CN100478424C - Hydrocarbon oil cracking method - Google Patents
Hydrocarbon oil cracking method Download PDFInfo
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- CN100478424C CN100478424C CNB2004100736416A CN200410073641A CN100478424C CN 100478424 C CN100478424 C CN 100478424C CN B2004100736416 A CNB2004100736416 A CN B2004100736416A CN 200410073641 A CN200410073641 A CN 200410073641A CN 100478424 C CN100478424 C CN 100478424C
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- 238000000034 method Methods 0.000 title claims abstract description 96
- 238000005336 cracking Methods 0.000 title claims abstract description 46
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 58
- 229930195733 hydrocarbon Natural products 0.000 title claims description 58
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 57
- 239000000203 mixture Substances 0.000 claims abstract description 142
- 239000003054 catalyst Substances 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 229910052751 metal Inorganic materials 0.000 claims abstract description 87
- 239000002184 metal Substances 0.000 claims abstract description 86
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000011029 spinel Substances 0.000 claims abstract description 61
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 61
- 238000012546 transfer Methods 0.000 claims abstract description 57
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 35
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 29
- 239000005864 Sulphur Substances 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 64
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 64
- 229910052717 sulfur Inorganic materials 0.000 claims description 64
- 239000011593 sulfur Substances 0.000 claims description 63
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 62
- 239000004411 aluminium Substances 0.000 claims description 62
- 229910052684 Cerium Inorganic materials 0.000 claims description 34
- 239000011787 zinc oxide Substances 0.000 claims description 31
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 22
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 21
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- 238000011069 regeneration method Methods 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- 238000010517 secondary reaction Methods 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- 239000002245 particle Substances 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000004231 fluid catalytic cracking Methods 0.000 description 30
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 29
- 239000003502 gasoline Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 21
- 239000003546 flue gas Substances 0.000 description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 18
- 238000007598 dipping method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 16
- 239000011148 porous material Substances 0.000 description 14
- 238000000926 separation method Methods 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- -1 actinium series rare earth metal Chemical class 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000035939 shock Effects 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 235000012245 magnesium oxide Nutrition 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010009 beating Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 150000003682 vanadium compounds Chemical class 0.000 description 5
- 238000004438 BET method Methods 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003637 basic solution Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229910020068 MgAl Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- 239000000295 fuel oil Substances 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A cracking method for alkymer with sulphur includes that the alkymer passes through a reactor including two reacting regions and contacts with a catalyst for a first and second reaction, in which, said alkymer contains sulphur and said catalyst is a mixture containing cracking catalyst and S-transfer catalyst, which contains spinel composition with alkali earth and Al and oxide with additional metal component, said spinel composition contains alkali earth, Al, rare earth metal and V except Ce, said additional metal oxide is CeO AND ZnO, the weight percentage of the spinel is 50-90% and that of CeO and ZnO IS 10-15%, the mean particle diameter measured by xRD method is less than 130A and that of ZnO is less than 300A.
Description
Technical field
The invention relates to a kind of cracking method of hydrocarbon ils.
Background technology
Fluid catalytic cracking (FCC) is a main method of being obtained gasoline, the contour use value light-end products of diesel oil by heavy raw oil.FCC apparatus is made up of a riser reactor and a revivifier usually, in operating process, cracking catalyst microballoon and hydrocarbon oil crude material with cracking activity carry out the pyrolytic cracking reaction in riser reactor, generate lightweight oil and gas products, meanwhile, cracking catalyst also loses cracking activity because of coking.The cracking catalyst of inactivation need enter in the revivifier, carries out high temperature and burn in the presence of oxygen-containing atmosphere, makes catalyst regeneration.If described hydrocarbon ils is a hydrocarbon oil containing surphur, can contain a large amount of sulphur compounds in the catalyst surface coke, therefore, in burning process, can generate a large amount of sulfur oxide SO
x(SO
2And SO
3), SO
xCan corrode regenerator device on the one hand, on the other hand, can enter atmosphere, cause serious pollution, therefore, must adopt otherwise effective technique, control flue gas SO with regenerator flue gas
xDischarging.
At present, control SO
xA kind of effective means of discharging is to add a small amount of fluidizing performance SO close with cracking catalyst in cracking catalyst
xSorbing material (sulfur transfer catalyst), sulfur transfer catalyst can promote SO in the FCC catalyst regeneration process
2Be oxidized to SO
3, and with SO
3Be adsorbed on the surface and form metal sulfate, be adsorbed with SO
3Sulfur transfer catalyst with regeneration after catalyzer enter riser reactor, under the reductive condition in reactor, the metal sulfate that is adsorbed on the sulfur transfer catalyst is reduced into H
2S, H
2S enters the FCC gaseous product, reclaims by sulfur recovery facility, thereby, make the SO that enters in the atmosphere
xReduce.Metal sulfate is reduced into H
2In the time of S, described sulfur transfer catalyst obtains regeneration simultaneously, and is circulated to revivifier again with decaying catalyst, performance absorption SO
xEffect.
US4,472,532 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that (1) mix a kind of acidic aqueous solution of at least a alkaline earth metal component and aluminium wherein of containing with the basic solution that contains at least a al composition that anionic form exists, form a kind of mixture that contains liquid phase and alkaline including earth metal and aluminum precipitation, wherein, the pH value of liquid phase remains on the scope of 7.0-8.5 in mixing process, (2) the described precipitation of roasting obtains the spinel composition of alkaline including earth metal and aluminium.This method can also comprise with at least a additional metal component dipping said composition or sedimentary process.Described additional metal component is selected from I B in the periodic table of elements, II B, IV B, VIA, VIB, VIIA and VIII family metal, rare earth metal, vanadium, iron, tin, antimony and their mixture.
US4,476,245 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, this method comprises 1) a kind of acidic solution and a kind of wherein aluminium are mixed with the basic solution that contains at least a al composition that anionic form exists, (2) with the product and the aqueous solution that contains at least a alkaline earth metal component, the precipitation that (3) roasting obtains that obtain.Can also further described precipitation or spinel composition be contacted with at least a additional metal component in this method, in said composition in the load significant quantity can under oxidizing condition, promote SO
2Be oxidized to SO
3Additional genus component, described additional metal component also is selected from I B, II B, IV B, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.
US4,492,677 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, this method comprise (1) with a kind of acidic medium that contains at least a alkaline earth metal component, at least aly have the organic compound of inherent alkalescence and aluminium wherein mixes with the aluminium basic solution that contains that anionic form exists, obtain a kind of sedimentary material that contains liquid phase and alkaline-earth metal and aluminium, in the mixing process, the pH value is maintained at about 8.0 or higher, (2) the described precipitation of roasting obtains the spinel composition of alkali metal containing and aluminium.Can also contain in the described composition and a kind ofly can promote SO
2Oxidation or SO
3The additional metal component, described additional metal component is selected from I B, IIB, IVB, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.
US4,522,937 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that (1) mix a kind of acidic solution that contains at least a alkaline earth metal component and at least a wherein aluminium with the alkaline aqueous solution that contains at least a al composition that anionic form exists, obtain containing the sedimentary material of a kind of liquid phase and a kind of alkaline including earth metal and al composition, wherein, at least a in described acidic solution and the basic solution contains at least a additional metal component, and the consumption of described additional metal component is enough to make contain in the composition of described alkaline including earth metal and al composition and can effectively promotes SO
2Oxidation or SO
3At least a additional metal component of amount, and, remain on the scope of 7.0-10.S, the precipitation that (2) roasting obtains in the pH of liquid phase described in mixing process value.Described additional metal component is selected from I B, II B, IV B, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.
