CN104762100B - A kind of eutectic solvent extraction removes the method for nitrogenous compound in oil product - Google Patents
A kind of eutectic solvent extraction removes the method for nitrogenous compound in oil product Download PDFInfo
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- CN104762100B CN104762100B CN201510141450.7A CN201510141450A CN104762100B CN 104762100 B CN104762100 B CN 104762100B CN 201510141450 A CN201510141450 A CN 201510141450A CN 104762100 B CN104762100 B CN 104762100B
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- extraction
- eutectic solvent
- oil
- nitrogenous compound
- oil product
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- 230000005496 eutectics Effects 0.000 title claims abstract description 95
- -1 nitrogenous compound Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000638 solvent extraction Methods 0.000 title claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 91
- 238000000605 extraction Methods 0.000 claims abstract description 87
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 57
- 235000019743 Choline chloride Nutrition 0.000 claims description 57
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 57
- 229960003178 choline chloride Drugs 0.000 claims description 57
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 22
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000002283 diesel fuel Substances 0.000 claims description 16
- 229940040102 levulinic acid Drugs 0.000 claims description 11
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003502 gasoline Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- 239000004135 Bone phosphate Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Chemical class 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 117
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 81
- 229910052757 nitrogen Inorganic materials 0.000 description 41
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 239000002253 acid Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 239000001630 malic acid Substances 0.000 description 12
- 235000011090 malic acid Nutrition 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 230000001172 regenerating effect Effects 0.000 description 12
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 11
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 11
- 229960002920 sorbitol Drugs 0.000 description 11
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical group O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 description 8
- 150000002830 nitrogen compounds Chemical class 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 229960003487 xylose Drugs 0.000 description 8
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical group OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 4
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000811 xylitol Substances 0.000 description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 4
- 229960002675 xylitol Drugs 0.000 description 4
- 235000010447 xylitol Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IRSVMGYCAXSOCN-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCC[NH+]1CN(C)C=C1 IRSVMGYCAXSOCN-UHFFFAOYSA-N 0.000 description 1
- KXCVJPJCRAEILX-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 KXCVJPJCRAEILX-UHFFFAOYSA-M 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 125000005523 4-oxopentanoic acid group Chemical group 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- VCAQPYXOWLIOSF-UHFFFAOYSA-N acetic acid;sulfuric acid;hydrate Chemical compound O.CC(O)=O.OS(O)(=O)=O VCAQPYXOWLIOSF-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000001993 wax 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/16—Oxygen-containing compounds
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/18—Halogen-containing compounds
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses the method that the extraction of a kind of eutectic solvent removes nitrogenous compound in oil product, comprise the steps: that (1) take oil product as stock liquid, take eutectic solvent as extraction agent, in extraction equipment, carry out single-stage extraction or multi-stage solvent extraction, obtain the extraction liquid of raffinate oil and enrichment nitrogenous compound; (2) by the raffinate oil in step (1) through washing, dry, obtain denitrogenation oil; (3) extraction liquid in step (1) to be stripped removing nitrogenous compound wherein through weak polar solvent, then after evaporation, obtain the eutectic solvent that regenerates.The present invention is based on liquid-liquid two-phase system, and employing eutectic solvent is extraction agent, through single-stage extraction or multi-stage solvent extraction, removes the nitrogenous compound in oil product, and operating process is simple, and denitrification percent is high, oil product yield is high.
Description
Technical field
The present invention relates to the removal methods of nitrogenous compound in oil product, belong to technical field of chemical engineering, be specifically related to the method that the extraction of a kind of eutectic solvent removes nitrogenous compound in oil product.
Background technology
Containing certain density nitrogenous compound in the products (being referred to as oil product) such as the petroleum naphtha that refining of petroleum obtains, gasoline, kerosene, diesel oil, lubricating oil, wax oil, comprise basic nitrogen compound and non basic nitrogen compound.Basic nitrogen compound mainly contains pyridine, quinoline, naphthazin(e), aza-phenanthrenes etc. and homologue thereof, and non basic nitrogen compound mainly contains pyrroles, carbazole, indoles etc. and homologue thereof.The existence of these nitrogenous compounds has disadvantageous effect to the colourity of oil product, anti-oxidative stability and use properties, and easily causes the inactivation of noble metal catalyst in the oil product courses of processing such as catalytic cracking, hydrocracking, hydrofining.In addition, nitrogenous compound can form oxynitride NO in combustion
x, be the one of the main reasons causing topsoil and acid rain to be formed.Therefore, the nitrogenous compound removed in oil product is very important.
