition. Obviously, none of these patents disclose the synthesis of selective ring-opened products, and the prepared catalysts have poor performance, resulting in poor yields of the desired products.
The present invention has been made in order to solve the above-mentioned problems.
Disclosure of Invention
The invention discloses a novel technical approach for synthesizing high-energy-density heat-absorbing aviation fuel. The invention adopts the enhanced strong electrostatic adsorption method to prepare the multifunctional metal molecular sieve catalyst with highly dispersed active metal, and the catalyst shows excellent deep hydrogenation activity, excellent hydroisomerization and selective ring opening performance; the catalyst has excellent catalytic property in the reaction of synthesizing the high-energy-density heat-absorbing aviation fuel by taking polycyclic aromatic hydrocarbon as a raw material through one-step hydroconversion, and greatly enhances the yield of the high-energy-density heat-absorbing aviation fuel.
The technical scheme of the invention is as follows:
a method for synthesizing high-energy density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon comprises the following steps of catalyst preparation and fuel synthesis:
(1) Selecting a proper molecular sieve carrier, taking a certain amount of molecular sieve and measuring the saturated water absorption capacity of the molecular sieve; repeating for three times, and taking an average value;
(2) Preparing an active metal precursor solution, and adjusting the pH to 9-13; wherein the mass of water in the solution is equal to the saturated water absorption of the molecular sieve carrier used;
(3) Adding the molecular sieve in the step (1) into the active metal precursor solution in the step (2), generally stirring vigorously at not less than 850rpm, carrying out an electrostatic adsorption process, and loading active metal onto a molecular sieve carrier; ultrasonic treatment is carried out for a period of time after uniform mixing; then vacuum drying is carried out at a certain temperature;
(4) Calcining the solid obtained in the step (3) at a high temperature to obtain a catalyst;
(5) Preparing the catalyst obtained in the step (4) into particles with the particle size of 30-40 meshes, fixing the particles in a reaction tube, and then mounting the particles on a fixed bed reactor;
(6) Introducing hydrogen to reduce the catalyst in the reaction tube;
(7) Inputting a polycyclic aromatic hydrocarbon solution serving as a reaction raw material into a reaction tube; adjusting reaction conditions;
(8) And after the reaction reaches a steady state, collecting a liquid product to obtain the high-energy-density heat-absorbing aviation fuel.
Preferably, the molecular sieve selected in the step (1) is one or more of ZSM-5, beta, HY, SAPO-11 or Al-MCM-41; still more preferably, the molecular sieve supports are Beta and HY.
Preferably, the active metal precursor solution of step (2) is a metal compound solution of one or more of Pt, pd, ir, ru, rh, au, ni, cu, zn, co, fe; still more preferably, the active metal precursor solution is a platinum tetrammine nitrate solution.
Preferably, ammonia is used to adjust the pH of the solution to 9-13.
Preferably, the addition amount of the active metal precursor solution in the step (3) is 0.02-6.00wt% of active metal in the molecular sieve; the ultrasonic treatment time is not less than 0.5h; vacuum drying at 60-120deg.C for 6-24h.
Preferably, the high temperature calcination in step (4) is carried out at a temperature of 300-500 ℃ for 3-10 hours.
Preferably, the hydrogen is used for reduction in the step (6), the hydrogen pressure is 2-6MPa, and the temperature is 300-500 ℃ for 2-6h.
Preferably, the step (7) is performed by using a polycyclic aromatic hydrocarbon solution as a reaction raw material, wherein the polycyclic aromatic hydrocarbon is one or more of fluorene, phenanthrene, anthracene or alkyl substituent thereof, and the solvent is one or more of decalin, cyclohexane, octane, hexane and heptane.
Preferably, step (7) adjusts the reaction conditions as follows: the reaction pressure is regulated to 2-6MPa, the reaction temperature is 150-300 ℃, the hydrogen-oil ratio is 200-800NmL/mL, and the raw material feeding mass airspeed is 5-50h -1.
