CN101370913A - 烃溶性钼催化剂前体及其制备方法 - Google Patents
烃溶性钼催化剂前体及其制备方法 Download PDFInfo
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- CN101370913A CN101370913A CNA2007800020003A CN200780002000A CN101370913A CN 101370913 A CN101370913 A CN 101370913A CN A2007800020003 A CNA2007800020003 A CN A2007800020003A CN 200780002000 A CN200780002000 A CN 200780002000A CN 101370913 A CN101370913 A CN 101370913A
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- molybdenum
- catalyst precursor
- organic
- acid
- reaction
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 118
- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 114
- 239000011733 molybdenum Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims description 45
- 239000000295 fuel oil Substances 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 230000002829 reductive effect Effects 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 26
- -1 molybdenum cations Chemical class 0.000 claims abstract description 20
- 150000002891 organic anions Chemical class 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 35
- 229930195733 hydrocarbon Natural products 0.000 claims description 34
- 239000004215 Carbon black (E152) Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 10
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 10
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 9
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 claims description 8
- OVBFMEVBMNZIBR-UHFFFAOYSA-N 2-methylvaleric acid Chemical compound CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 claims description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229940005605 valeric acid Drugs 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 46
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 77
- 235000016768 molybdenum Nutrition 0.000 description 53
- 239000002243 precursor Substances 0.000 description 27
- 150000002430 hydrocarbons Chemical class 0.000 description 24
- 238000004517 catalytic hydrocracking Methods 0.000 description 22
- 239000002994 raw material Substances 0.000 description 18
- 238000012545 processing Methods 0.000 description 16
