CN112779050A - Processing method of poor-quality catalytic diesel oil - Google Patents
Processing method of poor-quality catalytic diesel oil Download PDFInfo
- Publication number
- CN112779050A CN112779050A CN201911098862.1A CN201911098862A CN112779050A CN 112779050 A CN112779050 A CN 112779050A CN 201911098862 A CN201911098862 A CN 201911098862A CN 112779050 A CN112779050 A CN 112779050A
- Authority
- CN
- China
- Prior art keywords
- diesel oil
- oil
- catalytic
- catalytic cracking
- catalyst
- 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.)
- Pending
Links
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 96
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 83
- 238000003672 processing method Methods 0.000 title claims abstract description 23
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 88
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 71
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 28
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- 238000000638 solvent extraction Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000000605 extraction Methods 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 239000011230 binding agent Substances 0.000 claims description 16
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002619 bicyclic group Chemical group 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 35
- -1 ethylene, propylene, butane Chemical class 0.000 abstract description 17
- 239000003502 gasoline Substances 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 65
- 239000000203 mixture Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 230000008569 process Effects 0.000 description 20
- 239000002808 molecular sieve Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000009826 distribution Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Images
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
- 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
- C10G67/04—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 including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0409—Extraction of unsaturated hydrocarbons
- C10G67/0436—The hydrotreatment being an aromatic saturation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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 provides a processing method of poor-quality catalytic diesel oil, which comprises the following steps: step 1, carrying out solvent extraction on poor-quality catalytic diesel to obtain raffinate oil rich in alkane and extract oil rich in aromatic hydrocarbon; step 2, performing mild hydrotreating on the extract oil rich in aromatic hydrocarbon to obtain hydrogenated diesel oil; and 3, carrying out catalytic cracking treatment on the hydrogenated diesel oil obtained in the step 2. The processing method can produce high-quality product gasoline, high-value byproducts such as ethylene, propylene, butane and butylene, and the like, obviously increases the utilization rate of the catalytic diesel oil, greatly reduces the hydrogenation cost, and greatly increases the yield of the high-value product.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a processing method of poor-quality catalytic diesel oil.
Background
Catalytic cracking technology plays an important role in the oil refining industry: catalytic cracking can provide ethylene, propylene, gasoline, and can also provide etherification and alkylation feedstocks as needed by the market. However, this results in a greatly reduced yield of high value products in their catalytic cracking products as the crude oil is upgraded and downgraded. In order to improve the yield of high-value products, the improvement of reaction severity is an effective way, but the catalytic diesel oil product has high aromatic hydrocarbon content and low cetane number content, and is difficult to blend and leave a factory. How to treat the low-quality catalytic diesel oil product becomes a big problem to be solved by oil refining enterprises.
Meanwhile, as the economic growth speed of China is slowed, the diesel oil demand is gradually increased, and the automobile holding capacity of China is increased, so that the gasoline demand is increased year by year, and therefore, a key problem is also faced on how to adopt a proper method to reduce the diesel oil-steam ratio to meet the requirements of the consumer market.
The main reason for the low cetane number of catalytic diesel oil is related to the composition, and the catalytic diesel oil has low alkane content and very high aromatic hydrocarbon content, and the alkane is a high cetane component and the aromatic hydrocarbon is a low cetane component, which determines the low cetane number characteristic of the catalytic diesel oil. Wherein, the aromatic hydrocarbon in the diesel component mainly comprises bicyclic aromatic hydrocarbon and monocyclic aromatic hydrocarbon. How to treat the bicyclic aromatics and monocyclic aromatics in the diesel fraction becomes the key to solve the problem.
CN 1197834A discloses a method for refining catalytic diesel oil by extraction and denitrification, which adopts a two-component compound extractant composed of a sulfur-containing polar solvent and a hydrogen bond-containing compound as additives to carry out multi-stage countercurrent extraction on catalytic diesel oil, and the process can separate fluorine-containing and sulfur-containing compound impurities in the catalytic diesel oil from the catalytic diesel oil, but is only suitable for reducing the contents of fluorine-containing and sulfur-containing compounds of the catalytic diesel oil, but does not obviously reduce the content of aromatic hydrocarbon in the catalytic diesel oil, and the cetane number of the catalytic diesel oil is not greatly improved.
CN 103773491B discloses a method for improving the quality of heavy diesel oil. The heavy diesel oil is subjected to aromatic extraction treatment to obtain raffinate oil containing saturated hydrocarbon and extract oil containing polycyclic aromatic hydrocarbon, the raffinate oil is subjected to hydrofining, the extract oil is subjected to hydro-upgrading, and the upgraded extract oil and the heavy diesel oil are mixed and then subjected to aromatic extraction. The method can improve the quality of heavy diesel oil. However, in the hydro-upgrading process, the hydrogenation severity is high, the energy consumption is high, and the cost is high.
CN 103214332A discloses a method for producing light aromatic hydrocarbon and high-quality oil products by catalyzing diesel oil. The method comprises the steps of firstly carrying out aromatic extraction treatment on catalytic diesel oil to obtain extract oil rich in polycyclic aromatic hydrocarbon and raffinate oil rich in alkane. In the patent, the obtained extract oil rich in polycyclic aromatic hydrocarbon is subjected to hydrofining treatment and then hydrocracking treatment to generate light aromatic hydrocarbon fraction. But the hydrogenation severity required by hydrocracking is higher, the equipment cost is high, and the gas component generated in the hydrocracking process is low-carbon alkane, so that the market value is low.