The method of nitrogenous compound in oil product that removes at present mainly contains the method such as hydrodenitrification, absorption denitrogenation, acid extraction denitrogenation, organic solvent extraction denitrogenation, complexometric extraction denitrogenation, ion liquid abstraction denitrogenation.Wherein hydrodenitrification technology has easy to operate, oil product yield advantages of higher, current exploitation is more, but the denitrification percent of the method is usually lower, general hydrogenation catalyst denitrification percent is adopted to only have 10% ~ 25%, adopt extraordinary Hydrobon catalyst denitrification percent also can only reach 70% ~ 75%, and need to consume a large amount of hydrogen sources, facility investment is large, and working cost is high.
Chinese patent CN200910082846.3 adopts ADSORPTION IN A FIXED BED technique to remove nitrogenous compound in hydrocracking tail oil and sulfocompound, consisting of of the denitrification adsorbent adopted: sulfuric acid agent 3 ~ 20%, ferric sulfate complexing agent 2 ~ 20%, alumina supporter powder 60 ~ 95%, water 5 ~ 20%.The nitrogen content of refining back end hydrogenation tail oil is less than 2 μ gg
-1, meet the requirement of follow-up oil product complete processing.The nitric efficiency of absorption method denitrogenation is higher, but there is the deficiencies such as treatment capacity is little, adsorbent amount is large, level of automation is low, generation solid waste is more.
US Patent No. 4790930 adopt massfraction be 20 ~ 95% carboxylic acid aqueous solution from decompressed wax oil and coker gas oil, extract nitrogen-containing heterocycle compound, denitrification percent is 26 ~ 63%.US4960508 adopts dense carboxylic acid, rare carboxylic acid two-step approach extracts nitrogen-containing heterocycle compound from oil product, and the yield of raffinate oil is higher than a step extraction process, but denitrification percent is lower.Russ P RU2257398 employing sulfuric acid-Acetic Acid-Water mixture extraction removes the nitrogenous compound in oil product.Generally, acid extraction method is better to the removal effect of basic nitrogen compound, but existence is low to non basic nitrogen compound decreasing ratio usually, oil product yield is on the low side, etching apparatus, environmental pollution acid sludge that is large, that produce are difficult to the problems such as process.
The extraction agent that Chinese patent CN92113955.1 adopts a kind of low-carbon alcohol and water or a kind of low-carbon alcohol and dilute alkaline aqueous solution to form extracts the total nitrogen removed in liquid petroleum product, basic nitrogen, mercaptan sulfur and low molecular organic acids, and the decreasing ratio of total nitrogen and basic nitrogen all can reach 50-80%.US Patent No. 5494572 adopts the organic solvents such as the mixture of nitrogen heterocyclic ring kind solvent, amide solvent or the pyridinium salts such as pyrrolidone and water or liquid low-carbon alcohol to remove nitrogenous compound in lightweight oil and sulfocompound as extraction agent, find the increase along with Solvent quantity, denitrification percent is increased to more than 90% gradually, but oil product yield is reduced to less than 61% gradually.Because organic solvent and oil product exist certain mutual solubility, organic solvent extraction denitride technology ubiquity oil product yield is low, oil product after denitrogenation easily by organic solvent secondary pollution problems, also not ideal enough to the removal effect of basic nitrogen.
US Patent No. 4113607 adopts the furfuryl aldehyde solution of iron(ic) chloride to extract the nitrogenous compound removed in oil product, and utilize the complex reaction of iron(ic) chloride and nitrogenous compound to strengthen separation selectivity to nitrogenous compound, denitrification percent can reach 99%.Complexing abstraction is general higher to the decreasing ratio of basic nitrogen, but complexing product is partially soluble in oil product unavoidably, easily makes oil product color burn, and the hydrocarbon component in oil product can be dissolved in the organic solvent that complexometric extraction uses, and reduces the yield of treated oil.
