CN106675623A - 烃物流的重级分的光化学加氢 - Google Patents
烃物流的重级分的光化学加氢 Download PDFInfo
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- CN106675623A CN106675623A CN201611040674.XA CN201611040674A CN106675623A CN 106675623 A CN106675623 A CN 106675623A CN 201611040674 A CN201611040674 A CN 201611040674A CN 106675623 A CN106675623 A CN 106675623A
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- heavy duty
- hydrocarbon stream
- hydrotreating
- alcohol
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- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 11
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 17
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 150000001491 aromatic compounds Chemical class 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229960004592 isopropanol Drugs 0.000 claims description 12
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000004281 calcium formate Substances 0.000 claims description 4
- 229940044172 calcium formate Drugs 0.000 claims description 4
- 235000019255 calcium formate Nutrition 0.000 claims description 4
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000004032 porphyrins Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229940087373 calcium oxide Drugs 0.000 claims description 2
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- 239000008240 homogeneous mixture Substances 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 241001597008 Nomeidae Species 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 239000010779 crude oil Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
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- 239000003205 fragrance Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- -1 hydroxyl organic compound Chemical class 0.000 description 5
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- 230000001360 synchronised effect Effects 0.000 description 5
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000005281 excited state Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241000735215 Lepidocybium flavobrunneum Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
-
- 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
- C10G15/00—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs
- C10G15/08—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs by electric means or by electromagnetic or mechanical vibrations
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
-
- 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
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- 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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0871—Heating or cooling of the reactor
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0877—Liquid
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/12—Processes employing electromagnetic waves
- B01J2219/1203—Incoherent waves
-
- 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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Abstract
本发明描述了用于烃物流的重级分的光化学加氢方法，其中存在于所述级分中的芳族和多(聚)芳族化合物在醇盐的存在下，在经受电磁辐照时选择性反应。
Description
技术领域
本发明提供用于烃物流的重级分的光化学加氢方法，所述重级分转化成较轻级分，以改进这样的流的物理化学特性，尤其是粘度和密度。
发明背景
油是世界上第二最大的能源来源，随着全球发现重油(12至22.3°API，由ANP[Agência Nacional do Petróleo,Gás Natural e Biocombustíveis(Brazilian NationalAgency of Petroleum,Natural Gas and Biofuels)]定义)和超重油(≤12°API，由ANP定义)的增多，这些油的生产、运输和精炼成为研究和探讨的主题。
油的价值和生产和精炼的成本与它的物理化学特性相关。它的粘度和密度越小，原油的附加值越大和生产链成本越低。
存在于原油中的一些芳族化合物会导致密度和粘度的增加，尤其是较重级分例如树脂和沥青质。沥青质构成较重且极性的原油化合物的级分，通常具有多稠合(缩聚)芳族结构，和包含不同的官能团、分子结构和相对大的分子质量分布。
除了提供增加的油密度和粘度以外，在获得原油时沥青质沉淀的倾向会导致严重的后果，例如油流动降低或甚至在油的生产、运输和精炼期间堵塞加工生产线，和可以使催化剂在精炼过程中中毒。
最小化沥青质的有害作用的一个选项是它的加氢，因为加氢降低沥青质分子的芳族烃的“核”之间的吸引力，以及降低悬浮液中分子的沉淀或团簇的发生，这最终导致它的粘度的降低。
因此，已经对该主题进行了许多研究。文献US2013/0277273例如描述了在催化剂和氢气的存在下存在于原油中的芳族化合物的加氢。所使用的催化剂为包含来自元素周期表的IB族、IVB族、VB族、VIB族、VIIB族或VIII族的金属的负载催化剂，所述金属包括但是不限于：铬，铁，锰，钼，钨，钒，银，金，镍，钯，铂，铑，钌或其混合物。
同时，文献US5,824,214描述了直接在石油生产井的底部在金属加氢催化剂的存在下通过声能以400Hz-10kHz的低频率处理包含至少1重量％的水的重原油。在该方法中，如由以下反应所定义的，由水形成氢气:
2H2O>>>2H2+O2
在本发明的另一个实施方案中，如果重原油不具有充足的水含量，可以通过使重原油在井底部与包含氨、肼和甲酸的化学化合物接触而原位形成氢气，这在金属加氢催化剂和声能的存在下，通过引起加氢反应导致氢气的形成和由此导致粘度降低。
然而，没有用于加氢存在于烃物流中的芳族化合物，特别是沥青质以降低这样的流的粘度和密度而不需要使用催化剂的方法的文献、描述或建议，和在下文中进行描述和要求保护该方法。
发明内容
以广泛的方式，本发明是关于通过光化学方法加氢来自烃物流的包括沥青质的含有一个或多个芳环的芳族重级分的方法，其中重级分的这些芳族化合物在醇盐存在下在经受电磁辐照时加氢。
附图描述
图1示出了作为温度的函数的在异丙醇钠和80质量％的油的存在下进行的实验中的粘度(以厘泊计)降低。
图2示出了在2-丙醇中在碱性介质(200mM NaOH)中的萘样品的同步荧光光谱，和曲线A对应于未受辐照时的样品和曲线B对应于在UV-VIS辐照之后的样品。
图3示出了对在2-丙醇中在碱性介质(200mM NaOH)中未受辐照的萘样品的GCMS分析结果.