The above techniques all have their limitations. How to correctly process alkane and bicyclic aromatic hydrocarbon in the catalytic diesel oil is a problem which needs to be noticed when the catalytic diesel oil is processed. How to further improve the conversion rate of catalytic diesel oil and the yield of high-value products in the products is still the focus of research in the field.
Disclosure of Invention
The invention mainly aims to provide a processing method of poor-quality catalytic diesel oil, which aims to solve the problems of low conversion rate of catalytic diesel oil and low yield of high-value products in the prior art.
In order to achieve the aim, the invention provides a processing method of poor-quality catalytic diesel oil, which comprises the following steps:
and 3, carrying out catalytic cracking treatment on the hydrogenated diesel oil obtained in the step 2.
The processing method of the poor quality catalytic diesel oil of the invention is characterized in that the content of saturated components in the poor quality catalytic diesel oil is 20-50%; the solvent is an organic solvent; the mass ratio of the poor-quality catalytic diesel oil to the solvent is 0.4-3.0: 1, the extraction temperature is 30-40 ℃, and the extraction time is 2-10 hours.
The processing method of the poor quality catalytic diesel oil, provided by the invention, comprises the step of adding one or more organic solvents selected from dimethyl phthalate, triethylene glycol, sulfolane, dimethyl sulfoxide, furfural and N-methyl pyrrolidone into the organic solvent.
The invention relates to a processing method of poor quality catalytic diesel oil, wherein the mild hydrotreating conditions are as follows: the hydrogen partial pressure is less than 8MPa, the reaction temperature is 300-400 ℃, and the reaction space velocity is 0.5-3 h-1The hydrogen-oil ratio is 800-1200: 1.
the processing method of the poor quality catalytic diesel oil comprises the following steps of (1) taking a metal hydrogenation catalyst as a catalyst for mild hydrotreatment, wherein the active metal in the metal hydrogenation catalyst is nickel, tungsten and/or molybdenum; the mild hydrotreating causes the production of naphthenic aromatics from the bicyclic aromatics in the extract oil.
The processing method of the poor quality catalytic diesel oil comprises the step of enabling the active metal to account for 10-50% of the metal hydrogenation catalyst by mass in terms of metal.
The invention relates to a processing method of poor quality catalytic diesel oil, wherein the catalytic cracking treatment conditions are as follows: the reaction temperature is 500-650 ℃, the reaction pressure is normal pressure, and the reaction space velocity is 3-6 h-1(ii) a The catalytic cracking treatment enables naphthenic aromatics and monocyclic aromatics to generate short-side-chain monocyclic aromatics.
The processing method of the poor quality catalytic diesel oil comprises the step of preparing a catalyst for catalytic cracking treatment, wherein the catalyst for catalytic cracking treatment comprises a modified molecular sieve, the modified molecular sieve is one or more of modified ZSM-5, modified USY and modified ZSM-11, and modified elements of the modified molecular sieve are phosphorus, magnesium or transition elements.
The processing method of the poor-quality catalytic diesel oil comprises the following steps of (1) taking phosphorus, magnesium or iron as a modifying element, wherein the modifying element accounts for 0.01-10 wt% of the modified molecular sieve; the silicon-aluminum ratio of the modified molecular sieve is 25-300.
The processing method of the poor quality catalytic diesel oil comprises the following steps that the catalyst for catalytic cracking treatment further comprises a carrier and a binder, wherein the modified molecular sieve is loaded on the carrier by the binder; the carrier is one or more of silica, alumina, kaolin and montmorillonite, and the binder is one or more of silica sol, alumina sol and pseudo-boehmite; based on the total mass of the catalyst for catalytic cracking treatment, the content of the carrier is 10-60 wt%, the content of the modified molecular sieve is 10-50 wt%, and the content of the binder is 0.5-40 wt%.
The invention has the beneficial effects that:
the invention effectively combines the extraction technology, the hydrogenation technology and the catalytic cracking technology, adopts the solvent extraction separation mode, can separate the saturated component and the aromatic component in the catalytic diesel oil, and greatly increases the alkane content in the raffinate oil diesel oil, thereby greatly improving the cetane number of the diesel oil. And the excessive double-ring aromatic hydrocarbon in the extract oil can generate naphthenic aromatic hydrocarbon through a mild hydrogenation mode, the naphthenic aromatic hydrocarbon and the monocyclic aromatic hydrocarbon in the diesel oil continuously react under the catalytic cracking condition to generate a short-side-chain monocyclic aromatic hydrocarbon component, and the component belongs to a high-octane gasoline component. In addition, high value by-products, lower olefins, are also produced.
Drawings
FIG. 1 is a schematic flow chart of the poor quality catalytic diesel oil processing method of the present invention.
Wherein, the reference numbers:
1. extraction tower
2. Distillation column
3. Hydrogenation device
4. Catalytic cracking device
5. Distillation apparatus
6. Water washing tower
7. Separation tower
8. Drying tower
9-20, pipeline
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The invention provides a processing method of poor-quality catalytic diesel oil, which comprises the following steps:
and 3, carrying out catalytic cracking treatment on the hydrogenated diesel oil obtained in the step 2.
Poor quality and low cetane number of the poor catalytic diesel oil are caused by the high content of the bicyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon. The method adopts a solvent extraction separation mode to separate saturated components and aromatic components in the catalytic diesel oil, and then treats the saturated components and the aromatic components respectively, so that the treatment capacity can be reduced, and a targeted treatment mode can be adopted to obtain an expected product efficiently.