US Patent No. 2010270211 adopts the mixed extractant solvent be made up of at least one ionic liquid and at least one metal-salt to remove sulfide in petroleum products and nitride.Chinese patent CN200880116144.6 adopts acidic ion liquid 1-butyl-3-methylimidazolium hydrogen sulphate salt ([Bmim] HSO
4), 1-butyl-3-Methylimidazole methyl sulfate ([Bmim] CH
3sO
4) or 1-ethyl-3-methylimidazole sulfovinic acid ([Emim] C
2h
5sO
4) extract the nitride removed in diesel oil for medium.Compared with traditional organic solvent; ionic liquid has features such as volatilizing hardly, structures and characteristics easily regulates; the environmental pollution contributing to reducing denitrification process also obtains higher nitric efficiency; but the preparation cost of ionic liquid is higher, limit the mass-producing application of ion liquid abstraction denitride technology.
Summary of the invention
The invention provides the method that the extraction of a kind of eutectic solvent removes nitrogenous compound in oil product, based on liquid-liquid two-phase system, employing eutectic solvent is extraction agent, through single-stage extraction or multi-stage solvent extraction, remove the nitrogenous compound in oil product, operating process is simple, and denitrification percent is high, oil product yield is high.
Eutectic solvent extraction removes a method for nitrogenous compound in oil product, comprises the steps:
(1) be stock liquid with oil product, be extraction agent with eutectic solvent, in extraction equipment, carry out single-stage extraction or multi-stage solvent extraction, obtain the extraction liquid of raffinate oil and enrichment nitrogenous compound;
(2) by the raffinate oil in step (1) through washing, dry, obtain denitrogenation oil;
(3) extraction liquid in step (1) to be stripped removing nitrogenous compound wherein through weak polar solvent, then after evaporation, obtain the eutectic solvent that regenerates.
Extraction denitrogenation have easy to operate, device simple, be easy to the advantages such as industrialization continuous seepage, its key issue is the design of extraction agent.When removing the nitrogenous compound in oil product with selected extraction agent, extraction agent must have good dissolving power to nitrogenous compound, and does not dissolve each other with oil product.And extraction agent should have good biodegradability and comparatively cheap preparation cost.
Eutectic solvent be mixed by a certain percentage by two or more solid matter after the fluent meterial that formed, be a class novel dissolvent.Eutectic solvent have volatilize hardly, feature that polarity is strong, therefore, compared with conventional organic solvents, eutectic solvent not only can reduce the volatile contaminant of conventional solvent as extraction agent, and significantly can reduce the solubleness of oil product in extraction agent, improve the yield of denitrogenation oil, and reduce the secondary pollution of extraction agent to oil product.Meanwhile, eutectic solvent has stronger hydrogen bonding ability, therefore all has good dissolving power for basic nitrogen compound and non basic nitrogen compound, thus obtains higher nitric efficiency.Eutectic solvent is usually by choline chloride 60 or trimethyl-glycine and 2-hydroxyl-1, 2, 3-tricarballylic acid (another name " citric acid "), 2-hydroxy-butanedioic acid (another name " oxysuccinic acid "), 2, 3-dyhydrobutanedioic acid (another name " tartrate "), monose, the good solid matter of the biocompatibilities such as urea simply mixes and prepares, therefore compared with ionic liquid, it is simple that eutectic solvent has preparation technology, raw materials is easy to get, cost is low, the advantages such as degradability is good, thus while the higher nitric efficiency of acquisition and oil product yield, improve Technical Economy and the environment friendly of oil denitrification process.
In the present invention preferably, described eutectic solvent is made up of hydrogen bond acceptor compounds A and hydrogen bond donor compd B;
Described hydrogen bond acceptor compounds A is at least one in choline chloride 60, trimethyl-glycine and amino acid.Described hydrogen bond donor compd B to be carbonatoms be 2 ~ 6 aliphatic dicarboxylic acid, carbonatoms is the aliphatics tribasic carboxylic acid of 6, carbonatoms is the aromatic series monocarboxylic acid of 7 ~ 9, the carbonatoms with hydroxyl substituent is the aliphatic dicarboxylic acid of 3 ~ 6, the carbonatoms with hydroxyl substituent is the aliphatics tribasic carboxylic acid of 6, the carbonatoms with hydroxyl substituent is the aromatic series monocarboxylic acid of 7 ~ 9, carbonatoms is the monose of 5 ~ 6, carbonatoms is the sugar alcohol of 5 ~ 6, urea, at least one in 1-methyl urea and levulinic acid.
The fusing point of described hydrogen bond acceptor compounds A, hydrogen bond donor compd B is all higher than 25 DEG C; The zero pour of described eutectic solvent is lower than 60 DEG C.
