CN1635054A - Catalyst for gasoline heavy fraction pyrolysis and selective hydrogenation, process for preparation and use thereof - Google Patents
Catalyst for gasoline heavy fraction pyrolysis and selective hydrogenation, process for preparation and use thereof Download PDFInfo
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- CN1635054A CN1635054A CN 200310124229 CN200310124229A CN1635054A CN 1635054 A CN1635054 A CN 1635054A CN 200310124229 CN200310124229 CN 200310124229 CN 200310124229 A CN200310124229 A CN 200310124229A CN 1635054 A CN1635054 A CN 1635054A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 39
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 37
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 25
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001993 dienes Chemical class 0.000 claims description 17
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 11
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- 239000011630 iodine Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- 241000370738 Chlorion Species 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- -1 carbon atom alkynes Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 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 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- PHTHEUNUXVDUOD-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[O-2].[Al+3] PHTHEUNUXVDUOD-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Abstract
The invention relates to a catalyst for pyrolysis gasoline C5-C9 distillation fraction, in particular C8-C9 heavy distillate selection hydrogenation into olefin, which comprises aluminum oxide as carrying agent, alkaline-earth metal or its oxide covered on the surface of the carrier and metal Pd, Mo or Pd, W loaded on the carrier as active component, wherein the content of the alkaline-earth metal is 1-3wt% of the total weight of the catalyst, the content of the Pd is 0.24-0.35wt% of the total weight of the catalyst, the weight ratio of Pd and Mo or Pd and W is 1:0.5-2.5. The crushing strength of the catalyst is greater than 18N/mm.
Description
Technical field
The present invention relates to a kind of petroleum hydrocarbon and select hydrogenation catalyzer, particularly pyrolysis gasoline C
5～C
9Cut, especially C
8～C
9The hydrogenation catalyzer is selected in last running.The invention still further relates to this Preparation of catalysts method and application thereof.
Background technology
Pyrolysis gasoline C
5～C
9Cut is the by product of ethylene industry, and according to the difference of cracking stock and cracking severity, its output accounts for more than the 50 weight % of ethylene production capacity, and wherein aromaticity content accounts for 40～80 weight %, is the main source of aromatic hydrocarbons therefore.Cut C on the industrial production
8And C
9Cut through one-stage hydrogenation, is removed the height unsaturated hydrocarbons, as chain conjugated dienes, vinylbenzene, alkynes and cyclic conjugated diene class, and again through the secondary hydrogenation desulfurization, behind the organic compound such as removal monoene and sulphur, nitrogen, oxygen, C
8Cut is used to produce dimethylbenzene, and C
9Cut is used to produce aromatic solvent naphtha.C
8Cut also can be removed diolefin only through a hydrogenation, keeps most of monoene, obtains stable motor spirit admixture or the higher motor spirit of octane value.
Present industrial pyrolysis gasoline C
5～C
9Fraction selective hydrogenation mainly is Ni/Al with catalyzer
2O
3Or Pd/Al
2O
3, Pd-Cr/Al is also arranged
2O
3Bimetallic catalyst.Because pyrolysis gasoline C
8And C
9Impurity such as As, S, O, N and gum level are higher in the last running, make the very fast inactivation of catalyzer, thereby catalyzer have to frequent activation and regeneration.The Pd/Al of present industrial use
2O
3The shortest regeneration period of catalyzer is 7 days.Therefore, wish that hydrogenation catalyst has higher low temperature active, higher anti-impurity poisoning capability and suitable appearance glue ability, increasing the catalyst regeneration cycle, thereby prolong catalyzer work-ing life, this is very important in industrial production.