- 238000009835 boiling Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000000084 colloidal system Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000005078 molybdenum compound Substances 0.000 description 6
- 150000002752 molybdenum compounds Chemical class 0.000 description 6
- VXIWJTFRRIZCQJ-UHFFFAOYSA-N 2-ethylhexanoic acid;molybdenum Chemical compound [Mo].CCCCC(CC)C(O)=O VXIWJTFRRIZCQJ-UHFFFAOYSA-N 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 5
- 150000003624 transition metals Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical group CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 238000005162 X-ray Laue diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- AGNOBAWAZFBMMI-UHFFFAOYSA-N dicesium dioxido(dioxo)molybdenum Chemical compound [Cs+].[Cs+].[O-][Mo]([O-])(=O)=O AGNOBAWAZFBMMI-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000002584 immunomodulator Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- RLCOZMCCEKDUPY-UHFFFAOYSA-H molybdenum hexafluoride Chemical compound F[Mo](F)(F)(F)(F)F RLCOZMCCEKDUPY-UHFFFAOYSA-H 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- YJBMMHPCGWCCOH-UHFFFAOYSA-N octan-3-yl dihydrogen phosphate Chemical compound CCCCCC(CC)OP(O)(O)=O YJBMMHPCGWCCOH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002028 premature Effects 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
- 238000005086 pumping Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 239000008096 xylene 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
- C10G47/06—Sulfides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0021—Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
-
- 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
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
-
- 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
- C10G2300/4037—In-situ processes
-
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Abstract
烃溶性钼催化剂前体含有大量钼阳离子,这些阳离子各自结合多个有机阴离子形成油溶性钼盐。部分钼原子处于3+氧化态,因此,大量钼原子的平均氧化态低于4+,例如低于3.8+,尤其是,低于3.5+。所述催化剂前体可在重油原料中形成硫化钼氢加工催化剂。所述油溶性钼盐在氢气等还原剂存在下制备以获得所需氧化态的钼。较好的是,用氢气或有机还原剂并在适当温度下进行反应从而将钼原子还原至基本上不含任何氧化钼。
Description
技术领域
本发明涉及将重油原料提升为低沸点高质量原料的领域。更具体地说,本发明涉及含有钼盐的催化剂前体及其制备方法,所述催化剂前体可与重油混合而原位形成氢加工催化剂。
背景技术
精炼化石燃料的世界需求量日益增长,势必超出优质原油的供应量。随着优质原油短缺的日益加剧,亟需找到更好的方法来利用低品质原料从中制取可用燃料。