US4,497,902 disclose a kind of SO that removes from gas
xComposition, said composition contains a kind of inorganic oxide compositions and at least a free or bonded rare earth metal, described rare earth metal is selected from one group that is made up of lanthanum, cerium, praseodymium, samarium, dysprosium, and described inorganic oxide compositions is selected from by magnesium-aluminium spinel (MgAl
2O
4), a group of forming of the mixture of aluminum oxide and magnesian mixture and magnesium oxide and spinel.Do not provide the character and the preparation method of spinel in the specification sheets of this patent, find from the example, with calcium oxide, a water Alpha-alumina and magnesium oxide mix, and adding nitric acid mixes to be pinched, and obtains a kind of magnesium oxide, Ca of containing after the roasting
3Al
10O
18And magnesium-aluminium spinel (MgAl
2O
4) mixture, roasting, and dipping goes up cerium, can obtain the described SO of taking off
xComposition.
US4,728,635 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that the acidic composition that there is a kind of aluminium wherein with positively charged group form in (1) and a kind of alkaline compositions of alkaline including earth metal mix, (2) mixture that obtains of roasting obtains the spinel composition of alkaline including earth metal and aluminium.
CN 1334316A discloses a kind of sulfur transfer catalyst, this catalyzer contains the composition that contains magnesium-aluminium spinel and the cerium of 2-30 weight % and/or the oxide compound of vanadium of 70-98 weight %, the described composition that contains magnesium-aluminium spinel contains the magnesium oxide of 25-30 weight %, the rare-earth oxide except that cerium of the aluminum oxide of 60-70 weight % and 5-15 weight %, wherein, magnesium and aluminium form spinel structure, the content of free magnesium is lower than the described 5 weight % that contain the total composition of magnesium-aluminium spinel, and the described most probable bore dia that contains the composition of magnesium-aluminium spinel is not less than 100 dusts.
The sulfur-bearing raw material is being carried out in the process of catalytic cracking, not only can generate sulfur oxide SO in the flue gas
x, also can generate a large amount of organosulfur compounds in the FCC gasoline product.The existence of organosulfur compound can aggravate the discharging of dusty gas in the vehicle exhaust in the gasoline, simultaneously its products of combustion SO
xAlso can cause the poisoning and the inactivation of cleaning catalyst for tail gases of automobiles.Disclosed composition of above-mentioned patent (application) and catalyzer are used for the FCC process, though can reduce SO in the FCC flue gas effectively
xDischarging, and can not reduce sulphur content in the FCC gasoline product.In addition, the ability of the sulphur content in the cracking method reduction FCC regenerated flue gas of the disclosed sulfur transfer catalyst of use prior art also has much room for improvement.
CN1078094C discloses a kind of riser reactor that is used for fluid catalytic cracking, this reactor vertically is followed successively by co-axial each other pre lift zone from bottom to up, second reaction zone of first reaction zone, enlarged-diameter, the outlet area of reduced are connected with one section level pipe at the outlet area end.It is different with the processing condition of second reaction zone that this reactor both can satisfy first reaction zone, can make stock oil of different nature carry out the segmentation cracking again.
CN1076751C discloses a kind of catalysis conversion method of producing Trimethylmethane and being rich in isoparaffin gasoline, the stock oil that comprises preheating enters in the reactor that comprises 2 reaction zones, in the presence of water vapor, contact with the cracking catalyst of heat, carry out once and secondary reaction, the cracking reaction condition comprises that first reaction zone temperature is 530-620 ℃, reaction times is 0.5-2 second, second reaction zone temperature is 460-530 ℃, reaction times is 2-30 second, reaction product isolated, reclaimable catalyst enters revivifier behind stripping, recycle after burning.The purpose of this method is the gasoline of producing Trimethylmethane and being rich in isoparaffin, can not reduce the SO in the FCC regenerated flue gas
xDischarging can not reduce the sulphur content in the FCC gasoline product.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can reduce FCC regenerated flue gas SO simultaneously
xSulphur content in discharging and the FCC gasoline product, and have the cracking method of the hydrocarbon ils of the ability of sulphur content in the higher reduction FCC regenerated flue gas.
The present inventor finds that the lower reason of sulfur transfer catalyst activity of prior art is that its contained additional metal component oxide is present in the sulfur transfer catalyst with bigger crystal grain, and for example, the average particulate diameter of cerium oxide is greater than 130 dusts.If introduce the less additional metal component oxide of particle in sulfur transfer catalyst, and described additional metal component oxide is limited in a kind of specific combination, the sulfur transfer catalyst that then obtains can not only reduce FCC regenerated flue gas SO simultaneously
xSulphur content in discharging and the FCC gasoline product, and reduce FCC regenerated flue gas SO
xThe activity of discharging is also higher.
Method provided by the present invention comprises hydrocarbon ils by a reactor that comprises 2 reaction zones, under the cracking hydrocarbon oil condition, contact with a kind of catalyzer, carry out primary first-order equation and secondary reaction, reaction product isolated and catalyzer, with isolated catalyst regeneration and recycle, wherein, described hydrocarbon ils is a hydrocarbon oil containing surphur, described catalyzer is the catalyst mixture that contains cracking catalyst and sulfur transfer catalyst, described sulfur transfer catalyst contains the spinel composition of alkaline including earth metal and aluminium and the oxide compound of additional metal component, and the spinel composition of described alkaline including earth metal and aluminium contains alkaline-earth metal, aluminium, contain or do not contain the rare earth metal except that cerium, contain or do not contain vanadium; Described additional metal component oxide is cerium oxide and zinc oxide, is benchmark with the sulfur transfer catalyst, and the content of the spinel composition of alkaline including earth metal and aluminium is 50-90 weight %, and the content of cerium oxide is 5-25 weight %, and the content of zinc oxide is 5-25 weight %; The average particulate diameter of the cerium oxide that records with XRD method is less than 130 dusts, and the average particulate diameter of zinc oxide is less than 300 dusts.
Because the particle of additional metal component is less in the described sulfur transfer catalyst of method provided by the invention, the average particulate diameter of the cerium oxide that records with XRD method is less than 130 dusts, the average particulate diameter of zinc oxide is less than 300 dusts, be significantly less than the average particulate diameter (being respectively greater than 130 dusts with greater than 500 dusts) of cerium oxide and zinc oxide in the sulfur transfer catalyst of prior art, the active centre number of unit surface is significantly improved in the sulfur transfer catalyst.Therefore, method provided by the invention has higher reduction FCC regenerated flue gas SO
xThe ability of discharging because the present invention has adopted and contained small-particle cerium and this specific combination sulfur transfer catalyst of zinc, can also significantly reduce the content of sulphur in the FCC gasoline product.
In addition, this illustrates when method provided by the invention reduces gasoline and flue gas sulphur content at the same time, has also improved the quality and the quality of gasoline of liquefied gas.Show that adopt method provided by the invention that hydrocarbon oil containing surphur is carried out catalytic cracking, in the liquefied gas that obtains, Trimethylmethane content is higher, olefin content in gasoline is lower.