The solvent extraction method of the present invention is not particularly limited, and any method commonly used in the art may be used. Preferably, an organic solvent is adopted to extract poor-quality catalytic diesel, and the mass ratio of the catalytic diesel to the organic solvent is preferably 0.4-3.0: 1, preferably 1 to 1.5: 1, the extraction temperature is preferably 30-40 ℃. The organic solvent is selected from dimethyl phthalate, triethylene glycol, sulfolane, dimethyl sulfoxide, furfural and N-methyl pyrrolidone. The extraction solvent of the present invention may be one of the solvents, or a mixed solvent of two or more of the solvents.
The solvent extraction of the invention can be carried out in an extraction tower, the catalytic diesel oil is injected from the lower part of the extraction tower, the extraction solvent is injected from the upper part of the extraction tower, and the catalytic diesel oil and the extraction solvent are in countercurrent contact to generate extraction exchange. After extraction, the raffinate oil rich in alkane flows out of the upper part of the extraction tower and enters a water washing tower, and is dried and collected through a drying tower after being washed by water in the water washing tower. The extract oil rich in aromatic hydrocarbon can flow out from the lower part of the extraction tower for further treatment. Of course, the solvent extraction of the present invention may be carried out in other apparatuses, such as a mixing apparatus in which mixing is carried out and then a layer-separation treatment is carried out, as long as extraction can be achieved.
In the invention, the extract oil which flows out from the lower part of the extraction tower and is rich in aromatic hydrocarbon is subjected to hydrogenation treatment under the mild hydrogenation condition, so that bicyclic aromatic hydrocarbon or a small amount of polycyclic aromatic hydrocarbon in the extract oil generates naphthenic aromatic hydrocarbon, and in addition, part of aromatic hydrocarbon is also hydrogenated to form naphthenic hydrocarbon, thus being beneficial to the generation of high-value products, namely low-carbon olefin and gasoline.
The catalyst for mild hydrotreatment of the invention is a metal hydrogenation catalyst, and preferably the metal hydrogenation catalyst is prepared by the following method:
pseudo-boehmite (10-30%), alumina carrier (20-80%) and sesbania powder (5-10%) are used as raw materials, and proper amount of water is added and mixed uniformly. And modified by using a proper amount of nickel nitrate, phosphotungstic acid and the like. And drying and roasting the modified catalyst to obtain the metal hydrogenation catalyst. The mass ratio of the metal in terms of oxide is 10-50%.
Among them, alumina commonly used in the art can be used in the present application. As a preferred technical scheme, the invention provides a preparation method of an alumina carrier, which comprises the following steps: dissolving soluble starch or glucose or carbon nanospheres in water, adding aluminum isopropoxide under vigorous stirring, adjusting pH value with dilute nitric acid, and standing in shade for 1-24 hr after aluminum isopropoxide is completely dissolved. The resulting gel is dried, ground to a powder and calcined in air at moderately high temperatures (e.g., 700 ℃). The obtained alumina carrier has larger specific surface area and richer mesopores, and the prepared catalyst has better catalytic activity.
The mild hydrotreating conditions are preferably: the hydrogen partial pressure is less than 8MPa, the reaction temperature is 300-400 ℃, and the best temperature is 330-360 ℃. The reaction space velocity is 0.5-3 h-1Preferably 0.8 to 2 hours-1In the meantime. The hydrogen-oil ratio is 800-1200: 1.
The extracted oil after mild hydrogenation treatment is subjected to naphthenic aromatic ring opening reaction and side chain breaking reaction of monocyclic aromatic hydrocarbon in a catalytic cracking unit to generate catalytic gasoline rich in short side chain monocyclic aromatic hydrocarbon and byproducts such as ethylene, propylene, butane, butylene and the like.
The catalyst used in the catalytic cracking treatment process of the invention is a catalytic cracking catalyst, and the catalyst can be any catalytic cracking catalyst commonly used in the field. As a preferred technical scheme, the catalytic cracking catalyst comprises a modified molecular sieve, a carrier and a binder, wherein the modified molecular sieve is one or more of modified ZSM-5, modified USY and modified ZSM-11, and a modified element of the modified molecular sieve is phosphorus, magnesium or a transition element, preferably phosphorus, magnesium or iron. The proportion of the modified elements in the modified molecular sieve is 0.01-10 wt%; the silicon-aluminum ratio of the modified molecular sieve is 25-300. The modified molecular sieve is loaded on a carrier by a binder; the carrier is one or more of silica, alumina, kaolin and montmorillonite, and the binder is one or more of silica sol, alumina sol and pseudo-boehmite; based on the total mass of the catalyst for catalytic cracking treatment, the content of the carrier is 10-60 wt%, the content of the modified molecular sieve is 10-50 wt%, and the content of the binder is 0.5-40 wt%.
As a preferred technical scheme, the preparation method of the catalytic cracking catalyst comprises the following steps:
step a, element modification is respectively carried out on a molecular sieve and a carrier, and the modified elements are one or more of Fe, Mg, P and S;
step b, mixing a binder and a solvent to form colloidal slurry;
and c, mixing the modified ZSM-5 molecular sieve and the carrier with the colloidal slurry, drying and roasting to obtain the catalytic cracking catalyst.
The molecular sieve and the carrier can be modified by an impregnation method. For example, nitrate or acid solution of the supported element is dissolved in deionized water, a ZSM-5 molecular sieve or a carrier is added, the nitrate solution or the acid solution is supported on the ZSM-5 molecular sieve or the carrier in a way of incipient wetness impregnation for multiple times, the ions are uniformly dispersed by ultrasonic treatment in each impregnation process, and finally, the roasting is carried out, wherein the roasting temperature is 550 ℃ for 4 hours for example.