The invention has the beneficial effects that:
1. The method adopts an enhanced strong electrostatic adsorption method to prepare the acidic molecular sieve loaded high-dispersion active metal catalyst. The enhanced strong electrostatic adsorption method is adopted to promote the high dispersion of the active metal, the active metal and the carrier have strong interaction, and the high-energy-density heat absorption type aviation fuel prepared by one-step hydrogenation conversion of the polycyclic aromatic hydrocarbon has excellent catalytic performance. The technical approach for synthesizing the high-energy-density heat-absorbing aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon is developed. Compared with the multi-step catalytic reaction in the prior art, the method simplifies the technological catalytic process, is simpler and more convenient to operate, and saves the reaction cost. In addition, the prepared high-dispersion active metal catalyst can achieve very high yield of high-energy-density endothermic aviation fuel under the relatively mild reaction temperature condition, and comprises alkyladamantane and selective ring-opening products; wherein the yield of the alkyladamantane is up to 34.9wt percent, the yield of the selective ring-opening product is up to 13.9wt percent, and the method is obviously superior to the method in the prior art.
2. The invention uses molecular sieve surface with a large amount of acid sites and hydroxyl, when the metal impregnating solution with pH 9-13 is contacted with molecular sieve by ammonia water, the molecular sieve surface can be deprotonated, presents strong negative surface, and has strong electrostatic adsorption interaction with positively charged active metal ions such as Pt (NH 3)4 2+), in the stirring process, the active metal is electrostatically adsorbed on the molecular sieve, the metal particle diameter can reach 1.6-2.0nm, thereby realizing high dispersion of active metal load, and the excellent catalytic performance can be realized in the one-step hydroconversion of polycyclic aromatic hydrocarbon to synthesize high energy density endothermic aviation fuel, thereby realizing high energy density endothermic aviation fuel yield.
Drawings
FIG. 1 is an X-ray crystal diffraction pattern (XRD) of the Pt/Beta and Pt/HY catalysts prepared in the examples.
FIG. 2 is a graph of Transmission Electron Microscopy (TEM), high Resolution Transmission Electron Microscopy (HRTEM), and element distribution (mapping) of Pt/Beta (a, b, c) and Pt/HY (d, e, f) catalysts prepared in the examples. .
FIG. 3 is a schematic of a fixed bed reactor apparatus used in the examples. Wherein, 1: feed tank, 2: electronic balance, 3: filter, 4: high pressure liquid chromatography pump, 5: mass flowmeter, 6: safety valve, 7: heating furnace, 8: temperature sensor, 9: condenser, 10: gas-liquid separator, 11: pressure sensor, 12: back pressure valve, 13: wet-type anticorrosive gas flowmeter, 14: waste liquid tank, 15: and a computer.
FIG. 4 is an overall two-dimensional gas chromatogram of a Pt/HY catalyzed one-step hydrogenation reaction product of a polycyclic aromatic hydrocarbon phenanthrene at 220℃in an example.
Fig. 5 is a structural formula of different alkyladamantanes (C 14H24, m/z=192) in a one-step hydroconversion product of a polycyclic aromatic hydrocarbon phenanthrene.
FIG. 6 is a schematic of the selective ring-opening product of a typical one-step hydroconversion product of a polycyclic aromatic hydrocarbon phenanthrene.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments. It should be noted that the following examples are only for the purpose of describing and illustrating the present invention in detail, and the scope of application of the present invention is not limited by the conditions of the examples.
Examples: the method for synthesizing the high-energy-density heat-absorbing aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon comprises the following steps:
Step (1): preparing the metal molecular sieve catalyst with highly dispersed active metal.
0.072G of platinum tetrammine nitrate is weighed and dissolved in water, ammonia water is added dropwise, the pH value of the solution is adjusted to 11.5, after the solution is stirred for 1.0h and the pH value is stabilized, 2.0g of Beta or HY molecular sieve is added, the solution is vigorously stirred for 0.5h, and then the solution is subjected to ultrasonic treatment for 0.5h. And then vacuum drying is carried out for 10 hours at 80 ℃ in a drying oven, a muffle furnace is placed, the temperature is increased to 450 ℃ at a speed of 1 ℃/min, and the high-dispersion multifunctional metal molecular sieve catalyst is obtained after roasting for 4 hours.
According to the different molecular sieve carriers, the molecular sieve carriers are respectively named as Pt/Beta or Pt/HY; wherein the loading of the active metal Pt is 1.8wt%.
FIG. 1 is an X-ray crystal diffraction pattern (XRD) of the Pt/Beta and Pt/HY catalysts prepared; from the graph, the Pt/HY and Pt/Beta catalysts respectively show obvious BEA and FAU characteristic diffraction peaks, and have good molecular sieve crystallinity; meanwhile, no obvious diffraction signal of metal Pt is observed, which indicates that the active metals in the two catalysts have excellent dispersity and excellent metal-carrier interaction strength.