低质原料的特点在于含有大量沸点达524℃(975℉)或以上的烃类。它们还含有较高浓度的硫、氮和/或金属。高沸点组分一般分子量高且/或氢/碳比低,其例之一是被称统为“沥青烯”的一类复杂化合物。沥青烯加工困难,常造成催化剂和氢加工设备积垢。
含高浓度沥青烯、硫、氮和金属的低质原料包括:例如重粗油和油渣沥青,以及传统炼油工艺留下的罐底物和渣油(统称“重油”)。“罐底物”和“渣油”一般指沸点至少343℃(650℉)的常压塔塔底馏分或沸点至少524℃(975℉)的减压塔塔底馏分。“减压渣油”和“渣油沥青”常用来指沸点至少达524℃(975℉)的馏分。
将重油转化为有用的目标产品需要大量加工,其中包括降低重油的沸点,提高氢/碳比和去除金属、硫、氮和成碳化合物等杂质。
用于重油时,现有产业化催化性加氢裂化工艺会受阻,或很快发生催化剂钝化。重油加氢裂化过程中的不良反应和积垢大大提高了重油加工的催化剂和维护成本。
前景良好的一种重油氢加工技术采用烃溶性钼盐,氢加工过程中,这种烃溶性钼盐在重油中分解,原位形成氢加工催化剂即硫化钼。美国专利No.5,578,197(Cyr等)描述了这样一种方法。原位形成后,所述硫化钼催化剂能够非常高效地降解沥青烯及其他复杂烃类,同时避免积垢和焦化。
油溶性钼催化剂商品化的一个重要问题是催化剂的成本。即使催化剂性能的小改进也会因产量增加和/或催化剂用量减少而显著降低加氢裂化的成本。
油溶性钼催化剂的性能与重油中的金属浓度以及催化剂前体在重油中的分散情况显著相关。提高催化剂前体中金属百分比的同时保持或提高溶解度能够提高采用油溶性钼化合物进行的重油加氢裂化的效率。
发明概述
本发明涉及含有烃溶性钼盐的催化剂前体,所述催化剂前体能够原位形成用于重油精炼的加氢裂化催化剂。所述催化剂前体包含这样的钼盐,该钼盐含有大量阳离子性钼原子和大量有机阴离子。所述有机阴离子优选含有2至14碳原子。优选实施方式之一中,钼原子中至少部分结合3个有机阴离子,具有3+氧化态,因此,所述大量钼原子的平均氧化态低于4+。
为了获得至少部分钼原子呈3+氧化态的催化剂前体,采用强还原剂来制备催化剂前体。合适的还原剂包括氢和/或有机还原剂。在有机反应物与钼原子反应过程中,还原剂将钼原子还原并稳化。水被去除,以使反应产物能溶于重油。
优选实施方式之一中,本发明方法制得一种平均氧化态低于4+的催化剂前体。催化剂前体中存在Mo3+强化了MoS2催化剂的原位形成。Mo3+不如Mo4+、Mo5+和Mo6+等钼的其他形式稳定。因为Mo3+的稳定性低,在重油中它更容易分解和形成所需的催化性硫化钼化合物。虽然以上原理被认为是本发明催化剂性能提高的至少部分原因,本发明并不受这些原理的限制。
使用还原剂还有利于避免钼原子与有机反应物的氧化物之间形成非所需配合物。还原剂的存在抑制有机反应物分子之间相互氧化,并且将钼原子迅速还原。由于迅速还原钼原子并抑制非所需有机反应物分子氧化,本发明催化剂前体不易在钼原子与非所需有机反应物氧化物之间形成配合物,而配合物的形成会降低催化剂前体在重油中的性能。
将钼原子的氧化态降至低于4+还提高了催化剂前体中钼的百分比,使之高于氧化态通常等于或大于4+的现有油溶性钼盐。本发明的发明人发现,只结合三个有机阴离子的钼能够保持充分溶于重油,同时提高钼的重量百分比。提高催化剂前体中钼的百分比能够显著降低催化剂前体成本。
据信,还原剂有助于减少终产物中的氧化钼,和/或减少钼原子和/或钼盐的结合水。氢对于去除钼的氧化物和/或钼盐的结合水特别有效。在氢和/或有机还原剂存在下、在本发明所述反应条件下制得的催化剂前体被发现具有特别好的烃溶解性和烃分散性。据信,这种高于现有催化剂前体的溶解度至少部分得益于去除了钼氧化物和/或结合水和/或非所需钼配合物。然而,本发明的特征不限于此
本发明还包括制备钼催化剂前体的方法。一般说来,所述制备钼催化剂前体的方法包括:(1)提供大量钼原子;(2)提供包含大量有机分子(优选含有2-14碳原子)的有机反应物;(3)在高于100℃的温度、在还原剂存在下令所述大量钼原子与所述有机反应物反应。所述反应生成钼盐,其中钼原子的平均氧化态低于4+,以低于3.8+为佳,低于3.5+尤佳。
所述有机反应物可以是各种能与钼反应并形成阴离子的C2至C14烃。合适的有机反应物的例子包括:丁酸、戊酸、己酸、庚酸、辛酸、癸酸、2-乙基丁酸、2-甲基戊酸、2-乙基己酸等。
可在各种反应器和各种加氢裂化过程中采用所述氢加工催化剂来进行重油精炼。与传统氢加工催化剂相比,本发明氢加工催化剂能够更有效地加工沥青烯分子,减少或消除焦炭前体和沉积的形成,减少设备积垢,和/或提高转化率。
以下描述及后文权利要求将进一步充分展现包括以上所述的以及其他的本发明优点。
优选实施方式的具体描述
I.简介与定义
本发明涉及烃溶性钼催化剂前体及其制备方法,所述前体能够在重油原料中形成硫化钼氢加工催化剂。所述催化剂前体具有大量与多个阴离子性有机分子结合的阳离子性钼原子。优选实施方式之一中,至少部分钼原子处于3+氧化态,这使得大量催化剂原子的平均氧化态低于4+,以低于3.8+为佳,低于3.5+尤佳。本发明的油溶性钼盐在还原剂存在下制备,由此制得所需氧化态的钼原子。优选实施方式之一中,所述还原剂是氢或有机还原剂。
“胶态催化剂”和“以胶体形式分散的催化剂”指颗粒大小符合胶体标准的催化剂颗粒,例如直径小于约100nm,以直径小于约10nm为佳,直径小于约5nm更好,直径小于约3nm最好。“胶态催化剂”包括但不限于分子催化剂化合物或以分子形式分散的催化剂化合物。
