CN108409522A - 一种重苯萘生产精萘方法 - Google Patents
一种重苯萘生产精萘方法 Download PDFInfo
- Publication number
- CN108409522A CN108409522A CN201810201010.XA CN201810201010A CN108409522A CN 108409522 A CN108409522 A CN 108409522A CN 201810201010 A CN201810201010 A CN 201810201010A CN 108409522 A CN108409522 A CN 108409522A
- Authority
- CN
- China
- Prior art keywords
- naphthalene
- catalyst
- selective hydrogenation
- heavy
- heavy benzol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 58
- LMIZORQOLSLQRY-UHFFFAOYSA-N benzene;naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 LMIZORQOLSLQRY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000007670 refining Methods 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002041 carbon nanotube Substances 0.000 claims description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 19
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 5
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 239000013504 Triton X-100 Substances 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/883—Molybdenum and nickel
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
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- 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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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种重苯萘生产精萘的方法，所述方法包括：重苯萘首先通过选择性加氢精制反应区，此选择性加氢精制反应区催化剂采用针对粗萘特制的新型选择性加氢催化剂，所得反应流出物经精馏塔蒸馏得到轻、中、重馏分，其中中间馏分再经结晶得到精萘产品。此发明方法使重苯萘脱硫率99.8％以上。同时使重苯萘得到充分利用，除得到精萘产品外，还副产汽油调和组分和甲基萘油产品。
Description
技术领域
本发明涉及一种重苯萘的加工方法，具体地说是涉及一种重苯萘利用新型选择性加氢催化剂进行选择性加氢反应，再结合精馏和结晶工艺，生产精萘的方法。
背景技术
