CN107446618B - A kind of method of hydrotreating of Fischer-Tropsch synthesis oil - Google Patents
A kind of method of hydrotreating of Fischer-Tropsch synthesis oil Download PDFInfo
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- CN107446618B CN107446618B CN201610365749.5A CN201610365749A CN107446618B CN 107446618 B CN107446618 B CN 107446618B CN 201610365749 A CN201610365749 A CN 201610365749A CN 107446618 B CN107446618 B CN 107446618B
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- molecular sieve
- ammonium
- oil
- sodium
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- 238000000034 method Methods 0.000 title claims abstract description 77
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 51
- 239000002283 diesel fuel Substances 0.000 claims abstract description 26
- 239000003245 coal Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims abstract description 6
- 230000003247 decreasing effect Effects 0.000 claims abstract description 3
- 238000005194 fractionation Methods 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 62
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 62
- 239000003921 oil Substances 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 159000000000 sodium salts Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000003863 ammonium salts Chemical class 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000000295 complement effect Effects 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 9
- 230000005494 condensation Effects 0.000 abstract description 9
- 238000007710 freezing Methods 0.000 abstract description 5
- 230000008014 freezing Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 18
- 238000007598 dipping method Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 238000005336 cracking Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000002803 maceration Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000005360 mashing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000013589 supplement 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- 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
- C10G2300/70—Catalyst aspects
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a kind of method of hydrotreating of Fischer-Tropsch synthesis oil, including following content: (1) F- T synthesis oil-producing and hydrogen are mixed into hydrocracking reactor, it is reacted under the action of hydrocracking catalyst, the average pore size of the hydrocracking catalyst is in decreasing trend along stream flow direction；(2) hydrogenation effluent of step (1) is separated into gas phase and liquid phase, and gas phase is recycled, and liquid phase enters fractionating column；(3) fractionation obtains naphtha, boat coal, diesel oil and tail oil in fractionating column；Tail oil is recycled to hydrocracking reactor.Light oil yield can be greatly improved in this method, reduce boat coal freezing point and condensation point of diesel oil.
Description
Technical field
The present invention relates to a kind of hydrogenation of Fischer-Tropsch synthesis oil methods, and it is excellent to relate in particular to a kind of hydrogenation of Fischer-Tropsch synthesis oil production
The method of matter clean fuel.
Background technique
With the fast development of car industry, aircraft industry etc., supply falls short of demand for natural oil, and countries in the world all joined coal liquid
The research ranks for changing new technology make coal base synthesis (F-T synthesis) fuel oil " CTL " gradually put on industrialization schedule.Switch through by
Fischer-Tropsch synthesis oil is converted the chemical products such as gasoline, diesel oil, wax, ethylene, propylene, polymer, ammonia, alcohol, aldehyde, ketone by change technology.
The oil product of ICL for Indirect Coal Liquefaction (F-T) synthesis, composition and property and natural oil have very big difference: without impurity such as sulphur, nitrogen-frees,
The features such as (nothing) cyclic hydrocarbon, high linear paraffin, product condensation point is high, and density is small.Therefore, F-T synthetic oil only has hydrofinishing or adds
Hydrogen cracking could produce qualified automotive fuel.
CN200510028649.5 discloses a kind of method that Fischer-Tropsch synthetic produces diesel oil or diesel component, this method
The whole or lighter part of Fischer-Tropsch synthetic is subjected to hydrotreating, the Fischer-Tropsch synthetic of hydrotreating is part or all of
And/or the heavier part of Fischer-Tropsch synthetic of non-hydrotreating is hydrocracked, product is fractionated obtained heavy end
It is recycled to hydrocracking reactor.This method is complicated for operation, although condensation point of diesel oil can be effectively reduced, reduces limited extent.