Description of drawings
Fig. 1 is the schematic flow sheet of method provided by the invention.
Embodiment
According to method provided by the invention, described reactor comprises 2 reaction zones, flows to along hydrocarbon ils and is followed successively by first reaction zone and second reaction zone.
Described reactor can be the reactor with 2 reaction zones of arbitrary form.For example, described reactor can be the riser reactor with 2 reaction zones.Described reactor also can be that 2 reactors with a reaction zone are contacted, the reactor with 2 reaction zones that obtains.For example, described reactor can be the reactor with 2 reaction zones that 2 fixed-bed reactor are formed, or 2 reactor with 2 reaction zones or 2 reactors that moving-burden bed reactor is formed that fluidized-bed reactor is formed with 2 reaction zones, or 2 reactors with 2 reaction zones that riser reactor is formed, also can be the reactor that 2 kinds of combinations in fixed-bed reactor, fluidized-bed reactor, moving-burden bed reactor, the riser reactor obtain with 2 reaction zones.Under the preferable case, described reactor with 2 reaction zones is the riser reactor with 2 reaction zones, as have 2 reaction zones the equal diameter riser reactor, have 2 reaction zones etc. linear speed riser reactor or the disclosed reducing riser reactor that is used for fluid catalytic cracking of CN1078094C.
The cracking hydrocarbon oil condition of first reaction zone and the cracking hydrocarbon oil condition of second reaction zone can be the same or different, and are conventional cracking hydrocarbon oil condition, and these conditions are conventionally known to one of skill in the art.In general, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-650 ℃, is preferably 420-600 ℃, and agent-oil ratio (weight ratio of catalyzer and hydrocarbon ils) is 1-25, is preferably 3-20.
According to embodiment preferred of the present invention, described reactor with 2 reaction zones is the disclosed reducing riser reactor that is used for fluid catalytic cracking of CN1078094C, this reactor vertically is followed successively by co-axial each other pre lift zone from bottom to up, second reaction zone of first reaction zone, enlarged-diameter, the outlet area of reduced are connected with one section level pipe at the outlet area end.Under the preferable case, the diameter of first reaction zone of this reactor and the ratio of pre lift zone diameter are 1-1.2, and the ratio of the diameter of second reaction zone and first reaction zone diameter is 1.5-5.0, and the ratio of the diameter of outlet area and first reaction zone diameter is 0.8-1.5; The height of pre lift zone accounts for the 5-20% of total reactor height, the height of first reaction zone accounts for the 10-30% of total reactor height, the height of second reaction zone accounts for the 30-60% of total reactor height, the height of outlet area accounts for the 0-20% of total reactor height, first reaction zone and the second reaction zone combining site are round table-like, its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is the 30-80 degree, second reaction zone and outlet area combining site also are round table-like, its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is the 45-85 degree.The cracking hydrocarbon oil condition of first reaction zone comprises that temperature of reaction is 450-600 ℃, is preferably 480-550 ℃, and the reaction times is 0.2-5 second, is preferably 0.5-3 second; The cracking hydrocarbon oil condition of second reaction zone comprises that temperature of reaction is 420-550 ℃, is preferably 460-510 ℃, and the reaction times is 1-30 second, is preferably 2-15 second; Agent-oil ratio is 1-20, is preferably 2-12.The temperature of outlet area is generally 410-520 ℃, is preferably 440-500 ℃.
According to method provided by the invention, as a concrete embodiment, can be by flow implementation the present invention shown in Figure 1.As shown in Figure 1, enter the pre lift zone of reactor through pipeline 2 from the catalyzer of revivifier 1, up under the water vapor that the conduct from pipeline 3 promotes medium in advance drives, enter first reaction zone 6.Meanwhile, from the hydrocarbon ils after the preheating of pipeline 4 separately or with atomized water vapor mixing from pipeline 5 after enter first reaction zone 6, described hydrocarbon oil containing surphur and described catalyst mixture carry out primary first-order equation in first reaction zone 6.Reactant flow continues to go upward to second reaction zone 7, proceeds secondary reaction in second reaction zone 7.Logistics behind the secondary reaction continues up, by outlet area 8, through level pipe 9, enters the settling vessel 10 of separation system, and the cyclonic separator in the settling vessel 10 separates catalyzer with crackate.Isolated catalyzer enters the stripper 11 of separation system, and with the water vapor counter current contact from pipeline 12, stripping goes out remaining crackate on the catalyzer, obtains reclaimable catalyst.Isolated crackate and stripped product are mixed the back from pipeline 13 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 1 through inclined tube 14 to be generated, in revivifier 1, under regeneration temperature, reclaimable catalyst is contacted with oxygen containing atmosphere from pipeline 15, removes coke wherein, and reacted flue gas is discharged from pipeline 16.
Can adopt conventional method to adjust the cracking hydrocarbon oil condition of each reaction zone, inject the cold shock agent as combining site the second reaction zone temperature of reaction is reduced at first reaction zone and second reaction zone; Combining site at second reaction zone and outlet area injects the cold shock agent, and perhaps the method with gas-solid sharp separation makes the reaction mixture that enters outlet area carry out quick gas-solid separation, to slow down or to stop the reaction of outlet area; When needed, the temperature that interchanger is regulated the catalyst mixture that enters reactor is set before reactor.Regulate hydrocarbon oil feed speed and come adjusting reaction time.Described interchanger and setting thereof, gas-solid isolating method, cold shock agent and using method thereof are conventionally known to one of skill in the art fast.For example, described interchanger can be tube and shell heat exchanger, plate-type heat exchanger, floating coiler heat exhanger and/or hot-blast heater.The method of gas-solid sharp separation is referring to EP163978, EP139392, EP564678, US5104517, US5308474.The method that adds the cold shock agent is referring to US5089235, EP593823.Described cold shock agent can be selected from one or more in cold catalyzer, raw gasline, gasoline, diesel oil, separation column turning oil, the water.
The effect of atomized water steam is to make the hydrocarbon ils atomizing effect better, makes hydrocarbon ils and catalyst mix more even.The effect that is used as the water vapor of pre-lifting medium is that catalyzer is quickened, and forms density uniform catalyst piston flow at pre lift zone.Described atomized water steam and the pre-consumption that promotes water vapor are conventionally known to one of skill in the art, and in general, atomized water steam and the pre-total amount that promotes water vapor account for the heavy % of 1-30 of hydrocarbon ils, and preferred 2-15 weighs %.
Water vapor from pipeline 12 is a water stripping steam, and the effect of water stripping steam is that the oil gas that is full of between the granules of catalyst and in the particle hole is cemented out, and improves the oil product productive rate.The consumption that is used for steam stripped water vapor is conventionally known to one of skill in the art.In general, the consumption that is used for steam stripped water vapor accounts for the 0.1-0.8 weight % of catalyst recirculation amount, is preferably 0.2-0.4 weight %.
Wherein, promoting water vapor in advance can be with other pre-medium that promotes, as in refinery dry gas, light paraffins, the light olefin one or more, or one or more and the gas mixture replacement of water vapor in them.