“分子态催化剂”和“以分子形式分散的催化剂”指在重油烃原料、非挥发性液体馏分、塔底馏分、渣油或可能包含所述催化剂的其他原料或产物中基本“溶解”或与其他催化剂化合物或分子完全解离的催化剂化合物。这还包括只含有少量结合在一起的催化剂分子(例如15个或更少的分子)的非常小的催化剂颗粒。
“混合原料组合物”指这样的重油原料,其中添加了油溶性催化剂前体组合物,充分混合后,随着催化剂前体的分解和形成催化剂,所得催化剂将包含分散于原料中的胶态或分子态催化剂。
“重油原料”指重粗油、油渣沥青以及炼油工艺留下的罐底物和渣油(例如减粘裂化炉罐底物),以及以高沸点(例如,沸点至少343℃(650℉),尤其是,沸点至少524℃(975℉))烃类为主要成分的其他低质原料,和/或含有大量沥青烯的其他低质原料,沥青烯会造成固相载体上的催化剂钝化,和/或造成焦炭前体和沉积的形成。重油原料包括但不限于,例如劳埃德明斯特重油(Lloydminster heavyoil)、冷湖渣油(Cold Lake bitumen)、阿萨巴斯卡渣油(Athabasca bitumen)、常压塔塔底馏分、减压塔塔底馏分、渣油(residuum)、渣油沥青、减压渣油以及粗油、沥青沙、液化炭或煤焦油原料蒸馏、热分离等处理后残留的且含有高沸点馏分和/或沥青烯的非挥发性液体馏分。
II.用于制备催化剂前体的成分
制备本发明催化剂前体主要包括在还原剂存在下将大量钼原子与多个有机反应物分子反应。视需要,反应可在溶剂中进行。
A.过渡金属原子
所述石油催化剂前体的主要金属成分是钼。提供的钼原子的形式是能够与有机反应物(例如2-乙基己酸等羧酸)反应生成钼盐的钼化合物。合适的钼化合物包括卤化钼,如六氟钼和五氯钼;各种钼的氧化物,如二氧化钼、三氧化钼、倍半氧化钼等;碱金属或碱土金属钼酸盐,如钼酸铯、钼酸钠、钼酸钾、钼酸钙等;以及钼酸铵或钼酸。本发明优选钼酸。
本发明催化剂前体中还可含有其他金属。适宜的其他金属包括除钼以外的过渡金属。所述过渡金属可以包含在与有机反应物的反应中,并且/或者,在制备完成后与钼盐混合。优选的其他过渡金属是钴。
B.有机反应物分子
所述有机反应物是一种或多种油溶性有机化合物,它们各自含有2至14个碳原子,并具有能够与过渡金属反应形成油溶性过渡金属盐(例如钼盐)中阴离子的官能团。优选实施方式之一中,所述有机反应物是羧酸。合适的羧酸包括脂族酸、脂环酸、芳族酸和含磷酸。合适的脂族酸包括丁酸、戊酸、己酸、庚酸、辛酸、癸酸、α、β或γ位有侧链的羧酸(例如2-乙基丁酸、2-甲基戊酸、2-乙基己酸)等。脂环酸包括环己酸、环十二烷酸等。芳族酸可包含一个或两个稠合环,并含有7至14个碳原子,其中的羧基可连接或不连接在环上,例如苯甲酸、1-或2-萘羧、邻-、间-或对-甲基甲苯酸、苯乙酸、1或2萘乙酸、苯基丁酸等。含磷有机化合物包括2-乙基己基磷酸酯等。优选脂族酸,尤其是2-乙基己酸,因为它在重油中溶解度高且成本相对低廉。
本领域技术人员可以看出,在与钼原子的反应中,所述有机反应物分子可以被改变。例如,在羧酸与钼的反应中,有机反应物分子会失氢而成为羧酸根阴离子。
有时,有机反应物可以起到反应溶剂的作用,尤其当有机反应物(例如2-乙基己酸)在反应条件下呈液态时。然而,视需要,可以采用其他溶剂。所述其他溶剂必须能够溶解所述有机反应物和所述钼原子,但不能干扰它们之间的反应。合适的溶剂包括澄清油、液体石蜡、苯、甲苯、二甲苯、萘、矿物油、矿油精以及它们的混合物等等。
C.还原剂
还原剂加入反应混合物用以还原金属原子,使之更易形成金属盐,和/或获得金属盐并达到金属在催化剂前体中的所需重量百分比。优选实施方式之一中,用强还原剂将至少部分钼原子还原成并/或维持在低于4+的氧化态。较好的是,钼原子的平均氧化态低于约3.8+,低于约3.5+更好。
各种能在后文所述反应条件下将钼还原为3+氧化态的的还原剂均可用于本发明。优选的还原剂是氢和有机还原剂。合适的还原剂包括甲烷、乙烷、乙烯和丙烯等烯烃、甲醛等醛类和氢。因其高效和低廉,优选氢气。
还原剂的溶解度往往取决于反应温度。高温下(例如155℃),甲烷和甲醛等有机还原剂具有合格还原能力。然而,低温下(例如低于50℃)或室温下,则以使用氢气等强还原剂为佳。
III.制备氢加工催化剂前体的方法
本发明制造氢加工催化剂前体的方法包括直接将大量钼原子与大量有机反应物分子反应而形成烃溶性钼盐。该反应中,钼原子与有机反应物分子的摩尔比可以低于大约1:20,低于约1:4更好,低于约1:3.8还要好,低于约1:3.5最好。
钼原子与有机反应物分子的反应也可以在还原剂存在下进行的。还原剂降低钼原子的正氧化态。较好的是,将通常以氧化钼形式提供的钼原子还原至基本无氧化钼残留。与购得的烃溶性钼盐相比,基本消除氧化钼可提高烃溶性钼盐的溶解度。
优选实施方式之一中,还原剂和反应条件使得钼得以还原至3+氧化态。反应以这样一种方式进行,即使得所得烃溶性钼盐中钼原子的平均氧化态低于4+。实施方式之一中,平均氧化态低于4+的钼盐可通过将钼化合物与有机反应物分子按照以下摩尔比反应来获得,即钼原子与有机反应物分子的摩尔比低于1:4,以低于约1:3.8为佳,低于约1:3.5更好。在反应混合物中包含足量的还原剂,将至少部分钼原子还原成或维持在3+氧化态。