CN201310089452.7, which is disclosed, a kind of converts naphtha, diesel oil and liquefied petroleum gas for Fischer-Tropsch synthetic
Method, this method separates after Fischer-Tropsch synthetic is entered hydrofining reactor, obtains purification naphtha, purification bavin
Oil, purification heavy diesel fuel and purification tail oil, purification tail oil enter hydrocracking reactor and carry out hydrocracking reaction, reaction product point
From pressure naphtha, cracking oil-producing, cracking heavy diesel fuel and cracking tail oil is obtained, wherein purification heavy diesel fuel and the mixing of cracking heavy diesel fuel
Low freezing point diesel fuel is obtained into pour point depression reactor.Although condensation point of diesel oil, but complex process can be effectively reduced in this method, operation is difficult
Degree is big and plant investment is higher.
US5378348 discloses a kind of raw with hydroisomerisation process by being hydrocracked by raw material of Fischer-Tropsch synthetic
Produce intermediate oil method, this method by the way that Fischer-Tropsch synthetic is divided into three naphtha, light fraction, heavy distillat fractions,
Heavy distillat carries out hydrocracking reaction, and unconverted heavy end is recycled back to hydrocracking reactor and continues cracking.Due to the party
Method increases isomerization-visbreaking reaction process and fractionating column, keeps its process flow complex；Increase isomerization-visbreaking section, catalyst
Dosage is also significantly increased；Unifining process generates water and enters directly into isomerization-visbreaking reactor, and isomerization-visbreaking is catalyzed
Agent has certain influence；Midbarrel oil yield is not also high.
US6656342 discloses a kind of plus hydrogen upgrading Fischer-Tropsch synthetic method, and this method produces Fischer-Tropsch synthesis
Object be divided into it is light, weigh two fractions, two fractions of weight carry out hydrogenation reaction in two reaction zones respectively.Heavy distillat enters reactor
Upper catalyst bed layer, primary the protective agent bed and hydrocracking catalyst bed different by partial size；Light fraction is being reacted
Device middle and lower part enters, and enters after hydrotreating catalyst bed after mixing with the reactant for carrying out autoreactor top bed layer and divides
System is evaporated, unconverted heavy distillat can be recycled back to reactor, and the reaction was continued.In this method, light fraction is without Cracking catalyst
Bed improves the yield of light oil distillate, but two reaction zones, in same reactor, the reaction conditions such as pressure are convergent；If
Standby investment is high, complicated for operation.
US6309432 discloses a kind of method for processing upgrading Fischer-Tropsch synthesis oil, which is first cut into Fischer-Tropsch synthesis oil
Two fractions of weight, heavy end first pass through and are mixed into fractionating system with light fraction after hydroisomerizing cracker.By
Alkene and oxygen content are higher in Fischer-Tropsch synthesis oil, directly contacted with isocraking catalyst the stability that will affect catalyst and
Operation cycle, and product quality is poor.
CN200510068181.2 provides a kind of method of integrated form hydrogenation of Fischer-Tropsch synthesis oil upgrading, and this method will first take
Enter fractionating column, the product of isolated different fractions after holding in the palm synthetic oil whole fraction oil hydrotreating, tail oil, which enters, to be hydrocracked instead
Device is answered to be converted into midbarrel product for heavy end is the maximum amount of.Its shortcoming is using integrated form process, flexible operation
Property is smaller, and diesel product condensation point is higher, and yield is low.
CN200510068183.1 provides the process that a kind of Fischer-Tropsch synthetic adds hydrogen upgrading, is by F- T synthesis
Three components such as high temperature condensate, low temperature cold condensate and the synthetic wax that reaction natural separation obtains add hydrogen respectively, and high temperature is cold
Hydrotreating reactor is added in condensate and the mixing of low temperature cold condensate, and reaction effluent enters the isolated each fraction of fractionating column and produces
Object, wherein tower bottom heavy end and synthetic wax are mixed into hydroisomerizing cracker.But disadvantage is that Fischer-Tropsch is cold
Condensate individually removes hydrofining reactor, and catalyst is easy coking；Synthetic wax, directly into being hydrocracked, causes not into hydrofinishing
Investment is hydrocracked to increase；The condensation point of diesel product is not can guarantee simultaneously.