The regenerative process of described catalyst mixture is exactly the process that the coke in the catalyst mixture is burnt, and this process is to well known to a person skilled in the art general knowledge.For example, in general, described regeneration temperature is 600-770 ℃, preferred 650-730 ℃.When described hydrocarbon ils carries out in fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor with contacting of catalyst mixture, can feed oxygen-containing atmosphere regeneration in position.When described hydrocarbon ils carries out in riser reactor with contacting of catalyst mixture, can isolated catalyst recirculation to revivifier be regenerated according to the described method of Fig. 1, this regeneration can directly utilize existing reaction-regeneration system to finish." residual oil complete processing ", 282-338 page or leaf (Li Chunnian writes, and Sinopec press published in 2002) is summarized existing catalytic cracking reaction-regeneration system rapidly and revivifier.Described oxygen-containing atmosphere is selected from any one can make coke incendiary gas in the catalyzer, and oxygen-containing atmosphere commonly used is an air.
In the described catalyst mixture that contains cracking catalyst and sulfur transfer catalyst, cracking catalyst and sulfur transfer catalyst content separately is conventionally known to one of skill in the art.In general, in this catalyst mixture, the content of cracking catalyst is 75-99.5 weight %, is preferably 80-98 weight %, and the content of sulfur transfer catalyst is 0.5-25 weight %, is preferably 2-20 weight %.
Described cracking catalyst can be various cracking catalyst, as the various cracking catalyst that contain molecular sieve.The kind of described cracking catalyst and consist of conventionally known to one of skill in the art.
According to method provided by the invention, the average particulate diameter of the cerium oxide that records with XRD method is preferably and is not more than 100 dusts, more preferably the 20-100 dust less than 130 dusts.The average particulate diameter of zinc oxide preferably is not more than 200 dusts less than 300 dusts, more preferably the 120-200 dust.
Zinc oxide in the sulfur transfer catalyst (ZnO) and cerium oxide (CeO
2) the average particulate diameter measuring method referring to JohnWiley﹠amp; The Sons work, flourishing age hero etc. is translated " X-ray diffraction technology (polycrystal and amorphousness material) ", metallurgical industry press, 1986, p442.This method comprises with X-ray diffractometer at CuK
α, voltage 40kV, electric current 40mA, slit 2mm/2mm/0.2mm, 0.02 ° of step-length, step time 1s experiment condition under, catalyst sample is carried out thing phase spectrogram measures.According to 2 θ in the spectrogram
1Locate the peak for=28.63 ° and (belong to CeO
2Characteristic diffraction peak) peak width at half height B
1(baseline with spectrogram is a benchmark, the peak width that diffraction peak 1/2 is highly located), and 2 θ
2=42.72 ° of peak width at half height B that locate peak (belonging to the characteristic diffraction peak of ZnO)
2, calculate by the Scherrer equation:
CeO
2Average particulate diameter
β wherein
1=B
1-b
0
The average particulate diameter of ZnO
β wherein
2=B
2-b
0B under this experiment condition
0=0.09.λ is a wavelength, is 1.5415 dusts under this experiment condition.θ
1And θ
2Be respectively CeO
2XRD feature diffraction angle with ZnO.
With the sulfur transfer catalyst is benchmark, and the content of the spinel composition of alkaline including earth metal and aluminium is 50-90 weight %, and the content of cerium oxide and zinc oxide is 10-50 weight %, and the content of cerium oxide is 5-25 weight %, and the content of zinc oxide is 5-25 weight %.
According to embodiment preferred of the present invention, with the sulfur transfer catalyst is benchmark, the content of the spinel composition of alkaline including earth metal and aluminium is 60-85 weight %, the content of cerium oxide and zinc oxide is 15-40 weight %, under the preferable case, the content of cerium oxide is 7.5-20 weight %, and the content of zinc oxide is 7.5-20 weight %.
The spinel composition of described alkaline including earth metal and aluminium contains alkaline-earth metal, aluminium, contains or does not contain rare earth metal except that cerium, contains or do not contain vanadium.Wherein, all or part of formation spinel structure of described alkaline-earth metal and aluminium, rare earth metal except that cerium and vanadium can be with compounds independently, exist as the form of oxide compound or salt, also can combine with magnesium and aluminium wherein, exist with the form of complex compound.The content range of alkaline-earth metal, aluminium, the rare earth metal except that cerium and vanadium is the content of alkaline-earth metal in the spinel composition of prior art alkaline including earth metal and aluminium, aluminium, the rare earth metal except that cerium and vanadium routine, in general, spinel composition with alkaline including earth metal and aluminium is a benchmark, in oxide compound, the content of alkaline-earth metal is 20-70 weight %, the content of aluminium is 30-80 weight %, and the content of the rare earth metal except that cerium is 0-15 weight %, and the content of vanadium is 0-15 weight %; Under the preferable case, the content of alkaline-earth metal is 30-60 weight %, and the content of aluminium is 35-65 weight %, and the content of the rare earth metal except that cerium is 2-10 weight %, and the content of vanadium is 1-10 weight %.
Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, is preferably magnesium and/or calcium.
Described rare earth metal except that cerium is preferably group of the lanthanides and in the actinium series rare earth metal one or more except that cerium, more preferably lanthanum or rich lanthanum and do not contain the mixture of the lanthanide rare metal of cerium.
In the method provided by the invention, described sulfur transfer catalyst has conventional specific surface and pore volume, and in general, after 650 ℃ of roastings, the specific surface of measuring with cryogenic nitrogen absorption BET method is not less than 30 meters
2/ gram preferably is not less than 50 meters
2/ gram, more preferably 70-120 rice
2/ gram, pore volume are not less than 0.15 milliliter/gram, preferred 0.2-0.5 milliliter/gram.
The preparation method of the described sulfur transfer catalyst of method provided by the invention comprises the spinel composition that floods a kind of alkaline including earth metal and aluminium with the solution one or many that contains the additional metal component composition, dry also roasting, wherein, the spinel composition of described alkaline including earth metal and aluminium contains alkaline-earth metal, aluminium, contains or does not contain rare earth metal except that cerium, contains or do not contain vanadium; Each dipping is described to contain the volumetric usage of solution of additional metal component composition greater than the water droplet method pore volume of the spinel composition of alkaline including earth metal and aluminium, the time of dipping is enough to make described additional metal component composition to be dispersed in the spinel composition of alkaline including earth metal and aluminium, and described additional metal component composition is the compound of cerium and the compound of zinc.
In the preparation method of described sulfur transfer catalyst, the concentration of the solution of additional metal component composition is not particularly limited, as long as through the one or many dipping, the additional metal component that can introduce q.s in catalyzer gets final product.When the concentration of the solution of additional metal component composition is higher, can carry out single-steeping and just can introduce the additional metal component of q.s, and the concentration of the solution of additional metal component composition can repeatedly be flooded when low, can carry out liquid-solid separation or not carry out liquid-solid separation behind each dipping, can be dry or moist, roasting or not roasting.Described liquid-solid isolating method adopts any liquid-solid isolating method, as method of filtering method, cyclonic separation etc.
Under the preferable case, at least 1.5 times of the water droplet method pore volume of the spinel composition that to flood the described volumetric usage that contains the solution of additional metal component composition be alkaline including earth metal and aluminium at every turn, more preferably 2-20 is doubly.The time of dipping generally is no less than 5 minutes, is preferably to be no less than 10 minutes.In general, dipping time surpassed after 120 minutes, and the additional metal component is adsorbed in the spinel composition of alkaline including earth metal and aluminium can reach balance, and dipping time prolongs the influence of catalyzer very little again, therefore, dipping time is more preferably 10-120 minute.The consumption of each component makes in the catalyzer and contains, and is benchmark with the catalyzer, 50-90 weight %, the alkaline including earth metal of preferred 60-85 weight % and the spinel composition of aluminium, 10-50 weight %, cerium oxide and the zinc oxide of preferred 15-40 weight %.