The open CN85100761A of Chinese patent application discloses a kind of fibrous catalyst for selective hydrogenation of dienes and method for making thereof, wherein active ingredient comprises Pd or the Pt of 0.2～1 weight % at least and comprises a kind of in Na, K, Li, Mg or the rare earth element of 0.05～2 weight % at least, and the specific surface area of porous fiber carrier is greater than 200m
2/ g, pore volume is greater than 0.1ml/g.Its contriver claims that this catalyzer compares with the pelleted catalyst of industrial present employing, and the liquid air speed improves 1～2 order of magnitude, and selectivity is near 100%; In temperature of reaction is 40 ℃, and reaction pressure is 40kg/cm
2, the liquid air speed is under the 40ml/g.hr, 1000 hours activity of continuous operation do not descend, but its activity and stability still leave some room for improvement.The open CN1056068A of Chinese patent application discloses a kind of catalyzer that is used for selective hydrogenation of diolefin as, mainly is made up of nickel, sodium, sulphur and alumina supporter, and wherein alumina supporter is the solid matter based on amorphous phase, and its surface-area is lower than 100m
2/ g, total pore volume is less than 1.0cm
3/ g.Its contriver claims that this catalyzer is at processing C
7～C
16The mixture of hydrocarbon the time effective especially, but its low temperature active still remains to be improved.The open CN1228402A of Chinese patent application discloses a kind of method of 2 or 3 carbon atom alkynes gas phases being selected to be hydrogenated into corresponding alkene in the presence of special catalyst, and this catalyzer contains palladium, at least a periodic table of elements IB family's metal and aluminum oxide.Yet the low temperature active and the selectivity of this method catalyst system therefor all have much room for improvement.
In order to overcome the above-mentioned problems in the prior art, the present inventor discloses a kind of catalyzer that pyrolysis gasoline is selected hydrogenation that is used in the open CN1429890A of Chinese patent application, it comprises the titanium dioxide-aluminum oxide mixture as carrier, and be carried on activity component metal palladium on this complex carrier, wherein the content of palladium metal is 0.25-0.35 weight % based on described total catalyst weight.Compare with existing similar catalyst, the liquid phase air speed improves 30-40% when using this catalyzer, and selectivity is greater than 99%, and continuous operation 1500 hours is activity stabilized.Yet this catalyzer is to pyrolysis gasoline C
8～C
9Performance when hydrogenation is selected in last running still remains to be improved.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor selects hydrogenation to carry out research extensively and profoundly with catalyzer to pyrolysis gasoline, found that by using alkaline-earth metal that the aluminum oxide as carrier is carried out the catalyzer that the bimetal active ingredient obtains in modification and the load not only have good low temperature active, selectivity and stability, and especially at the C that is used for pyrolysis gasoline
8And C
9Have good anti-As, S, O, N impurity ability when hydrogenation is selected in last running, charging capacity is big and be difficult for inactivation.The present invention just is being based on above discovery and is being accomplished.
Therefore, the purpose of this invention is to provide a kind of new catalyzer that is used for pyrolysis gasoline selection hydrogenation, this catalyzer has low temperature active height, anti-impurity ability and holds the characteristics of glue ability height and good stability.
Another object of the present invention provides a kind of method for preparing above-mentioned catalyzer.
A further object of the present invention provides a kind of method of pyrolysis gasoline being selected hydrogenation.
One aspect of the present invention provides a kind of pyrolysis gasoline C that is used for
5～C
9Cut, especially C
8And C
9The catalyzer of hydrogenation is selected in last running, comprise aluminum oxide, be covered in alkaline-earth metal on the described carrier surface or its oxide compound and as metal Pd and Mo or the Pd and the W of active constituent loading on described carrier as carrier, wherein the content of alkaline-earth metal is 1-3 weight % based on described total catalyst weight, and the content of metal Pd is that the weight ratio of 0.24～0.35 weight % and metal Pd and metal M o or metal Pd and metal W is 1: 0.5～2.5 based on described total catalyst weight.