有机反应物分子的摩尔比低于1:4加上还原性环境,于是可形成钼原子氧化态低于4+的催化剂前体。优选实施方式之一中,还原剂是氢气,将氢气通过反应混合物之中和之旁,由此形成还原性环境。钼原子平均氧化态低于4+(低于约3.8+更好,低于约3.5+尤佳)的催化剂前体一般在重油中溶解度较高,这有利于原位形成硫化钼催化剂。此外,氧化态低的催化剂中有机反应物分子与钼原子之比低,因此,钼浓度提高,节约了成本。
反应以在一个较高温度进行为佳。在较高温度(例如高于100℃),钼化合物溶解度升高,与有机反应物反应更完全。然而,为避免钼盐分解,反应温度以维持低于约300℃为佳。优选实施方式之一中,反应在约100-350℃进行,以120-280℃为佳,约150-260℃最佳。需要明白的是,反应温度和反应时间等因素取决于所用的具体钼化合物和/或具体的有机反应物。反应时间应足够长以使反应基本完全,该时间一般约为2-48小时,或者更长。
在反应过程中保持一个还原性环境尤其有利,因为这能够加速钼与有机反应物之间的反应。此外,还原剂的存在抑制了有机反应物分子彼此氧化,否则,这种彼此氧化会导致非所需钼配合物的形成。反应过程中还原剂的存在还有助于将钼原子稳定在3+氧化态,这一氧化态不如4+等其他氧化态稳定。
反应混合物中的水被去除,由此获得可溶于重油的反应产物,并确保钼反应的继续推进。可用各种技术或技术的组合来去除水。优选实施方式之一中,反应在水的沸点以上的温度下进行,这样,水在反应过程中一经生成便被去除。让水以水蒸气的形式从反应容器中排出。当有氢和/或其他气体与反应混合物接触时,水会随此气体排出。如有必要,可令所述气体和水蒸气通过冷凝器来去除水。可选而非必须的是,然后可将所述气体回输并通过反应混合物。
据信,还原剂有助于减少与钼盐中的钼原子结合或配合的水和/或减少钼的氧化物。现已发现,在氢存在下制得的催化剂前体在烃中的溶解度和分散性特别好。据信,这种溶解度与现有催化剂前体相比的提高部分缘于去除了结合水和/或钼的氧化物,这些不容易通过加热去除。而且,还认为,在反应过程中和/或在较高温度和/或在还原性环境中去除钼的氧化物和/或结合水也是有益的。
如有必要,可用化学干燥剂去除反应产物中的水,但一般无此必要。各种已知干燥技术均可采用。例如,可用干燥剂(如氯化钙)或共沸剂来除水。干燥剂或共沸剂是本领域技术人员所熟知的。
IV.含钼催化剂前体组合物
本发明油溶性催化剂前体含有烃溶性钼盐。所述钼盐含有大量阳离子性钼原子和大量有机阴离子,各阴离子以含有2-14个碳原子为佳。优选实施方式之一中,至少部分钼原子与3个有机阴离子结合,具有3+氧化态,由此使得所述大量钼原子的平均氧化态低于4+,低于约3.8+更好,低于约3.5+尤佳。
钼盐中钼的百分比直接取决于与之结合的有机阴离子数目和有机阴离子的分子量。随着有机阴离子数量和分子量的上升,钼的重量百分比下降。如前所述,只要催化剂前体可溶于烃(例如重油),钼的重量百分比越高越好。本发明的发明人发现,可将有机阴离子/钼原子之比降至3而仍保持在烃(例如重油)中足够的溶解度。
本发明钼盐中至少部分的有机阴离子数减少使得催化剂前体中钼的重量百分比升高。例如,如果有机阴离子是2-乙基己酸根,钼原子平均氧化态在3至4之间的催化剂前体的钼重量百分比将达19-14%。因此,可以在提高钼重量百分比的同时不因为降低钼的氧化态和与之结合的有机阴离子数而降低溶解度。
V.烃与催化剂前体混合并由此形成氢加工催化剂
本发明催化剂前体可加入重油原料形成混合物催化剂前体。所述催化剂前体被设计为能在高达设定温度的条件下在烃中保持稳定。高温下,催化剂前体分解,与重油中的硫反应,形成硫化钼氢加工催化剂。
所述油溶性催化剂前体以具有约100-350℃(212-662℉)的分解温度为佳,约150-300℃(302-572℉)更好,约175-250℃(347-482℉)最好。上述优选分解温度使得催化剂前体能够在分解前与烃(例如重油)充分混合。
也可将催化剂前体组合物与稀释剂混合为具有所需钼盐浓度的混合物。合适的烃稀释剂包括但不限于:减压柴油(Vacuum Gas Oil)(沸点一般为360-524℃),澄清油(沸点一般为360-550℃)和轻柴油(沸点一般为200-360℃)。
催化剂前体组合物与烃油稀释剂重量比以约1:1000至1:1为佳,约1:100至1:1更好,约1:30至1:1最好(例如1:20,1:5或1:3)。
还可以在将所述前体与重油原料混合之前先将催化剂前体组合物与稀释剂预混合。最好在催化剂前体组合物尚未明显分解的温度下将催化剂前体组合物与烃稀释剂混合形成稀释前体混合物,以在约25-250℃混合为佳,约50-200℃更好,约75-150℃最好。可以看出,实际在何温度形成稀释前体混合物一般主要取决于所用具体前体组合物的分解温度。较好的是,前体组合物与烃油稀释剂的混合时间为约0.5-20分钟,约0.75-10分钟更好,约1-3分钟最好。实际混合时间至少部分取决于温度(会影响流体粘度)和混合强度。混合强度至少部分取决于混合阶段数(例如,对在线静态混合仪而言)。