The described solution that contains the additional metal component composition can be the aqueous solution or organic solution, is preferably the aqueous solution.
The compound of described cerium is preferably one or more in water-soluble compound of cerium, as in the muriate of cerium, nitrate, vitriol, phosphoric acid salt, the organic acid salt one or more, is preferably the muriate and/or the nitrate of cerium.The compound of described zinc is preferably one or more in water-soluble compound of zinc, as in the muriate of zinc, nitrate, vitriol, phosphoric acid salt, the organic acid salt one or more, is preferably the muriate and/or the nitrate of zinc.
Flood drying after the spinel composition of described alkaline including earth metal and aluminium and the condition of roasting is conventionally known to one of skill in the art with the solution one or many that contains the additional metal component composition.In general, the exsiccant temperature is a room temperature to 400 ℃, is preferably 100-300 ℃.Maturing temperature is generally 500-800 ℃, is preferably 550-750 ℃; Roasting time is 0.5-8 hour, preferred 1-5 hour.
The spinel composition of described alkaline including earth metal and aluminium can be according to any existing method, for example, and CN1334316A, US4,472,532, US4,476,245, US4,492,677, US4,522,937, US4,497,902, US4, the preparation of 728,635 disclosed methods.
Under the preferable case, the preparation method of the spinel composition of described alkaline including earth metal and aluminium comprises pseudo-boehmite and water making beating even, adding acid makes the pH value of slurries be 1.0-3.5, be preferably 1.5-2.5, the solution and the making beating that add or do not add vanadium compound are even, add the oxide compound of alkaline including earth metal and/or the slurries of oxyhydroxide then, making beating evenly, it is 5-20 weight % that the consumption of each component makes the solid content of the slurries that obtain, be preferably 8-15 weight %, the slurries that dry then also roasting obtains.Arbitrary steps before drying adds the rare earth compound except that cerium.Under the preferable case, the consumption of each component contains the spinel composition of alkaline including earth metal and aluminium, is benchmark with the said composition, in oxide compound, the alkaline-earth metal of 20-70 weight %, the aluminium of 30-80 weight %, the rare earth metal of 0-15 weight % except that cerium, the vanadium of 0-15 weight %; More under the preferable case, the consumption of each component contains the spinel composition of alkaline including earth metal and aluminium, is benchmark with the said composition, in oxide compound, the alkaline-earth metal of 30-60 weight %, the aluminium of 35-65 weight %, the rare earth metal of 2-10 weight % except that cerium, the vanadium of 1-10 weight %.
Wherein, described vanadium compound is selected from any vanadium compound, as in the water-soluble and water-fast vanadium compound one or more, is preferably the muriate of vanadium, one or more in nitrate, oxide compound, oxyhydroxide, the complex compound.These vanadium compound are conventionally known to one of skill in the art.
Described rare earth compound except that cerium is selected from any rare earth compound except that cerium, as in the water-soluble and water-fast rare earth compound except that cerium one or more, be preferably the muriate of the rare earth metal except that cerium, one or more in nitrate, oxide compound, the oxyhydroxide.These rare earth compounds except that cerium are conventionally known to one of skill in the art.
In the preparation process of the spinel composition of described alkaline including earth metal and aluminium, the drying means of described slurries and condition are conventional drying means and condition.Can adopt as the exsiccant method dry, oven dry, forced air drying, spray-dired method.The method of preferably spray drying.The exsiccant temperature can be room temperature to 550 ℃, is preferably 100-300 ℃.The condition of roasting also is conventional roasting condition.Be generally 550-800 ℃ as maturing temperature, be preferably 600-750 ℃; Roasting time 0.5-8 hour, preferred 1-5 hour.
According to method provided by the invention, described hydrocarbon oil containing surphur hydrocarbon ils can be sulphur-bearing crude and various fraction thereof, particularly sulphur-bearing crude or initial boiling point are greater than 330 ℃ petroleum cuts, as sulfur containing atmospheric, vacuum residuum, vacuum gas oil, atmospheric gas oil, straight run gas oil, propane is light/in heavy deasphalted oil and the coker gas oil one or more.
The following examples will the invention will be further described, and the alkaline-earth metal in the described sulfur transfer catalyst is example with magnesium, substitutes magnesium with other alkaline-earth metal and also have similar effect.
Among the embodiment, used pseudo-boehmite (solid content 32.0 weight %) is a technical grade, and Shandong Aluminum Plant produces; In chlorination mishmetal (technical grade, the Shanghai allosaurus rare earth company limited produces) solution, in rare earth oxide, content of rare earth is 244.1 grams per liters, and wherein, the weight ratio of each rare earth component is La
2O
3: Sm
2O
3: Yb
2O
3: Lu
2O
3=79.0: 4.5: 1.9: 0.44; Light magnesium oxide is a technical grade, and producing in magnesium salts chemical plant, Yongchang, Xingtai, contains magnesium oxide 97 weight %, 35 meters of specific surfaces
2/ gram; V
2O
5Be analytical pure, chemical reagent work of Hunan coal science institute produces; Oxalic acid (H
2C
2O
4.2H
2O) be analytical pure, Beijing company of China Drug Co. produces; Cerous chlorate is a technical grade, and Yaolong Non-ferrous Metal Co. Ltd., Shanghai produces; Zinc chloride is an analytical pure, and Beijing dicyclo chemical reagent factory produces; Lanthanum trichloride is an analytical pure, and Beijing dicyclo chemical reagent factory produces.
The zinc oxide of catalyzer and cerium oxide content are by x-ray fluorescence spectrometry among the embodiment, and the content of the spinel composition of alkaline including earth metal and aluminium is by calculating.The specific surface of catalyzer, pore volume are measured with cryogenic nitrogen absorption BET method and water droplet method (referring to " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, PP71-72, Science Press, 1990) respectively.
Embodiment 1
Spinel composition of this example explanation alkaline including earth metal and aluminium and preparation method thereof.
In a stirring tank, add 17.1 kilograms in decationized Y sieve water, under agitation add 5.625 kilograms of pseudo-boehmites, add the aqueous hydrochloric acid that concentration is 18 weight % again, stir, it is 2.0 that the consumption of aqueous hydrochloric acid makes the pH value of slurries.Continue to add 5 liters of V
2O
5-oxalic acid complex solution stirs.Continue to add 2 kilograms of light magnesium oxides and 4.5 kilograms of decationized Y sieve water, making beating stirs, and obtains the slurries that solid content is 11.5 weight %.The slurries that obtain 500 ℃ of temperature ins, are carried out spraying drying under the condition that exhaust temperature is 180 ℃, then in 650 ℃ of following roastings 2 hours, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT
1ZT
1Composition, specific surface and pore volume list in the table 1.
Wherein, V
2O
5The preparation method of-oxalic acid complex solution is as follows: take by weighing 400 gram V
2O
5With 950 gram oxalic acid and 10 liters of decationized Y sieve water and mix, be warming up to 60 ℃ and reacted 1 hour under stirring, promptly generate mazarine V
2O
5-oxalic acid complex solution.