图4示出了对在2-丙醇中在碱性介质(200mM NaOH)中辐照达8小时的萘样品的GCMS分析结果。
图5示出了在2-丙醇中在碱性介质(200mM NaOH)中的菲样品的同步荧光光谱，和曲线A对应于未受辐照时的样品和曲线B对应于在UV-VIS辐照之后的样品。
图6示出了在2-丙醇中在碱性介质(200mM NaOH)中未受辐照的的菲样品的GCMS分析结果。
图7示出了在2-丙醇中在碱性介质(200mM NaOH)中辐照达8小时的菲样品的GCMS分析结果。
图8示出了在2-丙醇中在碱性介质(200mM NaOH)中的石油样品的同步荧光光谱，和曲线A对应于未受辐照时的样品和曲线B对应于在UV-VIS辐照之后的样品。
具体实施方式
一般而言，本发明是基于存在于烃物流的重级分中的芳族化合物与醇盐在经受电磁辐照时的反应性。
在沥青质的情况下，由于它们具有表现出特征吸收光谱的芳族多稠合结构，它们能够吸收宽范围的波长的电磁辐射。取决于芳环稠合程度，分子吸收UV(紫外)波长范围直至近红外(NIR)波长范围的辐射，经过整个可见光谱(VIS)。
该方法包括使用电磁辐射，电磁辐射可以在紫外光谱(UV-100-400nm的波长)或可见光谱(400-780nm的波长)，优选在450和700nm之间。在该激发态的芳族分子中，可以从烷氧自由基提取电子，之后提取氢自由基，所述烷氧自由基可以由碱与羟基有机化合物的反应获得。
因此，在羟基有机化合物和碱的存在下，芳族分子在芳环中存在的不饱和度方面选择性降低。通常，反应是部分的，但这作为施加辐射的函数而变得更加具有选择性。因此，该方法对于重油级分和尤其是对于芳族化合物如沥青质具有选择性，而不干扰轻级分，如在图2-8中示出的对于萘样品、菲样品和油样品所获得的通过GCMS的结果分析和同步荧光光谱中可以观察到的。
因此，本发明是关于使烃物流与醇盐在UV-VIS范围的辐射作用下反应来加氢重级分而获得具有低的密度和粘度的烃物流的方法，所述方法包括以下步骤:
a)提供该方法的载料，所述载料由烃物流组成，所述烃物流包含烃的含有具有一个或多个稠环的芳族化合物(浓度高于0.1质量％)的重级分；
b)在搅拌下，在20-60℃的温度和在大气压力下，相对于待还原的烃以1：1摩尔的比例，将至少一种醇盐加入所述载料，以获得载料/醇盐的均匀混合物；
c)使所获得的混合物经受UV-VIS范围波长的电磁辐射达5分钟至48小时的时间，以获得密度和粘度小于初始载料的经处理的物流。
优选地，该方法的载料为包含不可忽略水平的沥青质的烃物流，和这些化合物在载料的粘度方面很显著。这样的物流可具有浓度大于0.1质量％的它们的重级分，优选包含1-80质量％的沥青质级分的链。
重级分基本上包含芳族化合物，特别是具有自动关联能力和显著影响载料的密度和粘度的高分子量的多(聚)芳族化合物。
更具体地，本发明的烃物流的重级分的光化学加氢方法涉及使醇盐与处于激发态的芳族化合物选择性反应。该机理涉及四个步骤:
-由于使用UV-VIS范围波长的电磁辐射的样品辐照，形成激发态的芳族化合物；
-该激发态氧化和从醇盐提取电子；
-芳族化合物的阴离子型自由基从烷氧自由基提取氢自由基，生产酮；和
-芳族阴离子提取中间质子。
反应产物为由醇羰基化的化合物和来自芳族化合物的环状不饱和化合物。
待加氢的芳族化合物的选择通过一定波长的可施加的电磁辐射(光)进行。波长越长，发生反应的在烃物流中存在的芳族化合物所包含的环的稠合程度越高。
在直接使用醇盐的情况下，原则上，这为包含1-6个碳原子的链和具有一个或多个羟基的任何有机化合物的任何共轭碱，例如，例如：乙醇盐，异丙醇盐，甲醇盐，甘油化盐(glyceroxide)等。醇盐应该以化学计算量存在以还原物流中希望的类型。
此外，醇盐可以为醇和碱之间的反应结果。待使用的醇原则上可以包含1-6个碳原子，为单羟基或多羟基，例如乙醇，异丙醇，和优选甘油(或丙三醇)，或其混合物。
在该方法中，碱仅用于增加反应介质中的醇盐阴离子的浓度，但也可以为能够从所用的羟基化合物或其混合物除去质子的任何碱。这些包括：氢氧化钠，氢氧化钾，金属钠，甲酸钠，甲酸钙，氧化钙，或其混合物。
当使用时，该方法中需要的碱和醇的量为对于以摩尔比例1:1:1转化各种油和/或其级分中的待加氢的芳族化合物成分而言化学计量的。
以下实施例对应于实验室规模实验，而没有限制该方法的范围，在此进行详细描述。
实施例
实施例1
下文所述的测试在光化学反应器中进行，其中芳族化合物以10-1000mg/L范围的不同浓度溶解于二氯甲烷。为了辐照样品，使用中压汞灯和450W。该灯主要发射250和450nm之间的UV。在存在和不存在反应介质中的氧气的情况下，每种样品在恒定搅拌下受辐照达12小时。
以下用作芳族化合物：由不同的巴西油获得的萘、菲、芘、苯并芘、六苯并苯、卟啉和沥青质样品。
为了与芳族化合物反应，使用通过使碱与醇反应获得的醇盐。
相对于醇测试芘：甲醇、乙醇、异丙醇和甘油。仅相对于乙醇测试其它芳族化合物。醇以10mg/L-10％的浓度使用。
对于碱，相对于碱测试芘：氢氧化钠、氢氧化钙和甲酸钙。仅相对于氢氧化钠测试其它芳族化合物。还相当于乙醇钠测试了芘，没有添加更多的醇。