The preparation method of eutectic solvent of the present invention is as follows:
In described ratio hydrogen bond acceptor compounds A and hydrogen bond donor compd B mixed be incorporated in 80 ~ 120 DEG C of temperature under heated and stirred until become homogeneous colourless liquid.
Further preferably, described hydrogen bond donor compd B is oxalic acid, phenylpropionic acid, wood sugar, 2,3-dyhydrobutanedioic acid, urea, Alpha-hydroxy toluylic acid, phenylformic acid, 2-hydroxyl-1,2,3-tricarballylic acid, D-Sorbitol Powder, levulinic acid, 2-hydroxy-butanedioic acid, wood sugar and 2-hydroxy-butanedioic acid mixture.
Further preferred, described eutectic solvent is the one in following combination:
Choline chloride 60/oxalic acid, choline chloride 60/phenylpropionic acid, choline chloride 60/wood sugar, choline chloride 60/2,3-dyhydrobutanedioic acid choline chloride/urea, trimethyl-glycine/Alpha-hydroxy toluylic acid, trimethyl-glycine/phenylformic acid, trimethyl-glycine/2-hydroxyl-1,2,3-tricarballylic acid, choline chloride 60/D-Sorbitol Powder, choline chloride 60/levulinic acid, Serine/2-hydroxy-butanedioic acid, choline chloride 60/Xylitol/2-hydroxy-butanedioic acid, choline chloride 60/trimethyl-glycine/D-Sorbitol Powder.
When selecting above-mentioned any combination, to the decreasing ratio of nitrogenous compound in oil product more than 80%, denitrogenation oil yield is more than 98%.
Further preferred, described eutectic solvent is the one in following combination:
Choline chloride 60/oxalic acid, choline chloride 60/phenylpropionic acid, choline chloride 60/wood sugar, trimethyl-glycine/Alpha-hydroxy toluylic acid, trimethyl-glycine/2-hydroxyl-1,2,3-tricarballylic acid, choline chloride 60/D-Sorbitol Powder, choline chloride 60/levulinic acid, choline chloride 60/Xylitol/2-hydroxy-butanedioic acid, choline chloride 60/trimethyl-glycine/D-Sorbitol Powder.
Extract oil product using any combination above-mentioned as eutectic solvent, denitrification percent reaches more than 90%, and denitrogenation oil yield reaches more than 98%.
Still more preferably, described eutectic solvent is the one in following combination:
Described hydrogen bond acceptor compounds A is choline chloride 60, and described hydrogen bond donor compd B is oxalic acid, and the mol ratio of choline chloride 60 and oxalic acid is 1:1;
Described hydrogen bond acceptor compounds A is choline chloride 60, and described hydrogen bond donor compd B is urea, and the mol ratio of choline chloride 60 and urea is 1:2;
Described hydrogen bond acceptor compounds A is choline chloride 60, and described hydrogen bond donor compd B is levulinic acid, and the mol ratio of choline chloride 60 and levulinic acid is 1:2.
Be that extraction agent carries out extraction denitrogenation to oil product when choosing any one eutectic solvent above-mentioned, denitrification percent reaches more than 95%, and denitrogenation oil yield reaches more than 99%.
Most preferably, choline chloride 60 and the levulinic acid mixture of described eutectic solvent to be mol ratio be 1:2.When selecting this to be combined as extraction agent, denitrification percent is up to 97%, and denitrogenation oil yield is up to 99.4%.
As preferably, described weak polar solvent to be carbonatoms be 6 ~ 8 alkane, boiling range be sherwood oil, ethyl acetate or the toluene of 60 ~ 90 DEG C.
As preferably, described oil product is petroleum naphtha, gasoline, kerosene, diesel oil, lubricant base or the wax oil that refining of petroleum obtains.
As preferably, described eutectic solvent is 2:1 ~ 1:5 with the ratio of the mass rate of oil product.
If the mass ratio of eutectic solvent and oil product is too high, the consumption of eutectic solvent is too large, be unfavorable for the economy of extraction process, and the yield of denitrogenation oil can reduce; If the mass ratio of eutectic solvent and oil product is too low, denitrification percent can reduce.Test proves that in the present invention, in oil product, the decreasing ratio of nitrogenous compound is more than 80% within the scope of aforementioned proportion, and denitrogenation oil yield is more than 98%.