Embodiment 2
Spinel composition of this example explanation alkaline including earth metal and aluminium and preparation method thereof.
In a stirring tank, add 20.2 kilograms in decationized Y sieve water, under agitation add 7.63 kilograms of pseudo-boehmites and 0.655 liter of chlorination mixed rare earth solution, add the aqueous hydrochloric acid that concentration is 18 weight % again, stir, it is 1.65 that the consumption of aqueous hydrochloric acid makes the pH value of slurries.Continue to add 1 liter of example 1 described V
2O
5-oxalic acid complex solution stirs, and continues to add 1.4 kilograms of light magnesium oxides and 3.18 kilograms of slurries that the making beating of decationized Y sieve water forms, and stirs, and obtains the slurries that solid content is 11.5 weight %.The slurries that obtain 500 ℃ of temperature ins, are carried out spraying drying under the condition that exhaust temperature is 180 ℃, then in 650 ℃ of following roastings 2 hours, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT
2ZT
2Composition, specific surface and pore volume list in the table 1.
Embodiment 3
Spinel composition of this example explanation alkaline including earth metal and aluminium and preparation method thereof.
Method preparation by example 2 contains the magnesium-aluminium spinel composition, and different just pseudo-boehmite consumptions are 6.9 kilograms, and 1.676 liters of chlorination mixed rare earth solutions, light magnesium oxide consumption are 1.79 kilograms, V
2O
5The consumption of-oxalic acid complex solution is 4 liters, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT
3ZT
3Composition, specific surface and pore volume list in the table 1.
Embodiment 4
Spinel composition of this example explanation alkaline including earth metal and aluminium and preparation method thereof.
Method preparation by example 2 contains the magnesium-aluminium spinel composition, and different just pseudo-boehmite consumptions are 5.625 kilograms, and the light magnesium oxide consumption is 1.68 kilograms, V
2O
5The consumption of-oxalic acid complex solution is 8 liters, with 0.8 liter lanthanum chloride solution (La
2O
3Content 250 grams per liters) replace the chlorination mixed rare earth solution, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT
4ZT
4Composition, specific surface and pore volume list in the table 1.
Table 1
1. wherein, La
2O
3: Sm
2O
3: Yb
2O
3: Lu
2O
3=79.0: 4.5: 1.9: 0.44; 2. La
2O
3Content.
Embodiment 5
This example explanation sulfur transfer catalyst and preparation method thereof.
Take by weighing 3 kilograms of (in base) carrier ZT respectively
1-ZT
4, and, flood after drying and roasting respectively with the cerous chlorate aqueous solution and/or solder(ing)acid dipping at every turn, obtain sulfur transfer catalyst ZJ
1-ZJ
7Table 2-3 has provided the used solution composition of each dipping and consumption, dipping time, drying temperature, maturing temperature and roasting time.Table 4 has provided sulfur transfer catalyst ZJ
1-ZJ
7Composition.Table 5 has provided sulfur transfer catalyst ZJ
1-ZJ
7Specific surface and the pore volume measured with cryogenic nitrogen absorption BET method, and CeO in the sulfur transfer catalyst that records by XRD method
2Average particulate diameter with ZnO.
Comparative Examples 1-2
Following Comparative Examples explanation reference sulfur transfer catalyst and preparation method thereof.
Method by example 6 and example 7 prepares sulfur transfer catalyst respectively, different when just flooding, adopt existing equi-volume impregnating, the volumetric usage that is dipping solution is identical with the pore volume of the spinel composition of alkaline including earth metal and aluminium, and employing is quantitatively flooded, make the content of cerium oxide and zinc oxide identical with example 6 respectively, obtain reference sulfur transfer catalyst DB with example 7
1And DB
2Table 2-3 has provided the used solution composition of each dipping and consumption, dipping time, drying temperature, maturing temperature and roasting time.Table 4 has provided reference sulfur transfer catalyst DB
1And DB
2Composition.Table 5 has provided reference sulfur transfer catalyst DB
1And DB
2Specific surface and the pore volume measured with cryogenic nitrogen absorption BET method, and CeO in the reference sulfur transfer catalyst that records by XRD method
2Grain size with the ZnO component.
Table 2
Table 3
Table 4
| Example number | Sulfur transfer catalyst | The composition kind | Composition levels, weight % | CeO 2Content, weight % | ZnO content, weight % |
| 5 | ZJ 1 | ZT 1 | 80.23 | 9.89 | 9.88 |
| 6 | ZJ 2 | ZT 2 | 79.88 | 8.07 | 12.05 |
| Comparative Examples 1 | DB 1 | ZT 2 | 79.88 | 8.06 | 12.06 |
| 7 | ZJ 3 | ZT 2 | 76.80 | 14.88 | 8.32 |
| Comparative Examples 2 | DB 2 | ZT 2 | 76.79 | 14.90 | 8.31 |
| 8 | ZJ 4 | ZT 2 | 65.40 | 19.78 | 14.82 |
| 9 | ZJ 5 | ZT 2 | 75.99 | 11.89 | 12.12 |
| 10 | ZJ 6 | ZT 3 | 75.94 | 11.91 | 12.15 |
| 11 | ZJ 7 | ZT 4 | 76.05 | 11.69 | 12.26 |
Table 5
| Example number | Sulfur transfer catalyst | CeO 2Average particulate diameter, dust | The ZnO average particulate diameter, dust | Specific surface, rice 2/ gram | Pore volume, milliliter/gram |
| 5 | ZJ 1 | 65.25 | 154.22 | 97 | 0.26 |
| 6 | ZJ 2 | 47.85 | 162.43 | 95 | 0.27 |
| Comparative Examples 1 | DB 1 | 135.14 | 589.62 | 62 | 0.19 |
| 7 | ZJ 3 | 70.43 | 145.08 | 90 | 0.25 |
| Comparative Examples 2 | DB 2 | 180.80 | 505.38 | 55 | 0.15 |
| 8 | ZJ 4 | 80.27 | 191.84 | 85 | 0.24 |
| 9 | ZJ 5 | 68.13 | 158.76 | 93 | 0.26 |
| 10 | ZJ 6 | 68.56 | 163.31 | 93 | 0.26 |
| 11 | ZJ 7 | 67.44 | 160.69 | 93 | 0.26 |
From the result of table 5 as can be seen, in the described sulfur transfer catalyst of method provided by the invention, the CeO that records by XRD method
2Average particulate diameter all less than 130 dusts, the average particulate diameter of ZnO is all less than 300 dusts, and the CeO that adopts the reference sulfur transfer catalyst of prior art for preparing to be recorded by XRD method
2Big a lot of with the average particulate diameter of ZnO, CeO
2Average particulate diameter all greater than 130 dusts, the average particulate diameter of ZnO is all greater than 500 dusts.In addition, the pore volume of reference sulfur transfer catalyst obviously reduces, and may be that cause in the metal oxide particle obstruction duct of load.
Example 12-18
Following example illustrates method provided by the invention.