FIG. 2 is a graph of Transmission Electron Microscopy (TEM), high Resolution Transmission Electron Microscopy (HRTEM), and element distribution (mapping) of Pt/Beta (a, b, c) and Pt/HY (d, e, f) catalysts prepared in the examples. As is apparent from its TEM (fig. 2a and 2 d) and HRTEM images (fig. 2b and 2 e), the active metal Pt exhibits a highly dispersed state, indicating that it has a strong metal-carrier interaction, which is beneficial to promote one-step hydroconversion of polycyclic aromatic hydrocarbons; it can be seen from FIGS. 2b and 2e that the average particle size of the metallic Pt in the Pt/Beta and Pt/HY catalysts is 2.0nm and 1.6nm, respectively; wherein the Pt/HY catalyst shows better metal dispersity, and the metal dispersity is obviously better than that of a supported catalyst prepared by an impregnation method in the literature. In addition, the elemental distributions in fig. 2c and 2f also show the high dispersion of the metallic Pt in the two molecular sieve catalysts. This shows that the invention adopts the enhanced strong electrostatic adsorption method to successfully prepare the metal molecular sieve catalyst with highly dispersed active metal.
Step (2): and (3) catalyzing the polycyclic aromatic hydrocarbon phenanthrene to be converted into the high-energy-density aviation endothermic aviation fuel by one step through the Pt/HY molecular sieve catalyst obtained in the step (1).
1G of Pt/HY catalyst is weighed and put into a stainless steel reaction tube, and both ends are sequentially filled with quartz cotton and silicon carbide and then are arranged into a fixed bed reactor; the tightness inspection is carried out by adopting 5MPa nitrogen, the pressure of the device is not obviously reduced within 0.5h, which indicates that the tightness of the device is good; pressurizing the device to 4MPa by using hydrogen, wherein the flow rate of the hydrogen is set to be 200mL/min; heating to in-situ reduce the catalyst at 450 ℃ for 3.5 hours for activation;
After the catalyst was reduced, the temperature of the heating furnace was lowered to the catalytic reaction temperature, and the hydrogen flow rate was set at 100mL/min. Starting a high-pressure liquid phase feed pump, inputting a reaction raw material polycyclic aromatic hydrocarbon phenanthrene solution into a reaction tube for catalytic reaction, wherein a solvent is octane, and regulating reaction conditions; after the reaction is stable, the liquid product is collected through a sampling port after gas-liquid separation, and then is analyzed by using Shimadzu (GC×GC-MS/FID, shimadzu QP2010 Ultra) full two-dimensional gas chromatography.
The synthesis of high energy density endothermic aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon is carried out on a fixed bed reactor, and fig. 3 is a schematic diagram of a fixed bed reactor used in this example. The reaction device consists of four parts, namely a feeding system; II, a reaction system; III, a sampling system; and IV, controlling a system. Inputting hydrogen and polycyclic aromatic hydrocarbon into a reaction system through a feeding system for catalytic reaction, and flowing into a sampling system for sampling analysis after the reaction is finished; the reaction temperature and pressure are regulated by a control system.
By adopting a fixed bed reactor and a Pt/HY catalyst, under the reaction conditions of 4MPa, 500NmL/mL of hydrogen-oil ratio and 8.4h -1 of weight, taking polycyclic aromatic hydrocarbon phenanthrene as a raw material and octane as a solvent, synthesizing high-energy-density endothermic aviation fuel through one-step hydroconversion, and as can be seen from the figure, the total two-dimensional gas chromatogram of the reaction product at 220 ℃ is shown in FIG. 4, the hydroconversion product of the polycyclic aromatic hydrocarbon phenanthrene is very complex and has hundreds or thousands of products, in the one-step hydroconversion reaction of phenanthrene, phenanthrene (PHE) is firstly subjected to hydrogenation saturation to form Quan Qing phenanthrene (PHP), then PHP is further subjected to isomerization to form skeleton isomerism Product (PSI), and then PSI is subjected to hydroisomerization, skeleton rearrangement and selective ring opening reaction to form alkyladamantane (PSA) and selective ring opening product (SRO). PSA and SRO are more excellent high energy density endothermic aviation fuel components.