As preferably, when the zero pour of eutectic solvent is higher than 25 DEG C, the service temperature of extraction is between the zero pour to 60 DEG C of eutectic solvent; When the zero pour of eutectic solvent is equal to or less than 25 DEG C, the service temperature of extraction is between 25 DEG C to 60 DEG C.
If temperature is too low, eutectic solvent may solidify and cause extracting operation to carry out, and two-phase rate of mass transfer reduces, and reaches extraction equilibrium required time longer, is unfavorable for production operation; If temperature is too high, the extraction partition ratio of nitrogenous compound and selectivity can reduce, and cause denitrification percent and oil product yield to reduce.Test proves that in the present invention, in oil product, the decreasing ratio of nitrogenous compound is more than 80% within the scope of said temperature, and denitrogenation oil yield is more than 98%.
The extraction plant that the extraction equipment used in described extraction process is packing tower, tray column, rotating disc contactor, mixer-settler, centrifugal extractor etc. are common.
The operating method of described multi-stage solvent extraction is the one in multistage cross flow extraction, multi-stage counter current extraction.
Described cross current solvent extraction and counter-current extraction are the art routine techniques means.Described multistage be in the present invention preferably 2 ~ 10 grades.
Compared with existing denitrogenation method, the invention has the advantages that:
(1) the present invention adopts eutectic solvent to be extraction agent, compared with traditional oil denitrification extraction agent, not only has higher removal efficiency to the nitrogenous compound in oil product, and can obtain higher oil product yield.According to the difference of processing condition, the present invention is to the decreasing ratio of nitrogenous compound in oil product more than 80%, and denitrogenation oil yield is more than 98%.
(2) eutectic solvent have volatilize hardly, advantage that degradability is good, few to the pollution of environment, and its preparation cost is lower, has broad application prospects.
Embodiment
The oxidizing fire that the boat sample introduction chemoluminescence method (measurement range: 100 μ g/g< nitrogen content <10000 μ g/g) adopting GB/T17674-2012 to specify in below implementing and SH/T0657-2007 specify and chemoluminescence method (measurement range: 0.3 μ g/g< nitrogen content≤100 μ g/g) are analyzed the nitrogen content of oil product, denitrification percent=(1-denitrogenation oil nitrogen content/stock oil nitrogen content) × 100%.
Embodiment 1
By straight-run diesel oil (nitrogen content: 205 μ g/g), (mol ratio of choline chloride 60 and oxalic acid is 1:1 with choline chloride 60/oxalic acid eutectic solvent, zero pour is 34 DEG C) in mixer-settler, carry out single-stage extraction at 40 DEG C, straight-run diesel oil is 1:1 with the ratio of the mass rate of eutectic solvent.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 9.8 μ g/g) after drying, denitrification percent is 95.2%, and denitrogenation oil yield is 99.5%.Extraction liquid to be stripped removing nitrogenous compound wherein through normal hexane at 40 DEG C, then after the residual normal hexane of evaporation removing, obtains choline chloride 60/oxalic acid eutectic solvent of regenerating.
Embodiment 2
By lubricant base (nitrogen content: 1390 μ g/g), (mol ratio of choline chloride 60 and urea is 1:2 with choline chloride/urea eutectic solvent, zero pour is lower than 25 DEG C) at 35 DEG C, in packing tower, carry out three stage countercurrent extractions, eutectic solvent is 1:1 with the ratio of the mass rate of lubricating oil.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 48.7 μ g/g) after drying, denitrification percent is 96.5%, and denitrogenation oil yield is 99.1%.Extraction liquid to be stripped removing nitrogenous compound wherein through normal heptane at 50 DEG C, then after the residual normal heptane of evaporation removing, obtains the choline chloride/urea eutectic solvent that regenerates.
Embodiment 3
Lubricant base (nitrogen content: 1390 μ g/g) and choline chloride 60/phenylpropionic acid eutectic solvent (mol ratio of choline chloride 60 and phenylpropionic acid is 1:1, and zero pour is lower than 25 DEG C) are carried out three stage countercurrent extractions at 40 DEG C in packing tower.Collection raffinate oil, washes raffinate profit, obtains denitrogenation oil after drying.Change eutectic solvent and the ratio of the mass rate of lubricating oil, obtain different denitrification percents and denitrogenation oil yield (table 1).Extraction liquid to be stripped removing nitrogenous compound wherein through normal heptane at 50 DEG C, then after the residual normal heptane of evaporation removing, obtains choline chloride 60/phenylpropionic acid eutectic solvent of regenerating.