The present invention provides a kind of method for preparing above-mentioned catalyzer on the other hand, comprises the steps:
(1) be 40～160m with specific surface area
2/ g, pore volume is 0.4～1.5ml/g, the most probable aperture is that the aluminum oxide of 80～260 dusts immerses at least in the alkaline earth metal compound solution with described aluminum oxide pore volume equivalent, stirred 10～30 minutes, drain away the water, under 100～150 ℃ temperature dry 4～10 hours, in 400～600 ℃ roasting temperature 4～8 hours, make the modified support that contains 1～3 weight % alkaline-earth metal based on described alumina weight then; Or
(2) used aluminum oxide in the step (1) is immersed at least in the mixing solutions with the mixing solutions of the alkaline earth metal compound of described aluminum oxide pore volume equivalent and Mo source compound or alkaline earth metal compound and W source compound, stirred 10～30 minutes, drain away the water, drying is 4～10 hours under 100～150 ℃ temperature, in 400～600 ℃ roasting temperatures 4～8 hours, make the catalyst precursor that contains 1～3 weight % alkaline-earth metal and 0.20～0.64 weight % metal M o or W based on described alumina weight; With
(3) modified support that makes in the step (1) is used with final catalyzer and contained Pd source compound and the Mo of 0.5～2.5 times of palladium amount or the mixing solutions of W source compound that Pd amount equates, solution amount with the described carrier of submergence was flooded 1～4 hour, the hydrazine hydrate reduction that adds 30～40 weight % of 1～2 times of carrier bulk after draining away the water, to there not being chlorion, drying is 4～10 hours under 100～150 ℃ temperature with deionized water wash; Then in 400～600 ℃ roasting temperature 4～8 hours; Or
(4) catalyst precursor that makes in the step (2) is used with final catalyzer and contained palladium source compound solution that the palladium amount equates with the solution amount dipping of submergence catalyst precursor 1～4 hour, the back that drains away the water adds the hydrazine hydrate reduction 1～2 hour of 30～40 weight % of 1～2 times of catalyst precursor volume, with deionized water wash to there not being chlorion, drying is 4～10 hours under 100～150 ℃, then in 400～600 ℃ of following roastings 4～8 hours.
Further aspect of the present invention provides a kind of pyrolysis gasoline has been selected the method for hydrogenation, comprising:
(1) be 100～150 ℃ in temperature, hydrogen pressure is that 2.0～5.0Mpa and hydrogen flowing quantity are reduction catalyzer of the present invention 6～18 hours under the condition of 2～15ml/min.g catalyzer; With
(2) be 30～100 ℃ in temperature, hydrogen pressure is 2.0～5.0MPa, and hydrogen to oil volume ratio is 50～600: 1, and the liquid phase air speed is 8.0～12.0h
-1Condition under hydrocracking gasoline.
These and other purposes of the present invention, feature and advantage will become more clear after reading this specification sheets.
Detailed Description Of The Invention
Select hydrogenation with in the catalyzer at pyrolysis gasoline of the present invention, the content of alkaline-earth metal is 1-3 weight % based on total catalyst weight; The content of metal Pd is 0.24-0.35 weight % based on described total catalyst weight, preferred 0.25-0.32 weight %; And the weight ratio of Pd and Mo or Pd and W is 1: 0.5～2.5, preferred 1: 0.8～2.0.
Pyrolysis gasoline of the present invention selects hydrogenation to use the crushing strength of catalyzer greater than 18N/mm.
Active component palladium loads on catalyst coating in the catalyzer of the present invention, and by finding that with scanning electron microscopic observation the epidermal thickness that palladium more than the 80 weight % concentrates on catalyzer is 0～0.25 millimeter place, and active ingredient Mo or W are distributed in the micropore of whole catalyzer.
In Preparation of catalysts method of the present invention, used aluminum oxide there is not particular restriction, as long as the modified support that this aluminum oxide of use obtains or the specific surface area of catalyst precursor are 50～120m
2/ g, preferred 70～100m
2/ g, pore volume are 0.4～1.2ml/g, preferred 0.5～1.0ml/g, and the most probable aperture is 100～260 dusts, preferred 110～200 dusts.For example, can use specific surface area to be 40-160m
2/ g; Pore volume is 0.4-1.5ml/g; The most probable aperture is the aluminum oxide of 80-260 dust.In addition, the shape of aluminum oxide is not had particular restriction, for example can be cylindricality, bar shaped, sphere and cloverleaf pattern.