萘是重要的化工原料，主要用于催化氧化制苯酐和染料中间体，也用于作水泥减水剂、表面活性剂、增塑剂、聚酯、合成纤维和药物等。国内70％以上的萘依赖于焦化行业，由煤焦油制工业萘技术已很成熟，但工业萘的纯度只有95％，不能满足其作为精细化学品原料的要求，以萘为原料生产的精细化学品均需要纯度大于99％的精萘。工业萘中主要杂质为苯并噻吩，含量约为2％～3％，其沸点与萘沸点仅差3℃，采用物理分离法较难除去。其次粗萘中还含量少量的四氢化萘、喹啉、β-甲基萘及灰分，这些杂质相对于苯并噻吩相对容易去除，因此，工业萘提纯制精萘关键在于脱除硫茚。
重苯萘源于重苯，重苯是煤化工行业粗苯加氢工艺过程中产生的副产物。重苯萘、工业萘或粗萘制得精萘的方法有物理法、化学法和联合法。物理法主要有乳化液膜法、结晶法、精馏法；化学法主要有醛类缩合法、酸类氧化法和选择性加氢法，其中选择性加氢国内研发较少，相对于已很成熟的粗苯选择性加氢，粗萘的选择性加氢尚属处于起步阶段。
日本川崎公司JP05085960粗萘选择性加氢技术，催化剂选自Ni-Co-Mo、铝/炭、Pt-Ni-Mo、Pd-氧化铝等，在0～2MPa下，100～300℃下反应，精萘中硫含量为0.025wt％。此技术有部分萘被加氢生成了四氢化萘，从而影响了精萘的收率。为了得到较高的精萘收率，选择性加氢后还需七步工序方可获得收率
提高的精萘。法国石油公司的US6217750和CN98105649中提及的方法，采用负载型催化剂，活性组分包括至少一种第Ⅷ和第Ⅵ族金属，还可以选择性地含有磷。催化剂比表面最大为220m2/g，且平均孔径大于10nm。选择性加氢反应温度150～325℃，压力0.1～0.9MPa，在进入下一步的汽提/结晶工序前的液流中，副产物四氢化萘的含量约为3.0％，精萘的收率仅为97％，此方法脱硫率仅为98％。为进一步提高精萘的收率，采用的是四氢化萘循环回加氢反应器入口及结合汽提/结晶工序的方法。
可以看出，现有技术中存在的问题是四氢萘副产物的生成，因此影响了精萘的收率，虽采用四氢萘循环的方法在一定程度上弥补了一些收率，但却消耗了更多的氢气原料，从而增加了加工成本。即现有技术需进一步提高所用催化剂的选择性加氢效果，从根本上提高精萘收率。日本川崎公司和法国石油公司方法，其所用催化剂均没有提及载体的改性和优化，且提及的催化剂孔径会使萘分子进入催化剂内表面，这是萘被加氢生成四氢萘的原因。另一方面，本发明采用的加工方法及选择性加氢反应工艺条件亦与日本川崎公司和法国石油公司方法不同。
发明内容
针对现有技术的不足，本发明提供了一种脱硫率高、步骤简单、精萘收率高、原料利用率高、加工成本低的重苯萘加工方法。
本发明提供了一种重苯萘生产精萘的方法，包括：重苯萘首先通过选择性加氢精制反应区，此选择性加氢精制反应区催化剂采用针对粗萘特制的新型选择性加氢催化剂，所得反应流出物经精馏塔蒸馏得到轻、中、重馏分，其中中间馏分再经结晶得到精萘产品。
本发明方法中，所述的选择性加氢精制反应区的操作条件为：反应的体积空速为0.3～1.0h-1，系统反应压力氢分压为4.0～6.0MPa，反应温度为340～360℃，氢油比为500～1000。优选的，反应的体积空速为0.5～0.7h-1，系统反应压力氢分压为5.0～6.0MPa，反应温度为345～355℃，氢油比为600～800。
本发明方法中，所述的催化剂由ⅥB族和/或Ⅷ族金属元素和改性载体组成，包括40％～90％载体以及5％～15％金属活性组分。
本发明方法中，所述的载体主要由碳纳米管与氧化铝经混合、挤条、成型及干燥、焙烧形成。
本发明方法中，所述的催化剂孔径8～10nm的孔占总孔容的90％以上，孔容0.6～0.8ml/g，比表面积为240～300m2/g。
本发明方法中，所述的ⅥB族和/或Ⅷ族金属元素，以载体为基准，第VIB族活性金属含量以氧化物计为4％～9％，第VIII族活性金属含量以氧化物计为2％～6％。
本发明方法中，所述的ⅥB族或Ⅷ族金属元素选自钼、钨、钴和镍中的任意一种或两种以上的组合；和/或，所述金属氧化物包括三氧化钼、三氧化钨、氧化镍和氧化钴中的任意一种或两种以上的组合；和/或，所述水溶性化合物包括钼酸铵、偏钨酸铵、硝酸镍、碱式碳酸镍、硝酸钴和醋酸钴中的任意一种或两种以上的组合。