According to flow process shown in Figure 1 hydrocarbon oil containing surphur is carried out catalytic cracking.Enter the pre lift zone of reactor through pipeline 2 from the catalyst mixture of revivifier 1, up under drive from the pre-lifting water vapor of pipeline 3, enter first reaction zone 6, meanwhile, from the hydrocarbon oil containing surphur after the preheating of pipeline 4 separately or with atomized water vapor mixing from pipeline 5 after enter first reaction zone 6, described hydrocarbon oil containing surphur and described catalyst mixture carry out primary first-order equation in first reaction zone 6.Reactant flow continues to go upward to second reaction zone 7, proceeds secondary reaction in second reaction zone 7.Logistics behind the secondary reaction continues up, by outlet area 8, through level pipe 9, enters the settling vessel 10 of separation system, and the cyclonic separator in the settling vessel 10 separates catalyzer with crackate.Isolated catalyzer enters the stripper 11 of separation system, and with the water vapor counter current contact from pipeline 12, stripping goes out remaining crackate on the catalyzer, obtains reclaimable catalyst.Isolated crackate and stripped product are mixed the back from pipeline 13 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 1 through inclined tube 14 to be generated, in revivifier 1, under regeneration temperature, reclaimable catalyst is contacted with air from pipeline 15, removes coke wherein, and reacted flue gas is discharged from pipeline 16.In order to reduce the temperature of reaction of second reaction zone 7, junction at first reaction zone 6 and second reaction zone 7, add the cold shock agent, the add-on of cold shock agent is reduced to shown in table 8 and 11 temperature of reaction of second reaction zone 7, and the kind of cold shock agent is also listed in table 8 and 11.
Described reactor is the disclosed reducing riser reactor of CN 1078094C, the height of reactor is 4000 millimeters, the height of pre lift zone is 500 millimeters, interior diameter is 12 millimeters, first reaction zone 6 highly is 1200 millimeters, second reaction zone 7 highly is 1550 millimeters, the interior diameter of first reaction zone 6 is 14 millimeters, the interior diameter of second reaction zone 7 is 22 millimeters, the interior diameter of outlet area 8 is 14 millimeters, highly be 750 millimeters, the combining site of first reaction zone 6 and second reaction zone 7 is round table-like, and its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is 60 degree, second reaction zone 7 also is round table-like with the combining site of outlet area 8, and its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is 60 degree.
(the industrial trade mark is the industrial equilibrium catalyst of the FCC of Orbit-3000 to described catalyst mixture with FCC catalyzer F1 for the sulfur transfer catalyst of example 5-11 preparation, Qilu Petrochemical company catalyst plant product), (the industrial trade mark is the FCC industry equilibrium catalyst of GOR-II to F2, Qilu Petrochemical company catalyst plant is produced) or the mixture of F3 (the industrial trade mark is the FCC industry equilibrium catalyst of GOR-DQ, and Qilu Petrochemical company catalyst plant is produced).Main active component and the character of F1, F2 and F3 are listed in the table 6.
Described hydrocarbon oil containing surphur is decompressed wax oil shown in the table 7 (T2), or long residuum (T1) content is 30 weight %, and decompressed wax oil (T2) content is the mixing oil (T1+T2) of 70 weight %.
Reaction conditions and reaction result are listed in table 8 and 11, and table 9 and table 12 have provided the composition of the gasoline that obtains, and table 10 and table 13 have provided the composition of the liquefied gas that obtains.Wherein, the percentage composition of catalyst mixture is the weight percentage composition.
Comparative Examples 3-5
Following Comparative Examples explanation is not used sulfur transfer catalyst and is used the situation of reference sulfur transfer catalyst.
Method by example 12 is carried out catalytic cracking to same stock oil, and different is that the catalyst system therefor mixture replaces with the mixture of 100% industrial FCC equilibrium catalyst F3, DB1 and industrial FCC equilibrium catalyst F3 and the mixture of DB2 and industrial FCC equilibrium catalyst F3 respectively.Reaction conditions and reaction result are listed in table 8 and 11, and table 9 and table 12 have provided the composition of the gasoline that obtains, and table 10 and table 13 have provided the composition of the liquefied gas that obtains.
Table 6
Table 7
| The hydrocarbon ils numbering | T1 | T2 |
| The stock oil title | Long residuum | Decompressed wax oil |
| Density (20 ℃), gram per centimeter 3Viscosity (100 ℃), millimeter 2/ second zero pour, ℃ carbon residue, weight % | 0.8906 24.84 43 4.3 | 0.9154 6.962 35 0.18 |
| Elementary composition, weight % C/H S/N | 86.54/13.03 0.13/0.3 | 85.38/12.03 2.0/0.16 |
| Four components, weight % stable hydrocarbon aromatic hydrocarbons gum asphalt | 51.2 29.7 18.3 0.8 | 64.0 32.0 4.0 0.0 |
| Boiling range, ℃ IBP/5% 10%/30% 50%/70% 90%/95% | 282/351 370/482 553/- - | 329/363 378/410 436/462 501/518 |
Table 8
| The kind stock oil sulphur of example number catalyzer hydrocarbon ils, the weight % hydrocarbon oil feed mode first reaction zone temperature of reaction, ℃ second reaction zone temperature of reaction, ℃ first reaction zone reaction times, the second reaction zone reaction times of second, second agent-oil ratio outlet area temperature regeneration temperature.℃ cold shock agent kind atomized water steam and the pre-total amount that promotes water vapor account for the weight percentage of hydrocarbon ils | Comparative Examples 3 100%F3 T2 2.0 hydrocarbon ils/atomized water steam 510 490 2.0 4.4 5 475 680 raw gasline 10 | 12 3%ZJ 2+ 97%F3 T2 2.0 hydrocarbon ils/atomized water steam 510 490 2.0 4.4 5 475 680 raw gasline 10 | Comparative Examples 4 3%DB 1+ 97%F3 T2 2.0 hydrocarbon ils/atomized water steam 510 490 2.0 4.4 5 475 680 raw gasline 10 | 13 3%ZJ 3+ 97%F3 T2 2.0 hydrocarbon ils/atomized water steam 510 490 2.0 4.4 5 475 680 raw gasline 10 | Comparative Examples 5 3%DB 2+ 97%F3 T2 2.0 hydrocarbon ils/atomized water steam 510 490 2.0 4.4 5 475 680 raw gasline 10 |
| Material balance, weight % dry gas liquefied gas C 5 +Gasoline, diesel heavy oil coke loss transformation efficiency, weight % content of sulfur in gasoline, mg/litre gasoline sulfur decrement, % is the flue gas sulphur content 3., milligram/rice 3Flue gas desulphuization rate, weight % are 3. | 1.52 12.30 47.86 18.84 15.37 3.89 0.22 65.79 1380-770- | 1.53 11.91 47.68 18.97 15.86 3.77 0.28 65.17 960 30.4 80 89.6 | 1.59 11.97 47.58 18.02 15.74 3.80 0.30 66.24 1,290 6.5 105 86.4 | 1.52 12.16 47.71 18.92 15.72 3.72 0.25 65.36 1,020 26.1 60 92.2 | 1.60 11.86 47.70 18.87 15.89 3.82 0.26 65.24 1,250 9.4 115 85.1 |
3. gasoline sulfur decrement and flue gas desulphuization rate are criterion calculation with Comparative Examples 3.