In Preparation of catalysts method of the present invention, used alkaline earth metal compound for example comprises the oxide compound or the inorganic salt of calcium and magnesium, as nitrate, vitriol etc.These alkaline earth metal compounds are 1.0～8.5 weight % with concentration preferably, and more preferably the aqueous solution of 1.5～6.0 weight % uses.Under the situation that at first prepares modified support, the amount of the alkaline earth metal compound aqueous solution should equate with the pore volume for the treatment of modified aluminas at least in step (1); And under the situation that at first prepares catalyst precursor, alkaline earth metal compound should equate with the pore volume for the treatment of modified aluminas at least with the amount of the mixed aqueous solution of Mo or W source compound in step (2).
In Preparation of catalysts method of the present invention, used tungsten source compound or molybdenum source compound for example comprise molybdate (as ammonium molybdate), molybdenum oxide, wolframic acid, tungstate (as ammonium metawolframate, positive ammonium tungstate) or tungsten oxide.These Mo or W source compound are 0.1～2.0 weight % with concentration preferably, and more preferably the aqueous solution of 0.25～1.5 weight % uses.Under the situation that at first prepares catalyst precursor, Mo or W source compound should equate with the pore volume for the treatment of modified aluminas at least with the amount of the mixed aqueous solution of alkaline earth metal compound in step (2); And under the situation that at first prepares modified support, the amount of the mixed aqueous solution of Mo or W source compound and Pd source compound should be enough to submergence modified support in step (3).
In Preparation of catalysts method of the present invention, used palladium source compound can be the disclosed any palladium compound that is suitable for preparing palladium catalyst of prior art, as the organic acid salt of palladium metal, Palladous chloride, Palladous nitrate, palladous sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, tetranitro palladium acid sodium, palladium such as oxalic acid palladium etc.These palladium source compounds are 0.15～0.75 weight % with concentration preferably, and more preferably the aqueous solution of 0.2～0.7 weight % uses.Under the situation that at first prepares modified support, the amount of the mixed aqueous solution of palladium source compound and Mo or W source compound should be enough to submergence modified support in step (3); And under the situation that at first prepares catalyst precursor, the water-soluble liquid measure of palladium source compound should be enough to the submergence catalyst precursor in step (4).
Catalyzer of the present invention can be used for pyrolysis gasoline C
5～C
9Cut, particularly C
8And C
9The selection hydrogenation of last running and have following outstanding advantage and effect:
(1) the existing palladium of low temperature hydrogenation specific activity or the nickel catalyst height of catalyzer of the present invention.
(2) catalyzer of the present invention is used for pyrolysis gasoline C
5-C
9Cut, particularly C
8And C
9During the hydrogenation of last running, has the ability of stronger anti-As, S, O, N impurity.
(3) catalyzer appearance colloidality of the present invention can be good, and hydrogenation activity is stable, can long period use.
Embodiment
Below by embodiment the present invention has been carried out further elaboration, but these embodiment are construed as limiting to scope of the present invention in no case.
Embodiment 1
1. the preparation of catalyst precursor
Getting specific surface area is 93m
2/ g, pore volume is 0.55ml/g, the most probable aperture is the cloverleaf pattern aluminum oxide 97.3g of 188 dusts, mixed aqueous solution 90ml dipping with nitrocalcite 0.14g/ml and ammonium molybdate 0.006g/ml, stirred 20 minutes, and drained away the water, in 120 ℃ of dryings 10 hours, in 550 ℃ of roastings 4 hours, make catalyst precursor then.The calcium contents of this catalyst precursor is that 2.1 weight %, Mo content are that 2.9 weight %, specific surface area are 92m
2/ g, pore volume are that 0.54ml/g and most probable aperture are 188 dusts.