虽然直接将催化剂前体组合物与重油原料混合也属于本发明内容,此时必须留意将各组分混合足够长的时间,从而在前体组合物明显分解发生前使前体组合物与原料油充分混合。例如,Cyr等的美国专利No.5,578,197记载了一种方法,在反应容器中将2-乙基己酸钼与沥青减压塔渣油混合24小时后将所得混合物加热,形成催化剂混合物,启动裂化(见第10栏,第4-43行)。虽然在测试环境下混合24小时是完全可以的,但在产业化运作中,如此长的混合时间在成本上不可行。
现已发现,先将前体组合物与烃稀释剂预混合,然后将稀释前体混合物与重油原料混合,这样明显有助于前体组合物与所述原料的充分混合,尤其是在较短的时间内实现这一点,这满足了大规模产业化运作的经济利益。形成稀释前体组合物缩短了总的混合时间,因为:(1)减少或消除了相对较高极性的催化剂前体组合物与重油原料之间的溶解度差异,(2)减少或消除了催化剂前体组合物与重油原料之间的流体学特征差异,和/或(3)在烃油稀释剂中将催化剂前体分子分散为溶质,使其在重油原料中的分散变得容易得多。当重油原料中含水(例如冷凝水)时,先形成稀释前体混合物尤其有利。要不然,水对极性催化剂前体组合物的高亲和性会造成前体组合物的局部凝聚,导致分散不良并形成微米大小或更大的催化剂颗粒。较好的是,烃油稀释剂基本上不含水(即含水量低于0.5%),以避免形成微米大小或更大的催化剂颗粒。
然后,以合适的方式将稀释前体混合物与重油原料混合足够长的时间,以将催化剂前体组合物充分分散于所述原料中为准,由此得到前体组合物与重油原料充分混合的经调制的原料组合物。为了将催化剂前体组合物与重油原料充分混合从而能够在所述前体组合物分解后得到胶体或分子催化剂,稀释前体混合物与重油原料的混合时间以0.5-20分钟为佳,约1-10分钟更好,约2-5分钟最好。提高混合强度和/或剪切力通常能够缩短实现充分混合所需的时间。
可用于将催化剂前体组合物与重油原料充分混合的混合设备的例子包括但不限于:高剪切混合仪,例如在容器内由搅拌桨或涡轮搅拌桨进行混合,多台静态在线混合仪,或一台或多台多段式离心泵。实施方式之一中,可用多腔室高能泵进行连续搅拌而不是分批式搅拌,在所述泵的多腔室中,催化剂前体组合物和重油原料被搅拌和混合,这样的搅拌和混合融合于泵送过程本身之中。上述混合设备也可用于前文所述的预混合过程,即催化剂前体组合物与烃油稀释剂混合成催化剂前体混合物。
如果重油原料在室温下呈固态或极端粘稠,宜先将这样的原料加热软化成粘度足够低的原料以便与油溶性催化剂前体充分混合。一般说来,降低重油原料的粘度可缩短将油溶性催化剂前体组合物与重油原料充分混合所需的时间。然而,不可以将所述原料加热到高于催化剂在经充分混合形成混合原料组合物之前就明显分解的温度。催化剂前体组合物过早分解常会导致形成微米大小或更大的催化剂颗粒而不是形成胶体或分子催化剂。较好的是,在约25-350℃的温度进行重油原料与稀释前体混合物的混合和调制,由此获得经调制的原料,所述温度约50-300℃更好,约75-250℃最好。
催化剂前体组合物与重油原料充分混合并得到经调制的原料组合物后,将该组合物加热至高于催化剂前体组合物明显分解的温度,由此释放出催化剂金属从而形成最终的活性催化剂。据实施方式之一中,来自所述前体组合物的金属首先形成金属氧化物,然后,金属氧化物与重油原料中释放的硫反应形成金属硫化物即最终的活性催化剂。如果重油原料含有足量或过量的硫,则将重油原料加热至足以从中释放出硫的温度,可原位形成最终的活性催化剂。有时,硫的释放温度与前体组合物的分解温度相同,有时则需要加热到更高的温度。
如果油溶性催化剂前体组合物与重油原料充分混合,释放出的金属离子中至少相当一部分得以与其他金属离子充分阻隔,这样,它们才能够在与硫反应生成金属硫化物后形成以分子形式分散的催化剂。某些情形下会发生轻微的聚集,并因此形成胶体大小的催化剂颗粒。然而,据信,注意将前体组合物与重油原料充分混合就可得到单个分子催化剂而非胶体颗粒。如果将催化剂前体组合物与重油原料粗略混合而非充分混合物,往往会形成微米大小或更大的金属硫化物的大聚集体。
为了形成金属硫化物催化剂,宜将混合原料组合物加热至约200-500℃,约250-450℃更好,300-400℃最好。实施方式之一中,经调制的原料在加氢裂化反应器中被加热至加氢裂化温度以下约100℃的温度。据实施方式之一,在将重油原料加入加氢裂化反应器之前,在预热过程中形成了胶体或分子催化剂。据另一实施方式,所述胶体或分子催化剂中至少一部分是在加氢裂化反应器中原位形成的。一旦形成,有些时候,在将重油原料加入加氢裂化反应器之前或之后,在重油原料被加热的过程中会形成胶体或分子催化剂。胶体或分子催化剂中催化剂金属的最初浓度以约1-500重量ppm为佳,5-300ppm更好,10-175ppm最好。从非挥发残留组分中去除挥发性组分后,催化剂会进一步浓缩。
虽然催化剂化合物的强极性导致或允许胶体或分子催化剂与沥青烯分子缔合,但必需如前所说在前体分解和形成胶体或分子催化剂之前将油溶性催化剂前体组合物与重油原料充分混合的原因是强极性催化剂化合物与疏水性重油原料之间的严重互不相容。由于金属催化剂化合物是强极性的,如果将它们直接加入重油原料或将它们溶于含水溶液或包含在油-水乳液中加入重油原料,它们无法以胶体或分子的形式充分分散在重油原料中,此类方法最终将导致形成微米大小或更大的催化剂颗粒。
VI.实施例