Table 9
Table 10
Table 11
Table 12
Table 13
From table 8 and 11 as can be seen, compare when only using poiser, use the catalyst mixture that contains the reference sulfur transfer catalyst, do not reduce pressure gasoline The product sulfur content basically.And adopt method provided by the invention, and use the catalyst mixture that contains sulfur transfer catalyst of the present invention, the sulphur content of pressure gasoline product significantly reduces, and shows better reduction flue gas SO
xThe effect of discharging.
From the table 9-10 and the table 12-13 the result as can be seen, adopt method provided by the invention that hydrocarbon oil containing surphur is carried out catalytic cracking, in the liquefied gas that obtains, Trimethylmethane content is up to 29.15-32.87 weight %, in the gasoline that obtains, olefin(e) centent has only 15.03-21.21 weight %.This illustrates when method provided by the invention reduces gasoline and flue gas sulphur content at the same time, has also improved the quality and the quality of gasoline of liquefied gas.
Example 19
Following example illustrates method provided by the invention.
Method according to example 12 is carried out catalytic cracking to same stock oil, and different is, and described reactor is the disclosed reducing riser reactor of CN1078094C.The total height of this reactor is 15 meters, the height of pre lift zone is 1.5 meters, diameter is 0.25 meter, the height of first reaction zone 6 is 4 meters, the diameter of first reaction zone 6 is 0.25 meter, the height of second reaction zone 7 is 6.5 meters, the diameter of second reaction zone 7 is 0.5 meter, the diameter of outlet area 8 is 0.25 meter, the height of outlet area 8 is 3 meters, the apex angle of the profile isosceles trapezoid of first reaction zone 6 and second reaction zone, 7 combining sites is 45 degree, and the base angle β of the profile isosceles trapezoid of second reaction zone and outlet area combining site is 45 degree.Reaction result is listed in the table 14.Table 15 and 16 has provided the composition of gasoline and liquefied gas respectively.
Table 14
Table 15
Table 16
Claims (17)
1. the cracking method of a hydrocarbon ils, this method comprises hydrocarbon ils by a reactor that comprises 2 reaction zones, under the cracking hydrocarbon oil condition, contact with a kind of catalyzer, carry out primary first-order equation and secondary reaction, reaction product isolated and catalyzer, with isolated catalyst regeneration and recycle, it is characterized in that, described hydrocarbon ils is a hydrocarbon oil containing surphur, described catalyzer is the catalyst mixture that contains cracking catalyst and sulfur transfer catalyst, described sulfur transfer catalyst contains the spinel composition of alkaline including earth metal and aluminium and the oxide compound of additional metal component, and the spinel composition of described alkaline including earth metal and aluminium contains alkaline-earth metal, aluminium, contain or do not contain the rare earth metal except that cerium, contain or do not contain vanadium; Described additional metal component oxide is cerium oxide and zinc oxide, is benchmark with the sulfur transfer catalyst, and the content of the spinel composition of alkaline including earth metal and aluminium is 50-90 weight %, and the content of cerium oxide is 5-25 weight %, and the content of zinc oxide is 5-25 weight %; The average particulate diameter of the cerium oxide that records with XRD method is less than 130 dusts, and the average particulate diameter of zinc oxide is less than 300 dusts.
2. method according to claim 1 is characterized in that, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-650 ℃, and agent-oil ratio is 1-25.
3. method according to claim 2 is characterized in that, described cracking hydrocarbon oil condition comprises that temperature of reaction is 420-600 ℃, and agent-oil ratio is 3-20.
4. method according to claim 1, it is characterized in that, described reactor with 2 reaction zones is the reducing riser reactor, this reactor vertically is followed successively by co-axial each other pre lift zone from bottom to up, second reaction zone of first reaction zone, enlarged-diameter, the outlet area of reduced are connected with one section level pipe at the outlet area end.
5. method according to claim 4, it is characterized in that, the diameter of first reaction zone of this reactor and the ratio of pre lift zone diameter are 1-1.2, the ratio of the diameter of second reaction zone and first reaction zone diameter is 1.5-5.0, and the ratio of the diameter of outlet area and first reaction zone diameter is 0.8-1.5; The height of pre lift zone accounts for the 5-20% of total reactor height, the height of first reaction zone accounts for the 10-30% of total reactor height, the height of second reaction zone accounts for the 30-60% of total reactor height, the height of outlet area accounts for the 0-20% of total reactor height, first reaction zone and the second reaction zone combining site are round table-like, its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is the 30-80 degree, second reaction zone and outlet area combining site also are round table-like, its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is the 45-85 degree.
6. according to claim 4 or 5 described methods, it is characterized in that the cracking hydrocarbon oil condition of first reaction zone comprises that temperature of reaction is 450-600 ℃, the reaction times is 0.2-5 second; The cracking hydrocarbon oil condition of second reaction zone comprises that temperature of reaction is 420-550 ℃, and the reaction times is 1-30 second; Agent-oil ratio is 1-20.
7. method according to claim 6 is characterized in that, the cracking hydrocarbon oil condition of first reaction zone comprises that temperature of reaction is 480-550 ℃, and the reaction times is 0.5-3 second; The cracking hydrocarbon oil condition of second reaction zone comprises that temperature of reaction is 460-510 ℃, and the reaction times is 2-15 second; Agent-oil ratio is 2-12.
8. method according to claim 1, it is characterized in that, in the described catalyst mixture that contains cracking catalyst and sulfur transfer catalyst, be benchmark with described catalyst mixture, the content of cracking catalyst is 75-99.5 weight %, and the content of sulfur transfer catalyst is 0.5-25 weight %.
9. method according to claim 8 is characterized in that, the content of cracking catalyst is 80-98 weight %, and the content of sulfur transfer catalyst is 2-20 weight %.
10. method according to claim 1 is characterized in that the average particulate diameter of cerium oxide is not more than 100 dusts, and the average particulate diameter of zinc oxide is not more than 200 dusts.
11. method according to claim 10 is characterized in that, the average particulate diameter of cerium oxide is the 20-100 dust, and the average particulate diameter of zinc oxide is the 120-200 dust.
12. method according to claim 1 is characterized in that, is benchmark with the sulfur transfer catalyst, the content of the spinel composition of alkaline including earth metal and aluminium is 60-85 weight %, and the content of cerium oxide and zinc oxide is 15-40 weight %.
13. method according to claim 1, it is characterized in that, spinel composition with alkaline including earth metal and aluminium is a benchmark, in oxide compound, the content of alkaline-earth metal is 20-70 weight %, the content of aluminium is 30-80 weight %, and the content of the rare earth metal except that cerium is 0-15 weight %, and the content of vanadium is 0-15 weight %.
14. method according to claim 13, it is characterized in that, spinel composition with alkaline including earth metal and aluminium is a benchmark, in oxide compound, the content of alkaline-earth metal is 30-60 weight %, the content of aluminium is 35-65 weight %, and the content of the rare earth metal except that cerium is 2-10 weight %, and the content of vanadium is 1-10 weight %.
15., it is characterized in that described alkaline-earth metal is magnesium and/or calcium according to any described method in the claim 1,12,13,14.
16., it is characterized in that described rare earth metal except that cerium is lanthanum or rich lanthanum and do not contain the mixture of the lanthanide rare metal of cerium according to any described method in the claim 1,13,14.
17. method according to claim 1 is characterized in that, described hydrocarbon oil containing surphur is sulphur-bearing crude or initial boiling point greater than 330 ℃ petroleum cuts.
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