2. Preparation of catalysts
The catalyst precursor of 100g step 1 preparation is immersed in the 0.509g/ml aqueous solution of 85ml Palladous chloride, take out after 1 hour, drain away the water, with 120ml concentration is the hydrazine hydrate reduction 1 hour of 40 weight %, with deionized water wash to there not being chlorion, drying is 6 hours under 120 ℃, and then in 480 ℃ of following roastings 4 hours, making palladium content is that 0.3 weight %, crushing strength are the PdO-MoO of 21N/mm
3/ CaO-Al
2O
3Catalyzer (A).
Embodiment 2
1. the preparation of modified support
Get the aluminum oxide 97.3g of embodiment 1, with nitrocalcite 0.14g/ml aqueous solution 90ml dipping, stir and drain away the water after 20 minutes, in 120 ℃ of dryings 10 hours, in 550 ℃ of roastings 4 hours, making calcium contents was that 2.1 weight %, specific surface area are 92m
2/ g, pore volume are that 0.54ml/g and aperture are the modified support of 188 dusts.
2. Preparation of catalysts
The modified support of 100g step 1 preparation is immersed in the 0.006g/ml mixed aqueous solution of the 0.509g/ml of 85ml Palladous chloride and ammonium molybdate, take out after 1 hour, drain away the water, with 120ml concentration is the hydrazine hydrate reduction 1 hour of 40 weight %, to there not being chlorion, drying was 6 hours under 120 ℃, in 500 ℃ of following roastings 4 hours with deionized water wash, make that to contain the palladium amount be 0.3 weight %, containing the molybdenum amount is that 0.3 weight % and crushing strength are the PdO-MoO of 21N/mm
3/ CaO-Al
2O
3Catalyzer (B).
Embodiment 3-8
Repeat the program of embodiment 1, different is to replace ammonium molybdate with ammonium metawolframate in embodiment 5 and 7, replaces nitrocalcite with magnesium nitrate in embodiment 6-8, and correspondingly changes the component concentration of catalyzer, make different catalyzer C, D, E, F, G, H respectively, the results are shown in Table 1.
Table 1
| The catalyzer numbering | ??C | ??D | ??E | ??F | ??G | ??H | |
| Loaded metal kind and content (weight %) | ????Pd | ??0.28 | ??0.3 | ??0.28 | ??0.3 | ??0.28 | ??0.3 |
| ????Ca | ??2.1 | ??2.7 | ??2.1 | ||||
| ????Mg | ??2.1 | ??2.1 | ??2.7 | ||||
| ????Mo | ??0.35 | ??0.45 | ??0.3 | ??0.45 | |||
| ????W | ??0.3 | ??0.3 | |||||
Embodiment 9
The catalyzer of present embodiment explanation embodiment 1-8 gained is at pyrolysis gasoline C
8Application in the fraction selective hydrogenation.
Getting catalyst A, B, C, D, E, F, G, each 100ml of H that embodiment 1-8 makes, is 2.8MPa at hydrogen pressure, and temperature is that 110 ℃ and hydrogen flowing quantity are reduction 8 hours under the condition of 4ml/min.g catalyzer.Be 2.8MPa at hydrogen pressure then, temperature of reaction is 50 ℃, and hydrogen to oil volume ratio is 80: 1, and the charging air speed is 8h
-1Condition under to feed diene content be that 20.27g iodine/100g oil, bromine valency are that 40.36g bromine/100g oil, gum level are that 232mg/100ml oil, nitrogen content are that 3.4mg/l oil, oxide content are that 2.19g/100ml oil, sulphur content are that 110ppm and arsenic content are the pyrolysis gasoline C of 180ppb
8Cut, hydrogenation the results are shown in Table shown in 2.