According to the invention, the acidity of the molecular sieve and the carrier is improved through the modification step of the molecular sieve and the carrier, so that the obtained catalyst can further increase the ring opening selectivity of the naphthenic aromatic hydrocarbon under the condition of ensuring high conversion rate of the naphthenic aromatic hydrocarbon.
Mixing the modified molecular sieve and the carrier with colloidal slurry formed by a binder and a solvent, drying and roasting to obtain the catalytic cracking catalyst. Wherein the drying temperature is 60-145 ℃, and the drying time is 1-24 h. The roasting temperature is 300-800 ℃, and the roasting time is 1-8 h. The colloidal slurry is preferably a transparent and uniform slurry formed by uniformly mixing water, hydrochloric acid and a binder. The step enables the molecular sieve and the carrier of the invention to be wrapped by the binding agent, thus further increasing the number of mesopores of the catalyst and improving the hydrothermal stability of the catalyst.
Wherein, the catalytic cracking treatment condition is preferably that the reaction temperature is 500-670 ℃, preferably 530-580 ℃, and the reaction space velocity is 3-6 h-1. In the catalytic cracking process of the invention, the catalyst is adoptedThe reaction temperature is high, so that the hydrogen transfer reaction activity can be reduced, and the conversion rate is improved; and a lower space velocity is adopted, so that the conversion rate of the raw materials is further increased.
In conclusion, the invention effectively combines the extraction technology, the hydrogenation technology and the catalytic cracking technology. Not only can provide high-quality diesel fraction required by the market, but also can greatly reduce the treatment capacity of the subsequent hydrogenation, and greatly reduce the hydrogenation cost. In addition, the invention uses a novel process combining mild hydrogenation and catalytic cracking to mildly hydrogenate the extract oil rich in the bicyclic aromatic hydrocarbon into the naphthenic aromatic hydrocarbon component easy to crack. Then the naphthenic aromatic hydrocarbon component is subjected to catalytic cracking treatment to efficiently produce high-quality gasoline fraction and low-carbon olefin component which are rich in monocyclic aromatic hydrocarbon, so that the hydrogenation cost is greatly reduced, and the efficient utilization of each component of the catalytic cracking gasoline is realized.
The processing method of the invention solves the problems of poor quality and excessive yield of the catalytic diesel oil on one hand. On the other hand, an effective way is provided for reducing the demand of the diesel-steam ratio in the market. Moreover, the processing method of the invention has the advantages of lower severity, lower hydrogenation cost and higher conversion efficiency.
A preferred process of the present invention is provided below with reference to FIG. 1.
The catalytic diesel oil raw material is injected into the middle-lower part of the extraction tower 1 through a pipeline 9, the extract liquid is injected into the middle-upper part of the extraction tower through a pipeline 13, and the catalytic diesel oil raw material and the extract liquid are subjected to countercurrent extraction to generate raffinate oil rich in alkane and extract oil rich in aromatic hydrocarbon. The raffinate oil is fed to the lower middle part of the water washing column 6 through the line 14, while the water is fed to the upper middle part of the water washing column 6 through the line 15, and the raffinate oil is washed by countercurrent contact with the water. The raffinate oil is washed with water and then enters a drying tower 8 through a pipeline 16 for drying treatment. And the water flows out from the bottom of the water washing tower 6 and enters a separation tower 7 to separate the extractant, the extractant is reused through a pipeline 12, and the water flows into the upper part of the water washing tower again through a pipeline 15. The extracted oil rich in aromatic hydrocarbon flows out from the lower part of the extraction tower and is injected into the distillation tower 2 through a pipeline 10 to separate the extractant from the extracted oil. The extractant is recycled by flowing out of the upper part of the distillation column via line 11. The extracted oil enters the hydrogenation device 3 through a pipeline 17 for mild hydrogenation treatment, the hydrogenated diesel oil product after hydrogenation enters the catalytic cracking device 4 through a pipeline 18 for catalytic cracking reaction, the generated cracking product flows into the distillation device 5 through a pipeline 19, the generated gas product is collected from the top of the distillation device, and the gasoline product is collected from the middle of the distillation device. The produced diesel oil and heavy oil products are re-injected into the hydrogenation device from the bottom of the distillation device through a pipeline 20 to continue the hydrogenation treatment.
The catalytic cracking diesel oil is treated according to the method of the invention to produce high-quality diesel oil products, gasoline fractions rich in monocyclic aromatic hydrocarbons and low-carbon olefin byproducts.
The technical solution of the present invention is further detailed by the following examples:
the hydrogenation catalysts used in the specific examples are hydrogenation catalyst a, hydrogenation catalyst B1 and hydrogenation catalyst B2, wherein the carrier used in the hydrogenation catalyst a is a common alumina carrier, and the hydrogenation catalysts B1 and B2 are alumina carriers with mesoporous structures. The preparation process of the hydrogenation catalysts B1 and B2 is as follows:
(1) synthesizing mesoporous alumina: selecting carbon nano-rods as an additive, dissolving the carbon nano-rods into water, adding 3g of aluminum isopropoxide into 1g of the carbon nano-rods under vigorous stirring, stirring for about 1h, and standing for 24 h. Drying the obtained gel solution at 120 ℃, grinding the obtained dry coke into powder, heating to 300 ℃ at the speed of 10 ℃/min in the air, then heating to 700 ℃ at the speed of 5 ℃/min, and then keeping the temperature for 4 hours to obtain the mesoporous alumina. The structural properties of mesoporous alumina and common alumina are shown in table 1.