US6863802 discloses a kind of by Fischer-Tropsch synthesis oil and fraction oil of petroleum production gasoline, distillate, crude lube stock
The technique of component, this method are to mix Fischer-Tropsch distillate and fraction oil of petroleum to obtain fuel by adding the method for hydrogen upgrading again
Or crude lube stock.But this method is still using petroleum base crude oil as the feedstock oil of production diesel oil.
CN200710065309 discloses a kind of hydroprocessing technique of Fischer-Tropsch synthesis oil, which is by Fischer-Tropsch synthesis oil
Full fraction carries out hydrotreating first, the first diesel oil distillate of product is then demultiplex out, tail oil is hydrocracked again, crackate
The second diesel oil distillate is isolated again, but this method equipment investment is high, it is complicated for operation, and can only production section low-coagulation diesel oil.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of side that Fischer-Tropsch synthetic adds hydrogen to produce high-grade fuel oil
Fischer-Tropsch synthetic is directly entered hydrocracking reactor by method, this method, and hydrocracking reactor effluent enters fractionating column and obtains
To the product of different fractions.Light oil yield can be greatly improved in this method, reduce boat coal freezing point and condensation point of diesel oil.
A kind of method of hydrotreating of Fischer-Tropsch synthesis oil, including following content:
(1) F- T synthesis oil-producing and hydrogen are mixed into hydrocracking reactor, under the action of hydrocracking catalyst
It is reacted, the average pore size of the hydrocracking catalyst is in decreasing trend along stream flow direction；
(2) hydrogenation effluent of step (1) is separated into gas phase and liquid phase, and gas phase is recycled, and liquid phase enters fractionating column；
(3) fractionation obtains naphtha, boat coal, diesel oil and tail oil in fractionating column；Tail oil is recycled to hydrocracking reactor.
In the method for the present invention, the Fischer-Tropsch synthesis oil includes that high temperature fischer-tropsch synthetic oil or Low Temperature Fischer Tropsch synthetic oil, high temperature take
Support synthetic oil preferably first passes through the oxygen in hydrofinishing removing raw material.The F- T synthesis oil-producing property is as follows: density 0.8g/
cm3~1.0 g/cm3, preferably 0.5g/cm3~0.95 g/cm3；Oxygen content is 0 ~ 2m%, preferably 0.2 ~ 0.5 m%；650 DEG C of the end point of distillation
~750 DEG C, preferably 680 DEG C~720 DEG C.
In the method for the present invention, hydrocracking operation condition is as follows: 5.0~35.0MPa of reaction pressure, preferably 6.0~
19.0MPa；Reaction temperature is 200 DEG C~480 DEG C, preferably 270 DEG C~450 DEG C；Volume space velocity is 0.1~15.0h-1, preferably 0.2
~3.0h-1；Hydrogen to oil volume ratio is 100:1~2500:1, preferably 400:1~2000:1.
In the method for the present invention, hydrocracking catalyst sets at least to two layers or more.When being set as a point upper layer and lower layer and loading
Admission space ratio is 1:5 ~ 5:1, preferably 1:2 ~ 2:1；The average pore size of upper layer hydrocracking catalyst is hydrocracked compared to lower layer
High 0.5 ~ the 5nm of the average pore size of catalyst, preferably 1 ~ 2 nm.The average pore size of upper layer hydrocracking catalyst is 7-11nm.