Table 2
| Catalyzer | ????A | ????B | ????C | ????D | ????E | ????F | ????G | ????H |
| Reaction times (hour) | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| The average bromine valency of product (g bromine/100g oil) | ??18.12 | ??20.95 | ??21.58 | ??18.82 | ??23.09 | ??21.27 | ??28.83 | ??19.38 |
| The average diene of product (g iodine/100g oil) | ??0.33 | ??0.45 | ??0.38 | ??0.57 | ??0.66 | ??0.59 | ??0.48 | ??0.41 |
| Diolefin hydrogenation rate (%) | ??98.3 | ??97.7 | ??98.1 | ??97.2 | ??96.7 | ??97.1 | ??97.6 | ??97.9 |
Embodiment 10
The catalyst A of present embodiment explanation embodiment 1 gained is at the pyrolysis gasoline C of embodiment 9
8Application in the fraction selective hydrogenation.The HTC-200 nickel catalyst that LD365 palladium series catalyst that itself and IFP are produced and Britain Hopkinson Associates Ltd. produce compares under the same conditions.
Respectively getting the embodiment of the invention 1 catalyst A and LD365 palladium catalyst 70ml, is 2.8MPa at hydrogen pressure, and temperature is that 110 ℃ and hydrogen flowing quantity are reduction 8 hours under the condition of 4ml/min.g catalyzer.
Getting HTC-200 nickel catalyst 70ml, is 0.5MPa at hydrogen pressure, and the hydrogen flow rate feeding hydrogen with the 250ml/min/g catalyzer with 100 ℃ of/hour heat-up rates, is heated to 230 ℃ with whole beds, keeps 1 hour, and catalyzer is reduced.Cool to room temperature is 2.8MPa at hydrogen pressure subsequently, and hydrogen flowing quantity is the 50ml/min/g catalyzer, and the vulcanized oil liquid phase air speed of virgin kerosene+1.5 weight % dithiocarbonic anhydride is 6.0～6.5h
-1Condition under, the catalyst reaction bed is warmed up to 100 ℃, finishes the prevulcanized of catalyzer, reduces to temperature of reaction.
At hydrogen pressure is 2.8MPa, and temperature of reaction is 60 ℃, and hydrogen to oil volume ratio is 80: 1, and the liquid phase air speed is 8.0h
-1, recycle ratio is that 3: 1 condition feeds embodiment 9 used pyrolysis gasoline C
8Feedstock, the hydrogenation of three kinds of catalyzer the results are shown in Table 3.
Table 3
| Catalyzer | Reaction times (hour) | The average bromine valency of product (g bromine/100g oil) | The average diene of product (g iodine/100g oil) |
| ??A ??LD365 ??HTC-200 | ????300 ????300 ????200 | ????22.8 ????28.9 ????28.3 | ????0.65 ????1.83 ????2.15 |
Annotate: the palladium content of LD365 catalyzer is 0.33 weight %
Embodiment 11
The present embodiment explanation embodiment of the invention 1 catalyst A is at pyrolysis gasoline C
81000 hours test-results in the fraction selective hydrogenation.
Getting embodiment 1 catalyst A 100ml, repeat the reduction process of embodiment 10, is 2.4～2.6MPa at hydrogen pressure, and hydrogen to oil volume ratio is 100: 1, and charging liquid phase air speed is 8.0h
-1Recycle ratio is 3: 1, reactor inlet temperature is 50 ℃, temperature out is under 56 ℃ the condition, feeding diene content is 16.87g iodine/100g oil, and the bromine valency is that 27.57g bromine/100g oil, gum level are that 146mg/100ml oil, nitrogen content are that 4.9mg/l oil, cl content are that 0.34mg/l oil, oxide content are that 2.11g/100ml oil, sulphur content are that 115ppm and arsenic content are the pyrolysis gasoline C of 150ppb
8Cut, hydrogenation the results are shown in Table 4.