(2) Preparing a hydrocracking catalyst A: 1g of nickel nitrate and 3g of phosphotungstic acid were weighed, and 7g of a common alumina carrier was weighed. The nickel nitrate solution and phosphotungstic acid are dissolved into 5g of deionized water, the mixture is loaded on a common alumina carrier in an incipient wetness impregnation method, and the ions are uniformly dispersed by ultrasonic treatment in each impregnation process. Extruding into strips by a strip extruding machine, drying at 120 ℃, and finally roasting at 550 ℃ for 4 hours.
(3) Preparation of hydrocracking catalyst B1: weighing 1g of nickel nitrate and 3g of phosphotungstic acid, and weighing 7g of mesoporous alumina carrier. The method comprises the steps of dissolving a nickel nitrate solution and phosphotungstic acid into 5g of deionized water, loading the mixture on a mesoporous alumina carrier in an incipient wetness impregnation method, and uniformly dispersing ions by ultrasonic treatment in each impregnation process. Extruding into strips by a strip extruding machine, drying at 120 ℃, and finally roasting at 550 ℃ for 4 hours.
(4) Preparation of hydrocracking catalyst B2: 1g of nickel nitrate and 3g of ammonium molybdate are weighed, and 7g of mesoporous alumina carrier is weighed. The method comprises the steps of dissolving a nickel nitrate solution and phosphotungstic acid into 5g of deionized water, loading the mixture on a mesoporous alumina carrier in an incipient wetness impregnation method, and uniformly dispersing ions by ultrasonic treatment in each impregnation process. Extruding into strips by a strip extruding machine, drying at 120 ℃, and finally roasting at 550 ℃ for 4 hours.
The catalytic cracking catalysts used in the specific examples are catalytic cracking catalyst a and catalytic cracking catalyst B. The preparation process of the catalytic cracking catalysts A and B comprises the following steps:
(1) the molecular sieve and the carrier of the catalytic cracking catalyst B are not modified, and the molecular sieve and the carrier of the catalytic cracking catalyst A are modified. The method for modifying the molecular sieve comprises the following steps: weighing 8g of molecular sieve, weighing a proper amount of ferric nitrate, dissolving in deionized water, soaking the prepared solution on the molecular sieve for multiple times in an incipient wetness impregnation method, and roasting the molecular sieve at 550 ℃ to prepare the modified molecular sieve with the load element content of 2%. Modifying kaolin: weighing 8g of kaolin, weighing a proper amount of ferric nitrate, dissolving in deionized water, dipping the prepared solution on a molecular sieve for multiple times in an incipient wetness dipping method, and roasting the molecular sieve at 550 ℃ to prepare the modified kaolin with the load element content of 2%.
(2) Adding 5g of pseudoboehmite into 16.8g of water, stirring uniformly, weighing 2g of hydrochloric acid, slowly dropping into the mixture to form a colloid, weighing 6g of unmodified molecular sieve and 4g of unmodified kaolin, mixing the colloid with the mixture, and adding 0.5g of phosphoric acid. Finally, 2.4g of alumina sol is added and stirred evenly. And (3) putting the synthesized catalyst into an oven for roasting treatment to synthesize the catalytic cracking catalyst B.
(3) Adding 5g of pseudoboehmite into 16.8g of water, stirring uniformly, weighing 2g of hydrochloric acid, slowly dropping into the mixture to form a colloid, weighing 6g of modified molecular sieve and 4g of modified kaolin, mixing the colloid with 0.5g of phosphoric acid. Finally, 2.4g of alumina sol is added and stirred evenly. And (3) placing the synthesized catalyst into an oven for roasting treatment. Synthesizing the catalytic cracking catalyst A.
Example 1
The catalytic cracking diesel oil A is taken as a raw material, is from a catalytic cracking Chinese device of China university of Petroleum, and has the composition shown in Table 2. 200g of catalytic cracking diesel oil A and 240g of organic solvent furfural are added into a separating funnel and stirred for 1 hour, fully and uniformly mixed, and then the mixture is kept stand for 0.5 hour. The solution was separated into upper and lower layers of solution, the upper layer of solution was 62g of raffinate oil, and the upper layer of solution was washed 2 times with deionized water to obtain 62g of raffinate oil, the composition of which is shown in Table 3. The lower solution is 377g of the mixed solution of the extract oil and the furfural. And separating the extract oil and the furfural from the mixed solution of the extract oil and the furfural by a vacuum distillation device to obtain 138g of extract oil and 139g of furfural solution, wherein the compositions of the extract oil are shown in Table 4.
And (2) carrying out a hydrotreating reaction on the obtained extract oil on a miniature fixed bed reactor, wherein the reaction temperature is 340 ℃, the hydrogen partial pressure is 6MPa, and the hydrogen-oil ratio is 1000: 1, the space velocity is 0.8h-1Is subjected to mild hydrotreating under the hydrogenation conditions of (1). The hydrogenation catalyst used was hydrogenation catalyst a. The composition of the hydrogenated diesel oil obtained by hydrotreating the extract oil is shown in table 5.
The extract oil after mild hydrotreatment is reacted on a micro catalytic cracking fixed bed reactor, the reaction temperature is 550 ℃, the normal pressure is realized, and the space velocity is 4h-1The catalytic cracking reaction is carried out under the catalytic cracking conditions of (1). The catalyst used was the above-mentioned catalytic cracking catalyst A. The product composition after catalytic cracking reaction is shown in table 6.
The overall product distribution of the poor quality catalytic diesel A is shown in Table 7 by combining extraction, hydrogenation and catalytic cracking.