以下实施例说明了用于制造本发明催化剂前体的配方范例。实施例1、2、3和4提供了制备烃溶性钼盐的配方。在实施例1、2、3和4中,用接装在烧瓶上的冷凝器来制备钼盐。开阀放出冷凝液。实施例5、6、7、8和9是关于用烃稀释催化剂前体,然后用于重油的加氢裂化。
实施例5、6、7、8和9中,所用重油的组成为(元素(wt%)):碳81.61%,氢9.86%,硫6.27%,氮0.68%,氧(算得)1.58%。油蒸馏液(无固体)(wt%):IBP-975℉21.16%,975℉+78.84%。
实施例1
实施例1描述制备钼催化剂前体的一种方法。在烧瓶中,4.84g钼酸(埃德利希(Aldrich),MoO3≥85.0%)与12.47g的2-乙基己酸(Aldrich,99%)混合,然后边加热边搅拌边以100ml/min的速度以N2吹洗,直到近液体上方蒸汽的温度达到约185℃。混合物在185℃保温1小时,然后,换以100ml含20%H2和80%N2的混合气体吹洗。然后,混合物保持6小时。所得钼催化剂前体的钼含量为18wt%
实施例2
实施例2描述制备钼催化剂前体的一种方法。在烧瓶中,4.84g钼酸(埃德利希(Aldrich),MoO3≥85.0%)与13.15g的庚酸(Aldrich,96%)混合,然后边加热边搅拌边以100ml/min的速度以N2吹洗,直到近液体上方蒸汽的温度达到约185℃。混合物在185℃保温1小时,然后,换以100ml含20%H2和80%N2的混合气体吹洗。然后,混合物保持6小时。所得钼催化剂前体的钼含量为18wt%。
实施例3
实施例3描述制备钼催化剂前体的一种方法。在烧瓶中,30.0g钼酸(埃德利希(Aldrich),MoO3≥85.0%)与102.2g的2-乙基己酸(Aldrich,99%)混合,加热至200℃并保持1小时,边加热边搅拌边以100ml/min的速度以N2吹洗。然后换以20%H2和80%N2的混合气体吹洗,并在该温度保温12小时。所得2-乙基己酸钼含14.6wt%的Mo。
实施例4
实施例4描述制备钼催化剂前体的一种方法。18.7g实施例3制备的2-乙基己酸钼与28.5g磷酸2-乙基己酯混合。所得2-乙基己酸钼含5.9wt%的Mo。
实施例5
实施例5描述了钼催化剂前体在加氢裂化中的用途。用澄清油稀释实施例1催化剂前体,使总重达到300.0g,由此制得稀释催化剂前体。将澄清油和催化剂前体加热至约80℃并搅拌。振荡该混合物,直至其变为均质体。然后将该样品与重油按照2g/181g的重量比混合,加入反应器A进行加氢裂化。
实施例6
实施例6描述了钼催化剂前体在加氢裂化中的用途。用澄清油稀释实施例2催化剂前体,使总重达到300.0g,由此制得稀释催化剂前体。将澄清油和催化剂前体加热至约80℃并搅拌。振荡该混合物,直至其变为均质体。然后将该样品与重油按照2g/181g的重量比混合,加入反应器B进行加氢裂化。
实施例7
实施例7描述了钼催化剂前体在加氢裂化中的用途。将按照实施例3制备的18.7g2-乙基己酸钼与281.3g澄清油混合,制成含9150ppm催化剂的催化剂浆。取2g所述催化剂浆与181g重油混合,制成最终的进料,将所得混合物加入反应器A进行加氢裂化。
实施例8
实施例8描述了钼催化剂前体在加氢裂化中的用途。用澄清油稀释实施例4催化剂前体,使总重达到300.0g,由此制得稀释催化剂前体。振荡该混合物,直至其变为均质体。然后将该样品与重油按照2g/181g的重量比混合,加入反应器B进行加氢裂化。
实施例9(参比)
实施例9采用购来的钼催化剂前体进行加氢裂化。将18.3g参比2-乙基己酸钼(15.0%Mo)与281.7g澄清油混合,制成含9150ppm催化剂的催化剂浆。取2g所述催化剂浆与181g重油混合,制成最终的加氢裂化进料。将实施例9制得的催化剂分别加入反应器A和反应器B,供比较之用。
反应器条件和结果
实施例5和7所述的加氢裂化反应在反应器A中进行,实施例6和8所述加氢裂化反应在反应器B中进行。反应器A与B中的反应条件相同:反应温度为824.5℉,反应压力为2200psig,H2与进料油重量比为19g/181g。反应结果归纳如下:
表A:反应器A中的反应结果
催化剂样本 | 参比 | 实施例5 | 实施例7 |
过程转化率(w%) | 81.3 | 84.5 | 84.1 |
过程HI转化率(w%) | 76.6 | 81.4 | 84.2 |
过程沥青烯转化率(w%) | 79.4 | 83.5 | 84.8 |
C1-C3气体得率(w%) | 4.91 | 5.84 | 7.27 |
塔底IP-375℉沉淀(w%) | 1.26 | 1.42 | 0.71 |
表B:反应器B中的反应结果
催化剂样本 | 参比 | 实施例6 | 实施例8 |
过程转化率(w%) | 80.5 | 83.5 | 82.8 |
过程HI转化率(w%) | 76.9 | 80.7 | 77.8 |
过程沥青烯转化率(w%) | 80.9 | 82.6 | 81.2 |
C1-C3气体得率(w%) | 5.55 | 5.61 | 5.81 |
塔底IP-375℉沉淀(w%) | 1.71 | 0.88 | 1.72 |
结果显示,与购来的钼催化剂前体相比,实施例5-8的催化剂都提高了烃转化率。
本发明还可有其它具体实施方式,均符合本发明的构思和主要特征。以上所述实施方式仅有示例意义而无限定意义。所以,本发明的范围由后文权利要求书限定,而非以上说明。权利要求的范围应包括等同手段的所有变化。