本发明方法中，所述的碳纳米管的用量为氧化铝载体总质量的0.5％～1.2％，尤其优选为0.6％～1.0％。
本发明方法中，所述的碳纳米管采用短多壁碳纳米管，其管径小于8nm，比表面大于500m2/g，长度为0.5～2.0μm。
本发明方法中，所述的氧化铝孔容为0.3～0.6ml/g，孔径的平均值为2～10nm。
本发明方法中，所述的精馏塔蒸馏得到轻、中和重馏分的馏程分别为＜210℃馏分、210～225℃馏分及＞225℃馏分。
本发明方法中，所述的结晶温度为60～90℃。
综上所述，本发明方法具有如下优点：
1、本发明针对硫茚和萘分子大小的差异，创造性地在选择性加氢催化剂氧化铝载体中添加短多壁碳纳米管对小孔氧化铝进行改性，使重苯萘的脱硫率得到提高，同时有效避免了萘加氢生成四氢化萘副反应的发生。催化剂在改性载体制备过程中添加短多壁碳纳米管，再配合常规扩孔剂的使用，使所制得催化剂孔径8～10nm的孔占总孔容的90％以上，此孔径是针对工业萘中主要杂质硫茚分子体积大小设计的。由量子化学gaussian软件计算知，硫茚分子三维空间立体结构近似看作一个球，其直径约为7～10埃，萘分子则大于10埃。
2、本发明采用粗萘专用的选择性加氢催化剂，使重苯萘原料中硫茚杂质经加氢反应生成乙苯得以除去，同时使萘得到了最大程度的保留，再结合精馏和结晶，最终得到收率高、纯度高的精萘产品。
3、本发明方法除得到精萘产品外，还副产汽油调和组分和富甲基萘油产品，具有原料利用率高，加工流程短，加工成本低，综合经济性好等优点。
附图说明
图1为本发明重苯萘加工方法的示意流程图。
具体实施方式
下面结合附图对本发明作进一步说明。原料重苯萘1经选择性加氢精制反应器2进行选择性加氢精制反应后，加氢产物3进入精馏塔4，经精馏得到5塔顶＜210℃馏分、6塔中210～225℃馏分及7塔底＞225℃馏分，塔中馏分6再经结晶器8进行结晶得到精萘产品9。＜210℃馏分为汽油调和组分产品，＞225℃馏分为富甲基萘油，可用于提纯制甲基萘产品。
本发明方法除适用重苯萘外，同样适用于萘含量大于80％的粗萘或工业萘。
下面的实施例将对本方法予以进一步说明，但并不仅限于此。
本发明实施例的一个方面提供的一种重苯萘选择性加氢催化剂，所述制备方法包括：
1)先配制碳纳米管分散液；
2)将氧化铝与步骤1)所获碳纳米管分散液混合均匀后挤条成型，之后干燥、焙烧，获得载体；
3)向金属活性组分的前驱体的水溶液中加入表面活性剂而形成混合液，所述金属活性组分的前驱体选自包含ⅥB族和/或Ⅷ族金属元素的水溶性化合物，所述金属活性组分选自金属氧化物，之后将步骤2)所获载体浸渍于所述混合液中，之后进行干燥、焙烧处理，获得所述选择性加氢催化剂。
在一些实施方案中，所述的工业萘选择性加氢催化剂由4％～9％的ⅥB族金属、2％～6％Ⅷ族金属和改性载体组成。改性氧化铝载体在制备过程中添加碳纳米管进行改性，再将活性组分负载其上。此催化剂孔径8～10nm的孔占总孔容的90％以上，孔容0.6～0.8ml/g，比表面积为240～300m2/g。
在一些实施方案中，所述的工业萘选择性加氢催化剂，其特征在于包括40％～90％载体以及5％～15％金属活性组分。
在一些实施方案中，所述ⅥB族或Ⅷ族金属元素选自钼、钨、钴和镍中的任意一种或两种以上的组合，但不限于此。
在一些实施方案中，在本发明所述催化剂金属氧化物包括三氧化钼、三氧化钨、氧化镍和氧化钴中的任意一种或两种以上的组合，但不限于此。优选的，所述水溶性化合物包括钼酸铵、偏钨酸铵、硝酸镍、碱式碳酸镍、硝酸钴和醋酸钴中的任意一种或两种以上的组合，但不限于此。