Example 2
The feedstock used in this example was catalytic cracking diesel B from a chinese unit of catalytic cracking of the university of petroleum in china, the specific composition of which is shown in table 2. 200g of catalytic diesel B were subjected to an extraction treatment according to the method of example 1, obtaining 78g of raffinate, the composition of which is shown in Table 3. And 122g of a draw-off oil was obtained, the composition of which is shown in Table 4. The composition of the hydrogenated diesel oil obtained by hydrotreating according to the hydrogenation method shown in example 1 is shown in table 5. The hydrotreated hydrogenated diesel oil was subjected to catalytic cracking reaction according to the catalytic cracking method shown in example 1, and the product distribution thereof is shown in table 6.
The overall product distribution of the poor quality catalytic diesel B is shown in table 7, combining extraction, hydrogenation and catalytic cracking.
Example 3
The feedstock used in this example was catalytic cracking diesel A, the specific composition of which is shown in Table 2. 200g of catalytic diesel A was extracted and hydrotreated according to the procedure of example 1, with the raffinate oil shown in Table 3. The extract oil is shown in table 4.
Different from the example 1, the catalytic diesel hydrogenation catalyst is hydrogenation catalyst B1, but the hydrogenation conditions are the same, namely the reaction temperature is 340 ℃, the hydrogen partial pressure is 6MPa, and the hydrogen-oil ratio is 1000: 1, the space velocity is 0.8h-1Is subjected to mild hydrotreating under the hydrogenation conditions of (1). The hydrogenated diesel fuel composition is shown in table 5. In the catalytic cracking process of hydrogenated diesel oil, the catalyst selected in the catalytic cracking process is a catalytic cracking catalyst A, the reaction condition is 550 ℃, the normal pressure is selected, and the space velocity is 4h-1. The specific product distribution is shown in Table 6.
The overall product distribution of the poor quality catalytic diesel A is shown in Table 7 by combining extraction, hydrogenation and catalytic cracking.
Example 4
The feedstock used in this example was catalytic cracking diesel A, the specific composition of which is shown in Table 2. 200g of catalytic diesel A was extracted and hydrotreated according to the procedure of example 1, with the raffinate oil shown in Table 3. The extract oil is shown in table 4.
Different from the example 1, the catalytic diesel hydrogenation catalyst is hydrogenation catalyst B2, but the hydrogenation conditions are the same, namely the reaction temperature is 340 ℃, the hydrogen partial pressure is 6MPa, and the hydrogen-oil ratio is 1000: 1, the space velocity is 0.8h-1Is subjected to mild hydrotreating under the hydrogenation conditions of (1). The hydrogenated diesel fuel composition is shown in table 5. In the catalytic cracking process of hydrogenated diesel oil, the catalyst selected in the catalytic cracking process is a catalytic cracking catalyst A, the reaction condition is 550 ℃, the normal pressure is selected, and the space velocity is 4h-1. The specific product distribution is shown in Table 6.
The overall product distribution of the poor quality catalytic diesel A is shown in Table 7 by combining extraction, hydrogenation and catalytic cracking.
Example 5
The feedstock used in this example was catalytic cracking diesel A, the specific composition of which is shown in Table 2. 200g of catalytic diesel A was extracted and hydrotreated according to the procedure of example 4, with the raffinate oil shown in Table 3. The extract oil is shown in table 4.
The hydrogenation catalyst and the hydrotreating conditions were exactly the same as in example 4. The hydrogenated diesel fuel composition is shown in table 5. Different from the example 4, in the hydrogenation diesel oil catalytic cracking process, the catalytic cracking catalyst is the catalytic cracking catalyst B, the reaction condition is 550 ℃, the normal pressure is selected, and the space velocity is 4h-1. The specific product distribution is shown in Table 6.
The overall product distribution of the poor quality catalytic diesel A is shown in Table 7 by combining extraction, hydrogenation and catalytic cracking.
Example 6
The feedstock used in this example was catalytic cracking diesel A, the specific composition of which is shown in Table 2. 200g of catalytic diesel A was extracted and hydrotreated according to the procedure of example 4, with the raffinate oil shown in Table 3. The extract oil is shown in table 4.
The hydrogenation catalyst is hydrogenation catalyst B2, compared with the example 4, the hydrogenation conditions are different: the reaction temperature is 350 ℃, the hydrogen partial pressure is 10MPa, and the hydrogen-oil ratio is 1000: 1, the space velocity is 0.8h-1Is subjected to deep hydrotreatment under the hydrogenation conditions of (1). The hydrogenated diesel fuel composition is shown in table 5. The catalytic cracking catalyst and catalytic cracking conditions were identical, and the specific product distribution is shown in table 6.
The overall product distribution of the poor quality catalytic diesel A is shown in Table 7 by combining extraction, hydrogenation and catalytic cracking.
Example 7
The feedstock used in this example was catalytic cracking diesel A, the specific composition of which is shown in Table 2. 200g of catalytic diesel A was extracted and hydrotreated according to the procedure of example 1, with the raffinate oil shown in Table 3. The extract oil is shown in table 4.
The catalyst selected by the hydrogenation catalyst is hydrogenation catalyst B2, and the hydrogenation treatment conditions are the same: namely, the reaction temperature is 340 ℃, the hydrogen partial pressure is 6MPa, and the hydrogen-oil ratio is 1000: 1, the space velocity is 0.8h-1Is subjected to mild hydrotreating under the hydrogenation conditions of (1). The hydrogenated diesel fuel composition is shown in table 5. In the catalytic cracking process of hydrogenated diesel oil, the catalytic cracking catalyst is catalytic cracking catalyst A, the reaction condition is 600 ℃, normal pressure and space velocity of 3h-1. The specific product distribution is shown in Table 6.