Table 4
| Reaction times (hour) | The average diene of product (g iodine/100g oil) | The average bromine valency of product (g bromine/100g oil) |
| ????50 ????100 ????200 ????300 ????400 ????500 ????600 ????700 | ????0.13 ????0.15 ????0.36 ????0.41 ????0.39 ????0.48 ????0.48 ????0.43 | ????10.35 ????9.87 ????8.64 ????10.24 ????11.21 ????10.62 ????10.95 ????11.52 |
| ????800 ????900 ????1000 | ????0.38 ????0.40 ????0.38 | ????10.23 ????10.17 ????11.32 |
Embodiment 12
The present embodiment explanation embodiment of the invention 1 catalyst A is at pyrolysis gasoline C
6-C
8Application in the fraction selective hydrogenation.
Getting embodiment 1 catalyst A 100ml, repeat the reduction process of 10 pairs of catalyzer of embodiment, is 4.7MPa at hydrogen pressure, and hydrogen to oil volume ratio is 400: 1, and charging liquid phase air speed is 12.0h
-1, temperature of reaction is under 50 ℃ the condition, and feeding diene content is 16.87g iodine/100g oil, and the bromine valency is 27.57g bromine/100g oil, and sulphur content is 173ppm, boiling range is 81-157 ℃ pyrolysis gasoline C
6-C
8Cut, hydrogenation the results are shown in Table 5.
Table 5
| Reaction times (hour) | The average diene of product (g iodine/100g oil) | The average bromine valency of product (g bromine/100g oil) |
| ????50 ????100 ????120 ????150 ????180 ????200 ????220 ????252 | ????0.06 ????0.03 ????0.18 ????0.103 ????0.25 ????0.30 ????0.21 ????0.34 | ????14.89 ????15.68 ????14.57 ????15.40 ????15.89 ????15.60 ????15.21 ????15.21 |
Embodiment 13
The present embodiment explanation embodiment of the invention 1 catalyst A is at pyrolysis gasoline C
9The application in the hydrogenation is selected in last running.
Getting embodiment 1 catalyst A 100ml, repeat the reduction process of 10 pairs of catalyzer of embodiment, is 2.4-2.6MPa at hydrogen pressure, and hydrogen to oil volume ratio is 100: 1, and charging liquid phase air speed is 8.0h
-1, reactor inlet temperature is 35～47 ℃, and temperature out is under 70～85 ℃ the condition, and feeding boiling range is 98～202 ℃, and the diene value is 9.64g iodine/100g oil, the bromine valency is that 34.37g bromine/100g oil, sulphur content are 104ppm and C
9Above component concentration is the C of 85.1 weight %
9Cut fraction pyrolysis gasoline, hydrogenation the results are shown in Table 6.
Table 6
| Reaction times (hour) | The average diene of product (g iodine/100g oil) | The average bromine valency of product (g bromine/100g oil) |
| ?50 ?100 ?140 ?200 ?250 ?300 ?350 ?400 ?450 ?500 ?550 ?600 | ????0.13 ????0.29 ????0.33 ????0.33 ????0.44 ????0.24 ????0.36 ????0.52 ????0.52 ????0.49 ????0.47 ????0.56 | ????11.72 ????14.86 ????14.68 ????16.81 ????17.26 ????17.76 ????16.62 ????16.50 ????17.82 ????16.94 ????16.39 ????16.74 |
Claims (7)
1. one kind is used for pyrolysis gasoline C
5～C
9Cut, especially C
8～C
9The catalyzer of hydrogenation is selected in last running, comprise aluminum oxide, be covered in alkaline-earth metal on the described carrier surface or its oxide compound and as metal Pd and Mo or the Pd and the W of active constituent loading on described carrier as carrier, wherein the content of alkaline-earth metal is 1～3 weight % based on described total catalyst weight, and the content of Pd is that the weight ratio of 0.24～0.35 weight % and Pd and Mo or Pd and W is 1: 0.5～2.5 based on described total catalyst weight.
2. catalyzer according to claim 1, wherein the content of Pd is that the weight ratio of 0.25～0.32 weight % and Pd and Mo or Pd and W is 1: 0.8～2.0 based on described total catalyst weight.