在一些实施方案中，所述的改性氧化铝载体是将小孔氧化铝与碳纳米管分散液混合后，加入扩孔剂、助挤剂，再挤条成型，之后进行干燥、焙烧处理；优选的，所述干燥处理的温度为80～160℃，干燥1～6h；优选的，所述焙烧处理的温度为400～700℃，焙烧时间为1～15h，尤其优选的3～5h；和/或，所述步骤3)中采用的干燥温度为80～160℃，干燥1～6h；优选的，焙烧温度为400～650℃，焙烧时间为1～9h，尤其优选的3～5h。
在一些实施方案中，本催化剂制备步骤3)中所述表面活性剂的用量为载体总质量的2％～10wt％。进一步的，所述表面活性剂采用配制碳纳米管分散液所用的非离子表面活性剂，如聚乙二醇辛基苯基醚Triton X-100，但不限于此。本发明步骤3)加入表面活性剂的作用是使活性金属浸渍地更加充分，提高活性金属组分的负载量和分散度。
在一些实施方案中，所述的氧化铝孔容为0.3～0.6ml/g，孔径的平均值为2～10nm。
在一些实施方案中，所述的改性氧化铝载体在成型时，所用的助挤剂和扩孔剂可选用本领域熟知的物质，扩孔剂为载体重量的1.0％～4.0％，优选为3.0％～4.0％。如可选用可选田菁粉、淀粉、聚乙烯醇、甲基纤维素等领域熟知的扩孔剂来进一步改善载体孔结构。助挤剂为载体重量的1.0％～2.0％。
在一些实施方案中，改性氧化铝载体在成型时，所述碳纳米管的用量为氧化铝载体总质量的0.5％～1.2％，尤其优选为0.6％～1.0％。
在一些实施方案中，所述的碳纳米管，其特征在于，先制得其分散液，碳纳米管分散液可按此领域共知的方法制备。一般地，先将表面活性剂溶于水中，溶解温度为40～70℃，所述表面活性剂优选为含芳香基官能团的表面活性剂如聚乙二醇辛基苯基醚TritonX-100；再将一定量的碳纳米管加入此表面活性剂水溶液中搅拌均匀，表面活性剂与碳纳米管质量比为0.5～1：1。优选的，可采用超声搅拌，超声时间5～30min，搅拌温度0～5℃；超声搅拌后，优选的，可采用离心沉降除去未分散开的团聚粒子，离心速率为1500～2000r/min，离心时间30～60min；离心结束后，再用滤布过滤上述分散液，得到稳定的碳纳米管分散液。选优的，滤布目数为300～500目。
短多壁碳纳米管分散液可采用北京德科岛金科技有限公司CNT402短多壁碳纳米管产品配制而成。
本发明实施例所用选择性加氢催化剂制备如下：
(1)选择性加氢催化剂A：
将孔容0.45ml/g的小孔氧化铝(市售的孔容为0.3～0.6ml/g的普通小孔氧化铝粉)、碳纳米管分散液、田菁粉混均后，加入适量柠檬酸的水溶液，水溶液的加入量以满足载体成型为准，然后捏合、挤出成型，此载体于110℃干燥2h后，再在500℃下焙烧4h；再用Mo/Ni共浸渍液浸渍，然后在120℃干燥5h，及550℃活化4h。催化剂最终组成为：氧化镍2.8wt％，氧化钼8.0wt％，碳纳米管1.0wt％。催化剂比表面积268m2/g，孔容0.64ml/g。孔径8.0-10.0nm的孔占总孔容的95％。
(2)选择性加氢催化剂B：
将孔容0.51ml/g的小孔氧化铝(市售的孔容为0.3～0.6ml/g的普通小孔氧化铝粉)、碳纳米管分散液、田菁粉混均后，加入适量柠檬酸的水溶液，水溶液的加入量以满足载体成型为准，然后捏合、挤出成型，此载体140℃干燥4h后，再在400℃下焙烧5h；再用W/Co共浸渍液浸渍，然后在100℃干燥4h，及600℃活化3h。催化剂最终组成为：氧化钨5.0wt％，氧化钴4.0wt％，碳纳米管0.8wt％。催化剂比表面积258m2/g，孔容0.62ml/g。孔径8.0-10.0nm的孔占总孔容的93％。
以下各实施例所用重苯萘原料性质列于表1。
各实施例和对比例所述重苯萘选择性加氢反应工艺条件、结晶条件及加氢所得产品收率和加氢产物性质见表2。反应所得汽油馏分作为清洁汽油调和组分，所得富甲基萘油馏分作为提纯甲基萘产品原料，最终结果见表3。
实施例1
选择性反应区所用催化剂为A催化剂。
实施例2
选择性反应区所用催化剂为B催化剂。
对比例1