In the method for the present invention, the hydrocracking catalyst by weight, including following component: carrier 55% ~ 85%, with oxygen
The group VIII and/or vib metals 15% ~ 45% of compound meter；Wherein the carrier is Y molecular sieve, amorphous silicon aluminium, oxygen
Change one or more of aluminium.When if carrier containing Y molecular sieve, the mass percent of molecular sieve in the carrier is 30% ~ 70%,
Surplus is amorphous silica-alumina and/or aluminium oxide.The group VIII metal can be Ni and/or Co, and group VIB active metal can
To be W and/or Mo, in terms of metal oxide, group VIII tenor be 3% ~ 15%, vib metals content be 10% ~
40%。
In the method for the present invention, the hydrocracking catalyst is prepared using commercial goods or by the prior art.Such as
Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide are uniformly mixed, dust technology is added, rear extruded moulding is slurried, through drying, roasting
Obtain the carrier containing Y molecular sieve.Using the maceration extract containing group VIII and/or vib metals to the carrier containing Y molecular sieve into
Row impregnates, and the carrier after dipping obtains hydrocracking catalyst through drying, roasting.Containing group VIII and/or vib metals
The liquid-solid ratio that impregnates when being impregnated to carrier of maceration extract be 1.5:1 ~ 3:1.The content of group vib metallic compound in maceration extract
It is calculated as 20 ~ 60g/100ml by corresponding oxide, the content of group VIII metallic compound is calculated as 3 ~ 20g/ by corresponding oxide
100ml, the concentration of metallic compound can need adjust accordingly according to product in maceration extract.The dried strip after dipping
Part are as follows: 2 ~ 8 hours dry at 90 ~ 150 DEG C；Roasting condition are as follows: roasted 1 ~ 5 hour at 400 ~ 700 DEG C.
In the method for the present invention, modified Y molecular sieve is contained in the hydrocracking catalyst of upper layer, the modified Y molecular sieve property is such as
Under, 500 ~ 800m of specific surface area20.4 ~ 0.6ml/g of/g, Kong Rong, wherein the secondary pore of 2 ~ 7nm holds 40% or more accounting, meleic acid
Measure 0.6 ~ 1.2mmol/g, Na2O mass content is less than 0.15%, SiO2/Al2O3Molar ratio 8 ~ 40, lattice constant 2.430 ~
The product that the secondary pore of 2.445,2 ~ 7nm holds accounting syncrystallization degree is 38% ~ 60%.
The preparation of above-mentioned modified Y molecular sieve, includes the following steps:
(1) Ammonium Salt Ionic is carried out in ammonium salt solution using NaY zeolite as original powder to exchange to Na2O weight content is less than 3.5%；
(2) to ammonium obtained in step (1) exchange after Y molecular sieve temperature be 500 ~ 620 DEG C, pressure be 0.01 ~
0.3MPa, processing time are 1.0 ~ 4.0 hours；
(3) the hydro-thermal process Y molecular sieve that step (2) obtains carries out sodium ion exchange in sodium salt solution；
(4) after the Y molecular sieve for obtaining step (3) carries out the processing of ammonium fluosilicate dealumination complement silicon, through filtering, drying, roasting
After obtain final Modified Zeolite Y.
The preparation of above-mentioned modified Y molecular sieve, Ammonium Salt Ionic exchange process described in step (1) are as follows: being original with NaY zeolite
Material is in ammonium salt aqueous solution, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, and exchange times are 1 ~ 2 time, are handed over
NaY zeolite after changing, Na2O content 1.3 ~ 2.8%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, and sodium oxide molybdena quality percentage contains
Amount 6% ~ 7%；Ammonium salt is one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, and ammonium salt aqueous solution is dense
Spend 0.3 ~ 6.0mol/L, preferably 1.0 ~ 3.0 mol/L.
The preparation of above-mentioned modified Y molecular sieve, sodium salt ion exchange process described in step (3) are as follows: with water in step (2)
Hot Y molecular sieve is raw material in sodium-salt aqueous solution, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, is exchanged 1 ~ 3 hour, exchange times are
1 ~ 4 time, the NaY zeolite after being exchanged, Na2O mass content is not less than 3.0%；Sodium salt be sodium chloride, sodium nitrate, sodium sulphate,
One or more of sodium citrate, sodium oxalate, sodium-salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L.It is excellent
It is selected in the removing for adding the non-framework aluminum that glycerine promotes hydrothermal treatment process to generate in sodium salt solution and improves sodium salt exchange effect
Rate, glycerol concentration is 0.1 ~ 2.0 in sodium salt solution, preferably 0.1-0.5 mol/L.