Table 1 choline chloride 60/phenylpropionic acid eutectic solvent three stage countercurrent extraction removes nitrogenous compound in lubricating oil (nitrogen content: 1390 μ g/g), 40 DEG C
Embodiment 4
By wax tailings (nitrogen content: 2793 μ g/g), (mol ratio of choline chloride 60 and wood sugar is 3:1 with choline chloride 60/wood sugar eutectic solvent, zero pour is lower than 25 DEG C) at 40 DEG C, in packing tower, carry out Pyatyi counter-current extraction, eutectic solvent is 2:1 with the ratio of the mass rate of wax tailings.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 413 μ g/g) after drying, denitrification percent is 85.2%, and denitrogenation oil yield is 98.2%.Extraction liquid to be stripped removing nitrogenous compound wherein through toluene at 60 DEG C, then after the residual toluene of evaporation removing, obtains choline chloride 60/wood sugar eutectic solvent of regenerating.
Embodiment 5
By catalytic cracking diesel oil (nitrogen content: 810 μ g/g) and choline chloride 60/2,3-dyhydrobutanedioic acid eutectic solvent (choline chloride 60 and 2, the mol ratio of 3-dyhydrobutanedioic acid is 2:1, zero pour is 47 DEG C) at 55 DEG C, in tray column, carry out four-stage counter-current extraction, eutectic solvent is 1:2 with the ratio of the mass rate of catalytic cracking diesel oil.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 59.1 μ g/g) after drying, denitrification percent is 92.7%, and denitrogenation oil yield is 99.5%.Extraction liquid to be stripped removing nitrogenous compound wherein through toluene at 55 DEG C, then after the residual toluene of evaporation removing, obtains choline chloride 60/2,3 dihydroxybutanedioic acid eutectic solvent of regenerating.
Embodiment 6
By the diesel oil be in harmonious proportion by straight-run diesel oil and catalytic cracking diesel oil (nitrogen content: 503 μ g/g), (mol ratio of choline chloride 60 and 1-methyl urea is 1:2 with choline chloride 60/1-methyl urea eutectic solvent, zero pour is lower than 25 DEG C) at 40 DEG C, in packing tower, carry out six stage countercurrent extractions, eutectic solvent is 1:5 with the ratio of the mass rate of diesel oil.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 83.5 μ g/g) after drying, denitrification percent is 83.4%, and denitrogenation oil yield is 99.7%.Be the sherwood oil reextraction removing nitrogenous compound wherein of 60 ~ 90 DEG C through boiling point at 40 DEG C by extraction liquid, then after evaporating the residual sherwood oil of removing, obtain the choline chloride 60/1-methyl urea eutectic solvent of regeneration.
Embodiment 7
By petroleum naphtha (nitrogen content: 4.6 μ g/g), (mol ratio of trimethyl-glycine and Alpha-hydroxy toluylic acid is 1:1 with trimethyl-glycine/Alpha-hydroxy toluylic acid eutectic solvent, zero pour is lower than 25 DEG C) at 25 DEG C, in packing tower, carry out two-stage countercurrent extraction, eutectic solvent is 1:5 with the ratio of the mass rate of petroleum naphtha.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 0.45 μ g/g) after drying, denitrification percent is 90.2%, and denitrogenation oil yield is 99.1%.Extraction liquid to be stripped removing nitrogenous compound wherein through ethyl acetate at 25 DEG C, then after the residual ethyl acetate of evaporation removing, obtains trimethyl-glycine/Alpha-hydroxy toluylic acid eutectic solvent of regenerating.
Embodiment 8
By catalytically cracked gasoline (nitrogen content: 68.2 μ g/g), (trimethyl-glycine and benzoic mol ratio are 1:1.5 with trimethyl-glycine/phenylformic acid eutectic solvent, zero pour is 53 DEG C) at 60 DEG C, in centrifugal extractor, carry out three stage countercurrent extractions, eutectic solvent is 1:4 with the ratio of the mass rate of catalytically cracked gasoline.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 9.5 μ g/g) after drying, denitrification percent is 86.1%, and denitrogenation oil yield is 98.9%.Extraction liquid to be stripped removing nitrogenous compound wherein through ethyl acetate at 60 DEG C, then after the residual ethyl acetate of evaporation removing, obtains trimethyl-glycine/phenylformic acid eutectic solvent of regenerating.