Claims (26)
1.一种适用于原位形成用于重油加氢裂化的硫化钼催化剂的钼催化剂前体,包含:
油溶性钼盐,所述钼盐包含大量阳离子性钼原子和大量有机阴离子,其中,至少部分所述钼原子结合3个有机阴离子并具有3+氧化态,大量钼原子的平均氧化态低于4+。
2.如权利要求1所述的方法,所述还原剂包含氢或有机还原剂或这两者。
3.如权利要求1所述的钼催化剂前体,所述有机阴离子包含具有2-14个碳原子的有机阴离子。
4.如权利要求1所述的钼催化剂前体,所述有机阴离子是羧酸根阴离子。
5.如权利要求4所述的钼催化剂前体,所述羧酸根阴离子选自;丁酸、戊酸、己酸、庚酸、辛酸、癸酸、2-乙基丁酸、2-甲基戊酸、2-乙基己酸或它们的组合。
6.如权利要求1所述的钼催化剂前体,所述平均氧化态低于约3.8+。
7.如权利要求1所述的钼催化剂前体,所述平均氧化态低于约3.5+。
8.如权利要求1所述的钼催化剂前体,其中,钼的重量百分比高于约15.5%。
9.如权利要求1所述的钼催化剂前体,其中,钼的重量百分比高于约17%。
10.如权利要求1所述的钼催化剂前体,还包含一种或多种其它金属盐,所述其它金属盐包含非钼过渡金属。
11.稀释的钼催化剂前体,包含权利要求1所述的催化剂前体和与之混合的稀释剂。
12.混合重油原料,包含与重油原料混合的权利要求11所述稀释的钼催化剂前体。
13.混合重油原料,包含与重油原料混合的权利要求1所述钼催化剂前体。
14.一种制备用于重油加氢裂化的钼催化剂前体的方法,包括:
提供大量钼原子;
提供有机反应物,所述有机反应物包含大量具有至少一个能够与钼原子反应的官能团的有机分子;
在还原剂存在下,按照钼原子与有机分子摩尔比小于1:4的比例,令所述大量钼原子与所述有机反应物反应,生成含有大量氧化态低于4+的钼原子的钼盐。
15.如权利要求14所述的方法,其中,所述还原剂包含氢或有机还原剂或这两者。
16.如权利要求14所述的方法,其中,反应在高于约100℃的温度进行,使得反应产物中的水在反应产物形成过程中被去除。
17.如权利要求14所述的方法,其中,反应在高于约155℃的温度进行.
18.如权利要求14所述的方法,其中,在用还原剂还原之前先用惰性气体吹洗反应混合物。
19.如权利要求14所述的方法,其中,所述平均氧化态低于约3.8+。
20.如权利要求14所述的方法,其中,所述平均氧化态低于约3.5+。
21.一种钼催化剂前体,它用权利要求14所述方法制得,用所述方法形成所含配合物分子少于不用还原剂所制得催化剂前体的钼盐,所述配合物分子为抑制钼盐形成硫化钼的配合物分子。
22.一种制备适用于重油加氢裂化的钼催化剂前体的方法,包括:
提供大量钼原子;
提供有机反应物,所述有机反应物包含大量具有至少一个能够与钼原子反应的官能团的有机分子;
在氢和/或有机还原剂存在下,在高于约90℃的温度,令所述大量钼原子与所述有机反应物反应,生成含有烃溶性钼盐的反应产物。
23.如权利要求22所述的方法,所述有机反应物分子选自;丁酸、戊酸、己酸、庚酸、辛酸、癸酸、2-乙基丁酸、2-甲基戊酸、2-乙基己酸或它们的组合。
24.如权利要求22所述的方法,所述钼原子与有机反应物在高于约100℃的温度进行反应。
25.如权利要求22所述的方法,所述钼原子与有机反应物在高于约155℃的温度进行反应。
26.一种钼催化剂前体,它由权利要求22所述方法制得,用所述方法形成溶解度高于不用氢所制得催化剂前体的钼盐。
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MY146937A (en) | 2012-10-15 |
US20070158238A1 (en) | 2007-07-12 |
WO2007082118A3 (en) | 2007-11-22 |
CA2636282C (en) | 2016-11-22 |
WO2007082118A2 (en) | 2007-07-19 |
KR101377620B1 (ko) | 2014-03-25 |
TW200728445A (en) | 2007-08-01 |
EP1973993A4 (en) | 2009-11-11 |
US20100051507A1 (en) | 2010-03-04 |
EP1973993B1 (en) | 2016-05-04 |
ES2583485T3 (es) | 2016-09-21 |
US7670984B2 (en) | 2010-03-02 |
EP1973993A2 (en) | 2008-10-01 |
JP2009522103A (ja) | 2009-06-11 |
CA2636282A1 (en) | 2007-07-19 |
US8445399B2 (en) | 2013-05-21 |
KR20080083059A (ko) | 2008-09-12 |
PL1973993T3 (pl) | 2017-03-31 |
JP5112334B2 (ja) | 2013-01-09 |
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