The preparation of above-mentioned modified Y molecular sieve, the processing of dealumination complement silicon described in step (4) is known to those skilled in the art
Method, mass ratio can be consolidated according to liquid using conventional ammonium fluosilicate dealumination complement silicon method, the Y molecular sieve that step (3) is obtained
3:1 ~ 20:1, preferably 5:1 ~ 10:1 are mixed with ammonium fluosilicate aqueous solution, and wherein ammonium fluosilicate concentration is in ammonium fluosilicate solution
0.01 ~ 1.0mol/L, preferably 0.1 ~ 0.8 mol/L are handled 0.5 ~ 6 hour in 50 ~ 100 DEG C.
The preparation of above-mentioned modified Y molecular sieve, during the ammonium fluosilicate dealumination complement silicon in step (4), ammonium fluosilicate solution
In can to add the inorganic acids such as nitric acid, hydrochloric acid, acetic acid, citric acid, oxalic acid or organic acid non-in molecular sieve preferably to remove
The concentration of framework aluminum, inorganic acid and/or organic acid is with H+It is calculated as 0.1 ~ 0.7mol/L, preferably 0.2 ~ 0.5mol/L.
The preparation process of above-mentioned modified Y molecular sieve by exchanging NaY original powder ammonia to reduce molecular sieve Na content, mentions first
High hydro-thermal process efficiency, and reduce hydrothermal treatment process skeleton extent of the destruction.Y molecular sieve after hydro-thermal process by supplement Na from
Son promotes the dealumination complement silicon of subsequent ammonium fluosilicate treatment process to react and carries out.Therefore, while hydro-thermal process and fluosilicic acid being improved
The reaction efficiency of ammonium, modified Y molecular sieve remain hydrothermal treatment process secondary pore and hold big and ammonium fluosilicate treatment process in depth
Spend dealuminzation and the high feature of skeleton crystal degree.
Fischer-Tropsch synthetic is by being hydrocracked or hydro-upgrading can produce high smoke point and navigate coal and high cetane number diesel oil
Component, but since Fischer-Tropsch synthetic boiling range span is larger, wherein midbarrel and heavy end are rich in, in hydrocracking process
In, since macromolecular substances polarity is big, it is easier to it is adsorbed on catalyst surface and cracking reaction occurs, and midbarrel is inhaled by competition
It is attached influence and in the biggish catalyst duct of catalyst molecule mesh size the residence time it is shorter, cause to react insufficient, and
This part is mainly enriched in boat coal and the diesel oil distillate in isocrackate by the midbarrel that linear paraffin forms, thus
Boat coal freezing point and condensation point can not be effectively reduced.Upper layer hydrocracking catalyst changes rich in the high silicon of meso-hole structure, high-crystallinity
Property Y molecular sieve, the secondary pore formed between Y molecular sieve is that being hydrocracked for macromolecular alkane provides place, makes it in Y
The outer surface of molecular sieve is cracked, while the microcellular structure of Y molecular sieve can be such that the small-molecule substance in raw material sufficiently occurs
Reaction, is translated into isoparaffin, the effective freezing point and condensation point of diesel oil for improving product Air China coal.
Specific embodiment
The technical characterstic of the method for the present invention is further described by embodiment in next step, but following embodiment cannot limit this
Invention.% is such as mass percentage without special marking in Examples and Comparative Examples.Wherein embodiment 1-3 is that upper layer adds hydrogen to split
Change the preparation of catalyst.
Embodiment 1
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 2.0mol/L with concentration is according to liquid-solid ratio
4:1 mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 1.8%；
(2) 550 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 2 hours under 0.3Mpa；
(3) sodium chloride solution that the Y molecular sieve obtained to step (2) is 1.7mol/L with concentration is mixed according to liquid-solid ratio 5:1
It closes, 65 DEG C exchange 1 hour, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 3.8%；
(4) ammonium fluosilicate and 0.3mol/L lemon of step (3) the resulting molecular sieve according to liquid-solid ratio 5:1 and 0.5mol/L
Acid is (with H+Meter) solution be mixed with beating, 85 DEG C handle 2 hours；
(5) through step (4) treated Y molecular sieve, 120 DEG C drying 2 hours, obtain molecular sieve, number Y-1, property
It is shown in Table 1.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water
Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, molten
Liquid number RY-1；
(2) Y-1 60g is taken to mix with 40g macroporous aluminium oxide, addition 4g/100ml dust technology mixes in a mixer to roll
To extrudable shape, extruded moulding obtains carrier T-1 on banded extruder；
(3) T-1 60g is taken 120ml RY-1 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings
It burns 3 hours, obtains hydrocracking catalyst, number Cat-1, average pore size 10.7nm.