FIG. 5 is a structural formula of different alkyladamantanes (C 14H24, m/z=192) in a one-step hydroconversion product of a polycyclic aromatic hydrocarbon phenanthrene; the alkyladamantane products mainly comprise 1,3,5, 6-tetramethyladamantane, 1,3,5, 7-tetramethyladamantane, 1, 3-dimethyl-5-ethyladamantane and 1, 3-diethyladamantane; in addition, there are also a variety of stereoisomeric products of the same alkyladamantane, and thus, the same alkyladamantane in fig. 4 has different retention times, which are different stereoisomers thereof.
As can be seen from the chromatogram in fig. 4, the hydroconversion products of polycyclic aromatic phenanthrenes are very complex, with a wide variety of selective ring-opening products, mainly including single ring-opening products (C 14H26, m/z=194) and double ring-opening products (C 14H28, m/z=196). Typical selective ring-opening products are shown in FIG. 6; wherein the monocyclic ring-opening products mainly comprise 2-butyl decalin, 1, 2-dicyclohexylethane, 1-cyclopentyl-4-isopropyl cyclohexane and 1- (cyclohexylmethyl) -2-methylcyclohexane; the double-ring opening products mainly comprise 1, 5-diisopropyl-2, 3-dimethylcyclohexane, 1,2,4, 5-tetraethylcyclohexane and 2, 4-diisopropyl-1, 1-dimethylcyclohexane; are all high-energy density heat absorption type aviation fuel components with excellent performance.
Table 1 shows the synthesis of high energy density endothermic aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon phenanthrene catalyzed by a Pt/Beta catalyst using a fixed bed reactor in this example. Reaction conditions: the pressure is 4MPa, the temperature is 210-240 ℃, the hydrogen-oil ratio is 500NmL/mL, the weight hourly space velocity is 8.4h -1, and the solvent is n-octane; as can be seen from Table 1, under the reaction conditions adopted, the conversion rate of phenanthrene reaches 100%, which indicates that the Pt/Beta catalyst has excellent deep hydrogenation catalytic activity; the yield of alkyladamantane is up to 10.9wt% at 210 ℃, and the yield of the selective ring-opening product is 9.2wt%; as the reaction temperature increases, the yields of alkyladamantane and the selectively opened product increase, with the highest alkyladamantane yield at 230 ℃ being 26.9wt% and selectively opened product yield at 13.9wt%. The result shows that the Pt/Beta catalyst prepared by the invention shows good yields of alkyladamantane and selective ring-opening products of the endothermic aviation fuel component with high energy density under relatively mild conditions.
TABLE 1Pt/Beta catalyst for catalytic Multi-aromatic phenanthrene one-step hydroconversion
Table 2 shows the synthesis of high energy density aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon phenanthrene using a fixed bed reactor and a Pt/HY catalyst. Reaction conditions: the pressure is 4MPa, the temperature is 200-230 ℃, the hydrogen-oil ratio is 500NmL/mL, the weight hourly space velocity is 8.4-12.6h -1, and the solvent is n-octane. As can be seen from Table 2, under the reaction conditions employed, the conversion of phenanthrene reached 100%, and the Pt/HY catalyst exhibited excellent deep hydrogenation catalytic activity. The yield of alkyladamantane is as high as 6.9wt% at 200 ℃, the yield of the selective ring-opening product is 12.5wt%, and the yield of alkyladamantane increases with increasing reaction temperature, and the yield of the selective ring-opening product decreases due to the fact that the further cracking of the selective ring-opening product is promoted by the excessively high reaction temperature. The Pt/HY catalyst showed the highest alkyladamantane yield of 34.9wt% and the selective ring-opened product yield of 6.5wt% at 220 ℃. The results also show that the Pt/HY catalyst prepared by the invention also shows excellent yields of alkyladamantane and selective ring-opening products of the endothermic aviation fuel component with high energy density under relatively mild conditions.
TABLE 2Pt/HY catalyst catalyzed one-step hydroconversion of polycyclic aromatic hydrocarbons phenanthrene
The foregoing is only used to describe the detailed embodiments of the present invention, but the technical solution of the present invention is not limited to the above-mentioned method. Equivalent modifications and variations of the proposed technique, which are known to those skilled in the art, are intended to be included within the scope of the claims of the present invention, without departing from the basic principles of the present technique.