与实施例1相比，选择性反应区所用催化剂为对比催化剂DC，此催化剂与A催化剂相比，制备过程只是不添加碳纳米管分散液，其它步骤同A催化剂。DC催化剂比表面156m2/g，孔容0.49ml/g。孔径8.0-10.0nm的孔占总孔容的79％。选择性加氢反应和结晶工艺条件亦同实施例1。
表1重苯萘性质
| 原油名称 | 重苯萘 |
| 密度(20℃)，kg·m-3 | 1150.2 |
| S，μg·g-1 | 5350 |
| N，μg·g-1 | 603 |
| 组成，wt％ | |
| 萘 | 97.2 |
| 茚 | 0.4 |
| 苯并噻吩 | 2.2 |
| β-甲基萘 | 0.1 |
| 其它 | 0.1 |
| 馏程，℃ | 140～252 |
表2选择性加氢/结晶工艺条件及产品性质
表3最终所得产品性质
| 方案 | 实施例1 | 实施例2 | 对比例1 |
| 精萘 | |||
| 收率，％ | 99.54 | 99.46 | 90.57 |
| 纯度，％ | 99.96 | 99.95 | 97.60 |
| 熔点，℃ | 80.3 | 80.4 | 75.8 |
| 富甲基萘油性质 | |||
| 收率，wt％ | 0.2 | 0.2 | 0.2 |
| 硫含量，μg/g | 150 | 250 | 1505 |
| 汽油馏分性质 | |||
| 收率，wt％ | 2.6 | 2.6 | 11.8 |
| 硫含量，μg/g | 5 | 6 | 10 |
由表3可以看到，本方法将重苯萘采用选择性加氢、精馏、结晶仅三步的加工方法，即得到收率和纯度均较高的精萘产品，脱硫率大于99.8％，好于现有技术。同时副少量汽油馏分和富甲基萘油产品，汽油馏分硫含量＜10μg/g，可作清洁汽油调和组分使用。重苯萘得到充分利用，综合经济性好。
Claims (11)
1.一种重苯萘生产精萘的方法，所述方法包括：重苯萘首先通过选择性加氢精制反应区，此选择性加氢精制反应区催化剂采用针对粗萘特制的新型选择性加氢催化剂，所得反应流出物经精馏塔蒸馏得到轻、中、重馏分，其中中间馏分再经结晶得到精萘产品。
2.按照权利要求1所述的方法，其特征在于：所述的选择性加氢精制反应区的操作条件为：反应的体积空速为0.3～1.0h-1，系统反应压力氢分压为4.0～6.0MPa，反应温度为340～360℃，氢油比为500～1000。
3.按照权利要求1所述的方法，其特征在于：所述的催化剂由ⅥB族和/或Ⅷ族金属元素和改性载体组成，包括40％～90％载体以及5％～15％金属活性组分。
4.按照权利要求1、3所述的方法，其特征在于：所述载体主要由碳纳米管与氧化铝经混合、挤条、成型及干燥、焙烧形成。
5.按照权利要求1、3所述的方法，其特征在于：所述的催化剂孔径8～10nm的孔占总孔容的90％以上，孔容0.6～0.8ml/g，比表面积为240～300m2/g。
6.按照权利要求1、3所述的方法，其特征在于：所述的ⅥB族和/或Ⅷ族金属元素，以载体为基准，第VIB族活性金属含量以氧化物计为4％～9％，第VIII族活性金属含量以氧化物计为2％～6％。
7.按照权利要求4所述的方法，其特征在于：所述的碳纳米管的用量为氧化铝载体总质量的0.5％～1.2％，尤其优选为0.6％～1.0％。
8.按照权利要求4所述的方法，其特征在于：所述的碳纳米管采用短多壁碳纳米管，其管径小于8nm，比表面大于500m2/g，长度为0.5～2.0μm。
9.按照权利要求4所述的方法，其特征在于：所述的氧化铝孔容为0.3～0.6ml/g，孔径的平均值为2～10nm。
10.按照权利要求1所述的方法，其特征在于：所述的精馏塔蒸馏得到轻、中和重馏分的馏程分别为＜210℃馏分、210～225℃馏分及＞225℃馏分。
11.按照权利要求1所述的方法，其特征在于：所述的结晶温度为60～90℃。
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