Embodiment 2
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium chloride for being 2.5mol/L with concentration is according to liquid-solid ratio
5:1 mixing, 85 DEG C exchange 2 hours, repeat this process 2 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 1.3%；
(2) 530 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 1.5 hours under 0.15Mpa；
(3) Y molecular sieve that step (2) obtains is mixed with the sodium nitrate that concentration is 1.5mol/L according to liquid-solid ratio 5:1,80
It DEG C exchange 1 hour, repeats this process 2 times, Na content is calculated as 3.6% with Na2O in the Y molecular sieve after exchange；
(4) step (3) resulting molecular sieve is mixed according to liquid-solid ratio 5:1 with the ammonium fluosilicate solution that concentration is 0.5mol/L
Mashing, 95 DEG C are handled 2 hours；
(5) through step (6) ammonium fluosilicate treated Y molecular sieve, 120 DEG C of dryings, 2 hours acquisition molecular sieves, number Y-
2, property is shown in Table 1.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water
Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, molten
Liquid number RY-2；
(2) Y-2 40g is taken to mix with 60g macroporous aluminium oxide, addition 4g/100ml dust technology mixes in a mixer to roll
To extrudable shape, extruded moulding obtains carrier T-2 on banded extruder；
(3) T-2 60g is taken 120ml RY-2 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings
It burns 3 hours, obtains hydrocracking catalyst, number Cat-2, average pore size 8.5nm.
Embodiment 3
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 1.6mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%；
(2) 550 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 2 hours under 0.2Mpa；
(3) Y molecular sieve obtained to step (2) is respectively 3.0mol/L and 0.2mol/L with containing sodium nitrate and glycerine
Mixed solution is mixed according to liquid-solid ratio 5:1, and 80 DEG C exchange 1 hour, is repeated this process 2 times, Na content in the Y molecular sieve after exchange
With Na2O is calculated as 5.3%；
(4) step (3) resulting molecular sieve is mixed according to the ammonium fluosilicate solution that liquid-solid ratio 10:1 and concentration are 0.7mol/L
Mashing is closed, 85 DEG C are handled 2 hours；
(5) through step (4) ammonium fluosilicate treated Y molecular sieve, 120 DEG C drying 2 hours, obtain molecular sieve, number is
Y-3, property are shown in Table 1.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water
Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, molten
Liquid number RY-3；
(2) Y-3 50g is taken to mix with 50g macroporous aluminium oxide, addition 4g/100ml dust technology mixes in a mixer to roll
To extrudable shape, extruded moulding obtains carrier T-3 on banded extruder；
(3) T-3 60g is taken 120ml RY-3 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings
It burns 3 hours, obtains hydrocracking catalyst, number Cat-3, average pore size 7.4nm.
Table 1
Embodiment 4-8
Raw material oil nature is shown in Table 2, and commercially available hydrocracking catalyst is the FC-14 that Fushun Petrochemical Research Institute develops
Catalyst series hydrocracking catalyst, property are shown in Table 3, and the filling of catalyst and process conditions are shown in Table 4, evaluation result is shown in Table 5,
Table 6, table 7.
2 raw material main character of table
The main physico-chemical property of 3 catalyst of table
Embodiment 4
Hydrocracking reactor from top to bottom successively loading catalyst aperture descending FC-14A, FC-14B, FC-
Tri- kinds of catalyst of 14C.
Comparative example 1
Hydrocracking reactor only loads a kind of FC-14A catalyst of large aperture.