该方法伴随有反应混合物的UV-VIS和荧光光谱。UV-VIS光谱记录在200和500nm之间。荧光光谱通过同步方法记录，已经观察到在激发和发射之间发射250-500nm和20nm的距离，UV-VIS光谱迁移至更短的波长和荧光光谱的强度降低，表明存在于介质中的芳环稠合降低。
实施例2
本发明是基于在通过使碱和醇反应获得的醇盐存在下在经受由来自使用汞蒸气450瓦灯的反应器的紫外或可见光的辐照时芳族化合物的反应性。该灯主要发射250和450nm之间的UV。在存在和不存在反应介质中的氧气的情况下，样品在恒定搅拌下受辐照达12小时。在UV-VIS辐照时在NaOH溶液存在下在2-丙醇中以化学计量比例部分加氢菲和萘。
所研究的芳族化合物为来自具有8-30°API的不同API程度的油的芘、苯并芘、六苯并苯、卟啉和沥青质样品。在该方法中所使用的一系列醇由甲醇、乙醇、2-丙醇、丁醇、戊醇、己醇和甘油组成。所使用的碱为氢氧化钠、氢氧化钾、甲酸钙。该方法方案在下表中给出:
在所用的所有系列醇中，以及使用测试的三种类型碱，发现芳族样品的加氢。2-丙醇与氢氧化钠一起产生最满意的结果，也就是相比于研究的其它物质，得到更高水平的加氢。
Claims (8)
1.用于烃物流的重级分的光化学加氢方法，其特征在于它包括使存在于烃物流的重级分中的芳族化合物与醇盐在UV-VIS范围的电磁辐照的存在下和在20-60℃的温度和大气压力下反应。
2.根据权利要求1所述的用于烃物流的重级分的光化学加氢方法，其特征在于它包括以下步骤：
a)提供该方法的载料，所述载料由烃物流组成，所述烃物流包含烃的重级分，所述重级分含有具有一个或多个稠环的芳族化合物，(浓度高于0.1质量％)；
b)在搅拌下，在20-60℃的温度和在大气压力下，相对于待还原的烃以1：1摩尔的比例，将至少一种醇盐加入所述载料，以获得载料/醇盐的均匀混合物；
c)使所获得的混合物经受UV-VIS范围波长的电磁辐射达5分钟至48小时的时间，以获得密度和粘度小于初始载料的经处理的物流。
3.根据权利要求1或2所述的用于烃物流的重级分的光化学加氢方法，其特征在于所述芳族化合物选自：菲、萘、芘、苯并芘、六苯并苯、沥青质、卟啉和它们的衍生物，或其混合物。
4.根据权利要求1或2所述的用于烃物流的重级分的光化学加氢方法，其特征在于醇盐通过使共轭碱与包含具有1-6个碳原子的链的醇反应而获得。
5.根据权利要求5所述的用于烃物流的重级分的光化学加氢方法，其特征在于所述醇为一元醇。
6.根据权利要求5所述的用于烃物流的重级分的光化学加氢方法，其特征在于所述醇为多元醇。
7.根据权利要求5的用于重油级分的光化学加氢方法，其特征在于所述醇选自：乙醇、2-丙醇、甘油或其混合物。
8.根据权利要求5所述的用于烃物流的重级分的光化学加氢方法，其特征在于共轭碱选自：氢氧化钠、氢氧化钾、金属钠、甲酸钠、甲酸钙、氧化钙或其混合物。
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| BRPI0816677B1 (pt) * | 2007-09-13 | 2018-01-23 | Kabushiki Kaisha Sangi | Método para produzir uma composição de combustível para um motor de combustão interna usando um ou mais álcoois como um material de partida |
| US9169448B2 (en) | 2012-04-19 | 2015-10-27 | Baker Hughes Incorporated | In-situ hydrogenation of aromatic compounds for heavy oil upgrading |
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- 2016-11-09 CA CA2948166A patent/CA2948166C/en active Active
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| BR102015028294B1 (pt) | 2020-05-12 |
| AU2016256749B2 (en) | 2022-04-28 |
| CA2948166C (en) | 2023-04-11 |
| BR102015028294A2 (pt) | 2017-05-23 |
| CN106675623B (zh) | 2021-01-12 |
| MX2016014669A (es) | 2018-05-08 |
| AU2016256749A1 (en) | 2017-05-25 |
| CA2948166A1 (en) | 2017-05-10 |
| US20170128907A1 (en) | 2017-05-11 |
| US10258958B2 (en) | 2019-04-16 |
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