The overall product distribution of the poor quality catalytic diesel A is shown in Table 7 by combining extraction, hydrogenation and catalytic cracking.
TABLE 1 structural Properties of mesoporous alumina and ordinary alumina
| Type (B) | BET specific surface area (m)2/g) | Pore volume (cm)3/g) | Pore diameter (cm)3/g) |
| Mesoporous alumina | 342.85 | 0.582 | 7.13 |
| Ordinary alumina | 258.43 | 0.312 | 2.94 |
TABLE 2 feed hydrocarbon composition for catalytic Diesel A and catalytic Diesel B
| Of the diesel type | A | B |
| Paraffin, wt.% | 25.11 | 30.14 |
| Cycloalkane, wt.% | 9.33 | 13.22 |
| Monocyclic aromatic hydrocarbon, wt.% | 15.53 | 13.05 |
| Bicyclic aromatic hydrocarbon, wt.% | 33.49 | 27.93 |
| Tetrahydronaphthalene, wt.% | 2.33 | 4.25 |
| Indene, wt% | 6.81 | 5.23 |
| Polycyclic aromatic hydrocarbons, wt.% | 7.40 | 6.18 |
TABLE 3 raffinate hydrocarbon composition
TABLE 4 oil hydrocarbon composition draw-off
TABLE 5 Hydrocarbon composition of the extract oil after hydrogenation
TABLE 6 hydroextract oil catalytic cracking product distribution
TABLE 7 Total diesel product distribution
Examples 1 and 2 show that the process of the present invention has general applicability to catalytic diesel feedstocks rich in polycyclic aromatic hydrocarbons. Examples 1, 3 and 4 show that hydrogenation catalysts containing mesostructured alumina can promote hydrogenation better and hydrogenation activity of supported Mo element is better. Examples 4 and 5 show that the modified catalytic cracking catalyst can better promote the generation of gasoline by cracking of naphthenic-rich aromatic hydrogenated diesel oil. Examples 4 and 6 show that the method of the invention is suitable for low severity hydrogenation, on one hand, the hydrogenation cost can be reduced, and on the other hand, the generation of high octane gasoline can be promoted. Examples 4 and 7 show that optimum cracking conditions exist for catalytic cracking of hydrogenated diesel, and not that the higher the severity of the reaction the better. Example 4 the conversion rate of the poor diesel oil is 82.54%, the yield of the high-quality diesel oil is 31%, the yield of the gasoline is 28.45, the yield of the ethylene is 1.49%, the yield of the propylene is 4.11%, the yield of the butylene is 2.31%, and the poor diesel oil has better treatment results.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A processing method of poor quality catalytic diesel oil is characterized by comprising the following steps:
step 1, carrying out solvent extraction on poor-quality catalytic diesel to obtain raffinate oil rich in alkane and extract oil rich in aromatic hydrocarbon;
step 2, performing mild hydrotreating on the extract oil rich in aromatic hydrocarbon to obtain hydrogenated diesel oil;
and 3, carrying out catalytic cracking treatment on the hydrogenated diesel oil obtained in the step 2.
2. The method for processing poor quality catalytic diesel oil according to claim 1, wherein the content of saturates in the poor quality catalytic diesel oil is 20-50%; the solvent is an organic solvent; the mass ratio of the poor-quality catalytic diesel oil to the solvent is 0.4-3.0: 1, the extraction temperature is 30-40 ℃, and the extraction time is 2-10 hours.
3. The method for processing poor quality catalytic diesel oil according to claim 2, wherein the organic solvent is one or more of dimethyl phthalate, triethylene glycol, sulfolane, dimethyl sulfoxide, furfural and N-methyl pyrrolidone.
4. Poor quality catalytic diesel oil according to claim 1The mild hydrotreating conditions of (1) are as follows: the hydrogen partial pressure is less than 8MPa, the reaction temperature is 300-400 ℃, and the reaction space velocity is 0.5-3 h-1The hydrogen-oil ratio is 800-1200: 1.
5. the method for processing poor quality catalytic diesel oil according to claim 4, wherein the mild hydrotreating catalyst is a metal hydrogenation catalyst, and the active metal in the metal hydrogenation catalyst is nickel, tungsten and/or molybdenum; the mild hydrotreating causes the production of naphthenic aromatics from the bicyclic aromatics in the extract oil.
6. The method for processing poor quality catalytic diesel oil as claimed in claim 5, wherein the mass ratio of the active metal in terms of metal in the metal hydrogenation catalyst is 10-50%.
7. The method for processing poor quality catalytic diesel oil according to claim 1, wherein the catalytic cracking conditions are as follows: the reaction temperature is 500-650 ℃, the reaction pressure is normal pressure, and the reaction space velocity is 3-6 h-1(ii) a The catalytic cracking treatment enables naphthenic aromatics and monocyclic aromatics to generate short-side-chain monocyclic aromatics.
8. The processing method of poor quality catalytic diesel oil according to claim 7, wherein the catalyst for catalytic cracking treatment comprises a modified molecular sieve, the modified molecular sieve is one or more of modified ZSM-5, modified USY and modified ZSM-11, and the modified molecular sieve has modified elements of phosphorus, magnesium or transition elements.
9. The processing method of poor quality catalytic diesel oil according to claim 8, wherein the modifying element is phosphorus, magnesium or iron, and the modifying element accounts for 0.01-10 wt% of the modified molecular sieve; the silicon-aluminum ratio of the modified molecular sieve is 25-300.