4 technological condition of table
The main character of 5 heavy naphtha of table
The main character of the boat coal of table 6
7 product diesel oil main character of table
Embodiment 5
Hydrocracking reactor from top to bottom successively urge by descending bis- kinds of Cat-1, FC-14A in loading catalyst aperture
Agent, admission space ratio are 1:2, and operating condition is constant, and evaluation result is shown in Table 8, table 9, table 10.
The main character of 8 heavy naphtha of table
The main character of the boat coal of table 9
10 product diesel oil main character of table
Embodiment 6
Hydrocracking reactor from top to bottom successively urge by descending bis- kinds of Cat-2, FC-14B in loading catalyst aperture
Agent, admission space ratio are 2:1, and operating condition is constant, evaluation results are shown in Table 11, table 12, table 13.
The main character of 11 heavy naphtha of table
The main character of the boat coal of table 12
13 product diesel oil main character of table
Embodiment 7
Hydrocracking reactor from top to bottom successively urge by descending bis- kinds of Cat-3, FC-14C in loading catalyst aperture
Agent, admission space ratio are 3:1, and operating condition is constant, evaluation results are shown in Table 14, table 15, table 16.
The main character of 14 heavy naphtha of table
The main character of the boat coal of table 15
16 product diesel oil main character of table
Fischer-Tropsch synthetic passes through the available good boat coal of this technology, bavin it can be seen from Examples and Comparative Examples
Oily blend component, and plant investment is at low cost, it is easy to operate.
Claims (15)
1. a kind of method of hydrotreating of Fischer-Tropsch synthesis oil, it is characterised in that: including following content:
(1) Fischer-Tropsch synthesis oil and hydrogen are mixed into hydrocracking reactor, carry out under the action of hydrocracking catalyst anti-
It answers, the average pore size of the hydrocracking catalyst is in decreasing trend along stream flow direction；
(2) hydrogenation effluent of step (1) is separated into gas phase and liquid phase, and gas phase is recycled, and liquid phase enters fractionating column；
(3) fractionation obtains naphtha, boat coal, diesel oil and tail oil in fractionating column；Tail oil is recycled to hydrocracking reactor.
2. according to the method described in claim 1, it is characterized by: the F- T synthesis oil nature is as follows: density 0.8g/cm3
~1.0 g/cm3；Oxygen content is 0 ~ 2m%；650 DEG C~750 DEG C of the end point of distillation.
3. according to the method described in claim 1, it is characterized by: hydrocracking operation condition is as follows: reaction pressure 5.0~
35.0MPa；Reaction temperature is 200 DEG C~480 DEG C；Volume space velocity is 0.1~15.0h-1；Hydrogen to oil volume ratio is 100:1~2500:
1。
4. according to the method described in claim 1, it is characterized by: hydrocracking catalyst sets at least to two layers or more.
5. according to the method described in claim 1, it is characterized by: hydrocracking catalyst is set as upper layer and lower layer filling fashionable dress
Filling out volume ratio is 1:5 ~ 5:1；The average pore size of upper layer hydrocracking catalyst compares the average hole of lower layer's hydrocracking catalyst
High 0.5 ~ the 5nm of diameter, the average pore size of upper layer hydrocracking catalyst are 7-11nm.
6. according to the method described in claim 1, it is characterized by: the hydrocracking catalyst by weight, including it is as follows
Component: carrier 55% ~ 85%, group VIII and/or vib metals 15% ~ 45% in terms of oxide；Wherein the carrier is
One or more of Y molecular sieve, amorphous silicon aluminium, aluminium oxide.
7. according to the method described in claim 6, it is characterized by: molecular sieve is in the carrier when if carrier containing Y molecular sieve
Mass percent be 30% ~ 70%, surplus be amorphous silica-alumina and/or aluminium oxide.