3. a method for preparing the described catalyzer of claim 1 comprises the steps:
(1) be 40～160m with specific surface area
2/ g, pore volume is 0.4～1.5ml/g, and the most probable aperture is that the aluminum oxide of 80～260 dusts immerses at least in the alkaline earth metal compound solution with described aluminum oxide pore volume equivalent, stirs 10～30 minutes, drain away the water, drying is 4～10 hours under 100～150 ℃ temperature; In 400～600 ℃ roasting temperature 4～8 hours, make the modified support that contains 1～3 weight % alkaline-earth metal based on alumina weight then; Or
(2) used aluminum oxide in the step (1) is immersed at least in the mixing solutions with the mixing solutions of the alkaline earth metal compound of described aluminum oxide pore volume equivalent and Mo source compound or alkaline earth metal compound and W source compound, stirred 10～30 minutes, drain away the water, drying is 4～10 hours under 100～150 ℃ temperature, in 400～600 roasting temperature 4～8 hours, make the catalyst precursor that contains 1～3 weight % alkaline-earth metal and 0.20～0.64 weight % metal M o or W based on described alumina weight then; With
(3) modified support that makes in the step (1) is used with final catalyzer and contained Pd source compound and the Mo of 0.5～2.5 times of palladium amount or the mixing solutions of W source compound that Pd amount equates, solution amount with the described carrier of submergence was flooded 1～4 hour, the hydrazine hydrate reduction that adds 30～40 weight % of 1～2 times of carrier bulk after draining away the water, to there not being chlorion, drying is 4～10 hours under 100～150 ℃ temperature with deionized water wash; Then in 400～600 ℃ roasting temperature 4～8 hours; Or
(4) catalyst precursor that makes in the step (2) is used with final catalyzer and contained palladium source compound solution that the palladium amount equates with the solution amount dipping of submergence catalyst precursor 1～4 hour, the back that drains away the water adds the hydrazine hydrate reduction 1～2 hour of 30～40 weight % of 1～2 times of catalyst precursor volume, with deionized water wash to there not being chlorion, drying is 4～10 hours under 100～150 ℃, then in 400～600 ℃ of following roastings 4～8 hours.
4. method according to claim 3, the specific surface area of wherein said modified support or catalyst precursor are 50～120m
2/ g, pore volume are 0.4～1.2ml/g, and the most probable aperture is 100～260 dusts.
5. method according to claim 4, the specific surface area of wherein said modified support or catalyst precursor are 70～100m
2/ g, pore volume are 0.5～1.0ml/g, and the most probable aperture is 110～200 dusts.
6. one kind pyrolysis gasoline selected the method for hydrogenation, comprising:
(1) be 100～150 ℃ in temperature, hydrogen pressure is that 2.0～5.0MPa and hydrogen flowing quantity are reduction catalyzer according to claim 1 and 2 6～18 hours under the condition of 2～15ml/min.g catalyzer; With
(2) be 30～100 ℃ in temperature, hydrogen pressure is 2.0～5.0MPa, and hydrogen to oil volume ratio is 50～600: 1, and the liquid phase air speed is 8.0～12.0h
-1Condition under hydrocracking gasoline.
7. method according to claim 6, wherein said pyrolysis gasoline are that the diene value is 8～60g iodine/100g oil, and the bromine valency is the C of 20～60g bromine/100g oil
5～C
9Cut, and the diene value of product is less than 1g iodine/100g oil.
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|---|---|---|---|
| CNB2003101242298A CN1317364C (en) | 2003-12-31 | 2003-12-31 | Catalyst for gasoline heavy fraction pyrolysis and selective hydrogenation, process for preparation and use thereof |
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| CN1107704C (en) * | 2000-02-03 | 2003-05-07 | 中国石油天然气股份有限公司兰州石化分公司 | Selective hydrogenation catalyst for pyrolysis gasoline |
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