Embodiment 9
By coker gas oil (nitrogen content: 2630 μ g/g) and trimethyl-glycine/2-hydroxyl-1,2,3-tricarballylic acid eutectic solvent (trimethyl-glycine and 2-hydroxyl-1,2, the mol ratio of 3-tricarballylic acid is 1:1.5, zero pour is 48 DEG C) at 55 DEG C, in rotating disc contactor, carry out four-stage counter-current extraction, eutectic solvent is 2:1 with the ratio of the mass rate of coker gas oil.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 234.1 μ g/g) after drying, denitrification percent is 91.1%, and denitrogenation oil yield is 98.1%.Extraction liquid to be stripped removing nitrogenous compound wherein through toluene at 55 DEG C, then after the residual toluene of evaporation removing, obtains trimethyl-glycine/2-hydroxyl-1,2,3-tricarballylic acid eutectic solvent of regenerating.
Embodiment 10
By virgin kerosene (nitrogen content: 5.1 μ g/g), (mol ratio of choline chloride 60 and D-Sorbitol Powder is 1:1 with choline chloride 60/D-Sorbitol Powder eutectic solvent, zero pour is lower than 25 DEG C) at 35 DEG C, in rotating disc contactor, carry out triple-stage cross-flow extraction, eutectic solvent is 1:5 with the ratio of the mass rate of virgin kerosene.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 0.35 μ g/g) after drying, denitrification percent is 93.2%, and denitrogenation oil yield is 99.3%.Extraction liquid to be stripped removing nitrogenous compound wherein through normal heptane at 45 DEG C, then after the residual normal heptane of evaporation removing, obtains choline chloride 60/D-Sorbitol Powder eutectic solvent of regenerating.
Embodiment 11
By straight-run diesel oil (nitrogen content: 205 μ g/g), (mol ratio of choline chloride 60 and levulinic acid is 1:2 with choline chloride 60/levulinic acid eutectic solvent, zero pour is lower than 25 DEG C) in rotating disc contactor, carry out four-stage counter-current extraction at 25 DEG C, straight-run diesel oil is 1:2 with the ratio of the mass rate of eutectic solvent.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 6.2 μ g/g) after drying, denitrification percent is 97.0%, and denitrogenation oil yield is 99.4%.Extraction liquid to be stripped removing nitrogenous compound wherein through normal hexane at 40 DEG C, then after the residual normal hexane of evaporation removing, obtains choline chloride 60/levulinic acid eutectic solvent of regenerating.
Embodiment 12
By catalytically cracked gasoline (nitrogen content: 68.2 μ g/g), (mol ratio of Serine and 2-hydroxy-butanedioic acid is 3:2 with Serine/2-hydroxy-butanedioic acid eutectic solvent, zero pour is lower than 25 DEG C) at 50 DEG C, in centrifugal extractor, carry out nine stage countercurrent extractions, eutectic solvent is 1:2.5 with the ratio of the mass rate of catalytically cracked gasoline.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 8.0 μ g/g) after drying, denitrification percent is 88.3%, and denitrogenation oil yield is 99.0%.Extraction liquid to be stripped removing nitrogenous compound wherein through ethyl acetate at 50 DEG C, then after the residual ethyl acetate of evaporation removing, obtains Serine/2-hydroxy-butanedioic acid eutectic solvent of regenerating.
Embodiment 13
By catalytic cracking diesel oil (nitrogen content: 810 μ g/g), (mol ratio of choline chloride 60, wood sugar, 2-hydroxy-butanedioic acid is 1:1:1 with choline chloride 60/Xylitol/2-hydroxy-butanedioic acid eutectic solvent, zero pour is lower than 25 DEG C) at 40 DEG C, in rotating disc contactor, carry out four-stage counter-current extraction, eutectic solvent is 1:1 with the ratio of the mass rate of catalytic cracking diesel oil.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 47.8 μ g/g) after drying, denitrification percent is 94.1%, and denitrogenation oil yield is 99.2%.Extraction liquid to be stripped removing nitrogenous compound wherein through normal hexane at 40 DEG C, then after the residual normal hexane of evaporation removing, obtains choline chloride 60/Xylitol/2-hydroxy-butanedioic acid eutectic solvent of regenerating.