8. according to the method described in claim 6, it is characterized by: the group VIII metal is Ni and/or Co, group VIB
Active metal is W and/or Mo, and in terms of metal oxide, group VIII tenor is 3% ~ 15%, and vib metals content is
10%~40%。
9. according to the method described in claim 5, it is characterized by: containing modified Y molecular sieve, institute in the hydrocracking catalyst of upper layer
It is as follows to state modified Y molecular sieve property, 500 ~ 800m of specific surface area20.4 ~ 0.6ml/g of/g, Kong Rong, wherein the secondary pore of 2 ~ 7nm holds
40% or more accounting, meleic acid amount 0.6 ~ 1.2mmol/g, Na2O mass content is less than 0.15%, SiO2/Al2O3Molar ratio 8 ~
40, lattice constant 2.430 ~ 2.445, the product that the secondary pore of 2 ~ 7nm holds accounting syncrystallization degree is 38% ~ 60%.
10. according to the method described in claim 9, it is characterized by: the preparation of modified Y molecular sieve, includes the following steps:
(1) Ammonium Salt Ionic is carried out in ammonium salt solution using NaY zeolite as original powder to exchange to Na2O weight content is less than 3.5%；
It (2) is 500 ~ 620 DEG C in temperature to the Y molecular sieve after ammonium obtained in step (1) exchange, pressure is 0.01 ~ 0.3MPa,
Handling the time is 1.0 ~ 4.0 hours；
(3) the hydro-thermal process Y molecular sieve that step (2) obtains carries out sodium ion exchange in sodium salt solution；
(4) after the Y molecular sieve for obtaining step (3) carries out the processing of ammonium fluosilicate dealumination complement silicon, after filtering, drying, roasting
To final Modified Zeolite Y.
11. according to the method described in claim 10, it is characterized by: Ammonium Salt Ionic exchange process described in step (1) is as follows:
It is raw material in ammonium salt aqueous solution using NaY zeolite, at 60 ~ 120 DEG C, exchanges 1 ~ 3 hour, exchange times is 1 ~ 2 time, are exchanged
NaY zeolite afterwards, Na2O content 1.3 ~ 2.8%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, sodium oxide molybdena mass percentage
6%~7%；Ammonium salt is one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution concentration
0.3~6.0mol/L。
12. according to the method described in claim 10, it is characterized by: sodium salt ion exchange process described in step (3) is as follows:
It is raw material in sodium-salt aqueous solution using hydro-thermal Y molecular sieve in step (2), at 60 ~ 120 DEG C, exchanges 1 ~ 3 hour, exchange times 1
~ 4 times, the NaY zeolite after being exchanged, Na2O mass content is not less than 3.0%；Sodium salt is sodium chloride, sodium nitrate, sodium sulphate, lemon
One or more of lemon acid sodium, sodium oxalate, 0.3 ~ 6.0mol/L of sodium-salt aqueous solution concentration.
13. according to the method for claim 12, it is characterised in that: add glycerine in sodium-salt aqueous solution, glycerine is dense
Degree is 0.1 ~ 2.0 mol/L.
14. according to the method described in claim 10, it is characterized by: the processing of dealumination complement silicon described in step (4) is ability
Method known to field technique personnel, the Y molecular sieve that step (3) is obtained consolidate mass ratio 3:1 ~ 20:1 and ammonium fluosilicate water according to liquid
Solution mixing, wherein ammonium fluosilicate concentration is 0.01 ~ 1.0mol/L in ammonium fluosilicate solution, small in 50 ~ 100 DEG C of processing 0.5 ~ 6
When.
15. according to the method described in claim 10, it is characterized by: during ammonium fluosilicate dealumination complement silicon in step (4),
The concentration of addition inorganic acid or organic acid in ammonium fluosilicate solution, inorganic acid and/or organic acid is with H+It is calculated as 0.1 ~ 0.7mol/L.
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| US7323100B2 (en) * | 2004-07-16 | 2008-01-29 | Conocophillips Company | Combination of amorphous materials for hydrocracking catalysts |
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| US6589415B2 (en) * | 2001-04-04 | 2003-07-08 | Chevron U.S.A., Inc. | Liquid or two-phase quenching fluid for multi-bed hydroprocessing reactor |
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| CN101177619A (en) * | 2007-04-13 | 2008-05-14 | 中科合成油技术有限公司 | Method for producing diesel oil and chemical materials by f-t synthetic wax |
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