Claims (6)
1. The method for synthesizing the heat absorption type aviation fuel by one-step hydroconversion of the polycyclic aromatic hydrocarbon is characterized by comprising the following steps of:
(1) Selecting a proper molecular sieve carrier, taking a certain amount of molecular sieve and measuring the saturated water absorption capacity of the molecular sieve; repeating for three times, and taking an average value;
(2) Preparing an active metal precursor solution, and adjusting the pH to 9-13; wherein the mass of water in the solution is equal to the saturated water absorption of the molecular sieve carrier used;
(3) Adding the molecular sieve in the step (1) into the active metal precursor solution in the step (2), vigorously stirring at not less than 850rpm, carrying out an electrostatic adsorption process, and loading active metal onto a molecular sieve carrier; ultrasonic treatment is carried out for a period of time after uniform mixing; then vacuum drying is carried out at a certain temperature;
(4) Calcining the solid obtained in the step (3) at a high temperature to obtain a catalyst;
(5) Preparing the catalyst obtained in the step (4) into particles with the particle size of 30-40 meshes, fixing the particles in a reaction tube, and then mounting the particles on a fixed bed reactor;
(6) Introducing hydrogen to reduce the catalyst in the reaction tube;
(7) Inputting a polycyclic aromatic hydrocarbon solution serving as a reaction raw material into a reaction tube; adjusting reaction conditions;
(8) After the reaction reaches a steady state, collecting a liquid product to obtain the heat absorption aviation fuel comprising alkyladamantane and the selective ring-opening product;
The active metal precursor solution of the step (2) is a metal compound solution of one or more of Pt, pd, ir, ru, rh, au, ni, cu, zn, co, fe;
Step (7) a polycyclic aromatic hydrocarbon solution serving as a reaction raw material, wherein the polycyclic aromatic hydrocarbon is one or more of fluorene, phenanthrene, anthracene or alkyl substitutes thereof, and the solvent is one or more of decalin, cyclohexane, octane, hexane and heptane;
Step (7) adjusting the reaction conditions as follows: the reaction pressure is regulated to be 2-6MPa, the reaction temperature is 150-240 ℃, the hydrogen-oil ratio is 200-800NmL/mL, and the raw material feeding mass airspeed is 5-50h -1.
2. The method for synthesizing heat absorption aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon according to claim 1, wherein the molecular sieve selected in the step (1) is one or more of ZSM-5, beta, HY, SAPO-11 or Al-MCM-41.
3. The method for synthesizing heat-absorbing aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon according to claim 1, wherein the step (2) uses ammonia to adjust the pH of the solution to 9-13.
4. The method for synthesizing the heat-absorbing aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon according to claim 1, wherein the addition amount of the active metal precursor solution in the step (3) is 0.02-6.00 wt% of the active metal in the molecular sieve; the ultrasonic treatment time is not less than 0.5 h; vacuum drying at 60-120deg.C to 6-24 h.
5. The method for synthesizing heat-absorbing aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon according to claim 1, wherein the high-temperature calcination temperature in the step (4) is 3-10 h at 300-500 ℃.
6. The method for synthesizing the heat-absorbing aviation fuel by one-step hydroconversion of polycyclic aromatic hydrocarbon according to claim 1, wherein hydrogen is used for reduction in the step (6), the hydrogen pressure is 2-6 MPa, and the temperature is 300-500 ℃ for reduction 2-6 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE674431A (en) * | 1964-12-28 | 1966-04-15 | ||
| BE811017A (en) * | 1973-02-16 | 1974-08-14 | MORDENITE-BASED CATALYST FOR HYDROCARBON CONVERSION | |
| CN103657709A (en) * | 2012-09-07 | 2014-03-26 | 中国石油天然气集团公司 | Reaction adsorption desulfurization-aromatization reaction process and catalyst thereof |
| CN113368891A (en) * | 2021-05-19 | 2021-09-10 | 天津大学 | Preparation method of hollow molecular sieve catalyst and application of hollow molecular sieve catalyst in preparation of high-density aviation fuel by hydrogenation of polycyclic aromatic hydrocarbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE674431A (en) * | 1964-12-28 | 1966-04-15 | ||
| BE811017A (en) * | 1973-02-16 | 1974-08-14 | MORDENITE-BASED CATALYST FOR HYDROCARBON CONVERSION | |
| CN103657709A (en) * | 2012-09-07 | 2014-03-26 | 中国石油天然气集团公司 | Reaction adsorption desulfurization-aromatization reaction process and catalyst thereof |
| CN113368891A (en) * | 2021-05-19 | 2021-09-10 | 天津大学 | Preparation method of hollow molecular sieve catalyst and application of hollow molecular sieve catalyst in preparation of high-density aviation fuel by hydrogenation of polycyclic aromatic hydrocarbon |
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