10. The method for processing poor quality catalytic diesel oil as set forth in claim 8, wherein said catalytic cracking treatment catalyst further comprises a carrier and a binder, said binder loading said modified molecular sieve on the carrier; the carrier is one or more of silica, alumina, kaolin and montmorillonite, and the binder is one or more of silica sol, alumina sol and pseudo-boehmite; based on the total mass of the catalyst for catalytic cracking treatment, the content of the carrier is 10-60 wt%, the content of the modified molecular sieve is 10-50 wt%, and the content of the binder is 0.5-40 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911098862.1A CN112779050A (en) | 2019-11-11 | 2019-11-11 | Processing method of poor-quality catalytic diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911098862.1A CN112779050A (en) | 2019-11-11 | 2019-11-11 | Processing method of poor-quality catalytic diesel oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112779050A true CN112779050A (en) | 2021-05-11 |
Family
ID=75749862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911098862.1A Pending CN112779050A (en) | 2019-11-11 | 2019-11-11 | Processing method of poor-quality catalytic diesel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112779050A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333777A (en) * | 2021-12-24 | 2023-06-27 | 中国石油天然气股份有限公司 | Method for catalyzing diesel oil hydrocracking and catalytic cracking product obtained by same |
| CN116355651A (en) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for lightening catalytic diesel oil and obtained product |
| CN116410793A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Combined processing method of light diesel oil |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745412A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN102219243A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing mesoporous aluminum oxide |
| CN102443436A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Combining method for residual oil hydroprocessing and catalytic-cracking, and aromatics extraction |
| CN103084205A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen liquefied gas yield increase cracking catalyst and preparation method thereof |
| CN103305272A (en) * | 2012-03-16 | 2013-09-18 | 中国石油化工股份有限公司 | Catalytic conversion method for reducing yield of cokes |
| CN103805247A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Combination method used for processing inferior diesel oil |
| CN106467757A (en) * | 2015-08-21 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of heavy oil separation-hydrogenation and catalystic cracking combined method |
| CN109988650A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Hydro-upgrading of inferior diesel and hydrofinishing combined method |
-
2019
- 2019-11-11 CN CN201911098862.1A patent/CN112779050A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745412A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN102219243A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing mesoporous aluminum oxide |
| CN102443436A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Combining method for residual oil hydroprocessing and catalytic-cracking, and aromatics extraction |
| CN103084205A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen liquefied gas yield increase cracking catalyst and preparation method thereof |
| CN103305272A (en) * | 2012-03-16 | 2013-09-18 | 中国石油化工股份有限公司 | Catalytic conversion method for reducing yield of cokes |
| CN103805247A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Combination method used for processing inferior diesel oil |
| CN106467757A (en) * | 2015-08-21 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of heavy oil separation-hydrogenation and catalystic cracking combined method |
| CN109988650A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Hydro-upgrading of inferior diesel and hydrofinishing combined method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333777A (en) * | 2021-12-24 | 2023-06-27 | 中国石油天然气股份有限公司 | Method for catalyzing diesel oil hydrocracking and catalytic cracking product obtained by same |
| CN116355651A (en) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for lightening catalytic diesel oil and obtained product |
| CN116410793A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Combined processing method of light diesel oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103121897B (en) | By the method for the mixture preparing aromatic hydrocarbon containing hydrocarbon with condensed rings | |
| CN112779050A (en) | Processing method of poor-quality catalytic diesel oil | |
| CN108624357B (en) | Catalytic diesel oil conversion process | |
| CN105802665B (en) | A kind of method for hydrogen cracking and reaction unit of maximum volume production heavy naphtha | |
| CN108624356B (en) | Catalytic diesel oil hydro-conversion process | |
| CN108795495B (en) | Method for treating diesel raw material | |
| CN104593068B (en) | A method of producing gasoline with a high octane number from residual oil | |
| CN112745922B (en) | Hydrocracking method for poor-quality diesel raw material | |
| CN113881457A (en) | Method for treating distillate oil rich in aromatic hydrocarbon | |
| CN107557064B (en) | Coal tar combined bed hydrogenation method and system for coal tar combined bed hydrogenation | |
| CN112745920B (en) | Hydrocracking method for producing high-octane gasoline | |
| CN114437803B (en) | Hydrotreatment method of catalytic diesel | |
| CN104611062B (en) | A kind of high-knock rating gasoline production method | |
| CN109988625B (en) | Hydrofining and hydrocracking combined process | |
| CN112877090A (en) | Coal direct liquefaction circulating solvent and preparation method and system thereof | |
| CN115141651B (en) | System and method for intensified production of chemical raw materials in aromatic fraction-rich oil region | |
| CN108102703B (en) | Processing method of catalytic diesel oil | |
| CN115703977B (en) | Method for producing light aromatic hydrocarbon and clean fuel oil | |
| CN115646540B (en) | Composite hydrocracking catalyst, preparation method thereof and preparation method of transformer oil | |
| CN103805256A (en) | Reaction distillation method of catalytic diesel oil | |
| CN103059951A (en) | Catalytic cracking and catalytic gasoline hydrogenation combined technological method | |
| CN111518590B (en) | Process and system for producing gasoline and aromatic hydrocarbon in high yield | |
| CN108239555A (en) | Processing method of poor quality catalytic cracking raw material | |
| CN111826195B (en) | Naphtha hydroisomerization conversion method | |
| CN102559259A (en) | Method for hydrotreatment of secondary processed inferior gasoline fraction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210511 |
|
| RJ01 | Rejection of invention patent application after publication |