Embodiment 14
By catalytically cracked gasoline (nitrogen content: 68.2 μ g/g), (mol ratio of choline chloride 60, trimethyl-glycine, D-Sorbitol Powder is 3:3:2 with choline chloride 60/trimethyl-glycine/D-Sorbitol Powder eutectic solvent, zero pour is lower than 25 DEG C) at 35 DEG C, in rotating disc contactor, carry out four-stage counter-current extraction, eutectic solvent is 1:3 with the ratio of the mass rate of catalytically cracked gasoline.Collection raffinate oil, washed by raffinate profit, obtain denitrogenation oil (nitrogen content: 6.6 μ g/g) after drying, denitrification percent is 90.3%, and denitrogenation oil yield is 99.5%.Extraction liquid to be stripped removing nitrogenous compound wherein through ethyl acetate at 50 DEG C, then after the residual ethyl acetate of evaporation removing, obtains choline chloride 60/trimethyl-glycine/D-Sorbitol Powder eutectic solvent of regenerating.
Claims (7)
1. an eutectic solvent extracts the method removing nitrogenous compound in oil product, it is characterized in that, comprise the steps: that (1) take oil product as stock liquid, take eutectic solvent as extraction agent, in extraction equipment, carry out single-stage extraction or multi-stage solvent extraction, obtain the extraction liquid of raffinate oil and enrichment nitrogenous compound;
(2) by the raffinate oil in step (1) through washing, dry, obtain denitrogenation oil;
(3) extraction liquid in step (1) to be stripped removing nitrogenous compound wherein through weak polar solvent, then after evaporation, obtain the eutectic solvent that regenerates;
Described eutectic solvent is made up of hydrogen bond acceptor compounds A and hydrogen bond donor compd B;
Described hydrogen bond acceptor compounds A is at least one in choline chloride 60, trimethyl-glycine and amino acid;
Described hydrogen bond donor compd B to be carbonatoms be 2 ~ 6 aliphatic dicarboxylic acid, carbonatoms is the aliphatics tribasic carboxylic acid of 6, carbonatoms is the aromatic series monocarboxylic acid of 7 ~ 9, the carbonatoms with hydroxyl substituent is the aliphatic dicarboxylic acid of 3 ~ 6, the carbonatoms with hydroxyl substituent is the aliphatics tribasic carboxylic acid of 6, the carbonatoms with hydroxyl substituent is the aromatic series monocarboxylic acid of 7 ~ 9, carbonatoms is the monose of 5 ~ 6, carbonatoms is the sugar alcohol of 5 ~ 6, urea, at least one in 1-methyl urea and levulinic acid.
2. eutectic solvent extraction removes the method for nitrogenous compound in oil product according to claim 1, and it is characterized in that, the zero pour of described eutectic solvent is lower than 60 DEG C.
3. eutectic solvent extraction removes the method for nitrogenous compound in oil product according to claim 1, it is characterized in that, described weak polar solvent to be carbonatoms be 6 ~ 8 alkane, boiling range be sherwood oil, ethyl acetate or the toluene of 60 ~ 90 DEG C.
4. eutectic solvent extraction removes the method for nitrogenous compound in oil product according to claim 1, and it is characterized in that, described oil product is petroleum naphtha, gasoline, kerosene, diesel oil, lubricant base or the wax oil that refining of petroleum obtains.
5. eutectic solvent extraction removes the method for nitrogenous compound in oil product according to claim 1, and it is characterized in that, described eutectic solvent is 2:1 ~ 1:5 with the ratio of the mass rate of oil product.
6. eutectic solvent extraction removes the method for nitrogenous compound in oil product according to claim 1, it is characterized in that, described multi-stage solvent extraction is multistage cross flow extraction or multi-stage counter current extraction.
7. eutectic solvent extraction removes the method for nitrogenous compound in oil product according to claim 1, it is characterized in that, when the zero pour of eutectic solvent is higher than 25 DEG C, the service temperature of extraction is between the zero pour to 60 DEG C of eutectic solvent; When the zero pour of eutectic solvent is equal to or less than 25 DEG C, the service temperature of extraction is between 25 DEG C to 60 DEG C.
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| PCT/CN2015/083069 WO2016155136A1 (en) | 2015-03-30 | 2015-07-01 | Method for removing nitrogen-containing compound from oil product through extraction of eutectic solvent |
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